JPH06215935A - Resin-bonded permanent magnet - Google Patents
Resin-bonded permanent magnetInfo
- Publication number
- JPH06215935A JPH06215935A JP15732993A JP15732993A JPH06215935A JP H06215935 A JPH06215935 A JP H06215935A JP 15732993 A JP15732993 A JP 15732993A JP 15732993 A JP15732993 A JP 15732993A JP H06215935 A JPH06215935 A JP H06215935A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- curing agent
- magnet
- imidazole
- epoxy resin
- 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
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- 239000003822 epoxy resin Substances 0.000 claims abstract description 32
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 229920005989 resin Polymers 0.000 abstract description 14
- 239000011347 resin Substances 0.000 abstract description 14
- 239000002904 solvent Substances 0.000 abstract description 5
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 238000012937 correction Methods 0.000 description 40
- 238000000034 method Methods 0.000 description 31
- 230000005347 demagnetization Effects 0.000 description 18
- 239000000126 substance Substances 0.000 description 18
- 230000008859 change Effects 0.000 description 16
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 12
- 230000002427 irreversible effect Effects 0.000 description 10
- -1 aliphatic amines Chemical class 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 206010040880 Skin irritation Diseases 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910000828 alnico Inorganic materials 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 231100001231 less toxic Toxicity 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 230000036556 skin irritation Effects 0.000 description 2
- 231100000475 skin irritation Toxicity 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- AJHFBIPDUISYDU-UHFFFAOYSA-N 2-(2-ethyl-5-methyl-1h-imidazol-4-yl)propanenitrile Chemical compound CCC1=NC(C(C)C#N)=C(C)N1 AJHFBIPDUISYDU-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Landscapes
- Manufacturing Cores, Coils, And Magnets (AREA)
Abstract
(57)【要約】
【目的】本発明は樹脂結合型永久磁石用の樹脂の硬化剤
の耐熱性、耐溶剤性、毒性の問題を改善することを目的
とする。
【構成】エポキシ樹脂の硬化剤にイミダゾールおよびそ
の誘導体を使用する。
(57) [Summary] [Object] The present invention aims to improve the problems of heat resistance, solvent resistance and toxicity of a curing agent for a resin for a resin-bonded permanent magnet. [Structure] Imidazole and its derivative are used as a curing agent for epoxy resin.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、硬化剤にイミダゾール
およびその誘導体を用いたエポキシ樹脂と、希土類磁石
粉末からなる混合物を、磁場中でプレス成形することに
よって得られる樹脂結合型永久磁石に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin-bonded permanent magnet obtained by press molding a mixture of an epoxy resin using imidazole and its derivative as a curing agent and rare earth magnet powder in a magnetic field. Is.
【０００２】[0002]
【従来の技術】樹脂結合型永久磁石は、焼結磁石にくら
べて （１）成形品の寸法精度が良い。 （２）欠け・割れの発生が少ない。 （３）複雑形状が可能。2. Description of the Related Art Resin-bonded permanent magnets are superior to sintered magnets in (1) dimensional accuracy of molded products. (2) Less chipping and cracking. (3) Complex shapes are possible.
【０００３】などの利点があり、現在注目されている。
しかし樹脂結合型磁石の場合、含んでいる樹脂の割合だ
け焼結磁石に比べて性能が下がり、また配向性も低下す
るので一般に焼結型磁石の1/2〜1/3程度の性能しか示さ
れない。そのため性能を向上させるにはできるだけ樹脂
の量を少なくする必要がある。また樹脂の量は少なくて
しかも、(1)強い接着力を有す、(2)耐熱性が良い、(3)
耐薬品性がある、等の条件を満たす必要が永久磁石に使
用される樹脂にはある。永久磁石に使用されている樹脂
には、熱硬化性、熱可塑性、そしてゴム系などがある
が、熱可塑性樹脂やゴム系の場合樹脂の充填量が多くな
るため大巾な性能低下を生じ、永久磁石として価値の乏
しいものになってしまう。残った熱硬化性樹脂の中でも
前述の条件を満たすものは、エポキシ樹脂に限られると
言える。Since it has advantages such as the above, it is currently receiving attention.
However, the performance of resin-bonded magnets is lower than that of sintered magnets by the proportion of the resin contained, and the orientation is also reduced, so generally only about 1/2 to 1/3 the performance of sintered magnets is shown. Not done. Therefore, it is necessary to reduce the amount of resin as much as possible to improve the performance. In addition, the amount of resin is small, and (1) it has a strong adhesive force, (2) it has good heat resistance, (3)
Resins used for permanent magnets need to meet the requirements such as chemical resistance. Resins used in permanent magnets include thermosetting, thermoplastic, and rubber-based materials, but in the case of thermoplastic resins and rubber-based materials, a large amount of resin is filled, resulting in a large decrease in performance. It becomes a poor permanent magnet. It can be said that among the remaining thermosetting resins, those that satisfy the above conditions are limited to epoxy resins.
