JP2653574B2 - Phenolic resin composition with excellent impact strength - Google Patents
Phenolic resin composition with excellent impact strengthInfo
- Publication number
- JP2653574B2 JP2653574B2 JP3193272A JP19327291A JP2653574B2 JP 2653574 B2 JP2653574 B2 JP 2653574B2 JP 3193272 A JP3193272 A JP 3193272A JP 19327291 A JP19327291 A JP 19327291A JP 2653574 B2 JP2653574 B2 JP 2653574B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- impact strength
- novolak
- strength
- 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.)
- Expired - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、レゾール樹脂にノボラ
ック樹脂、部分架橋ＮＢＲ、無機充填材を配合すること
により、曲げ強度、引張り強度等の静的強度と衝撃強度
及び耐熱性が高位にバランスした特性を与え、かつ流動
性がよく射出形成にも優れたフェノール樹脂組成物に関
するものである。BACKGROUND OF THE INVENTION The present invention provides a high balance between static strength such as bending strength and tensile strength, impact strength and heat resistance by blending a novolak resin, partially crosslinked NBR, and an inorganic filler with a resole resin. The present invention relates to a phenolic resin composition having excellent properties, excellent flowability, and excellent injection molding.
【０００２】[0002]
【従来の技術】フェノール樹脂成形材料は耐熱性、寸法
安定性、成形性等に優れ、自動車、電気、電子等の基幹
産業分野で使用されてきた。特に最近では自動車分野に
おいて鉄、アルミ、亜鉛等を使用した金属部品をガラス
繊維強化フェノール樹脂成形品に代替えすることによっ
てコストダウンを計る試みが積極的になされている。2. Description of the Related Art Phenolic resin molding materials are excellent in heat resistance, dimensional stability, moldability and the like, and have been used in basic industrial fields such as automobiles, electricity and electronics. Particularly in recent years, in the field of automobiles, attempts have been actively made to reduce costs by replacing metal parts using iron, aluminum, zinc, or the like with glass fiber reinforced phenolic resin molded products.
【０００３】しかし、フェノール樹脂を始めとする熱硬
化樹脂組成物は、耐熱性に優れるという利点を持ちなが
ら、その架橋構造から逆に非常に脆くて、割れやすいと
いう欠点を合わせ持ち、これが金属部品への適用拡大を
疎外してきた一因となっている。[0003] However, thermosetting resin compositions such as phenolic resins have the advantage of being excellent in heat resistance, but also have the drawback of being very brittle and fragile due to their crosslinked structure, and this is the problem of metal parts. This has contributed to the alienation of the expansion of the application to the market.
【０００４】この欠点を改善する試み、すわなち耐衝撃
性の付与は過去に多数くなされてきた。例えば、ヘンシ
ェルミキサー、スーパーミキサー等で材料化された一般
にチップ材と称される成形材料、或いはガラスロービン
グにフェノールワニスを含浸させ乾燥して溶媒を除去し
たプリプレグを適当な長さに切断した材料等があるが、
これらの成形材料はシャルピー衝撃強度が前者で５〜１
２kgcm/cm2、後者で５０〜１００kgcm/cm2と非常に高い
値を示す。しかし、いずれも充填材と基材との密着性が
低下し静的強度が極端に低下する。また後者では圧縮成
形のみと成形方法が限定されてしまう欠点がある。Many attempts have been made in the past to remedy this drawback, ie, to provide impact resistance. For example, a molding material generally called a chip material made into a material with a Henschel mixer or a super mixer, or a material obtained by impregnating a glass roving with a phenol varnish, drying and removing a solvent, and cutting the prepreg into an appropriate length. There is,
These molding materials have a Charpy impact strength of 5-1 in the former.
2kgcm / cm 2, a very high value as 50~100kgcm / cm 2 in the latter. However, in any case, the adhesion between the filler and the substrate is reduced, and the static strength is extremely reduced. In the latter case, there is a drawback that the molding method is limited to only compression molding.
