JPS6362898A - Method for manufacturing coated striatum - Google Patents

Abstract

PURPOSE:To provide a coated wire rod having the coated film which withstands severe bending and twisting such as net forming by subjecting the surface of the wire rod made of Al or Al-plated steel to electrodeposition coating with the coated film made of an emulsion resin contg. fluorine or hydrofluoric acid ion. CONSTITUTION:60-300V DC voltage is impressed between the above-mentioned wire rod traveling in an emulsion resin soln. as an anode and a cathode facing thereto in a bath liquid cell. The emulsion resin is thus deposited on the surface of the wire rod by an electrophoresis method; thereafter, the wire rod is washed and subjected to baking and drying to continuously and efficiently form the uniform coated film. The above-mentioned emulsion resin is an org. high-polymer resin having coating formability, for which >=1 kinds of copolymers of vinyl type, etc., such as vinyl acetate and vinyl chloride are used. The mol.wt. of said resin is preferably >=1,000, more particularly >=3,000. The coated film mentioned above has the good adhesiveness to the wire rod and the good self- slipperiness of the coated film surface; in addition, the thickness of the coated film is uniform.

Description

[Detailed description of the invention] (Industrial application field) In the present invention, the coating film is subjected to severe bending such as netting.

The present invention relates to a coated filament that can withstand twisting and a manufacturing method that can efficiently produce the coated filament.

(Prior art) There are two types of coated filament bodies: coated filament bodies coated with a coating film by general painting, that is, roll coating, dipping coating, or spray painting, and general-purpose chloride coated filament bodies coated with vinyl chloride. It has vinyl coated wire.

(Problems to be Solved by the Invention) General-purpose vinyl chloride-coated wires have poor adhesion between the filament and the coating film, and the coating film is as thick as 500 to 2000μ, making it difficult to bend. The problem is that the adhesion with the filament is further deteriorated due to twisting and twisting, making it easy to crack or peel off, and corrosion of the filament from the defective portion cannot be avoided.

On the other hand, only a small number of coated filaments have been manufactured using general painting, and although they are manufactured using the dip coating method,
The thickness of the coating film is not uniform, and therefore, in addition to the same problems as those of vinyl chloride-coated wires, there is a problem in that the self-sliding properties of the coating film surface are poor, making it easy to cause galling during net processing.

The covered filament has various problems as described above, and at the same time, there are also the following problems regarding the manufacturing method.

In other words, not only the dip coating method but also the roll coating and spraying methods cannot coat the surface of a continuously long and non-planar filament with a coating film of uniform thickness. Very difficult and unproductive.

In this way, there are problems with both the coated striatum and its manufacturing method.
Improvements are requested.

The present invention has been made in view of the above-mentioned points, and has good adhesion of the coating film to the filament and self-sliding property of the coating film surface so that the coating film can withstand bending and twisting. It is an object of the present invention to provide a coated filament whose coating film thickness is uniform and a manufacturing method capable of efficiently producing the coated filament.

(Means for Solving the Problems) The basic means taken by the present invention to achieve the above-mentioned objects is that the coating film coated on the surface of the striatum contains fluorine ions or fluorine ions. It is characterized by forming an electrodeposited coating using an emulsion resin.

More specifically, in the present invention, as the fluorine ion or fluorine ion, ammonium fluoride, potassium fluoride, sodium fluoride, chromium fluoride, hydroxide of zirconium fluoride, salts of ammonium, potassium, sodium, etc., titanium fluoride, etc. Hydrogen acid, ammonium.

Salts such as potassium and sodium may be used, most preferably ammonium fluoride, potassium fluoride, and sodium fluoride, which exist in aqueous solution in the form of free fluoride ions. These fluorine ions or fluorine ions increase the electrical conductivity of the aqueous solution and maintain it at a constant value, causing the emulsion resin particles to precipitate, and the Joule heat generated during electrodeposition to semi-melt the emulsion resin particles. promotes the formation of a dense coating film.

