JP3514843B2 - Epoxy resin for metal powder binder and cured product thereof - Google Patents
Epoxy resin for metal powder binder and cured product thereofInfo
- Publication number
- JP3514843B2 JP3514843B2 JP27965794A JP27965794A JP3514843B2 JP 3514843 B2 JP3514843 B2 JP 3514843B2 JP 27965794 A JP27965794 A JP 27965794A JP 27965794 A JP27965794 A JP 27965794A JP 3514843 B2 JP3514843 B2 JP 3514843B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- metal powder
- resin composition
- present
- powder
- 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
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/06—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder
- H01F1/08—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
- H01F1/083—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together in a bonding agent
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Hard Magnetic Materials (AREA)
- Soft Magnetic Materials (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、エポキシ樹脂組成物お
よびその硬化物に関する。更に詳しくは金属粉、特にプ
ラスチックマグネット磁石用合金粉等のバインダーとし
て、優れた耐熱性、機械特性を有するエポキシ樹脂組成
物およびそれから得られる硬化物に関する。TECHNICAL FIELD The present invention relates to an epoxy resin composition and a cured product thereof. More specifically, it relates to an epoxy resin composition having excellent heat resistance and mechanical properties as a binder for metal powder, particularly alloy powder for plastic magnet magnets, and a cured product obtained therefrom.
【０００２】[0002]
【従来の技術】従来の焼結磁石に変わり、フェライト粉
末や希土類合金粉末をプラスチックのバインダーで固め
たボンデッド磁石、いわゆるプラスチック磁石の需要が
拡大している。このようなプラスチック磁石用のバイン
ダーとして求められる要求特性としては、硬化せしめて
プラスチック磁石とした時、磁石としての磁気特性を失
うことなく、加えて、加工性が良い、寸法安定性が高
い、割れにくい、１５０℃以上の高温時でも強度がある
等が要求される。しかしながら、従来使用されているバ
インダーは、硬化せしめた時に高温時の強度が劣り、要
求される強度以下で破壊してしまうという欠点があり充
分満足がいくものではなかった。2. Description of the Related Art Demand for bonded magnets, so-called plastic magnets, in which ferrite powders or rare earth alloy powders are hardened with a plastic binder has been increasing in place of conventional sintered magnets. The required properties required as a binder for such plastic magnets are that when they are hardened into plastic magnets, they do not lose their magnetic properties, and in addition, they have good workability, high dimensional stability, and cracking. Difficulty, strength at high temperature of 150 ° C or higher is required. However, the conventionally used binders are not sufficiently satisfactory because they have a drawback that they are inferior in strength at high temperature when they are cured, and they break at a strength not higher than the required strength.
【０００３】[0003]
【発明が解決しようとする課題】作業性に優れ、かつ高
温時でも優れた機械強度を与えるエポキシ樹脂バインダ
ーの開発が望まれている。It has been desired to develop an epoxy resin binder which is excellent in workability and gives excellent mechanical strength even at high temperatures.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記の課
題を達成しようと鋭意研究を重ねた結果、トリスフェノ
ールメタン型エポキシ樹脂及び式（１）のMeans for Solving the Problems As a result of intensive studies to achieve the above-mentioned objects, the present inventors have found that a trisphenolmethane type epoxy resin and a compound of formula (1)
【０００５】[0005]
【化２】 [Chemical 2]
【０００６】（式中、ｎは０から５である）で示される
エポキシ樹脂の中から選択される一種類または二種類以
上を５０ｗ／ｗ％以上含むエポキシ樹脂からなる樹脂組
成物が、金属粉を加えて硬化せしめた時に加工性、寸法
安定性等のみならず高温時の強度が優れていることを見
出し、本発明を完成させたものである。即ち本発明は、
前記エポキシ樹脂からなる金属粉用バインダーを提供す
るものである。さらに詳しくは、前記エポキシ樹脂、硬
化剤及び有機溶媒を含有するエポキシ樹脂組成物からな
る金属粉用バインダーを提供するものである。また、本
発明は、（１）ａ．トリスフェノールメタン型エポキシ
樹脂及び式（１）A resin composition comprising an epoxy resin containing 50 w / w% or more of one kind or two or more kinds selected from the epoxy resins represented by the formula (n is 0 to 5) is a metal powder. It was found that not only the workability and dimensional stability but also the strength at high temperature is excellent when the composition is hardened by adding the above composition, and the present invention has been completed. That is, the present invention is
The present invention provides a binder for metal powder, which is made of the epoxy resin. More specifically, the present invention provides a metal powder binder comprising an epoxy resin composition containing the epoxy resin, a curing agent and an organic solvent. The present invention also relates to (1) a. Trisphenol methane type epoxy resin and formula (1)
【０００７】[0007]
【化３】 [Chemical 3]
【０００８】（式中、ｎは０から５である）で示される
エポキシ樹脂の中から選択される一種類又は二種類以上
を５０ｗ／ｗ％以上含むエポキシ樹脂、ｂ．芳香族ジア
ミン、フェノールノボラック樹脂及び酸無水物の中から
選ばれる一種類または二種類以上からなる硬化剤、ｃ．
有機溶媒、を含有するエポキシ樹脂組成物を提供するも
のでもある。さらに本発明は、上記のエポキシ樹脂を含
有する組成物及び金属粉からなる組成物を硬化させて得
られる固形物を提供するものである。本発明は、高温時
の機械強度に優れたプラスチック磁石を提供するもので
ある。即ち、上記のエポキシ樹脂を含有する組成物及び
磁性金属粉からなる組成物を硬化させて得られるプラス
チック磁石を提供する。磁性金属粉としては、磁性を付
与しうるものであれば特に制限はないが、希土類系の磁
性金属粉が好ましく、より好ましくはＮｄ−Ｆｅ−Ｂ合
金粉である。An epoxy resin containing 50 w / w% or more of one kind or two or more kinds selected from the epoxy resins represented by the formula (n is 0 to 5), b. A curing agent composed of one or more selected from aromatic diamines, phenol novolac resins and acid anhydrides, c.