【０００５】本出願人は特願平１−２７４８５６明細書
でレゾール樹脂／ノボラック樹脂併用の系にカルボキシ
ル変性ＮＢＲ（アクリロニトリルブタジエンラバー）を
添加し、無機充填材で強化することにより、耐熱性に優
れ、衝撃強度と静的強度が高位にバランスした成形材料
が得られることを提唱した。ここで使用されるカルボキ
シル変性ＮＢＲはＳＰ値が９〜１０のものが推奨されて
いるが、カルボキシル基の存在はＳＰ値を高くするた
め、同じＳＰ値を持つ一般的なＮＢＲのブタジエン、ア
ルリロニトリル結合比とは異なる結合比を持つ。さらに
樹脂が硬化する際にカルボキシル基が反応に関与するた
め、同じＳＰ値を持つＮＢＲを添加した場合と比較し成
形時の溶融粘度が非常に高い。そのため複雑な形状をし
た金型では、高い熱安定性を持ちながら充填不良が生じ
ることがあった。The applicant of the present invention has disclosed in Japanese Patent Application No. 1-274856 the addition of a carboxyl-modified NBR (acrylonitrile butadiene rubber) to a resol resin / novolak resin combination system, and strengthening with an inorganic filler to provide excellent heat resistance. It has been proposed that a molding material having a high balance between impact strength and static strength can be obtained. It is recommended that the carboxyl-modified NBR used here has an SP value of 9 to 10. However, the presence of a carboxyl group increases the SP value. Therefore, general NBR butadiene and allylo having the same SP value are used. It has a binding ratio different from the nitrile binding ratio. Furthermore, since the carboxyl group participates in the reaction when the resin is cured, the melt viscosity at the time of molding is much higher than when NBR having the same SP value is added. Therefore, in a mold having a complicated shape, poor filling may occur while having high thermal stability.
【０００６】以上、述べた様に耐熱性に優れ、静的強度
と衝撃強度にバランスがとれ、更に流動性に優れたフェ
ノール樹脂成形材料は今までに得られていなかった。As described above, a phenolic resin molding material having excellent heat resistance, a good balance of static strength and impact strength, and further excellent flowability has not been obtained.
【０００７】[0007]
【発明が解決しようとする課題】自動車の中でもエンジ
ンルーム内に使用される部品は３〜４０Ｇの振動と、１
５０〜２００℃の温度、又、走行中に石が跳ねる等の環
境条件にさらされる。従来、金属である部品を樹脂に置
換するためには、これらの諸条件に抗するだけの特性を
有していなければならない。本発明者は、このような部
品に対応可能な材料を提供せんとして鋭意研究を重ねた
結果、耐熱性に優れ、静的強度と衝撃強度が高位にバラ
ンスして、かつ生産性良く射出成形可能な材料を得る方
法を見い出したのである。The parts used in an engine room of a motor vehicle include vibrations of 3 to 40 G and 1
It is exposed to temperatures of 50 to 200 ° C. and environmental conditions such as stones jumping during running. Conventionally, in order to replace a metal component with a resin, it is necessary to have characteristics that can withstand these conditions. The inventor of the present invention has conducted intensive studies to provide materials that can respond to such parts, and as a result, has excellent heat resistance, has a high balance between static strength and impact strength, and can be injection molded with high productivity. I found a way to get the right material.
【０００８】[0008]
【課題を解決するための手段】本発明は、レゾール樹脂
２０〜４０重量部、ノボラック樹脂５〜１５重量部、部
分架橋ＮＢＲ３〜１０重量部、無機充填材３５〜６５重
量部からなるフェノール樹脂組成物であり、曲げ強度、
引張り強度等の静的強度と衝撃強度及び耐熱性が高位に
バランスした特性を与え、かつ、流動性がよく、射出成
型性にも優れたフェノール樹脂成形材料を提供するもの
である。The present invention provides a phenolic resin composition comprising 20 to 40 parts by weight of a resole resin, 5 to 15 parts by weight of a novolak resin, 3 to 10 parts by weight of partially crosslinked NBR, and 35 to 65 parts by weight of an inorganic filler. Object, bending strength,
It is an object of the present invention to provide a phenolic resin molding material which provides properties in which static strength such as tensile strength, impact strength and heat resistance are balanced at a high level, has good fluidity, and is excellent in injection moldability.
【０００９】ここで使用されるレゾール樹脂はジメチレ
ン型でもレゾール型でもよく、単独でも併用でもよい。
軟化点（ボールリング法）は７０℃以上であることが好
ましい。次にノボラック樹脂は通常いかなる分子量のも
のでも使用可能であるが、重量平均分子量が４０００以
上のものであれば好ましく使用でき、特に５０００〜９
０００のものが好ましい。The resole resin used here may be of the dimethylene type or resole type, and may be used alone or in combination.
