JP2895684B2 - Method for producing Ni-Fe alloy core - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a soft magnetic Ni--Fe
In connection with the improvement of the method of manufacturing cores such as wound cores and laminated cores of base alloys, the decomposition products are coated on the surface of the alloy ribbon and gelled to form an interlayer insulating film. After machining, the temperature is raised at a predetermined rate. The present invention also relates to a method for producing a Ni—Fe alloy core in which heat treatment is performed at a constant temperature to remove organic substances and prevent deterioration of magnetic properties.

[0002]

2. Description of the Related Art Soft magnetic Ni--Fe alloys have a high magnetic permeability, and thin ribbons thereof are used in large quantities as core materials mainly for weak electricity. Conventionally, a Ni-Fe-based alloy is generally cut into a coil having a final width by slitting a wide and thin coil, and then winding or punching, further bending, drawing, or the like to obtain a final shape. 130
It is heated to a temperature of 0 ° C. and subjected to magnetic annealing to remove internal strain and impurities in the ribbon, and is incorporated in various devices as a magnetic core material.

When the above-mentioned Ni-Fe alloy core is manufactured, an AC magnetic characteristic can be improved by providing an interlayer insulating film between the Ni-Fe alloy ribbons. Therefore, it is essential to form a coating.

[0004] Conventionally, in order to improve the interlayer insulation and corrosion resistance of a Ni-Fe alloy ribbon, the surface of the Ni-Fe alloy ribbon is coated with Al.
There is known a method in which metal oxide fine powder such as ₂ O ₃ or MgO is dispersed in a solvent and applied, or a resin is coated.

[0005]

In the method in which the metal oxide fine powder is dispersed in a solvent and applied, the adhesion of the formed film is poor. In the method of coating the resin, the heat resistance temperature of the resin is low. In this case, there is a problem that the ribbon is burned, and it is difficult to decompose and remove the organic matter in the resin, thereby deteriorating the magnetic characteristics of the Ni—Fe alloy ribbon.

In view of the above, a method has been proposed in which an Ni—Fe-based alloy ribbon surface is coated with a coating made of an organometallic compound having at least one of a metal alkoxide group or an alkoxyl group as an insulating coating (JP-A-63-121670). Have been.

[0007] However, the method of coating a coating made of an organometallic compound is to hydrolyze the organometallic compound coated on the surface of the ribbon, and to dry the obtained decomposition product sol at 400 ° C or lower to form a gel. after ized, order to Ni-Fe-based alloy ribbon by being magnetic annealing, after drying process during the coating remains organic matter, and syntan of the organic material in the core during magnetic annealing, magnetic properties There was a problem of inferiority.

According to the present invention, there is provided a method for coating a thin-film surface with a coating made of an organometallic compound as an insulating coating, wherein an organic substance does not remain in the coating and a magnetic property of the Ni-Fe alloy core can be prevented from deteriorating. The purpose is to provide a manufacturing method.

[0009]

Means for Solving the Problems The present inventors have conducted various studies on methods for preventing organic substances from remaining in an insulating film, and as a result,
Between the drying step and the magnetic annealing step in the manufacturing process of the Ni—Fe alloy core, the Ni—Fe alloy obtained by heating at a specific temperature rising rate at a specific temperature and performing heat treatment at a specific temperature. magnetic properties after magnetic annealing of the alloy core is a single stage
Was found that the improvement on the improvement.

According to the present invention, there is provided an organometallic compound having at least one metal alkoxyl group or alkoxide group adhered to at least one principal surface of a Ni-Fe alloy ribbon having a clean surface cut to a final width. After being hydrolyzed and coated with the decomposition product, after forming an interlayer insulating film having a film thickness of 0.3 μm to 30 μm gelled by drying, winding or punching into a predetermined shape and dimensions is performed. Heating rate 1 ° C / 200 ° C to 600 ° C
This is a method for producing a Ni—Fe-based alloy core, characterized in that the temperature is raised at a rate of 5 to 5 ° C./min, heat treatment is performed at 600 ° C. for at least one hour, and magnetic annealing is performed.

