JPH047313A - Phenol resin composition - Google Patents
Phenol resin compositionInfo
- Publication number
- JPH047313A JPH047313A JP10839790A JP10839790A JPH047313A JP H047313 A JPH047313 A JP H047313A JP 10839790 A JP10839790 A JP 10839790A JP 10839790 A JP10839790 A JP 10839790A JP H047313 A JPH047313 A JP H047313A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- resin composition
- parts
- phenolic resin
- heat resistance
- 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
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 40
- 229920003986 novolac Polymers 0.000 claims abstract description 15
- HHVCCCZZVQMAMT-UHFFFAOYSA-N 1-hydroxy-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(O)C(=O)C=C1C1=CC=CC=C1 HHVCCCZZVQMAMT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 31
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 2
- 238000013329 compounding Methods 0.000 abstract 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 12
- 238000005452 bending Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 7
- 239000004312 hexamethylene tetramine Substances 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 6
- BLLFPKZTBLMEFG-UHFFFAOYSA-N 1-(4-hydroxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(O)=CC=C1N1C(=O)C=CC1=O BLLFPKZTBLMEFG-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- CNDOSNMFHUSKGN-UHFFFAOYSA-N 1-(2-hydroxyphenyl)pyrrole-2,5-dione Chemical compound OC1=CC=CC=C1N1C(=O)C=CC1=O CNDOSNMFHUSKGN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QCIAOHRLCMQEDL-UHFFFAOYSA-N 1,3-dihydroxy-4-phenylpyrrole-2,5-dione Chemical compound ON1C(C(=C(C1=O)O)C1=CC=CC=C1)=O QCIAOHRLCMQEDL-UHFFFAOYSA-N 0.000 description 1
- YWODHBPFOGXUFX-UHFFFAOYSA-N 1-(3-hydroxyphenyl)pyrrole-2,5-dione Chemical compound OC1=CC=CC(N2C(C=CC2=O)=O)=C1 YWODHBPFOGXUFX-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、機械的強度および耐熱性に優れており、機械
部品、自動車分野、電子材料分野等の広い分野への利用
が可能である熱硬化性のフェノール樹脂組成物に関する
。Detailed Description of the Invention (Industrial Field of Application) The present invention is a heat-resistant material that has excellent mechanical strength and heat resistance and can be used in a wide range of fields such as mechanical parts, the automobile field, and the electronic material field. The present invention relates to a curable phenolic resin composition.
（従来の技術）
フェノール樹脂は、その機械的強度、耐熱性、電気絶縁
性、寸法安定性、耐薬品性、加工性、成形性等多くの優
れた物性を有するため、工業材料として従来より多用さ
れている。例えば、フェノール樹脂を用いて形成された
成形品は、電気通信関係の分野では絶縁材料として利用
され、また自動車部品や機械部品としての重要も多い。(Prior art) Phenolic resins have many excellent physical properties such as mechanical strength, heat resistance, electrical insulation, dimensional stability, chemical resistance, processability, and moldability, so they have been widely used as industrial materials. has been done. For example, molded articles formed using phenolic resin are used as insulating materials in the telecommunications field, and are also important as automobile parts and mechanical parts.
しかし、近年では用途のさらなる拡大を目的として高性
能化が要望されている。その一つは耐熱性の向上である
。フェノール樹脂の耐熱性を向上させる方法として、従
来では熱処理や硬化剤の増量による架橋密度の向上、あ
るいは耐熱性を有する改質剤の添加等の手段が用いられ
てきた。しかし、これらの手段では耐熱性は向上するも
のの得られる成形品の曲げ強度および耐衝撃性をはじめ
とする機械的強度が低下するなど実用化において問題点
が多かった。すなわち、耐熱性を向上させるためには、
機械的強度を犠牲にしなければならず、優れた機械的強
度と耐熱性とを同時に備えたフェノール樹脂組成物の開
発が望まれていた。However, in recent years, there has been a demand for higher performance in order to further expand the range of applications. One of them is improved heat resistance. Conventionally, methods for improving the heat resistance of phenolic resins include improving crosslinking density by heat treatment or increasing the amount of curing agent, or adding a modifier having heat resistance. However, although these methods improve heat resistance, there are many problems in practical use, such as a decrease in mechanical strength including bending strength and impact resistance of the resulting molded product. In other words, in order to improve heat resistance,
However, it has been desired to develop a phenolic resin composition that has both excellent mechanical strength and heat resistance, since mechanical strength must be sacrificed.