It also provides an epoxy resin composition containing an organic solvent. Furthermore, the present invention provides a solid product obtained by curing the composition containing the epoxy resin and the composition containing metal powder. The present invention provides a plastic magnet having excellent mechanical strength at high temperatures. That is, there is provided a plastic magnet obtained by curing the composition containing the epoxy resin and the composition containing magnetic metal powder. The magnetic metal powder is not particularly limited as long as it can impart magnetism, but rare earth magnetic metal powder is preferable, and Nd-Fe-B alloy powder is more preferable.
【０００９】本発明で使用するエポキシ樹脂としては、
硬化せしめたものの熱変形温度や高温時の機械強度の点
から、トリスフェノールメタン型エポキシ樹脂または上
記式（１）で示されるエポキシ樹脂のいずれか一種類ま
たは二種類以上を必須成分として５０ｗ／ｗ％以上含む
エポキシ樹脂が用いられる。トリスフェノールメタン型
エポキシ樹脂としては、例えばＥＰＰＮ−５０１Ｈ（商
品名、日本化薬（株）社製、エポキシ当量１６５）があ
げられる。上記式（１）で示されるエポキシ樹脂として
は、例えばＮＣ−７０００（商品名、日本化薬（株）社
製、エポキシ当量２２５）があげられる。The epoxy resin used in the present invention includes:
From the viewpoint of the heat distortion temperature of the cured product and the mechanical strength at high temperature, one or two or more of the trisphenolmethane type epoxy resin or the epoxy resin represented by the above formula (1) is used as an essential component at 50 w / w. % Or more epoxy resin is used. Examples of the trisphenolmethane type epoxy resin include EPPN-501H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 165). Examples of the epoxy resin represented by the above formula (1) include NC-7000 (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 225).
【００１０】本発明で使用するエポキシ樹脂組成物に
は、上記の必須成分以外の任意のエポキシ樹脂が、最高
５０ｗ／ｗ％の割合で存在していてもよい。任意のエポ
キシ樹脂としては、例えばエポキシ当量が３００〜２０
００のビスフェノールＡ型エポキシ樹脂等の固体状のエ
ポキシ樹脂、エポキシ当量が１８０〜３００のビスフェ
ノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ
樹脂等の液状のエポキシ樹脂、またこれらをゴム変性し
たエポキシ樹脂等があげられる。本発明のエポキシ樹脂
組成物は、これらの任意のエポキシ樹脂の添加は必須で
はないが、これらの他のエポキシ樹脂の添加により、金
属粉の流動性が高まったり、機械強度がより向上するこ
とがあり、これらの他のエポキシ樹脂を添加することは
本発明の好ましい態様のひとつでもある。このように他
のエポキシ樹脂を添加する場合、本発明で使用するエポ
キシ樹脂組成物中の前記の必須成分の使用量は、５０〜
９５ｗ／ｗ％、好ましくは５５〜９０ｗ／ｗ％、より好
ましくは６０〜８５ｗ／ｗ％、さらに好ましくは６５〜
８０ｗ／ｗ％程度である。The epoxy resin composition used in the present invention may contain any epoxy resin other than the above-mentioned essential components in a ratio of up to 50 w / w%. As an arbitrary epoxy resin, for example, an epoxy equivalent is 300 to 20.
00 is a solid epoxy resin such as bisphenol A type epoxy resin, liquid epoxy resin such as bisphenol A type epoxy resin having an epoxy equivalent of 180 to 300, bisphenol F type epoxy resin, and epoxy resin obtained by modifying these with rubber. can give. In the epoxy resin composition of the present invention, the addition of any of these epoxy resins is not essential, but the addition of these other epoxy resins may increase the fluidity of the metal powder or further improve the mechanical strength. Therefore, addition of these other epoxy resins is also one of the preferable embodiments of the present invention. When the other epoxy resin is added as described above, the amount of the above-mentioned essential components used in the epoxy resin composition used in the present invention is 50 to 50%.
95 w / w%, preferably 55-90 w / w%, more preferably 60-85 w / w%, further preferably 65-
It is about 80 w / w%.