【０００４】[0004]
【発明が解決しようとする課題】エポキシ樹脂は主に二
液（主剤と硬化剤）からなり、加熱すると硬化剤が主剤
中に含まれるエポキシ基と反応を越し重合が行われ、そ
の結果強固な硬化物が得られる。この硬化剤には色々な
種類があるが、最も多く使われている硬化剤は脂肪族ア
ミン系硬化剤であり、強い接着力および良好な機械的特
性がその特徴である。このため従来より永久磁石に使用
されてきたエポキシ樹脂の硬化剤もこの脂肪族アミン系
であった。しかし、脂肪族アミン硬化エポキシ樹脂は、
耐熱性に問題があり、永久磁石に使用した時その永久磁
石の限界使用温度は1000℃にすぎなかった。また耐溶剤
性にも問題があり、このため高い信頼性が要求される用
途には樹脂結合型磁石が使用されることはなかった。さ
らに脂肪族アミンは毒性が強いため使用に際し十分な注
意を必要としたり、可使時間が短いため一度に多くの混
合物をつくって置くことが出来ない等の欠点を持ってい
る。The epoxy resin is mainly composed of two liquids (a main agent and a curing agent), and when heated, the curing agent undergoes a polymerization reaction with the epoxy groups contained in the main agent, resulting in a strong solidification. A cured product is obtained. There are various kinds of this curing agent, but the curing agent most often used is an aliphatic amine curing agent, which is characterized by strong adhesive force and good mechanical properties. For this reason, the curing agent for the epoxy resin that has been conventionally used for permanent magnets is also the aliphatic amine type. However, the aliphatic amine cured epoxy resin
There was a problem with heat resistance, and when used for a permanent magnet, the limit operating temperature of the permanent magnet was only 1000 ° C. Further, there is also a problem with solvent resistance, and therefore, resin-bonded magnets have not been used in applications requiring high reliability. Furthermore, aliphatic amines have the drawbacks of requiring great care when used because they are highly toxic, and that many mixtures cannot be prepared and stored at once due to their short pot life.
【０００５】[0005]
【課題を解決するための手段】本発明はこの様な欠点を
解消するために、エポキシ樹脂の硬化剤にイミダゾール
およびその誘導体を使用するものである。SUMMARY OF THE INVENTION The present invention uses imidazole and its derivatives as a curing agent for epoxy resins in order to eliminate such drawbacks.
【０００６】本発明において使用するイミダゾールおよ
びその誘導体の構造式を次に示す。The structural formulas of imidazole and its derivatives used in the present invention are shown below.
【０００７】[0007]
【化１】 [Chemical 1]
【０００８】（式中のR1,R2,R4およびR5は、水素原子、
ハロゲン原子、アルキル基、シクロアルキル基、アリー
ル基、そして分子中の水素原子の少なくとも１つ以上が
シアノ基あるいはヒドロキシル基で置換されたアルキル
基、シクロアルキル基およびアニール基を表わす。） イミダゾール系硬化剤によるエポキシ樹脂の硬化は低温
で反応が遅く、高温で激しく反応する。このためエポキ
シ樹脂の可使時間が長くなり、磁石粉末とエポキシ樹脂
の混合物を大量に製造・保存することが可能になる。ま
たイミダゾール硬化エポキシ樹脂は一般に良好な耐熱性
および耐薬品性を有することが知られており、これが樹
脂結合型磁石の耐熱性および耐薬品性の向上に大きく寄
与している。イミダゾールは脂肪族アミンに比べて、発
揮性が低くまた毒性も低いため作業時の安全性は高くな
った。(In the formula, R1, R2, R4 and R5 are hydrogen atoms,
It represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, and an alkyl group, a cycloalkyl group and an annealing group in which at least one or more hydrogen atoms in the molecule are substituted with a cyano group or a hydroxyl group. ) The curing of the epoxy resin with the imidazole-based curing agent is slow at low temperature and violent at high temperature. Therefore, the pot life of the epoxy resin becomes long, and it becomes possible to manufacture and store a large amount of a mixture of the magnet powder and the epoxy resin. Further, imidazole-cured epoxy resin is generally known to have good heat resistance and chemical resistance, and this greatly contributes to the improvement of heat resistance and chemical resistance of the resin-bonded magnet. Imidazole was less toxic and less toxic than aliphatic amines, so it was safer during work.
【０００９】この様に硬化剤にイミダゾールを使ったエ
ポキシ樹脂は、樹脂結合型磁石に最も適しており、従来
からの弱点であった磁石の温度特性、信頼性を改善し、
また低コスト化にとっても大きな役割を果たしている。
使油する希土類磁石粉末にはR2TM17系（RはYを含むラン
タン系金属元素 La,Ce,Pr,Nd,Pm,Sm,Eu,Gd,Tb,Dy,Ho,E
r,Tm,Yb,Lu の一種または２種以上の組合せ、TMは遷移
金属を表わす。）粉末を用いる。このR2TM17系粉末は、
SmCo5磁石粉末やアルニコ及びフェライト磁石粉末に比
べて非常に高い磁気性能を有するため、樹脂結合型磁石
に使用しても高性能を保持しうることができる。エポキ
シ樹脂の添加量は、磁石粉末に対し1〜6wt%が適当であ
り、これより多いと密度の低下およびプレス成形時の樹
脂の浸みだし等の問題が生じてくる。As described above, the epoxy resin using imidazole as the curing agent is most suitable for the resin-bonded magnet, and improves the temperature characteristics and reliability of the magnet, which have been weak points in the past.
