WO2010071184A1

WO2010071184A1 - Colored metal wire

Info

Publication number: WO2010071184A1
Application number: PCT/JP2009/071074
Authority: WO
Inventors: 河島芳久; 菊地真樹夫; 菅原克俊; 阿部和央; 新井卓; 康諭基泰
Original assignee: 株式会社ガルバート・ジャパン
Priority date: 2008-12-18
Filing date: 2009-12-11
Publication date: 2010-06-24
Also published as: JPWO2010071184A1

Abstract

Conventional colored metal wires involve such a problem that the production costs are high due to use of expensive materials such as synthetic resin coating materials (such as polyester coating materials) used for metal wires, particularly for colored coated plated iron wires (steel wires), and vinyl chloride resins and polyethylene resins used for resin-coated plated iron wires (steel wires), in addition to use of pigments and dyes. The present invention provides a colored metal wire which can be colored only by a comparatively low-cost chemical conversion liquid, without using the above-mentioned expensive materials at all. The colored metal wire is characterized by comprising a plating layer on the surface of a metal wire and a color layer that is formed on top of the plating layer and colored by chemical conversion, said layers being formed by a step of forming the plating layer by plating the surface of the metal wire which serves as the base material, and a succeeding step of forming the color layer by chemical conversion.

Description

Color metal wire

The present invention relates to a color metal wire obtained by coloring the surface of a metal wire by a chemical reaction and a method for producing the same.

In order to color metal wires, especially iron wires (steel wires) and plated wires, a method in which the surface is treated according to the purpose, and then the synthetic resin paint is applied and baked is repeated 1 to 2 times. Colored coated iron wire) and methods of cooling (manufacturing) a vinyl chloride resin and polyethylene resin mixed with pigments (or dyes) and then cooling (manufacturing) (resin coated iron wire) It has been broken.

However, a large-scale facility is required for the method of applying a synthetic resin paint or the method of welding (fusing) a resin with a mixed color.

In addition, synthetic resin paints (for example, polyester paints) used for colored painted iron wires and vinyl chloride resins and polyethylene resins used for resin-coated plated iron wires are expensive materials and are manufactured because pigments, dyes, etc. are used. Cost is high.

In order to solve such a problem, an object of the present invention is to provide a color metal wire that exhibits coloration only with a relatively inexpensive chemical conversion treatment solution without using any of the above-mentioned expensive materials.

It is another object of the present invention to provide a color metal wire with improved surface corrosion resistance by a simple treatment.

As a result of intensive studies to solve the above problems, the present inventors apply a reaction (color reaction) that exhibits a color by a chemical reaction of a metal contained in a plating layer of a plated metal wire. As a result, it was found that a color metal wire which is inexpensive and exhibits uniform coloring can be obtained, and the present invention has been achieved.

In addition, since a good surface can be formed only by a chemical reaction, it is possible to manufacture in a continuous and consistent process from plating to coloring, which is an advantageous processing method in terms of productivity and quality control. And the present invention relating to the production method has been completed.

The gist of the present invention is shown below.
(1) A color metal wire having a plating layer on the surface of the metal wire, and further having a coloration layer formed thereon by chemical conversion treatment thereon.

(2) The color metal wire according to (1), wherein the plating layer is a zinc plating layer.

(3) The color metal wire according to (1) or (2), wherein a rust-proof coating is provided on the upper layer of the colored layer.
(4) The outermost layer is coated with one or more of organic substances having a fluorine coating agent, synthetic wax, paraffin, and benzene nucleus, according to any one of (1) to (3) The color metal wire described.

(5) In the method for producing a color metal wire according to (1), a step of forming a plating layer by plating on the surface of the metal wire as a base material, and a step of forming a colored layer by chemical conversion treatment thereafter A method for producing a color metal wire, comprising:

(6) The method for producing a color metal wire according to (5), wherein the chemical conversion treatment solution used for the chemical conversion treatment forms a metal and an organometallic compound contained in the plating layer.

