JPS60242604A - Plastic magnet composition - Google Patents

Abstract

PURPOSE:To obtain the plastic magnet composition showing a highly efficient magnet characteristics at relatively low cost by a method wherein Nd-Fe-B family is used as a magnetic material, and its powder is coated with dyestuffs. CONSTITUTION:The magnetic powder indicated by the composition formula RxMyBz (the R in the formula indicates rare-earth element, M indicates iron group element, and x, y and z indicate atom% on condition of 8<=x<=30, 2<=z <=20 and y=100-x-z) has excellent magnet characteristics, but as it is inflammable when it comes in contact with air when it is heated up while it is mixed and fused with plastic, the magnetic material is coated by dyestuffs in advance. As the dyestuffs, direct dyes, acid dyes, basic dyes, mordant dyes, sulphite dyes, vat dyes, disperse dyes, oil-soluble dyes, reactive dyes and a fluorescent brightening agent can be included. Pertaining to the quantity of the dyes to be coated, 0.02-2wt% is considered desirable for the magnetic powder.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel glasstic magnet composition that exhibits high performance.

Sintered magnets and cast magnets are conventionally known.

Because it is hard and brittle, it is difficult to process it into complex shapes, and if high-precision machining is required, it is inevitable that the cost will increase, and it is difficult to mold it integrally with other parts. Even if an attempt is made to manufacture a radial anisotropic or multipolar anisotropic magnet, there are problems such as damage and manufacturing difficulty.

Plastic magnets were developed to solve the above problems, and attempts have been made to use various magnetic materials and various plastics. Especially recently, magnetic parallelepipeds have become stronger, smaller and
Due to the demand for weight reduction, 8B-C was used instead of the original 7-elite magnetic material.

Magnetic materials such as those that exhibit extremely excellent magnetic performance have come into use. However, -8m is extremely expensive because it has a particularly low content among rare earth ores and its purification and separation requires a large amount of cost.On the other hand, Do is not only expensive but also has problems in stable supply.

As a result of intensive study by the present inventors - i-type material (i-type powder)
By using a Nd-Fe-B type material as a plastic magnet composition, a plastic magnet composition exhibiting high performance magnetic properties can be obtained at a relatively low cost.

Similarly to the Sm-9o magnetic powder, this magnetic powder has the problem of being easily ignited by contact with air when the temperature reaches a high temperature when mixed and melted with plastic. The present invention was completed after confirming that the problem could be solved by coating.

That is, the present invention provides a plastic coated with a dye or a dye and an organopolysiloxane with the composition formula R.
MB (R in the formula is a rare earth element.

yz M is an iron group element, x, y and 2 indicate atomic radius,
However, 8≦X≦30-2≦2≦20.7-100-X-
The present invention relates to a plastic magnet composition comprising a magnetic powder represented by Z). In the composition formula, R is Nd or N
(It is a rare earth element mainly composed of 1, and 1M is Fe or Fe.
It is an iron group element mainly composed of Practically, as R, a mixture of two or more types mainly containing Nd (such as Mitshmeklujidim) should be used, and as M, a mixture of Fe and a small amount of Oo or N1 should be used (improving the curie point). is desirable. In addition, -B (boron) includes AA, Si
, O, etc. may be mixed as impurities. The values of X, y, and 2 indicating the composition, that is, the atomic ratio, are as described above. It is desirable that the coercive force we increases as the value of
It is preferable that the range is 0≦X≦20. Also, if the value of 2, which indicates the amount of B, becomes large, the coercive force Ha will increase in this case as well, but it will be too large (then the residual magnetic flux density Br will decrease, so it should be less than 20 atoms, Preferably, the range is 5≦2≦15.Y, which indicates the amount of M, is the remaining amount.In order to further improve the coercive force, -At is used.

Ti, zr, Hf, V, Nb, Ta
+Or%M.

One or more of W-Mn, Sn, Pb, 8b, Bi, Ou, Zn, etc. may be added in a relatively small amount.

As a method for producing magnetic powder, ■Material metal element (N
d, Fe, B, etc.) in a predetermined composition by high frequency melting to make an ingot. ■ This is coarsely crushed using a shoku crusher and a brown mill to a particle size of 35 mesh or less, and then a ball mill to a particle size of about 2 to 10μ. Finely grind until ■
Oriented press molding in a magnetic field, ■ Argon gas 91000
Sintering at a temperature of ~1200°C, aging after cooling - (2) This product is crushed in the same manner as in (2) above, and dried to obtain magnetic powder. Of course, magnetic powder may be produced by other methods. In addition.

In order to highly fill plastics, it is desirable to use a mixture of fine powder and powder with a slightly larger particle size, and for multi-polar radial anisotropic magnets, it is desirable to use a mixture of fine powder and powder with a slightly larger particle size. It is best to use powder with a sufficiently small particle size.