In the present invention, the Ni-Fe alloy may have any known composition. However, in order to produce a core material having a high magnetic permeability, a Ni-Fe alloy containing 40% to 90% Ni is preferable. Mo, Cu, Co, S as elements
one or two of i, Cr, Mn, B, V, Nb, Ti, etc.
It may contain more than one species. The dimensions of the Ni-Fe alloy ribbon may be 0.01 mm to 5 mm in thickness, and the width of the sheet may be appropriately selected depending on the final product.

In the present invention, the organometallic compound used for the interlayer insulating film covering at least one principal surface of the ribbon having a clean surface slit to the final width includes:
There is at least one selected from the group of organometallic compounds having one or more metal alkoxyl groups or alkoxide groups represented by the following general chemical formulas 1 and 2. Also,
The reaction formula in which the organometallic compound is hydrolyzed, substituted with an alkoxide group or a hydroxyl group to change into a decomposition product sol, and then dried, that is, gelled by dehydration condensation, is expressed by the following three formulas.
It is expressed by Equation 4.

[0013]

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In the above formula, M represents a metal atom excluding a radioactive element or a metalloid atom. R has 1 to 1 carbon atoms.
The alkyl group preferably represents an alkyl group, preferably an alkoxyl group or a phenyl group, and the alkyl group is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group or the like.

The following are examples of the organic compound of the metal alkoxyl group. Aluminum ethylate Al (OC ₂ H ₅ ) ₃ aluminum isopropylate Al (OCH (CH
₃ ) ₂ ] mono Sec butoxy aluminum propylate Al [OCH (CH ₃ ) ₂ ] ₂ [OCH (CH ₃ )] (CH
₂ CH ₃ ) Aluminum Iptoxy Al (OC ₄ H ₉ ) ₃ Magnesium Sotylate Mg (OCH ₂ ) Magnesium Ethylate Mg (OC ₂ H ₅ ) ₂

The organic compounds of the alkoxide group include the following. Aluminum chelate compound

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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In the present invention, the organometallic compounds may be used alone or in combination. The organometallic compound is dissolved in a solvent such as N-hexane, benzene, trichlene, or isopropanol at a concentration of 5 wt% to 10 wt%.
However, if the concentration is less than 5 wt%, the coating thickness is small and the insulation resistance value is small, and if the concentration exceeds 10 wt%, the coating is too thick and the insulation resistance value is saturated, which is not preferable in terms of cost.

In the present invention, as a method of coating the surface of the Ni—Fe alloy ribbon with the organic metal compound, as described above, the concentration of the organic metal compound in the organic solvent is 5 wt%.
After dissolution of 10 wt% to 10 wt%, N ₂
After shielding the air with a gas or the like and immersing the ribbon in an organic solvent, the organometallic compound is hydrolyzed, and the alkoxide group is replaced with a hydroxyl group. The film is dried (dehydrated and condensed) at 400 ° C. or lower to form a film having a thickness of 0.3 μm to 30 μm. Further, in the present invention, as a method of coating the surface of the ribbon with the organometallic compound, in addition to the dipping method, a roll coater,
A thin film surface can be uniformly coated with a film by a method such as a dave coater or a curtain flow coater. Also,
If the thickness is less than 0.3 μm, the effect as a magnetic annealing separator cannot be achieved, and if it exceeds 30 μm, there is a problem that the space factor is impaired.

In the present invention, the organic solvent evaporates with the gelation of the decomposition product sol obtained by hydrolysis by drying, but the drying is preferably carried out continuously by short-time heating at 400 ° C. or less, The film formed by the gelation of the above decomposition products is mostly oxides, but hydroxides, hydrates, and one part of organic solvent remain, and the organic matter in this organic solvent is The magnetic annealing significantly deteriorates the magnetic properties of the Ni—Fe alloy ribbon, so that after the drying treatment, the rate of temperature rise between 200 ° C. and 600 ° C. is 1 ° C./min.
It is important to raise the temperature in minutes and perform heat treatment at 600 ° C. for at least one hour.

