JPH04157705A - Magnetic-material resin composite material - Google Patents

Abstract

PURPOSE:To obtain a magnetic-material resin composite material whose magnetic characteristic is high, whose surface smoothness, mechanical strength and dimensional stability are excellent and whose molding property and magnetic-field orientation property are excellent by a method wherein the following are contained in specific amounts: a rare earth-iron-nitrogen-based magnetic pulverulent body; a specific coupling agent; a thermoplastic resin; and a lubricant. CONSTITUTION:This magnetic-material resin composite material is constituted of the following: 70 to 95wt.% of a rare earthiron-nitrogen-based pulverulnent body; 0.01 to 5wt.% of a coupling agent which has one kind or two or more kinds of organic chains out of an amino group, an alkyl group, a >=3 C alkoxy group, a >=10 C phenoxy group, a methacrylic group, a sulfonyl group, a mercapto group, an ester bond, a phosphoric ester bond, a pyrophosphoric ester bond, a phosphorus ester bond, a urea bond and an amide bond and which contains at least one kind out of titanium and silicon; 3 to 30wt.% of a thermoplastic resin; and 0 to 5wt.% of a lubricant. The magnetic-material resin composite material is excellent in its molding property and its magnetic characteristic, and it is possible to obtain a bonded magnet whose dimensional stability and surface smoothness are extremely good.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a magnetic resin composite material that uses a rare earth-iron-nitrogen material and has excellent moldability and magnetic properties.

According to the present invention, a rare earth-iron-nitrogen bonded magnet having high magnetic properties with excellent surface smoothness, mechanical properties, and dimensional stability can be obtained.

[Conventional technology] Bonded magnets have better formability than sintered magnets,
It has attracted particular attention in recent years because it can be molded into complex shapes and integrally, is resistant to cracking and chipping, and has good dimensional accuracy, and its range of industrial applications is expanding.

Among them, the market for bonded magnets with high magnetic properties using rare earth magnetic materials such as Sm-Co and Nd-Fe-B is rapidly growing.

In addition to these rare earth magnetic materials, there are also rare earth magnetic materials.
An iron-nitrogen magnetic material was invented (Japanese Patent Application Laid-Open No. 2-57
683). This material is Sm-C.

Unlike Nd-Fe-B and Nd-Fe-B based materials, even fine powder of less than 10 μm in size has high magnetic properties.

If this material with small particle size is used, we can expect magnetic resin composite materials and their magnets with excellent surface smoothness and mechanical strength, and high magnetic properties.

However, since this material has a small particle size and a large specific surface area, when mixed with a resin, the molten material has a high viscosity, resulting in poor flowability and difficulty in molding, especially injection molding and extrusion molding. In order to obtain a bonded magnet with high magnetic properties, magnetic particles are magnetically oriented by applying an external magnetic field. However, if the viscosity of the melt is high, the magnetic field orientation becomes poor and the material exhibits its inherent high magnetic force. Can not.

Furthermore, since the particle size is small, it is easily oxidized during processing, resulting in significant deterioration of magnetic properties.

Therefore, it has high magnetic properties, surface smoothness, mechanical strength,
In order to obtain bonded magnets with excellent dimensional stability, rare earth -
There is a strong desire for a magnetic resin composite material that contains iron-nitrogen and has good flowability, moldability, and magnetic field orientation.

[Problems to be Solved by the Invention] The present invention uses a rare earth-iron-nitrogen magnetic material that has fine particles of 1 μm or less and has high magnetic properties to create a magnetic material with excellent formability and magnetic field orientation. The aim is to provide resin composite materials.

[Means for solving the problem] In order to obtain an excellent magnetic resin composite material using a rare earth-iron-nitrogen magnetic material that has high magnetic properties even with fine particles of 10 μm or less, a magnetic powder surface treatment method is proposed. As a result of extensive research into the affinity between surface treatment agents and resins, kneading methods, molding methods, and their combinations, we discovered a composition with low melt viscosity, excellent moldability, and magnetic orientation. The present invention has been accomplished. Note that the present invention exhibits similar effects on rare earth-iron-nitrogen particles having a particle size larger than 1 μm.