Dyes used to coat the magnetic powder include direct dyes, acid dyes, and basic dyes.

Mordant dye, sulfur dye, vat dye 1 Disperse dye, oil-soluble dye 1
Included are fluorescent brighteners such as reactive dyes and the like. Specific examples of these are as follows.

Direct dye 0. Engineering, Direct Yellow 26.28.39°44.
50.86.88.8198% 100°a, 1. Direct Orange 39.51.107°0.1. Direct Red 79.80.81.83゜84.89.218.
O, 1, Direct Green 37.63. O,1,
Direct Violet 47.51.90.94. 0
．． 1. Direct proof 1.78.86.90.98
．． 106°160.194-196-202.225°226.246. O, 1, Direct Orange Direct Black 19.3151.75.94.105-1
06-107.108, 113°118.146, etc.

Acid dye 0.1. Acid Yellow 7.17.23.25゜40
．． 44.72.75.98.99.114゜131.1
41 0.1. Acid Orange 19°45.74-8
5.95. 0.1. Acid Red 6.32.42.
52.57-7k 80.94゜Ill 111115
-118.119-130.131.133.134.
145°168.180.184.194.198°2
17.249.303. O, 1, acid violet 34-47.48. O, 1, acid blue 15.
29.4145.54.59.80゜100.102.
113.120-130°14 (L 151.154-
184.187°229, O, 1, Acid Green 7
．． 12.16°20-44.57. O, 1, Acid Brown 39° 301 0° Engineering, Acid Black 1.
2.24゜26.29.314B, 52.63.131
゜140.155 etc.

Basic Dye 0, Process, Paysic Yellow 11.14.19゜21
28-33. 34. : U5.36, C, I.

Paysic Orange 2.14, 15.21-32°0.
1. Paysic Red 13.1118.22゜23.2
4-29.32.35-36.37゜3139.40.
0.1. Paysic Violet) 7.1 (L 15.
21,25.26.27゜Od, Paysic Blue 12
4.54.58゜60, O, 1, Paysic Black 8
Such.

Mordant dye 0.1. Modern Tread-1, 23, 59°0.1.
Mordant Geringe 5. O, 1, modern tread 2
1.26.63,89. O, 1, Mordant Violet 5. O, 1, Mordand Blue 1゜29.47.
O, 1, Mordant Guerin 11°0.1. Mordand Brown 1.14.87°a, X, Mordand Brown l 3.7%9.11°13.17.26.38.54
．． 75.84 etc.

Sulfur dye 0, Sulfur orange 1.3. O, 1, t lure pull 2.3.6.7.9. l 3. O, I.

Sulfur Red 3.5. 0.1. Sulfur Green 2.6-11.14. O, 1, Sulfur Brown 7, 8. 0.1. Sulfur Yellow 4°0.1. Sulfur black 1. O, 1, Solbilized Sulfur Orange 3. O, 1, Solbilized Sulfur Yellow 2. , O,1, Solbilized Sulfur Red 7. 0.1. Solbilized Sarno Hable-4,
0, 1, Solbilized Sulfur Green 3. O,
1.Fulvirized Sulfur Brown 8 etc.

Vat dye 0.1. Bat Yellow 2.4.10% 20°22.
23. O, 1, Bat Orange L, 2.3°5.13
．． O, 1, Bat Red 1.10.13゜16.31
．． 52. O, 1, Bat Violet 1゜2.13.
O, 1, Bat Blue 4.5-6°0.1. Solbilized Putt Pull - 6,0,1, Bat Blue 14.2
9.41.64. 0.1. Bat Green 1.2. a
-s, 9.43.44°0.1. Solbilized bat green 1. 0.1° Bat Brown 1.3.22.
25.39.41°44.46% 0. X, butt black 9.14°25.57, etc.

Disperse dye 0, Technique, Dispensing dye day -1, 3, 4°0, L Dispersion thread l 2.80 0.1. Dispense Blue 27 etc.

Oil-Soluble Dye 0, Polymer Bento Yellow 2.6.14.1921.
33.61. 0.1. Solvent orange l.

5.6.14.37.44.4B, 0. X, bent red 1.3.8.23.24.25.27゜30.4
9.81.82.83.84.100°109-12
1. 0.1. Solvent Violet 1.8.13.
14.21, 27. O, 1, Solvent Blue 2.11
, 12.2B, 35.36°55.73. O, 1, Solvent Green l, 3゜0, Engineering, Solvent Brown 3.5.20.37゜Ojl, Solvent Black 3.
5.22.23°123 etc.