(7) After the step of forming the plating layer, before the step of forming the coloration layer by chemical conversion treatment, one or more mixed acids of hydrochloric acid, sulfuric acid, and nitric acid are used for the purpose of surface activation. The method for producing a color metal wire according to (5) or (6), further comprising a step of performing a surface activation treatment using the method.
(8) After the step of forming the plating layer and before the step of forming the coloration layer by chemical conversion treatment, among sodium hydroxide, potassium hydroxide, ammonium chloride, and zinc ammonium chloride for the purpose of surface activation. The method for producing a color metal wire according to (5) or (6), comprising a step of performing a surface activation treatment using one type or two or more types of alkaline solutions.

(9) The method for producing a color metal wire as described in (5) or (6), wherein the step of forming the plating layer and the step of forming the color layer are successively performed.

(10) The color metal wire according to (7) or (8), wherein the step of forming the plating layer, the step of performing a surface activation process, and the step of forming a color layer are performed continuously. Manufacturing method.

(11) The method for producing a color metal wire according to any one of (5) to (10), wherein a rust prevention layer is formed after the step of forming the colored layer.
(12) The outermost layer is coated with one or more of organic substances having a fluorine coating agent, synthetic wax, paraffin, and benzene nuclei, according to any one of (5) to (11) The manufacturing method of the color metal wire of description.

According to the present invention, it is possible to provide a color metal wire with a beautiful surface that is inexpensive and exhibits uniform coloring without using any conventional paint, dye, pigment, colored resin or the like.

Also, because of coloration by chemical conversion treatment, it is possible to produce from a process of forming a plating layer to a continuous integrated process, which contributes not only to improving quality but also improving productivity.

Furthermore, since the process of forming an existing rust prevention layer can be applied as it is, a simple process can provide a color metal wire with high rust prevention, high quality and high productivity.

FIG. 1 shows a cross-sectional view of a colored iron wire according to Embodiment 1 of the present invention.
FIG. 2 shows a schematic view of the production process of the colored iron wire.
FIG. 3 shows a salt spray test result (corrosion weight loss index).

In the present invention, the metal wire and the plating material are not particularly limited. Various combinations are possible as long as the layer containing the organometallic compound is formed by the metal element and the chemical conversion treatment liquid contained in the plating layer and can be colored by that.

For example, the base material of the metal wire may be a single metal or an alloy, and iron, steel, aluminum, zinc, etc. are adopted.

Plating can also be applied to various types of plating. Examples of commonly performed plating include zinc plating, zinc-aluminum alloy, zinc-aluminum-magnesium alloy, tin plating, chromium plating, aluminum plating and the like.

Hereinafter, as an example of a color metal wire, the present invention will be described using a color iron wire (name of a steel wire whose surface is colored. The same shall apply hereinafter). That is, the metal wire used as the base material is made of generally used steel, and a galvanized layer is formed on the surface of the metal wire (steel wire). To do. Needless to say, the metal wire is not particularly limited, and a wire that can be galvanized can be adopted.

In the present invention, by performing chemical conversion treatment, an organometallic compound is generated by reaction with a metal contained in the plating layer, and coloration is thereby performed. Therefore, the combination of the type of plating and the chemical conversion solution is important. The process of forming a galvanized layer on a steel wire can conventionally utilize the manufacturing process of a galvanized wire as it is.

In order to perform plating, it may be necessary to generate an alloy layer. However, when the alloy layer is thick, the properties of the resulting plated wire are significantly reduced due to the extremely hard and brittle layer. For this reason, conditions, such as plating bath temperature, plating bath passage speed (henceforth linear velocity), and cooling after plating, are adjusted, and the target galvanized wire is obtained. For example, the plating bath temperature is preferably 450 ± 10 ° C. and the linear velocity is about 10 to 50 m / mim (adjusted by the wire diameter and the amount of adhesion). The amount of cooling water and the cooling position are also adjusted as appropriate.

In particular, in order to make the galvanized layer sound, the Fe—Zn alloy layer forming the solid solution of the intermetallic compound, which is an alloy layer, is made as thin as possible (for example, several tens of μm or less is desirable), and workability is improved. It is desirable to increase the proportion of the plating layer rich in.

After the plating treatment is finished, the galvanized wire is continuously introduced into the step of forming the colored layer by the chemical conversion treatment (coloring step).

The coloration process need not be continuous with the plating process. After winding up after the plating step, coloration can also be performed on a chemical conversion treatment line installed on a separate line from the plating step.

