TW440611B - A surface-treated steel wire for reinforcing structures for articles of manufacture made of elastomeric material and an article of manufacture comprising the same - Google Patents

Abstract

A surface-treated steel wire for reinforcing structures for articles of manufacture made of vulcanized elastomeric material, in which the said wire is coated with a layer of metal alloy, wherein the said alloy is a zinc/manganese binary alloy comprising from 0.3 to 4.9% by weight of manganese.

Description

A7 B7 4406 1 ί 5. Description of the invention (1 Description of the invention The invention relates to a steel wire for strengthening the structure of an object made of a vulcanized elastomer material, which is surface-treated with a metal alloy, and a type of steel wire embedded in the vulcanization. Articles made of elastomer materials. The invention further relates to a method for coating steel wires using the alloy. In particular, the invention relates to steel wires coated with zinc / bell alloys, in which the manganese content is below 4.9% by weight. The invention It also relates to a reinforced structure containing the steel wire, and a manufactured article made of the vulcanized elastomer material containing the reinforced structure. As is known, tires and many other manufactured articles made of vulcanized elastomer materials often incorporate metal Reinforced structures made of cords are each made of a plurality of metal wires properly locked by standard weaving operations. Considering the excellent mechanical properties of steel wires, steel is known as the metal of choice for this structure. However, The chemical properties of steel are not excellent because they do not adhere well to vulcanized elastomer materials and have poor corrosion resistance. To overcome these Point, steel is often coated with a metal layer or a metal alloy layer. Generally, the coating is a brass layer containing about 70% by weight steel and about 30% by weight zinc. In this case, the reason for the adhesion enhancement is via Sulfur itself forms a thin CuxS layer of copper sulfide through its known derivatives that exist in the vulcanization mixture as a vulcanizing agent. Although brass-coated steel has good adhesion to the elastomeric parent material, the adhesion changes with time. Decay 'is due to the effects of humidity and oxygen. It is true that this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) — ^ 1' --- m 1 ^ 1 u «ll \ t /. H ^ -HI n · HI m ^ —r Ping ·,-&-«I (Please read the notes on the back of the dish before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 4 4406 1 t A7 --- --- B7 V. Description of the invention (2) '', an object made of a vulcanized elastomer material reinforced with yellow steel coated steel wire, optionally in the form of a cord, for example, for tires, because the moisture penetrates the elastomer due to moisture , As well as water made through brass holes or tears in contact with brass-coated steel Strong materials. Brass / elastomer adhesion failure can be partially counteracted by adding some salt form of cobalt (US 5 356 711). It is believed that cobalt can reduce the conductivity of the copper sulfide layer. 'This slows down the diffusion of Zn ++ ions. Rate, and as a result, the growth rate of the ZnO / Zn (OH) 2 interface, which caused film damage, was slowed down. As a result, a partial improvement was obtained. However, brass-coated steel has only mild resistance to corrosion. This facilitates Research on different metal or alloy layers. US-4,651,513 describes steel cables used to reinforce rubber products such as tires. Steel cables contain a plurality of steel wires twisted together to form a multifilament laminate with two or more continuous steel wire layers surrounding a common center. Cable. The outermost steel wire cover-can be adhered to a rubber coating such as brass, while the inner steel wire is coated with an anticorrosive coating such as zinc itself or zinc alloy. Among the various binary and ternary alloys mentioned in this patent (column 5, lines 49-54) are also zinc / tungsten alloys. However, the document did not exemplify or specify the manganese content of the alloy. In fact, the aforementioned patents clearly state that the most practical coatings are pure zinc coatings (column 5, lines 54-58). ΕΡ-Α-0 188 851 describes a steel reinforcing element for vulcanized rubber products, wherein the element is covered with a coating that can be adhered to rubber. This layer is made of brass and contains at least 50% copper and 0.01 to 15% The weight ratio is fierce. This paper size applies to China National Standard (CNS) Α4 size (210 × 297 mm) ml n--. ^ 1 »r -------- I — installed! -'(Please open the note on the back of Jing 呗 #% 写 本 耳' '订 Order-7. Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7