The reasons for limiting the heat treatment conditions are as follows. If the heating temperature is lower than 200 ° C., the organic matter is not decomposed (combusted), so it is difficult to remove the organic matter.
When the temperature exceeds ℃, organic matter is decomposed (burned) and removed, but there is a problem that the reaction is violent and the organic matter remains. If the rate of temperature rise is less than 1 ° C./min, it is effective for decomposition removal, but the temperature rise time is long and uneconomical, and if it exceeds 5 ° C./min, the decomposition (combustion) of organic matter is severe and complete removal is difficult. Is not preferred. If the heat treatment time is less than 1 hour, it is difficult to remove organic substances, and the preferable heat treatment time is 1 hour ^■ 5 hours.

[0027]

The present invention relates to a method for coating a thin film of an organic metal oxide as an insulating film on a surface of a thin ribbon of a Ni--Fe alloy core, wherein a specific temperature range is specified between a drying step and a magnetic annealing step in a specific temperature range. By heating at a specific temperature, an organic material is not left in the insulating film, an extremely thin film is uniformly formed, and has a sufficient interlayer insulating property, adhesion, corrosion resistance, Excellent heat resistance,
As a core material, a stable Ni—Fe alloy core having excellent magnetic properties even when molded can be provided.

[0028]

【Example】

Example 1 F containing 77.9% of Ni, 4.6% of Mo, and 3.3% of Cu
A 0.05 mm thick Ni-Fe-based alloy ribbon made of e-alloy is slit to a final width of 50 mm, and is punched out into a ring shape having an outer diameter of 45 mm x an inner diameter of 33 mm x a thickness of 0.05 mm by press punching. It was degreased and washed with Triclean. The obtained ring core was made of 10% Mg (OCH) ₂ N
-After immersion in a hexane solution, the solvent is evaporated, and a mixed sol composed of a hydrolysis product of Mg hydroxide, Mg hydrate, and Mg oxide is dried at 350 ° C., and the gel coating is dehydrated and condensed. A 0.5 μm / sheet film-formed ring core was obtained.
Thereafter, 200 ° C. to 600 was heated at a heating rate of 2 ° C. / min during ° C., after 1 hour hold to decompose the residual organic organics removal at 600 ° C., 3 hours 1100 ° C. in a dry of H ₂ stream The magnetic annealing was performed to obtain five magnetically annealed ring cores of 20 sheets stacked. The magnetic properties of each ring core were measured and the results are shown in Table 1. The initial relative magnetic permeability is a value at H = 5 mOe.

Example 2 The same ring core as in Example 1 was degreased with trichlene and washed, and then the ring core was immersed in a 20% aluminum diisopropoxide ethyl acetoacetate chelate butanol solution. A mixed sol composed of decomposition product Al hydroxide, Al hydrate, and Al oxide was dried at 350 ° C. and dehydrated and condensed to a thickness of 0.7.
A μm coating was obtained. Thereafter, heat treatment and magnetic annealing were performed under the same conditions as in Example 1, and twenty ring cores were stacked to obtain five ring cores. Thereafter, the magnetic properties were measured in the same manner as in the examples, and the results are shown in Table 1.

Comparative Example 3 The same ring core as in Example 1 was degreased with trichlene and cleaned, then the ring core was immersed in an alumina powder methanol slurry having an average particle size of 0.2 μm, dried at 180 ° C. A ring core having a coating of 3 μm / sheet was obtained.
Further, magnetic annealing was performed at 1100 ° C. for 3 hours in a stream of dry H ₂ to obtain five ring cores of 20 layers. afterwards,
The magnetic properties were measured under the same conditions as in Example 1, and the results are shown in Table 1.

Comparative Example 4 The same triclinic degreasing agent ring core as in Example 1 was used in an amount of 10%.
After immersion in a Mg (OCH ₃ ) ₂ N-hexane solution, the solvent is evaporated, and a mixed sol composed of a hydrolysis product of Mg hydroxide, Mg hydrate and Mg oxide is dried at 350 ° C. The thickness of the dehydrated and condensed gel coating was 0.5 μm / sheet.
Furthermore, magnetic annealing was performed directly under the same conditions as in Example 1,
Five ring cores obtained by stacking 20 pieces were obtained. Thereafter, the magnetic properties were measured under the same conditions as in Example 1, and the results are shown in Table 1.