That is, the composition of the present invention is as follows: (1) 70 to 95% by weight of rare earth-iron-nitrogen magnetic powder, an amino group, an alkyl group, an alkoxy group having 3 or more carbon atoms, a phenoxy group having 10 or more carbon atoms, methacryl has an organic chain containing one or more of the group, sulfonyl group, mercapto group, ester bond, phosphate ester bond, pyrophosphate ester bond, phosphite bond, urea bond, amide bond, and titanium, 0.01 to 5% by weight of a coupling agent containing at least one type of silicone
It is a magnetic material-resin composite material characterized by comprising 3 to 39% by weight of a thermoplastic resin and 0 to 5% by weight of a lubricant.

More preferably, (2) the thermoplastic resin described in item (1) above is a resin containing one or more of polyamide, polyphenylene sulfide, polybutylene terephthalate, polyether ketone, and wholly aromatic polyester. Magnetic material resin composite material.

(3) The lubricant described in item (1) above is a magnetic resin composite material containing at least one of waxes, polysiloxanes, and fatty acid salts.

Furthermore, in order to manufacture this composite material, (4) the above (1)
It is preferable to add 0.05 to 20% by weight of the coupling agent described in item ). In addition, magnets using this material include (5) a bonded magnet characterized by being manufactured using the magnetic material resin composite material described in item <1) above, and (6) item (5) above. In the bonded magnet described in , the bonded magnet is obtained by injection molding, extrusion molding, compression molding, or flow molding.

First, rare earth-iron-nitrogen (Re-Pe-
N) The magnetic materials will be explained.

Rare earths (Re) include Y, La, Ce, and Pr.

Nd, Sm, Eu, Gd, Tb, Dy, Ho.

It is sufficient to include at least one of Er, Tm, Yb, and Lu, and therefore, a mixture of two or more rare earth elements such as missing metal and didymium may be used.

Although iron (Fe) is the basic composition of the present magnetic material that is responsible for ferromagnetism, 0.01 to 49 atomic percent of Fe can be replaced with Co.

It is important that the composition of the rare earth-iron-nitrogen magnetic material be in a composition range that contains at least rare earth, iron, and nitrogen, and exhibits ferromagnetism. Furthermore, in the present invention, in order to obtain high magnetic properties, Re should be contained in an amount of 5 to 20 atomic %, and Fe should be contained in an amount of 40 to 20 atomic %.
It is preferable that the composition range is 85 at%, N is in the composition range of 10 to 25 at%, and further hydrogen (H) is 0.01 to 5 at%,
Oxygen (0) may be contained in an amount of 0.0 L to 10 atomic %.

In addition, Li, Na, Mg, Ca, Sr.

Ba, Ti, Zr, Hf, V, Nb, Ta.

Cr, Mo, W, Mn, Pd, Cu, Ag.

Zn, B, AI, Ga, In, C, Si, Ge.

Sn, Pb, Bi elements, and oxides, fluorides, carbides, nitrides, hydrides, carbonates of these elements and Re,
It is also possible to contain 0.1 to 40% by weight of at least one of sulfates, silicates, chlorides, and nitrates (component M).

The content of the rare earth-iron-nitrogen magnetic material in the magnetic resin composite material of the present invention needs to be 70 to 95% by weight. When the content is less than 70% by weight, the magnetization is low and the practicality as a permanent magnet is low. Moreover, if it exceeds 93% by weight, the flowability deteriorates, and although the magnetic properties become high, the material becomes inferior in moldability. 95
If it exceeds % by weight, the flowability will be extremely poor and it cannot be used for injection molding applications. The average particle size of the rare earth-iron-nitrogen magnetic powder is preferably in the range of 0.1 to 30 μm. When producing a material that is particularly excellent in moldability and surface smoothness, which are the characteristics of the composite magnetic material of the present invention,
Preferably, the average particle size is 1-10 μl.