【００１１】次に本発明で用いられる硬化剤としては、
エポキシ樹脂の硬化剤として使用できるものであれば特
に制限はないが、ポリアミン、酸無水物、ポリフェノー
ルなどが好ましい。ポリアミンとしては、ジエチレント
リアミン、トリエチレンテトラミン、メタキシリレンジ
アミンなどの脂肪族ポリアミン、イソホロンジアミンな
どの脂環族ポリアミン、ジアミノジフェニルメタン（Ｄ
ＤＭ）、ジアミノジフェニルスルホン（ＤＤＳ）、ｍ−
フェニレンジアミン（ＭＰＤＡ）などの芳香族ポリアミ
ン、又は、これらの変性物などを挙げることができる
が、金属粉の流動性の点から常温で固体の芳香族ポリア
ミンが好ましく、より好ましくはＤＤＭ，ＤＤＳなどの
芳香族ジアミンを挙げることができる。また、芳香族ジ
アミンのなかでもジアミノジフェニルメタン、ジアミノ
ジフェニルスルホン等の２個のアニリン類が架橋基を介
して結合しているものが好ましい。当該架橋基として
は、例えばメチレン鎖等のアルキレン鎖、スルホニル基
等があげられ、その置換位置は、アニリン類のアミノ基
の４位が好ましい。又、アニリン類にはメチル基等の置
換基が１〜４固、好ましくは２個程度結合していてもよ
い。さらに具体的には、例えば、４，４’−ジアミノ−
３，３’，５，５’−テトラメチルジフェニルメタン、
４，４’−ジアミノジフェニルスルホン等の使用が好ま
しい。ポリフェノールとしては、好ましくはフェノール
ノボラック樹脂などをあげることができる。より具体的
には、例えば、ＰＮ−１００（商品名、日本化薬（株）
社製）等があげられる。酸無水物としては、ドデセニル
無水コハク酸、ポリアゼライン酸無水物などの脂肪族酸
無水物、ヘキサヒドロ無水フタル酸、メチルテトラヒド
ロ無水フタル酸、無水メチルナジック酸などの脂環族酸
無水物、無水トリメリット酸、無水ピロメリット酸、テ
トラブロモ無水フタル酸などの芳香族酸無水物などを挙
げることができるが、脂環族酸無水物が好ましく、より
好ましくは、例えば、無水メチルナジック酸などを挙げ
ることができる。Next, as the curing agent used in the present invention,
There is no particular limitation as long as it can be used as a curing agent for the epoxy resin, but polyamine, acid anhydride, polyphenol and the like are preferable. Examples of the polyamine include aliphatic polyamines such as diethylenetriamine, triethylenetetramine, and metaxylylenediamine, alicyclic polyamines such as isophoronediamine, and diaminodiphenylmethane (D
DM), diaminodiphenyl sulfone (DDS), m-
Examples thereof include aromatic polyamines such as phenylenediamine (MPDA), and modified products thereof. From the viewpoint of fluidity of metal powder, aromatic polyamines that are solid at room temperature are preferable, more preferably DDM, DDS and the like. Aromatic diamines can be mentioned. Further, among the aromatic diamines, those in which two anilines such as diaminodiphenylmethane and diaminodiphenylsulfone are bonded via a crosslinking group are preferable. Examples of the bridging group include an alkylene chain such as a methylene chain, a sulfonyl group, and the like, and the substitution position thereof is preferably the 4-position of the amino group of anilines. The anilines may have 1 to 4 substituents such as methyl group, preferably about 2 substituents bonded thereto. More specifically, for example, 4,4′-diamino-
3,3 ', 5,5'-tetramethyldiphenylmethane,
The use of 4,4′-diaminodiphenyl sulfone or the like is preferable. Preferable examples of polyphenols include phenol novolac resins. More specifically, for example, PN-100 (trade name, Nippon Kayaku Co., Ltd.)
Manufactured by the company) and the like. As the acid anhydride, dodecenyl succinic anhydride, aliphatic acid anhydride such as polyazelainic acid anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, alicyclic acid anhydride such as methylnadic acid anhydride, trihydric anhydride. Examples thereof include aromatic acid anhydrides such as mellitic acid, pyromellitic dianhydride, and tetrabromophthalic anhydride, but alicyclic acid anhydrides are preferable, and more preferable examples include methylnadic acid anhydride. You can
【００１２】これらの硬化剤は、一種類または二種類以
上の硬化剤を任意の比率で用いることができるが、好ま
しくはアミン系硬化剤と酸無水物系硬化剤との併用は避
けたほうがよい。これら硬化剤の使用量は通常、エポキ
シ樹脂に対して０．７〜１．３化学当量、好ましくは
０．９〜１．１化学当量である。As these hardeners, one kind or two or more kinds of hardening agents can be used in an arbitrary ratio, but it is preferable to avoid the combined use of an amine hardening agent and an acid anhydride hardening agent. . The amount of these curing agents used is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, relative to the epoxy resin.
