JPH02212524A - Lubricant for steel wire drawing, surface treatment of steel wire and steel wire/rubber bonded composite - Google Patents

Abstract

PURPOSE:To provide a lubricant for steel wire drawing which can be desirably used in surface-treating a steel wire while drawing it and can give a dense and strong film by using a specified triazinethiol derivative. CONSTITUTION:A triazinethiol derivative of the formula (wherein R is -OR', -SR', -NHR' or -N(R')2; R' is an alkyl, an alkenyl, a phenyl, a phenylalkyl, an alkylphenyl or a cycloalkyl; and M is H, Na, Li, K, 1/2 Mg, 1/2 Ba, 1/2 Ca, an aliphatic prim., sec. or tert. amine, a quat. ammonium salt or a phosphonium salt), e.g. 1,3,5-triazine-2,4,6-trithiol, is mixed with necessary additives such as an extreme pressure inhibitor, an oiliness agent, an emulsiifer and an antifoamer, and the obtained mixture is dispersed in water, a glycol or the like to produce a lubricant for steel wire drawing.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a steel wire drawing lubricant used when drawing a steel wire, a surface treatment method performed using this lubricant, and a surface treatment method for this surface treatment. The present invention relates to adhesive composites of treated steel wire and rubber.

[Conventional technology]

Steel radial tires, steel wire reinforced conveyor belts, steel wire reinforced timing belts, steel wire reinforced hoses, steel wire reinforced hand rails, etc., in which steel wire or twisted steel wire is combined with steel cord and rubber, use steel wire. The surface condition of the wire has a significant effect on the corrosion resistance and the adhesive strength between wire rubber. Therefore, in order to keep the surface clean, for example, steel wires are currently shipped and stored in polyethylene bags with a dehydrating agent and nitrogen sealed. As a result of this overpackaging, the cost of steel wire is high. Moreover,
Even with such packaging, it was difficult to keep the surface condition of the steel wire clean. Therefore, conventional adhesive composites such as steel radial tires obtained using steel wires have problems in the adhesion between the wire rubbers and the heat resistance, oil resistance, and water resistance of the product.

On the other hand, the present inventors have revealed that the corrosion resistance of the metal and the adhesion to rubber can be improved by treating the surface of the metal with a triazinethiol derivative (for example, Kunito Mori: Practical Metal Surface Technology, 37). .373(1
989); Japanese Patent Publication No. 80-41084; Japanese Patent Publication No. 1983-
No. 87034). In these known techniques, surface treatment is performed by immersing the metal in a solution of the triazinethiol derivative dissolved in water or an organic solvent to form a film of the triazinethiol derivative on the metal surface.

[Problem to be solved by the invention]

However, conventionally, the immersion treatment process required a long treatment time. In addition, the film of triazinethiol derivative formed on the metal surface by dipping treatment lacks density, and the wire rubber adhesive composite manufactured using this film has poor heat resistance, water resistance, steam resistance, and fatigue resistance. It could not be said to be sufficient.

The present invention has been made to solve the above problems, and provides a surface treatment method that enables processing speed suitable for industrial production, a lubricant containing a triazinethiol derivative suitable for this surface treatment, and a surface treatment. Made of steel wire and rubber, it has heat resistance, water resistance, steam resistance,
The purpose of the present invention is to provide a steel wire rubber bonded composite with excellent fatigue resistance.

[Means and actions to solve the problem]

The lubricant for steel cord wire drawing of the present invention has the following properties:
-N (R');R' is an alkyl group, an alkenyl group,
Phenyl group, phenylalkyl group, alkylphenyl group, or cycloalkyl group, M is H, Na.

L +, k, 1/2 Mgs 1/2 Bas l/
2 Ca, aliphatic primary, secondary or tertiary amine, quaternary
It is characterized by containing a triazinethiol derivative represented by the following (class ammonium salt or phosphonium salt).

The steel wire surface treatment method of the present invention is characterized in that the steel wire drawing lubricant is stored in a wire drawing machine, and the steel wire is surface treated while being drawn.

The steel wire rubber adhesive composite of the present invention is produced by bringing the surface-treated steel wire into contact with a rubber compound and heating the mixture.

The lubricant according to the present invention is a so-called emulsion type lubricant. This lubricant contains a triazine thiol derivative, an extreme pressure inhibitor, an oily agent, an emulsifier, and a foaming suppressant as shown in the above-mentioned formula, and these components are mixed with water (neutral or alkaline), ethylene glycol derivatives, polyethylene It consists of an emulsion dispersed in a glycol such as glycol or diglyme. In addition to the above-mentioned components, some may contain, for example, an iron rust preventive agent or a preservative and fungicide. This lubricant is used as is during processing or diluted up to 20 times, preferably 5 to 10 times.