The softening point (ball ring method) is preferably 70 ° C. or higher. Next, the novolak resin can be usually used with any molecular weight, but it can be preferably used as long as it has a weight average molecular weight of 4000 or more, and particularly preferably 5000 to 9
000 is preferred.
【００１０】ノボラックを併用する目的であるが、一つ
は成形材料化時における安定生産性である。もう一つは
硬化物の靭性向上効果である。例えば樹脂系をレゾール
のみにすると、衝撃強度の大幅な向上は望めないし、成
形材料化時のフローコントロールが難しい。又、ノボラ
ック併用系でもノボラックの重量平均分子量が大きいほ
ど衝撃強度は高くなる傾向がある。即ち、ノボラック併
用系、特に重量平均分子量４０００以上の高分子量ノボ
ラック併用系の硬化物がミクロ硬化物の集合体ではな
く、一つの均一な硬化物になると考えられる。[0010] The purpose of using the novolak is to use it together. One of them is the stable productivity at the time of forming a molding material. Another is the effect of improving the toughness of the cured product. For example, if the resin system is only resol, a significant improvement in impact strength cannot be expected, and it is difficult to control the flow when forming a molding material. Even in a novolak combination system, the impact strength tends to increase as the weight average molecular weight of the novolak increases. That is, it is considered that the cured product of the novolak combination system, particularly the high molecular weight novolak combination system having a weight average molecular weight of 4000 or more is not an aggregate of micro-cured products, but one uniform cured product.
【００１１】又、重量平均分子量が９０００以上になる
と系全体の粘度が上昇しすぎて、材料化が困難となり、
材料化できても射出成形が困難となる傾向がある。On the other hand, if the weight average molecular weight is more than 9,000, the viscosity of the whole system becomes too high, and it becomes difficult to materialize.
Even if it can be made into a material, injection molding tends to be difficult.
【００１２】ノボラックのオルソ／パラ結合比（Ｏ／Ｐ
比）は特に限定するものではないが、１．０以上のもの
を使用すれば、成形時の硬化性が良くなる特長が得られ
る。Novolak ortho / para bond ratio (O / P
The ratio) is not particularly limited, but if a ratio of 1.0 or more is used, a characteristic that the curability at the time of molding is improved can be obtained.
【００１３】又、レゾールとノボラックの併用比率は６
０／４０〜９０／１０であれば使用可能であり、７０／
３０〜８０／２０が効果的である。レゾール比率を高く
すると衝撃強度が低下し、又ノボラック比率をこの範囲
以上にすると硬化性が悪くなるので、特許請求の範囲が
好ましいのである。The combination ratio of resol and novolak is 6
If it is 0/40 to 90/10, it can be used.
30-80 / 20 is effective. When the resol ratio is increased, the impact strength is decreased, and when the novolak ratio is more than this range, the curability is deteriorated. Therefore, the claims are preferred.
【００１４】次に部分架橋ＮＢＲはモノマーの段階でブ
タジエンの二重結合とアクリロニトリルを架橋させたも
のを適当な割合で添加し重合させたものであればよく、
ノーマルなアクリロニトリルブタジエンに対する架橋部
分の比率は特に限定しない。しかし、架橋の比率が高い
と樹脂との相溶性が悪くなるため、１％以下の比率で架
橋しているものが好ましい。また、アクリロニトリルと
ブダジエンの結合比率はフェノール樹脂との相溶性を考
えてＳＰ値９〜１０程度に調整されていればよい。Next, the partially cross-linked NBR may be any obtained by adding a polymer obtained by cross-linking a double bond of butadiene and acrylonitrile in a monomer stage at an appropriate ratio and polymerizing the same.
The ratio of the crosslinked portion to normal acrylonitrile butadiene is not particularly limited. However, if the cross-linking ratio is high, the compatibility with the resin deteriorates, so that the cross-linking at a ratio of 1% or less is preferable. The binding ratio between acrylonitrile and butadiene may be adjusted to an SP value of about 9 to 10 in consideration of compatibility with the phenol resin.
【００１５】部分架橋ＮＢＲの分子量は特に限定しない
が、ロール作業性を考慮すれば２０万から５０万程度が
望ましい。The molecular weight of the partially crosslinked NBR is not particularly limited, but is preferably about 200,000 to 500,000 in consideration of roll workability.