【００１３】本発明で使用する有機溶媒としては、特に
制限はないが、芳香族炭化水素系有機溶媒、ケトン系有
機溶媒、アルコール系有機溶媒などが好ましい。より好
ましくは、ケトン系有機溶媒、アルコール系有機溶媒な
どの極性有機溶媒を挙げることができる。芳香族炭化水
素系有機溶媒としては、例えば、トルエン、キシレン等
があげられる。ケトン系有機溶媒としては、例えば、ア
セトン、メチルエチルケトン、メチルイソブチルケトン
等があげられる。アルコール系有機溶剤としては、メタ
ノール等があげられる。これらの有機溶媒は１種類また
は２種類以上を任意の比率で用いることができる。有機
溶媒の使用量は接着物の形態、使用法により任意の量を
用いることができるが、本発明の組成物中、４０〜９０
ｗ／ｗ％、好ましくは５０〜８０ｗ／ｗ％程度がよい。The organic solvent used in the present invention is not particularly limited, but aromatic hydrocarbon organic solvents, ketone organic solvents, alcohol organic solvents and the like are preferable. More preferably, polar organic solvents such as ketone organic solvents and alcohol organic solvents can be mentioned. Examples of the aromatic hydrocarbon organic solvent include toluene and xylene. Examples of the ketone-based organic solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the alcohol organic solvent include methanol and the like. One kind or two or more kinds of these organic solvents can be used in an arbitrary ratio. The amount of the organic solvent to be used may be any amount depending on the form of the adhesive and the method of use, but is 40 to 90 in the composition of the present invention.
w / w%, preferably about 50 to 80 w / w%.
【００１４】本発明のエポキシ樹脂組成物には必要であ
れば硬化促進剤やカップリング剤を添加してもよい。使
用できる硬化促進剤としては、一般にエポキシ樹脂の硬
化に使用出来るものであれば特に限定されないが、例え
ばイミダゾール類、トリスジメチルアミノメチルフェノ
ール、トリフェニルフォスフィン、ジアザビシクロウン
デセン（ＤＢＵ）、ＤＢＵの塩類及び三フッ化ホウ素の
アルキルアミン錯体等があげられ、その使用量はエポキ
シ樹脂１００重量部に対し１０重量部以下、好ましくは
０．１〜５重量部である。使用できるカップリング剤と
しては、一般にエポキシ樹脂の硬化に使用出来るもので
あれば特に限定されないが、例えばシラン系カップリン
グ剤、チタン系カップリング剤等があげられ、その使用
量はエポキシ樹脂１００重量部に対し１０重量部以下、
好ましくは０．５〜５重量部である。If necessary, a curing accelerator and a coupling agent may be added to the epoxy resin composition of the present invention. The curing accelerator that can be used is not particularly limited as long as it can be generally used for curing an epoxy resin, and examples thereof include imidazoles, trisdimethylaminomethylphenol, triphenylphosphine, diazabicycloundecene (DBU), and DBU. And an alkylamine complex of boron trifluoride, and the amount thereof is 10 parts by weight or less, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the epoxy resin. The coupling agent that can be used is not particularly limited as long as it can be generally used for curing an epoxy resin, and examples thereof include a silane coupling agent and a titanium coupling agent. 10 parts by weight or less to parts,
It is preferably 0.5 to 5 parts by weight.
【００１５】本発明のエポキシ樹脂組成物は、前記した
エポキシ樹脂、硬化剤を、前記した所定量の有機溶媒に
加え必要ならば加熱溶解した後、必要によりカップリン
グ剤、硬化促進剤を加え均一に撹拌することにより得ら
れる。本発明のエポキシ樹脂組成物は、バインダーとし
て、特にプラスチック磁石用金属粉のバインダーとして
有用である。この組成物中の固形分（有機溶媒除去後の
残渣）の量は１０〜６０ｗ／ｗ％、好ましくは２０〜５
０ｗ／ｗ％程度である。In the epoxy resin composition of the present invention, the above-mentioned epoxy resin and curing agent are added to the above-mentioned predetermined amount of the organic solvent and heated and dissolved if necessary, and then a coupling agent and a curing accelerator are added if necessary to obtain a uniform mixture. It can be obtained by stirring. The epoxy resin composition of the present invention is useful as a binder, particularly as a binder for metal powder for plastic magnets. The amount of solid content (residue after removal of the organic solvent) in this composition is 10 to 60 w / w%, preferably 20 to 5
It is about 0 w / w%.
【００１６】本発明の硬化物は、前記エポキシ樹脂組成
物を金属粉等と均一に混合し、有機溶剤を任意の方法で
除去し、これを加圧成形機等で成形し、１００℃〜２２
０℃、好ましくは１５０℃〜２００℃で０．５〜５時間
硬化させることによって得ることが出来る。ここで金属
粉としては、例えば鉄粉、ニッケル粉、アルミ粉、銅
粉、Ａｌ−Ｎｉ合金、金属磁性粉、金属酸化物粉（例え
ばフェライト粉）等があげられる。金属磁性粉として
は、例えば磁性鉄粉、アルニコ等の磁性合金鋼粉、希土
類系の磁性金属粉等があげられる。希土類系の磁性金属
粉としては、例えばＮｄ−Ｆｅ−Ｂ合金粉、Ｓｍ−Ｃｏ
合金粉、Ｓｍ−Ｆｅ合金粉、Ｐｒ−Ｆｅ合金粉、Ｃｅ合
金粉等があげられる。金属粉と本発明のエポキシ樹脂組
成物の混合割合は、本発明のエポキシ樹脂組成物が、固
形分として、混合物中に通常０．５〜３０ｗ／ｗ％、好
ましくは１〜３０ｗ／ｗ％となるような割合がよい。The cured product of the present invention is prepared by uniformly mixing the epoxy resin composition with metal powder or the like, removing the organic solvent by an arbitrary method, and molding the resulting product with a pressure molding machine or the like at 100 ° C. to 22 ° C.
