JPS6031046B2 - Manufacturing method of anodized electric wire - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing an alumite electric wire having excellent heat resistance, insulation properties, and heat dissipation properties.

BACKGROUND ART Conventionally, so-called alumite electric wires, which are aluminum or aluminum alloy wires subjected to anodizing treatment, have been used as electric wires with good heat resistance, insulation properties, and heat dissipation properties. The anodic oxide film of this alumite wire has many micropores, and if moisture in the atmosphere enters these micropores, the insulation may deteriorate. For this reason, conventionally, the micropores have been sealed by sealing with water, water vapor, etc., but it is impossible to completely seal the micropores with the sealing treatment. In addition, there was a drawback that the anodic oxide film was hydrated and changed in quality due to the sealing treatment, making it more likely to cause cracks. In addition, alumite wires can be wire-wound processed,
When subjected to processing such as stranding or heated to about 150 qo, the anodic oxide film is relatively brittle and the hot air elongation is significantly lower than that of the base aluminum or aluminum alloy, resulting in cracks. There is also the problem that the insulation properties are further deteriorated due to the cracks that occur. Due to these factors, the actual dielectric strength voltage of conventional alumite wires is 10V per thickness of the anodic oxide film.
It was below. This invention was made in view of the above circumstances, and aims to provide a method for manufacturing an alumite wire that can produce an alumite wire with extremely good heat resistance, electrical insulation, and heat dissipation. The method is characterized in that an aluminum alloy wire is anodized and the resulting anodic oxide film is treated with a polymerizable organometallic compound. This invention will be explained in detail below.

The aluminum wire or aluminum alloy wire used in this invention may be a hard aluminum wire obtained by wire drawing a general electrical aluminum base metal, a soft aluminum wire obtained by dulling this, or a No. 1 aluminum alloy. Lines etc. are used.

This aluminum wire or aluminum alloy wire is first subjected to pretreatment such as degreasing, mechanical polishing, chemical polishing, electrolytic polishing, etc. to remove oil, dirt, scratches, etc. from the wire surface. Then, anodic oxidation treatment is performed.

In this anodizing treatment, since the object to be treated is a long wire rod, a continuous treatment method is adopted. The continuous processing method is carried out, for example, by an apparatus as shown in the drawings. The pretreated aluminum wire or aluminum alloy wire 1 is wound into a coil, set in a delivery device (not shown), and delivered to the electrolytic cell 2. The sent out aluminum wire or aluminum alloy wire 1 enters a contact cell 2a at the front stage of an electrolytic cell 2, and is connected to an anode of a source 5 via an electrolytic solution 3 and a magnetic pole 4. Next, the aluminum wire or aluminum electric wire 1 passes through a baffle 6 that partitions the contact cell 2a and the anodic acid bath 2b, and is led to the anodic acid bath 2b.
A cathode 7 connected to the cathode of a power source 5 is provided submerged in an electrolyte 8. Connected to the anode, anodic acid irrigating tank 2
The aluminum wire or aluminum alloy wire 1 guided to b is anodized here, and an anodic oxide film is successively formed on the surface. Sagi-kai-ba 8 can contain acids such as ordinary sulfuric acid, double acid, chromic acid, sulfamic acid aqueous solution, and alkali I
J case etc. are used. Further, as the electrolytic current, a direct current, an AC/DC superimposed current, or the like is used. The thickness of the anodic oxide film is
It can be controlled by adjusting the electrolysis conditions (temperature, current density, etc.) and the wire speed of the aluminum wire or aluminum alloy wire 1. The aluminum wire or aluminum alloy wire 1 that has been anodized is washed with water to remove the electrolyte 8 adhering to the surface, dried, and wound into a winder (not shown). In the above example, continuous anodic oxidation treatment using a so-called liquid power supply method has been described, but the present invention is not limited to this, and continuous anodization treatment using a corona power supply method may also be used. The aluminum wire or aluminum alloy wire on which the anodic oxide film has been formed as described above is then treated with a polymerizable organometallic compound, but if necessary, heat treatment or bending treatment is performed before that. Sometimes.

In the heat treatment, in order to prevent cracks from occurring when the obtained alumite electric wire is heated, it is heated in advance to actively generate cracks, and the cracks are impregnated with a polymerizable organometallic compound. The aim is to improve the insulation properties of alumite wires at high temperatures. Specifically, this heat treatment is performed on aluminum wire or aluminum alloy wire wound in a heating furnace of 300 to 400 oo.
This is done by heating for ~10 minutes. In addition, in the bending process, in order to prevent cracks that occur when the obtained alumite wire is wound into a 4 mm diameter coil, bending deformation is applied in advance to actively generate cracks. The cracks are soaked with a polymerizable organometallic compound to measure the insulation properties after secondary processing. Specifically, this bending process is performed by winding the coil into a coil having a diameter of about 3 m. The aluminum wire or aluminum alloy wire having an anodized film that has been heat-treated or bent as necessary in this way is
Treated with polymerizable organometallic compounds.