As coupling agents in the present invention, isopropyltriisostearoyl titanate, isopropyltri(
N-aminoethyl-aminoethyl) titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraoctyl bis(ditridecyl phosphite) titanate, isopropyl trio Cutanoyl titanate, Isopropyl tridodecylbenzenesulfonyl titanate, Ibrovir tri(dioctyl phosphate) titanate, Bis(dioctyl pyrophosphate) ethylene titanate, Isopropyl dimethacrylylisostearoyl titanate, Tetra(2,2-diallyloxymethyl-1-butyl) bis( Titanium-based coupling agents such as ditridecyl phosphite) titanate and isopropyl tricumylphenyl titanate, N-β
-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-
Mercaptopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-(3-)ethoxysilylprobyl)urea,
Examples include coupling agents containing silicon such as methyltrimethoxysilane, octadecyltriethoxysilane, and perfluoroalkyltrimethoxysilanes.

The organic chains of the above coupling agents include amino groups such as N-aminoethyl-aminoethyl groups, alkyl groups having 1 to 30 carbon atoms such as methyl groups and octadecyl groups, and 3 carbon atoms such as isopropoxy groups and butoxy groups. 10 or more and 4 or more carbon atoms such as an alkoxy group or a cumyl phenyl group having 15 or more
0 or less phenoxy group, methacrylic group having 4 to 80 carbon atoms such as γ-methacryloxypropyl group, sulfonyl group such as tridodecylbenzenesulfonyl group, mercapto group such as γ-mercaptopropyl group, isostearoyl group and octanoyl group Ester ' bonds included in octyl phosphate groups, pyrophosphate bonds included in octyl pyrophosphate groups, phosphite bonds included in octyl phosphite groups, urea bonds, etc. , it is necessary to have one or more types of amide bonds.

These titanium-based and silicone-based coupling agents can be used alone or in combination of two or more, but in general, adding a large amount of titanium-based coupling agents improves flowability and moldability.
As a result, the orientation of the magnetic powder is improved, resulting in a material with excellent magnetic properties. On the other hand, when a silicone-based coupling agent is used, the effect of increasing mechanical strength can be obtained, but the flowability is generally deteriorated. In order to take advantage of the advantages of both, by adding 1 to 50% by weight of a silicon-based coupling agent to the titanium-based material, a material having excellent magnetic properties, mechanical properties, and moldability can be obtained.

In addition to titanium-based and silicon-based coupling agents,
Coupling agents such as aluminum-based, zirconium-based, chromium-based, iron-based, and tin-based coupling agents such as acetalkoxyaluminum diisopropylate can also be added. In this case, it must contain at least 0.01% by weight of either titanium or silicone, and the total content must not exceed 5% by weight.

The total amount of coupling agent added is determined by the particle size, particle shape, and specific surface area of the magnetic powder, but since rare earth-iron-nitrogen materials mainly contain powder of several micrometers, it exceeds 5% by weight. This is not preferable because as the content increases, the moldability does not improve and the magnetic properties and mechanical strength decrease. When the content is less than 0.01% by weight, almost no effect of addition is observed.

Coupling agents generally combine hydrophilic functional groups such as alkoxy groups such as methoxy, ethoxy, isopropoxy, butoxy with high affinity for magnetic powder, and amino, diamino,
It is an organic metal with a backbone of methacryl, alkyl, alkoxy, ester, sulfonyl, etc., and has functional groups that have a high affinity with resins. However, some organic metals containing only an alkoxy group and those without an alkoxy group are also effective.

The group of force/twisting agents that are most effective in the present invention are organic metals whose hydrophilic functional groups drop off and form chemical bonds with the magnetic powder surface, or which interact with the magnetic powder surface through adsorption, coordination, etc. . For example, a titanium-based coupling agent having an isopropoxy group substitutes with the hydroxyl group present on the surface of the rare earth-iron-nitrogen magnetic powder, and a reaction occurs to produce isopropyl alcohol.

In this case, the weight percentage of the coupling agent finally contained in the magnetic material resin composite material is less than the amount added,
At most, 80% of the added amount may be lost. The 310.01 to 5% by weight of the coupling agent defined in the present invention is the amount remaining in the magnetic resin composite material. The amount added must be 0.05 to 20% by weight, taking into account losses during processes such as mixing and kneading, and detachment of organic chains.