It also plays a major role in cost reduction.
R2TM17 series (R is Y-containing lanthanum metal element La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, E
One or a combination of two or more of r, Tm, Yb and Lu, and TM represents a transition metal. ) Use powder. This R2TM17 series powder is
Since it has much higher magnetic performance than SmCo5 magnet powder and Alnico and ferrite magnet powder, it can maintain high performance even when used in resin-bonded magnets. An appropriate amount of the epoxy resin added is 1 to 6 wt% with respect to the magnet powder, and if it is more than this, problems such as a decrease in density and resin seepage during press molding occur.
【００１０】以上の通り、本発明における永久磁石およ
びその製造方法は、イミダゾールを硬化剤としたエポキ
シ樹脂と希土類磁石粉末からなる混合物をプレス成形し
て造るため、耐熱性や耐薬品性の優れた永久磁石が安価
で造れるのである。As described above, the permanent magnet and the method for producing the same according to the present invention are excellent in heat resistance and chemical resistance because they are formed by press molding a mixture of an epoxy resin using imidazole as a curing agent and rare earth magnet powder. Permanent magnets can be manufactured at low cost.
【００１１】[0011]
【実施例】つぎに、実施例を用いて本発明を詳細に説明
する。EXAMPLES Next, the present invention will be described in detail with reference to examples.
【００１２】（実施例１）Sm(Cobal Cu0.07 Fe0.3 Zr0.
016)7.8の組成の合金を高周波溶解炉で溶解しインゴッ
トをつくる。このインゴットに溶体化処理そして時効処
理などの熱処理を行う。その後にこのインゴットをジェ
ットミルで2〜80μm程度まで粉砕する。獲られた粉末に
エポキシ樹脂を混合し、この混合物を型の中に挿入し
て、電磁石と油圧プレスを用いて、印加磁場16(KG)をか
けながら、3 ton/cm2 加圧し、脱磁後、型内から試料を
抜き出す。この磁石成型体は、その後恒温槽中で加熱硬
化される。Example 1 Sm (Cobal Cu0.07 Fe0.3 Zr0.
016) The alloy having the composition of 7.8 is melted in a high frequency melting furnace to form an ingot. This ingot is subjected to heat treatment such as solution treatment and aging treatment. Then, this ingot is crushed by a jet mill to about 2 to 80 μm. Epoxy resin was mixed with the obtained powder, this mixture was inserted into a mold, and while applying an applied magnetic field of 16 (KG), it was pressurized to 3 ton / cm2 using an electromagnet and a hydraulic press, and after demagnetization. , Remove the sample from the mold. This magnet molding is then heat-cured in a constant temperature bath.
【００１３】使用されるエポキシ樹脂は、主剤に対し、
硬化剤をイミダーゾール類の場合2〜5重量部、脂肪族ア
ミン類の場合10〜20重量部加えてよく攪拌して、均一に
なったら磁石粉末に対し2重量%を添加する。The epoxy resin used is based on
Add 2 to 5 parts by weight of a curing agent in the case of imidazoles and 10 to 20 parts by weight in the case of aliphatic amines, and stir well. When uniform, add 2% by weight to the magnet powder.
【００１４】イミダゾール系硬化剤1-シアノエチル-2-
エチル-4-メチルイミダゾールを用いた樹脂結合磁石
（試料-1）と、脂肪族アミン系硬化剤を使用した磁石
(試料2,3)の耐熱性と耐薬品性を比較した。表１は耐熱
性を表わし、表２は耐薬品を表わしている。Imidazole type curing agent 1-cyanoethyl-2-
Resin-bonded magnet using ethyl-4-methylimidazole (Sample-1) and magnet using aliphatic amine curing agent
The heat resistance and chemical resistance of (Samples 2 and 3) were compared. Table 1 shows the heat resistance, and Table 2 shows the chemical resistance.
【００１５】磁石を着磁後加熱すると減磁が生じる。減
磁の中には、(1)可逆減磁と(2)不可逆減磁があり、樹脂
結合型磁石の不可逆減磁は焼結磁石にくらべて相当大き
な値を持つ。表１は、硬化剤を変えた樹脂結合型磁石を
着磁し、その後恒温槽中に1000時間放置した時不可逆減
磁率を表わしたものである。Demagnetization occurs when the magnet is heated after being magnetized. Among the demagnetizations, there are (1) reversible demagnetization and (2) irreversible demagnetization, and the irreversible demagnetization of the resin-bonded magnet has a considerably larger value than the sintered magnet. Table 1 shows the irreversible demagnetization rate when a resin-bonded magnet with a different hardening agent was magnetized and then left in a constant temperature bath for 1000 hours.
