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JP3543924B2 - Phenolic resin molding material - Google Patents

Phenolic resin molding material Download PDF

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Publication number
JP3543924B2
JP3543924B2 JP23878198A JP23878198A JP3543924B2 JP 3543924 B2 JP3543924 B2 JP 3543924B2 JP 23878198 A JP23878198 A JP 23878198A JP 23878198 A JP23878198 A JP 23878198A JP 3543924 B2 JP3543924 B2 JP 3543924B2
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JP
Japan
Prior art keywords
weight
molding material
phenolic resin
inorganic filler
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
Application number
JP23878198A
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Japanese (ja)
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JP2000063621A (en
Inventor
伸一 前佛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Bakelite Co Ltd
Original Assignee
Sumitomo Bakelite Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sumitomo Bakelite Co Ltd filed Critical Sumitomo Bakelite Co Ltd
Priority to JP23878198A priority Critical patent/JP3543924B2/en
Publication of JP2000063621A publication Critical patent/JP2000063621A/en
Application granted granted Critical
Publication of JP3543924B2 publication Critical patent/JP3543924B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Description

【0001】
【発明の属する技術分野】
本発明は、絶縁破壊強さ、耐トラッキング性、耐燃性、強度に優れたフェノール樹脂成形材料に関するものである。
【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、成形性等に優れ、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ている。特に最近では製品の信頼性に対する要求は厳しくなり、絶縁破壊強さ、耐トラッキング性といった電気性能も要求されつつある。
【0003】
通常、電気特性が要求される部品には、不飽和ポリエステル樹脂、ジアリルフタレート樹脂、メラミン樹脂、メラミン・フェノール樹脂といった、電気特性に優れた樹脂を使用することが多いが、耐熱性、成形性、コストなどの点で問題があり、フェノール樹脂成形材料の優れた耐熱性、成形性を維持したまま、より高度な耐トラッキング性、絶縁破壊強さ、耐燃性を付与することが望まれている。また電子部品とりわけコイルボビンといったものは電気特性の他に衝撃強さ、曲げ強さ等の機械的強度も要求される。
【0004】
レゾール樹脂を用いた成形材料の特徴は、成形品からアンモニアガスを発生しない事に加え、含有する無機充填材などのイオン性不純物を低く抑えることにより、電気特性とりわけ耐湿性、絶縁破壊強さがよいことを特徴としている。一般的には、充填材として積層板の粉砕物、無機充填材などが多く用いられており、結晶水を含有する無機充填材を配合することによりさらに耐トラッキング性等を改良することも検討されている(特願平07−68241号公報等)が、強度不足からもろいという問題もあり、必ずしも満足できるものではなかった。
【0005】
衝撃強さ、曲げ強さのみに注目すれば、従来から用いられているガラス繊維を添加することで十分な効果があるが、弾性率の増加により、硬く、脆いという欠点が現れる。
同様に成形品の撓み量を大きくするために、NBR、SBRといったゴム成分を添加することにより、撓み量とともに衝撃強さの向上を図ることが出来るものの、曲げ強さが低下するという欠点が生じる。
【0006】
【発明が解決しようとする課題】
本発明は、従来のレゾール型フェノール樹脂を用いた成形材料のこのような問題点を解決するために種々の検討の結果なされたもので、その目的とするところは、耐トラッキング性、絶縁破壊強さ、耐燃性、曲げ強さ、衝撃強さ等の機械的強度に優れたフェノール樹脂成形材料を提供することにある。
【0007】
【課題を解決するための手段】
本発明は、成形材料中に、レゾール型フェノール樹脂を25〜35重量%含有し、難燃成分として、硼酸亜鉛、未焼成クレーから選ばれる少なくとも1種類の第1の無機充填材と、硼酸カルシウム、水酸化アルミニウム、水酸化マグネシウムから選ばれる少なくとも1種類の第2の無機充填材とを合計で40重量%以上含有し、かつ、上記第2の無機充填材の含有量が10重量%以上であり、更に、ガラス繊維を5〜15重量%、及びポリビニルブチラールを2〜5重量%含有することを特徴とするフェノール樹脂成形材料に関するものである。
【0008】
ここで使用するレゾール型フェノール樹脂は通常のフェノール樹脂成形材料に使用されるもので、ジメチレンエーテル型レゾール樹脂、メチロール型レゾール樹脂等であり、必要に応じてノボラック型フェノール樹脂を併用することも出来るが、硬化剤としてヘキサメチレンテトラミンを用いると、成形品からのアンモニアの発生による耐湿性や電気特性が低下するという問題から、ヘキサメチレンテトラミンを用いることは出来ない。フェノール樹脂量は成形材料全体に対して25〜35重量%である。25重量%未満では基材との濡れが十分に行われず、強度低下、及び流れ不足による成形性の低下がある。また35重量%を越えると耐トラッキング性の低下、材料のコストアップが起こり実用性に欠ける。
【0009】
難燃成分として用いられる無機充填材としては、硼酸亜鉛、未焼成クレーから選ばれる少なくとも1種類の第1の無機充填材と、硼酸カルシウム、水酸化アルミニウム、水酸化マグネシウムから選ばれる少なくとも1種類の第2の無機充填材との合計で、成形材料中に40重量%以上、好ましくは45重量%以上含有する必要がある。
さらに、上記第2の無機充填材の含有量が10重量%以上である。難燃成分としての無機充填材総量が40重量%未満では、十分な耐燃性、耐トラッキング性が得られず、上記第2の無機充填材を成形材料中に10重量%以上用いない場合、十分な耐燃性が得られない。
【0010】
ガラス繊維は一般的に用いられるチョップドストランドでよく、イオン性不純物などの少ないEガラスが好ましいが、この限りではない。添加量は成形材料中に5〜15重量%が好ましく、5重量%未満では十分な強度付与の効果が得られず、15重量%を越えると弾性率が上がりすぎ、ポリビニルブチラール(PVB)を併用しても、もろさを十分に克服することができない。
【0011】
ポリビニルブチラールは、その種類は特に限定されるものではないが、好ましくは、重合度が250〜2500、ブチラール化度が60〜80モル%のものである。また、100メッシュ以下の粒状のものが好ましい。添加量は2〜5重量%が好ましく、2重量%未満では十分な強度アップの効果が小さく、5重量%を超えると撓み量はますものの曲げ強さは低下するという問題がある。
その他の充填材としては、通常のレゾール型フェノール樹脂成形材料に用いられる粉砕布、積層板粉砕粉、焼成クレー、炭酸カルシウムなどが用いられるが、電気特性面からイオン性不純物の少ないものが望ましい。
【0012】
本発明におけるフェノール樹脂成形材料は、通常上記組成物に一般的なフェノール樹脂成形材料に使用される離型剤、硬化促進剤等を加え、これらの原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で加熱混練し、粉砕して製造される。
本発明のフェノール樹脂組成形材料は、絶縁破壊強さ、耐トラッキング性、衝撃強さ、曲げ強さ等の機械的強度の要求される電機、電子部品、とりわけコイルボビン等の電子部品に好適である。
【0013】
【実施例】
表1の上欄に示す原料及び配合割合にて通常の二本ロールで加熱混練して成形材料を得た。これらの成形材料について成形品特性を測定し、表1の下欄に示す結果を得た。なお、使用した無機充填材の結晶水解離温度と結晶水放出量を表2に示す。
【0014】
(測定方法)
1.結晶水放出量:200〜500℃での放出量(重量%)示差熱分析法
2.結晶水解離温度:示差熱分析法による
3.耐トラッキング性:JIS C 2134に準じて測定した。
4.その他の特性:JIS K 6911に準じて測定した。
成形品特性のテストピースはすべてトランスファー成形(175℃にて3分間成形)した成形物を使用した。
【0015】
【表1】
【0016】
【表2】
【0017】
【発明の効果】
本発明のフェノール樹脂成形材料は、これから得られた成形品が耐熱性、絶縁破壊強さ、耐トラッキング性及び衝撃強さ、曲げ強さ等の機械的強度に優れ、これらの特性が要求される電機、電子部品、とりわけコイルボビン等の電子部品に好適である。