Example 5 A cold-rolled foil strip of a Ni-Fe alloy having a thickness of 0.05 mm and a width of 20 mm made of a Fe alloy containing 77.8% of Ni and 4.6% of Mo was subjected to tricren degreasing and cleaning, and then to an interlayer insulating film. After immersing in a 10 ml% N-hexane solution of Mg (OCH ₃ ) _{2 as} a solution, the solvent was evaporated, and a mixed sol composed of a hydrolysis product of Mg hydroxide, Mg hydrate and Mg oxide was added to the solution.
Dry at 50 ° C and dehydrated condensed gel coating thickness 0.5μ
Outer diameter 21 mm x inner diameter 14 mm x width 20 m
An m-sized wound core was obtained. Further, 200 ° C to 600 ° C
Is heated in a N ₂ atmosphere at a heating rate of 2 ° C./min.
Heat treatment was performed at 0 ° C. for 3 hours, and then magnetic annealing was performed at 1100 ° C. for 3 hours in a stream of dry H ₂ to obtain 100 wound cores. Thereafter, the magnetic characteristics were measured, and the results are shown in Table 2.

Example 6 A wound core having the same material, shape and dimensions as in Example 5 was formed in a vacuum furnace at a temperature rising rate of 3 ° C./200° C. to 600 ° C.
After heating at 600 ° C. for 3 hours and performing heat treatment at 600 ° C. for 3 hours, magnetic annealing was performed at 1100 ° C. for 3 hours in a dry H ₂ stream to obtain 100 wound cores. Table 2 shows the measurement results of the magnetic characteristics.

Comparative Example 7 A Ni-Fe alloy cold rolled foil strip having the same material and dimensions as in Example 5 was subjected to trichlene degreasing and washing, and then Al _{2 having} an average particle diameter of 0.2 μm.
After immersing the foil strip in a slurry in which O ₃ powder is dispersed in methyl alcohol, the foil strip is dried at 180 ° C.
A foil strip on which an interlayer insulating film of m to 5 μm was formed was continuously wound to obtain a wound core having the same dimensions as in Example 5. The obtained wound core was subjected to magnetic annealing at 1000 ° C. for 3 hours in a stream of dry H ₂ , and then the magnetic properties were measured. The results are shown in Table 2.

Comparative Example 8 A Ni-Fe alloy cold rolled foil strip having the same material and dimensions as in Example 5 was degreased and washed with trichlene, and then used as an interlayer insulating coating solution.
g (OCH ₃ ) _{2 in} a 10 wt% N-hexane solution, and then evaporate the solvent to obtain a mixed sol composed of a hydrolysis product of Mg hydroxide, Mg hydrate and Mg oxide.
C. to obtain a wound core having the same dimensions as in Example 5 in which a dehydrated and condensed gel coating having a film thickness of 0.5 .mu.m was formed. Thereafter, magnetic annealing was performed at 1100 ° C. for 3 hours in a directly dried airflow, and the magnetic properties of the obtained wound core are shown in Table 2.
As is clear from the examples, it is clear that the present invention further improves and improves the DC magnetic characteristics and AC magnetic characteristics.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

According to the present invention, the decomposition product is coated on the surface of the alloy ribbon and gelled to form an interlayer insulating film. After machining, the temperature is raised between 200 ° C. and 600 ° C. at a rate of 1 ° C./min.
The temperature was raised at a rate of 600 ° C./min, a heat treatment of holding at 600 ° C. for at least one hour or more was performed, and a magnetic annealing was further performed.
Extremely thin film is formed uniformly, has sufficient interlayer insulation, has excellent adhesion, corrosion resistance, and heat resistance. Even when molded as an iron core material, DC magnetic properties and AC magnetic properties are further improved. In addition, a stable Ni—Fe alloy core can be provided.

Claims (1)

(57) [Claims] 1. An N having a clean surface cut to a final width.
After hydrolyzing the organometallic compound containing at least one metal alkoxyl group or alkoxide group attached to at least one main surface of the i-Fe alloy ribbon, coating the decomposition product, and then gelling by drying After forming an interlayer insulating film having a thickness of 0.3 μm to 30 μm, winding or punching into a predetermined shape and dimensions is performed, and then the temperature is raised between 200 ° C. and 600 ° C. at a rate of 1 ° C./min. ° C
A method for producing a Ni—Fe alloy core, comprising: performing heat treatment at 600 ° C. for at least one hour or more, and performing magnetic annealing.