It can be obtained by curing at 0 ° C, preferably 150 ° C to 200 ° C for 0.5 to 5 hours. Examples of the metal powder include iron powder, nickel powder, aluminum powder, copper powder, Al—Ni alloy, metal magnetic powder, metal oxide powder (for example, ferrite powder), and the like. Examples of the magnetic metal powder include magnetic iron powder, magnetic alloy steel powder such as alnico, and rare earth magnetic metal powder. Examples of the rare earth magnetic metal powder include Nd-Fe-B alloy powder and Sm-Co.
Examples thereof include alloy powder, Sm-Fe alloy powder, Pr-Fe alloy powder, and Ce alloy powder. The mixing ratio of the metal powder and the epoxy resin composition of the present invention is such that the epoxy resin composition of the present invention has a solid content of usually 0.5 to 30 w / w%, preferably 1 to 30 w / w% in the mixture. A good ratio is
【００１７】本発明のエポキシ樹脂の組成物と磁性金属
粉との組成物は、常法により着磁を行うことにより、プ
ラスチック磁石とすることができる。また、必要に応じ
て着磁前に磁場成形中で磁気配向を行ってもよい。The composition of the epoxy resin and the magnetic metal powder of the present invention can be made into a plastic magnet by magnetizing it by a conventional method. Further, if necessary, magnetic orientation may be performed during magnetic field shaping before magnetization.
【００１８】又、本発明の硬化物は缶等の金属成型品や
ラベル等の金属シート等の表面に前記エポキシ樹脂組成
物を塗布、または含浸等した後有機溶媒を任意の方法で
除去し、これを他の金属製の物品と貼り合わせ、硬化さ
せることによって得ることができる。このような本発明
の硬化物は、機械強度に優れ、かつ高温時でも機械強度
の信頼性に優れている。The cured product of the present invention is obtained by applying or impregnating the surface of a metal molded product such as a can or a metal sheet such as a label with the epoxy resin composition, and then removing the organic solvent by an arbitrary method. It can be obtained by laminating it with another metal article and curing it. Such a cured product of the present invention has excellent mechanical strength and mechanical strength reliability even at high temperatures.
【００１９】[0019]
【実施例】次に本発明を実施例によって更に具体的に説
明するが、本発明はこれらの実施例により限定されるも
のではない。EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.
【００２０】実施例１
トリスフェノールメタン型エポキシ樹脂（ＥＰＰＮ−５
０１Ｈ、日本化薬社製、エポキシ当量１６５）７０ｇ
と、ビスフェノールＡ型エポキシ樹脂（エポミックＲ−
３０４、三井石油化学社製、エポキシ当量９１５）３０
ｇ、４、４−ジアミノジフェニルスルホン（ＤＤＳ、和
歌山精化社製）２８ｇ、硬化促進剤として三フッ素化ホ
ウ素のモノエチルアミン錯体１ｇ、カップリング剤とし
てｒ−グリシジドキシプロピルトリメトキシシラン（サ
イラエースＳ５１０、チッソ社製）２ｇ、及び溶媒とし
てメチルエチルケトンを６５重量％となるように加え、
撹拌溶解して本発明のエポキシ樹脂組成物（ワニス）３
７５ｇを得た。得られたエポキシ樹脂組成物１００ｇを
Ｎｄ−Ｆｅ−Ｂ合金粉１０００ｇに加えケミミックス撹
拌機にて約２時間撹拌し、常温にて溶媒を留去して樹脂
分約３．５％を含むＮｄ−Ｆｅ−Ｂ合金粉（２８％Ｎｄ
−１％Ｂ−残Ｆｅ）１０３５ｇを得た。このＮｄ−Ｆｅ
−Ｂ合金粉７０ｇをタブレット成型機にて１０ｔ×８秒
の条件でプレス成型し、これを１７０℃×１時間で加熱
して本発明の硬化物（直径４０ｍｍ、厚さ１２ｍｍ）を
得た。Example 1 Trisphenol methane type epoxy resin (EPPN-5
01H, Nippon Kayaku Co., epoxy equivalent 165) 70g
And bisphenol A type epoxy resin (Epomic R-
304, manufactured by Mitsui Petrochemical Co., Ltd., epoxy equivalent 915) 30
28 g of 4,4,4-diaminodiphenyl sulfone (DDS, manufactured by Wakayama Seika Co., Ltd.), 1 g of a monoethylamine complex of boron trifluoride as a curing accelerator, and r-glycididoxypropyltrimethoxysilane (Sila Ace S510 as a coupling agent). (Manufactured by Chisso Corporation) 2 g, and methyl ethyl ketone as a solvent to be 65% by weight,
Epoxy resin composition (varnish) 3 of the present invention by dissolving with stirring
75 g was obtained. 100 g of the obtained epoxy resin composition was added to 1000 g of Nd-Fe-B alloy powder, and the mixture was stirred with a Chemix stirrer for about 2 hours, and the solvent was distilled off at room temperature to contain Nd containing about 3.5% resin content. -Fe-B alloy powder (28% Nd
1035 g of -1% B-remaining Fe) was obtained. This Nd-Fe
70 g of -B alloy powder was press-molded with a tablet molding machine under the condition of 10 t x 8 seconds, and this was heated at 170 ° C x 1 hour to obtain a cured product of the present invention (diameter 40 mm, thickness 12 mm).