As pre-treatment for coloration with the chemical conversion treatment solution, for activation of the plating layer surface and removal of foreign matter, deposits, etc., hydrochloric acid, sulfuric acid, or nitric acid, and mixed acids thereof (collectively referred to below) Surface activation treatment may be performed using an acid). For the purpose of activating the surface, the concentration of the acid used may be 0.5-10 wt%, and more preferably 1-10 wt%.
In addition to the acid, surface activation treatment may be performed by degreasing the surface, removing foreign matter / attachments, etc. with an alkaline solution. The type of the solution is not particularly limited as long as it is an alkaline solution. For example, a sodium hydroxide solution or a calcium hydroxide solution may be used. In particular, in the case of a galvanized metal wire, surface zinc dissolves rapidly both acidic (PH 6 or less) and alkaline (PH 12 or more), and therefore has an effect of removing the oxide film on the surface as well as acid. The concentration of the alkaline solution may be 0.5 to 10 wt%, and more preferably 1 to 10 wt%.
It is also possible to use ammonium zinc chloride or ammonium chloride (both 5 to 20 wt%) used in the plating bath pretreatment.

In the case of a galvanized metal wire, depending on the surface properties of the plating, the coloration state (color development, tint, etc.) varies between pretreatment with acid and pretreatment with an alkaline solution. For example, a glossy surface and a dull (non-glossy) surface can be created depending on the cooling conditions during plating. When pretreatment with an alkaline solution is performed on a metal wire on a glossy surface, a glossy colored iron wire is obtained. This is presumed to be because the surface is not roughened because the dissolution rate of zinc is slow during the pretreatment with an alkaline solution.

This surface activation treatment is effective in order not to cause uneven coloring in the chemical conversion treatment. In the continuous treatment, the activation process may be omitted because the coloration process can be performed immediately after plating. However, as described above, when winding is performed after the plating step and the coloration step is performed after a certain time, it is desirable to perform an activation process.

Next, the galvanized wire on which the galvanized layer is formed is passed through a coloration step to cause a color reaction. As the chemical conversion treatment liquid, it is necessary to select one that generates an organometallic compound. For example, if an organic acid such as tartaric acid, citric acid and tannic acid contains 1 to 5 wt% of antimony, manganese and molybdenum, this reacts with zinc to produce a colored organometallic compound. Specific examples of the chemical conversion treatment liquid include potassium antimony tartrate (KSb (C ₄ H ₂ O ₆ ) 1.5H ₂ O).

Since the chemical conversion treatment solution is mainly intended for chemical reaction, the temperature is preferably 20 to 40 ° C. in order to obtain an appropriate reaction rate, and the reaction time varies depending on the size of the galvanized wire, but the diameter is 4.0 mm (φ4.0). 3 minutes or less is desirable.

In order to further improve the corrosion resistance of the colored iron wire colored by chemical conversion treatment and to improve the workability at the time of processing a product such as a net, a rust preventive layer is formed on the colored layer as necessary. It is possible to apply an existing rust prevention treatment technique, and the rust prevention layer can be formed by existing equipment and existing treatment technique. As the rust prevention treatment, for example, a Si-based rust prevention treatment solution is applied on the colored layer. In this case, the temperature of the treatment liquid is preferably 10 to 30 ° C. The concentration is preferably 1-30 wt%, more preferably 3-10 wt%.

Furthermore, in order to improve the weather resistance of the colored layer of colored iron wire (prevent discoloration) and prevent discoloration and peeling of the colored layer due to rubbing of the metal wire, fluorine coating agents, synthetic wax, paraffin, organic substances having a benzene nucleus, etc. It is effective to apply to the outermost layer.

Hereinafter, a description will be given based on the drawings.
FIG. 1 shows a cross section of a colored iron wire 1 as an example of the present invention. In this colored iron wire 1, 2 is a steel wire (wire whose base metal is steel), and 3 is a galvanized layer formed in the plating step. Reference numeral 4 denotes a colored layer formed by a reaction between the galvanized layer and the chemical conversion treatment liquid.

The basic structure of the colored iron wire is up to 4 colored layers. FIG. 1 shows a structure in which a rust prevention layer 5 is formed by performing a rust prevention treatment to further improve the corrosion resistance, if necessary. Yes.