Reactive dye 0.1. Reactive Yellow 1.2.7.17°22
, O, 1, Reactive Orange 1, 5.7° 14, O
, 1, Reactive Red 3.6.1"2゜a, 1.
Riff/? (Pupu #-2, '4.6.7.15゜19, O
,1,Reactive Green 7,O,I.

Reactive Black 1 etc.

Fluorescent brightener c, 1. Fluorescent brightening agent 2
4.84.85.91162.163゜164.167
．． 169.172, 174°175.176 etc.

In the present invention, one or more of the dyes exemplified above are dissolved in a suitable solvent at approximately 0.01 to 5 times 1 ttlJ to prepare a coating solution, and this coating solution is used to coat the target magnetic powder. Coating treatment is performed by dipping the magnetic powder or by spraying this treatment liquid onto the surface of the magnetic powder.

This is then carried out by heating and drying at a temperature ranging from room temperature to about 150°C.

Examples of solvents for dissolving dyes include alcohol solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ketone solvents, ether solvents, ester solvents, and water. For example, these are 1
Used as a seed or a mixed solvent of two or more types. The amount of dye to be coated is 0.02~
The content is desirably 2% by weight (preferably 0.05 to 1% by weight). If the amount of coating is too small, the antioxidant ability will deteriorate, while if it is too large, it will not only increase the cost, but also
Since the proportion of plastic as a binder is relatively reduced, it becomes difficult to increase the filling of magnetic powder from the viewpoint of fluidity.

In the present invention, magnetic powder is coated with a dye in this manner, and in this case, an organopolysiloxane compound may be used in combination if necessary.

According to this, the effect of imparting oxidation resistance by the coating treatment is further improved, and there is an advantage that a lubricity effect is also imparted during molding of the plastic magnet composition.

How to use organopolysiloxane compounds.

Either a method in which the dye is added to the treatment solution together with the dye, or a method in which coating treatment with the dye is followed by a coating treatment with the treatment solution containing the organopolysiloxane compound is possible. According to this method, the proportion of dye used can be reduced. can.

The organopolysiloxane compound used for the above purpose is not particularly limited to one type of molecular structure, and various modified organopolysiloxanes such as silicone oil, silicone rubber, silicone resin (silicone face), etc. As for the exemplified molecular weight, any one from low molecular weight to high molecular weight can be used.

When organopolysiloxane is added to the dye coating treatment solution, the amount of organopolysiloxane added is approximately 1 to 10 parts by weight per 1 part by weight of dye, and the surface treatment with organopolysiloxane is carried out after the dye coating treatment is completed. If you do.

The amount to be treated may be approximately 0.02 to 2% by weight based on the magnetic powder.

The plastic magnet composition according to the present invention is as follows.

It is obtained by mixing the coated magnetic powder and plastic, and the plastics used here include polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylate resin, etc., and so-called engineering plastics. For example, polyamide, polyphenylene sulfide, polyphenylene oxide, polyacetal, polyethylene terephthalate, polybutylene terephthalate.

Examples include polycarbonate.

According to the present invention, magnetic powder can be mixed with glass in an extremely high content, and the magnetic powder content in the composition can be increased to about 95% by weight.

In this regard, in the past, it has been difficult to increase the packing density of magnetic powder from the viewpoint of moldability and magnetic orientation, so it has been impossible to obtain plastic magnets with excellent magnetic properties.

Molding methods for obtaining plastic magnets include conventionally known methods such as injection molding and extrusion molding.

It may be formed by means such as compression molding, and the molding method itself is not limited.

According to the present invention, the following advantages can be obtained.

(1) High performance plastic magnets can be obtained at low cost.

(2) Since the magnetic powder is coated, it will not undergo oxidative deterioration or catch fire even if it comes into contact with air at high temperatures during molding, so a plastic magnet with extremely high magnetic properties can be obtained.

(3) Even if engineering plastics that require high-temperature molding such as 200°C or higher are used, highly filled molded products of magnetic powder can be molded by injection molding, extrusion molding, etc. without any inconvenience. It can be easily obtained by means.

This plastic magnet can withstand use under high temperatures, and its magnetic properties do not change (degrade) over time, making it highly reliable.

(4) Integral molding is simple, it can be easily molded into complex shapes, and the cost required for post-processing is significantly reduced.

(5) A plastic magnet with high performance radial anisotropy and radial multipolarity can be obtained in a container.

(6) The obtained plastic magnet exhibits uniform magnetic performance and has high impact resistance, so it can be used as a relay,
It is advantageous for use in buzzers, etc.

(7) As mentioned above, even if molded at high temperatures, it will not undergo oxidative deterioration and will not cause ignition, so safety is ensured in the production process, and it can be recycled and used without deteriorating performance. .

Next, reference examples and examples will be given.