【００２１】実施例２
式（１）で示されるエポキシ樹脂（ＮＣ−７０００、日
本化薬社製、エポキシ当量２２５）６０ｇと、ビスフェ
ノールＡ型エポキシ樹脂（エポミックＲ−３０４、三井
石油化学社製、エポキシ当量９１５）４０ｇ、４、４−
ジアミノジフェニルスルホン（ＤＤＳ、和歌山精化社
製）を２２ｇ、カップリング剤としてｒ−グリシジドキ
シプロピルトリメトキシシラン（サイラエースＳ５１
０、チッソ社製）２ｇ、及び溶媒としてメチルエチルケ
トンを６５重量％となるように加え、撹拌溶解して本発
明のエポキシ樹脂組成物（ワニス）３４８ｇを得た。得
られたエポキシ樹脂組成物１００ｇをＮｄ−Ｆｅ−Ｂ合
金粉１０００ｇに加えケミミックス撹拌機にて約２時間
撹拌し、常温にて溶媒を留去して樹脂分約３．５％を含
むＮｄ−Ｆｅ−Ｂ合金粉（２８％Ｎｄ−１％Ｂ−残Ｆ
ｅ）１０３５ｇを得た。このＮｄ−Ｆｅ−Ｂ合金粉７０
ｇをタブレット成型機にて１０ｔ×８秒の条件でプレス
成型し、これを１７０℃×１時間で加熱して本発明の硬
化物（直径４０ｍｍ、厚さ１２ｍｍ）を得た。Example 2 60 g of an epoxy resin represented by the formula (1) (NC-7000, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 225) and bisphenol A type epoxy resin (Epomic R-304, manufactured by Mitsui Petrochemical Co., Ltd., Epoxy equivalent 915) 40 g, 4, 4-
22 g of diaminodiphenyl sulfone (DDS, manufactured by Wakayama Seika Co., Ltd.) and r-glycididoxypropyltrimethoxysilane (Sila Ace S51 as a coupling agent)
0, manufactured by Chisso Co., Ltd.) and methyl ethyl ketone as a solvent to be 65% by weight, and dissolved by stirring to obtain 348 g of the epoxy resin composition (varnish) of the present invention. 100 g of the obtained epoxy resin composition was added to 1000 g of Nd-Fe-B alloy powder, and the mixture was stirred with a Chemix stirrer for about 2 hours, and the solvent was distilled off at room temperature to contain Nd containing about 3.5% resin content. -Fe-B alloy powder (28% Nd-1% B-remaining F
e) 1035 g was obtained. This Nd-Fe-B alloy powder 70
g was press-molded with a tablet molding machine under the condition of 10 t × 8 seconds and heated at 170 ° C. × 1 hour to obtain a cured product (diameter 40 mm, thickness 12 mm) of the present invention.
【００２２】実施例３
実施例１で使用した４、４−ジアミノジフェニルスルホ
ン（ＤＤＳ、和歌山精化社製）２８ｇの代わりに、軟化
点１００℃のフェノールノボラック樹脂（ＰＮ−１０
０、日本化薬社製）２３ｇと軟化点８０℃のフェノール
ノボラック樹脂（ＰＮ−８０、日本化薬社製）２３ｇを
用い、硬化促進剤として三フッ素化ホウ素のモノエチル
アミン錯体１ｇの代わりに２−メチル４エチルイミダゾ
ール１ｇを用いた他は、実施例１と全く同様にして本発
明のエポキシ樹脂組成物４２６ｇを得た。得られたエポ
キシ樹脂組成物を用いて実施例１と同様にして本発明の
硬化物（直径４０ｍｍ、厚さ１２ｍｍ）を得た。Example 3 Instead of 28 g of 4,4-diaminodiphenyl sulfone (DDS, manufactured by Wakayama Seika Co., Ltd.) used in Example 1, a phenol novolac resin (PN-10 having a softening point of 100 ° C.) was used.
0, 23 g of Nippon Kayaku Co., Ltd. and 23 g of a phenol novolak resin (PN-80, manufactured by Nippon Kayaku Co., Ltd.) having a softening point of 80 ° C. were used, instead of 1 g of a monoethylamine complex of boron trifluoride as a curing accelerator. 426 g of the epoxy resin composition of the present invention was obtained in exactly the same manner as in Example 1 except that 1 g of -methyl 4-ethylimidazole was used. Using the obtained epoxy resin composition, a cured product of the present invention (diameter 40 mm, thickness 12 mm) was obtained in the same manner as in Example 1.