[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a phenolic resin molding material having excellent dielectric breakdown strength, tracking resistance, flame resistance, and strength.
[0002]
[Prior art]
Phenolic resin molding materials are excellent in heat resistance, dimensional stability, moldability, and the like, and have been used for a long time in key industrial fields such as automobiles, electricity, and electronics. In particular, recently, the demand for reliability of products has become strict, and electrical performance such as dielectric breakdown strength and tracking resistance has been demanded.
[0003]
Usually, for parts requiring electrical characteristics, resins having excellent electrical characteristics such as unsaturated polyester resin, diallyl phthalate resin, melamine resin, and melamine / phenol resin are often used, but heat resistance, moldability, There is a problem in terms of cost and the like, and it is desired to impart higher tracking resistance, dielectric breakdown strength and flame resistance while maintaining excellent heat resistance and moldability of the phenol resin molding material. Electronic components, especially coil bobbins, are required to have mechanical strength such as impact strength and bending strength in addition to electrical characteristics.
[0004]
The characteristics of molding materials using resole resin are that, in addition to not generating ammonia gas from the molded product, and suppressing ionic impurities such as inorganic fillers contained, the electrical characteristics, especially moisture resistance and dielectric breakdown strength, are reduced. It is characterized by good things. In general, pulverized laminates, inorganic fillers, and the like are often used as fillers, and it has been studied to further improve tracking resistance and the like by blending an inorganic filler containing crystallization water. (Japanese Patent Application No. 07-68241, etc.), however, there was also a problem that the strength was brittle, and it was not always satisfactory.
[0005]
If attention is paid only to the impact strength and the bending strength, the addition of the conventionally used glass fiber has a sufficient effect, but the drawback of being hard and brittle appears due to the increase in the elastic modulus.
Similarly, by adding rubber components such as NBR and SBR in order to increase the amount of bending of the molded product, it is possible to improve the impact strength together with the amount of bending, but there is a disadvantage that the bending strength decreases. .
[0006]
[Problems to be solved by the invention]
The present invention has been made as a result of various studies in order to solve such a problem of the molding material using the conventional resol type phenol resin, and its purpose is to achieve tracking resistance and dielectric breakdown strength. Another object of the present invention is to provide a phenolic resin molding material having excellent mechanical strength such as flame resistance, bending strength and impact strength.
[0007]
[Means for Solving the Problems]
The present invention provides a molding material containing 25 to 35% by weight of a resole type phenol resin, at least one kind of a first inorganic filler selected from zinc borate and unfired clay as a flame retardant component, and calcium borate. , A total of at least one kind of a second inorganic filler selected from aluminum hydroxide and magnesium hydroxide and at least 40% by weight, and the content of the second inorganic filler is at least 10% by weight. In addition, the present invention relates to a phenol resin molding material containing 5 to 15% by weight of glass fiber and 2 to 5% by weight of polyvinyl butyral.
[0008]
The resole type phenolic resin used here is used for a general phenolic resin molding material, and is a dimethylene ether type resole resin, a methylol type resole resin, and the like. However, if hexamethylenetetramine is used as a curing agent, hexamethylenetetramine cannot be used due to the problem that the moisture resistance and electrical characteristics are reduced due to the generation of ammonia from the molded article. The amount of the phenolic resin is 25 to 35% by weight based on the whole molding material. If the content is less than 25% by weight, the wettability with the substrate is not sufficiently obtained, and the strength is reduced and the formability is reduced due to insufficient flow. On the other hand, if it exceeds 35% by weight, the tracking resistance is lowered and the cost of the material is increased, which is not practical.