1 I V. Description of the invention (3) In the previous reference, the wire coating whose function is to adhere to rubber includes separate yellow steel (copper / zinc alloy contains about 70% copper and about 30% zinc), or Yellow Steel and Meng (Ternary Alloy) However, the aforementioned coatings still have the disadvantages associated with steel. Therefore, it is still necessary to meet the requirements of good corrosion resistance of steel wires and good adhesion of steel wires to vulcanized elastomer parent materials. This is unexpected. It was found that the coating made of zinc / manganese binary alloy, which has a manganese content of 0'3 to 4.9%, has improved corrosion resistance after aging and hardening, and has a higher corrosion resistance than brass, zinc itself or brass and manganese. Element alloys have higher adhesion to vulcanized elastomer materials. On the one hand, the present invention relates to a surface-treated steel wire made of reinforced vulcanized elastomer materials for the manufacture of object structures, wherein the steel wire is coated with a layer of metal alloy And its feature is that the alloy is a zinc / manganese binary alloy containing 0.3 to 4.9% by weight. Preferably, the content of the one-component alloy of the present invention is to 4.5% by weight, and more preferably 1,5 to 4% by weight. Typical 'surface coating is made of electricity It is formed on the surface of the steel wire. Prior to calendering, the thickness of the coating layer of the steel wire is preferably 丨 to 4 micrometers. However, the thickness of the layer after rolling is typically 0J to 0.4 micrometers. It is suitable for the electricity of the present invention. Preferred examples of the zinc salt of the deposition method are selected from the group consisting of sulfates, sulfamates, hypophosphites, picrates, selenate and thiocyanates. More preferred are sulfates and sulfamates. A preferred example of a manganese salt suitable for use in the electrodeposition method of the present invention is that the standard of the paper is applicable to the Chinese National Standard (CNS) A4 (2ΐ〇χ297 公 楚) IIIII ί I II I _ I j; τ., '-i (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -6 Α7 Β7 44 06 1 1 V. Description of the invention (4) Selected from the group including sulfate , Amino acid salts, Acetates, Formates, Iodates, Lactates, Phosphates, Selenates, Thiocyanates, Bisulphates and Pivalates. And even better, 'Zheng Salt' It is a sulfate and an amine sulfonate. In a second aspect, the present invention relates to an electrolytic deposition containing 0.3 to 4.9% by weight. A method of passing zinc and via a binary alloy through electrolysis and steel wire, characterized in that the steel wire is passed through an electrolytic bath composed of at least one aqueous solution selected from zinc salt and manganese salt. The electrolytic bath has: a temperature of 20 To 50 ° C; pH 2 to 6; and cathode density 10 to 50 A / dm2. Typical 'wire flux speed is 10 to 70 m / min, and more typically 18 to 50 m / min. Typical' The zinc and manganese salts used by horses are sulfates. More typically, zinc sulfate is zinc sulfate heptahydrate and manganese sulfate is sulfate chain monohydrate. In a preferred embodiment of the method of the present invention, the steel wire is immersed in manganese-containing Single electrolytic bath of salt and zinc salt. Preferably, the electrolytic bath of the preferred embodiment of the present invention has a temperature of 25 to 40 ° C 'pH 3.0 to 4.5 and a cathode density of 10 to 40 A / dm2. In a second specific example of the method of the present invention, the steel wire is first immersed in a first electrolytic bath containing a manganese salt, then immersed in a second electrolytic bath containing a zinc salt, and finally a thermal diffusion process is performed. Preferably, the first electrolytic bath also contains citrate. It is even better that the paper is applied to the Chinese National Standard (CNS) Α4 · _ (210 > < 297mm) '--7-(Please read the precautions on the back before filling this page) & quot Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4406 1 1 at ___ B7 V. Description of the Invention (5) Salt is sodium citrate. Preferably, the temperature of the first electrolytic bath is 30 to 40 °. 〇, pH is 4.5 to 5.5 and cathode density is 25 to 35 A / dm2. Preferably, the second electrolytic bath has a temperature of 20 to 30. 〇, the pH is 2.5 to 3.5 and the cathode maleity is 25 to 35 A / dm2. Preferably, the 'thermal diffusion process is performed by heating the steel wire at a temperature of 450 to 500 ° C for 5 to 10 seconds using the Joule effect.' In the foregoing two specific examples, the electrolytic bath is composed of an aqueous solution of at least one salt selected from the group consisting of zinc salts and manganese salts. It also contains sodium citrate, sodium sulfate and magnesium sulfate heptahydrate. In a third aspect, the present invention relates to a reinforced structure of an article made of a vulcanized elastomer material, characterized in that it comprises at least one steel wire coated with a zinc / manganese binary alloy according to the present invention. In a fourth aspect, the present invention relates to a vulcanized elastomer material, which is characterized by being reinforced by a structure comprising at least a steel wire coated with a zinc / manganese binary alloy according to the present invention. Typically, the item is a tire, a conveyor belt, a drive belt, or a hose. Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ^^^ 1 l »l ^ i HB— E ^-II nfl ^ im ^ i 4HH n ^.-, (Please read the precautions on the back before filling this page ) It was further unexpectedly discovered that the surface of the steel wire coated with the binary alloy of the present invention has better adhesion to the vulcanized elastomer matrix than the steel wire coated with brass. At this time, the vulcanized elastomer matrix contains The material weight corresponds to a suitable adhesion promoter of at least 0.2% by weight of divalent cobalt metal. Therefore, another aspect of the present invention relates to a manufacturing object including at least one metal wire embedded in a vulcanized elastomer matrix. The vulcanized elastomer matrix paper size is applicable to Chinese national standards (CNS > A4 specifications (21〇). > < 297 Gong Chu :) 4406 1 A7 B7 V. Description of the invention (The quality is obtained by a mixture of a vulcanizing agent containing at least one vulcanizable elastomer and at least one sulfur or a derivative. The characteristics of the manufactured article are: The metal wire is made of a steel wire coated with a zinc / manganese binary alloy containing 0.3 to 4.9% manganese by weight, and the mixture further includes a divalent salt, the content of which corresponds to at least 0% based on the weight of the elastomer % By weight of divalent cobalt metal.. Preferably, the amount of divalent cobalt salt corresponds to 0.2 to 1% by weight of divalent cobalt metal based on the weight of the elastomer. Preferably, the 'divalent cobalt salt is selected from the group consisting of Formula ⑴carboxylate compound (R ~ C 0-0-) 2 Co (I) where R is a C6.24 aliphatic or aromatic group, and a cobalt-boron complex Q-Co-0-COR , --------------.-- Order,-(Please read the notes on the back before filling this page) R ,, OC-0-Co-〇 / \ O-Co- O-COR5 (Π) Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs where R ', R "and R," are the same or different from each other. Each is a C6 24 aliphatic or aromatic group, and mixtures thereof. R-CO Preferred examples of -O-, r'_C0_0 ·, R "_c〇_〇 and R", _c〇〇 are selected from the group consisting of n-heptanoate, 2,2-dimethylvalerate, and 2-ethylpentyl. The preferred examples of the acid '4,4-dimethylvalerate' 2-ethylhexanoate, n-octyl. Acid, 2,2_diamidinohexanoate 'neodecanoate and feltate β-type phosphonium salts are neodecanoate Cobalt acid. A preferred example of the salt of formula (Π) is 2-ethylhexanoate-cobalt neodecanoate-boron.

