JPH0912686A - Phenolic resin composition, prepreg using the phenolic resin composition, and laminated board wherein that prepreg is used - Google Patents
Phenolic resin composition, prepreg using the phenolic resin composition, and laminated board wherein that prepreg is usedInfo
- Publication number
- JPH0912686A JPH0912686A JP16038495A JP16038495A JPH0912686A JP H0912686 A JPH0912686 A JP H0912686A JP 16038495 A JP16038495 A JP 16038495A JP 16038495 A JP16038495 A JP 16038495A JP H0912686 A JPH0912686 A JP H0912686A
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- prepreg
- phenol resin
- phenolic resin
- curing catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、フェノール樹脂組成
物、このフェノール樹脂組成物を用いたプリプレグ、及
びこのプリプレグを用いた積層板に関するものであり、
具体的には例えば、電子機器等に使われる紙基材フェノ
ール樹脂積層板等に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenol resin composition, a prepreg using the phenol resin composition, and a laminate using the prepreg.
Specifically, for example, it relates to a paper-based phenolic resin laminated plate used in electronic devices and the like.
【０００２】[0002]
【従来の技術】従来、電子機器に使用される紙基材フェ
ノール樹脂積層板は、桐油等で変性したレゾール型フェ
ノール樹脂を溶剤等で粘度調整し、紙基材に含浸乾燥さ
せ、これを複数枚重ね、用途に応じてこの片面または両
面に接着剤つき金属箔を重ねた後、加熱・加圧成形して
製造されている。そして、耐湿性、電気特性等の改良の
ため、これらの特性の良好なエポキシ樹脂でフェノール
樹脂を変性する方法が行われている。しかし、この樹脂
の場合、生産性向上及び省エネルギーのために成形時間
を短縮しようとすると、耐熱性や吸水率等の特性が低下
するという問題がある。2. Description of the Related Art Conventionally, a paper-based phenolic resin laminated board used for electronic equipment has a resol-type phenolic resin modified with tung oil or the like whose viscosity is adjusted with a solvent, impregnated into a paper-based material and dried, and then a plurality of sheets are obtained. It is manufactured by stacking sheets, stacking a metal foil with an adhesive on one side or both sides depending on the application, and then heating and pressing. In order to improve moisture resistance and electric characteristics, a method of modifying a phenol resin with an epoxy resin having good characteristics is used. However, in the case of this resin, if the molding time is shortened in order to improve productivity and save energy, there is a problem that characteristics such as heat resistance and water absorption are deteriorated.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、上記問題点
を改善するために成されたもので、その目的とするとこ
ろは、生産性向上及び省エネルギーのために成形時間を
短くしても、耐熱性や吸水率等の特性が良好に維持でき
るフェノール樹脂組成物、このフェノール樹脂組成物を
用いたプリプレグ、及びこのプリプレグを用いた積層板
を提供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and its object is to improve the productivity and save energy by shortening the molding time. It is an object of the present invention to provide a phenol resin composition capable of maintaining excellent properties such as heat resistance and water absorption, a prepreg using the phenol resin composition, and a laminate using the prepreg.
【０００４】[0004]
【課題を解決するための手段】本発明の請求項１に係る
フェノール樹脂組成物は、重量平均分子量が４０００〜
１７０００であり、分子量１００００以上の分子を１３
重量％（以下％と記す）以上含むフェノール樹脂と、エ
ポキシ樹脂と、硬化触媒を含有することを特徴とする。The phenol resin composition according to claim 1 of the present invention has a weight average molecular weight of 4,000 to 4,000.
17,000, and the number of molecules with a molecular weight of 10,000 or more is 13
It is characterized in that it contains a phenol resin containing not less than wt% (hereinafter referred to as%), an epoxy resin, and a curing catalyst.