Further, the selection of the coupling agent is also influenced by its affinity and compatibility with the resin. For example, in the case of highly polar polyamide resins such as 6-nylon and B-6-nylon, coupling agents having a diamino group, an amino group, an amide bond, or an ester bond are most preferred. - A highly polar coupling agent is used for a highly polar resin in the membrane, and a less polar coupling agent is used for a less polar resin. Compatibility can be estimated by comparing solubility parameter values, but in reality, the optimal combination is selected by conducting kneading tests, various flowability tests, and photographs showing magnetic properties and dispersibility.

The effect of the coupling agent of the present invention is not only to improve the compatibility between the rare earth-iron-nitrogen magnetic powder, which originally has low affinity, and the organic compound resin, but also to improve the molding processability.
This improves the orientation in a magnetic field and contributes to improving the squareness ratio and magnetization. Furthermore, by coating the metal surface with a coupling agent or resin to reduce voids near the magnetic powder, it has the effect of suppressing deterioration of magnetic properties such as oxidation and increasing mechanical strength.

However, coupling agents that have organic chains that are easily polymerized, such as vinyl groups, glycidyl groups, and acrylic groups, and hydrophilic groups, such as methoxy groups and ethoxy groups, cannot be used with rare earth-iron-nitrogen magnetic materials. This is not preferable because it has little effect on improving the conformability of the plastic resin and actually worsens molding processability.

Thermoplastic resins used in the present invention include polyamide resins such as 12-nylon, 6-nylon, and 6.6-nylon, polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, and polyvinyl Alcohol, polyvinyl resins such as ethylene-vinyl acetate copolymer, acrylic resins such as ethylene-ethyl acrylate copolymer, polymethyl methacrylate, acrylonitrile resins such as polyacrylonitrile, acrylonitrile/butadiene/styrene copolymer, etc. In addition to resins and polyurethane resins, polyacetal, polycarbonate, polyimide, polysulfone, polybutylene terephthalate, polyethylene terephthalate, polyarylate, polyphenylene oxide, polyether sulfone, poly, phenyl sulfide, polyamideimide, polyoxybenzylene, polyether ketone, etc. It is possible to use one or more of the following engineering plastics, liquid crystal resins such as polyaramid, fully aromatic polyester, and polyester amide, and thermoplastic elastomers such as polyamide elastomer, polyester elastomer, and polyurethane elastomer. It is.

For applications where heat resistance is particularly required, 6.6-nylon, polybutylene terephthalate, polyphenylsulfide,
Engineering plastics such as polyetherketone and wholly aromatic polyester, and liquid crystal resins are preferred.

In addition, mechanical strength, elasticity, dimensional accuracy, oil resistance, water resistance,
Various resins are selected depending on required performance such as chemical resistance and weather resistance.

Among the thermoplastic resins used in the present invention, 12-nylon, 6-nylon, which have a good balance of performance such as toughness, dimensional accuracy, cost, and moldability, and are compatible with rare earth-iron-nitrogen magnetic materials, Polyamide resins such as 6.6-nylon are particularly preferred components.

The content of the thermoplastic resin of the present invention needs to be in the range of 3 to 30% by weight. If it is less than 3% by weight, the flowability becomes extremely poor and it cannot be used for injection molding applications. If the amount is more than 30% by weight, the magnetization will be low and the practical use as a permanent magnet will be low.

The lubricant used in the present invention includes waxes such as paraffin wax, liquid paraffin, polyethylene wax, polypropylene wax, ester wax, carnauba, and micro wax, fatty acids such as stearic acid, 12-oxystearic acid, and lauric acid, and zinc stearate. , calcium stearate, barium stearate,
Aluminum stearate, magnesium stearate, zinc laurate, calcium laurate, zinc ricinoleate, calcium ricinoleate, zinc 2-ethylhexoate, etc., stearic acid amide, hydroxystearic acid amide, valmitic acid amide, etc. fatty acid amides, fatty acid esters such as butyl stearate, alcohols such as ethylene glycol and stearyl alcohol, silicone oils, silicone greases, silicone resins, polysiloxanes such as polysilane coupling agents, Sia N4, SICSMgO, Al103,
Tic.

Examples include inorganic compound powder such as 5b20z.

