KR100291467B1 - Steel tire cord having a superior rubber adhesion properties - Google Patents

Abstract

The present invention relates to the improvement of rubber adhesiveness of steel tire cords used as reinforcement materials for tires.

The present invention relates to a steel tire cord comprising a plurality of strands of steel wire having a surface plating layer formed therein, wherein the steel wire has a brass plating layer attached to the surface thereof in a range of 1 to 8 g per 1 kg of wire, and a cobalt plating layer on the brass plating layer. There is a technical feature in that it is attached in the range of 0.1 to 1.0 g per 1 Kg of wire, and the copper plating layer is further formed on the cobalt plating layer in the form of a triple layer plating layer attached in the range of 0.1 to 1.0 g per 1 Kg of wire.

According to the present invention, the brass plating layer, the cobalt plating layer, and the copper plating layer are sequentially coated on the surface of the steel wire constituting the steel tire cord, thereby exhibiting improved over time adhesion characteristics without deterioration of initial adhesiveness compared to conventional steel tire cords. Compared with plated or ternary alloy plated steel cords, it is expected to extend the life of tires when used for reinforcing tires.

Description

Steel tire cord having a superior rubber adhesion properties

The present invention relates to a steel tire cord used as a reinforcing material of a tire, and more particularly, a brass plating layer, a cobalt plating layer, and a copper plating layer are sequentially laminated and coated on the surface of the element wire constituting the steel cord. The present invention relates to a steel tire cord having excellent rubber adhesiveness, which is capable of improving initial adhesion, improving corrosion resistance by cobalt in an intermediate layer, and protecting base metals by brass inside.

In general, a steel tire cord used for reinforcing tires of a vehicle has a brass (Cu / Sn) plated layer formed on its surface to improve adhesion to tire rubber and freshness in steel wire manufacturing. The formed steel wire is embedded in tire rubber as a single body, or several strands of brass plated steel wire are manufactured in the form of a twisted cord and used in tire rubber.

Particularly, in case of steel tire cords made of brass plated steel wire, they show relatively high adhesiveness with tire rubber even at high temperature, moisture, and brine atmosphere generated during high-speed running of the tire, and thus are preferred to other tire reinforcement materials. .

On the other hand, the adhesion between the steel cord and rubber composed of brass coated steel wire is known to be caused by the copper sulfide in the brass and the sulfur in the rubber react with each other to form a copper sulfide. As described above, the brass layer coated on the steel wire for reinforcing rubber products such as tires to improve adhesion to rubber is generally made of 60 to 70% copper and 30 to 40% zinc.

The adhesion between the brass plated steel and the tire rubber decreases gradually over time (usually called time-of-day adhesion) by a number of factors. The cause of the decrease in adhesion over time is that the reaction of copper and sulfur is promoted under high heat, moisture, or brine atmosphere generated during high-speed running of the tire, so that the thickness of the copper sulfide layer formed at the initial stage of adhesion is gradually increased. The increase in thickness continues as time passes and when the thickness reaches an excessively increased point, the copper sulfide layer is easily destroyed, and thus the adhesive strength decreases.

Therefore, in order to prolong the life of the tire reinforced by the steel cord, it is important to prevent the drop of the adhesive force over time as well as to maintain a high initial adhesive force between the steel cord and the tire rubber. Many studies and various attempts have been made to prevent such a drop in time-lapse adhesion, and some of them are as follows.

In general, time-dependent adhesion is known to be able to suppress the growth of the copper sulfide layer over time by reducing the composition ratio of copper in brass, British Patent No. 1,250,419 lowers the copper content to 60% or less The solution is being presented.

However, brass having a low copper content of 60% or less, such that the crystal becomes β-brass with extremely poor workability, resulting in wire breakage during wire drawing using a continuous die as a subsequent step to the plating wire. There is a problem that the deterioration of the properties is difficult to use.