【００２３】実施例４
実施例１で得られたエポキシ樹脂組成物１００ｇを鉄粉
（ミリスケール粉砕、ダイテツ工業社製）１０００ｇに
加えケミミックス撹拌機にて約２時間撹拌し、常温にて
溶媒を留去して樹脂分３．５％を含む鉄粉１０３５ｇを
得た。得られた鉄粉１２０ｇをタブレット成形機にて１
０ｔ×８秒の条件でプレス成形し、これを１７０℃で１
時間加熱して本発明の硬化物（直径４０ｍｍ、厚さ１
３．５ｍｍ）を得た。Example 4 100 g of the epoxy resin composition obtained in Example 1 was added to 1000 g of iron powder (millimeter scale, manufactured by Daitetsu Kogyo Co., Ltd.), and the mixture was stirred with a Chemix stirrer for about 2 hours and the solvent was kept at room temperature. Was distilled off to obtain 1035 g of iron powder containing 3.5% of resin. 120 g of the obtained iron powder was tableted with a tablet machine.
Press-molded under the condition of 0t × 8 seconds, and this was 170 ° C for 1
After being heated for a time, the cured product of the present invention (diameter 40 mm, thickness 1
3.5 mm) was obtained.
【００２４】実施例５
実施例３で得られたエポキシ樹脂組成物を１００ｇを用
いた他は実施例４と同様にして本発明の硬化物（直径４
０ｍｍ、厚さ１３．５ｍｍ）を得た。Example 5 The cured product of the present invention (diameter 4) was prepared in the same manner as in Example 4 except that 100 g of the epoxy resin composition obtained in Example 3 was used.
0 mm, thickness 13.5 mm) was obtained.
【００２５】実験例
上記実施例１〜５で得られた硬化物のＴｇ（ガラス転移
温度）及び圧延強度を測定した。その結果を表１に示
す。尚、Ｔｇは実施例で得られた各エポキシ樹脂組成物
を１７０℃×１時間で硬化させ、ＤＳＣ法（示差熱分析
法）により測定した。圧延強度試験は、ＪＩＳ Ｋ ６９
１１の圧縮試験に準じて行い、温度２３℃、１５０℃、
１８０℃、２１０℃において、サンプルの円を圧縮する
方向に加重して破壊されたときの加重（Ｋｇｆ）を測定
した。結果を表１に示す。Experimental Example Tg (glass transition temperature) and rolling strength of the cured products obtained in Examples 1 to 5 were measured. The results are shown in Table 1. The Tg was measured by the DSC method (differential thermal analysis method) after curing each epoxy resin composition obtained in the examples at 170 ° C. for 1 hour. The rolling strength test is JIS K 69.
11 compression test, temperature 23 ℃, 150 ℃,
At 180 ° C. and 210 ° C., the load (Kgf) when the sample circle was broken by being applied in the direction of compression was measured. The results are shown in Table 1.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【発明の効果】本発明により、金属粉末、特にフェライ
ト粉や希土類合金粉、アルニコ合金粉のバインダーとし
て、機械強度に優れ、かつ高温時でも機械強度の信頼性
に優れたエポキシ樹脂組成物が得られた。Industrial Applicability According to the present invention, an epoxy resin composition having excellent mechanical strength and excellent mechanical strength reliability even at high temperatures is obtained as a binder for metal powders, particularly ferrite powders, rare earth alloy powders, and alnico alloy powders. Was given.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｌ 63/00 Ｃ０８Ｌ 63/00 Ｈ０１Ｆ 1/08 Ｈ０１Ｆ 1/08 1/44 1/28 (72)発明者 黒沢 学 岐阜県中津川市昭和町８番41号 (56)参考文献 特開 平２−143405（ＪＰ，Ａ) 特開 平６−260312（ＪＰ，Ａ) 特開 平６−267719（ＪＰ，Ａ) 特開 平６−333712（ＪＰ，Ａ) 特開 平７−115011（ＪＰ，Ａ) 特開 平７−122417（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 59/00 - 59/72 C08L 63/00 - 63/10 H01F 1/08 H01F 1/44 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI C08L 63/00 C08L 63/00 H01F 1/08 H01F 1/08 1/44 1/28 (72) Inventor Manabu Kurosawa Nakatsugawa, Gifu Prefecture 8-41, Showa-machi, Japan (56) Reference JP-A-2-143405 (JP, A) JP-A-6-260312 (JP, A) JP-A-6-267719 (JP, A) JP-A-6- 333712 (JP, A) JP-A-7-115011 (JP, A) JP-A-7-122417 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C08G 59/00-59 / 72 C08L 63/00-63/10 H01F 1/08 H01F 1/44
Claims (7)
脂及び式（１） 【化１】 （式中、ｎは０から５である）で示されるエポキシ樹脂
の中から選択される一種類または二種類を５０ｗ／ｗ％
以上含むエポキシ樹脂、ｂ．硬化剤、ｃ．有機溶媒、を
含有する金属粉バインダー用エポキシ樹脂組成物。1. A. Trisphenol methane type epoxy resin and formula (1) 50 w / w% of one or two kinds selected from the epoxy resins represented by the formula (n is 0 to 5)
An epoxy resin containing the above, b. A curing agent, c. An epoxy resin composition for a metal powder binder containing an organic solvent.