Specific examples of the triazinethiol derivatives used in the present invention include the following. For example, 1.3.5-triazine-2,4,8-trithiol, 1. ．． 3.5-)Ryazine-2,4,8-)lithiol monosodium, 1,3.5-triazine-2,4
, [i-trithiol monopotassium, 1. ．． 3.5-
1-Ryazine-2,4,6-trithiol monoethanolamine, 1.3.5-triazine-2,4,6-)
Octylamine in lithiol, 1. , 3,5-triazine-2,4,6-)lithio-ru-tetrabutylammonium salt, 6-anili2-1.3.5-triazine-
2,4-dithiol, 6-anilino-1,3,5-triazine-2,4-dithiol monosodium, 6-anili-2,4-dithiol triethylamine, 6-sibutylamino- 1, 3, 5
4 riazine-2,4-dithiol◆triethylamine,
6-cyptylamino-1,3.5-) riazine-2,
4-dithiol, 6-cyptylamino-1.3.5-
Triazine-2,4-dithiol monosodium, 6-
cyptylamino-1.3.5-) riazine-2,4-
Dithiol/ethanolamine, 6-cyptylamino-1,3,5-triazine-2,4-dithiol/ethylamine, B~dibutylamine, no 1,3,5-triazine-2,4-dithiol/tetrabutylphosphonium salt, 6- diallylamino-1,, L5-triazine-2
, 4-dithiol-butylamine, 6-diallylamino-1,3,5-triazine-2,4-dithiol/ethylenediamine, 6-diallylamino-1,3,5-)riazine-2,4-dithiol/ethylenetriamine ,6
-diallylamino-1,3,5-triazine-2,4-dithiol, 6-octylamino-1,3,5-triazine-2,4-dithiol, 6-octylamino-1,3
, 5-) riazine-2,4-dithiol monosodium. One or more of these may be used. The self-existence rate of the triazinethiol derivative in the lubricant (undiluted) is usually 0.001 to 20% by weight, preferably 0.001 to 20% by weight.
It is desirable that the content is 0.01 to 5%.

The extreme pressure inhibitor has the function of preventing the wire from seizing during wire drawing. Examples of extreme pressure inhibitors include ethylenediamine phosphate, ethylenetriamine phosphate, pentaethylenetetramine phosphate, propylenediamine phosphate, butylenediamine phosphate, butylamine phosphate, octylamine phosphate, and oleylamine. Examples include phosphates, fatty acid ester/ethylene oxide adducts, phosphoric acid methyl ester/propylenoxide adducts, phosphoric acid butyl ester/propylenoxide adducts, phosphoric acid octyl ester/propylenoxide adducts, phosphoric acid oleyl ester/propylenoxide adducts, etc. . One or more of these may be used. It is desirable that the content of the extreme pressure inhibitor in the lubricant (undiluted) is 0.1 to 15% by weight, preferably 1 to 1% by weight.

The oil agent has the function of preventing wire seizing during wire drawing and improving wettability. As an oily agent,
Generally, amine salts of fatty acids are used. For example, acetic acid
Examples include octylamine, stearic acid and ethanolamine, stearic acid and jetanolamine, octylic acid and jetanolamine, lylunic acid and jetanolamine, oleic acid and jetanolamine, and oleic acid and butylamine. In addition, as oily agents, reaction products of fatty acids and epoxy compounds (for example, tetraethylene glycol oleate, pentaethylene glycol octylate, nonaethylene glycol stearate, decaethylene glycol erucate, decaethylene glycol linoleate, etc.), Reaction products of fatty acid esters and epoxy compounds (e.g. octylic acid butanediol ester tetraethylene glycol, oleic acid butanediol ester hexaethylene glycol, stearic acid butanediol ester bentaethylene glycol, caproic acid butanediol ester bentaethylene glycol,
caproic acid hexanediol ester pentaethylene glycol, etc.). These may be used alone or in a mixture of two or more. The content of the oily agent in the lubricant (undiluted) is preferably 0.1 to 20% by weight, preferably 1 to 15% by weight.

The emulsifier has the effect of emulsifying extreme pressure inhibitors, oil-based agents, foaming inhibitors, etc. in water. As the emulsifier, a reaction product of an alkylamine and an epoxy compound is generally used. Examples include octylamine tetraethylene glycol, dodenylamine decaethylene glycol, oleylamine decaethylene glycol, and stearylamine octaethylene glycol. The content of emulsifier in the lubricant (undiluted) is 0.1 to 10% by weight
, preferably 0.5 to 5% by weight.