The polymerizable organometallic compound used here has a hydrolyzable group, a halogen group, or an organic functional group bonded to a metal atom, and has polymerizability.

And the general formula XmMRmM: Si, Ti, A, Zr
, G, and metal atoms such as B, P, Sn, Pb, Be, and Th. X: Organic functional groups such as vinyl groups, amino groups, mercapto groups, and epoxy groups. It is an organometallic compound represented by an organic group n+m=3,4,5 or 6, such as phenyltriethoxysilane, methyltriethoxysilane, vinyltris(8-methoxyethoxy)silane, 8-(3.4
Organosilicon compounds such as -epoxycyclohexyl)ethyltrimethoxysilane, y-glycidoxypropyltrimethoxysilane, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, titanium acetylaceto organotitanium compounds such as titanate, titanium octylene glycolate, dihydroxybis(lactato)titanium, tetrastearoxytitanium, aluminum n
- Organoaluminum compounds such as butoxide, methylaluminum chloride, aluminum isopropoxide, zirconium n-butoxide, zirconium isof.

Organic zirconium compounds such as ropoxide and tetra(t-butoxy)zirconium, organic phosphorus compounds such as tri-n-butyl phosphate, diethyl phosphate, and organic boron such as tri-n-butyl borate and triisopropyl borate. compounds, organogermanium compounds such as dimethyloxydimethylgermanium, organometallic compounds such as dimethyloxyethyltin, phenyl lead triacetate, isopropyl beryllium methoxide, and tetra(ethyloxy)thorium, and derivatives and low polymers of these compounds. (oligomers) can be used, but those having an aromatic ring in the organic functional group are preferred because they have a greater improvement in heat resistance. Furthermore, it is better to use hydrolysis that occurs gradually. These polymerizable organometallic compounds include methanol, ethanol, acetone,
Organic solvents such as ethyl acetate and methyl ethyl ketone are used after being dissolved in water or a mixture of water and a water-soluble organic solvent. As this water-soluble organic solvent, methanol, ethanol, isopropanol, acetone, dioxane, ethylene glycol, methyl acetate, methyl ethyl ketone, diacetone alcohol, ethyl formate, dimethyl formamide, etc. are used. Additives such as agents can be added.
Then, the anodic oxide film is immersed in such a polymerizable organometallic compound solution to diffuse and penetrate the polymerizable organometallic compound into the cracks and micropores, or the aforementioned solution is applied to the oxide film surface to oxidize it. This is done by forming a polymerizable organometallic compound layer on the surface of the film, or by using a vacuum impregnation method. Alternatively, the oxide film is soaked in a solution in which a polymerizable organometallic compound is dissolved in water or a mixture of water and a water-soluble organic solvent, and a direct current is applied using the oxide film as an anode and a suitable inert conductor as a cathode. By applying electricity, the polymerizable organometallic compound can be sufficiently impregnated from the bottom of the cracks in the oxide film and the micropores to the pore openings by electrophoresis, infiltration, etc. When the resulting anodic oxide film requires higher thermal conductivity, the polymerizable organometallic compound solution adhering to the oxide film surface is completely wiped off.
When higher electrical insulation is required, the polymerizable organometallic compound solution adhering to the surface of the oxide film is left as it is without being wiped off. Once the polymerizable organometallic compound has been sufficiently adhered and deposited on the surface of the anodic oxide film or on the cracks and micropores, the oxide film is dried and excess water and organic solvent are removed. The polymerizable organometallic compound that has adhered to the surface of the anodic oxide film or to the cracks and micropores as described above is polymerized by a polymerization means such as heating.

Through this polymerization, the polymerizable organometallic compound becomes a delicate organometallic compound polymer, and since these organometallic compounds have a high affinity with the oxide film, the surface of the oxide film,
It firmly adheres to the inside of the hole, effectively filling cracks and micropores or covering the surface. The above treatment of the anodic oxide film formed on the aluminum wire or aluminum alloy wire with a polymerizable organometallic compound is usually carried out with the anodized aluminum wire or aluminum alloy wire wound into a coil shape. Following the anodic oxidation treatment, the linear treatment can also be performed continuously.

Alternatively, the alumite electric wire may be processed in advance into a usage form, and this processed product may be processed. In the anodic oxide film treated with the polymerizable organometallic compound as described above, the cracks and micropores are completely filled with the organometallic compound polymer, or the film surface is also covered with the polymer, so it has a very high Provides electrical insulation.

Furthermore, since only cracks and micropores can be filled with the polymer, electrical insulation is improved while maintaining high heat dissipation. Furthermore, electrical insulation properties at high temperatures (approximately 150 CO) are also improved. Furthermore, since the filled and coated polymer is metallic, the polymer itself has excellent thermal conductivity, and the anodic oxide film whose surface is coated with this polymer also has high heat dissipation. Hereinafter, this invention will be specifically explained based on Examples.