【００１６】[0016]
【表１】 [Table 1]
【００１７】表１より、脂肪族アミン系硬化剤を使用し
た試料２と試料３にくらべてイミダゾールを使用した試
料１は不可逆減磁率が大幅に低下していることが判る。
不可逆減磁の原因となる樹脂の熱劣化や樹脂と磁石粉末
間の磁石粉末間の接着力の低下などがイミダゾールによ
って改善されたためであると言える。From Table 1, it can be seen that the irreversible demagnetization ratio of Sample 1 using imidazole is significantly lower than that of Samples 2 and 3 using the aliphatic amine curing agent.
It can be said that imidazole has improved the thermal deterioration of the resin causing the irreversible demagnetization and the decrease in the adhesive force between the resin and the magnet powder between the magnet powders.
【００１８】表１と同じ硬化剤を使用した試料について
耐薬品性を調べた結果を表２に示す。Table 2 shows the results of examining the chemical resistance of the samples using the same curing agent as in Table 1.
【００１９】[0019]
【表２】 [Table 2]
【００２０】表２よりイミダゾール硬化エポキシ樹脂を
使用した場合、耐溶剤性が著しく改善されているのが判
る。この実施例から判るように、イミアゾールを使用す
れば樹脂結合型磁石の信頼性が大きく改善されることは
確実である。耐熱性実験は次の要領で行った。つまりφ
10×7mmの円柱形状をした、異方性方向が7mm長軸方向に
ある試料をパルス法で着磁し、図１に示された測定装置
中のプラスッチックでできた測定台(3)にセットする。
次に(4)の円筒の先端につけられたコイル(2)を上へ引き
上げることによって得られた信号を(5)のデジタル磁束
計で読む。(1)の試料は120℃および150℃の恒温槽中に1
000時間放置する。耐薬品性実験は次の要領で行った。5
×5×5mmの立方体の試料を作り各薬品に室温中で120時
間放置する。その後試料を取り出し試料の表面を乾いた
ガーゼでふき、直ちにその重量を計り重量変化率を調べ
る。It can be seen from Table 2 that the solvent resistance is remarkably improved when the imidazole-cured epoxy resin is used. As can be seen from this example, it is certain that the use of imiazole will greatly improve the reliability of the resin-bonded magnet. The heat resistance experiment was conducted as follows. That is φ
A 10 × 7 mm cylindrical sample with anisotropy of 7 mm in the major axis direction was magnetized by the pulse method and set on the measuring table (3) made of plastic in the measuring device shown in Fig. 1. To do.
Next, the signal obtained by pulling up the coil (2) attached to the tip of the cylinder (4) is read by the digital magnetometer (5). The sample in (1) was placed in a 120 ° C and 150 ° C constant temperature bath.
Leave for 000 hours. The chemical resistance test was conducted as follows. Five
Make a 5 x 5 x 5 mm cube sample and leave each chemical for 120 hours at room temperature. After that, the sample is taken out and the surface of the sample is wiped with dry gauze, and the weight is immediately measured to examine the rate of change in weight.
【００２１】（実施例２）イミダゾールを使用した試料
と脂肪族アミンを使用した試料について、その混練物の
可使時間を調べた。実験は各硬化剤を含んだエポキシ樹
脂と磁石粉末を混練し、この混練物を室温中で放置後形
成し磁気性能の劣化を見る。図２よりイミダゾール系硬
化剤(1-シアニエチル-2-エチル-4-メチルイミダゾール)を
使用した場合と脂肪族炭化水素系硬化剤（ジエチルアミ
ンノプロビルアミン）を使用した場合を比較するとイミ
ダゾール系の可使時間の長いことがはっきりと判る。可
使時間が長いと混練物を１度に大量に生産し保存するこ
とができるため、コストの低減化が可能となる。またイ
ミダゾールは揮発性が低く皮膚に対する刺激毒性が低い
ことからも大量に扱うことが可能と言える。Example 2 The pot life of the kneaded product was examined for the sample using imidazole and the sample using aliphatic amine. In the experiment, the epoxy resin containing each curing agent and the magnetic powder were kneaded, and the kneaded material was left standing at room temperature and then formed to observe the deterioration of the magnetic performance. From Fig. 2, comparing the case of using the imidazole-based curing agent (1-cyanethyl-2-ethyl-4-methylimidazole) and the case of using the aliphatic hydrocarbon-based curing agent (diethylaminenoprobylamine), It is clear that the pot life is long. When the pot life is long, the kneaded product can be produced and stored in a large amount at one time, and the cost can be reduced. In addition, since imidazole has low volatility and low skin irritation toxicity, it can be said that it can be handled in a large amount.
