JPS60166356A - Plated wire with rustproof treatment - Google Patents

Abstract

PURPOSE:To obtain the titled wire capable of pollution-free prevention of generating coarsely particulate corroded product, for use in wire cloth, by coating an e.g. iron wire, specified thickness of coating material comprising organic resin, SiO2, PO4-component and gamma-glycidoxypropyltrimethoxysilane in specific proportion. CONSTITUTION:The objective plated wire can be obtained by coating, on iron or steel wire (pref. with a diameter 0.9-8mm.) to such a thickness as to correspond to an amount 3-12g/m<2>, a coating material comprising (A) 35-70wt% (on a solid basis) of an organic resin component (e.g. acrylic aqueous emulsion). (B) 20- 60wt% of SiO2 component, (C) 1-7wt% of PO4 component (e.g. metaphosphoric acid) and (D) 0.1-5wt%, as a silane coupling agent, of gamma-glycidoxypropyltrimethoxysilane and/or gamma-mercaptopropyltrimethoxysilane. EFFECT:Having coated layer with outstanding short-term rustproof ability in the outdoor atmosphere.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a plated wire having a rust-preventing coating layer.

(Prior art and problems) In general, plated wires used for wire mesh, ropes, etc. are coated with zinc, zinc-aluminum alloy, or aluminum on the surface of iron wire or steel wire by electrolytic method, melt-dipping method, or cladding method. Covered materials are often used.

These plated wires are used in a variety of environments in the form of solid or stranded wires. Plated wire itself has anti-rust properties, and most of them are used without special anti-rust treatment, but they are used when a beautiful surface appearance is required or when long-term durability is required. When soldering, an additional paint or plastic coating is usually applied to the plated lines. However, painting and plastic coatings are expensive to process;
Its use is limited.

Originally, when zinc or aluminum-based metals are left in the atmosphere, a relatively dense oxide layer is formed on the surface, which suppresses the rate of corrosion. However, depending on the use of the plated wire, such as in a wire mesh, moisture tends to accumulate at the locations where the wires intersect, and in the case of twisted wire ropes, it is difficult for moisture d that has entered between the wires to escape. Furthermore, the surface of the plated wire may be wet due to condensation or rainwater in a warehouse or outdoors until it is put into actual use. When these plated metals are left in such a humid environment for a long time, large corrosive particles easily form on their surfaces. These corrosion products not only deteriorate the surface appearance of the plated wire, but also cause significant wear on the plated metal, resulting in a shortened life span of the entire plated wire.

Measures to prevent this type of corrosion include chromate treatment, which is used for galvanized steel sheets, etc., and recently, as a non-polluting treatment, for example, non-chromate type tannic acid treatment (% Publication No. 56-5825, Japanese Patent Publication No. 55-1988) 18786)
and organic-inorganic composite treatment (% publication 54-34406)
etc. have been proposed.

With respect to these prior art techniques, the present inventors conducted various studies in consideration of the characteristics of the plated wire. First, although chromate treatment has the best rust-preventing effect, it has been concluded that, depending on the application, chromium may be leached into the environment, making it undesirable from a practical standpoint. On the other hand, non-chromate type tannic acid treatment poses no problem in terms of environmental protection, but the film has insufficient moisture resistance and cannot withstand storage in a warehouse for 1 to 2 years, and organic-inorganic composite treatment has anti-rust properties. It was found that the rust resistance of plated wires cannot be satisfied unless the coating thickness is relatively thick.

(Object of the Invention) The present invention provides a plated wire having a coating layer that prevents the generation of the above-mentioned coarse-grained corrosion products, is environmentally friendly, and has an excellent short-term rust prevention ability, especially in the outdoor atmosphere. The purpose is to provide the following.

(Structure of the Invention) That is, the present invention has an organic resin content of 35 to 7%, a 5i02 content of 20 to 6%, and a PO of 7% to 7% in terms of solid weight percentage.
4 minutes, and a total of 01-5% as a silane coupling agent.
γ-glycidoxypropyltrimethoxysilane and r-
This is a rust-preventing plated wire characterized in that the surface is coated with a coating material containing one or both of mercaptopropyltrimethoxysilanes at a rate of 3 to 12 f/rn'.

