JP3536342B2 - Phenolic resin molding material - Google Patents
Phenolic resin molding materialInfo
- Publication number
- JP3536342B2 JP3536342B2 JP08104094A JP8104094A JP3536342B2 JP 3536342 B2 JP3536342 B2 JP 3536342B2 JP 08104094 A JP08104094 A JP 08104094A JP 8104094 A JP8104094 A JP 8104094A JP 3536342 B2 JP3536342 B2 JP 3536342B2
- Authority
- JP
- Japan
- Prior art keywords
- resin molding
- molding material
- phenolic resin
- weight
- parts
- 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 - Lifetime
Links
Description
【発明の詳細な説明】
【０００１】
【産業上の利用分野】本発明は、強靭性を有するフェノ
ール樹脂成形材料に関する。
【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、電気特性等に優れ、自動車、電気、電子等の
基幹産業分野で長期にわたり使用されてきた実績があ
る。特に最近それら分野での製品は、小型化、薄肉化の
傾向にあるが、フェノール樹脂成形材料を始めとする熱
硬化性樹脂組成物は脆い欠点があり、各種用途への適用
上大きな制約となっている。
【０００３】従来、フェノール樹脂成形材料の脆さを改
良するため、（１）フェノール樹脂に天然ゴム、アクリ
ロニトリル、ブタジエンゴムなどの可塑剤を添加する方
法（特開昭５８−１１８８４５号公報、特開昭５６−１
０５４６号公報）や、（２）フェノール樹脂のフェノー
ル核間に長鎖のポリメチレン基を導入したり、フェノー
ル樹脂のフェノール核間にウレタン結合や可撓性エポキ
シ樹脂によるアルキレンオキサイド鎖を導入したりして
可塑化を行う方法、また（３）充填材に布チップやガラ
ス繊維などを使用し、充填材で脆さを補う方法（特開昭
５９−２４７４２号公報）などがある。
【０００４】
【発明が解決しようとする課題】しかし、従来の方法で
は、衝撃値が向上しても強度が極度に低下したり、又
は、衝撃値が不十分で満足な靭性を付与するには至らな
い。
【０００５】本発明は、フェノール樹脂成形材料の強度
を下げずに衝撃値を向上させて、強靭性を有するフェノ
ール樹脂成形材料を提供するものである。
【０００６】
【課題を解決するための手段】本発明は、前記問題点を
解決するためになされたものであり、フェノール樹脂、
下記式（１）で表される化合物及び充填材を含有するこ
とを特徴とするフェノール樹脂成形材料を提供するもの
である。
【化２】
（式中、ｎは１〜１０の数である。）
【０００７】本発明で用いるフェノール樹脂は、ノボラ
ック型、レゾール型いずれでもよく、また両者の混合物
であってもよい。
【０００８】式（１）で表される化合物の添加量は、フ
ェノール樹脂１００重量部に対し、好ましくは３〜５０
重量部、更に好ましくは３〜２０重量部である。３重量
部未満では、衝撃値や靭性の向上の効果が小さくなるこ
とがあり、５０重量部を超えると、強度が大幅に低下
し、衝撃値向上の効果が薄れることがある。
【０００９】本発明のフェノール樹脂成形材料には、通
常充填材が含有される。充填材としては、通常の木粉、
パルプ、布チップ、ポリビニルアルコール繊維、アクリ
ロニトリル−ブタジエンゴム等の有機質充填材や、炭酸
カルシウム、水酸化アルミニウム、シリカ、クレー、マ
イカ、ゼオライト、タルク、ガラスパウダー、ガラス繊
維等の無機質充填材が用いられる。充填材の配合量は、
樹脂成分１００重量部に対して好ましくは３０〜２５０
重量部である。３０重量部未満では、寸法安定性等の特
性面で劣ることがあり、また２５０重量部を超えると、
成形性の点で問題となることがある。
【００１０】また充填材の他に通常の硬化剤（例えばヘ
キサメチレンテトラミン）、助硬化剤（例えば消石
炭）、離型剤（例えばステアリン酸亜鉛）、その他必要
に応じて、着色剤（例えばカーボンブラック）、表面処
理剤（例えばシランカップリング剤）、難燃剤（例えば
ホウ酸）等を添加することができる。
【００１１】これら配合物を均一に混合した後、ロー
ル、ニーダ、二軸押出機等の混練機等で加熱混練、粉砕
し必要に応じて造粒化するとフェノール樹脂成形材料が
得られる。
【００１２】
【実施例】以下、本発明を具体的に説明するために実施
例を示す。なお、部及び％は特に断らない限り重量部、
重量％を示す。
【００１３】実施例１、２及び比較例１、２、３
表１の配合表に従って各成分を配合、均一混合した後、
熱ロールで混練、冷却、粉砕してフェノール樹脂成形材
料を得た。
【００１４】
【表１】【００１５】１）アロニックスＭ−５７００（アクリル
系不飽和基１個のオリゴエステルアクリレート、東亜合
成化学社商品名）
２）アロニックスＭ−８０６０（アクリル系不飽和基数
個のオリゴエステルアクリレート、東亜合成化学社商品
名）
【００１６】比較例４、５
表２の配合表に従って各成分を配合、均一混合した後、
ニーダ混練、冷却、粉砕してフェノール樹脂成形材料を
得た。
【００１７】
【表２】
【００１８】１）アロニックスＭ−５７００（アクリル
系不飽和基１個のオリゴエステルアクリレート、東亜合
成化学社商品名）
２）ＰＮＣ−３８（アクリロニトリルーブタジエンゴ
ム、日本合成ゴム（株）社商品名）
３）ＲＥＳ０１５ＢＭ３８（ガラス繊維、日本板硝子
（株）社商品名）
【００１９】実施例１〜２及び比較例１〜５について下
記の評価を実施した。
（１）シャルピー衝撃強度
ＪＩＳ Ｋ ６９１１によりインジェクション成形した
試験片を、東京衝機（株）社製シャルピー衝撃試験機で
測定した。
（２）曲げ強度、曲げ弾性率、引張強度、破断歪
ＪＩＳ Ｋ ６９１１によりインジュクション成形した
試験片を島津製作所（株）社製テンシロンにて測定し
た。
【００２０】実施例１、２及び比較例１、２、３の上記
評価結果を表３に、比較例４、５の上記評価結果を表４
に示す。
【００２１】
【表３】
【００２２】
【表４】表３、表４の結果から明らかなように、本発明のフェノ
ール樹脂成形材料が機械的強度、特に衝撃強度が優れ、
強靭であることを確認した。
【００２３】
【発明の効果】本発明のフェノール樹脂成形材料は、機
械的強度、特に衝撃強度に優れ、かつ強靭であり、今ま
で脆い欠点があり適用上大きな制約となっていた、部品
の小型化、薄肉化の進む、自動車、電気、電子分野への