本発明は、かかる実情に鑑みてなされたものであり、そ
の目的とするところは機械的強度と耐熱性の両物性がと
もに優れたフェノール樹脂組成物を提供することにある
。The present invention has been made in view of these circumstances, and its purpose is to provide a phenolic resin composition that is excellent in both mechanical strength and heat resistance.
（課題を解決するための手段）
本発明者らは、従来のフェノール樹脂を改良して優れた
機械的強度及び優れた耐熱性を有する新規なフェノール
樹脂を得るべく研究を行った。改良方法としては、本発
明ではフェノール樹脂中間体であるノボラックに機械的
強度及び耐熱性に優れた種々の高分子化合物を配合し、
それをヘキサメチレンテトラミン等の硬化剤により硬化
させ、硬化物の機械的強度を維持しつつ耐熱性を向上さ
せる方法を採用した。配合する高分子化合物の必要条件
としては、機械的強度を維持できる程度の分子量を有す
ること、耐熱性が優れていること、ノボラックに相溶す
ること、および成形性を低下させないこと等である。(Means for Solving the Problems) The present inventors conducted research to improve conventional phenolic resins to obtain a novel phenolic resin having excellent mechanical strength and excellent heat resistance. As an improvement method, in the present invention, various polymeric compounds with excellent mechanical strength and heat resistance are blended with novolak, which is a phenolic resin intermediate, and
We adopted a method of curing it with a curing agent such as hexamethylenetetramine to improve heat resistance while maintaining the mechanical strength of the cured product. The necessary conditions for the polymer compound to be blended are that it has a molecular weight sufficient to maintain mechanical strength, that it has excellent heat resistance, that it is compatible with novolac, and that it does not reduce moldability.
本発明では、これらの条件を満足させる高分子化合物と
して、Ｎ−ヒドロキシフェニルマレイミド（以下、ＨＰ
ＭＩと記す。）の重合体を見い出した。In the present invention, N-hydroxyphenylmaleimide (hereinafter referred to as HP) is used as a polymer compound that satisfies these conditions.
It is written as MI. ) was discovered.
すなわち、フェノール樹脂の中間体であるノボラックに
対してＨＰＭＩの重合体を配合することにより、フェノ
ール樹脂本来の機械的強度を損なうごとなく耐熱性を向
上できることを見いだし、本発明を完成するに至った。That is, the inventors discovered that by blending a HPMI polymer with novolac, which is an intermediate of phenolic resin, heat resistance could be improved without sacrificing the inherent mechanical strength of phenolic resin, and the present invention was completed. .
このＨＰＭＩの重合体の添加によりフェノール樹脂の機
械的強度が低下せず、しかも耐熱性が向上する理由は、
ＨＰＭ ＋重合体は耐熱性骨格を持ち、しかも硬化剤と
硬化反応を起こすことによって架橋構造を形成するため
と推測される。The reason why the addition of this HPMI polymer does not reduce the mechanical strength of the phenolic resin and improves its heat resistance is as follows.
This is presumably because the HPM + polymer has a heat-resistant skeleton and forms a crosslinked structure by causing a curing reaction with the curing agent.
すなわち、本発明のフェノール樹脂組成物は、式
（ｎは１〜３の整数である）
で表されるＮ−ヒドロキシフェニルマレイミドの重合体
と、フェノール樹脂中間体であるノボラックとが配合さ
れてなり、そのことにより上記目的が達成される。That is, the phenol resin composition of the present invention is a mixture of a polymer of N-hydroxyphenylmaleimide represented by the formula (n is an integer of 1 to 3) and novolac, which is a phenol resin intermediate. , thereby achieving the above objective.