I 9 Printed by the Central Standards Bureau, Ministry of Economic Affairs, Consumer Cooperatives 44 06 1 1 A7 B7 V. Description of the Invention (7)-The mixture typically contains other conventional ingredients, such as "oxygen, metabenzidine and hexamethyloxymethyl" A Brief Description of the Drawings The present invention is further illustrated by the following examples and the drawings, which are used for illustrating the present invention and are by no means limited. Figure 1 shows that the cord of the present invention is embedded in a vulcanized elastic Zhao Base material; 2) is a sectional view of a tire according to the present invention; 3 is a perspective view of a conveyor belt according to the present invention; 4 is a perspective view of a drive belt according to the present invention; 5 is a view according to the present invention Sectional perspective view of a flexible hose. Detailed description of the invention In particular, Figure 2 shows a tire made of a vulcanized elastomer matrix and a reinforcing material, comprising at least one steel wire coated with a zinc / manganese binary alloy layer according to the present invention. 》 In a preferred embodiment, the vulcanized elastomer matrix of the tire is obtained from a mixture containing at least one vulcanizable elastomer, at least one vulcanizing agent consisting of sulfur or a derivative thereof, and a second cobalt salt selected root The 2-ethylhexanoate-cobalt neocaprate_boron and neodecanoic acid drill of the present invention. The tire is mounted on the bead 13 and its composition is: a tire lip 10, a tire core 12 'a reinforcing layer 14' a belt 15, tread 16 and sidewall 17 »The belt 15 is made of steel cord coated with a layer of the zinc / violet binary alloy of the present invention. Figures 3 to 5 show a conveyor belt 20, a drive belt 30 and a flexible hose 40, each of which is reinforced by a vulcanized elastomer base material with cords 丨 5, the cords are made of steel wire coated with a layer of the zinc / manganese binary alloy of the present invention. Fresh (CNS) A4 ^ (21QX297 Gongchu) --------- 』> Outfit -------- · Order ------! Ten-_-.-'(Please listen first Read the notes on the back and fill in this page again) 10 440611 A7 '________B7 V. Description of the Invention (S) In each of the articles, the parent material of the vulcanized elastomer is derived from a mixture containing at least one vulcanizable elastomer and at least one made of sulfur The vulcanizing agent 'or its divalent cobalt salt composed of or its derivative is selected from the group consisting of 2-ethylhexanoate-cobalt neo-caprate-boron and cobalt neodecanoate according to the present invention. The abbreviations 3 X 0.28 in the following examples represent cords It is made of 3 steel wires straight 0.28 mm; the abbreviation 2+ 1 X0.28 means that the cord is made of 2 steel wires with a diameter of 0.28 mm and is round with a third wire of equal diameter wound around it; the abbreviation 2 + 3X0.28 indicates that the cord is made of two strands, one strand is made of two steel wires with a diameter of 0.28 mm and the second strand is made of three steel wires with the same diameter. The other abbreviations used in the examples are defined as follows: NR = natural rubber, C. B, = carbon black, HMMM = hexamethoxymethyl melamine DCBS = N, N, dicyclohexyl-2-benzothiazolylsulfenimide vulcanizable mixture. Number-to-weight ratio. Printed by a member of the Ministry of Health and Human Services Bureau, printed by a consumer cooperative-I ^^ 1 —II ί.--I- ......---· — I HI. Ζ I-(谙Note: Please fill in this page again} Example 1 A single-stage deposition can deposit a layer of zinc / magnesium binary alloy zinc bath according to the present invention, which consists of 99.7% zinc by weight and 0.3% manganese by weight, with the following Composition: This paper size applies the Chinese National Standard (CMS) M specification (210X297 mm) 4 4 061 1 B7 V. Description of the invention (9) Zn ++ 1.13 mol / l Mn ++ 1.06 mol / l Mg ++ 0.25 mol / l The starting materials for the preparation of the aforementioned bath are: 325 g of zinc sulfate heptahydrate / liter of sulphate monohydrate 180 g / liter of sulphuric acid heptahydrate of 50 g / liter. The operating conditions are: bath temperature 30 ° C bath pH 3.5 (Please read the precautions on the back before filling out this page) The cathode current density (zinc anode) of the 30A / dm2 steel wire printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs has a flux speed of 25 seconds / min. / Mn binary alloy layer. Example 2 A single-stage deposition can be used to deposit a layer on steel wire. The zinc / manganese binary alloy galvanizing bath of the present invention is composed of 95.5% by weight and 4.5% by weight of manganese, and has the following composition:

Zn ++ 1.13 moles / liter Mn ++ 1.06 moles / liter Na + 0.35 moles / liter This paper size applies to Chinese national standards (CNS > A4 size (210 X 297 cm) 12 4406 1 1 A7 B7 V. Description of the invention (i〇 The starting materials used to prepare the aforementioned bath are: zinc sulfate heptahydrate, sodium sulfate citrate monohydrate, sodium citrate. 325 g / L 180 g / L 30 g / L Operating conditions: 35 ° C 4 Cathodic current of the bath Density (zinc anode) 15A / dm2 Flux speed of steel wire 15 seconds / min. Thus, a layer of zinc / manganese binary alloy with a thickness of 1.5 micron is obtained (please read #note on the back side before filling this page) Central standard of the Ministry of Economy 30 grams / liter 180 grams / liter printed by Bureau employee consumer cooperative Example 3 Two-stage deposition The steel wire of the present invention is first immersed in a zinc bath which can deposit 0.3% by weight manganese, the composition is as follows:

Mn ++ 0.177 mol / l

Na + 1.84 Molars / liter The starting compounds used in the preparation of the aforementioned baths are: Sodium citrate monohydrate sodium citrate This paper is sized to the Chinese National Standard (CNS) A4 (2 丨 0X297 mm) 13 4 ^ 06 1 t A7 B7 V. Description of invention (Π) The operating conditions are: (Please read the precautions on the back before filling this page) Bath temperature 35 ° c Bath pH 5 Cathodic current density (manganese anode) 20 A / dm2 Wire flux At a speed of 70 m / min, a layer of manganese with a thickness of 0.005 microns was thus deposited. The aforementioned steel wire is then immersed in a galvanizing bath, which can deposit 99.7% zinc by weight, the composition is as follows:

Zn ++ 1.39 moles / liter Na + 0.70 moles / liter The starting materials used to prepare the aforementioned bath are: zinc sulfate heptahydrate 400 g / liter sodium sulfate 50 g / liter Operating conditions are: bath temperature 25 ° C bath pH 3 Cathode current density (zinc anode) 30 A / dm2 Wire flux speed 70 m / min. The Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs printed a zinc layer so deposited to a thickness of 1.6 micrometers. The steel wire is then heated at 500 ° C for 5-10 seconds, and the Joule effect is used to receive thermal diffusion, thus obtaining a layer of zinc / manganese binary alloy with a thickness of 1.6 microns. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 14 ^ .4 〇6 1 I a? B7 V. Description of the invention (12) Example 4 Two-stage deposition A galvanizing bath that deposits 4.5% by weight manganese has the following composition:

Mn ++ 0.177 mol / l

Na + 1.84 mol / L The starting compounds used to prepare the aforementioned bath are: manganese sulfate monohydrate 30 g / L sodium citrate 180 g / L The operating conditions are:

Bath temperature 35 ° C Bath pH 5 Cathode current density (manganese anode) 20 A / dm2 Wire flux speed 60 m / min This deposits a layer of 0.07 micron manganese. Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Then the aforementioned steel wire is immersed in a galvanizing bath, which can deposit 95.5% by weight. The composition is as follows:

Zn ++ 1.39 mol / l

Na + 0.35 mol / liter The starting materials used to prepare the aforementioned bath are: zinc laurate heptahydrate 400 g / liter sodium sulfate 50 g / liter. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 15 4406 1 1 V. Description of the invention (13) Α7 Β7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Operating conditions: Bath temperature 25 ° C Bath pH 3 Cathode current density (zinc anode) 30A / dm2 Wire flux At a speed of 60 m / min, a 1.55 micron thick zinc layer was thus deposited. Then, the steel wire was heated for 5 to 10 seconds through 500 hours, and the Joule effect was used to receive thermal diffusion, so as to obtain a layer of zinc / manganese binary alloy with a thickness of 162 microns. Example 5 ° Anti-corrosion and anti-corrosion properties were measured by measuring 5 steel cords coated with the present invention (each made of 3 steel wires with a diameter of 0 28 mm) immersed in 2Γ (: 4% sodium chloride aqueous solution, measured Determination of the time required to initiate rust. The coating has the following composition: Cord A: 99.7% zinc and 0.3% manganese; Cord B: 99.3% zinc and 0.7% manganese; Cord C: 99% zinc and manganese; cord D: 97.5% zinc and 2.5% manganese; cord E: 96% zinc and manganese. The results are shown in Table 1. I, crack --- order | (please read the notes on the back before writing Page) Paper rule μ Cai Guanxuan X X 297 @) --- -16-440611

Table 1 Coating rusting time (minutes) Cord A · 190 Cord B 210 Cord C 250 Cord D 420 Cord E 480 Printing Comparative Example 1 Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The method of Example 5 is the same as above, but the test was performed on 4 steel cords (each made of 3 steel wires with a diameter of 028 mm) coated according to the prior art. The coating composition is as follows: Cord F: 70% steel '29% zinc and 1% manganese (EP-Α-0 188 851); Cord G: 70% copper' 26% zinc and 4% manganese (EP-Α- 0 188 851); cord Η: 67% copper and 33% zinc (brass); cord I: 100% zinc. The results are not in Table 2. Table 2 Pig iron coating time (minutes) Cord F 60 Cord G 85 Cord Η 15 Cord I 50 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 〇 > < 297 public directors) 17 ^^ 1 ^^ 1 ^^ 1 n 1 ^ 1 —II---ml ^^ 1 n ^ i ^^ 1 ml ------* (Please read the precautions on the back before filling in this page } Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4406 1 1 A7 1 -____ B7 V. Description of Invention (15) Example 6 Residual and Corrosion Resistance The cords measured before and after simulated aging under two different conditions were also simulated Final tensile strength (TS) evaluation: 30 days in a 65 ° C and 90% relative humidity climatic room (Test I); and in a so-called "salt spray, room (5% aqueous sodium vaporized solution) at 40 ° C And 100% relative humidity for two days (test. Coat one layer (0.3 micron thick) of the zinc / manganese binary alloy of the present invention (manganese content = 0.5%)) with steel cord coated with an equal thickness (0.3 micron) Comparison of steel cords of yellow steel (67% copper and 33% zinc) layers. Results are shown in Tables 3a and 3b »Table 3a Final tensile strength drop (%) 2 + 1X0.28 cord zinc / manganese brass test I 30 41 Test II 19 41 Table 3b Final tensile strength reduction (%) 2 + 3X0.28 Cord zinc / manganese brass test I 9 25 Test Π 4 15 Example 7 Adhesion to vulcanized elastomer material Size of this paper Applicable to China National Standard (CNS) A4 specification (Magic 0X297 Gongchu) --------- 、 'Installation ------ Order 1 (Please read the precautions on the back before filling this page) 18 Λ7 B7 V. Description of the invention (16) The adhesion of dished elastomeric materials is "Kautschk und Gummi Kunststoffe", 5,288-232, (1969), and the vulcanization mixture is used in three types of plastic materials. Measurement of test specimens of invented steel cords (each made of three steel wires with a diameter of 0 · 28 mm). This test measures the force required to remove the cord from a vulcanized rubber cylinder. "Pulling force" is measured using an electronic dynamometer Amount, unit is Newton. The value is measured on freshly prepared vulcanized samples, and the samples were aged and hardened for one week at 65 ° C and 90% relative humidity (RH). The mixture layer forming vulcanized rubber is as follows, in parts% by weight Ratio representation: Natural rubber 100 ZnO 8 divalent cobalt 0.2 carbon black 50 Siloxane 10 Resorcinol 3 Hexamethoxymethylenemelamine 2.4 Dicyclohexylbenzothiazole sulfenylamine 1.1 Sulfur 4 Trismethyltri ™ 0.5 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. ^ N-- I--1 ^ 1 II!--I I— n Av ^ n.---I — ^ ϋ m HI (Read the precautions on the back and then fill in this purchase) The results are shown in Table 4. This paper size applies Chinese National Standard {CNS) A4 specification (210X 297 mm) 19 4 in 1 1 A7 B7 V. Description of invention (17) Table 4 Zinc fierce coating initial tensile force (N) ± SD (N) Final opening force (N) iSD (N) Mn = 0.3% 321 26 254 18 Μ = 2% 330 18 260 19 Μ = 4% 327 26 247 21 SD = standard deviation Comparative Example 2 Adhesion to vulcanized elastomer material This method was performed in a manner similar to that of Example 7 above, but using a vulcanized mixture having the aforementioned composition on two types of prior art steel cords (each made of 3 steel wires with a diameter of 0.28 mm). The results are shown in Table 5. Table 5 Coatings Initial tensile force (N) Soil SD (N) Final tensile force (N) Soil SD (N)

Zn (100) 300 24 195 20 Brass * 332 27 261 22 CuZnMn ** 318 19 248 20 CuZnMn *** 303 22 231 21 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ---------- -*… · '(Please read the notes on the back before filling this page) SD = standard deviation * Cu = 67% and Zn = 33%; “Cu = 70%, Zn = 29% and Mn = l%; * " Cu = 70%, Zn = 26% and Mn = 4% This paper size applies to Chinese National Standard (CNS) A4 specification (210XM7 mm) 20 Λ7 _____ B7_________ V. Description of the invention (18) Example 8 The three steel wires (diameter 1.60 mm) of the present invention were rolled at a speed of 16 meters per second to a final diameter of 0.28 mm in a device obtained from Herborn's model HT 18. The number of meters of steel wires produced before the rolled plate was consumed was measured. The deposited zinc was also measured / Manganese alloy loss weight percentage β Table 6 shows the results obtained. Table 6 ZMn / Mn coating alloy wire production X 103 Loss of deposited Zn / Mn alloy Mn = 1% 2000 10 Mn = 2.5% 2000 10 Mn = 4.9% 2000 10 Printed by the Central Bureau of Standards, Ministry of Economic Affairs and Consumer Cooperatives H-1-- II— I H. -—! II ϋ ί— n In ^ r-(Please read the note on the back first Please fill in this page again.) Comparative Example 3 Calendering This method is carried out in the same manner as in Example 8 above, except that 3 prior-art steel wires are calendered. Table 7 shows the results obtained. This paper size is applicable to China National Standards (CNS) A4 specification (210 X297 mm) 21 4 ^ 〇6 1 1 A7-^ ____ B7 V. Description of the invention (19) Table 7 Loss of Zn / Mn alloy deposited by coating on steel wire X 103 Deposited ηηΜη * 1000 20 Brass ** 2000 12 Zη (100%) 2000 10 * Zη = 93% and Mη = 1% ** Cu = 67% and Zη: = 33% Example 9 The preparation of a cylindrical sample of a vulcanized elastomer material was performed by embedded coating The steel cords (2+ 1 X 0.28, 2+ 3 X 0.28 and 3 × 0 · 28) of the zinc / manganese binary alloy layer (thickness 0.3) of the present invention are used in a mixture, and the mixture has the following formula: Vulcanization at 40 ° C for 40 minutes. The embedded length of the cord in the sample is 6 mm for 2+ 1 X 0.28 and 3 X 0.28 cords and 12 mm for 2+ 3 X 0.28 cords. 1 lit-I!-I n I I --- 1-:-I ^ i ^ 1 * η I ^ '(Please read the precautions on the back before filling out this page) Paper standards for paper production use Chinese National Standard (CNS) A4 specifications (2 丨 0X297 mm) 22 44 06 1 1 A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (20) Mixture ingredients ABCD NR 100 100 100 100 ZnO 5 5 5 5 CB 42 42 42 42 Siloxane 13 13 13 13 Aromatic oil 5 5 5 5 C 〇 ++ 0.3a) 0.5a) 0.2a) 0.2b) Resorcinol 2.5 2.5 2.5 2.5 HMMM 3.3 3.3 3.3 3.3 DCBS 0.8 0.8 0.8 0.8 Sulfur 5 5 5 5 Protective agent 3 3 3 3 a = 2-ethylhexanoate-boronic neo-decanoate-cobalt; b = N-decanoate. Example 10 Adhesiveness to a vulcanized elastomer material Adhesiveness was measured in a manner similar to that of Example 7 above, except that a sample was prepared as described in Example 9 above. The opening force is measured in Newtons using an electronic dynamometer. The degree of coating of the cords extracted from each sample is based on the surface of the cords. The paper size is still subject to the Chinese National Standard (CNS) A4 (210 X 297 mm) --------- > ------ Order .------ j-(Read the precautions on the back before filling out this page) 23 Printed by Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs on 4.06 A7 B7 V. Description of Invention (21) Percentage of good coatings that retain the elastomeric material, based on a coating index score of 1 to 4. The initial adhesion values (test I) and the adhesion properties (test II) of the test specimens maintained at 8 ° C after 65 ° C and 90% relative humidity are shown in the following tables 8a, 8b and 8c, where the first number It is the adhesion value and is the average of 8 tests, and the index of the brackets is the degree of coating of the cord. Table 8a Mixture