【００１６】次に無機充填材は炭酸カルシウム、焼成ク
レー、未焼成クレー、マイカ、シリカ、ワラステナイ
ト、水酸化マグネシウム、水酸化アルミニウム、ガラス
繊維、アルミナ繊維等が単独又は併用することが可能で
ある。特に、少なくとも無機充填材の５０〜６０％をガ
ラス繊維、アルミナ繊維を使用すれば一層効果が得られ
る。Next, as the inorganic filler, calcium carbonate, calcined clay, unfired clay, mica, silica, wollastenite, magnesium hydroxide, aluminum hydroxide, glass fiber, alumina fiber and the like can be used alone or in combination. . In particular, more effect can be obtained by using glass fiber and alumina fiber for at least 50 to 60% of the inorganic filler.
【００１７】更に、充填材と樹脂の密着性を上げるの
に、アミノシラン、エポキシシラン等のカップリング剤
を使用すれば、強度、耐熱性向上に効果的である。Further, if a coupling agent such as aminosilane or epoxysilane is used to improve the adhesion between the filler and the resin, it is effective to improve the strength and heat resistance.
【００１８】本発明は射出成形可能で、曲げ強度、引張
り強度等の静的強度と衝撃強度及び耐熱性が高位にバラ
ンスした特性を与えるフェノール樹脂組成物を提供する
もので、レゾール樹脂２０〜４０重量部（好ましくは２
０〜３０重量部）、ノボラック樹脂５〜１５重量部、部
分架橋ＮＢＲ３〜１０重量部、無機充填材３５〜６５重
量部（好ましくは４０〜５５重量部）及び通常フェノー
ル樹脂成形材料に使用される顔料、離型剤、硬化促進剤
等の原材料を均一混合した後、ロール、コニーダー、二
軸押出機等の混練機等で加熱混練、粉砕して作られる。The present invention provides a phenolic resin composition which can be injection-molded and provides a property in which static strength such as bending strength and tensile strength and impact strength and heat resistance are balanced at a high level. Parts by weight (preferably 2
0 to 30 parts by weight), 5 to 15 parts by weight of novolak resin, 3 to 10 parts by weight of partially crosslinked NBR, 35 to 65 parts by weight of inorganic filler (preferably 40 to 55 parts by weight) and usually used for a phenol resin molding material. After uniformly mixing raw materials such as a pigment, a release agent, and a curing accelerator, the mixture is heated and kneaded by a kneader such as a roll, a co-kneader, a twin-screw extruder, or the like, and pulverized.
【００１９】レゾール樹脂とノボラック樹脂の割合は、
前述の通り６０／４０〜９０／１０の範囲が好ましい。
こられのフェノール樹脂の合計量が２５重量部以下であ
ると、樹脂分が少ないため成形性が悪くなり、成型品の
種々の特性が低下するようになる。一方、５５重量部以
上であると、成形材料製造時の作業性が劣り、硬化時の
揮発分も多くなるため、射出成形が難しくなってくる。
また成形収縮が大きく、成形物の強度も低下する傾向が
出てくる。必要により前述した混練物を冷却前に押出造
粒機を等しくしてペレット化することも可能である。The ratio between the resole resin and the novolak resin is
As described above, the range of 60/40 to 90/10 is preferable.
If the total amount of the phenolic resin is 25 parts by weight or less, the resin content is small, so that the moldability is deteriorated and various characteristics of the molded product are deteriorated. On the other hand, when the amount is 55 parts by weight or more, the workability at the time of producing a molding material is inferior and the volatile matter at the time of curing increases, so that injection molding becomes difficult.
In addition, molding shrinkage is large, and the strength of the molded product tends to decrease. If necessary, the above-mentioned kneaded product can be pelletized by using an extrusion granulator before cooling.
【００２０】このようにして得られた本発明の衝撃強度
に優れたフェノール樹脂組成物は、自動車エンジンルー
ム内に装着されるスタータモーター部品、耐熱強度を要
求されるコンミテータ等に適用できる。The thus obtained phenolic resin composition having excellent impact strength of the present invention can be applied to a starter motor component mounted in an automobile engine room, a commutator requiring heat resistance, and the like.