【０００５】本発明の請求項２に係るフェノール樹脂組
成物は、請求項１記載のフェノール樹脂組成物におい
て、硬化触媒がアミン系化合物であることを特徴とす
る。A phenol resin composition according to a second aspect of the present invention is characterized in that, in the phenol resin composition according to the first aspect, the curing catalyst is an amine compound.
【０００６】本発明の請求項３に係るフェノール樹脂組
成物は、請求項１記載のフェノール樹脂組成物におい
て、硬化触媒がアミド系化合物であることを特徴とす
る。The phenol resin composition according to claim 3 of the present invention is characterized in that, in the phenol resin composition according to claim 1, the curing catalyst is an amide compound.
【０００７】本発明の請求項４に係るフェノール樹脂組
成物は、請求項１記載のフェノール樹脂組成物におい
て、硬化触媒がイミダゾール系化合物であることを特徴
とする。The phenol resin composition according to claim 4 of the present invention is characterized in that, in the phenol resin composition according to claim 1, the curing catalyst is an imidazole compound.
【０００８】本発明の請求項５に係るプリプレグは、請
求項１から請求項４までのいずれかに記載のフェノール
樹脂組成物を、基材に含浸していることを特徴とする。A prepreg according to a fifth aspect of the present invention is characterized in that a base material is impregnated with the phenol resin composition according to any one of the first to fourth aspects.
【０００９】本発明の請求項６に係る積層板は、請求項
５記載のプリプレグを用いて、成形していることを特徴
とする。A laminated plate according to a sixth aspect of the present invention is characterized by being molded using the prepreg according to the fifth aspect.
【００１０】以下、本発明を詳細に説明する。本発明の
フェノール樹脂組成物を構成するフェノール樹脂は、重
量平均分子量がゲル・パーミエーション・クロマトグラ
フィー（ＧＰＣ）で測定したポリスチレン換算で、４０
００〜１７０００でかつ、分子量１００００以上の分子
を溶剤を除く全フェノール樹脂の合計重量に対し、１３
％以上含む物であり、フェノール類とアルデヒド類を触
媒を用いて反応させて作られる。フェノール類として
は、例えばフェノール、クレゾール、レゾルシン、プロ
ピルフェノール等、フェノール性水酸基を有するものの
単独または、混合物が挙げられ、アルデヒド類として
は、パラホルムアルデヒド、ホルマリン水溶液等が挙げ
られる。フェノール類としては、桐油、脱水ヒマシ油等
の油で変性されたものを使用することが好ましい。Hereinafter, the present invention will be described in detail. The phenol resin constituting the phenol resin composition of the present invention has a weight average molecular weight of 40 in terms of polystyrene measured by gel permeation chromatography (GPC).
13 with respect to the total weight of all phenolic resins excluding the solvent having a molecular weight of 0,000 to 17,000 and a molecular weight of 10,000 or more.
% Or more, and is made by reacting phenols and aldehydes with a catalyst. Phenols include, for example, phenol, cresol, resorcin, propylphenol, and the like having a phenolic hydroxyl group, alone or in a mixture, and as the aldehydes, paraformaldehyde, formalin aqueous solution and the like can be mentioned. As the phenols, those modified with oils such as tung oil and dehydrated castor oil are preferably used.