【００２２】[0022]
【発明の効果】以上のように本発明磁石は、従来の樹脂
結合型永久磁石にくらべて耐熱性、耐薬品性などの信頼
性が格段にすぐれておりまた低コストも可能なことから
今後産業用モーターなどの新しい分野への応用も考えら
れ、本発明の持つ工業適意義は大きいと言える。INDUSTRIAL APPLICABILITY As described above, the magnet of the present invention is much more reliable than conventional resin-bonded permanent magnets in heat resistance, chemical resistance, etc., and can be manufactured at low cost. It can be said that the present invention has great industrial suitability because it can be applied to new fields such as motors for automobiles.
【図１】本発明で用いた熱減磁試験における磁束検出装
置を示した図。FIG. 1 is a diagram showing a magnetic flux detection device in a thermal demagnetization test used in the present invention.
【図２】混練物の可使時間を表わしたグラフ。（−○
−）イミダゾール硬化剤使用、（・・・●・・・）脂肪
族アミン硬化剤使用を表わす。縦軸は残留磁束密度Br、
横軸は混練後経過日数、０日は混練当日を示す。FIG. 2 is a graph showing the pot life of the kneaded product. (-○
−) Use of imidazole curing agent, (... ● ...) Use of aliphatic amine curing agent. The vertical axis represents the residual magnetic flux density Br,
The horizontal axis indicates the number of days elapsed after kneading, and the 0th day indicates the day of kneading.
１・・磁石 ２・・コイル ３・・測定用ケース(A) ４・・測定用ケース(B) ５・・デジタル磁束計 1 ... Magnet 2 ... Coil 3 ... Measurement case (A) 4 ... Measurement case (B) 5 ... Digital magnetometer
【手続補正書】[Procedure amendment]
【提出日】平成５年７月２６日[Submission date] July 26, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】特許請求の範囲[Name of item to be amended] Claims
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【特許請求の範囲】[Claims]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００４[Correction target item name] 0004
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００４】[0004]
【発明が解決しようとする課題】エポキシ樹脂は主に二
液（主剤と硬化剤）からなり、加熱すると硬化剤が主剤
中に含まれるエポキシ基と反応を起こし重合が行われ、
その結果強固な硬化物が得られる。この硬化剤には色々
な種類があるが、最も多く使われている硬化剤は脂肪族
アミン系硬化剤であり、強い接着力および良好な機械的
特性がその特徴である。このため従来より永久磁石に使
用されてきたエポキシ樹脂の硬化剤もこの脂肪族アミン
系であった。しかし、脂肪族アミン硬化エポキシ樹脂
は、耐熱性に問題があり、永久磁石に使用した時その永
久磁石の限界使用温度は１００℃にすぎなかった。また
耐溶剤性にも問題があり、このため高い信頼性が要求さ
れる用途には樹脂結合型磁石が使用されることはなかっ
た。さらに脂肪族アミンは毒性が強いため使用に際し十
分な注意を必要としたり、可使時間が短いため一度に多
くの混合物をつくって置くことが出来ない等の欠点を持
っている。The epoxy resin is mainly composed of two liquids (a main agent and a curing agent), and when heated, the curing agent reacts with the epoxy group contained in the main agent to cause polymerization,
As a result, a strong cured product can be obtained. There are various kinds of this curing agent, but the curing agent most often used is an aliphatic amine curing agent, which is characterized by strong adhesive force and good mechanical properties. For this reason, the curing agent for the epoxy resin that has been conventionally used for permanent magnets is also the aliphatic amine type. However, the aliphatic amine-cured epoxy resin has a problem in heat resistance, and when used in a permanent magnet, the limit operating temperature of the permanent magnet was only 100 ° C. Further, there is also a problem with solvent resistance, and therefore, resin-bonded magnets have not been used in applications requiring high reliability. Furthermore, aliphatic amines have the drawbacks of requiring great care when used because they are highly toxic, and that many mixtures cannot be prepared and stored at once due to their short pot life.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００８[Correction target item name] 0008
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００８】（式中のＲ１，Ｒ２，およびＲ５は、水素
原子、ハロゲン原子、アルキル基、シクロアルキル基、
アリール基、そして分子中の水素原子の少なくとも１つ
以上がシアノ基あるいはヒドロキシル基で置換されたア
ルキル基、シクロアルキル基およびアニール基を表わ
す。） イミダゾール系硬化剤によるエポキシ樹脂の硬化は低温
で反応が遅く、高温で激しく反応する。このためエポキ
シ樹脂の可使時間が長くなり、磁石粉末とエポキシ樹脂
の混合物を大量に製造・保存することが可能になる。ま
たイミダゾール硬化エポキシ樹脂は一般に良好な耐熱性
および耐薬品性を有することが知られており、これが樹
脂結合型磁石の耐熱性および耐薬品性の向上に大きく寄
与している。イミダゾールは脂肪族アミンに比べて、揮
発性が低くまた毒性も低いため作業時の安全性は高くな
った。(In the formula, R1, R2 and R5 are a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group,
An aryl group, and an alkyl group in which at least one or more hydrogen atoms in the molecule are substituted with a cyano group or a hydroxyl group, a cycloalkyl group, and an annealing group. ) The curing of the epoxy resin with the imidazole-based curing agent is slow at low temperature and violent at high temperature. Therefore, the pot life of the epoxy resin becomes long, and it becomes possible to manufacture and store a large amount of a mixture of the magnet powder and the epoxy resin. Further, imidazole-cured epoxy resin is generally known to have good heat resistance and chemical resistance, and this greatly contributes to the improvement of heat resistance and chemical resistance of the resin-bonded magnet. Imidazole is more volatile than aliphatic amines.