One or more of these lubricants are used, and at least one of waxes, polysiloxanes, and fatty acid salts is used.
When seeds are included, molding processability is improved, which is particularly preferable.

A lubricant is not necessarily necessary as long as the amount of magnetic powder does not exceed 90% by weight, but it may be necessary depending on the type of resin if the amount is 90 to 93% by weight. If the content exceeds 93% by weight, a lubricant becomes essential. In this case, the content is preferably 0.1% by weight or more. If the content of the lubricant exceeds 5% by weight, the plasticizing effect increases, resulting in problems such as decreased mechanical strength, bleed-out, and decreased magnetization, which is not preferable.

In addition, inorganic compound powder such as Si3N+ is added in advance as the above-mentioned M component in the rare earth-iron-nitrogen magnetic powder in an amount of 0.1 to
It may be added in an amount of 40% by weight. In this case, the amount of inorganic compound powder, including the amount used as the M component, in the magnetic material resin composite material of the present invention is 0.07 to 4.
It can be contained in a range of 3% by weight.

In addition, in order to mainly improve the heat resistance of the thermoplastic resin, the magnetic side resin composite material of the present invention contains stabilizers such as heat-resistant anti-aging agents and antioxidants at each stage of mixing, cross-wiring, molding, or It can be added to the thermoplastic resin component in advance.

As the heat-resistant anti-aging agent and heat-resistant stabilizer, for example, N
, N'-hexamethylene-bis(3,5-di-tert-butyl-hydroxycinnamic acid amide), 4,4'-bis(2
, 6-di-tert-butylphenol), various hindered phenols such as 2,2°-methylenebis(4-ethyl-6-tert-butylphenol), N,N'-bis(β-
naphthyl)-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, poly(2,2,4-
Examples include aromatic amines such as trimethyl-1,2-dihydroquinoline, copper salts such as copper chloride and copper iodide, sulfur compounds such as dilaurylthiodipropionate, and phosphorus compounds.

Furthermore, additives such as ultraviolet absorbers, antistatic agents, colorants, and fillers, or fibrils such as silica and whiskers may be added to the magnetic material resin composite material in the present invention, if necessary.

Next, a method for manufacturing the magnetic resin composite material of the present invention will be described, but the method is not particularly limited to the manufacturing method described below.

(1) Mixing process This is a process in which a coupling agent is mixed with rare earth-iron-nitrogen magnetic powder, which usually has an average particle diameter of about several microns. At this time, in order to homogeneously mix the magnetic powder and the coupling agent, it is desirable to dissolve the coupling agent in advance in a diluent such as an organic solvent or an aqueous solvent.

The diluent is selected to be compatible with the coupling agent used.

For example, in the case of isopropyl tri(N-aminoethyl-aminoethyl) titanate, an alcohol solvent is preferably used as the diluent, and in the case of isopropyl triisostearoyl titanate, a hydrocarbon solvent is preferably used as the diluent.

The mixer is not particularly limited, and examples thereof include a ribbon mixer, a V-type mixer, a rotary mixer, a Henschel mixer, a flash mixer, a Nauta mixer, a tumbler, and the like.

If a mixer with a large shear such as a Henschel mixer is used, it is possible to sufficiently mix the coupling agent and magnetic powder without dissolving it in a diluent.

Also effective is a method of adding and mixing using a pulverizer such as a rotary ball mill, vibrating ball mill, planetary ball mill, wet mill, jet mill, 1 mm mill, or cutter mill.

When mixing using a diluent, it is effective to stir and mix, collect the diluent, and perform heat treatment to cause the coupling agent to sufficiently react on the surface of the magnetic powder. The temperature is preferably 250° C. or less, and may be under normal pressure, reduced pressure, or increased pressure, but when the diluent is recovered at the same time as the heat treatment, the temperature is preferably below normal pressure. The atmosphere is atmospheric, but
When the temperature exceeds 100° C., it is preferable to use an inert gas such as nitrogen gas, argon gas, or helium gas. Even during stirring and mixing, the reaction of the coupling agent may occur on the surface of the magnetic powder.