【００２１】[0021]
実施例１ （Ａ）ジメチレンエーテル型レゾール（住友デュレズ
(株)ＰＲ−５３５２９）２５.５重量部、（Ｂ）重量平
均分子量6500のノボラック（仕込みモル比０.８８、シ
ュウ酸触媒、Ｏ／Ｐ比＝０.８）１０.５重量部、（Ｃ）
日本合成ゴム(株)部分架橋ＮＢＲ ＰＮＣ−３８（架橋
率０.８％、ＳＰ値９.７）８重量部、（Ｄ）ガラス繊維
日本電気ガラス(株) ECSO15B154H ５１.５重量部、
(Ｅ）顔料、離型剤他 ４.５重量部を均一混合しロール
で材料化した。Example 1 (A) dimethylene ether type resole (Sumitomo Durez)
(PR-53529) 25.5 parts by weight, (B) 10.5 parts by weight of novolak having a weight average molecular weight of 6,500 (prepared molar ratio 0.88, oxalic acid catalyst, O / P ratio = 0.8), C)
Nippon Synthetic Rubber Co., Ltd. 8 parts by weight of partially crosslinked NBR PNC-38 (crosslinkage 0.8%, SP value 9.7), (D) 51.5 parts by weight of glass fiber NEC Corporation ECSO15B154H,
(E) 4.5 parts by weight of pigment, release agent, etc. were uniformly mixed and made into a material by a roll.
【００２２】実施例２ （Ａ）メチロール型レゾール（住友デュレズ(株)ＰＲ−
５３５２９）３０重量部、（Ｂ）重量平均分子量5000の
ノボラック（仕込みモル比０.８３、塩酸触媒、Ｏ／Ｐ比
＝０.７５）１０重量部、（Ｃ）日本合成ゴム(株)部分
架橋ＮＢＲ ＰＮＣ−３８ ８重量部、（Ｄ）ガラス繊維
日本硝子繊維(株) RES015BM38 ５０重量部、（Ｅ）顔
料、離型剤他 ５.０重量部を二軸押出機で混練後、造粒
機でペレット化した。Example 2 (A) Methylol-type resole (PR-, Sumitomo Durez Co., Ltd.)
53529) 30 parts by weight, (B) 10 parts by weight of novolak having a weight-average molecular weight of 5,000 (charged molar ratio 0.83, hydrochloric acid catalyst, O / P ratio = 0.75), (C) Nippon Synthetic Rubber Co., Ltd. partially crosslinked 8 parts by weight of NBR PNC-38, (D) 50 parts by weight of glass fiber Nippon Glass Fiber Co., Ltd. RES015BM38, (E) 5.0 parts by weight of pigment, mold release agent, etc. After kneading with a twin screw extruder, granulator And pelletized.
【００２３】実施例３ （Ａ）メチロール型レゾール（住友デュレズ(株)ＰＲ−
５１１４１）２５重量部、（Ｂ）重量平均分子量5000の
ノボラック（実施例２と同じ）８重量部、（Ｃ）日本合
成ゴム(株)部分架橋ＮＢＲ ＰＮＣ−３８ ５重量部、
（Ｄ）ガラス繊維日本電気ガラス(株) ECSO15B154H ３
０重量部、未焼成クレー ２５重量部、（Ｅ）顔料、離型
剤他 ５重量部を均一混合しロールで材料化した。Example 3 (A) Methylol-type resole (PR-, Sumitomo Durez Co., Ltd.)
51141) 25 parts by weight, (B) 8 parts by weight of novolak having the weight average molecular weight of 5,000 (same as in Example 2), (C) 5 parts by weight of Nippon Synthetic Rubber Co., Ltd. partially crosslinked NBR PNC-38,
(D) Glass fiber NEC Corporation ECSO15B154H 3
0 parts by weight, 25 parts by weight of unfired clay, 5 parts by weight of (E) a pigment, a release agent and others were uniformly mixed and made into a material by a roll.
【００２４】実施例４ （Ａ）ジメチレンエーテル型レゾール（住友デュレズ
(株)ＰＲ−５３５２９）２５重量部、（Ｂ）重量平均分
子量6500のノボラック（実施例１と同じ）１０重量部、
（Ｃ）日本合成ゴム(株)ＰＮＣ−３８ ８重量部、
（Ｄ）焼成クレー ２０重量部、（Ｅ）ワラステナイト
３２重量部、（Ｆ）顔料、離型剤他 ５重量部を均一混
合し二軸押出機で混練後、造粒機でペレット化した。Example 4 (A) A dimethylene ether type resole (Sumitomo Durez)
(PR-53529) 25 parts by weight, (B) 10 parts by weight of novolak having a weight average molecular weight of 6,500 (same as in Example 1),
(C) Japan Synthetic Rubber Co., Ltd. PNC-38 8 parts by weight,
(D) calcined clay 20 parts by weight, (E) wollastenite
32 parts by weight, 5 parts by weight of (F) pigment, release agent and the like were uniformly mixed, kneaded by a twin screw extruder, and then pelletized by a granulator.