ボラック樹脂及び酸無水物の中から選ばれる一種類また
は二種類以上からなる請求項１に記載のエポキシ樹脂組
成物。2. The epoxy resin composition according to claim 1, wherein the curing agent comprises one kind or two or more kinds selected from an aromatic diamine, a phenol novolac resin and an acid anhydride.
ノ基の４位に架橋基を介して結合したものであり、また
酸無水物が脂環族酸無水物である請求項２に記載のエポ
キシ樹脂組成物。3. The method according to claim 2, wherein the aromatic diamine is bound to the 4-position of the amino group of two anilines via a crosslinking group, and the acid anhydride is an alicyclic acid anhydride. Epoxy resin composition.
らなる組成物を硬化させて得られる固形物。4. A solid product obtained by curing the composition comprising the binder according to claim 3 and a metal powder.
粉からなる組成物を硬化させて得られるプラスチック磁
石。5. A plastic magnet obtained by curing the composition comprising the binder according to claim 3 and magnetic metal powder.
請求項５のプラスチック磁石。6. The plastic magnet according to claim 5, wherein the magnetic metal powder is a rare earth-based magnetic metal powder.
金粉である請求項６のプラスチック磁石。7. The plastic magnet according to claim 6, wherein the rare-earth magnetic metal powder is Nd-Fe-B alloy powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27965794A JP3514843B2 (en) | 1994-10-07 | 1994-10-07 | Epoxy resin for metal powder binder and cured product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27965794A JP3514843B2 (en) | 1994-10-07 | 1994-10-07 | Epoxy resin for metal powder binder and cured product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08109244A JPH08109244A (en) | 1996-04-30 |
| JP3514843B2 true JP3514843B2 (en) | 2004-03-31 |
Family
ID=17614044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27965794A Expired - Fee Related JP3514843B2 (en) | 1994-10-07 | 1994-10-07 | Epoxy resin for metal powder binder and cured product thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3514843B2 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4116690B2 (en) * | 1998-04-30 | 2008-07-09 | セイコーエプソン株式会社 | Rare earth bonded magnet composition and rare earth bonded magnet |
| US6342167B1 (en) * | 1999-04-27 | 2002-01-29 | Bridgestone Corporation | Synthetic resin magnet composition and synthetic resin magnet molded-product using the same |
| JP2001214034A (en) * | 2000-01-31 | 2001-08-07 | Nippon Kayaku Co Ltd | Epoxy resin composition and resin bonded type metal mold part |
| JP2001214035A (en) * | 2000-01-31 | 2001-08-07 | Nippon Kayaku Co Ltd | Epoxy resin composition and resin bonded type metal mold part |
| JP3429503B2 (en) * | 2001-08-08 | 2003-07-22 | ソニー株式会社 | Magnetic adsorption sheet |
| JP5329069B2 (en) * | 2007-10-25 | 2013-10-30 | Ｔｄｋ株式会社 | Composite material for magnetic core |
| JP6812091B2 (en) * | 2014-05-29 | 2021-01-13 | 日東電工株式会社 | Soft magnetic resin composition and soft magnetic film |
| JP2016108561A (en) * | 2014-12-04 | 2016-06-20 | 日東電工株式会社 | Soft magnetic resin composition and soft magnetic film |
| ITUB20151291A1 (en) * | 2015-05-28 | 2016-11-28 | Itt Italia Srl | BRAKING DEVICE FOR VEHICLES |
| JP6606908B2 (en) * | 2015-07-31 | 2019-11-20 | 日立化成株式会社 | Resin compound for Sm-based bonded magnet, bonded magnet using the same, and method for producing Sm-based bonded magnet |
| JP6463326B2 (en) * | 2016-01-19 | 2019-01-30 | ミネベアミツミ株式会社 | Rare earth bonded magnet |
| WO2019106810A1 (en) * | 2017-11-30 | 2019-06-06 | 日立化成株式会社 | Compound powder |
| JP2019212664A (en) * | 2018-05-31 | 2019-12-12 | 住友ベークライト株式会社 | Resin composition for forming magnetic member, magnetic member, coil, manufacturing method of magnetic member, and kit for forming magnetic member |
| JP7127366B2 (en) * | 2018-06-04 | 2022-08-30 | 住友ベークライト株式会社 | Resin composition for molding magnetic member, magnetic member, coil, method for manufacturing magnetic member, and kit for molding magnetic member |
| WO2020225885A1 (en) * | 2019-05-08 | 2020-11-12 | 昭和電工マテリアルズ株式会社 | Compound for rare earth-bonded magnet, rare earth-bonded magnet, method for producing rare earth-bonded magnet, and resin composition |
| CN114898961A (en) * | 2022-04-11 | 2022-08-12 | 横店集团东磁股份有限公司 | Magnetic slurry of fully-integrated voltage regulation module inductor and preparation method thereof |
-
1994
- 1994-10-07 JP JP27965794A patent/JP3514843B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08109244A (en) | 1996-04-30 |
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