In particular, when mixing without using a diluent, it is desirable to raise the temperature during stirring and mixing to cause the coupling agent to react. or,
It is also possible to advance the coupling reaction using the heat of stirring.

It is more preferable to add a lubricant such as a fatty acid, a fatty acid salt, or a polysiloxane containing an alkoxy group during the mixing step.

Also in this case, more homogeneous mixing can be achieved by dissolving in an organic solvent or an aqueous solvent.

Adding the thermoplastic resin at the same time during the mixing process is effective for more homogeneous mixing.

Of course, after homogeneously mixing the magnetic powder and the coupling agent, it is also possible to mix the thermoplastic resin or the thermoplastic resin dissolved in a solvent. The thermoplastic resin may be in any form such as pellets, beads, powder, paste, etc., but from the viewpoint of improving the homogeneity of the mixture, a form with fine particles is desirable.

(2) Kneading process The mixed magnetic powder, coupling agent, thermoplastic resin, and lubricant are mixed in a batch kneader, Banbury mixer, Henschel mixer, helical rotor, roll, and single-screw extruder.
This is a process of kneading the thermoplastic resin while melting it in a temperature range of 50 to 400°C using a twin-screw extruder or the like.

The crosstalk temperature is selected in a temperature range where the thermoplastic resin melts and does not decompose.

The kneaded material can be extruded onto strands or sheets, or cut into cylindrical,
Grind into rice grains, powder, irregular chips, etc. It is also possible to mix and add a lubricant before, during or after grinding. For example, it is also possible to tamp a fatty acid salt with the pellet and sprinkle it on the surface of the pellet.

(3) Molding process When producing a bonded magnet from the magnetic resin composite material obtained in the present invention, a molding process is further performed.

Among them, a method for producing a bonded magnet with high magnetic properties includes a method in which a pellet is melted and subjected to injection molding, extrusion molding, compression molding, or blow molding while applying a magnetic field. In particular, injection molding produces bonded magnets with excellent surface smoothness and magnetic properties.

The compact is usually further magnetized to improve its performance as a permanent magnet. Magnetization is performed by a commonly used method, such as an electromagnet that generates a static magnetic field or a capacitor magnetizer that generates a pulsed magnetic field. The magnetic field strength for sufficient magnetization is preferably 15 koe or more,
More preferably, it is 30 kOe or more.

By the method exemplified above, the magnetic resin composite material and bonded magnet of the present invention can be produced.

[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1 Sas, 4 Fete, 6N 1 with an average particle size of 3 μ-
3. A solution of 4 g of aH1,5049 magnetic powder 1B and 3.28 g of isopropyltri(N-aminoethyl-aminoethyl) titanate dissolved in an alcoholic diluent was stirred for 3 minutes in a mixer, and then 18. 2g was added and stirred for 2 minutes. Then 1O
The diluent was recovered by heating at 120° C. for 30 minutes.

A mixture of the surface-treated magnetic powder and 12-nylon was charged into a batch kneader with an internal volume of 40 cc, and heated to 260°C.
After kneading for 20 minutes at
It was cut into a size of m.

Table 1 shows the magnetic properties and melt viscosity of this pellet, as well as the results of visual inspection of the kneaded product in a spiral flow test. however,
The evaluation method is as follows.

(1) Magnetic properties Approximately 0.1 g of pellets that are not oriented in a magnetic field are heated at room temperature for 60 minutes.
After pulse magnetization at kOe, a vibrating sample magnetometer (VSM)
). Materials with excellent magnetic properties have saturation magnetization (Isi-g -') and intrinsic coercive force (0°e).
is high.

(2) Using a melt viscosity capillary flow characteristic tester (Cabilograph),
Measurements were made at 80°C with a shear rate in the range of 1.5 to 7608"1. Materials with good flowability have melt viscosity (NS-m-
2) is low.

(3) Spiral flow test Using an injection molding machine with a screw diameter of 12++v in a spiral spiral flow mold with a flow path length of 2Qc-・, a diameter of the outermost periphery of 5.5cm, and a flow path width of 0.4c■, the injection temperature was 28
The material was driven at 5° C. and the mold temperature was room temperature, and the length of the material flowing was measured. Materials with good flowability have a long spiral flow length (cS).