On the other hand, in view of the above problems revealed in the improvement of the time-dependent adhesive properties through the change of composition of the brass alloy, attempts to improve the time-lapse adhesive strength by forming a plating layer consisting of three-membered alloy by adding a third element to the brass As a representative example of the improvement of the time-lapse adhesive strength by the third element addition known so far, FR-2,198,830, GB-1,122,528, US-2,912,355, Korean Patent Publication No. 82-631 and Domestic Patent Publication No. 82 -1983.

In the above-described third element-added type steel tire cord manufacturing technology, the surface of the wire is first plated with copper, followed by zinc plating on the surface of the wire, followed by plating of cobalt on the upper layer. By applying a heat of 500 ℃ to cause the mutual diffusion between the elements constituting each plating layer to form a plating layer of a three-alloy alloy consisting of copper, zinc and cobalt. At this time, the cobalt used has an effect of increasing the durability of the adhesive layer by stabilizing the adhesive layer even in a harsh environment.

However, in the method of improving the time-dependent adhesion by the addition of the third element, the concentration of cobalt is high at the surface of the wire pole where the wire is bonded to the rubber, and therefore the concentration of copper bonding to sulfur in the rubber is relatively low. There is a disadvantage that the initial adhesive strength does not reach a satisfactory level.

In addition, EP-188,036 and US-4,226,918 disclose a method of plating nickel after brass plating. However, the steel cord produced by the above method has a disadvantage in that it shows an improvement effect of the time-lapse adhesive force only for rubber having a very limited rubber composition ratio.

In addition, Korean Patent Publication No. 90-13046 and Korean Patent Publication No. 94-283 disclose that instead of plating a third element on the surface of a brass plating layer, an organic substance containing a third element, for example, nickel stearate in a hydrocarbon oil A method has been proposed in which an oil containing cobalt stearate is added to a strand of a steel cord to coat a brass-plated steel cord with an oil coating so that a plating layer of a ternary alloy is applied to the surface of the steel wire.

However, even in the ternary alloy of copper + zinc + cobalt (nickel) obtained by using an organic material containing a third element such as nickel or cobalt, the pole surface portion of the wire has a low copper concentration, so that the initial adhesive strength is still lowered. Remains.

Therefore, the present invention is to solve the problem of shortening the life of the tire as a result of the conventional steel tire cord does not satisfy both the initial adhesion and the time-lapse adhesion at the same time, and plate the ordinary brass on the surface of the steel wire, and It is aimed to provide a steel tire cord having excellent initial adhesion as well as time-lapse adhesion by plating cobalt and copper sequentially.

In the steel tire cord having excellent adhesion of the present invention, in a steel cord formed by twisting a plurality of steel wires, a brass plating layer is attached to the surface of the steel wire in the range of 1 to 8 g per 1 kg of wire, and a cobalt plating layer is formed on the brass plating layer. There is a technical feature in the structure is attached in the range of 0.1 to 1.0g per 1Kg of wire, and the copper plating layer is attached to the cobalt plating layer in the range of 0.1 to 1.0g per 1Kg of wire.

That is, the steel wire constituting the steel cord of the present invention is a structure in which three plating layers of a brass plating layer, a cobalt plating layer, and a copper plating layer are sequentially coated on the surface thereof, and the characteristics and roles of each plating layer and the reason for limiting the coating weight are as follows. same.

First, the bottom of the brass plating layer, which is directly coated on the surface of the steel wire, is made of the internal steel (Fe) in the process of being drawn through a continuous die while the steel wire receives a processing amount of about 95% or more of the initial cross section. ) Serves to prevent the exposure to the surface portion. In other words, by covering the steel wire with a brass plated layer, the brass plated layer is in direct contact with the die tip during the passage of the fresh die.

The plating amount of the brass is preferably in the range of 1 to 8 g per 1 kg of wire, and more preferably in the range of 3 to 4 g. If the amount of brass is less than 1 g, the surface portion of the steel wire may be exposed during the stretching process. In this way, the exposed steel has no property of bonding with sulfur in the rubber, and rapid oxidation proceeds in an oxidizing atmosphere, which may have a fatal adverse effect on rubber adhesion. Therefore, the lower limit of plating adhesion amount of brass was set at 1 g.