Next, the plated wire of the present invention will be explained in detail.

First, in the present invention, as the material for the plated wire, iron wire or steel wire with a diameter of about 0.9 to 8% of the normal diameter can be used, and the surface of these wires is coated with zinc-based metal by electroplating or (
d. By melt dipping method, trench, zinc-aluminum metal or aluminum metal by melt dipping method, or by cladding method, 90 to 600% of these metals.
It is possible to use a material coated to a degree of y/silence.

Next, the reasons for limiting the ingredients in the coating material used in the present invention will be explained. First, the organic resin component is the main component in forming the skin 11ψ and is responsible for ensuring full adhesion to the plated surface. For example, acrylic, styrene, or epoxy water emulsion resins can be used. If the solid content of these organic resins in the film is less than 35%, the adhesion of the film will be insufficient and the rust prevention ability will also be poor. If the angle exceeds 7°, the inorganic components in the film will be reduced, the film will have poor dimensional resistance to scratches, and this is inconvenient for plating where the surface is frequently rubbed.

Next, the 5i02 part is mainly to improve the rust prevention ability of the film,
Necessary to provide appropriate film hardness.

As the 5i02 min, for example, an aqueous dispersion of colloidal liquid can be used. When the solid content of SiO□ in the film is less than 20 parts, the hardness of the film becomes low, the scratch resistance becomes poor, and the rust prevention property becomes unsatisfactory. On the other hand, if it exceeds 60%, the amount of inorganic components in the film becomes too large, the film itself becomes brittle, and the adhesion of the film is adversely affected. In addition, during treatment, PO4 plays the role of etching and activating the plating surface, allowing the treatment solution to be applied uniformly, forming a uniform film, and at the same time improving the rust prevention properties of the film. As for po, minute,
For example, orthophosphoric acid, metaphosphoric acid, birophosphoric acid, etc. can be used. The effect of the queen cannot be expected unless there is a solid content in the film in terms of PO4. On the other hand, if it exceeds 7%, it will reduce the adhesion of the film and at the same time have a negative effect on the stability of the organic resin emulsion in the processing solution. pH value 15~
It is preferable to add the amount within the range of 2.5.

Furthermore, although there are various types of silane coupling agents in general, the treatment solution for film formation of the present invention includes either γ-glyndoxybrobyltrimethoxysilane or γ-mercaptopropyltrimethoxysilane. Or you need to use both. These substances do not dissolve in the FD processing solution and cannot achieve the intended purpose. This 7
Run force springing agent ID is used to improve the bonding force between organic resin and inorganic material, and is useful for densifying the film. If the total amount of 1-1 type in the film is less than 0.1%, no contribution to improvement in rust prevention is recognized. Further, even if the content exceeds 5φ, no further improvement in rust prevention ability is observed. In addition, a small amount of pigment for coloring may be added. A treatment solution prepared to achieve the film composition range described above is applied to the surface of the plated wire, dried, and the film weight is 3 to 12 y/n? Forms a film. If the coating weight is less than 3 f/l)Z', sufficient rust prevention performance cannot be obtained due to the effects of scratches between the plated lines. As the number of coatings increases, the rust prevention ability also improves to a certain extent, but as mentioned above, it is difficult to obtain the short-term rust prevention ability in the outdoor atmosphere required for the purpose of the present invention, which is the use of plated wire rods. 12 with the film composition of the invention? / +++
” is sufficient, and even if the amount of adhesion is increased beyond this,
If the effect is saturated, it will lead to higher costs.