【００２５】比較例１ （Ａ）ジメチレンエーテル型レゾール（住友デュレズ
(株)ＰＲ−５３５２９）２５.５重量部、（Ｂ）重量平
均分子量6500のノボラック（実施例１と同じ）１０.５
重量部、（Ｃ）日本合成ゴム(株)カルボキシル変性ＮＢ
Ｒ ＰＮＣ−２５（ＳＰ値９.３、カルボキシル基４mol
％）８重量部、（Ｄ）ガラス繊維 日本電気ガラス(株)
ECSO15B154H ５１.５重量部、（Ｅ）顔料、離型剤他４
５重量部を均一混合しロールで材料化した。Comparative Example 1 (A) dimethylene ether type resole (Sumitomo Durez)
PR-53529) 25.5 parts by weight, (B) novolak having a weight average molecular weight of 6,500 (same as in Example 1) 10.5
Parts by weight, (C) Nippon Synthetic Rubber Co., Ltd. carboxyl-modified NB
R PNC-25 (SP value 9.3, carboxyl group 4 mol
%) 8 parts by weight, (D) glass fiber NEC Glass Co., Ltd.
ECSO15B154H 51.5 parts by weight, (E) pigment, release agent, etc. 4
5 parts by weight were uniformly mixed and made into a material by a roll.
【００２６】比較例２ （Ａ）ジメチレンエーテル型レゾール（住友デュレズ
(株)ＰＲ−５３５２９）２５.５重量部、(Ｂ）メチロー
ル型レゾール（住友デュレズ(株)ＰＲ−５１７２３）１
０.５重量部、（Ｃ）日本合成ゴム(株)部分架橋ＮＢＲ
ＰＮＣ−３８ ８重量部、（Ｄ）ガラス繊維 日本電気
ガラス(株) ECSO15B154H ５１.５重量部、（Ｅ）顔料、
離型剤他 ４,．５重量部を均一合成しロールで材料化し
た。Comparative Example 2 (A) dimethylene ether type resole (Sumitomo Durez)
PR-53529) 25.5 parts by weight, (B) methylol-type resol (Sumitomo Durez PR-51723) 1
0.5 parts by weight, (C) Nippon Synthetic Rubber Co., Ltd. partially crosslinked NBR
8 parts by weight of PNC-38, (D) glass fiber NEC Glass Co., Ltd. ECSO15B154H 51.5 parts by weight, (E) pigment,
Release agent, etc. 5 parts by weight were uniformly synthesized and made into a material by a roll.
【００２７】比較例３ （Ａ）ジメチレンエーテルレゾール（住友デュレズ
（株）ＰＲ−５３５２９）２５.５重量部、（Ｂ）重量平
均分子量6500のノボラック（実施例１と同じ)１０．５
重量部、（Ｃ）日本合成ゴム(株)ＮＢＲＰＮ−２０ＨＡ
（ＳＰ値９.６、ノーマルＮＢＲ）８重量部、（Ｄ）ガ
ラス繊維 日本電気ガラス(株)ECSO15B154H５１．５重量
部、（Ｅ）顔料、離型剤他 ４．５重量部を均一混合し
ロールで材料化した。Comparative Example 3 (A) 25.5 parts by weight of dimethylene ether resole (PR-53529, Sumitomo Durez Co., Ltd.), (B) 10.5 novolak having a weight average molecular weight of 6,500 (same as in Example 1) 10.5
Parts by weight, (C) NBRPN-20HA, Japan Synthetic Rubber Co., Ltd.
(SP value: 9.6, normal NBR) 8 parts by weight, (D) glass fiber NEC Glass Co., Ltd. ECSO15B154H 51.5 parts by weight, (E) pigment, release agent, etc. 4.5 parts by weight and uniformly mixed and rolled Was made into a material.