The plated wire 3 manufactured from the steel wire through the plating process has a diameter of about 2 to 8 mm, and the thickness of the plated layer is about 3 to 90 μm.

Next, an example of the manufacturing method of the said color iron wire is demonstrated.
FIG. 2 shows an outline of the manufacturing process. In the figure, reference numeral 6 denotes a wire rod 6 serving as a strand, which is a steel wire having a diameter of about 5 to 10 mm. A steel wire 8 is obtained by drawing out this wire in a cold state, drawing 7 to a predetermined size, and winding it.

The steel wire 8 is annealed 9 after being treated with a lubricant. Depending on the application, this annealing 9 may be omitted. Then, after pickling 10 in a pickling tank and performing a pretreatment for plating, plating 11 is performed in a plating bath. After the plating 11 is finished, it is wound up by a winding device to become a plated wire 12.

Immediately after plating, the surface activation treatment (also referred to as pretreatment) 13 and the coloration step 14 are taken up, and the wire is wound once and then the plating wire 12 goes to the surface activation treatment (pretreatment) 13 and the coloration step 14 There is.

Next, the manufacturing method in the coloration process 14 will be described. The surface is activated by surface activation treatment (pretreatment) 13 of the plated wire 12.

The plated wire is subjected to chemical conversion 14 after being washed and dried immediately after the pretreatment. A chemical conversion solution is selected according to the color to be obtained, and a predetermined color is formed by a color reaction. Thereafter, washing with water and drying are performed to form a colored iron wire 15 which is wound up.

In order to further improve the corrosion resistance, after washing and drying after completion of the coloring step, a rust-preventing film is formed through the rust-preventing treatment liquid, and then wound after drying. In this way, the color iron wire 15 is obtained.
Finally, if necessary, an Si-based antirust treatment liquid, a fluorine coating material, synthetic wax, paraffin, an organic substance having a benzene nucleus, or the like is applied to the outermost layer.

Chemical conversion treatment was performed after surface activation treatment 13 using galvanized iron wire 12.
The target color is dark brown.
Chemical conversion treatment liquid A: Sb (4%), Mn (4%), tannic acid (trace amount), citric acid (trace amount), manganese sulfate (trace amount) contained, antimony potassium tartrate

Table 1 shows the galvanized iron wire used in Example 1 and the chemical conversion treatment conditions. Three types of galvanized iron wire (S) φ4.0 were used. Since the target color was dark brown, chemical conversion treatment A solution (containing Sb (4%), Mn (4%), and tannic acid (trace amount)) was used. The chemical conversion treatment conditions were a liquid temperature of 30 ° C. and a linear velocity of 10 m / min from the viewpoint of color tone.
For the surface activation treatment, a mixed acid of hydrochloric acid and nitric acid (5 wt%) and a sodium hydroxide solution (5 wt%) were prepared. Examples 1-1 and 1-2 were subjected to a surface activation treatment with a mixed acid, and Examples 1-3 and 1-4 were subjected to a surface activation treatment with a sodium hydroxide solution.

Table 2 shows the results of the winding test and the pencil hardness test of the colored iron wire manufactured in Example 1. In all Examples, the color iron wire was good without any cracks or the like in the visual inspection of the winding test (6 winding times) defined in JIS G3542. Although color peeling is not in JIS regulations, it was done by in-house inspection. As described above, since the colored layer is an organometallic compound generated by a chemical reaction, no color separation was observed. It was good that no scratches or scratches were observed in the visual inspection of the pencil hardness test. As described above, good results were obtained in all examples. However, the shades of Examples 1-1 and 1-2 subjected to surface activation treatment with acid and Examples 1-3 and 1-4 subjected to surface activation treatment with an alkaline solution are different. -3, 1-4 became glossy dark brown.

The corrosion resistance of the color iron wire produced in Example 1 was evaluated. Evaluation was performed by the salt spray test prescribed | regulated to JISZ2371.

In addition, the galvanized iron wire used in Example 2-1 and Example 2-2 is obtained by dividing the same coil as that shown in Comparative Example 2.

Table 3 shows the test materials subjected to the salt spray test. There are three types of test materials, Example 2-1 applies the color iron wire manufactured in Example 1-1, and Example 2-2 applies Example 1-2 with a Si-based anticorrosion treatment solution (5 wt%). We used what we did. Comparative Example 2 is the galvanized iron wire (S) type 3 φ4 itself that is the bus bar of Examples 2-1 and 2-2.