本発明において使用できるＨＰＭＩの重合体を製造し得
ることが可能な単量体としては、Ｎ−２−ヒドロキシフ
ェニルマレイミド、Ｎ−３−ヒドロキシフェニルマレイ
ミド、Ｎ−４−ヒドロキシフェニルマレイミド、Ｎ−２
，３−ジヒドロキシフェニルマレイミド、Ｎ−２，４−
ジヒドロキシフェニルマレイミド、Ｎ−２，５−ジヒド
ロキシフェニルマレイミド、Ｎ−２，６−ジヒドロキシ
フェニルマレイミド、Ｎ−３，４−ジヒドロキシフェニ
ルマレイミド、Ｎ−３，５−ジヒドロキシフェニルマレ
イミド、Ｎ−２，４，６−）ジヒドロキシフェニルマレ
イミドが例示できるが、これらに限定されるものではな
い。特に好ましくは、Ｎ−４−ヒドロキシフェニルマレ
イミドの重合体が用いられる。Monomers capable of producing the HPMI polymer that can be used in the present invention include N-2-hydroxyphenylmaleimide, N-3-hydroxyphenylmaleimide, N-4-hydroxyphenylmaleimide, N-2-hydroxyphenylmaleimide, and N-2-hydroxyphenylmaleimide.
, 3-dihydroxyphenylmaleimide, N-2,4-
Dihydroxyphenylmaleimide, N-2,5-dihydroxyphenylmaleimide, N-2,6-dihydroxyphenylmaleimide, N-3,4-dihydroxyphenylmaleimide, N-3,5-dihydroxyphenylmaleimide, N-2,4, 6-) Dihydroxyphenylmaleimide is an example, but the present invention is not limited thereto. Particularly preferably, a polymer of N-4-hydroxyphenylmaleimide is used.
本発明においてＨＰＭＩの重合体を用いることにより、
フェノール樹脂の優れた機械的強度を維持したままで耐
熱性を向上させることができる。この理由は、ＨＰＭＩ
の重合体が７ボラツクと相溶し、ヘキサメチレンテトラ
ミンの如き硬化剤を用いてフェノール樹脂を硬化せしめ
る場合に、ＨＰＭＩの重合体とノボラックとが硬化反応
に寄与し、大きな三次元構造を形成することによってフ
ェノール樹脂の機械的強度を維持し、かつ樹脂骨格にイ
ミド樹脂を含有しているので耐熱性が向上するものと推
測される。By using a polymer of HPMI in the present invention,
Heat resistance can be improved while maintaining the excellent mechanical strength of phenolic resin. The reason for this is that HPMI
The polymer of HPMI is compatible with 7-volac, and when curing phenolic resin using a curing agent such as hexamethylenetetramine, the polymer of HPMI and novolac contribute to the curing reaction and form a large three-dimensional structure. It is presumed that this maintains the mechanical strength of the phenol resin and improves heat resistance since the resin skeleton contains an imide resin.
本発明に使用されるＨＰＭＩの重合体は、ＨＰＭＩの単
量体を公知の重合方法、例えば、乳化重合、懸濁重合、
溶液重合などの方法により得ることができる。ＨＰＭＩ
の重合体は、フェノール樹脂中間体であるノボラック１
００重量部に対して通常１〜５０重量部、好ましくは５
〜２０重量部の割合で配合させることによって所望の耐
熱性を付与することができる。The HPMI polymer used in the present invention can be prepared by polymerizing HPMI monomers using known polymerization methods, such as emulsion polymerization, suspension polymerization,
It can be obtained by methods such as solution polymerization. HPMI
The polymer is novolac 1, a phenolic resin intermediate.
Usually 1 to 50 parts by weight, preferably 5 parts by weight per 00 parts by weight.
Desired heat resistance can be imparted by blending in a proportion of ~20 parts by weight.