Reference Example 1 Rare earth-iron-boron magnetic powder Nd, Fe, 8f3. (Particle size: 3μ by Fisher method) was weighed out. On the other hand, solvent solutions of various dyes shown in Table 1 (all concentrations 0.5% by weight) were prepared,
A predetermined amount of this was added to the weighed sample and stirred so that the entire sample was evenly moistened and adsorbed, then dried at 60°C to remove the solvent, and further heated at 110°C for 1 hour. The coating amount of the dye was as shown in the table.

In order to examine the oxidation resistance of the magnetic powder sample coated with dye in this manner, it was heated at 250° C. for 20 minutes in an open air heating furnace and the rate of weight change was calculated using the following formula. The results were as shown in Table 1.

w1 = Weight of weighing bottle w, = Weight of weighing bottle + sample W3 = Weight after coating and heating at 110°C for 1 hour W4 = = Weight after heating at 250°C for 20 minutes Results in Table 1 As can be seen from the figure, the weight increase due to oxidation was large in the case of the sample not coated with dye, whereas the increase in M amount was small in the sample coated with dye, indicating that the coating film imparted oxidation resistance. The effect is great.

Example 1 In a 1 ton beaker, rare earth-iron-boron magnetic powder N
d Fe B (particle size 3 μ by Fisher method) 15 71
1 Kf was weighed out, and 0.5% of the dye shown in Table 2 was added to it.
Add toluene solution to achieve the coating amount shown in the table.

The mixture was thoroughly stirred and mixed, and if necessary, toluene was added to moisten the whole, followed by drying at 60°C to volatilize the solvent, and further heat treatment at 110°C for 1 hour. however,
Experiment &6 to A8 in Table 2. AlO is added to 1% of various silicone compounds for magnetic powder coated with dye.
The place where the toluene solution is shown in the same table 5! ! Amount A was added to moisten the entire body, and the mixture was dried at 110° C. for 30 minutes.

440.1 g of each magnetic powder coated in this manner and 55.1 g of each magnetic powder coated with UBE Ny4in 12P-3014U (manufactured by Ube Industries, Ltd.). 'l and stearic acid amide 1.2 lI were weighed into a beaker, stirred at room temperature, and then heated using Brabender's S-300 with a jacket temperature of 200°C in a nitrogen gas atmosphere.
The mixture was stirred and granulated using an 0H type Myasa.

This granulated product is manufactured using Tanabe Kogyo Co., Ltd.'s fission field injection molding machine TL.
-50MGB was used to measure the ignitability when injected into the air and the magnetic properties of the molded product.

The results were as shown in Table 2.

Injection molding conditions Niji cylinder temperature (from hopper side) O+
= 170°C, C2 = 230°C - nozzle temperature 220°C.

Mold temperature: 90°C, screw rotation speed: 28 Orpm (setting at no load), orientation magnetic field: 20 kOe From the results in Table 2, if surface coating treatment was not performed, the injection into the air would cause instant ignition. However, it has been found that dye coating imparts remarkable oxidation resistance and suppresses the zero ignition phenomenon.

Furthermore, when the surface was treated with a silicone compound in addition to dye coating, a reduction in load (screw rotation increased) and an improvement in squareness were observed.

O silicone oil KF96: Shin-Etsu Chemical product name,
Dimethyl silicone oil 0 Silicone oil KP358: Shin-Etsu Chemical Co., Ltd. trade name, modified silicone oil Example 2 In the same manner as in Example 1, rare earth-iron-boron magnetic powder Nd1B' 618 B? were coated with dyes and silicone compounds. The magnetic powder and UBK nylon 12P-3014U were blended in the composition shown in Table 3, and the mixture was stirred, granulated, and molded under the same conditions as in Example 1. The results were as shown in Table 3.

In the conventional technology, the degree of filling of magnetic powder was 88% by weight, but in the present invention, it was possible to increase the degree of filling by 92.6% by weight, and therefore the magnetic properties were able to be significantly improved. In addition, in the case of the present invention, the appearance of the molded products was good in all cases.

Claims (1)

[Claims] 1. Compositional formula RM coated with plastic and dye
B (R in the formula is a rare earth element, 1M is an iron group YZ element, and I) L z , y and 2 represent atoms. However, 8≦X≦30.2≧2≦20.7=Zoo−x−
A patent claim in which R is a rare earth element mainly composed of Nd or Nd7 and 1M is Fe or an iron group element mainly composed of Fe in the composition formula RMB of a plastic magnet composition consisting of magnetic powder represented by z) Plastic magnet composition 3 according to item 1, coated with plastic, dye and organopolysiloxane Compositional formula RMB C2X, 7z where R is a rare earth element 1M is an iron group element; , y and 2 represent atoms, provided that 8≦X≦30.2≦2≦2
0.7-100-x-z)