JP2002505376A - Surface-treated steel wire for reinforcing structures for articles made from elastomeric materials and articles comprising same - Google Patents

Abstract

  (57) [Summary] A surface treated steel wire for a reinforcing structure for a product made from a vulcanized elastomeric material, wherein the wire is coated with a layer of a metal alloy, wherein the alloy comprises A zinc / manganese binary alloy comprising 0.3-4.9% by weight manganese.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a steel wire for a reinforcing structure for products made from vulcanized elastomeric material, which is surface-coated with a metal alloy, and the wire embedded in the vulcanized elastomeric material. Related to a product comprising. The invention further relates to a method for coating the wire with the alloy.

More particularly, the present invention relates to a steel wire coated with a zinc / manganese alloy having a manganese content of less than 4.9% by weight. Furthermore, the invention relates to a reinforcing structure comprising the wire and an article made from a vulcanized elastomer comprising the reinforcing structure.

[0003] As is known, tires, as well as many other products made from vulcanized elastomeric materials, incorporate reinforcing structures, usually made of metal cord, each of which is a standard. It consists of a plurality of metal wires that are suitably interconnected by a braiding operation.

[0004] Furthermore, the following is known; steel, because of its excellent material properties, is the metal of choice for the structure. However, its chemistry is not good because it cannot adhere well to the vulcanized elastomeric material and it has poor corrosion resistance.

To overcome these drawbacks, steel is usually coated with a metal or metal alloy layer. Typically, the coating is a brass layer comprising about 70% by weight copper and about 30% by weight zinc. In this case, the adhesion is promoted due to the formation of a thin layer of copper sulfide Cu _x S by sulfur itself or its known derivatives present in the vulcanization mixture as vulcanizing agent.

[0006] Even if the brass-coated steel adheres well to the vulcanized elastomeric matrix, the adhesion will eventually deteriorate due to the action of moisture and oxygen. Indeed, in articles made from vulcanized elastomeric materials, optionally reinforced with brass-coated steel in the form of cords, such as tires, corrosion is caused by moisture permeating the elastomer and through holes or crevices in the elastomer. Caused by both water in contact with reinforcing structures made from brass coated steel.

[0007] The brass / elastomer adhesion failure can be partially counteracted by the addition of some cobalt in salt form (US Pat. No. 5,356,711). It is believed that: cobalt reduces the conductivity of the layer of copper sulfide; this slows down the diffusion rate of Zn ⁺⁺ ions and, consequently, is responsible for the destruction of the Cu _x S film. / Zn (OH) ₂ interface layer growth rate decreases. The result is some improvement in adhesion.

[0008] However, brass-coated steel is slightly resistant to corrosion. This facilitates the development of different metal or alloy coatings. U.S. Pat. No. 4,651,513 describes a steel rope for reinforcing rubber products such as tires, the rope comprising a multi-wire having two or more continuous layers around a common core. Includes a plurality of steel wires twisted together to form a laminated rope. The outermost wire is covered with a coating that can adhere to rubber, such as brass, while the inner wire is covered with a corrosion resistant coating, such as zinc itself or an alloy.

[0009] Of the various binary and ternary alloys mentioned in the patent (col. 5, lines 49-54), mention is also made of zinc / manganese alloys. However, the document does not illustrate or specify what the manganese content of the alloy is. Indeed, the above patents clearly indicate that the most practical coating is a coating consisting solely of zinc (col. 5, lines 54-58).

[0010] EP 01888851 describes a steel reinforcing element for use in vulcanized rubber products, wherein the element is covered with a coating layer capable of adhering to the rubber, This layer is made of brass and has at least 50% copper and 0.01-15% by weight manganese.

In both of the above documents, the coating on the steel wire, whose function is to adhere to rubber, alone or with manganese (ternary alloy), has brass (about 70% copper and about 30% zinc) (Copper / zinc alloy).

However, said coatings still have the disadvantages associated with copper. Therefore, it is still necessary today to comply with the requirements of both good corrosion resistance of the wire and good adhesion of the wire to the vulcanized elastomer matrix.

The following has now surprisingly been found: a manganese content of 0.3
A coating made from a zinc / manganese binary alloy, which is about 4.9% by weight, has an improved corrosion resistance after aging-hardening when compared to brass, zinc itself or a ternary alloy consisting of brass and manganese. And has greater adhesion to the vulcanized elastomeric material.

In a first aspect, the invention therefore relates to a surface-treated steel wire for a reinforcing structure for an article made from a vulcanized elastomeric material, wherein the wire comprises a metal alloy. Layer and the alloy has a
It is a zinc / manganese binary alloy comprising 4.9% by weight of manganese.

Preferably, the manganese content of the binary alloy according to the invention is from 0.3 to 4.5% by weight,
More preferably, it is 1.5 to 4% by weight. Typically, the surface coating layer is formed by electrodeposition on the surface of the steel wire.

The thickness of the coating layer on the steel wire before drawing is preferably from 1 to 4
Micron. However, after drawing, the thickness of the layer typically ranges from 0.1 to
0.4 microns.

Preferred zinc salts for performing the electrodeposition method according to the present invention are zinc salts selected from the group comprising sulfate, sulfamate, hypophosphate, picrate, selenate and thiocyanate. More preferably, these are sulfates and sulfamates.

Preferred examples of preferred manganese salts for performing the electrodeposition method according to the present invention comprise sulfate, sulfamate, acetate, formate, iodidate, lactate, phosphate, selenate, thiocyanate, dithiocyanate and valerate. A manganese salt selected from the group. Even more preferably, these salts are sulfates and sulfamates.

[0019] In a second aspect, the invention relates to a method for fabricating a steel wire passing through an electrolytic bath.
A method for electrodepositing a zinc / manganese binary alloy comprising ４4.9% by weight of manganese, wherein the steel wire comprises an aqueous solution of at least one salt selected from zinc and manganese salts. Through two electrolytic baths, the electrolytic baths
It has a temperature of 50 ° C., a pH of 2 to 6, and a cathode density of 10 to 50 A / dm ² .

Typically, the processing speed of the wire is 10-70 m / min, more typically 18
５０50 m / min. Typically, the zinc and manganese salts used in the method of the invention are sulfates.

Even more typically, the zinc sulfate is zinc sulfate heptahydrate and the manganese sulfate is manganese sulfate monohydrate. In a preferred embodiment of the method of the present invention, the steel wire is immersed in a single electrolytic bath comprising a manganese salt and a zinc salt.

Preferably, the electrolytic bath of a preferred embodiment of the present invention has a temperature of 25-40 ° C.,
. Having a cathode density of pH and 10~40A / dm ² of 0 to 4.5. In a second embodiment of the method of the present invention, the steel wire is first immersed in a first electrolytic bath comprising a manganese salt and then in a second electrolytic bath comprising a zinc salt, Then it is finally subjected to a thermal diffusion process.

[0023] Preferably, the first electrolytic bath also comprises citrate. Even more preferably, the citrate is sodium citrate. Preferably, the first electrolytic bath is at a temperature of 30-40 ° C, a pH of 4.5-5.5,
And it has a cathode density of 15 to 25 A / dm ² .

Preferably, the second electrolytic bath has a temperature of 20 to 30 ° C., a pH of 2.5 to 3.5,
Having a cathode density of 25~35A / dm ^2. Preferably, the heat diffusion process is performed by Joule effect by heating at a temperature of 5 to 10 seconds and 450 to 500.

In both of the above embodiments, at least one selected from zinc and manganese salts
The electrolytic bath comprising an aqueous solution of the two salts further comprises sodium citrate, sodium sulfate and manganese sulfate heptahydrate.

In a third aspect, the invention relates to a reinforcing structure for an article made from a vulcanized elastomeric material, which comprises at least one zinc / manganese binary alloy according to the invention. It is characterized by including a steel wire.

In a further fourth aspect, the invention relates to a vulcanized elastomer characterized by being reinforced with a structure comprising at least one steel wire coated with a zinc / manganese binary alloy according to the invention. About the material.

Typically, the product is a tire, a conveyor belt, a transmission belt or a flexible hose. Furthermore, it has surprisingly been found that the steel wire coated with the binary alloy of the invention has a vulcanized elastomeric matrix of at least 0.2% by weight with respect to the weight of the elastomeric material. When comprising a suitable adhesion promoter corresponding to divalent cobalt metal, it has better adhesion to the vulcanized elastomeric matrix than brass-coated steel wire.

Thus, a further aspect of the present invention is embedded in a vulcanized elastomer matrix obtained from a mixture comprising at least one vulcanizable elastomer and at least one vulcanizing agent consisting of sulfur or a derivative thereof. Article comprising at least one metal wire, wherein the metal wire is made of steel coated with a zinc / manganese binary alloy comprising 0.3-4.9% by weight manganese. And wherein the mixture further comprises a divalent cobalt salt in an amount corresponding to at least 0.2% by weight of divalent cobalt metal with respect to the weight of the elastomer.

Preferably, the amount of the divalent cobalt salt is 0.2% with respect to the weight of the elastomer.
It corresponds to an amount of divalent cobalt metal of １1% by weight. Preferably, the divalent cobalt salt has the formula (I)

[0031]

Embedded image (Wherein R is a C _6-24 aliphatic or aromatic group), a carboxylate represented by the formula (II):

[0032]

Embedded image Wherein R ′, R ″ and R ′ ″ are the same or different and are C _6-24 aliphatic or aromatic groups, and mixtures thereof. Is selected from the group consisting of

Preferred examples of R—CO—O—, R′—CO—O—, R ″ —CO—O—, and R ′ ″ — CO—O— are n-heptanoate, 2,2- Dimethylpentanoate, 2-ethyl-pentanoate, 4,4-dimethyl-pentanoate, 2-ethyl-esanoate, n-octanoate, 2,2-dimethyl-esanoate,
It is selected from neodecanoate and naphthenate.

A preferred example of a salt of formula (I) is cobalt neodecanoate. A preferred example of a salt of formula (II) is cobalt-boron 2-ethyl-esanoate toneodecanoate.

Typically, the mixture further comprises other conventional components, for example, silica, resorcin and hexamethoxymethylamine. The present invention is further described by the following examples and figures which are intended to illustrate the invention but do not limit the invention in any way.

FIG. 1 shows a wire cord of the present invention embedded in a vulcanized elastomer matrix; FIG. 2 is a cross-sectional view of a tire according to the present invention; FIG. 3 is a cross-sectional view of a conveyor belt according to the present invention. FIG. 4 is a cross-sectional perspective view of a transmission belt according to the present invention; FIG. 5 is a cross-sectional perspective view of a flexible hose according to the present invention.

In particular, FIG. 2 shows a tire made from a reinforcing structure comprising a vulcanized elastomeric matrix and at least one steel wire coated with a layer of a zinc / manganese binary alloy according to the invention. . In a preferred embodiment, the vulcanized elastomeric matrix of the tire comprises at least one vulcanizable elastomer,
At least one vulcanizing agent comprising sulfur or a derivative thereof, and a divalent cobalt salt selected from the group comprising cobalt-boron 2-ethyl-esanoate toneodecanoate and cobalt neodecanoate according to the present invention Obtained from a mixture comprising:

The tire is mounted on a rim 13 and the bead 10, bead core 12
, Carcass ply 14, belt 15, tread 16 and side wall 17. The belt 15 is made of a cord of steel wire coated with a zinc / manganese binary alloy layer according to the invention.

FIGS. 3 to 5 show a conveyor belt 20, a transmission belt 30 and a flexible hose 40, respectively, each of which is made of a steel wire coated with a zinc / manganese binary alloy layer according to the invention. Made of vulcanized elastomeric matrix reinforced by cord 15. Preferably, in each of the products, the vulcanized elastomeric matrix comprises at least one vulcanizable elastomer, at least one vulcanizing agent consisting of sulfur or a derivative thereof, and a cobalt-boron 2-ethyl-esanoate according to the invention. Obtained from a mixture comprising a divalent cobalt salt selected from the group comprising toneodecanoate and cobalt neodecanoate.

In the following examples, the abbreviation 3 × 0.28 means a cord made of three wires 0.28 mm in diameter; the abbreviation 2 + 1 × 0.28 means a cord of 0.28 mm in diameter.
Means a cord made of two wires and a third wire of the same diameter wound around it; the abbreviation 2 + 3 × 0.28 is a cord made of two strands, one of which is: The second means a cord made of two wires of 0.28 mm diameter, and the second made of three wires of the same diameter.

Other abbreviations used in the examples have the following meanings: R. = Natural rubber C.I. B. = Carbon black HMMM = Hexamethoxymethyl melamine DCBS = N, N'-dicyclohexyl-2-benzothiazylsulfenamide The amounts of the components of the exemplified vulcanizable mixture are expressed in parts by weight. Example 1 One-Step Deposition A galvanic bath capable of depositing a layer of a zinc / manganese binary alloy according to the invention consisting of 99.7% by weight of zinc and 0.3% by weight of manganese on a steel wire comprises:
The following components: Zinc ⁺⁺ 1.13 mol / l Mn ⁺⁺ 1.06 mol / l Mg ⁺⁺ 0.25 mol / l

The starting material used to make the bath was: zinc sulfate heptahydrate 325 g / l manganese sulfate monohydrate 180 g / l magnesium sulfate heptahydrate 50 g / l.

The operating conditions were: bath temperature 30 ° C. pH of the bath 3.5 cathodic current density (zinc anode) 30 A / gm ² Wire treatment speed 25 m / min.

A 1.8 micron thick layer of a Zn / Mn binary alloy was thus obtained. Example 2 One-Step Deposition A galvanic bath capable of depositing a layer of a zinc / manganese binary alloy according to the invention consisting of 95.5% by weight of zinc and 4.5% by weight of manganese on a steel wire comprises:
It has the following components: Zn ⁺⁺ 1.13 mol / l Mn ⁺⁺ 1.06 mol / l Na ⁺ 0.35 mol / l

The starting material used to make the bath was: zinc sulfate heptahydrate 325 g / l manganese sulfate monohydrate 180 g / l sodium citrate 30 g / l.

The operating conditions were: bath temperature 35 ° C. bath pH 4 cathodic current density (zinc anode) 15 A / gm ² wire treatment speed 15 m / min.

In this way, a Zn / Mn binary alloy 1.5 μm thick layer was obtained. Example 3 Two-Step Deposition The steel wire according to the invention can firstly be deposited with 0.3% by weight of manganese having the following composition: Mn ⁺⁺ 0.177 mol / l Na ⁺ 1.84 mol / l. It was immersed in a galvanic bath.

The starting material used to make the bath was: manganese sulfate monohydrate 30 grams / liter sodium citrate 180 grams / liter.

The operating conditions were: bath temperature 35 ° C. bath pH 5 cathodic current density (manganese anode) 20 A / gm ² wire treatment speed 70 m / min.

In this way, a layer having a thickness of 0.005 μm of Mn was deposited. The steel wire was then immersed in a galvanic bath capable of depositing 99.7% by weight of zinc, having the following composition: Zn ⁺⁺ 1.39 mol / l Na ⁺ 0.70 mol / l.

The starting material used to make the bath was: zinc sulfate heptahydrate 400 grams / liter sodium sulfate 50 grams / liter.

The operating conditions were: Bath temperature 25 ° C. Bath pH 3 Cathode current density (zinc anode) 30 A / gm ² Wire treatment speed 70 m / min.

Thus, a layer of Zn 1.6 μm thick was deposited. The steel wire is then subjected to thermal diffusion by the Joule effect by heating it at 500 ° C. for 5-10 seconds, thus obtaining a zinc / Mn binary alloy 1
. A 6 micron thick layer was obtained. Example 4 Two-Step Deposition The steel wire according to the invention can first be deposited with 4.5% by weight of manganese having the following composition: Mn ⁺⁺ 0.177 mol / l Na ⁺ 1.84 mol / l. It was immersed in a galvanic bath.

The starting material used to make the bath was: manganese sulfate monohydrate 30 grams / liter sodium citrate 180 grams / liter.

The operating conditions were: Bath temperature 35 ° C. Bath pH 5 Cathode current density (manganese anode) 20 A / gm ² Wire processing speed 60 m / min.

Thus, a layer having a thickness of 0.07 μm of Mn was deposited. The steel wire was then immersed in a galvanic bath capable of depositing 99.5% by weight of zinc having the following composition: Zn ⁺⁺ 1.39 mol / l Na ⁺ 0.35 mol / l.

The starting material used to make the bath was: zinc sulfate heptahydrate 400 grams / liter sodium sulfate 50 grams / liter.

The operating conditions were: Bath temperature 25 ° C. Bath pH 3 Cathode current density (zinc anode) 30 A / gm ² Wire treatment speed 60 m / min.

A layer 1.55 μm thick Zn was thus deposited. The steel wire is then subjected to thermal diffusion by the Joule effect by heating it at 500 ° C. for 5-10 seconds, thus obtaining a zinc / Mn binary alloy 1
. A 62 micron thick layer was obtained. Example 5 Corrosion Resistance Initiation of rust formation on five steel wires coated according to the invention (made from three wires of 0.28 mm diameter each) immersed in a 4% aqueous NaCl solution at 25 ° C. It was determined by measuring the time required.

The coating has the following composition: Code A: 99.7% zinc and 0.3% manganese; Code B: 99.3% zinc and 0.7% manganese; Code C: 99% zinc and 1% manganese Code D: zinc 97.5 and manganese 2.5%; code E: zinc 96% and manganese 4%.

Table 1 shows the results.

[0062]

[Table 1] Comparative Example 1 Corrosion Resistance The process was performed as in Example 5 above; except that the test was performed using four steel cords coated according to the prior art (each made with three wires 0.28 mm in diameter). I went about.

The coating has the following composition: Code F: 70% copper, 29% zinc and 1% manganese (EP 01
Code G: 70% copper, 26% zinc and 4% manganese (EP-A-01)
No. 88851); code H: 67% copper and 33% zinc (brass); code I: 100% zinc.

Table 2 shows the results.

[0065]

[Table 2] Example 6 Corrosion Resistance Corrosion resistance was measured at two different conditions: 65 ° C. and 90% R.C. H. 3 in the climate room
0 days (Test I) and at 40 ° C. and 100% R.C. H. The so-called “Salty Fog (
The ultimate tensile strength (TS) simulated before and after aging for 2 days (Test II) in a “salty fog” room (5% aqueous NaCl solution) was measured and evaluated. A steel wire cord coated with a layer (0.3 micron thick) of a manganese binary alloy (manganese content = 0.5%) is coated with brass (67% Cu and 33% Zn) having the same thickness (0.3 micron) Compared with steel wire cord coated with.

The results are shown in Tables 3a and 3b.

[0067]

[Table 3]

[0068]

[Table 4] Example 7 Adhesion to Vulcanized Elastomer Material Adhesion to vulcanized elastomer material is measured by measuring the force required to remove a cord from a cylinder of vulcanized rubber, "Kautschk und Gummi Kunststoffe", 5,228-23
Using the method described in 2, measurements were made on test samples of the vulcanized mixture on three types of steel wire of the invention, each made of three wires 0.28 mm in diameter.

“Pull-out force” was measured in Newtons using an electronic dynamometer. Values are for a freshly prepared vulcanization test sample and a temperature of 65 ° C. and 90% relative humidity (RH
. ) For one week after aging-curing.

The composition of the mixture forming the vulcanized rubber was as follows in parts by weight (%): natural rubber 100 ZnO 8 divalent cobalt 0.2 carbon black 50 silica 10 resorcin 3 hexamethoxymethylene melamine 2.4 Dicyclohexylbenzothiazole sulf 1.1 phenamide sulfur 4 trimercaptotriazine 0.5 The results are shown in Table 4.

[0071]

[Table 5] SD = standard deviation Comparative Example 2 Attachment to Vulcanized Elastomer Material The process was performed in a manner analogous to the method of Example 7 above, except that two types of prior art steel cord (each 0.28 mm diameter) A test sample of the mixture having the above composition vulcanized on the above (made of three wires) was used.

Table 5 shows the results.

[0073]

[Table 6] SD = standard deviation * u = 67% and Zn = 33%; * * Cu = 70%, Zn = 29% and Mn = 1%; * * * Cu = 70%, Zn = 26% and Mn = 4% Example 8 Drawability Three steel wires (diameter 1.60 mm) according to the invention were drawn to a final diameter of 0.28 mm at a speed of 16 m / s using a device of type HP18 from Herborn. Before the drawer plate was exhausted, the number of meters of the manufactured wire was measured. The weight loss% of the deposited zinc / manganese alloy was also measured.

Table 6 shows the results obtained.

[0075]

[Table 7] Comparative Example 3 Drawability The process was performed in a manner similar to that of Example 8 above; however, three prior art steel wires were drawn.

Table 7 shows the results obtained.

[0077]

[Table 8] ★ Zn = 93% and Mn = 7% ★★ Cu = 67% and Zn = 33% Example 9 Vulcanized Elastomer Material A cylindrical test sample was prepared according to the present invention in a mixture having the composition shown below. Steel wire cord coated with zinc / manganese binary alloy layer (0.3 thickness)
2 + 1 × 0.28, 2 + 3 × 0.28 and 3 × 0.28). The mixture was then vulcanized at 151 ° C. for 40 minutes.

The embedded length of the code in the test sample is 2 + 1 × 0.28 and 2 + 3 × 0
. 6 mm for 28 codes and 1 for 2 + 3 × 0.28 codes
2 mm.

Mixture Component ABCD N. R. 100 100 100 100 ZnO 55 55 C. B. 42 42 42 42 Silica 13 13 13 13 Aromatic oil ⁵⁵ 55 Co ⁺⁺ 0.3 ^a) 0.5 ^a) 0.2 ^a) 0.2 ^b) Resorcin 2.5 2.5 2.5 2.5 5 HMMM 3.3 3.3 3.3 3.3 DCBS 0.8 0.8 0.8 0.8 Sulfur 55 55 Protecting agent 33 33 a = boron-cobalt 2-ethylhexanoate As neodecanoate b = as cobalt neodecanoate. Example 10 Adhesion to Vulcanized Elastomer Material Adhesion was measured in a manner analogous to that of Example 7 above; except that test samples were prepared as described in Example 9 above.

The pullout force was measured in Newtons using an electronic dynamometer. The degree of coating of the cord drawn from each test sample was evaluated according to a coating index rating from 1 to 4, depending on the percentage of the cord surface still well covered by the elastomeric material.

The initial adhesion values (Test I) and the adhesion values measured after holding the test samples in a climatic room at 65 ° C. and 90% RH for 8 days (Test II) are shown in Tables 8a and 8b below.
And 8c, where the first number is the adhesion value as an average of eight tests, while the index in parentheses is the degree of coating of the cord.

[0082]

[Table 9] (★) Made of wire coated with a zinc / manganese binary alloy with a manganese content of 0.5%.

[0083]

[Table 10] (★) Made of wire coated with a zinc / manganese binary alloy with a manganese content of 0.5%.

[0084]

[Table 11] (★) Made of wire coated with a zinc / manganese binary alloy with a manganese content of 0.5%.

(★★) Made with a wire coated with a zinc / manganese binary alloy with a manganese content of 1.1%. Comparative Example 4 Attachment to Vulcanized Elastomer Material The process was performed in a manner similar to that of Example 10 above, except embedded in the vulcanized elastomer matrix obtained by vulcanization of the mixture described in Example 9 above. A steel wire coated with brass (67% copper and 33% zinc) was used.

The results are shown in Tables 9a, 9b and 9c.

[0087]

[Table 12]

[0088]

[Table 13]

[0089]

[Table 14]

[Brief description of the drawings]

FIG. 1 shows a wire cord of the present invention embedded in a vulcanized elastomeric matrix.

FIG. 2 is a sectional view of a tire according to the present invention.

FIG. 3 is a sectional perspective view of a conveyor belt according to the present invention.

FIG. 4 is a sectional perspective view of a transmission belt according to the present invention.

FIG. 5 is a sectional perspective view of a flexible hose according to the present invention.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), AL, AU, BR, BY, CA, CN, CZ, ID, JP, KR, LT, LV, MK, MX, RO, RU, SI, SK, TR, UA, US Lotti, Pietro Luigi Italy-20131 Milan, Viale Abruzzi 72 (72) Inventor Bozini, Benedetto Italy-20121 Milan, Via Luigi Albertini 18 F-term (reference) 4F072 AA04 AA07 AB11 AB22 AC16 AD02 AE01 AF01 AF13 AF14 AF17 AF26 AK14 AL03 AL18 AL19 4K023 AB29 BA06 CA09 CB03 DA02 DA06 DA 07 DA08 4K024 AA15 AA17 BA02 BC03

Claims (24)

[Claims] 1. A surface treated steel wire for a reinforcing structure for an article made from a vulcanized elastomeric material, wherein the wire is coated with a layer of a metal alloy, A reinforcing structure for a product made from said vulcanized elastomeric material, characterized in that the alloy is a zinc / manganese binary alloy comprising 0.3 to 4.9% by weight of manganese. Surface treated steel wire for. 2. The surface-treated steel wire according to claim 1, wherein the manganese content is 0.3 to 4.5% by weight. 3. The surface-treated steel wire according to claim 2, wherein the manganese content is 1.5 to 4.0% by weight. 4. The surface-treated steel wire according to claim 1, wherein said layer of a surface coating is formed by electrodeposition. 5. A reinforcing structure for a product made from a vulcanized elastomeric material, which is coated with a zinc / manganese binary alloy according to claim 1. A reinforcing structure for articles made from the vulcanized elastomeric material, characterized in that it comprises at least one steel wire. 6. A product made from a vulcanized elastomeric material, comprising at least one steel wire coated with a zinc / manganese binary alloy according to claim 1. Characterized by being strengthened by structures
Articles of manufacture made from the vulcanized elastomeric material. 7. The product according to claim 6, wherein the product is a tire, a conveyor belt, a transmission belt or a flexible hose. 8. At least one metal wire embedded in a vulcanized elastomer matrix obtained from a mixture comprising at least one vulcanizable elastomer and at least one vulcanizing agent comprising sulfur or a derivative thereof. 5. The product according to claim 1, wherein the metal wire is a zinc / metal alloy according to any one of claims 1 to 4.
Characterized in that it is made of steel coated with manganese binary, and the mixture has at least 0.1% of divalent cobalt metal with respect to the weight of the elastomer.
The above product further comprising a divalent cobalt salt in an amount corresponding to 2% by weight. 9. The method according to claim 1, wherein the amount of the divalent cobalt salt corresponds to an amount of 0.2 to 1% by weight of divalent cobalt metal with respect to the weight of the elastomer.
A product according to claim 8. 10. The divalent cobalt salt has the formula (I): Wherein R is a C _6-24 aliphatic or aromatic group, a carboxylate of the formula (II): Wherein R ′, R ″ and R ′ ″ are the same or different and are C _6-24 aliphatic or aromatic groups, and mixtures thereof. 10. The product according to claim 8 or 9, wherein the product is selected from the group consisting of: 11. R-CO-O-, R'-CO-O-, R "-CO-O-,
R ′ ″ — CO—O— is n-heptanoate, 2,2-dimethylpentanoate, 2-ethyl-pentanoate, 4,4-dimethylpentanoate, 2-
The product according to claim 10, characterized in that it is selected from ethyl-esanoate, n-octanoate, 2,2-dimethyl-esanoate, neodecanoate and naphthenate. 12. The product according to claim 8, wherein the divalent cobalt salt of the formula (I) is cobalt neodecanoate. 13. The method according to claim 8, wherein the divalent cobalt salt of the formula (II) is cobalt-boron 2-ethyl-esanoate-neodecanoate. Product. 14. The product according to claim 8, wherein the product is a tire, a conveyor belt, a transmission belt, or a flexible hose. 15. A method for electrodepositing a zinc / manganese binary alloy comprising 0.3-4.9% by weight manganese on a steel wire passing through an electrolytic bath, the steel wire comprising: Passing through at least one electrolytic bath consisting of an aqueous solution of at least one salt selected from zinc and manganese salts, wherein the electrolytic bath has a temperature of 20-50 ° C., a pH of 2-6, and a cathode of 10-50 A / dm ² . The electrodeposition method, wherein the electrodeposition method has a density. 16. The method according to claim 15, wherein the processing speed of the wire is 10 to 70 m / min. 17. The method according to claim 15, wherein the zinc salt and the manganese salt are sulfates. 18. The method according to claim 17, wherein the zinc sulfate is zinc sulfate heptahydrate. 19. The method according to claim 17, wherein the manganese sulfate is manganese sulfate monohydrate. 20. The method according to claim 15, wherein the steel wire is immersed in a single electrolytic bath comprising a manganese salt and a zinc salt. 21. The steel wire is immersed first in a first electrolytic bath comprising a manganese salt, then in a second electrolytic bath comprising a zinc salt, and finally in a heat diffusion process. 21. A method according to any one of claims 15 to 20, characterized in that: 22. A method for improving the drawability of a steel wire for drawing, comprising coating the steel wire with a zinc / manganese binary alloy containing 0.3-4.9% manganese. A method for improving the drawability of the wire drawing steel wire. 23. The zinc / manganese binary alloy having a manganese content of 0.3
23. The method according to claim 22, characterized in that it is ~ 4.5%. 24. The zinc / manganese binary alloy having a manganese content of 1.5
23. The method according to claim 22, characterized in that it is ~ 4.0%.