ＨＰＭＩの重合体が１重量部未満では十分な耐熱性が得
られず、５０重量部を越えるとノボラックとのフェノー
ル樹脂組成物のガラス転移温度が上昇し、この樹脂組成
物の成形性が悪くなる。If the amount of HPMI polymer is less than 1 part by weight, sufficient heat resistance cannot be obtained, and if it exceeds 50 parts by weight, the glass transition temperature of the phenol resin composition with novolac will increase, and the moldability of this resin composition will deteriorate. .
本発明におけるＨＰＭＩの重合体の数平均分子量は特に
制限されないが、好適には１．０００〜１０．０００で
ある。ＨＰ帽の重合体の数平均分子量が１．０００未満
であると、得られたフェノール樹脂組成物の機械的強度
が低下する傾向にあり、１０，０００を越えるとフェノ
ール樹脂組成物のガラス転移温度が上昇し成形性が悪く
なる。The number average molecular weight of the HPMI polymer in the present invention is not particularly limited, but is preferably 1.000 to 10.000. If the number average molecular weight of the HP cap polymer is less than 1.000, the mechanical strength of the resulting phenolic resin composition tends to decrease, and if it exceeds 10,000, the glass transition temperature of the phenolic resin composition tends to decrease. increases, and moldability deteriorates.
本発明のフェノール樹脂組成物は、フェノール樹脂中間
体であるノボラック、ＨＰＭＩの重合体および必要に応
じて硬化剤、滑剤等の添加剤、強化材等を公知の方法に
より混和させて得られる。ノボラック、ＨＰＭＩの重合
体および必要に応じて硬化剤等を混和するには、必要に
応じて加熱しながら混合すればよい。ＨＰＭＩの重合体
とノボラックとの相溶性は、両者それぞれ単独のガラス
転移点、および両者の溶融混合物のガラス転移点をＤＳ
Ｃ法により測定することによって確認することができる
。フェノール樹脂組成物を製造するにあたって、硬化剤
としては、例えば、ヘキサメチレンテトラミンの如き硬
化剤が一般的に用いられる。The phenolic resin composition of the present invention is obtained by mixing a polymer of novolac and HPMI, which are phenolic resin intermediates, and optionally additives such as a curing agent and a lubricant, reinforcing materials, etc. by a known method. In order to mix the novolak, HPMI polymer and, if necessary, a curing agent, etc., it is sufficient to mix them while heating if necessary. The compatibility between the HPMI polymer and novolac is determined by the glass transition point of each individual and the glass transition point of a molten mixture of both.
This can be confirmed by measurement using method C. In producing a phenol resin composition, a curing agent such as hexamethylenetetramine is generally used as a curing agent.
このようにして得られたフェノール樹脂組成物は、通常
の成形法に従って成形することができ、機械的強度およ
び耐熱性に優れたエンジニアリングプラスチックとして
種々の分野に使用することができる。The phenolic resin composition thus obtained can be molded according to a conventional molding method, and can be used in various fields as an engineering plastic with excellent mechanical strength and heat resistance.
（実施例）
以下に本発明を実施例について述べる。実施例中におい
て「部」とあるのは、全て「重量部」を意味する。(Example) The present invention will be described below with reference to Examples. In the examples, all "parts" mean "parts by weight."