The specimens were evaluated by comparing the amount of corrosion reduction. Three types of galvanized iron wires (S) were empirically compared with the amount of decrease in corrosion after 4 days since the adhesion amount almost disappeared after 4 days.

Figure 3 shows the results. If the corrosion reduction of the galvanized iron wire is indexed as 1.0, the corrosion reduction of the color iron wire is 0.9, the corrosion reduction of the rust-proof color iron wire is 0.3, and the corrosion resistance of the rust-proof color iron wire is Very good.

Color iron wire also has better corrosion resistance than galvanized iron wire due to chemical conversion treatment. It can be seen that the corrosion resistance of the rust-proof colored iron wire is greatly improved compared to the galvanized iron wire.

The effects based on the above embodiment are not limited to the material of this embodiment. As described above, various types of metals can be used as the base metal, and a layer containing an organometallic compound can be formed by the metal element contained in the plating layer and the chemical conversion treatment liquid, thereby allowing coloration. If there are, various combinations are possible.

The present invention can be used for a colored metal wire colored on a metal wire. According to the present invention, it is possible to provide a color metal wire having a beautiful surface that is durable, inexpensive, and exhibits uniform coloring.
In addition, because of the coloration by chemical conversion treatment, it is possible to produce from a process of forming a plating layer to a continuous integrated process, which contributes not only to improving quality but also improving productivity.

1 Color metal wire 2 Metal wire (iron wire)
3 Plating layer 4 Colored layer 5 Anticorrosive layer 6 Wire 7 Wire drawing process 8 Metal wire (iron wire)
9 Annealing process 10 Pickling process 11 Plating layer forming process 12 Plating wire (plated iron wire)
13 Surface activation treatment step 14 Colored layer formation step 15 by chemical conversion treatment Color metal wire (color iron wire)

Claims

A color metal wire having a plating layer on the surface of the metal wire, and further having a coloration layer formed by chemical conversion treatment on the upper layer.
The color metal wire according to claim 1, wherein the plated layer is a galvanized layer.
The color metal wire according to claim 1 or 2, further comprising a rust preventive coating on an upper layer of the colored layer.
The color metal wire according to any one of claims 1 to 3, wherein one or more of a fluorine coating agent, a synthetic wax, a paraffin, and an organic substance having a benzene nucleus are applied to the outermost layer. .
The method for producing a color metal wire according to claim 1, further comprising a step of forming a plating layer by a plating treatment on the surface of the metal wire as a base material, and a step of forming a colored layer by a chemical conversion treatment thereafter. A method for producing a colored metal wire.
6. The method for producing a color metal wire according to claim 5, wherein the chemical conversion treatment solution used for the chemical conversion treatment forms a metal and an organometallic compound contained in the plating layer.
After the step of forming the plating layer and before the step of forming the coloration layer by chemical conversion treatment, the surface is formed using one or more mixed acids of hydrochloric acid, sulfuric acid and nitric acid for the purpose of surface activation. The method for producing a color metal wire according to claim 5 or 6, further comprising a step of performing an activation treatment.
After the step of forming the plating layer and before the step of forming the coloration layer by chemical conversion treatment, one of sodium hydroxide, potassium hydroxide, ammonium chloride, and zinc ammonium chloride for the purpose of surface activation or The method for producing a color metal wire according to claim 5 or 6, further comprising a step of performing a surface activation treatment using two or more kinds of alkaline solutions.
The method for producing a color metal wire according to claim 5 or 6, wherein the step of forming the plating layer and the step of forming the coloration layer are successively performed.
The method for producing a color metal wire according to claim 7 or 8, wherein the step of forming the plating layer, the step of performing a surface activation treatment, and the step of forming a colored layer are successively performed.
The method for producing a color metal wire according to any one of claims 5 to 10, wherein a rust preventive layer is formed after the step of forming the colored layer.
The color metal wire according to any one of claims 5 to 11, wherein one or more of a fluorine coating agent, a synthetic wax, a paraffin, and an organic substance having a benzene nucleus are applied to the outermost layer. Manufacturing method.