【００１１】フェノール樹脂の重量平均分子量が４００
０以下の場合、及び分子量１００００以上の分子が１３
％以下のフェノール樹脂の場合は、未反応のフェノール
樹脂が積層板中に残りやすく、耐熱性や吸水率等の特性
が低下する。重量平均分子量が１７０００以上のフェノ
ール樹脂の場合は、基材への含浸性が低下する。 本発
明のフェノール樹脂組成物を構成するエポキシ樹脂とし
ては、多官能エポキシ樹脂であればどのようなものでも
よいが、ビスフェノールＡ型、ビスフェノールＦ型、フ
ェノールノボラック型、ビスフェノールＡノボラック
型、クレゾールノボラック型、ジアミノジフェニルメタ
ン型、及び、これらのエポキシ樹脂構造体中の水素原子
の一部をハロゲン化することにより難燃化したエポキシ
樹脂等が好ましいが、特に限定しない。The weight average molecular weight of the phenol resin is 400
When it is 0 or less, and when the number of molecules with a molecular weight of 10,000 or more is 13,
When the amount of the phenol resin is not more than%, unreacted phenol resin is likely to remain in the laminated plate, resulting in deterioration of properties such as heat resistance and water absorption. In the case of a phenol resin having a weight average molecular weight of 17,000 or more, the impregnability into the base material is lowered. The epoxy resin constituting the phenol resin composition of the present invention may be any polyfunctional epoxy resin as long as it is a bisphenol A type, bisphenol F type, phenol novolac type, bisphenol A novolac type, cresol novolac type. , Diaminodiphenylmethane type, and an epoxy resin flame-retarded by halogenating a part of hydrogen atoms in these epoxy resin structures, but are not particularly limited.
【００１２】エポキシ樹脂の配合量としては、フェノー
ル樹脂の重量の５〜３０％、より好ましくは１０〜２０
％の範囲が好ましい。The amount of the epoxy resin compounded is 5 to 30% of the weight of the phenol resin, more preferably 10 to 20.
% Range is preferred.
【００１３】本発明のフェノール樹脂組成物を構成する
硬化触媒としては、エポキシ樹脂または、フェノール樹
脂用の公知の物が単独または併用して使われるが、アミ
ン系、アミド系、イミダゾール系が好ましい。As the curing catalyst constituting the phenolic resin composition of the present invention, known epoxy resins or phenolic resins may be used alone or in combination, and amine type, amide type and imidazole type are preferable.
【００１４】アミン系硬化触媒としては、例えば、アン
モニア、トリエチルアミン、ジエチルアミン、トリメチ
ルアミン、ジメチルアミン、メチルアミン、エチルアミ
ン、ヘキサメチレンテトラミン、ジプロピルアミン、ｎ
−プロピルアミン、イソプロピルアミン、トリエタノー
ルアミン、トリメタノールアミン、ベンジルアミン、ジ
ベンジルアミン、ジエタノールアミン、ジメタノールア
ミン、エタノールアミン等が挙げられる。Examples of the amine-based curing catalyst include ammonia, triethylamine, diethylamine, trimethylamine, dimethylamine, methylamine, ethylamine, hexamethylenetetramine, dipropylamine, n.
-Propylamine, isopropylamine, triethanolamine, trimethanolamine, benzylamine, dibenzylamine, diethanolamine, dimethanolamine, ethanolamine and the like.
【００１５】アミド系硬化触媒としては、例えば、ジシ
アンジアミド、脂肪族ポリアミド等が挙げられる。Examples of the amide curing catalyst include dicyandiamide and aliphatic polyamide.
【００１６】イミダゾール系硬化触媒としては、例え
ば、２−エチル−４メチルイミダゾール、２−フェニル
イミダゾール、２−メチルイミダゾール、２−エチルイ
ミダゾール、２−エチル−４−メチル−１−プロピオニ
トリルイミダゾール等が挙げられる。Examples of the imidazole type curing catalyst include 2-ethyl-4methylimidazole, 2-phenylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methyl-1-propionitrileimidazole and the like. Is mentioned.
【００１７】上記フェノール樹脂組成物は、必要に応じ
て、アンチモン、トリフェニルホスフェイト、ビスフェ
ノールＡのブロム化物等の難燃剤、無機、有機の充填剤
を適宜に配合してもよい。本発明のフェノール樹脂組成
物は、フェノール樹脂とエポキシ樹脂の硬化反応により
未反応のフェノール樹脂が残り難く、耐熱性や吸水率等
の特性が確保される。The above-mentioned phenol resin composition may be optionally blended with a flame retardant such as antimony, triphenyl phosphate, brominated bisphenol A, or an inorganic or organic filler. In the phenol resin composition of the present invention, the unreacted phenol resin is unlikely to remain due to the curing reaction of the phenol resin and the epoxy resin, and the properties such as heat resistance and water absorption are secured.