On the contrary, if the amount of brass adhesion exceeds 8g, the plating time should be increased by that much, and the consumption of brass is also increased, which leads to an increase in manufacturing cost.

Next, the cobalt plated layer forming an intermediate layer between the brass plated layer and the copper plated layer serves as a barrier to prevent copper in the lower brass from bonding with the rubber, thereby inhibiting excessive growth of the copper sulfide layer over time. .

The brass plating layer in the present invention may be replaced by a plating layer made of only one metal of copper or zinc in addition to brass.

In addition, the cobalt plated layer combines with sulfur in the rubber to form a cobalt sulfide bridge to exhibit high corrosion resistance in a corrosive environment, thereby stabilizing the adhesive layer to increase the durability of the adhesive layer.

The plating deposition amount of the cobalt is preferably in the range of 0.1 to 1.0 g per 1 Kg of wire, and more preferably in the range of 0.3 to 0.6 g. At this time, when the coating adhesion amount of the cobalt is less than 0.1g, it becomes difficult to act as a barrier between the lower brass layer and the rubber, and also the formation of the cobalt sulfide layer is insufficient and the corrosion resistance is poor in an oxidizing atmosphere.

On the contrary, when the adhesion amount of cobalt exceeds 1.0g, cobalt is poor in workability, resulting in wire cutting in the stretching process through a continuous die, and in addition, expensive cobalt consumption is increased to increase manufacturing costs.

Next, the copper plating layer forming the outermost shell on the cobalt plating layer serves to exhibit an excellent initial adhesion by forming a copper sulfide layer by directly reacting with sulfur in the rubber.

At this time, the preferred coating amount of copper is 0.1 to 1.0 g per 1 kg of wire, more preferably in the range of 0.3 to 0.6 g. If the amount of copper is less than 0.1 g, the amount of copper that reacts with sulfur in the rubber Because of this lack, there is a problem that the initial adhesive strength is lowered, if the amount of copper adhesion exceeds 1.0g, the copper sulfide layer continues to grow over time, weakening the adhesion over time.

On the other hand, in the above, the adhesion amount of each plating layer adhered to the surface of the steel wire is represented by weight, and in the case of converting it into a thickness, the thickness of the cobalt plating layer and the copper plating layer is about 50 nm.

Embodiments of the present invention are as follows.

Example 1

A wire having a diameter of 0.25 mm was obtained by plating the wire having a diameter of 1.40 mm by three different plating methods as shown in Table 1 below and passing the die continuously.

division Plating method Plating amount Manufacturing method Conventional example Brass 4.7 g / Kg (64.3% Cu + 35.7% Zn) After copper plating, zinc is plated on the upper layer and brass plating layer is formed by thermal diffusion method. Brass + Cobalt 5.1g / Kg (64.1% Cu + 34.1% Zn + 1.7% Co) After copper plating, zinc is plated on the upper layer and cobalt is plated on the upper layer to form three-way alloy of copper + zinc + cobalt by thermal diffusion method. Invention Brass + Cobalt + Copper Brass layer: 4.0g / Kg (63.7% Cu + 36.3% Zn) Cobalt layer: 0.47g / Kg Copper layer: 0.35g / Kg After copper plating, zinc is plated on the upper layer, a brass layer is formed by thermal diffusion method, cobalt is plated on the upper layer, and copper is plated on the upper layer.