2+ 1 X0.28 Cord (*) BCD Test I 250 (4) 285 (4) 277 (4) Test II 245 (3.5) 258 (3.5) 235 (3.5) (*) Coated with zinc / manganese The dry-form alloy is made of 0.5% manganese. Table 8b Mixtures 2+ 3 X0.28 cords ("BCD Test I 658 (4) 659 (4) 669 (4) Test II 454 (3) 436 (3) 350 (3) (*) The manganese binary alloy is dry-manufactured in which the manganese content is 0.5%. The paper scale is applicable to the Chinese national standard (CMS > A4 specification (210 X 297 mm) (please read the precautions on the back before filling in this purchase) Order 24 ^ 40611 Clothing and invention description (II) A7 B7 Table 8c Mixture 3X0.28 cord (*) AC test I 273 (4) 257 (4) Test Π 229 (3.5) 190 (2) 1 χ0.28 cord (**) AC Test I 287 (4) 266 (4) Test II 203 (2.5) 188 (2.5) (*) Made from a dry type coated with a zinc / manganese binary alloy where the manganese content is%. ~ (Please Read the precautions on the back before filling in this purchase) Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, made of dry coated zinc / manganese binary alloy with a manganese content of ^%. Comparative Example 4 Vulcanized elastomer Material Adhesion This method is performed in a similar manner to Example 10 above, but using a steel wire coated with brass (67% Cu and 33% Zn) is embedded in the vulcanization obtained by vulcanizing the mixture as described in Example 9 above. Sexual maternity. The results are shown in Tables 9a, 9b and 9c. This paper 1 ^^ 1 national standard (^^) eight 4 ^^ (2 丨 0: < 297 mm) ------ *- 25-

-, 1T 丨 Λ. 44 06 1 1 A7 B7 printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, the description of the invention (23) Table 9a Mixture 2 + 1 X0.28 cord (*) BCD test I 294 (4) 305 (4) 296 (4) Test II 182 (3) 184 (3) 186 (3) Table 9b Mixture 2 + 3X0.28 Cord ("BCD Test I 731 (4) 736 (4) 739 (4) Test II 263 (2) 287 (2) 265 (2) Table 9c Mixture 3 X 0.28 cord AC test I 295 (4) 314 (4) test II 125 (2) 144 (2) (Please read the precautions on the back before (Fill in this page) This paper size is in accordance with Chinese National Standard (CNS) A4 (21 OX29? Mm) 26 10... Tire lip 12... Tire lip core 13.. Bead 14... Strengthening layer 15 … Belt

4Λ 06 1 1 AV B7 V. Description of the invention (24) Comparison of component numbers 16... Tread 17.... Side wall 20... Conveyor belt 30... Transmission belt 40... in ^ — 11---I-ί I 11 m:-I s--1-1-- 、 一 _ ^--i -----; I------, ^,-. ( Please read the notes on the reverse side before filling out this page) The paper size printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, is printed on paper that applies to the Chinese National Standard (CNS) A < 4 (210X297 mm) 27

Claims (1)