爽立五１
（１） Ｎ−４−ヒドロキシフェニルマレイミド重合体
の製造
攪拌機および環流冷却管を備えた反応器に、Ｎ−４−ヒ
ドロキシフェニルマレイミド（以下４−ＨＰＭ＋ト記す
。） ２２４．７部、２，２°−アゾビスインブチロニ
トリル（以下、ＡＩＢＮと記す。）３２．９部、Ｎ、Ｎ
−ジメチルホルムアミド（以下、ＤＭＦと記す。） １
０００部を加え、窒素雰囲気下において７０°Ｃにて６
時間保持した。反応収量後、反応物を水中に滴下して重
合体を析出させた。重合物を濾別した後、真空乾燥して
水を除去したところ、淡黄色の４−ＨＰＭ＋重合体２０
６．７部が得られた。この重合体の数平均分子量をＧＰ
Ｃにて測定したところ、３．８００であった。また、こ
の重合体のガラス転移温度をＤＳＣにより測定したとこ
ろ、２５２℃であった。Sawatachigo 1 (1) Production of N-4-hydroxyphenylmaleimide polymer In a reactor equipped with a stirrer and a reflux condenser, 224.7 parts of N-4-hydroxyphenylmaleimide (hereinafter referred to as 4-HPM + T) was added. , 32.9 parts of 2,2°-azobisinbutyronitrile (hereinafter referred to as AIBN), N, N
-Dimethylformamide (hereinafter referred to as DMF) 1
6,000 parts at 70°C under nitrogen atmosphere.
Holds time. After the reaction was completed, the reactant was dropped into water to precipitate the polymer. After filtering the polymer and removing water by vacuum drying, a pale yellow 4-HPM+polymer 20
6.7 parts were obtained. The number average molecular weight of this polymer is GP
When measured at C, it was 3.800. Further, the glass transition temperature of this polymer was measured by DSC and was 252°C.
（２）フェノール樹脂組成物の調製および評価フェノー
ル樹脂中間体であるノボラック１００部に対し、（１）
項で得られた４−■ＰＭ＋重合体１０部、硬化剤として
ヘキサメチレンテトラミン（以下、へ牛サミンと記す。(2) Preparation and evaluation of phenolic resin composition For 100 parts of novolac, which is a phenolic resin intermediate, (1)
10 parts of the 4-■PM+polymer obtained in Section 1, and hexamethylenetetramine (hereinafter referred to as hexamethylenetetramine) as a curing agent.
）１３．２部、滑剤としてステアリン酸亜鉛２．２部、
および強化材としてガラス繊維１２３．２部を配合し、
１００〜１１０℃に加熱した熱ロールを用いて混練した
。) 13.2 parts, 2.2 parts of zinc stearate as a lubricant,
and 123.2 parts of glass fiber as a reinforcing material,
The mixture was kneaded using hot rolls heated to 100 to 110°C.
混練物を取り出して粉砕した後、トランスファ成形機に
より１７０°Ｃにて成形し、試験片を得た。この試験片
を用いて、ＪＩＳ Ｋ−６９１１の方法により曲げ強度
、曲げ弾性率、シャルピー衝撃強度、および荷重たわみ
温度を測定した。The kneaded material was taken out and pulverized, and then molded at 170°C using a transfer molding machine to obtain a test piece. Using this test piece, bending strength, bending modulus, Charpy impact strength, and deflection temperature under load were measured according to the method of JIS K-6911.
その結果、曲げ強度は２２．０３［ｇｆ／＋ａｍ２、曲
げ弾性率は１６９５にｇｆ／ｍ＋ｎ２、シャルピー衝撃
強度は６．８３Ｋｇｆ−ｃｍ／ｃｒｎ２そして荷重たわ
み温度は１６０°Ｃであった。これらの結果を表１に示
す。As a result, the bending strength was 22.03 gf/+am2, the bending modulus was 1695 gf/m+n2, the Charpy impact strength was 6.83 Kgf-cm/crn2, and the deflection temperature under load was 160°C. These results are shown in Table 1.
夫血丘１ （１） ４−ＨＰＭ＋重合体の製造 実施例１の（１）で得た４−ａｒｙ＋重合体を用いた。husband blood hill 1 (1) Production of 4-HPM+polymer The 4-ary+ polymer obtained in Example 1 (1) was used.