The emulsion resin used in the present invention is an organic polymer resin having coating-forming properties, such as vinyl acetate, vinyl chloride, J! ! Vinyl-based products such as vinyldene chloride, copolymers with other monomers, acrylic acid, methacrylic acid.

Acrylic acid ester, methacrylic acid ester.

Acrylic and other monomer copolymers such as hydroxyl acrylic acid, hydroxyl acrylic ester, acrylonitrile, alkyd, epoxy, urea, fluorine, urethane, ester, styrene,
An aqueous solution of one or more mixed resins such as olefins and their copolymers, synthetic rubbers such as butadiene, and natural polymer resins can be used, and the organic polymer resin used has a molecular weight of i, ooo or more, preferably 3,000 or more.

In addition, in order to improve the film formability of the deposited film of the coating-forming resin for coating used in the present invention, phthalic acid esters, aliphatic dibasic acid esters, glycol esters, fatty acid esters, phosphoric acid esters, epoxy plasticizers, etc. agent, trioctyl trimellitate, butylphthalyl butyl glycolate.

Plasticizers and cellosolves such as acetyl citric acid, tributyl chlorinated paraffin, polypropylene sebacate,
Glycol-based high point male agents can be used.

Furthermore, inorganic pigments such as carbon, iron oxide, and titanium dioxide, phthalocyanine, and benzidine yellow are used for purposes such as coloring and improving corrosion resistance.

Color pigments such as naphthol yellow and quinacridine can be used.

The treatment bath composition according to the method of the present invention is such that the electric type of the bath liquid is changed to 81 degrees with fluorine ions or fluorine ions.
, ooo~ioo, oooμS-α-1 are good. Optimal is 3,000~is, oooμS ”f:ll
-1.

If the electric type conductivity is less than 1,000 μs-υ-I, the film-forming properties of the deposited coating film will be poor and the coating surface will become rough. Also, 100.00
If it is 0 μS-cm-' or more, the deposited coating film will be thin and the practicality will be low. The concentration of the emulsion resin aqueous solution is usually 5 to 30
Used in %.

If the temperature of the aqueous resin solution is less than 5%, the efficiency of electrodeposition is low, and if it is more than 30%, a large amount of resin is deposited due to the liquid being drawn out, which is economically disadvantageous.

The temperature of the processing solution can be set at 10 to 60°C, but optimally the temperature is 10 to 60°C.
The temperature is 5-40°C. If the bath liquid temperature is below 10°C, it is difficult to control the temperature, and if it is above 60°C, there are problems with the dispersion of the emulsion resin and the stability of the bath liquid.

The baking process (drying) according to the method of the present invention varies depending on the emulsion resin used and the coating thickness, but is usually 1
The baking time is approximately 3 to 10 minutes at 30 to 250°C, which is shorter than the baking time for electroconductive coatings using ordinary low-molecular-weight resins. The semi-molten and mutually fused materials are further fused to improve quality and self-sliding properties.

The electrodeposition coating method according to the method of the present invention is as follows: (1) A striatum running in a multimulsion resin solution is used as an anode, and a DC voltage of 60 to 300 V is applied between the anode and a cathode facing each other in a bath liquid tank. By depositing the emulsion resin on the surface of the filament, washing with water and baking and drying, a uniform coating film can be formed continuously and most efficiently.

Furthermore, in the case of applying a DC voltage, the method of the present invention brings the filament body to zero potential with respect to the ground voltage, so that it is possible to avoid errors in the degreasing and cleaning process of the filament body before electrodeposition and the water washing process after electrodeposition. Prevents current from flowing, increasing safety.

In addition, in the method of the present invention, after washing the electrodeposited coating with water, a hydrogen or solvent-based clear coating is applied by dipping, spraying, or roll coating to continuously form a coating film with further improved corrosion resistance on the filament. urge

(Example) An example of the implementation of the present invention will be described below with reference to the drawings.

FIG. 1 shows an example of the coated filament (A) of the present invention, in which the surface of the aluminum or aluminum-plated steel filament (1) is coated with fluorine ions or Emulsion resin coating containing fluorine ions (
Electrodeposition coating is formed in step 2).

The coating film (2) has a uniform thickness within a range of ±10%.