In the present invention, when a plated wire is coated with a rust preventive treatment, it can be treated using an aqueous solution of the above-mentioned ingredients in a metal coating line or after metal coating in a dedicated rust preventive treatment line. It goes without saying that the wire surface before being subjected to anti-rust treatment is a clean surface free from any oil or fats. The treatment liquid can be applied by dipping, spraying, or FlowCo-1. 100-80 after application
The treated film is dried in an atmosphere at a temperature of 0°C to such an extent that the linear temperature rises to 90 to 150°C.

Next, the present invention will be explained in more detail with reference to Examples.

(Example) First, a hard steel wire (JIS-A type) with a diameter of 4 mm was coated with a coating weight of 120.
After electrolytic galvanizing of q/a, the back body f was processed.

Comparative Example-1 Phosphoric acid 0.4 g/L was added to an aqueous solution of tannic acid 5 o y/l and thiourea 20 y/l, and the pH value was adjusted to 3.
5 and heated to 60°C. The above-mentioned plated wire was immersed in this bath solution for 3 seconds, then pulled out and dried in an atmospheric oven at 120° C. for 30 seconds to form a rust-preventing film of film silk 3.5 fA++'.

Comparative Example-2 Acrylic water-based emulsion resin (concentration 40φ) 125
ml! and colloidal silica (concentration 20t), 250
mA and water 125rnI! A solution at 40°C consisting of a ratio of
Dry for minutes, film adhesion amount 67A? - manufactured a plated wire.

Comparative Example-5 Acrylic water-based emulsion resin (concentration 4.0%'
) 1, 25 ml, and colloidal silica (concentration 20%)
240rnI! A solution at 40°C consisting of 27 parts of phosphorus and 120 parts of water was applied to the surface of the plated line, and 250
Dry for 1.5 minutes in an atmosphere at ℃, and the film adhesion amount is 6? /7
71F plated wire was manufactured.

Comparative Example-4 Acrylic water-based emulsion resin (concentration 40 parts) 125
mg and colloidal silica (143 degrees 20%) 2
4.0 ml, γ-glyndoxypropyltrimethoxysolan 2y1 water 125 ml! A solution at 40° C. having a ratio of 40° C. was applied to the surface of the plated wire and dried in an atmosphere at 250° C. for 15 minutes to produce a plated wire with a film f of 69 An”.

Invention example-1 Acrylic water-based emulsion resin (concentration 40%) 125
ml, colloidal silica 23011! /, phosphoric acid 27,
A solution at 40°C consisting of γ-glycidoxy/propyltrimethine silane 29 and water l 20 +ne was applied to the plated wire and dried for 15 minutes in an atmosphere of 250°C to produce a plated wire needle with a coating weight of 697 m''. did.

Next, a total of 1509A for the 3φ hard wire (JIS-A, iI++)? ? After hot-dipped jAII zinc-5 strip aluminum plating was performed, the plating surface was cleaned by alkaline degreasing treatment, and then the following treatment was performed.

Comparative Example-5 Acrylic-epoxy water-based emulsion resin (concentration 25
%) 240ml, colloidal silica (concentration 20%) 20
0m1. A solution at 50° C. containing 60 mg of water was applied onto the surface of the plated wire, and dried for 1 minute in an atmosphere of 300° C. to produce a plated wire with a film adhesion of 82 mm.

Comparative Example-6 Acrylic-epoxy water-based emulsion resin (concentration 25
%) 24 On! /, colloidal silica (concentration 20
% ) 185 ml, a solution consisting of 37 ml of pyrophosphoric acid and 757 ml of water was applied to the surface of the plated wire and heated at 300°C.
After drying for 1 minute in an atmosphere of /n? Manufactured marked wire.

Comparative Example-7 Acrylic-epoxy water-based emulsion resin (concentration 25
%) 240mg, colloidal silica (concentration 20%) 18
5-1γ-mercaptropyltrimethoxysilane 32,
A solution consisting of 751 nA of water was applied to the surface of the plated wire and dried for 1 minute in an atmosphere of 300°C to form a film. Manufactures Nometsuki wire.