（２）フェノール樹脂組成物の調製および評価（１）項
で得た４−ＨＰＭ＋重合体を２０部、ヘキサミンを１４
．４部、ステアリン酸亜鉛を２．４部、およびガラス繊
維を１３４．４部としたこと以外は実施例１と同様にし
てフェノール樹脂組成物を得た。このフェノール樹脂組
成物を用いて実施例１と同様に成形して試験片を得た。(2) Preparation and evaluation of phenolic resin composition 20 parts of 4-HPM+polymer obtained in section (1), 14 parts of hexamine
．． A phenol resin composition was obtained in the same manner as in Example 1, except that the amount of zinc stearate was 2.4 parts, and the glass fiber was 134.4 parts. This phenolic resin composition was molded in the same manner as in Example 1 to obtain a test piece.
この試験片を用いて、実施例１と同様の方法により曲げ
強度、曲げ弾性率、シャルピー衝撃強度、および荷重た
わみ温度を測定した。Using this test piece, flexural strength, flexural modulus, Charpy impact strength, and deflection temperature under load were measured in the same manner as in Example 1.
その結果、曲げ強度は２０．８Ｋｇｆ／ｍｒａ２、曲げ
弾性率は１６８８Ｋｇｆ／ｓｍ２、シャルピー衝撃強度
は６．５５Ｋｇｆ−ｃＩＩｌ／ｃｍ２そして荷重たわみ
温度は１６４℃であった。これらの結果を表１に示す。As a result, the bending strength was 20.8 Kgf/mra2, the bending modulus was 1688 Kgf/sm2, the Charpy impact strength was 6.55 Kgf-cIIl/cm2, and the deflection temperature under load was 164°C. These results are shown in Table 1.
爽１匹主
（１） ４−ＨＰＭ＋重合体の製造
４−ＨＰＭＩを２２４．７部、ＡＩＢＮを３．２９部、
ＤＭＦを１０００部としたこと以外は実施例１と同様に
して、４−）ＩＰＭ１重合体２１６．０部を得た。この
重合体の数平均分子量を測定したところ、４．８００で
あった。また、この重合体のガラス転移温度をＤＳＣに
より測定したところ、２７０ ”Ｃであった。1 main fish (1) Production of 4-HPM + polymer 224.7 parts of 4-HPMI, 3.29 parts of AIBN,
216.0 parts of 4-) IPM1 polymer was obtained in the same manner as in Example 1 except that DMF was changed to 1000 parts. The number average molecular weight of this polymer was measured and found to be 4.800. Further, the glass transition temperature of this polymer was measured by DSC and was found to be 270''C.
（２）フェノール樹脂組成物の調製および評価（１）項
で得た４−ＨＰＭ＋重合体を用いたこと以外は、実施例
１と同様の方法により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用いて実施例１と同様に成形
して試験片を得た。(2) Preparation and evaluation of phenol resin composition A phenol resin composition was obtained in the same manner as in Example 1, except that the 4-HPM+polymer obtained in section (1) was used. This phenolic resin composition was molded in the same manner as in Example 1 to obtain a test piece.
この試験片を用いて、実施例１と同様の方法により曲げ
強度、曲げ弾性率、シャルピー衝撃強度、および荷重た
わみ温度を測定した。Using this test piece, flexural strength, flexural modulus, Charpy impact strength, and deflection temperature under load were measured in the same manner as in Example 1.
その結果、曲げ強度は１９．４Ｋｇｆ／■Ｉ２、曲げ弾
性率は１５８６Ｋｇｆ／＋ｕ＋２、シャルピー衝撃強度
は６．１１Ｋｇｆ−ｃ＋ａ／ｃｍ２そして荷重たわみ温
度は１６２℃であった。これらの結果を表１に示す。As a result, the bending strength was 19.4 Kgf/■I2, the bending modulus was 1586 Kgf/+u+2, the Charpy impact strength was 6.11 Kgf-c+a/cm2, and the deflection temperature under load was 162°C. These results are shown in Table 1.
工聚匠上
４−ＨＰＭ＋重合体のを加えず、ヘキサミンを１２．０
部、ステアリン酸亜鉛を２．２部、そしてガラス繊維を
１１２．０部としたこと以外は実施例１と同様にしてフ
ェノール樹脂組成物を得た。このフェノール樹脂組成物
を用いて実施例１と同様に成形して試験片を得た。Koju Takujo 4-HPM + without adding polymer, 12.0 hexamine
A phenol resin composition was obtained in the same manner as in Example 1, except that the amount of zinc stearate was 2.2 parts, and the glass fiber was 112.0 parts. This phenolic resin composition was molded in the same manner as in Example 1 to obtain a test piece.