FIG. 2 shows another embodiment of the coated filament (A) of the present invention, in which the surface of the coating film (2) electrodeposited on the surface of the coated filament (1) is coated with a water-soluble Or water-dispersible resin coating (
3) The coating is formed.

FIG. 3 shows an example of the apparatus (B) adopted in the method of the present invention, and the coated filament (A) of FIG.
An example of manufacturing will be described below.

This device (B) has a striatal feeding element (B+>).

Resin cleaning element (B2), anode junction point (Bz).

DC voltage supply power source (84), electrodeposition bath (Bs).

Anode plate (Bg), water washing element (87), clear coating element (88), baking drying oven (B9), winding element (B+o)
It is composed of

By this 5A position, the striatum (1) is transferred to the striatum supply element (B
+) to the winding element (BID). However, the clear coating element (B8) has been suspended.

The striatum (1) is resin, and in the cleaning process, it is immersed in a weak alkaline detergent (trade name: Fine Cleaner 315, Nippon Parriki Rising 3h/J 60-70°C) for 10 seconds, and after washing with water, it is soaked in potassium fluoride 3a/ 25°C thermoplastic acrylic resin containing J (trade name, Dianal LX10
0, Mitsubishi Rayon) 100g/e, dibutyl phthalate 30 (If/J) was electrodeposited for 10 seconds at 130V in an electrodeposition tank (B5) of an aqueous dispersion solution to form a coating film (
After coating 2), it is washed with water and then baked in a drying oven (B
9) at 250°C for 3 minutes, and the winding element (
B16) was continuously wound into a coil shape.

The filament (1) was made of A1100 material and had an aluminum wire diameter of 3.2 mm.

The performance of the coated filament (A) thus produced is shown in ■ in the table.

Next, another manufacturing example of the covered filament (A) having the same cross-sectional structure will be described below.

The striatum (1) is supplied with the striatum feeding element (B) by the device 1 (B).
1) to the winding element (BIG).

However, the clear coating element (B8) is suspended.

In the degreasing and cleaning process, the striatum (1) is immersed for 10 seconds in a weak alkaline detergent (trade name: Fine Cleaner 315 Nippon Parriki Rising, 30a/4 60-70°C).
After washing with water, ammonium fluoride 5g/J, acrylic emulsion resin (trade name Brimal^C331 Nippon Acrylic) 10017/J, dibutyl phthalate 10
(J/j, electrical conductivity fl!a containing phthalomianine green pigment 5Q/J, oooμS・a-' OH8 aqueous dispersion solution was deposited in an electrodeposition tank (B5) at 180 V for 3 seconds and wired. After coating the surface of the strip (1) with the coating film (2), it is baked at 300°C for 1 minute in a baking drying oven (B9), and then continuously wound into a coil shape with a winder 10. Ta.

The filament body (1) is made of Al100 material aluminum wire with a diameter of 3.2 mm.
was used.

The performance of the coated filament (A) thus produced is shown in ■ in the table.

Next, an example of manufacturing the coated filament (A) shown in FIG. 2 using the apparatus (B) will be described below.

The striatum (1) is supplied with the striatum feeding element (B1) by the device (B).
) to the winding element (BIG).

That is, the striatum (1) is degreased, and in the cleaning process, a weak alkaline cleaning agent (trade name Fine Cleaner 315) is used.
Japan par power rising, 30QlJ60~70℃) 1
After immersing for 0 seconds and washing with water, thermoplastic acrylic resin (trade name: Dyanaru IX 100. Mitsubishi Rayon) at 25°C containing 3 g/l of potassium fluoride, 100 g/j, dibdelphthalate 30 (1/2, f water) The striatum (1
) After coating the surface with coating film (2), it is washed with water, and then coated with clear coating element (B8) 1! I(2)
112 by applying commercially available acrylic clear lacquer to the surface.
(3) is coated and then baked for 3 minutes at 250°C in a baking drying oven (B9), and the winding element (BIG
) was continuously wound into a coil.

The filament (1) is made of Al100 material and aluminum wire 3.
2mφ was used.