Next, the four strands of the plated wire were twisted with each other to produce a steel cord having a 2 + 2 × 0.25 structure and then embedded in a rubber having a composition as shown in Table 2 below to investigate the rubber adhesion. At this time, the rubber adhesion test method was carried out according to ASTM D-2229, the vulcanization condition was heated at 170 ℃ for 12 minutes at 60 atm to obtain an adhesive composite of the steel tire cord and rubber.

ingredient content Natural rubber 100 parts by weight Carbon black 60 parts by weight Zinc oxide 3.5 parts by weight Stearic acid 0.5 parts by weight sulfur 3 parts by weight Benzothiazol 0.5 parts by weight Aromatic oils 1.5 parts by weight Resorcinol resin 1 part by weight

The rubber adhesive composite thus obtained was stored at 70 ° C. in a 96% relative humidity atmosphere for 4 days, 8 days, and 12 days, and then the adhesive strength (water resistance) was evaluated. Other adhesive complexes were stored in 20% NaCl aqueous solution for 4 days, 8 days, and 12 days, and then evaluated for adhesion (salt-resistant). Another adhesive complex was stored for 4 days, 8 days, and 12 days in a drying furnace at 100 ° C. After the adhesion (heat resistance) was evaluated. Table 3 below shows the rubber adhesive force evaluation results.

division Plating method Rubber Adhesion (Kg) Initial Adhesion Water resistance Salt Water Adhesion Heat adhesion 4 days 8th 12 days 4 days 8th 12 days 4 days 8th 14 days Conventional method Brass 47.0 43.3 35.6 32.6 46.7 40.2 36.8 40.3 33.6 32.9 Brass + Cobalt 40.2 41.2 40.2 35.6 38.5 38.2 36.5 40.3 35.2 34.1 Invention Brass + Cobalt + Copper 46.6 45.5 44.7 42.3 46.5 45.8 44.1 41.3 38.5 38.2

As shown in Table 3, the rubber adhesiveness of the steel wire formed with the triple layer (brass + cobalt + copper) plating layer of the present invention is equivalent to or superior to that of conventional brass or brass + cobalt plated steel wire in terms of initial adhesion. It can be seen that all aspects of water resistance, saline and heat resistance adhesive properties are significantly improved compared to the conventional steel wire.

Example 2

For wires with a diameter of 1.40 mm, the amount of brass deposited on the first layer was 3.7g / Kg (63.7% Cu + 36.3% Zn), and the amount of cobalt and copper was deposited on the second and third layers, respectively. Plating was performed as shown in Table 4.

Four plated wires obtained by stretching the plated plated wires in such a manner as to be 0.25 mm in diameter by successive dies were twisted together to form a steel cord having a 2 + 2 × 0.25 structure to test adhesion to rubber. The rubber adhesion test was carried out according to ASTM D-2229 using a rubber having a rubber composition ratio of Table 2, wherein the vulcanization conditions were heated at 170 ° C. for 12 minutes at 60 atm to obtain an adhesive composite between the tire cord and the rubber.

The rubber adhesive composite thus obtained was stored for 4 days, 8 days, and 12 days in a relative humidity 96% atmosphere at 70 ° C., and then the adhesive strength (water resistance) was evaluated. Another adhesive composite was 4 days and 8 days in a 20% NaCl aqueous solution. After storage for 12 days, the adhesive force (saline adhesion) was evaluated. Another adhesive composite was stored for 4 days, 8 days, and 12 days in a 100 ℃ drying furnace to evaluate the adhesion (heat resistance).

The evaluation results for the three types of rubber adhesive force are shown in Table 4.