この試験片を用いて、実施例１と同様の方法により曲げ
強度、曲げ弾性率、シャルピー衝撃強度、および荷重た
わみ温度を測定した。Using this test piece, flexural strength, flexural modulus, Charpy impact strength, and deflection temperature under load were measured in the same manner as in Example 1.
その結果、曲げ強度は２２． ＩＫｇｆ／ｍｍ２、曲げ
弾性率は１６５８Ｋｇｆ／ｍｍ２、シャルピー衝撃強度
は６．９８Ｋｇｆ−ｃｍ／ａｍ２そして荷重たわみ温度
は１５４℃であった。これらの結果を表１に示す。As a result, the bending strength was 22. IKgf/mm2, flexural modulus was 1658Kgf/mm2, Charpy impact strength was 6.98Kgf-cm/am2, and deflection temperature under load was 154C. These results are shown in Table 1.
（以下余白）
実施例および比較例から明らかなように、本発明のフェ
ノール樹脂組成物は、フェノール樹脂中間体であるノボ
ラックにＮ−４−ヒドロキシフーエニルマレイミド重合
体を配合することにより、曲げ強度、曲げ弾性率および
シャルピー衝撃強度のような機械的強度を維持し、かつ
荷重たわみ温度等の耐熱性が向上している。従って、本
発明のフェノール樹脂組成物は、機械的強度、耐熱性の
両者を必要とする分野に使用可能である。(Left below) As is clear from the Examples and Comparative Examples, the phenolic resin composition of the present invention has improved bending strength by blending N-4-hydroxyphenylmaleimide polymer with novolac, which is a phenolic resin intermediate. , mechanical strength such as flexural modulus and Charpy impact strength is maintained, and heat resistance such as deflection temperature under load is improved. Therefore, the phenolic resin composition of the present invention can be used in fields that require both mechanical strength and heat resistance.
（発明の効果）
本発明によれば、機械的強度および成形性が低下するこ
となく耐熱性が優れたフェノール樹脂組成物を得ること
ができ、耐熱要求の高い、例えば、機械部品、自動車分
野、電子材料分野等の広い分野へ好適に用いることがで
きる。(Effects of the Invention) According to the present invention, it is possible to obtain a phenolic resin composition with excellent heat resistance without deterioration of mechanical strength and moldability. It can be suitably used in a wide range of fields such as the field of electronic materials.
以上that's all
Claims (1)
と、フェノール樹脂中間体であるノボラックとが配合さ
れてなるフェノール樹脂組成物。[Claims] 1. A polymer of N-hydroxyphenylmaleimide represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼ (n is an integer from 1 to 3) and a phenol resin intermediate A phenolic resin composition containing novolac.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10839790A JP2793009B2 (en) | 1990-04-23 | 1990-04-23 | Phenolic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10839790A JP2793009B2 (en) | 1990-04-23 | 1990-04-23 | Phenolic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH047313A true JPH047313A (en) | 1992-01-10 |
| JP2793009B2 JP2793009B2 (en) | 1998-09-03 |
Family
ID=14483724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10839790A Expired - Fee Related JP2793009B2 (en) | 1990-04-23 | 1990-04-23 | Phenolic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2793009B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992621A (en) * | 2014-06-04 | 2014-08-20 | 苏州生益科技有限公司 | Thermosetting resin composition as well as prepreg and laminated board manufactured by utilizing same |
-
1990
- 1990-04-23 JP JP10839790A patent/JP2793009B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992621A (en) * | 2014-06-04 | 2014-08-20 | 苏州生益科技有限公司 | Thermosetting resin composition as well as prepreg and laminated board manufactured by utilizing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2793009B2 (en) | 1998-09-03 |
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