【００１８】本発明のプリプレグの製造方法は、上記フ
ェノール樹脂組成物を基材に含浸し、加熱することによ
り樹脂組成物を半硬化してプリプレグを得る。本発明の
フェノール樹脂組成物を用いると、従来の樹脂と同程度
まで半硬化させるのにかかる時間が短くなり、生産性向
上、省エネルギーによるコスト低減が可能になる効果も
得られる。フェノール樹脂組成物を含浸する基材は、ク
ラフト紙、リンター紙、その他クラフト紙又はリンター
紙に無機物又は有機物を混入した紙基材が挙げられる。
樹脂を大量に含有させる必要がある場合には、上記フェ
ノール樹脂組成物、又は、上記フェノール樹脂組成物と
は別の樹脂組成物を用い一次含浸処理を行い、次いで上
記フェノール樹脂組成物を用いて二次含浸処理を行うこ
とが有効である。In the method for producing a prepreg of the present invention, a substrate is impregnated with the above-mentioned phenol resin composition, and the resin composition is semi-cured by heating to obtain a prepreg. When the phenol resin composition of the present invention is used, the time required for semi-curing to the same extent as that of the conventional resin is shortened, and the effect of improving productivity and reducing cost by energy saving is also obtained. Examples of the base material impregnated with the phenol resin composition include kraft paper, linter paper, and other paper base materials obtained by mixing kraft paper or linter paper with an inorganic substance or an organic substance.
When it is necessary to contain a large amount of resin, the phenol resin composition, or, a primary impregnation treatment using a resin composition different from the phenol resin composition, then using the phenol resin composition It is effective to carry out the secondary impregnation treatment.
【００１９】本発明の積層板は、上述の製造方法で得ら
れたプリプレグ数枚と、必要により銅、アルミニウム、
ニッケル等の金属箔を重ね合わせ、加熱加圧成形を行う
ことにより得られる。The laminated plate of the present invention comprises several prepregs obtained by the above-mentioned manufacturing method and, if necessary, copper, aluminum,
It is obtained by stacking metal foils of nickel or the like and performing heat and pressure molding.
【００２０】[0020]
【作用】本発明の請求項１から請求項４記載のフェノー
ル樹脂組成物において、重量平均分子量が４０００〜１
７０００であり、分子量１００００以上の分子を１３％
以上含むフェノール樹脂と、エポキシ樹脂と、硬化触媒
を含有させることは、成形時間を短縮しても耐熱性や吸
水率等の特性が良好な積層板が得られる作用がある。In the phenol resin composition according to claim 1 to 4, the weight average molecular weight is 4000 to 1
7,000, 13% of molecules with a molecular weight of 10,000 or more
The inclusion of the above-described phenol resin, epoxy resin, and curing catalyst has the effect of obtaining a laminate having good properties such as heat resistance and water absorption even if the molding time is shortened.
【００２１】本発明の請求項５記載のプリプレグにおい
て、上記フェノール樹脂組成物を用いることは、成形時
間を短縮しても、耐熱性や吸水率等の特性が良好な積層
板が得られる作用がある。[0021] In the prepreg according to claim 5 of the present invention, the use of the above-mentioned phenol resin composition has an effect of obtaining a laminated board having excellent characteristics such as heat resistance and water absorption even if the molding time is shortened. is there.
【００２２】本発明の請求項６記載の積層板において、
上記プリプレグを用いることは、生産性向上及び省エネ
ルギーを達成して、コスト低減を可能にする。In the laminated plate according to claim 6 of the present invention,
The use of the above prepreg achieves productivity improvement and energy saving, and enables cost reduction.