(4) Visual inspection of kneaded product The degree of kneading and discoloration in a twin-roller kneader was visually evaluated on the following 4 and 3 scales.

Kneading: A soft, B slightly soft, C hard, D very hard Discoloration: A absent, B slightly present, C present Examples 1 to 4 and Comparative Example 1.2 show the effect of the presence or absence of coupling agent and the type. This shows the difference.

Examples 2 and 3 Bullets were produced in the same manner as in Example 1, except that the coupling agent was changed to the substance shown in Table 1. The results are shown in Table 1.

Example 4 A pellet was prepared in the same manner as in Example 1 except that isopropyl triisostearoyl titanate was used as the coupling agent and cyclohexane was used as the diluent. Comparative Example 1 A pellet was prepared in the same manner as in Example 1 except that no coupling agent was added. was created. The results are shown in Table 1.

Comparative Example 2 Mixing and kneading were carried out in the same manner as in Example 1 except that vinyltriethoxysilane was used as a coupling agent. During mixing, large torque was applied to the rollers, making it impossible to mix. The results are shown in Table 1.

Examples 1 and 5 to 7 show differences in effects depending on the presence or absence and type of lubricant.

Examples 5 to 7 Bullets were produced in the same manner as in Example 1, except that 1.64 g of the lubricant shown in Table 1 was added in the mixing step. The results are shown in Table 1.

Examples 1 and 8 to 9 show the difference in effect when the amount of coupling agent is changed.

Examples 8 and 9 Bullets were produced in the same manner as in Example 1 except that the weight of the coupling agent was changed to 8.20 g and 0.328 g. The results are shown in Table 1.

Next, Examples 10 to 11 and Example 1 show differences in effects depending on the type of thermoplastic resin.

Example 10 Pellets were produced in the same manner as in Example 1 except that 6-nylon was added instead of 12-nylon. The results are shown in Table 2.

Example 11 Pellets were produced in the same manner as in Example 1, except that 6,6-nylon was added instead of 12-nylon and kneading was carried out at a mixing temperature of 280°C. The results are shown in Table 2.

The following Examples 1'2 and 1 show the difference in effect when the amount of thermoplastic resin is changed. Second result
Shown in the table.

Example 12 Pellets were produced in the same manner as in Example 1 except that the amount of 12-nylon was changed to 14.3 g. The results are shown in Table 2.

Example 13 Amount of magnetic powder: 120 g, isopropyl tri(N-aminoethyl-aminoethyl) titanate: 3.60 g.

Using 21.2 g of 12-nylon, cross-wire was carried out in the same manner as in Example 1, and this operation was repeated to produce a pellet weighing about 2 kg. This pellet was subjected to a spiral flow test, and the average CS was 19CS.

Next, the pellet was heated to an injection temperature of 285°C and a mold temperature of 9[].
'C1 injection 8 pressure 1 ton/cm', magnetic field 15kOe
, injection molded under the conditions of mold clamping force of 20 tons, − side 10+
Three types of test pieces were prepared: a cube of +v, a disk of 15 φ x 5 ms thick, and a ring of wall thickness lag x outer diameter 20 sm x Bsi width.

The appearance of these molded bodies was clean, shiny, and beautiful, with dimensional variations of ±0.1% or less, and average surface roughness of 0.07 μm or less.

The magnetic properties of the cubic test piece are shown in Table 3.

Example 14 The coupling agent was 2.95 g of isopropyl tri(N-aminoethyl-aminoethyl) titanate.

Mixing was carried out in the same manner as in Example 1, except that 0.33 g of N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane was used, and this operation was repeated to produce a pellet of about 2 kg.

Next, the pellets were injection molded in the same manner as in Example 13, and three types of pellets were produced in the same manner.

The appearance of these molded bodies was beautiful, and the dimensional variation and surface smoothness were equivalent to those of Example 13.

Further, when the cross section of the molded body was polished and an SEM photograph was taken, it was observed that the magnetic powder was uniformly dispersed in the resin binder, and no voids were observed.

The magnetic properties of the 10 m cube test piece are shown in Table 3.