The foaming inhibitor has the effect of inhibiting foaming of the emulsion. As foam suppressants, use may be made, for example, of minerals such as decane, octane, hexadecane, heptadecane, nonadecane. The content of foam suppressor in the lubricant (undiluted) is 0.1-10% by weight,
The content is preferably 0.5 to 5% by weight.

The rust preventive agent has the effect of preventing corrosion of the iron and brass components of the wire during wire drawing. Examples of the rust preventive include methyl roseoxybenzoate, bisphenol A1 benzotriazole, and methylbenzotriazole. However, since the triazinethiol derivative also has a rust preventive effect, it is not necessarily necessary to include the above-mentioned rust preventive agent. The content of rust inhibitor in lubricant (undiluted) is:
It is desirable that the amount is 0.01 to 5% by weight, preferably 0.1 to 1% by weight.

Preservatives and antifungal agents have the effect of preventing contamination of liquids by microorganisms. Examples of the preservative and fungicide include 1,2-penzisothiazolin-3-one, chlorinated phenol, formaldehyde, and formaldehyde releasing agent. However, since the triazinethiol derivative also has a preservative and antifungal effect, it is not necessarily necessary to incorporate the above-mentioned preservative and antifungal agent. The content of the preservative and fungicide in the lubricant (undiluted) is 0.
0.01 to 5% by weight, preferably 0.1 to 1% by weight.

In the present invention, steel wires include unplated bare steel wire, copper-plated steel wire, brass-plated steel wire, nickel-plated steel wire, tin-plated steel wire, galvanized steel wire, copper-tin-plated steel wire, This means cobalt-plated steel wire, etc. The plating thickness before wire drawing is usually 100 to 10,000, preferably 1,500 to 400.
There are 0 people. In addition, if expressed in terms of plating amount, it is usually 0.1 to 4
0 g/kg, preferably 0.5-10 g/)cg.

In the present invention, the steel wire is drawn using a wet type wire drawing machine. That is, a die is attached to a lubricating tank of a wet wire drawing machine, a lubricant is contained therein, and the die is filled with a diameter of, for example, 0.1 to 1 OIIlfl, preferably 1 to 4II.
11 diameter steel wire is passed through 1 to 2000 m at a speed of 7 minutes, with a diameter of 0.01 to 5 mm, usually 0.1 to 1
Draw the wire to a diameter of mm. In general, hard steel wires such as bare steel wires and nickel-plated steel wires are drawn at low speeds and have a low degree of wire drawing. In the case of a soft steel wire (with a wire-drawing ratio of 65% or more), it can be drawn at high speed and the degree of wire-drawing can be increased. Therefore, the plating thickness mentioned above,
The optimum values for the wire drawing speed and degree of wire drawing naturally vary depending on the type of steel wire.

By the wire drawing operation as described above, a dense and strong film of the triazinethiol derivative is formed on the surface of the steel wire. Although the detailed mechanism has not been completely elucidated, it is estimated as follows.

First, when a steel wire comes into contact with a lubricant, a triazinethiol derivative is adsorbed onto the wire surface. This state is considered to be not much different from the state in which a triazinethiol derivative film is formed on the wire surface by the conventional dipping method.

In the subsequent wire drawing process, the film on the wire surface is momentarily exposed to high temperature and pressure. For example, when a brass-plated steel wire is drawn at a drawing pressure of loOkgf'/mm2, the surface temperature is said to reach several hundred degrees Celsius. As a result, the film of the triazinethiol derivative becomes dense and strong, and it is presumed that the adhesion to rubber changes to better properties.

The steel wire that has been surface-treated at the same time as the wire drawing as described above is used as a single wire or twisted together as a cord. There are various methods of twisting, but the method currently used for boat fishing (for example, Setsuo Fukuhara; textile and industry;
40. No. 11, 827 (1984)) can be applied, and the above-described processing will not cause any inconvenience in twisting.

These steel wires or steel cords made of twisted steel wires are bonded with rubber compounds to produce products such as steel radial tires, steel cord reinforced conveyor belts, steel cord reinforced timing belts, steel cord reinforced hoses, steel cord reinforced handrails, etc. is manufactured.

The composition of the rubber compound used in the present invention is not particularly limited. As the rubber compound, one containing the following components is used: rubber, filler, softener, crosslinking agent, and crosslinking accelerator. In addition to the above-mentioned components, the rubber compound may also contain components such as a lubricant, a stabilizer, and an adhesion promoter.