【００２３】[0023]
実施例１ フェノール６０重量部（以下部と記す）と桐油４０部と
触媒パラトルエンスルホン酸０．５部を１００℃で１時
間反応させ、桐油フェノール反応物を得た。次いで、こ
の桐油フェノール反応物をトリエタノールアミンで中和
し、３７％ホルマリン４６部と２５％アンモニア２部と
トリエチルアミン２部を添加し、８０℃で３時間反応さ
せた後、１５０ｍｍＨｇの減圧下で脱水し、溶剤として
メタノールを添加し、重量平均分子量が５０００、分子
量１００００以上の成分を１５％含むフェノール樹脂を
合成した。このフェノール樹脂にエポキシ当量４００の
テトラブロムビスフェノールＡジグリシジルエーテル１
０部と硬化触媒トリエチルアミン２部を加え、フェノー
ル樹脂組成物を得た。Example 1 60 parts by weight of phenol (hereinafter referred to as “part”), 40 parts of tung oil, and 0.5 part of catalyst paratoluenesulfonic acid were reacted at 100 ° C. for 1 hour to obtain a tung oil phenol reaction product. Next, the tung oil phenol reaction product was neutralized with triethanolamine, 46 parts of 37% formalin, 2 parts of 25% ammonia and 2 parts of triethylamine were added, and the mixture was reacted at 80 ° C. for 3 hours, then under reduced pressure of 150 mmHg. After dehydration, methanol was added as a solvent, and a phenol resin containing 15% of a component having a weight average molecular weight of 5000 and a molecular weight of 10,000 or more was synthesized. Tetrabrom bisphenol A diglycidyl ether 1 with an epoxy equivalent of 400
A phenol resin composition was obtained by adding 0 part and 2 parts of a curing catalyst triethylamine.
【００２４】プリプレグの調整は、次のように行った。
フェノール１００部と３７％ホルマリン７０部を反応さ
せたフェノール樹脂生成物と、メラミン１００部と３７
％ホルマリン１００部を反応させたメラミン樹脂生成物
を等量混合した樹脂に、水とメタノールを等量混合した
メタノール水溶液を添加し、固形分１５％の一次含浸ワ
ニスを得た。この一次含浸ワニスを重量１２６ｇ／m2の
クラフト紙に含浸した後に、１３５℃の乾燥機で３０秒
処理し、一次プリプレグＡを得た。このプリプレグ中に
おける樹脂の含有率は１５％であった。この一次プリプ
レグＡにメタノールで希釈し固形分５０％とした上記フ
ェノール樹脂組成物を含浸した後、１５５℃の乾燥機で
８０秒処理し、二次プリプレグＢを得た。このプリプレ
グ中における樹脂の総含有率は５０％であった。The prepreg was adjusted as follows.
Phenolic resin product obtained by reacting 100 parts of phenol with 70 parts of 37% formalin, and 100 parts of melamine and 37
% Formalin 100 parts of the melamine resin product was reacted in an equal amount, and an aqueous solution of methanol in which water and methanol were mixed in equal amounts was added to the resin to obtain a primary impregnated varnish having a solid content of 15%. Kraft paper having a weight of 126 g / m 2 was impregnated with this primary impregnated varnish and then treated with a dryer at 135 ° C. for 30 seconds to obtain primary prepreg A. The resin content in this prepreg was 15%. This primary prepreg A was impregnated with the above phenol resin composition diluted with methanol to a solid content of 50% and then treated with a dryer at 155 ° C. for 80 seconds to obtain a secondary prepreg B. The total content of the resin in this prepreg was 50%.
【００２５】次に、プリプレグＢを８枚重ね、最上層に
厚さ０．０３５ｍｍの銅箔を接着剤を介して配設し、こ
れを圧力１００ｋｇ／ｃm2、温度１６０℃で５０分間成
形し１．６ｍｍの積層板を得た。Next, eight prepregs B were stacked, a copper foil having a thickness of 0.035 mm was disposed on the uppermost layer via an adhesive, and this was molded at a pressure of 100 kg / cm 2 and a temperature of 160 ° C. for 50 minutes. A 1.6 mm laminated plate was obtained.
【００２６】実施例２ フェノール６０部と桐油４０部と触媒パラトルエンスル
ホン酸０．５部を１００℃で１時間反応させ、桐油フェ
ノール反応物を得た。次いで、この桐油フェノール反応
物に３７％ホルマリン４６部と２５％アンモニア３．２
部とトリエチルアミン２部を添加し、８０℃で３時間反
応させた後、１５０ｍｍＨｇの減圧下で脱水し、重量平
均分子量が１６０００、分子量１００００以上の成分を
１５％含むフェノール樹脂を合成した。このフェノール
樹脂にエポキシ当量４００のテトラブロムビスフェノー
ルＡジグリシジルエーテル１０部と硬化触媒トリエチル
アミン２部を加え、フェノール樹脂組成物を得た。この
フェノール樹脂組成物をプリプレグの二次含浸に用いた
以外は実施例１と同様にして積層板を得た。Example 2 60 parts of phenol, 40 parts of tung oil, and 0.5 part of catalyst paratoluenesulfonic acid were reacted at 100 ° C. for 1 hour to obtain a tung oil phenol reaction product. Next, 46% of 37% formalin and 3.2% of 25% ammonia were added to the tung oil phenol reaction product.
And 2 parts of triethylamine were added and reacted at 80 ° C. for 3 hours, followed by dehydration under reduced pressure of 150 mmHg to synthesize a phenol resin containing 15% of a component having a weight average molecular weight of 16000 and a molecular weight of 10,000 or more. To this phenol resin, 10 parts of tetrabromobisphenol A diglycidyl ether having an epoxy equivalent of 400 and 2 parts of a curing catalyst triethylamine were added to obtain a phenol resin composition. A laminated board was obtained in the same manner as in Example 1 except that this phenol resin composition was used for the secondary impregnation of the prepreg.
【００２７】実施例３ 硬化触媒としてトリエタノールアミンを２部添加した以
外は実施例１と同様にして積層板を得た。Example 3 A laminated plate was obtained in the same manner as in Example 1 except that 2 parts of triethanolamine was added as a curing catalyst.
【００２８】実施例４ 硬化触媒としてトリエチルアミン２部と、２−エチル−
４−メチルイミダゾール０．０３部を添加した以外は実
施例１と同様にして積層板を得た。Example 4 2 parts of triethylamine as a curing catalyst and 2-ethyl-
A laminated board was obtained in the same manner as in Example 1 except that 0.03 part of 4-methylimidazole was added.
【００２９】実施例５ 硬化触媒としてトリエチルアミン２部と、ジシアンジア
ミドを１部添加した以外は実施例１と同様にして積層板
を得た。Example 5 A laminated plate was obtained in the same manner as in Example 1 except that 2 parts of triethylamine and 1 part of dicyandiamide were added as a curing catalyst.
【００３０】実施例６ 硬化触媒として２−エチル−４−メチルイミダゾール
０．０３部を添加した以外は実施例１と同様にして積層
板を得た。Example 6 A laminated plate was obtained in the same manner as in Example 1 except that 0.03 part of 2-ethyl-4-methylimidazole was added as a curing catalyst.
【００３１】実施例７ 硬化触媒として２−メチルイミダゾールを０．０３部添
加した以外は実施例１と同様にして積層板を得た。Example 7 A laminate was obtained in the same manner as in Example 1 except that 0.03 part of 2-methylimidazole was added as a curing catalyst.
【００３２】実施例８ 硬化触媒としてジシアンジアミド１部と、２−エチル−
４−メチルイミダゾール０．０３部添加した以外は実施
例１と同様にして積層板を得た。Example 8 1 part of dicyandiamide as a curing catalyst and 2-ethyl-
A laminated board was obtained in the same manner as in Example 1 except that 0.03 part of 4-methylimidazole was added.
【００３３】実施例９ 硬化触媒としてジシアンジアミドを１部添加した以外は
実施例１と同様にして積層板を得た。Example 9 A laminated plate was obtained in the same manner as in Example 1 except that 1 part of dicyandiamide was added as a curing catalyst.
【００３４】比較例１ 重量平均分子量が５０００、分子量１００００以上の成
分を１５％含むフェノール樹脂、にエポキシ当量４００
のテトラブロムビスフェノールＡジグリシジルエーテル
１０部を加え、硬化触媒であるトリエチルアミンは添加
しないで、フェノール樹脂組成物を得た以外は実施例１
と同様にして積層板を得た。Comparative Example 1 A phenol resin containing 15% of a component having a weight average molecular weight of 5,000 and a molecular weight of 10,000 or more was added to an epoxy equivalent of 400.
Example 10 except that a phenol resin composition was obtained without adding 10 parts of tetrabromobisphenol A diglycidyl ether described above and triethylamine as a curing catalyst.
A laminate was obtained in the same manner as described above.
【００３５】比較例２Ａ フェノール６０部と桐油４０部と触媒パラトルエンスル
ホン酸０．５部を１００℃で１時間反応させ、桐油フェ
ノール反応物を得た。次いで、この桐油フェノール反応
物に３７％ホルマリン４６部と２５％アンモニア１．５
部とトリエチルアミン２部を添加し、８０℃で３時間反
応させた後、１５０ｍｍＨｇの減圧下で脱水し、重量平
均分子量が２０００、分子量１００００以上の成分を５
％含むフェノール樹脂を合成した。このフェノール樹脂
にエポキシ当量４００のテトラブロムビスフェノールＡ
ジグリシジルエーテル１０部を加え、硬化触媒は添加し
ないで、フェノール樹脂組成物を得た。このフェノール
樹脂組成物をプリプレグの二次含浸に用いた以外は実施
例１と同様にして積層板を得た。Comparative Example 2A 60 parts of phenol, 40 parts of tung oil, and 0.5 part of catalyst paratoluenesulfonic acid were reacted at 100 ° C. for 1 hour to obtain a tung oil phenol reaction product. Next, 46 parts of 37% formalin and 1.5% of 25% ammonia were added to the tung oil phenol reaction product.
Parts and 2 parts of triethylamine were added, and the mixture was reacted at 80 ° C. for 3 hours and then dehydrated under reduced pressure of 150 mmHg to give a component having a weight average molecular weight of 2,000 and a molecular weight of 10,000 or more to 5 parts.
% Phenolic resin was synthesized. This phenolic resin has an epoxy equivalent of 400 Tetrabrom Bisphenol A
A phenol resin composition was obtained without adding a curing catalyst by adding 10 parts of diglycidyl ether. A laminated board was obtained in the same manner as in Example 1 except that this phenol resin composition was used for the secondary impregnation of the prepreg.
【００３６】比較例２Ｂ 得られたプリプレグを、圧力１００ｋｇ／ｃm2、温度１
６０℃で７０分間成形した以外は比較例２Ａと同様にし
て積層板を得た。Comparative Example 2B The prepreg thus obtained was subjected to a pressure of 100 kg / cm 2 and a temperature of 1.
A laminated board was obtained in the same manner as in Comparative Example 2A except that molding was performed at 60 ° C for 70 minutes.
【００３７】得られた実施例１〜９と、比較例１、２
Ａ、２Ｂの積層板の半田耐熱性、及び吸水率を評価し
た。半田耐熱性は２６０℃の半田にフロートし、剥離、
膨れなどの異常が発生するまでの時間を測定した。吸水
率はＪＩＳ−Ｃ−６４８１に基づいて測定した。結果は
表１に示したとおり、実施例１〜９は成形時間が短くて
も（１６０℃５０分）、成形時間が長い（１６０℃７０
分）比較例２Ｂの場合と同様に、半田耐熱性、吸水率と
も優れた積層板が得られた。The obtained Examples 1 to 9 and Comparative Examples 1 and 2
The solder heat resistance and water absorption of the A and 2B laminated plates were evaluated. Solder heat resistance floats to 260 ° C solder, peels off,
The time until an abnormality such as swelling occurred was measured. The water absorption rate was measured based on JIS-C-6481. The results are shown in Table 1. In Examples 1 to 9, the molding time was long (160 ° C 50 minutes) but the molding time was long (160 ° C 70%).
Min) As in Comparative Example 2B, a laminate having excellent solder heat resistance and water absorption was obtained.
【００３８】[0038]
【表１】 [Table 1]
【００３９】[0039]
【発明の効果】本発明の請求項１〜４に係るフェノール
樹脂組成物を用いると、成形時間を短縮しても、耐熱性
や吸水率等の特性が良好な積層板を得ることができる。By using the phenol resin composition according to the first to fourth aspects of the present invention, it is possible to obtain a laminated board having excellent properties such as heat resistance and water absorption even if the molding time is shortened.
【００４０】本発明の請求項５に係るプリプレグを用い
ると、成形時間を短縮しても、耐熱性や吸水率等の特性
が良好な積層板を得ることができる。By using the prepreg according to the fifth aspect of the present invention, it is possible to obtain a laminated plate having excellent characteristics such as heat resistance and water absorption even if the molding time is shortened.
【００４１】本発明の請求項６に係る積層板では、生産
性向上及び省エネルギーによるコスト低減が可能にな
る。In the laminated plate according to the sixth aspect of the present invention, it is possible to improve productivity and reduce costs by saving energy.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０８Ｌ 63:00 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 6 Identification code Office reference number FI technical display area // C08L 63:00
Claims (6)
であり、分子量１００００以上の分子を１３重量％以上
含むフェノール樹脂と、エポキシ樹脂と、硬化触媒を含
有することを特徴とするフェノール樹脂組成物。1. A weight average molecular weight of 4,000 to 17,000.
And a phenol resin composition containing a phenol resin containing 13% by weight or more of molecules having a molecular weight of 10,000 or more, an epoxy resin, and a curing catalyst.
を特徴とする、請求項１記載のフェノール樹脂組成物。2. The phenol resin composition according to claim 1, wherein the curing catalyst is an amine compound.
を特徴とする、請求項１記載のフェノール樹脂組成物。3. The phenol resin composition according to claim 1, wherein the curing catalyst is an amide compound.
ることを特徴とする、請求項１記載のフェノール樹脂組
成物。4. The phenol resin composition according to claim 1, wherein the curing catalyst is an imidazole compound.
物のいずれかを基材に含浸していることを特徴とするプ
リプレグ。5. A prepreg obtained by impregnating a substrate with any one of the phenolic resin compositions according to claim 1.
形していることを特徴とする積層板。6. A laminated plate formed by using the prepreg according to claim 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16038495A JPH0912686A (en) | 1995-06-27 | 1995-06-27 | Phenolic resin composition, prepreg using the phenolic resin composition, and laminated board wherein that prepreg is used |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16038495A JPH0912686A (en) | 1995-06-27 | 1995-06-27 | Phenolic resin composition, prepreg using the phenolic resin composition, and laminated board wherein that prepreg is used |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0912686A true JPH0912686A (en) | 1997-01-14 |
Family
ID=15713806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16038495A Withdrawn JPH0912686A (en) | 1995-06-27 | 1995-06-27 | Phenolic resin composition, prepreg using the phenolic resin composition, and laminated board wherein that prepreg is used |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0912686A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234280A (en) * | 2020-03-16 | 2020-06-05 | 无锡市立帆绝缘材料科技有限公司 | Red end seal and preparation method thereof |
-
1995
- 1995-06-27 JP JP16038495A patent/JPH0912686A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234280A (en) * | 2020-03-16 | 2020-06-05 | 无锡市立帆绝缘材料科技有限公司 | Red end seal and preparation method thereof |
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