Comparative Example 3 Kneading was carried out in the same manner as in Example 1 except that γ-glycidoxypropyltrimethoxysilane was used as the coupling agent, and this operation was repeated to produce a pellet of about 2 kg.

Next, the pellet was injection molded in the same manner as in Example 13, but it was not possible to produce a molded product in the shape of a mold due to poor flowability. The results are shown in Table 3.

Example 15 From the cubic test piece obtained in Example 14, 10X5X
Cut out a 2av rectangular parallelepiped and place it in 150” C1 atmosphere.
It was left for 0 hours. As a result of this durability test, residual magnetic flux density (Br), intrinsic magnetic force (lHc), maximum energy product [
(BH)Ilax] retention rates were 99% and 10%, respectively.
They were 0% and 100%.

Examples 16-19 Example 1 except that the coupling agent and thermoplastic phase duck fat shown in Table 4 were used in the amounts shown in Table 4.
The mixture was kneaded and injection molded in the same manner as in Step 3.

However, the crosstalk temperature was 295°C and the injection temperature was 300"C. Also, the injection molded test piece was a cube with a side of LOSm, and the variation in dimensions and surface smoothness were on the same level as in Example 13. .

Their magnetic properties are shown in Table 4.

Example 20 S18.5 Fe71.2N13 with average particle size of 2.2 μm
．． 5.HO magnetic powder was kneaded in the same manner as in Example 8, and injection molding was performed in the same manner as in Example 14.

The injection molded test piece is a cube with sides of 10 cm. The appearance was very beautiful, there was no shrinkage, and the mechanical strength was sufficiently strong. The magnetic properties are shown in Table 5.

Comparative Example 4 Kneading and injection molding were performed in the same manner as in Example 20 without using a coupling agent.

The injection-molded test piece is a cube with sides of 10 cm. The exterior was uneven in color and some stains were visible. In addition, it was extremely brittle and had only the mechanical strength to break if dropped from a height of 11 on concrete. The magnetic properties are shown in Table 5.

Table 5 1: Comparative Example 4 [Effects of the Invention] As explained above, according to the present invention, no special process was required. A magnetic resin composite material with excellent moldability and magnetic properties can be provided, and a bonded magnet with extremely good dimensional stability and surface smoothness can be provided.

208 November 1990 Commissioner of the Japan Patent Office Satoshi Uematsu 1, Indication of the case Patent Application No. 281913 of 1990 2, Name of the invention Magnetic material resin composite material 3, Person making the amendment Case and Relationship Patent applicant name (008) Asahi Kasei Kogyo Co., Ltd. 4, Agent 107 (telephone 586-8854) Address 4-13-5 Akasaka, Minato-ku, Tokyo (1) Page 2, line 16 of the specification Correct "Tokkai Akira" to "Tokkai Hei".

(2) Correct "flow molding" in lines 5 and 6 of page 6 to "blow molding".

(3) Correct "ferromagnetism" in line 19 to "hard magnetism."

(4) "Polyphenylsulfide" on page xe, lines 6-7 is corrected to "polyphenylene sulfide."

(5) “Correct 1m1J to remuJ” on page 26, line 7.

(6) Insert the following phrase between page 27, line 18 and line 19.

"... was produced. The results are shown in Table 1." (
7) Insert "j13" before "composition of magnetic powder" in the bottom line of Table 1 on page 29.

(8) Correct the unit of intrinsic coercive force, rKOeJ, in the 10th column from the left in the first column of Table 2 on page 31, to rkoeJ.

Claims (1)

[Claims] (1) 70 to 95% by weight of rare earth-iron-nitrogen magnetic powder, amino group, alkyl group, alkoxy group with 3 or more carbon atoms, phenoxy group with 10 or more carbon atoms, methacrylic group, sulfonyl group, mercapto group, ester Coupling that has an organic chain containing one or more of the following: bond, phosphate ester bond, pyrophosphate ester bond, phosphite bond, urea bond, amide bond, and at least one of titanium and silicon. 0.01 to 5% by weight of agent, 3 to 30% by weight of thermoplastic resin, and 0 to 5% by weight of lubricant.
A magnetic resin composite material comprising: