JP2858967B2 - Surface treatment method for steel wire - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating a surface of a steel wire used as a rubber reinforcing material.

[0002]

2. Description of the Related Art Steel wires conventionally used as steel cords for reinforcing automobile tires, hose wires for reinforcing hoses, belt cords for reinforcing conveyor belts, timing belt cords for reinforcing timing belts, steel cords for reinforcing escalators, and the like are rubber. Brass plating is applied to the surface in order to adhere to the surface. However, simple brass plating alone does not provide sufficient corrosion resistance, adhesion stability, wet adhesion, heat resistance, and the like. To solve these problems, various types of binary plating, ternary plating, quaternary plating, and the like have been studied. However, all of the above-mentioned problems have not been solved yet, and the production process is further complicated, resulting in a significant increase in cost.

On the other hand, it is known that treating a metal surface with a triazinethiol derivative can improve the corrosion resistance of the metal and the adhesiveness to rubber (for example, Kunio Mori: Practical Metal Surface Technology, 37, 373 (1989)). JP-B-60-41084; JP-A-58-87034
No.). In these known techniques, a metal is immersed in a solution in which a triazine thiol derivative is dissolved in water or an organic solvent, so that the surface is treated by adsorbing the triazine thiol derivative on the metal surface. However, this method requires a relatively high temperature and a long processing time in the immersion processing step. In addition, because the adsorption layer of the triazine thiol derivative formed on the metal surface by the immersion treatment lacks denseness, the heat resistance, water resistance, steam resistance, Fatigue resistance is not sufficient. Furthermore, since this method is a batch process, it is not suitable for industrially processing a large amount of steel wire.

Accordingly, the present inventors have proposed a Japanese Patent Application No. Hei.
No. 54 discloses a method of drawing and surface-treating a steel wire in a lubricant containing a triazinethiol derivative.

[0005]

However, even when a triazine thiol derivative is added to a lubricant, the solubility of the triazine thiol derivative is limited, and most of the solubility is in a suspended state. Therefore, even if the steel wire is drawn in such a lubricant, the surface treatment cannot be effectively performed.

An object of the present invention is to provide a method capable of effectively treating the surface of a steel wire with a triazinethiol derivative, and to improve corrosion resistance and adhesion to rubber.

[0007]

According to the surface treatment method of a steel wire of the present invention, a solution in which a triazinethiol derivative is dissolved in ethanolamines is added to a lubricant, and the steel wire is drawn in the lubricant. Together with a surface treatment.

In the present invention, as the steel wire, unplated bare steel wire, copper-plated steel wire, brass-plated steel wire, nickel-plated steel wire, tin-plated steel wire, zinc-plated steel wire, copper-tin plating A steel wire, a cobalt-plated steel wire, or the like is used.
When a plated steel wire is used, the plating thickness before drawing is usually 10 to 1000 nm, and further 150 to 4 nm.
It is preferably 00 nm. The plating amount is usually 0.1 to 40 g / kg, preferably 0.5 to 10 g / kg.

In the present invention, the triazinethiol derivative is represented by the following general formula:

[0010]

Embedded image (Wherein R is -OR ', -SR', -NHR ',-
N (R ′) ₂ ; R ′ is H, an alkyl group, an alkenyl group,
A phenyl group, a phenylalkyl group, an alkylphenyl group, or a cycloalkyl group, M is H, Na, Li, K,
1 / 2Mg, 1 / 2Ba, 1 / 2Ca, aliphatic first grade, 2
Or tertiary amines, quaternary ammonium salts, or phosphonium salts).

The following are specific examples of the triazine thiol derivative used in the present invention. For example, 1,3,5-triazine-2,4,6
-Trithiol (F), 1,3,5-triazine-2,
4,6-trithiol monosodium (FMN),
1,3,5-triazine-2,4,6-trithiol.
Monopotassium, 1,3,5-triazine-2,4,6-
Trithiol monoethanolamine (FME), 1,
3,5-triazine-2,4,6-trithiol diethanolamine (FDE), 1,3,5-triazine-
2,4,6-trithiol triethylamine (FT
EA), 1,3,5-triazine-2,4,6-trithioloctylamine, 1,3,5-triazine-
2,4,6-trithiol tetrabutylammonium salt, 1,3,5-triazine-2,4,6-trithiolbis (tetrabutylammonium salt) (F2A),
6-anilino-1,3,5-triazine-2,4-dithiol (AF), 6-anilino-1,3,5-triazine-2,4-dithiol monosodium (AMN),
6-anilino-1,3,5-triazine-2,4-dithioltriethylamine, 6-dibutylamino-1,
3,5-triazine-2,4-dithiol (DB), 6
-Dibutylamino-1,3,5-triazine-2,4-
Dithiol monosodium (DBMN), 6-dibutylamino-1,3,5-triazine-2,4-dithiol monoethanolamine (DBME), 6-dibutylamino-1,3,5-triazine-2,4 -Dithiolethylamine, 6-dibutylamino-1,3,5-triazine-2,4-dithioltriethylamine, 6
-Dibutylamino-1,3,5-triazine-2,4-
Dithiol-butylamine (DBB), 6-dibutylamino-1,3,5-triazine-2,4-dithiol.
Tetrabutylammonium salt (DBA), 6-dibutylamino-1,3,5-triazine-2,4-dithioltetrabutylphosphonium salt, 6-diallylamino-
1,3,5-triazine-2,4-dithiol, 6-diallylamino-1,3,5-triazine-2,4-dithiol monosodium (DAMN), 6-diallylamino-1,3,5- Triazine-2,4-dithiol
Monoethanolamine (DAME), 6-diallylamino-1,3,5-triazine-2,4-dithiolbutylamine, 6-diallylamino-1,3,5-triazine-2,4-dithiolethylenediamine, 6 -Diallylamino-1,3,5-triazine-2,4-dithiolethylenetriamine, 6-octylamino-
There are 1,3,5-triazine-2,4-dithiol, 6-octylamino-1,3,5-triazine-2,4-dithiol monosodium and the like. One or more of these are used.

The lubricant used in this method is a so-called emulsion type. This lubricant comprises an emulsion in which an extreme pressure inhibitor, an oil agent, an emulsifier, a foam inhibitor, and the like are dispersed in a solvent. As the solvent, neutral or alkaline water or glycol (for example, ethylene glycol derivative, polyethylene glycol or diglyme) is used. In addition to the above components, for example, a rust preventive or an antiseptic / antifungal agent may be contained.

The extreme pressure inhibitor has an action of preventing seizure of the wire during drawing. Examples of the extreme pressure inhibitor include ethylenediamine phosphate, ethylenetriamine phosphate, pentaethylenetetramine phosphate, propylenediamine phosphate, butylenediamine phosphate, butylamine phosphate, octylamine phosphate,
Oleylamine phosphate, fatty acid ester / ethylenoxide adduct, phosphate methyl ester / propylenoxide adduct, butyl phosphate / propylenoxide adduct, octyl phosphate / propylenoxide adduct, oleyl phosphate / propylenoxide adduct, etc. No. One or more of these are used. The content of the extreme pressure inhibitor in the lubricant (undiluted) is preferably 0.1 to 15% by weight, more preferably 1 to 10% by weight.

The oily agent has the function of preventing seizure of the wire during drawing and improving the wettability of the lubricant. As the oil agent, an amine salt of a fatty acid is generally used. For example, acetic acid / octylamine, stearic acid /
Ethanolamine, stearic acid / diethanolamine, octylic acid / diethanolamine, linolenic acid / diethanolamine, oleic acid / diethanolamine,
Oleic acid, butylamine, and the like. Examples of the oil agent include: reaction products of fatty acids and epoxy compounds (eg, tetraethylene glycol oleate, pentaethylene glycol octylate, nonaethylene glycol stearate, decaethylene glycol erucate, decaethylene glycol linoleate, and the like); Reaction products of fatty acid esters and epoxy compounds (for example, butanediol octylate tetraethylene glycol, butanediol oleate hexaethyleneglycol, butanediol stearate pentaethyleneglycol, butanediol caproate pentaethyleneglycol, caproic acid Hexanediol ester pentaethylene glycol). These are used alone or in combination of two or more. The content of the oily agent in the lubricant (undiluted) is preferably 0.1 to 20% by weight, more preferably 1 to 15% by weight.

The emulsifier has an action of emulsifying an extreme pressure inhibitor, an oil agent, a foam inhibitor and the like in water. As an emulsifier, a reaction product of an alkylamine and an epoxy compound is generally used. For example, octylamine tetraethylene glycol, dodecylamine decaethylene glycol, oleylamine decaethylene glycol, stearylamine octaethylene glycol and the like can be mentioned. The content of the emulsifier in the lubricant (undiluted) was 0.1
It is preferably from 10 to 10% by weight, more preferably from 0.5 to 5% by weight.

The foaming inhibitor has an action of suppressing foaming of the emulsion. As the foam inhibitor, for example, mineral spirits such as decane, octane, hexadecane, heptadecane, and nonadecane are used. The content of the foam inhibitor in the lubricant (undiluted) is 0.1 to 1
It is preferably 0% by weight, more preferably 0.5 to 5% by weight.

The rust inhibitor has an action of preventing corrosion of iron and brass components of the steel wire. Examples of the rust preventive include methyl paraoxybenzoate, bisphenol A, benzotriazole, methylbenzotriazole and the like. However, since the triazine thiol derivative also has a rust-preventing action, it is not always necessary to mix the rust-preventing agent described above. The content of the rust inhibitor in the lubricant (undiluted) is preferably 0.01 to 5% by weight, more preferably 0.1 to 1% by weight.

An antiseptic / antifungal agent has an action of preventing contamination of a lubricant by microorganisms. Examples of the antiseptic / antifungal agent include 1,2-benzisothiazolin-3-one, chlorinated phenol, formaldehyde, and a formaldehyde releasing agent. However, since the triazine thiol derivative also has an antiseptic and fungicidal action, it is not always necessary to add the above-mentioned antiseptic and antifungal agent. The content of the preservative / antifungal agent in the lubricant (undiluted) is 0.01 to 5% by weight, and further 0.1 to 1% by weight.
% By weight.

In the present invention, the triazine thiol derivative is dissolved in triethanolamine (TEA) heated to about 100 ° C. in advance. The solubility limit of the triazinethiol derivative in triethanolamine is about 50% by weight.
It is. This solution is added into the lubricant. As a result, the triazine thiol derivative is completely dissolved in the lubricant. Therefore, the concentration of the triazine thiol derivative in the lubricant can be made higher than before.
This lubricant can be used as is during processing or
It is used after being diluted within 0 times, preferably 5 to 10 times.

In the present invention, the steel wire is drawn using a wet type drawing machine. That is, a die is attached to a lubrication tank of a wet wire drawing machine, the above-described lubricant is contained, and a steel wire having a diameter of, for example, 0.1 to 10 mm, preferably 1 to 4 mm is passed through the die, for 1 to 2000 m.
The wire is drawn to a diameter of 0.01 to 5 mm, preferably 0.1 to 1 mm at a speed of 1 / min. Generally, in the case of a hard steel wire such as a bare steel wire or a nickel-plated steel wire, the wire is drawn at a low speed and the degree of drawing is low. On the other hand, in the case of a soft steel wire such as a copper-plated steel wire or a brass-plated steel wire (copper content in plating is 65% or more), it can be drawn at high speed.
The degree of wire drawing can also be increased. Therefore, the optimum values of the drawing speed and the degree of drawing are naturally different depending on the type of the steel wire.

By the above-described drawing operation, a coating layer containing a polymer of a triazine thiol derivative is formed on the surface of the steel wire. The mechanism by which this coating layer is formed is presumed to be as follows. When the steel wire comes into contact with the lubricant, the triazine thiol derivative is adsorbed on the wire surface. This state is considered to be the same as the state in which the triazine thiol derivative is adsorbed on the wire surface by the conventional immersion method. In the subsequent drawing process, the wire surface becomes an active metal surface. Also,
The triazine thiol derivative on the wire surface is exposed to high temperature and pressure, albeit instantly. For example, when a brass-plated steel wire is drawn at a drawing pressure of 100 kgf / mm ² , the surface temperature is said to reach several hundred degrees Celsius. As a result, a coating layer containing the polymer of the triazinethiol derivative is formed.

Gel permeation chromatography confirmed that the coating layer contained a polymer. In addition, by analysis such as infrared spectroscopy,
It has been confirmed that this coating layer contains a disulfide group, a thiol group, an unsaturated group, and the like. This coating layer
Since it is dense and strong, it improves the corrosion resistance of the steel wire, and since it contains a disulfide group, it reacts with components in the rubber to improve the adhesion between the two. Of the above-mentioned triazine thiol derivatives, for example, use of F or DAN is effective for improving the adhesion of the steel wire to rubber, and use of DB is effective for improving the corrosion resistance of the steel wire. Therefore, a plurality of triazine thiol derivatives may be appropriately mixed and used.

As described above, by performing the surface treatment at the same time as the wire drawing treatment, the steel wire having the coating layer containing the polymer of the triazine thiol derivative formed on the surface is used as a single wire or a twisted cord. . There are various methods of twisting, but methods generally used at present (for example, Fukuhara Setsuo; Textile and Industry, 40,
No. 11, 627 (1984)) are all applicable.

These steel wires or steel cords twisted with these steel wires are bonded to a rubber compound,
For example, steel radial tire, steel wire reinforced conveyor belt, steel wire reinforced timing belt,
Products such as steel wire reinforced hoses and steel wire reinforced handrails are manufactured.

The composition of the rubber compound is not particularly limited. As the rubber compound, those containing the components of rubber, filler, softener, vulcanizing agent, vulcanization accelerator, and vulcanization accelerator are used. Further, the rubber compound may contain components such as a lubricant, a stabilizer, and an adhesion assistant (adhesion promoter) in addition to the above components.

Examples of the rubber include various natural rubbers (NR), isoprene rubber, butadiene rubber (BR), solution-polymerized butadiene rubber, solution-polymerized styrene-butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer rubber (NBR), Ethylene-propylene copolymer rubber, ethylene-propylene terpolymer rubber (EPDM), silicone rubber, butyl rubber, chlorinated butyl rubber, brominated butyl rubber, chloroprene rubber, fluorine rubber, hydrin rubber,
Epichlorohydrin-ethylene oxide copolymer rubber,
Epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer rubber, epichlorohydrin-
Propylene oxide-allyl glycidyl ether terpolymer rubber, chlorinated polyethylene rubber, acrylic rubber and its copolymer rubber (chlorine, epoxy, unsaturated), ethylene-vinyl acetate-acrylate terpolymer, Urethane rubber and the like can be mentioned.

The filler is blended for the purpose of increasing the weight and reinforcing.
As the filler, for example, carbon black, carbon black for reinforcing rubber, white carbon, hard clay,
Examples include calcium carbonate and silicate. The amount of the filler is 5 to 200 parts by weight based on 100 parts by weight of rubber,
Preferably it is 30 to 100 parts by weight.

The softener is blended in order to improve the processability and moldability of the rubber. Examples of the softening agent include phthalate plasticizers such as dioctyl phthalate (DOP) and dibutyl phthalate; fatty acid ester plasticizers such as dioctyl adipate and dioctyl sebacate;
Phosphate ester plasticizers such as triphenyl phosphate and tricresyl phosphate; paraffin chloride, process oil, naphthenic oil, and the like. The amount of the softening agent is 10 to 100 parts by weight of rubber.
0 parts by weight or less, preferably 5 to 50 parts by weight.

[0029] The vulcanizing agent is blended to exhibit the elasticity of the rubber. The vulcanizing agent to be used varies depending on the type of rubber, but the main ones are as follows.
For example, sulfur, dicumyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, α, α′-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl- 2,5-
Di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-
3,1,3,5-triazine-2,4,6-trithiol, 6-butylamino-1,3,5-triazine-2,
4-dithiol, ethylenethiourea, hexamethylenediamine, ammonium benzoate, bisphenol A and the like. Since the amount of the vulcanizing agent varies depending on the individual rubber, it cannot be unconditionally limited, but generally 0.1 to 10 parts by weight is appropriate for 100 parts by weight of the rubber. For example, the amount of sulfur added is 0.5 to 100 parts by weight of rubber.
It is preferably from 10 to 10 parts by weight, more preferably from 2 to 6 parts by weight. If the amount of sulfur is less than 0.5 parts by weight, the vulcanization of the rubber becomes insufficient, and the adhesion to the steel wire also becomes weak. 10 sulfur
If the amount exceeds the weight part, the heat resistance of the rubber and the water resistance of the composite material are significantly impaired.

The vulcanization accelerator and the vulcanization accelerator are blended in order to promote the action of the vulcanizing agent. As the vulcanization accelerator,
For example, 2-mercaptobenzothiazole (M),
Thiazole accelerators such as (4-morpholinyldithio) benzothiazole and dibenzothiazyldisulfide (DM); N-cyclohexyl-2-benzothiazylsulfenamide (CBS), N-oxydiethylene- 2-
Benzothiazylsulfenamide, N, N-dicyclohexyl-2-benzothiazylsulfenamide, Nt
Sulfenamide-based accelerators such as -butyl-2-benzothiazylsulfenamide; turum-based accelerators such as tetramethylturum monosulfide, tetramethylturum disulfide, tetrabutyltururam disulfide; fatty acid amines; Quaternary ammonium salts,
Examples include polyfunctional monomers such as organic phosphonium salts, triallyl isocyanurate, trimethylolpropane triacrylate, diallyl phthalate. As the vulcanization accelerator, ZnO, MgO, BaO, Ca (OH) ₂
And the like. These may be used alone or in combination of two or more.

The amounts of the vulcanization accelerator and the vulcanization accelerator are different depending on the type of the rubber and the vulcanizing agent, and thus cannot be limited unconditionally.
-20 parts by weight are suitable.

In order to produce a steel wire-rubber adhesive composite, it is preferable that at least the above-mentioned components are contained in the rubber compound. Further, the following components such as a lubricant, a stabilizer, and an adhesion aid are not necessarily required to obtain a steel wire-rubber adhesive composite,
The presence of these components is advantageous for improving the water resistance, heat resistance, steam resistance, and fatigue resistance of the steel wire-rubber adhesive composite.

A lubricant is compounded to improve the flow of the rubber compound during bonding and bonding. As the lubricant, for example, stearic acid, Na salt, Mg salt of stearic acid, C
a salt, Ba salt or Zn salt, ethylene bisamide stearate, ethylene bisamide erucate, paraffin wax and the like. The lubricant is generally rubber 1
0.1 to 5 parts by weight is added to 00 parts by weight.

[0034] Stabilizers are included to prevent degradation of the adhesive composite. Examples of the stabilizer include a phenylenediamine antioxidant, a phenolic antioxidant, nickel dithiocarbamate, and benzophenone. The stabilizer is generally used in an amount of 0.1 to 100 parts by weight of rubber.
1 to 5 parts by weight is blended.

Examples of the adhesion aid include 1,3,5-triazine-2,4,6-trithiol, 6-butylamino-1,3,5-triazine-2,4-dithiol,
-Diallylamino-1,3,5-triazine-2,4-
Dithiol, cobalt naphthenate, cobalt stearate, metal aminobenzoate (Co, Mn, Zn, Mo,
Cr), resorcin, cresol, resorcin-formalin latex, resole type phenolic resin (including uncured), formalin-alkylphenol resin, formalin-cresol resin (including uncured), monomethylolmelamine, dimethylolmelamine , Trimethylolmelamine, hexamethylolmelamine, monomethoxymethylolmelamine, tetramethoxymethylolmelamine, pentamethoxymethylolmelamine, monomethylolurea, trimethylolurea, trimethoxymethylolurea, ethylenemaleimide, butylenemaleimide, phenylenemaleimide, abietic acid metal salt (Co, Ni, Fe, Mn) and the like. 0.1 to 20 parts by weight of the bonding aid is used for 100 parts by weight of rubber,
Preferably, 0.5 to 5 parts by weight is blended.

The steel wire / rubber adhesive composite of the present invention is obtained by bringing a steel wire (cord) having been subjected to a surface treatment into contact with a rubber compound, hot pressing or steam heating, and simultaneously vulcanizing the rubber to form a composite. It is manufactured by The conditions of this step are usually 80 to 230 ° C, preferably 130 to 180 ° C, for 5 to 180 minutes, preferably 10 to 60 minutes. Depending on the type of rubber or vulcanizing agent, post-crosslinking may be further performed.

[0037]

Embodiments of the present invention will be described below.

Example 1 4 parts by weight of ethylenediamine phosphate, 8 parts by weight of triethanolamine oleate, 4 parts by weight of laurylamine octaethylene glycol, 3 parts by weight of octadecane, 2 parts by weight of tetraethylene glycol octylate, dodecyl phosphoric acid 0.5 part by weight of methyl butanediol ester pentapropylene glycol paraoxybenzoate, 1 part by weight of methylbenzotriazole, and 0.5 part by weight of 1,2-benzoisothiazolin-3-one were dispersed in 72.5 parts by weight of water. A lubricant was prepared.

The triethanolamine is heated to 100 ° C. to prepare 1,3,5-triazine-2,4,6-trithiol (F) or 6-dibutylamino-1,3,5-triazine-2,4-dithiol. (DB) was added and dissolved so as to be 50% by weight. This solution was added to the lubricant so that the concentration of F or DB was 3, 5 or 10% by weight. In the lubricant, F or DB was in a completely dissolved state (the lubricant of the present invention).