Example 1 An aluminum wire with a diameter of 2 mm was treated with 2 tons of sulfuric acid.
Continuously anodized in an aqueous solution at a linear speed of 2 h/min and a current density of 20 A/d with alternating current (current ratio 1:1) to form an anodized film with a thickness of about 10 A. It was rolled up into a cigarette with a diameter of 30 yen.

About lk9 of this tobacco is phenyltriethoxysilane, C6
Day 6 Si (OC2 day 5) was immersed in a solution of 37 small ol%, isopropanol 24 vol%, acetic acid 5 vol%, water 1 vol%, and DC 1000 was applied using an aluminum wire as an anode.
A voltage of V was applied. The anode current at this time is approximately 1 A/d.
It was a pleasure. After removing the aluminum wire from the solution, it was thoroughly drained, dried, and heated at 130° C. for 2 hours to polymerize. Approximately 20 pieces of the obtained anodized electric wire
When the wires were cut to the desired length, two alumite wires were twisted together, and the dielectric strength between the wires was measured, a value of 30 V/m was obtained. Example 2 An aluminum wire tab on which an anodized film was formed in the same manner as in Example 1 was prepared, and this tab was placed in a heating furnace at 300°C for 10 minutes, and then polymerized in the same manner as in Example 1. An alumite electric wire was obtained by treatment with an organometallic compound.

This alumite electric wire was heated at 30 pi○ for 30 minutes,
No cracks were observed. Further, the dielectric strength voltage after heating was 30V/〃. Example 3 An aluminum wire on which an anodic oxide film was formed in the same manner as in Example 1 was prepared, and with this aluminum wire, an inner diameter of 2,
A multilayer coil with an outer diameter of 6 arms was created.

Tin foil for dielectric strength measurement was inserted between each layer of this coil. Cracks occurred in the oxide film of the aluminum wire, which formed a layer with an inner diameter of 4 mm or less, due to the external bending force. The above coil is made of vinyl tris (8-mexyethoxy)
Silane CH2=CHSj (OCQC day 20CH3) 35
The coil was immersed in a vol% aqueous solution, and current was applied at a voltage of 200 to 500 V at a current density of 10 hA/d using the coil as an anode. The coil was taken out from the aqueous solution, the liquid was thoroughly drained, the coil was dried, and the coil was heated at 100° C. for 1 hour to perform polymerization. When the dielectric strength voltage between the tin foil between the eyebrows of the coil and the aluminum wire was measured, a value of 35 V/A was obtained. Example 4 In Example 1, as the polymerizable organometallic compound solution,
Titanium lactate ethyl ester (C3H?○)2Ti
(Day 903) 25 small ol%, isopropanol 5 river o
The dielectric strength of the alumite wire was determined by dipping the alumite wire into this solution in a 10-2 ton vacuum using a mixed solution of 1%, followed by immersion in a vacuum chamber and then heating at 130°C for 2 hours. When measured, a breakdown voltage of 25 V/mu was obtained.

Example 5 In Example 4, as the polymerizable organometallic compound solution,
Methyldibutoxyaluminum CH3A (OC4)
When the dielectric strength voltage of the alumite wire was similarly vacuum impregnated using a mixed solution of 26 vol % and inpropyl alcohol 4 vol %, a value of 30 y/m was obtained.

After heating this product for 30 minutes at 300 o'clock, the dielectric strength voltage was measured in the same manner, but no decrease in the dielectric strength voltage was observed. As explained above, the method for manufacturing an alumite electric wire of the present invention involves performing anodizing treatment on an aluminum wire or aluminum alloy wire, and treating the obtained anodic oxide film with a polymerizable organometallic compound. The micropores and cracks present in the anodic oxide film are filled with organometallic compound polymer, which provides high electrical insulation and the organometallic compound polymer has excellent thermal conductivity, resulting in the high heat dissipation properties of alumite wire. is maintained.

In addition, when an aluminum wire or aluminum alloy wire with an anodized film is heat-treated or bent and then treated with a polymerizable organometallic compound, the dielectric strength at high temperatures or after secondary processing improves. .

[Brief explanation of the drawing]

The drawing is a schematic plan view showing an example of a diamond counterfeit suitable for carrying out the manufacturing method of the present invention. 1... Aluminum wire or aluminum alloy wire, 2
... Electrolytic cell, 2a ... Power supply tank, 2b.
...Anodic acid iris tank, 4,7... Electrode, 5
······power supply.

Claims (1)

[Claims] 1. A method for producing an alumite electric wire, which comprises subjecting an aluminum wire or aluminum alloy wire to anodizing treatment, and treating the resulting anodized film with a polymerizable organometallic compound.