440611 Patent Application Patent No. 088101780 Patent Application Patent Amendment Amendment Date: October 89 1. A surface-treated steel wire used to strengthen the structure of manufactured articles made of vulcanized elastomer materials, where the steel wire is Coated with a layer of metal alloy, which is characterized in that the alloy is a zinc / manganese binary alloy containing 0.3 to 4,9 wt% manganese. 2. The surface-treated steel wire according to the scope of the patent application, wherein the manganese content is 0.3 to 4.5% by weight. 3. The surface-treated steel wire according to item 2 of the patent application, wherein the manganese content is from 1.5 to 4.0% by weight. 4. The surface-treated steel wire according to item 1 of the patent application, wherein the surface coating is formed by electrodeposition. 5. — A reinforcing structure for a manufactured article made of a vulcanized elastomer material, the reinforcing structure comprising at least one zinc / manganese binary alloy coated with any one of claims 1 to 4 of the scope of patent application Steel wire β 6 · —a kind of manufactured article, which is made of vulcanized elastomer material, characterized in that the manufactured article is reinforced by a structure that includes at least one piece of cloth as described in the scope of patent applications No. .1 to 4. Any of the zinc / manganese binary alloy steel wires. 7. The article of manufacture as claimed in claim 6 wherein the article of manufacture is a tire, a carousel, a transmission belt or a flexible hose. 8 · —A manufactured article containing at least one metal wire embedded in a vulcanizate elastomer matrix. The matrix is obtained from a mixture containing at least one of the paper paper scales applicable to China National Standard (CNS) A4 specifications ( 210X2f7 mm) (Please read the notes on the back before filling this page) Printed by the Employees 'Cooperative of the Ministry of Economic Affairs and the Consumer Cooperatives of the Ministry of Economic Affairs / Printed by the Ministry of Economic Affairs and the Intellectual Property Office of the Ministry of Economic Affairs / | Printed by the Consumers' Cooperative of the Ministry of Economic Affairs A8 B8 C8 D8 , Characterized in that the metal wire is made of steel coated with a zinc / manganese binary alloy as in any one of claims 1 to 4 of the scope of patent application; and the mixture further comprises a divalent cobalt salt, the The divalent cobalt salt is a divalent cobalt metal β 9 corresponding to at least 0.2% by weight relative to the weight of the elastomer. For example, the article of manufacture of item S of the patent application scope, wherein the content of the divalent cobalt salt is relative to The weight of the elastomer is a divalent metal corresponding to 0.2 to 1% by weight. 10. The article of manufacture as claimed in claim 8 or 9, wherein the divalent cobalt salt is selected from the group consisting of a carboxylic acid salt of formula (I) (R-CO-OOjCo (I) where the rule is (6.24 aliphatic Or an aromatic group, a cobalt-boron complex of formula (II) O-Co-0-COR1 IB / \ R''OC-0-Co-O O-Co-0-COR " (Π) where R ', R " and R "' are each the same or different and are C624 aliphatic or aromatic groups, and mixtures thereof. 11. As for the article of manufacture in the scope of application for item 10, wherein R_c〇_〇_, R '-C0-0-, R'co-O- and R "'-CO-〇- are selected from the group consisting of n-heptanoate, 2,2-di, methylvalerate, 2-ethylvalerate, 4, 4-dimethylvalerate and 2-ethyl paper sizes are applicable to China National Standard (CNS) A4 (210 / 17mm) (Please read the cautions on the back before filling in this page) 4406 1 1 A8 B8 C8 D8 Printed by the Consumers' Cooperative of the 4th Bureau of the Ministry of Economic Affairs, Zhicongcai. 6. Scope of patent application. Hexanoate, n-octanoate, 2,2-dimethylhexanoate, neodecanoate and naphthenate. 12. The article of manufacture as claimed in claim 8 wherein the divalent cobalt salt of formula (I) is cobalt neodecanoate. u. If the article of manufacture in the scope of the patent application item 8, where the divalent cobalt salt of formula (II) is 2-ethylhexanoate, neodecanoate __B 14. If the manufacture of the scope of patent application item 8 Article 'which makes the article a tyre' Conveyor, drive belt or flexible hose. 15. An electrolytic deposition method ', wherein the electrolytic deposition comprises 0.3 to 49 weights. / 〇Mn of manganese / manganese binary alloy on a steel wire passing through an electrolytic bath, characterized in that the wire is passed through at least one electrolytic bath, the electrolytic bath is composed of at least one salt solution selected from zinc salt and manganese salt, the The electrolytic bath has: a temperature of 20 to 50 ° C; a pH of 2 to 6; and a cathode density of 10 to 50 A / dm2. 16. The method according to item 15 of the patent application, wherein the flux speed of the steel wire is _ 10 to 70 m / min, 17. The method according to item 15 of the patent application, wherein the zinc salt and manganese salt are sulfates 》 18. The method according to item 17 of the application, wherein the zinc sulfate is zinc sulfate heptahydrate. 19. The method according to claim 17 in which the manganese sulfate is manganese sulfate monohydrate. This paper music scale is applicable _ national standard 窣 i CNS) A # see grid (210χ297 public race) n ^ i-逦 J ^ iJ · ml-J f ^ i ^ 11 fu. One eJ. (Please read the first Note: Please fill in this page again) 44 06 1 t A8 B8 C8 D8 VI. Application for patent scope 20 'If the patent application scope is any of the methods of items 15 to 19, where the steel wire is immersed in a solution containing fierce salt and zinc In a single electrolytic bath of salt. 2 1. The method according to item 15 of the scope of patent application, wherein the steel wire is first immersed in a first electrolytic bath containing a manganese salt, then immersed in a second electrolytic bath containing a zinc salt, and finally subjected to a thermal diffusion process . (Please read the notes on the back before filling in this page) Printed by the consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is sized for the Chinese National Standard (CNS) A4 (2! 0x2 ^ 7 mm)