The performance of the coated filament (A) thus produced is shown in ■ in the table.

■ in the table indicates the striatum (A) of the present invention and this striatum (
A comparative example is shown to clarify the effectiveness of the method of the present invention for producing A).

In this comparative example, the same aqueous dispersion solution that does not contain potassium fluoride was used in the process of the manufacturing example of the coated wire conditioner (A) having the cross-sectional structure shown in FIG. 2 in the present invention, and everything else was the same. As a result of carrying out the test under the same conditions as in the production example, the coating film had a thickness of about 50 μm, had severe roughness, and was easily peeled off by netting, making it impractical.

Note 1 Pencil hardness Note 2 Time required for paint film to peel off when immersed in a 5% NaOH aqueous solution at room temperature Note 3 Time required for white rust to occur in an area ratio of 5% using a test method based on JIS-Z 2371 4. Coating film condition at bent portions when diamond-shaped mesh processing is performed Note 5: The uniformity of the film thickness is equivalent to that obtained by general electrodeposition coating method (effects of the invention) Therefore, according to the coated filament of the present invention, the following There are advantages.

■ The adhesion between the filament and the coating film formed on its surface is good, and the coating itself is highly self-sliding, and the coating thickness is uniform. It can withstand severe bending and twisting without cracking or peeling off, and the strands are permanently protected.As a result, it is extremely useful as a groove bottom wire material for tortoiseshell nets and diamond-shaped nets. Valid and galling during its processing.

There is no handling after processing, and galling can be prevented to a large extent, making it useful for general purpose use.

The manufacturing method of the present invention has the following advantages.

■ It is possible to form a coating film on the linear body, which is not flat and continuous, and has a uniform thickness in a relatively short period of time by electrodeposition, which allows for longer equipment. It is efficient and extremely practical, as it can avoid problems and can be produced at high speed.

■ By performing baking after forming the coating film by electrodeposition, the emulsion resin particles that are semi-fused and attached to each other during electrodeposition can be further fused and the coating film can be made dense. The quality of the surface can be improved to smooth.

[Brief explanation of drawings]

FIG. 1 is a sectional view showing one embodiment of the coated filament of the present invention. FIG. 2 is a vertical plan view showing another embodiment, and FIG. 2 and 3 are schematic diagrams of an apparatus used in the manufacturing method of the present invention. In the figure, (A) is the coated striatum (B) is the device (B1) is the striatum supply element (B2) is the degreasing/cleaning element (B3) is the anode junction (B4) is the DC voltage supply power source (B5) The electrodeposition bath (B6) is the cathode plate (B7> is the water washing element (Ba), the clear coating element (B9) is the drying oven (BIo), the winding element (1) is the filament body (2) (3 ) is the coating film patent applicant Kokoku Steel Wire Cable Co., Ltd. Patent applicant Nihon Bar Riki Rising Co., Ltd.'・.ノ

Claims (6)

[Claims] (1) A coated filament in which the surface of the filament made of aluminum or aluminum-plated copper wire is electrodeposited with an emulsion resin coating containing fluorine ions or fluorine ions. (2) The coated filament according to claim 1, wherein the coating surface is coated with a water-soluble or water-dispersible resin coating. (3) A filament made of aluminum or aluminum-plated copper wire is immersed in an aqueous emulsion resin solution containing fluorine ions or fluoride ions, and a coating film made of the emulsion resin is applied to the surface of the filament by electrodeposition coating. 1. A method for manufacturing a covered filament, which comprises forming a coating and then performing a baking process. (4) A patent claim characterized in that, in the electrodeposition coating method, the electrodeposition coating film is continuously formed by applying a DC voltage of 60 to 300 V with the filament as the anode side. The method for producing a coated filament according to item 3. (5) After forming the coating film and before baking, the surface of the coating film is coated with a water-soluble or water-dispersible resin coating film. A method for producing any coated filament described in Section 1. (6) A method for manufacturing any coated filament according to any one of claims 3 to 5, characterized in that in the electrodeposition coating method, the voltage to the ground of the filament is zero.