Since it has low toxicity and low toxicity, the safety during work is high.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００９】この様に硬化剤にイミダゾールを使ったエ
ポキシ樹脂は、樹脂結合型磁石に最も適しており、従来
からの弱点であった磁石の温度特性、信頼性を改善し、
また低コスト化にとっても大きな役割を果たしている。
使用する希土類磁石粉末にはＲ２ＴＭ１７ 系（ＲはＹを
含むランタン系金属元素Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｐ
ｍ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ，Ｔ
ｍ，Ｙｂ，Ｌｕの一種または２種以上の組合せ、ＴＭは
遷移金属を表わす。）粉末を用いる。このＲ２ＴＭ１７
系粉末は、ＳｍＣｏ５ 磁石粉末やアルニコ及びフエライ
ト磁石粉末に比べて非常に高い磁気性能を有するため、
樹脂結合型磁石に使用しても高性能を保持しうることが
できる。エポキシ樹脂の添加量は、磁石粉末に対し１〜
６ｗｔ％が適当であり、これより多いと密度の低下およ
びプレス成形時の樹脂の浸みだし等の問題が生じてく
る。As described above, the epoxy resin using imidazole as the curing agent is most suitable for the resin-bonded magnet, and improves the temperature characteristics and reliability of the magnet, which have been weak points in the past.
It also plays a major role in cost reduction.
The rare earth magnet powder used is R 2 TM 17 system (R is a lanthanum-based metal element containing Y, La, Ce, Pr, Nd, P).
m, Sm, Eu, Gd, Tb, Dy, Ho, Er, T
One or a combination of two or more of m, Yb and Lu, and TM represents a transition metal. ) Use powder. This R 2 TM 17
The system powders have much higher magnetic performance than the SmCo 5 magnet powder and the alnico and ferrite magnet powders.
Even when used in a resin-bonded magnet, high performance can be maintained. The amount of epoxy resin added is 1 to magnet powder.
6 wt% is appropriate, and if it is more than this, problems such as a decrease in density and seepage of resin during press molding occur.
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１２[Correction target item name] 0012
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１２】（実施例１）Ｓｍ（ＣｏｂａｌＣｕ
０．０７Ｆｅ０．３Ｚｒ０．０１６）７．８ の組成の合
金を高周波溶解炉で溶解しインゴットをつくる。このイ
ンゴットに溶体化処理そして時効処理などの熱処理を行
う。その後にこのインゴットをジェットミルで２〜８０
μｍ程度まで粉砕する。得られた粉末にエポキシ樹脂を
混合し、この混合物を型の中に挿入して、電磁石と油圧
プレスを用いて、印加磁場１６（ｋＧ）をかけながら、
３ｔｏｎ／ｃｍ ２ 加圧し、脱磁後、型内から試料を抜き
出す。この磁石成型体は、その後恒温槽中で加熱硬化さ
れる。Example 1 Sm ( Co bal Cu
An alloy having a composition of 0.07 Fe 0.3 Zr 0.016 ) 7.8 is melted in a high frequency melting furnace to form an ingot. This ingot is subjected to heat treatment such as solution treatment and aging treatment. After that, this ingot is jet milled for 2-80
Grind to about μm. An epoxy resin was mixed with the obtained powder, the mixture was inserted into a mold, and an applied magnetic field of 16 (kG) was applied using an electromagnet and a hydraulic press.
After pressurizing 3 ton / cm 2 and demagnetizing, the sample is taken out from the mold. This magnet molding is then heat-cured in a constant temperature bath.
【手続補正６】[Procedure correction 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１３[Correction target item name] 0013
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１３】使用されるエポキシ樹脂は、主剤に対し、
硬化剤をイミダゾール類の場合２〜５重量部、脂肪族ア
ミン類の場合１０〜２０重量部加えてよく撹拌して、均
一になったら磁石粉末に対し２重量％を添加する。The epoxy resin used is based on
A curing agent is added in an amount of 2 to 5 parts by weight in the case of imidazoles and 10 to 20 parts by weight in the case of aliphatic amines and well stirred, and when uniform, 2% by weight is added to the magnet powder.