【００２８】比較例４ （Ａ）重量平均分子量5000のノボラック（実施例２と同
じ）３４重量部、（Ｂ）ヘキサメチレンテトラミン ６
重量部、（Ｃ）日本合成ゴム(株)部分架橋ＮＢＲ ＰＮ
Ｃ−３８（ＳＰ値９.７）８重量部、（Ｄ）ガラス繊維
日本電気ガラス(株)ECSO15B154H ４７重量部、（Ｅ）顔
料、離型剤他 ５重量部を均一混合しロールで材料化し
た。Comparative Example 4 (A) 34 parts by weight of novolak having the weight average molecular weight of 5000 (same as in Example 2), and (B) hexamethylenetetramine 6
Parts by weight, (C) Nippon Synthetic Rubber Co., Ltd. partially crosslinked NBR PN
8 parts by weight of C-38 (SP value 9.7), (D) glass fiber
47 parts by weight of ECSO15B154H of NEC Corporation, 5 parts by weight of (E) a pigment, a release agent and others were uniformly mixed and made into a material by a roll.
【００２９】実施例１〜４及び比較例１〜４について下
記の評価を実施し、その結果を表１及び表２に示す。The following evaluations were performed on Examples 1 to 4 and Comparative Examples 1 to 4, and the results are shown in Tables 1 and 2.
【表１】 [Table 1]
【００３０】[0030]
【表２】 [Table 2]
【００３１】（１）シャルピー衝撃度：ＪＩＳ Ｋ ６９
１１によりトランスファー成形した試験片を１８０℃、
８時間加熱エージングした後、シャルピー衝撃試験機で
測定した。(1) Charpy impact strength: JIS K69
The test piece transfer-molded according to
After heating and aging for 8 hours, the measurement was performed using a Charpy impact tester.
【００３２】（２）曲げ強度、曲げ弾性率、引張強度：
ＪＩＳ Ｋ ６９１１によりトランスファー成形した試験
片を１８０℃、８時間加熱エージングした後、東洋ボー
ルドウィン(株)テンシロンにて測定した。(2) Flexural strength, flexural modulus, tensile strength:
A test piece subjected to transfer molding according to JIS K 6911 was heat-aged at 180 ° C. for 8 hours, and then measured by Toyo Baldwin Co., Ltd. Tensilon.
【００３３】（３）熱変形温度 ＡＳＴＭ Ｄ６４８によりトランスファー成形した試験
片を１８０℃、８時間加熱エージングした後、東洋精機
（株）熱変形温度試験機で測定した。(3) Heat Deformation Temperature A test piece formed by transfer molding according to ASTM D648 was heat-aged at 180 ° C. for 8 hours, and then measured by a heat deformation temperature tester manufactured by Toyo Seiki Co., Ltd.
【００３４】（４）溶融粘度 島津製作所(株)の高化式フローテスターＣＦＴ−５００
Ｃを使用して１３０℃での溶融粘度を測定し、流動性の
評価とした。(4) Melt viscosity Koka type flow tester CFT-500 manufactured by Shimadzu Corporation
The melt viscosity at 130 ° C. was measured using C to evaluate fluidity.
【００３５】実施例１及び２のように、無機充填材とし
てガラス繊維を使用した場合は曲げ強度がそれぞれ２
２.０kg／mm2、１８.０kg／mm2と高い値を示し、かつシ
ャルピー衝撃強度は１０.５kgcm／cm2、９.０kgcm／cm2
と射出成形可能なフェノール樹脂成形材料とては非常に
高い強度を示す。また、熱変形温度の低下も見られな
い。実施例４及び５は、無機充填材としてクレー、ワラ
ストナイトを使用した場合であるが、硝子繊維と同様
に、静的強度、耐熱性を維持しながら高い衝撃強度を示
す。When glass fiber is used as the inorganic filler as in Examples 1 and 2, the bending strength is 2
It shows high values of 2.0 kg / mm 2 and 18.0 kg / mm 2 , and has Charpy impact strength of 10.5 kgcm / cm 2 and 9.0 kgcm / cm 2.
And a phenolic resin molding material that can be injection molded exhibit extremely high strength. Also, no decrease in the heat distortion temperature is observed. Examples 4 and 5 are cases in which clay and wollastonite are used as the inorganic filler, but exhibit high impact strength while maintaining static strength and heat resistance, similarly to glass fibers.