[0009]
As the inorganic filler used as the flame retardant component, at least one first inorganic filler selected from zinc borate and unfired clay, and at least one type selected from calcium borate, aluminum hydroxide and magnesium hydroxide It is necessary to contain 40% by weight or more, preferably 45% by weight or more in the molding material in total with the second inorganic filler .
Further, the content of the second inorganic filler is 10% by weight or more. If the total amount of the inorganic filler as a flame-retardant component is less than 40% by weight, sufficient flame resistance and tracking resistance cannot be obtained, and if the second inorganic filler is not used in the molding material in an amount of 10% by weight or more, it is insufficient. High flame resistance cannot be obtained.
[0010]
The glass fiber may be a commonly used chopped strand, and E glass with little ionic impurities is preferred, but not limited thereto. The addition amount is preferably 5 to 15% by weight in the molding material, and if it is less than 5% by weight, the effect of imparting sufficient strength cannot be obtained. If it exceeds 15% by weight, the elastic modulus is too high, and polyvinyl butyral (PVB) is used in combination. Even so, fragility cannot be fully overcome.
[0011]
The type of polyvinyl butyral is not particularly limited, but preferably has a degree of polymerization of 250 to 2500 and a degree of butyralization of 60 to 80 mol%. Further, a granular material having a size of 100 mesh or less is preferable. The addition amount is preferably 2 to 5% by weight, and if it is less than 2% by weight, the effect of sufficiently increasing the strength is small, and if it exceeds 5% by weight, there is a problem that the bending strength is reduced although the bending amount is increased.
As the other fillers, crushed cloth, laminated board crushed powder, calcined clay, calcium carbonate, and the like used in ordinary resol-type phenolic resin molding materials are used, and those having little ionic impurities are desirable from the viewpoint of electrical characteristics.
[0012]
The phenolic resin molding material of the present invention is generally prepared by adding a release agent, a curing accelerator, and the like used for a general phenolic resin molding material to the above-described composition, and uniformly mixing these materials. It is manufactured by heating and kneading with a kneading machine such as a shaft extruder and pulverizing.
The phenolic resin composition-shaped material of the present invention is suitable for electric parts and electronic parts that require mechanical strength such as dielectric strength, tracking resistance, impact strength, and bending strength, and particularly for electronic parts such as coil bobbins. .
[0013]
【Example】
The molding material was obtained by heating and kneading with the usual two rolls at the raw materials and mixing ratios shown in the upper column of Table 1. The molded article characteristics of these molding materials were measured, and the results shown in the lower column of Table 1 were obtained. Table 2 shows the dissociation temperature of crystal water and the amount of released crystal water of the inorganic filler used.
[0014]
(Measuring method)
1. Crystal water release amount: Release amount (% by weight) at 200 to 500 ° C. Differential thermal analysis method Crystal water dissociation temperature: determined by differential thermal analysis Tracking resistance: Measured according to JIS C 2134.
4. Other properties: Measured according to JIS K 6911.
All the test pieces having the characteristics of the molded product were formed by transfer molding (molding at 175 ° C. for 3 minutes).
[0015]
[Table 1]
[0016]
[Table 2]
[0017]
【The invention's effect】
The phenolic resin molding material of the present invention is such that a molded article obtained therefrom is excellent in heat resistance, dielectric strength, tracking resistance and mechanical strength such as impact strength and bending strength, and these properties are required. It is suitable for electric machines and electronic components, especially electronic components such as coil bobbins.