【手続補正７】[Procedure Amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１４[Correction target item name] 0014
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１４】イミダゾール系硬化剤１−シアノエチル−
２−エチル−４−メチルイミダゾールを用いた樹脂結合
磁石（試料−１）と、脂肪族アミン系硬化剤を使用した
磁石（試料２，３）の耐熱性と耐薬品性を比較した。表
１は耐熱性を表わし、表２は耐薬品性を表わしている。Imidazole type curing agent 1-cyanoethyl-
The heat resistance and chemical resistance of the resin-bonded magnet using 2-ethyl-4-methylimidazole (Sample-1) and the magnet using the aliphatic amine-based curing agent (Samples 2 and 3) were compared. Table 1 represents the heat resistance, Table 2 represents the chemical resistance.
【手続補正８】[Procedure Amendment 8]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１５[Name of item to be corrected] 0015
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１５】磁石を着磁後加熱すると減磁が生じる。減
磁の中には、（１）可逆減磁と（２）不可逆減磁があ
り、樹脂結合型磁石の不可逆減磁は焼結磁石にくらべて
相当大きな値を持つ。表１は、硬化剤を変えた樹脂結合
型磁石を着磁し、その後恒温槽中に１０００時間放置し
た時の不可逆減磁率を表わしたものである。Demagnetization occurs when the magnet is heated after being magnetized. Among the demagnetizations, there are (1) reversible demagnetization and (2) irreversible demagnetization, and the irreversible demagnetization of the resin-bonded magnet has a considerably larger value than the sintered magnet. Table 1 shows the irreversible demagnetization rate when a resin-bonded magnet with a different hardening agent was magnetized and then left in a constant temperature bath for 1000 hours.
【手続補正９】[Procedure Amendment 9]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１６[Correction target item name] 0016
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１６】[0016]
【表１】 [Table 1]
【手続補正１０】[Procedure Amendment 10]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１７[Correction target item name] 0017
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１７】表１より、脂肪族アミン系硬化剤を使用し
た試料２と試料３にくらべてイミダゾールを使用した試
料１は不可逆減磁率が大幅に低下していることが判る。
不可逆減磁の原因となる樹脂の熱劣化や樹脂と磁石粉末
間の接着力の低下などがイミダゾールによって改善され
たためであると言える。From Table 1, it can be seen that the irreversible demagnetization ratio of Sample 1 using imidazole is significantly lower than that of Samples 2 and 3 using the aliphatic amine curing agent.
Heat deterioration of resin that causes irreversible demagnetization and resin and magnet powder
It can be said that this is because the decrease in the adhesive force between the two was improved by imidazole.
【手続補正１１】[Procedure Amendment 11]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１９[Correction target item name] 0019
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１９】[0019]
【表２】 [Table 2]
【手続補正１２】[Procedure Amendment 12]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２０[Correction target item name] 0020
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２０】表２よりイミダゾール硬化エポキシ樹脂を
使用した場合、耐溶剤性が著しく改善されているのが判
る。この実施例から判るように、イミダゾールを使用す
れば樹脂結合型磁石の信頼性が大きく改善されることは
確実である。耐熱性実験は次の要領で行った。つまりφ
１０×７ｍｍの円柱形状をした、異方性方向が７ｍｍ長
軸方向にある試料をパルス法で着磁し、図１に示された
測定装置中のプラスチックでできた測定台（３）にセッ
トする。次に（４）の円筒の先端につけられたコイル
（２）を上へ引き上げることによって得られた信号を
（５）のデジタル磁束計で読む。（１）の試料は１２０
℃および１５０℃の恒温槽中に１０００時間放置する。
耐薬品性実験は次の要領で行った。５×５×５ｍｍの立
方体の試料を作り各薬品に室温中で１２０時間放置す
る。その後試料を取り出し試料の表面を乾いたガーゼで
ふき、直ちにその重量を計り重量変化率を調べる。It can be seen from Table 2 that the solvent resistance is remarkably improved when the imidazole-cured epoxy resin is used. As can be seen from this example, it is certain that the reliability of the resin-bonded magnets With Imi da tetrazole is greatly improved. The heat resistance experiment was conducted as follows. That is φ
Was 10 × 7mm cylindrical anisotropy direction is magnetized sample in 7mm long axis direction pulse method, measuring table made of plastics steel click in the measuring apparatus shown in FIG. 1 (3 ). Next, the signal obtained by pulling up the coil (2) attached to the tip of the cylinder (4) is read by the digital magnetometer (5). The sample of (1) is 120
Leave for 1000 hours in a constant temperature bath at 150 ° C and 150 ° C.
The chemical resistance test was conducted as follows. A 5 × 5 × 5 mm cube sample is prepared and left to stand for 120 hours at room temperature with each chemical. After that, the sample is taken out and the surface of the sample is wiped with dry gauze, and the weight is immediately measured to examine the rate of change in weight.