Rubbers include various natural rubbers (NR), isoprene rubber, butadiene rubber, solution-polymerized butadiene rubber, solution-polymerized butadiene-styrene copolymer rubber, acrylonitrile-butadiene copolymer rubber, ethylene-propylene copolymer rubber, and ethylene-propylene terpolymer rubber. Rubber, silicone rubber, butyl rubber, chlorinated butyl rubber, brominated butyl rubber, chloroprene rubber, fluororubber, hydrin rubber,
epichlorohydrin-ethylene oxide copolymer rubber,
Epichlorohydrin-ethylene oxide-allyl glycidyl ether ternary copolymer rubber, epichlorohydrin-
Propylene oxide-allyl glycidyl ether ternary copolymer rubber, chlorinated polyethylene, acrylic rubber and its copolymer rubber (chlorine-based, epoxy-based, unsaturated), ethylene-vinyl acetate acrylic ester ternary copolymer rubber, urethane rubber etc. can be mentioned.

Fillers are added for the purpose of increasing volume or reinforcing. Examples of fillers include carbon black, rubber reinforcing carbon black, white carbon, hard clay, calcium carbonate, and silicates. The blending amount of the filler is 5 to 200 parts by weight, preferably 3 parts by weight per 100 parts by weight of rubber.
It is 0 to 100 parts by weight.

Softeners are added to improve the processability and moldability of rubber. Examples of softeners include phthalate ester plasticizers such as dioctyl phthalate and dibutyl phthalate, fatty acid ester plasticizers such as dioctyl adipate and dioctyl sebacate, and phosphorus such as triphenyl phosphate and tricresyl phosphate. Examples include acid ester plasticizers, chlorinated paraffins, process oils, and naphthenic oils. The blending amount of the softener is 100 parts by weight or less, preferably 5 parts by weight, per 100 parts by weight of rubber.
~50 parts by weight.

A crosslinking agent is blended in order to exhibit the elasticity of the rubber material. The crosslinking agent used varies depending on the type of rubber, but the main ones include the following. for example,
Sulfur, dicumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, α, α°-bis(t-butylperoxy)isopropylbenzene, 2,5-dimethyl-2, 5-di(t-
butylperoxy)hexane, 2,5-dimethyl-2,
5-di(t-butylperoxy)hexyne-3, berheximone-P-40,1,3,5-triazine-2,4
,8-) dithiol, 6-butylamino-1゜3.5-
) riazine-2,4-dithiol, ethylenethiourea, hexamethylenediamine, ammonium benzoate, bisphenol A, etc. Since the amount of the crosslinking agent varies depending on the individual rubber, it cannot be generally limited, but for boat fishing, 0.1 to 10 parts by weight per 100 parts by weight of rubber is suitable.

A crosslinking accelerator is added to promote the action of the crosslinking agent. Examples of crosslinking accelerators include MgO.

Metal activators such as ZnO, Bad, Ca(OH)2;
Thiazole promoters such as 2-mercaptobenzothiazole and dibenzothiazolyl disulfide; Sulfenamide promoters such as N-cyclohexyl-2-benzothiazyl sulfenamide and N~morphonylylbenzole sulfenamide; Examples include thuramic accelerators such as tetramethylthuram disulfide; polyfunctional monomers such as fatty acid amines, quaternary ammonium salts, organic phosphonium salts, triallyl isocyanurate, trimethylolpropane triacrylate, and diallyl phthalate. These may be used alone or in combination. The amount of crosslinking accelerator varies depending on the type of rubber and crosslinking agent, so it cannot be generally limited, but for boat fishing it is 0 per 100 parts by weight of rubber.
．． 1 to 20 parts by weight is suitable.

To produce steel wire rubber bonded composite,
The rubber compound must contain at least each of the above components. In addition, the following lubricants, stabilizers,
] Components such as auxiliary agents are not necessarily necessary to obtain a union after bonding steel wire rubber, but if these components contain H, the water resistance, heat resistance, and steam resistance of the steel wire rubber bonded composite will be improved. This is advantageous in improving properties and fatigue resistance.

A lubricant is added to improve the flow of the rubber compound during adhesive compounding. Examples of the lubricant include stearic acid, Na salt, Mg salt, Ca salt, Ba salt, or Zn salt of stearic acid, ethylene bisamide stearate, ethylene bisamide erucate, paraffin, and wax. The lubricant is generally added in an amount of 0.1 to 5 parts by weight per 100 parts by weight of rubber.

Stabilizers are added to prevent deterioration of the FxVt bond. Examples of the stabilizer include phenylene diamine anti-aging agents, phenolic anti-aging agents, nickel dithiocarbamate, and benzophenone. The stabilizer is generally added in an amount of 0.1 to 5 parts by weight per 100 parts by weight of rubber.

As an adhesion aid, for example, 1,3,5-triazine-2
, 4,6-h dithiol, 6-butylamino 1.3.
Cobalt salts such as 5-triazine-2,4-dithiol, 6-diallylamino-1,3,5-triazine-2,4-dithiol, cobalt naphthenate, cobalt stearate, aminobenzoic acid metal salts (Co, Mn, Zn
.

Moq Cr), resorcinol, cresol, resol-formalin latex, resol type phenolic resin (including uncured), formalin-alkylphenol resin, formalin-cresol resin (including uncured), monomethylolmelamine, Methylolmelamine, trimethylolmelamine, hexamethylolmelamine, monomethinemethylolmelamine, tetramethoxymethylolmelamine, pentamethoxymethylolmelamine, monomethylolurea, trimethylolurea,
Trimethoxymethylol urea, ethylene maleimide, butylene maleimide, phenylene maleimide, abietic acid metal salt (CoSNi, Fe.

M n ), etc. Adhesion aid is rubber 100
0.1 to 20 parts by weight of ffi, preferably 0.5 to 5 parts by weight, is added to the melon part.

In the present invention, the above-mentioned surface-treated steel wire (cord) is brought into contact with a rubber compound,
By hot pressing or steam heating, adhesive compounding is carried out simultaneously with the completion of crosslinking, and a combination of steel wire and rubber is obtained after bonding. This r condition is usually 80
~230'C1 Preferably i, ao~ [5 to 180 minutes at 80°C, preferably 10 to 60 minutes. In addition,
Depending on the type of rubber or crosslinking agent system, additional post-crosslinking may be performed.

〔Example〕

The F1 invention will now be described in detail.

First, a wet wire drawing apparatus used in an embodiment of the present invention will be described with reference to FIGS. 1 and 2. 1st
In the figure, a lubricating fluid 21 is contained in a lubricating tank 20 . The steel wire 22 is passed from the supply bobbin 1 through the guide roll 2 to the free roll 3 and drive roll 5 so as to pass through the die 4 inside the lubricating tank 20, and then again to pass through the die 7 in the same manner as above. It is passed through a free roll 6 and a drive roll 8, passes through a die 9, and is wound onto a take-up bobbin 12 via a capstan 10 and a guide roll 11 outside the lubricating tank 20.

The dice 4.7 are stacked with multiple stages of dice. The individual dice that make up these dice 4.7 are
As shown in the figure, a carbide tip 1 is placed inside the die case 13.
It has a structure with 4 attached.

Examples 1 to 5 and Comparative 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 , 5 parts by weight of dodecyl phosphate butanediol ester bentapropylene glycol, 0.5 parts by weight of methyl roseoxybenzoate, 1 part by weight of methylbenzotriazole, ■, 0.5 parts by weight of 2-benzisothiazolin-3-one, 72.5 parts by weight of water parts by weight, and 0.0 parts by weight of the triazinethiol derivatives shown in Table 1.
Five new emulsion-type lubricants were prepared (Examples 1-5) consisting of 5 parts by weight. In addition, an emulsion type lubricant having the same composition as above except that it did not contain a triazinethiol derivative was prepared (Comparative Example 1).

The above six types of lubricants were diluted 7 times and stored in the lubricating tank of a wet wire drawing device, respectively, and 1.68 mm diameter brass plated steel wire (plating ff14.1 g/) cg,
A steel wire having a diameter of 0.30 mm was obtained by drawing the wire at a wire drawing speed of about 850 m/min (Cu content in plating: 65%). Using these 6 types of steel wire, 2
In total, six types of adhesive steel cord samples were prepared.

On the other hand, 100 parts by weight of natural rubber (NR), 50 parts by weight of carbon black (HAF), 5 parts by weight of process oil, 5 parts by weight of sulfur, 0.8 fflfilt of N-cyclhexyl-2-benzothiazylsulfenamide (CBS).
10 parts by weight of zinc oxide, 2 parts by weight of cobalt naphthenate, 1 part by weight of 6-nitoxy 2.2.4-trimethyl-1,2-dihydroquinone, 3 parts by weight of resorcinol, and 4 parts by weight of hexamethylolmelamine. A compound has been prepared.

Each of the six types of adhesive cord samples described above was embedded in this NR compound for 1.8 times (up to 1.8 mm), and vulcanization was performed at 140° C. for 30 minutes to produce a plurality of six types of adhesive composite samples.

For each adhesive composite sample, two
By pulling out the cord at a pulling speed of 50 mm/min at 0° C., the pulling strength at the initial stage and after deterioration for a predetermined period of time in a steam atmosphere (steam deterioration) was determined as ΔP1. In addition, the adhesion rate of rubber on the surface of the pulled cord was investigated. In addition, steam deterioration was performed by placing each adhesive composite sample in a steam atmosphere of 120'C and humidity loo% for 1 hour.
This was carried out by leaving the samples for a different time in the range of 0 to 25 hours (shown in Table 1). These results are summarized in Table 1.

As is clear from Table 1, the adhesive composites of Examples 1 to 5, in which drawn brass steel wire and rubber were bonded using a lubricant containing a triazinethiol derivative, did not contain a triazinethiol derivative. Compared to the adhesive composite of Comparative Example 1 in which a drawn brass steel wire and rubber were bonded using a lubricant, the initial pull-out strength was similar, but the pull-out strength after steam aging was significantly improved. and has excellent adhesion.

Examples 6 to IO and Comparative Example 2.3 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 parts by weight, 5 parts by weight of dodecyl phosphate butanediol ester bentabrobylene glycol, 0.5 parts by weight of methyl hydroxybenzoate, 1 part by weight of methylbenzotriazole, and 72.5 parts by weight of water.
Add 1 part by weight to 1 part by weight, and add 1 part to 6-cyptylamino. ．． 3.5
- Triazine-2,4-dithiol monoethanolamine (DBME) at 0.15-3 g/1. QO
Five novel emulsion-type lubricants were prepared (Examples 6-10, Comparative Example 2) by blending at varying concentrations in the ml range (shown in Table 2). In addition, an emulsion type lubricant having the same composition as described above except for not containing DBME was prepared in Comparative Example 3).

The above six types of lubricants were diluted 7 times and placed in the lubricating tank of a wet wire drawing machine, respectively, and used to prepare bare (unplated) steel wire or brass-plated steel wire (plating thickness: 5800 mm) with a diameter of 0.8 mm. Cu content in plating: 65%
) was drawn at a wire drawing speed of 0.5 to 100 m/min as shown in Table 2, and six kinds of bare steel wires with a diameter of 1.50++ m (Examples 6 to 10, Comparative Example 2) and one kind were drawn. 1.50 of
A brass-plated steel wire (Comparative Example 3) with a diameter of m+s was obtained. These were used as seven types of adhesive steel wire samples.

On the other hand, 100 parts by weight of N R, carbon black (HAF
) 50 parts by weight, 5 parts by weight of process oil, 4 parts by weight of sulfur, 0.8 parts by weight of N-cyclhexyl-2-benzothiazylsulfenamide (CBS), 10 parts by weight of zinc oxide, G
An NR compound consisting of 1 part by weight of -ethoxy-2,2,4-)limethyl=1,2-dihydroquinone, 3 parts by weight of resorcinol, and 4 parts by weight of hexamethylolmelamine was prepared.

Each of the seven types of adhesive wire samples was embedded to a length of 2.54 cm into this NR compound, and vulcanization was performed at 153° C. for 30 minutes to produce a plurality of seven types of adhesive composite samples.

For each adhesive composite sample, two
The pulling strength was measured initially and after deterioration (steam deterioration) for a predetermined period of time in a steam atmosphere by a method of pulling out the cord at a tensile speed of 50 mm/min at 0°C. For steam deterioration, each contacting composite sample was heated to 100% humidity.
, respectively 10-25 in a water vapor atmosphere at 120'C.
The test was carried out by changing the time within the range of time (shown in Table 2) and leaving it for a while. These results are summarized in Table 2.

As is clear from Table 2, the adhesive composite of Comparative Example 2, in which rubber was bonded to a bare steel wire drawn at a very low speed using a lubricant containing DBME, had a high pullout strength. is small.

This pullout strength value is comparable to a bonded composite of bare steel wire and rubber compound without drawing (and therefore surface treatment). Since it is conventionally said that unplated bare steel wire does not come into contact with rubber at all, it is thought that in Comparative Example 2, the bare steel wire and rubber are hardly bonded to each other. Although not shown in Table 2, the fact that no rubber was attached to the wire pulled out of the adhesive composite of Comparative Example 2 makes it clear that there is almost no adhesion between the bare steel wire and rubber. . Therefore, the pull-out strength exhibited by the adhesive composite of Comparative Example 2 is due solely to the friction when the wire embedded in the vulcanized rubber is pulled out.

On the other hand, the adhesive composite of Comparative Example 3, in which the drawn brass-plated wire and rubber were bonded using a lubricant that does not contain triazinethiol derivatives, showed a high initial pull-out strength, but after steam degradation The pull-out strength of is small.

On the other hand, a lubricant containing DBME was used and the wire drawing speed was increased compared to Comparative Example 2 (same level or higher than Comparative Example 3).
In the adhesive composites of Examples 6 to 10, in which drawn bare steel wire and rubber were bonded, the initial pull-out strength was significantly higher than that of Comparative Example 2, and the pull-out strength after steam degradation was also higher than that of Comparative Example 2 and Comparative Example. This is a marked improvement over Example 3. These results show that wire drawing treatment using a lubricant containing a triazinethiol conductor is effective.

Examples 11 to 15 and Comparative Examples 4 to 8 3 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 laurate parts by weight, dodecyl phosphate butanediol ester bentabrobylene glycol 5 parts by weight, methyl roseoxybenzoate 0.5 parts by weight, benzotriazole 1 part by weight, water 72.5 parts by weight, and 1.3.5-triazine-2, 1 part by weight of 4,6-trithiol jetanolamine (FDE)
Several novel emulsion-type lubricants were prepared (Examples 11-15). In addition, an emulsion-type lubricant having the same composition as above except that it did not contain FDE was prepared (
Comparative Examples 4-8).

The above two types of lubricants were diluted 7 times and placed in the lubricating tank of a wet wire drawing device.
1 diameter brass plated steel wire (plating amount 4.1g/
kg, Cu content in plating: 65%), approximately 80 kg, respectively.
It was drawn at a wire drawing speed of 0 m/min to obtain a diameter of 0.38 mm and a wire drawing speed of 0.38 mm.
A 20 mm diameter brass-plated steel wire was obtained.

Using wires drawn using each lubricant, three wires each with a diameter of 0.20 m + s on the inside and 0.3 wire on the outside.
Two types of 1.26 diameter adhesive steel cord samples were prepared by twisting six 8 diameter wires.

On the other hand, 100 parts by weight of NR, Carbon Bra Tsuku (HAF
) 50 parts by weight, 5 parts by weight of process oil, 1 to 8 parts by weight of sulfur (shown in Table 3), parts by weight of N-cyclhexyl-2-benzothiazylsulfenamide (CBS) O,lt,
Five types of NR compound sheets were prepared consisting of 10 parts by weight of zinc oxide and 1 part by weight of N,N'-dioctylphenylenediamine (Nonflex 0O-3) and having dimensions of 1.5 mm x 12 mm x foCm. there was.

On these five types of NR compound sheets, 10 each of the above two types of adhesive cord samples were arranged, and heated to 153°C.
Vulcanization was carried out for 30 minutes to produce 10 types of adhesive composites. For each of these 10 types of adhesive composites, one cord at each end was cut out, and the remaining eight cords were used as adhesive composite samples.

For each adhesive composite sample, two
Initially, after hot water treatment (moisture degradation), the vulcanized rubber was peeled from the adhesive composite at a tensile rate of 50 μ/min at 0°C.
And the peel strength after heat treatment (heat deterioration) was measured. Note that hot water treatment (moisture deterioration) was performed by heating the adhesive composite sample to 95°C.
It was left in hot water for 5 days. Further, heat treatment (heat deterioration) was performed by leaving the adhesive composite sample in a test tube at 100° C. for 3 days. These results are summarized in Table 3.

As is clear from Table 3, in the adhesive composites of Comparative Examples 4 to 8 using cords drawn with a lubricant that does not contain triazinethiol derivatives, the initial peel strength was lowered by the sulfur in the rubber compound. It becomes larger as the content increases. In addition, regarding the peel strength after deterioration,
Sulfur content in rubber compound is 2 parts by weight (phr)
The amount of sulfur in the rubber compound reaches its maximum value, and decreases as the amount of sulfur in the rubber compound increases further. For this reason, there is no suitable composition of a rubber compound that provides good peel strength both at the initial stage and after deterioration.

On the other hand, in the adhesive composites of Examples 11 to 15 using cords drawn (surface treated) with a lubricant containing 3 FDEs, the tendency of change in peel strength both at the initial stage and after deterioration was not as described above. However, the initial peel strength, especially when the sulfur content in the rubber compound is low,
The peel strength after aging is improved when the sulfur content in the rubber compound is high. As a result, by setting the optimum composition of the rubber compound, it is possible to satisfy both the initial and post-deterioration peel strength of the adhesive composite.

Example 16, I7 and Comparative Example 9.10 3 parts by weight of ethylenediamine phosphate, 8 parts by weight of oleic acid triethanolamine salt, 4 parts by weight of laurylamine octaethylene glycol, 3 parts by weight of octadecane, lyrinic acid butanediol ester tetra 2 parts by weight of ethylene glycol, 5 parts by weight of dodecyl phosphate butanediol ester bentabrobylene glycol, 5 parts by weight of methyl hydroxybenzoate, 1 part by weight of benzotriazole,
72.5 parts by weight of water, and 6-cyptylamino L, 3.
A novel emulsion-type lubricant was prepared consisting of 1 part by weight of 5-triane-2,4-dithiol monoethylenediamine (DBME) (Example 16.1)
7). In addition, an emulsion type lubricant having the same composition as above except that it did not contain DBME was prepared (Comparative Example 9).
10).

The above two types of lubricants were diluted 7 times and placed in the lubricating tank of a wet wire drawing device, respectively, and a brass-plated steel wire with a diameter of 1.25 m+* (plating ff14.1/kg, Cu content in the plating) was prepared. (-j ratio 65%) was drawn at a wire drawing speed of about 800 m/min to obtain 2 g of brass-plated steel wire with a diameter of 0.25 mm.Using these two types of wire, five wires each were twisted, Two types of adhesive steel cord samples were prepared.

The treated cord (Example 16) and the untreated cord (Comparative Example 9) were each left in an atmosphere of 70°C and 90% humidity for 3 days, and then tested under constant pressure by the staircase method using a Hunter fatigue tester. The rupture strength (estimated fatigue limit) was determined.

As a result, the breaking strength (estimated fatigue limit) was 8 kgf/mm2 in Comparative Example 9, whereas it was 7 kgf/mm2 in Example 18.

As is clear from this result, the processing code (Example 16
) exhibited higher fatigue strength even when exposed to a corrosive environment than the untreated cord (Comparative Example 9), indicating that the corrosion resistance was significantly improved.

On the other hand, 70 parts by weight of NR, 30 parts by weight of butadiene rubber (BR), 50 parts by weight of carbon black (HAF), 5 parts by weight of process oil, 5 parts by weight of sulfur, 0. 8
An NR-BR compound was prepared, which consisted of 1 part by weight, 10 parts by weight of zinc oxide, and 1 part by weight of N-(],]3-dimethylbutyl-N-phenyl-p-phenylenediamine.

A treated cord (Example 17) or an untreated cord (Comparative Example 9) was embedded in this NR-BR compound, placed in a mold, and vulcanized at 150°C for 30 minutes. An adhesive composite sample of X1m was prepared. These adhesive composite samples were heated at 70°C and humidity at 90°C.
After being left in an atmosphere of 96° C. for 31 hours, the fracture strength (estimated fatigue limit) under constant pressure was determined by the staircase method using a Hunter fatigue tester. As a result, the breaking strength (estimated fatigue limit) was 68 kgl in Comparative Example 10.
'/m112, whereas in Example 17 it was 1.
It was 03 kgf'/mm2.

In general, even in the case of an adhesive composite, it is said that if it is left in a corrosive environment, the fatigue strength of the joints embedded in the joint will deteriorate significantly, and in fact Comparative Example 1
The Δ-1 constant result for the fatigue strength of 0 shows this.

On the other hand, it is clear that the contact Mt composite using the treated cord (Example 17) is resistant to corrosive environments.

〔Effect of the invention〕

As detailed above, the present invention provides a steel wire surface treatment method that enables processing speeds suitable for industrial production;
A lubricant containing a triazinethiol derivative suitable for this surface treatment, and a steel wire-rubber adhesive composite made of surface-treated steel wire and rubber, with excellent heat resistance, water resistance, steam resistance, and fatigue resistance. The industrial value of this product is extremely large.

[Brief explanation of the drawing]

FIG. 1 is a schematic configuration diagram of a wet wire drawing device used in an embodiment of the present invention, and FIG. 2 is a sectional view showing a die of the wet wire drawing device. 1... Supply bobbin, 2.11... Guide roll, 3
．． 6...Free roll, 4.7.9...Dice, 5
．． 8... Drive roll, 10... Capstan, 12
... Winding bobbin 12.13 ... Dice case, 14
... Carbide tip, 20... Lubricating tank, 21... Lubricant, 22... Steel wire.

Claims (3)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the above formula, R is -OR', -SR', -NHR', -
N(R')_2;R' is an alkyl group, an alkenyl group, a phenyl group, a phenylalkyl group, an alkylphenyl group,
or cycloalkyl group, M is H, Na, Li, K, 1/
2Mg, 1/2Ba, 1/2Ca, aliphatic primary, secondary or tertiary amine, quaternary ammonium salt, or phosphonium salt) A drawn steel wire characterized by containing a triazinethiol derivative represented by lubricant for use. (2) A method for surface treatment of a steel wire, comprising storing the lubricant for steel wire wire drawing according to claim (1) in a wire drawing machine, and surface treating the steel wire while drawing the steel wire. (3) A steel wire-rubber adhesive composite obtained by bringing the surface-treated steel wire according to claim (2) into contact with a rubber compound and heating the mixture.