展開が大巾に図れるものである。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phenol resin molding material having toughness. 2. Description of the Related Art Phenolic resin molding materials are excellent in heat resistance, dimensional stability, electric properties and the like, and have a long track record of being used in key industries such as automobiles, electricity and electronics for a long time. In recent years, products in those fields have tended to be smaller and thinner, but thermosetting resin compositions such as phenolic resin molding materials have a brittle defect, which is a major constraint on application to various applications. ing. Conventionally, in order to improve the brittleness of a phenolic resin molding material, (1) a method of adding a plasticizer such as natural rubber, acrylonitrile, butadiene rubber or the like to a phenolic resin (JP-A-58-118845; 56-1
No. 0546) and (2) introduction of a long-chain polymethylene group between phenol nuclei of a phenol resin and introduction of an urethane bond or an alkylene oxide chain by a flexible epoxy resin between phenol nuclei of a phenol resin. (3) a method of using a cloth chip, glass fiber, or the like as a filler to compensate for brittleness with the filler (JP-A-59-24742). [0004] However, in the conventional method, even if the impact value is improved, the strength is extremely reduced, or the impact value is insufficient to provide satisfactory toughness. I can't. An object of the present invention is to provide a phenol resin molding material having toughness by improving the impact value without lowering the strength of the phenol resin molding material. SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and comprises a phenol resin ,
An object of the present invention is to provide a phenolic resin molding material containing a compound represented by the following formula (1) and a filler . Embedded image (In the formula, n is a number of 1 to 10.) The phenolic resin used in the present invention may be either a novolak type or a resol type, or a mixture of both. The amount of the compound represented by the formula (1) is preferably 3 to 50 based on 100 parts by weight of the phenol resin.
Parts by weight, more preferably 3 to 20 parts by weight. If the amount is less than 3 parts by weight, the effect of improving the impact value and toughness may be reduced. If the amount exceeds 50 parts by weight, the strength may be significantly reduced and the effect of improving the impact value may be reduced. The phenolic resin molding material of the present invention usually contains a filler. As the filler, normal wood flour,
Organic fillers such as pulp, cloth chips, polyvinyl alcohol fiber, acrylonitrile-butadiene rubber, and inorganic fillers such as calcium carbonate, aluminum hydroxide, silica, clay, mica, zeolite, talc, glass powder, and glass fiber are used. . The amount of the filler is
It is preferably 30 to 250 with respect to 100 parts by weight of the resin component.