Claims (2)

成形材料中に、レゾール型フェノール樹脂を25〜35重量%含有し、難燃成分として、硼酸亜鉛、未焼成クレーから選ばれる少なくとも1種類の第1の無機充填材と、硼酸カルシウム、水酸化アルミニウム、水酸化マグネシウムから選ばれる少なくとも1種類の第2の無機充填材とを合計で40重量%以上含有し、かつ、前記第2の無機充填材の含有量が10重量%以上であり、更に、ガラス繊維を5〜15重量%、及びポリビニルブチラールを2〜5重量%含有することを特徴とするフェノール樹脂成形材料。The molding material contains 25 to 35% by weight of a resole type phenol resin, and as a flame retardant component, at least one first inorganic filler selected from zinc borate and unfired clay; calcium borate; and aluminum hydroxide. And at least one type of second inorganic filler selected from magnesium hydroxide in a total amount of 40% by weight or more, and the content of the second inorganic filler is 10% by weight or more , A phenolic resin molding material containing 5 to 15% by weight of glass fiber and 2 to 5% by weight of polyvinyl butyral. ヘキサメチレンテトラミンを含まないことを特徴とする請求項1又は2に記載のフェノール樹脂成形材料。The phenolic resin molding material according to claim 1, wherein hexamethylenetetramine is not contained.
JP23878198A 1998-08-25 1998-08-25 Phenolic resin molding material Expired - Fee Related JP3543924B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP23878198A JP3543924B2 (en) 1998-08-25 1998-08-25 Phenolic resin molding material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP23878198A JP3543924B2 (en) 1998-08-25 1998-08-25 Phenolic resin molding material

Publications (2)

Publication Number Publication Date
JP2000063621A JP2000063621A (en) 2000-02-29
JP3543924B2 true JP3543924B2 (en) 2004-07-21

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Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4492388B2 (en) * 2005-02-28 2010-06-30 住友ベークライト株式会社 Phenolic resin molding material
JP5402142B2 (en) * 2009-03-25 2014-01-29 住友ベークライト株式会社 Phenolic resin molding material
JP6651853B2 (en) * 2013-12-20 2020-02-19 住友ベークライト株式会社 Thermosetting resin composition and metal resin composite
JP2015204729A (en) * 2014-04-16 2015-11-16 住友ベークライト株式会社 Housing of electric power conversion system, thermosetting resin composition, and power conversion system
CN110577718B (en) * 2019-10-30 2022-05-20 上海欧亚合成材料股份有限公司 Aniline modified phenolic molding plastic for low-voltage electrical apparatus and preparation method thereof
CN114031891A (en) * 2021-11-29 2022-02-11 浙江南方塑胶制造有限公司 Phenolic molding plastic with good tracking resistance and preparation method thereof

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