Invention Example-2 Acrylic-dipoxy water-based emulsion resin (11 degrees 2
5%) 240d, colloidal silica (concentration 20t) 17
A solution consisting of 32 parts of pyrophosphoric acid, 37 parts of γ-mercappropyltrimethoxysila, and 90 parts of water was applied to the surface of the plated wire to produce a plated wire with a film thickness of IJ 897 m''.

Furthermore, after hot-dip aluminum plating with a coating weight of 150 f/lri was applied to a 3φ hard steel wire (TIS-A type), the plating surface was cleaned by degreasing with trichlorethylene solvent, and then the following treatment was performed. I did it.

Comparative Example-8 Styrene-based aqueous emulsion resin (1m f 20%
) 200m/, colloidal silica (concentration 20chi) 30
A @ solution consisting of a ratio of 0 mA was applied to the surface of the plated wire, dried for 40 seconds in an atmosphere of 300°C, and the film weight a
A y/lri plated wire was manufactured.

Comparative Example-9 Styrene-based aqueous emulsion resin (concentration 20%) 200
ml, colloidal silica (concentration 20 t) 275-1 phosphoric acid 5? , a solution consisting of 20 m/20 m of water was applied to the surface of the plating line and dried for 40 seconds in an atmosphere of 300°C,
A plated wire with a coating weight of 4 was produced.

Comparative example-10 Styrenic aqueous emulsion resin (concentration 20%) 200
m7! , colloidal silica (#degree 20chi) 250πl
! , γ-glycidoxypropyltrimethoxysilane, 5
A solution consisting of 7 and 20 nf of water was applied to the surface of the plated wire and dried in an atmosphere at 300° C. to produce a plated wire with a film weight of 49 nf.

Invention example-3 Styrenic aqueous emulsion resin (concentration 20%) 200
Go, colloidal silica (concentration 20φ) 250r7! A solution consisting of 5 parts of phosphoric acid, 5 parts of γ-glycidoxypropyltrimethoxysilane, and 50 parts of water was applied to the surface of the plated wire and dried for 40 seconds in an atmosphere at 300°C, resulting in a coating weight of l 4 yAt. ? Manufactured marked wire.

Finally, the adhesion amount was 34 on the 5φ hard @ wire (JIS-A type).
0 f/lr? After applying hot-dip galvanizing and cleaning the plating surface with alkaline degreasing treatment, acrylic water-based emulsion resin (?ef3o%) was applied to 185-, colloidal silica (concentration 20 range) 2001 nA, phosphoric acid 31,
A solution consisting of 2 parts of γ-glycidoxypropyltrimethoxysilane and 120 parts of water was applied to the surface of the plated wire and dried for 1 to 2 minutes in an atmosphere at 250°C. By varying the amount of treatment liquid applied, film amounts 1 and 2 f/d (
Comparative Examples 11.12) and 3.4.5.10 and 1
2nd Ar? Each plated wire (Examples 4 to 8 of the present invention) was manufactured.

The performance of the antirust coatings of the plated wires according to the above comparative examples and inventive examples was evaluated by the following method.

Test method: A test wire was inserted at right angles between two stainless steel wires with a diameter of 5φ stacked in parallel, a load of 5K5+ was applied between the stainless steel wires, and the test wire was pulled out at a speed of 1n1/min. After that, it was tested with a wet box tester in JIS, Z-0236.
Corrosion acceleration is performed for 670 hours at 0° C. and 100% RH.

Evaluation method After the test, we investigated the rate of white rust on the surface of the plated wire. White rust occurs 17□○ 1-20% occurrence □Δ Occurrence of 20-50 cases--× 50-1.00% occurrence□×× It was evaluated as

The results are shown in Table 1.

Table 1

Claims (1)

[Claims] Organic resin content of 35 to 70 inches by solid weight percentage, 20 to 6
0% (7) 5i02min, 1-7ti po,min, and a total of 0.1-5% γ-gly7doxypropyltrimethoxysilane and r-mercaptopropyltrimethoxysilane as silane coupling agents. 3 to 12 W/rr? Rust-proof plated wire characterized by being coated.