【００３６】比較例１はカルボキシ変性ＮＢＲを使用し
た場合であるが、本発明のフェノール樹脂組成物と同等
な強度と耐熱性が得られる。しかし、１３０℃での溶融
粘度を比較すると、１オーダ以上高い値であり、複雑な
形状を有する成形品の成形には不適当である。Comparative Example 1 is a case where a carboxy-modified NBR is used, and the same strength and heat resistance as those of the phenol resin composition of the present invention can be obtained. However, when the melt viscosity at 130 ° C. is compared, the melt viscosity at 1 ° C. is higher than the order of 1 order or more, which is unsuitable for molding a molded article having a complicated shape.
【００３７】比較例２はフェノール樹脂をレゾールのみ
としたものであるが、衝撃強度の改善はほとんどみられ
ない。比較例３はノーマルなＮＢＲを使用した場合であ
り、衝撃強度の向上は得られるものの本発明のフェノー
ル樹脂組成物のレベルまでには至らない。比較例４はノ
ボラック樹脂とヘキサメチレンテトラミンの系である
が、衝撃強度の向上はほとんどみられない。In Comparative Example 2, the phenolic resin was only resol, but the improvement in impact strength was hardly observed. Comparative Example 3 is a case where normal NBR was used, and although the impact strength was improved, it did not reach the level of the phenolic resin composition of the present invention. Comparative Example 4 is a system of a novolak resin and hexamethylenetetramine, but shows little improvement in impact strength.
【００３８】[0038]
【発明の効果】本発明のフェノール樹脂組成物は、レゾ
ール樹脂にノボラック樹脂、部分架橋ＮＢＲ、無機充填
材を配合することにより、機械強度、特に衝撃強度が優
れ、耐熱性が良好で、かつ成形時の流動性に優れたもの
であり、複雑な形状の成形品の成形にも適しており、自
動車部品等の金属部品のプラスチック部品への置換を大
幅に促進するものである。The phenolic resin composition of the present invention has excellent mechanical strength, particularly excellent impact strength, good heat resistance, and good moldability by blending a novolak resin, partially crosslinked NBR, and an inorganic filler with a resole resin. It has excellent fluidity at the time, is suitable for molding a molded article having a complicated shape, and greatly promotes replacement of metal parts such as automobile parts with plastic parts.
Claims (1)
(2) ノボラック樹脂５〜１５重量部、(3) 部分架橋ＮＢ
Ｒ３〜１０重量部、(4) 無機充填材３５〜６５重量部か
らなるフェノール樹脂組成物。(1) 20 to 40 parts by weight of a resole resin,
(2) 5 to 15 parts by weight of novolak resin, (3) partially crosslinked NB
R3 to 10 parts by weight; (4) a phenolic resin composition comprising 35 to 65 parts by weight of an inorganic filler.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3193272A JP2653574B2 (en) | 1991-08-01 | 1991-08-01 | Phenolic resin composition with excellent impact strength |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3193272A JP2653574B2 (en) | 1991-08-01 | 1991-08-01 | Phenolic resin composition with excellent impact strength |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0532863A JPH0532863A (en) | 1993-02-09 |
| JP2653574B2 true JP2653574B2 (en) | 1997-09-17 |
Family
ID=16305182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3193272A Expired - Fee Related JP2653574B2 (en) | 1991-08-01 | 1991-08-01 | Phenolic resin composition with excellent impact strength |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2653574B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2878044B2 (en) | 1992-10-20 | 1999-04-05 | 住友ベークライト株式会社 | Phenolic resin composition |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06107902A (en) * | 1992-09-30 | 1994-04-19 | Sumitomo Bakelite Co Ltd | Phenol resin composition |
| US5336723A (en) * | 1992-09-30 | 1994-08-09 | Sumitomo Bakelite Company Limited | Phenolic resin molding materials |
| JP3763740B2 (en) | 2000-12-28 | 2006-04-05 | 株式会社ジェイテクト | Resin pulley |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5128103B2 (en) * | 1971-12-15 | 1976-08-17 | ||
| JPH0689220B2 (en) * | 1988-02-20 | 1994-11-09 | 株式会社イノアックコーポレーション | Tray for integrated circuits |
-
1991
- 1991-08-01 JP JP3193272A patent/JP2653574B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2878044B2 (en) | 1992-10-20 | 1999-04-05 | 住友ベークライト株式会社 | Phenolic resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0532863A (en) | 1993-02-09 |
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