【手続補正１３】[Procedure Amendment 13]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２１[Correction target item name] 0021
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２１】（実施例２）イミダゾールを使用した試料
と脂肪族アミンを使用した試料について、その混練物の
可使時間を調べた。実験は各硬化剤を含んだエポキシ樹
脂と磁石粉末を混練し、この混練物を室温中で放置後成
形し磁気性能の劣化を見る。図２よりイミダゾール系硬
化剤（１−シアノエチル−２−エチル−４−メチルイミ
ダゾール）を使用した場合と脂肪族炭化水素系硬化剤
（ジエチルアミノプロピルアミン）を使用した場合を比
較するとイミダゾール系の可使時間の長いことがはっき
りと判る。可使時間が長いと混練物を１度に大量に生産
し保存することができるため、コストの低減化が可能と
なる。またイミダゾールは揮発性が低く皮膚に対する刺
激毒性が低いことからも大量に扱うことが可能と言え
る。Example 2 The pot life of the kneaded product was examined for the sample using imidazole and the sample using aliphatic amine. Experiments were kneaded epoxy resin and a magnet powder containing a respective curing agent, after standing the kneaded product at room temperature formed
Shape and see deterioration of magnetic performance. Imidazole curing agent than 2 (1 shear Roh-ethyl-2-ethyl-4-methylimidazole) If an aliphatic hydrocarbon-based curing agent used imidazole Comparing a case of using a (Jiechirua amino pro Pi triethanolamine) It is clear that the system has a long pot life. When the pot life is long, the kneaded product can be produced and stored in a large amount at one time, and the cost can be reduced. In addition, since imidazole has low volatility and low skin irritation toxicity, it can be said that it can be handled in a large amount.
【手続補正１４】[Procedure Amendment 14]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２２[Name of item to be corrected] 0022
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２２】[0022]
【発明の効果】以上のように本発明磁石は、従来の樹脂
結合型永久磁石にくらべて耐熱性、耐薬品性などの信頼
性が格段にすぐれておりまた低コストも可能なことから
今後産業用モーターなどの新しい分野への応用も考えら
れ、本発明の持つ工業的意義は大きいと言える。INDUSTRIAL APPLICABILITY As described above, the magnet of the present invention is much more reliable than conventional resin-bonded permanent magnets in heat resistance, chemical resistance, etc., and can be manufactured at low cost. application to new areas such as use motor also considered, the industrial significance with the present invention can be said to be large.
Claims (1)
用いたエポキシ樹脂と、希土類磁石粉末からなる混合物
を、磁場中でプレス成形して得られることを特徴とする
樹脂結合型永久磁石。1. A resin-bonded permanent magnet, which is obtained by press-molding a mixture of an epoxy resin using imidazole and its derivative as a curing agent and rare earth magnet powder in a magnetic field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5157329A JPH0793207B2 (en) | 1993-06-28 | 1993-06-28 | Resin-bonded permanent magnet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5157329A JPH0793207B2 (en) | 1993-06-28 | 1993-06-28 | Resin-bonded permanent magnet |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58145321A Division JPH0618133B2 (en) | 1983-08-09 | 1983-08-09 | Resin-bonded permanent magnet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06215935A true JPH06215935A (en) | 1994-08-05 |
| JPH0793207B2 JPH0793207B2 (en) | 1995-10-09 |
Family
ID=15647321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5157329A Expired - Lifetime JPH0793207B2 (en) | 1993-06-28 | 1993-06-28 | Resin-bonded permanent magnet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0793207B2 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5623711A (en) * | 1979-08-02 | 1981-03-06 | Seiko Epson Corp | Production of intermetallic compound magnet |
| JPS5724504A (en) * | 1980-07-21 | 1982-02-09 | Takagi Kogyo Kk | Manufacture of plastic bound magnet |
| JPS58122705A (en) * | 1982-01-18 | 1983-07-21 | Toshiba Chem Corp | Composite magnetic material for molding |
| JPS58145321A (en) * | 1982-02-22 | 1983-08-30 | Sakamura Kikai Seisakusho:Kk | Method and apparatus for continuous heading and rolling in former |
| JPS6037106A (en) * | 1983-08-09 | 1985-02-26 | Seiko Epson Corp | Resin bonded permanent magnet |
-
1993
- 1993-06-28 JP JP5157329A patent/JPH0793207B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5623711A (en) * | 1979-08-02 | 1981-03-06 | Seiko Epson Corp | Production of intermetallic compound magnet |
| JPS5724504A (en) * | 1980-07-21 | 1982-02-09 | Takagi Kogyo Kk | Manufacture of plastic bound magnet |
| JPS58122705A (en) * | 1982-01-18 | 1983-07-21 | Toshiba Chem Corp | Composite magnetic material for molding |
| JPS58145321A (en) * | 1982-02-22 | 1983-08-30 | Sakamura Kikai Seisakusho:Kk | Method and apparatus for continuous heading and rolling in former |
| JPS6037106A (en) * | 1983-08-09 | 1985-02-26 | Seiko Epson Corp | Resin bonded permanent magnet |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0793207B2 (en) | 1995-10-09 |
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