For comparison, F or DB was added to the lubricant.
Was added to give a concentration of 3, 5 or 10% by weight. In this case, F or DB was in a suspended state in the lubricant (conventional lubricant).

A brass-plated steel wire having a diameter of 1.40 mm was drawn using these two kinds of lubricants containing a triazinethiol derivative to obtain a wire having a diameter of 0.60 mm. The number of dies used was 10, and the drawing speed was 700 m / min.

With respect to the steel wire after each wire drawing treatment using two kinds of lubricants, as a result of the reaction, it was measured by the ESCA how much sulfur, which is a main element of the triazine thiol derivative, entered into the plating. .
In addition, in order to eliminate the influence of contamination on the plating surface, the measurement was performed by sputtering to a depth of about 1 nm by an argon ion sputtering method. Figure 1 shows the results when F was used.
FIG. 2 shows the results when the DB is used.

As a method of analyzing the reaction amount of the triazinethiol derivative, there are a silver nitrate titration method, a high-frequency plasma emission analysis method and the like in addition to the ESCA.

From FIGS. 1 and 2, it was confirmed that the amount of the triazine thiol derivative penetrating in the depth direction of the brass plating was larger when the lubricant of the present invention was used than in the case of the conventional lubricant. Was done. It is considered that the reason why F has a larger reaction amount than DB is that F has a smaller molecular weight and is more likely to penetrate into the plating.

Example 2 An element wire for a steel cord was experimentally produced on an actual process line of a steel tire cord. Instead of the lubricant used in the actual process, a lubricant of the present invention or a lubricant of a conventional lubricant (triazine thiol concentration is 3, 5 or 10% by weight) was used, all under the same conditions as the actual process, A brass-plated steel wire having a diameter of 1.20 mm was drawn. Furthermore, 1 × 5 ×
A 0.25 steel cord was made.

These steel cords were bonded to rubber compound A or B shown in Table 1, and an adhesion test and a fatigue test were performed. Regarding the bonding conditions, the optimum vulcanization conditions were determined from the vulcanization-torque curve.

With respect to the adhesion test, the pull-out force of the steel cord was measured by the pull-out test method of the ASTM method. Table 2 shows the index of the pull-out force after the primary bonding and after the wet heat treatment. The moist heat treatment was performed using
The test was carried out by holding for 2 weeks under a moist heat condition of ° C x 96% RH.
As is clear from Table 2, it was found that the wire drawn using the lubricant of the present invention had better adhesiveness, and in particular, had better adhesiveness when subjected to wet heat treatment.

Regarding the fatigue test, a steel cord obtained by vulcanizing with a rubber coating was produced, and the number of rotations before breaking was measured by a Hunter rotating bending fatigue test. Table 3 shows the index of the number of rotations until the fracture after the primary bonding and after the wet heat treatment. In the wet heat treatment, the primary bonding is performed at 70 ° C x 96%.
The test was carried out by holding for 7 days under the moist heat condition of RH. As is evident from Table 3, both after the primary bonding and after the wet heat treatment, the fatigue resistance was better when the wire drawn using the lubricant of the present invention was used.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

As described in detail above, by using the method of the present invention, the surface of a steel wire can be effectively treated with a triazine thiol derivative, the adhesiveness with rubber can be improved, and the adhesive composite material can be further improved. Properties such as fatigue resistance can be improved.

[Brief description of the drawings]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a steel wire drawn with a lubricant containing F according to the method of the present invention and a conventional method.
The figure which shows the relationship between a density | concentration and the sulfur peak ratio measured by ESCA analysis.

FIG. 2 shows a steel wire drawn using a lubricant containing DB according to the method of the present invention and a conventional method.
The figure which shows the relationship between DB concentration and the sulfur peak ratio measured by ESCA analysis.

Continued on the front page (72) Inventor Nobunori Shiratori 1967, Shimoinayoshi, Chiyoda-mura, Niigata-gun, Ibaraki 9 (72) Inventor Masatoshi Katayama 2296, Shiyonayoshi, Chiyoda-mura, Niigata-gun, Ibaraki Tokyo No. 401, A-Building A1 (56) References JP-A-2-212524 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) B21C 9/00 C08J 5/00

Claims (1)

(57) [Claims] 1. A method for treating a surface of a steel wire, comprising adding a solution of a triazinethiol derivative in ethanolamines to a lubricant, drawing the steel wire in the lubricant, and treating the surface of the steel wire. .