Psalm Number Coating Weight (g / Kg) Rubber Adhesion (Kg) Brass cobalt Copper Initial Adhesion Water resistance Salt Water Adhesion Heat adhesion 4 days 8th 12 days 4 days 8th 12 days 4 days 8th 12 days Comparative Example 1 3.7 (Cu: 63.7%) (Zn: 36.3%) 0.05 0.35 48.1 35.4 30.2 22.5 33.0 28.5 20.4 25.4 22.1 18.2 Example 1 0.12 0.38 44.5 39.5 38.5 33.2 36.7 35.2 33.7 38.0 35.2 31.0 Example 2 0.22 0.33 48.5 42.1 40.2 38.5 42.5 38.5 35.8 40.5 36.8 35.7 Example 3 0.35 0.35 48.2 44.2 41.5 41.1 42.5 36.5 36.2 42.8 40.2 36.8 Example 4 0.47 0.35 46.6 45.5 44.7 42.3 46.5 45.8 44.1 41.3 38.5 38.2 Example 5 0.66 0.36 44.2 42.5 41.2 38.5 45.0 43.5 42.1 42.5 41.7 38.5 Example 6 0.82 0.41 46.1 44.2 41.5 40.2 44.2 44.2 40.3 43.1 41.8 40.2 Comparative Example 2 1.12 0.35 44.8 45.1 42.3 40.2 42.8 41.1 38.7 40.2 38.8 36.5 Comparative Example 3 0.45 0.08 15.2 12.0 12.5 10.4 16.2 14.2 11.5 13.2 10.2 11.5 Example 7 0.47 0.15 30.1 30.7 29.1 27.3 27.2 25.1 21.7 27.1 25.7 20.5 Example 8 0.47 0.28 42.1 41.7 40.3 39.2 40.1 37.2 35.7 41.1 36.3 35.5 Example 9 0.39 0.36 46.2 45.1 43.9 41.7 45.7 44.2 43.7 42.1 39.5 38.6 Example 10 0.44 0.44 45.9 46.1 44.2 40.1 44.1 41.7 40.6 41.7 39.6 37.4 Example 11 0.47 0.61 44.8 42.1 39.6 36.1 38.9 38.1 36.8 40.1 38.2 37.0 Example 12 0.51 0.75 47.1 45.1 38.2 36.1 42.5 40.1 39.2 41.8 39.1 35.7 Example 13 0.48 0.95 45.9 32.5 15.8 10.5 25.8 22.4 12.8 29.6 22.5 17.1 Comparative Example 4 0.47 1.23 40.1 20.5 15.4 11.0 18.9 10.5 10.4 20.5 14.2 10.8

As shown in Table 1, Comparative Examples 1, 3, and 4, which deviate from the coating adhesion range of the present invention, show characteristics inferior to those of Examples 1 to 13 of the present invention in water, saline, and heat resistance. Can be. However, in the case of Comparative Example 2, it shows excellent characteristics in all aspects such as initial adhesion, water resistance, saline and heat resistance, but this is due to the relatively high amount of cobalt plating. In the process of extending the wire through the wire is likely to cause cutting and also because the cobalt is expensive, there is a problem to apply in this way because the manufacturing cost is increased.

As described above, the present invention is a brass plated layer, cobalt plated layer and a copper plated layer is sequentially coated on the surface of the steel wire constituting the steel tire cord, improved initial adhesion without compromising the initial adhesiveness compared to the conventional steel tire cord It can be seen that the characteristics.

Therefore, the steel tire cord of the present invention exhibits excellent initial adhesive strength and aging adhesive strength compared to conventional brass plated or ternary alloy plated steel cords, and is expected to have an effect of extending the life of the tire when used for reinforcing tires.

Claims (4)

In a steel tire cord composed of multiple strands of steel wire having a surface plating layer formed thereon, the steel wire has a brass plating layer attached to the surface thereof in a range of 1 to 8 g per 1 kg of wire, and a cobalt plating layer per 1 kg of wire on the brass plating layer. The steel tire cord is attached in the range of 0.1 to 1.0g, and the copper plated layer is attached to the cobalt plated layer in the range of 0.1 to 1.0g per kilogram of wire. The steel tire cord according to claim 1, wherein the cobalt plating amount of the cobalt plating layer is 0.3 to 0.6 g per 1 kg of wire. The steel tire cord according to claim 1, wherein the copper plating amount of the copper plating layer is 0.3 to 0.6 g per 1 kg of wire. The steel tire cord according to claim 1, wherein the innermost brass plating layer of the plating layer coated on the steel wire is made of a copper or zinc plating layer plated with one metal of copper or zinc other than brass.