Parts by weight. If the amount is less than 30 parts by weight, characteristics such as dimensional stability may be inferior, and if it exceeds 250 parts by weight,
This may cause a problem in terms of moldability. In addition to the filler, a conventional curing agent (for example, hexamethylenetetramine), a co-curing agent (for example, extinguished coal), a release agent (for example, zinc stearate), and a coloring agent (for example, carbon Black), a surface treatment agent (for example, a silane coupling agent), a flame retardant (for example, boric acid), and the like. After uniformly mixing these components, the mixture is heated and kneaded by a kneader such as a roll, a kneader, or a twin-screw extruder, and then pulverized, and if necessary, granulated to obtain a phenolic resin molding material. The present invention will be described below in more detail with reference to Examples. Parts and percentages are by weight unless otherwise specified.
Indicates the weight%. [0013] After the respective ingredients were uniformly mixed according to the recipe of Example 1, 2及 Beauty Comparative Examples 1 Table 1,
The mixture was kneaded, cooled and pulverized with a hot roll to obtain a phenol resin molding material. [Table 1] 1) Aronix M-5700 (oligoester acrylate with one acrylic unsaturated group, trade name of Toa Gosei Chemical Co., Ltd.) 2) Aronix M-8060 (oligoester acrylate with several acrylic unsaturated groups, Toa Gosei Chemical) company trade name) [0016] ratio Comparative Examples 4 and 5 table 2 blending the ingredients following the recipe, were uniformly mixed,
The kneader was kneaded, cooled and pulverized to obtain a phenol resin molding material. [Table 2] 1) Aronix M-5700 (oligoester acrylate having one acrylic unsaturated group, trade name of Toa Gosei Chemical Co., Ltd.) 2) PNC-38 (acrylonitrile butadiene rubber, trade name of Nippon Synthetic Rubber Co., Ltd.) 3) RES015BM38 (glass fiber, trade name of Nippon Sheet Glass Co., Ltd.) The following evaluations were performed on Examples 1 and 2 and Comparative Examples 1 to 5. (1) Charpy impact strength A test piece injection-molded according to JIS K 6911 was measured with a Charpy impact tester manufactured by Tokyo Ikki Co., Ltd. (2) Flexural strength, flexural modulus, tensile strength, and strain at break A test piece injection-molded according to JIS K 6911 was measured with Tensilon manufactured by Shimadzu Corporation. [0020] Example 1, 2 the evaluation results of 及 beauty Comparative Examples 1 to Table 3, the evaluation results of specific Comparative Examples 4 and 5 Table 4
Shown in [Table 3] [Table 4] As is clear from the results of Tables 3 and 4, the phenolic resin molding material of the present invention has excellent mechanical strength, particularly excellent impact strength,
We confirmed that it was strong. The phenolic resin molding material of the present invention has excellent mechanical strength, especially impact strength, is tough, has a brittle defect, and has been a major limitation in its application. It can be widely applied to the fields of automobiles, electricity, and electronics, which are becoming thinner and thinner.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 相沢 輝樹 茨城県結城市大字鹿窪1772番地の１ 日 立化成工業株式会社 下館工場内 (72)発明者 柿迫 英樹 茨城県結城市大字鹿窪1772番地の１ 日 立化成工業株式会社 下館工場内 (56)参考文献 特開 昭60−219267（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08L 61/00 - 61/34 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Teruki Aizawa 1772, Shikadate, Oki, Yuki, Ibaraki Pref. Inside Shimodate Plant (72) Inventor Hideki Kakisako, 1772, 1772 Shikabo, Yuki, Yuki, Ibaraki (56) References JP-A-60-219267 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08L 61/00-61/34 CA (STN) REGISTRY (STN)
Claims (1)
る化合物及び充填材を含有することを特徴とするフェノ
ール樹脂成形材料。 【化１】 （式中、ｎは１〜１０の数である。） (57) [Claims] [Claim 1] A phenolic resin represented by the following formula (1)
Phenolic resin molding material comprising a compound and a filler . Embedded image (In the formula, n is a number from 1 to 10.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08104094A JP3536342B2 (en) | 1994-03-29 | 1994-03-29 | Phenolic resin molding material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08104094A JP3536342B2 (en) | 1994-03-29 | 1994-03-29 | Phenolic resin molding material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07268183A JPH07268183A (en) | 1995-10-17 |
| JP3536342B2 true JP3536342B2 (en) | 2004-06-07 |
Family
ID=13735338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08104094A Expired - Lifetime JP3536342B2 (en) | 1994-03-29 | 1994-03-29 | Phenolic resin molding material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3536342B2 (en) |
-
1994
- 1994-03-29 JP JP08104094A patent/JP3536342B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07268183A (en) | 1995-10-17 |
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