JP5213171B2 - Lubricant for wet wire drawing and wet wire drawing method - Google Patents

Description

  The present invention relates to a lubricant for wet wire drawing and a wet wire drawing method, and more specifically, is brass plating for reinforcing rubber articles used for steel cords used for reinforcement in various rubber articles such as tires and conveyor belts. Further, the present invention relates to a wet wire drawing lubricant (hereinafter also simply referred to as “lubricant”) and a wet wire drawing method (hereinafter also simply referred to as “wire drawing method”) of steel wires (hereinafter also simply referred to as “steel cords”).

  Steel cords for reinforcing rubber articles used for reinforcing rubber articles such as tires are usually obtained by drawing brass-plated wire (steel wire) to a desired wire diameter to obtain steel filaments. Manufactured by twisting together as appropriate. This wire drawing process is generally performed using a slip-type multistage wire drawing machine 10 as shown in FIG.

  In the illustrated slip type multi-stage wire drawing machine 10, two multi-stage drive capstans 13A and 13B are arranged opposite to each other in a lubricating liquid tank 12 filled with a lubricant 11. In the process of alternately passing the steel wires 1 through the dies 14 to the respective stages of the capstans 13A, 13B, the steel wires 1 are drawn by the dies 14 at each stage. The drawn steel wire 1 is sent to the winding process from the drive capstan 15 disposed outside the lubricating liquid tank 12 through the final die 16.

  When wet drawing of the steel wire 1 is performed using the slip-type multistage wire drawing machine 10 and the lubricant 11, conventionally, a zinc complex of a phosphate ester or the like is used as an extreme pressure coating to draw the wire. A technique has been used in which friction between a die and a wire is reduced to suppress damage to the die and the wire. This has played a very important role in producing steel wires and thus steel cords with high productivity.

  As an improved technique related to the wet drawing process of steel wire subjected to such brass plating, for example, Patent Document 1 uses a lubricant containing zinc and one or both of cobalt and nickel. A method of drawing a steel wire that combines high productivity and low cost with excellent initial adhesion of the wire has been reported. Further, Patent Document 2 uses a lubricant containing either one or both of cobalt and nickel, and provides a similar effect by passing a slip speed in a drive capstan through a predetermined drawing path. Realized steel wire drawing methods have been proposed.

  Patent Document 3 discloses that an organic carboxylic acid amine salt, an organic phosphate ester amic acid, and a specific organic metal are used for the purpose of improving the drawing processability and improving the adhesion of the resulting wire drawing material to rubber. It has been reported that a lubricant composition containing a predetermined proportion of salt is used.

Furthermore, Patent Document 4 proposes that a metal salt of benzoic acid is contained in the lubricant in order to enhance the adhesion between the steel wire plated with brass and the rubber.
JP 2002-11519 A (Claims etc.) JP 2002-11520 A (Claims etc.) JP 2002-241781 A (Claims etc.) JP 2005-246447 A (Claims etc.)

  When wet drawing is performed as described above, various types of lubricants are used to improve wire drawing workability, suppress damage to dies and wires, and further improve adhesion to rubber. It has played a major role in producing steel cords with high productivity. However, in wire drawing to produce high-strength steel wire, the steel wire to be processed has a high deformation resistance, so the heat generated by the processing increases, and the steel wire deteriorates due to age hardening and promotes die wear. Such problems are likely to occur, and the prior art has not been sufficient to solve such problems.

  Accordingly, an object of the present invention is to provide a lubrication for wet wire drawing that has excellent ductility that is difficult to break when drawing high-strength steel wire, and that does not decrease ductility even when twisted wire is added. It is in providing an agent and a wet wire drawing method.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a phosphazene derivative compound as a wet wire drawing lubricant, has excellent ductility that is difficult to break, and has added processing such as stranded wire. However, the present inventors have found that a brass-plated steel cord with little reduction in ductility can be obtained and the present invention has been completed.

  That is, the lubricant for wet wire drawing of the present invention includes a phosphazene derivative compound in the wet wire drawing lubricant used when wet-drawing a brass-plated steel wire, and the phosphazene derivative. The compound is a chain compound.

  Also, the wet wire drawing method of the present invention comprises adding the wet wire drawing lubricant of the present invention to water to form an aqueous solution, and wet-drawing a brass-plated steel wire in the aqueous solution. It is a feature.

  In the wet wire drawing method of the present invention, the concentration of the phosphazene derivative compound in the aqueous solution is preferably 0.01 to 10.0% by mass. In addition, a slip type multistage wire drawing machine including a die for the brass-plated steel wire and a drive capstan for drawing the steel wire that has passed through the die can be suitably used.

  According to the present invention, it is possible to obtain a brass-plated steel cord that has excellent ductility that is difficult to break, and has little reduction in ductility even when processing such as stranded wire is applied. Also, in wet wire drawing, it has an excellent effect on die life and speeding up.

Hereinafter, embodiments of the present invention will be specifically described.
In the present invention, it is important to include a phosphazene derivative compound in a wet drawing lubricant used for wet drawing of a brass-plated steel wire. Such a lubricant is added to water to form an aqueous solution, and in this aqueous solution, the steel wire plated with brass is wet-drawn so that it has excellent ductility that is difficult to break, and processing such as stranded wire can be added. A brass-plated steel cord with little reduction in ductility can be obtained.

  Specifically, by adding a phosphazene derivative compound to the lubricant, a strong lubricating film is formed between the die and the wire, and friction can be reduced and heat generation can be suppressed. Such a lubricant is an emulsion type, and contains an extreme pressure additive, an oily agent, a rust preventive, a preservative, an emulsifier, and the like.

  Suitable examples of the phosphazene derivative compound include a chain phosphazene derivative compound represented by the following general formula (1) or a cyclic phosphazene derivative compound represented by the following general formula (2).

但し、一般式（１）において、Ｒ^１、Ｒ^２、及びＲ^３は、一価の置換基又はハロゲン元素を表す。Ｘは、炭素、ケイ素、ゲルマニウム、スズ、窒素、リン、ヒ素、アンチモン、ビスマス、酸素、イオウ、セレン、テルル、及びポロニウムからなる群から選ばれる元素の少なくとも１種を含む有機基を表す。Ｙ^１、Ｙ^２、及びＹ^３は、二価の連結基、二価の元素、又は単結合を表す。 Formula (1),

However, in General formula (1), R < ¹ >, R < ² > and R < ³ > represent a monovalent substituent or a halogen element. X represents an organic group containing at least one element selected from the group consisting of carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, antimony, bismuth, oxygen, sulfur, selenium, tellurium, and polonium. Y ¹ , Y ² , and Y ³ represent a divalent linking group, a divalent element, or a single bond.

General formula (2),
(PNR ⁴ ₂ ) _n
However, in the general formula (2), R ⁴ represents a monovalent substituent or a halogen element. N represents 3-15.

In general formula (1), R ¹ , R ² , and R ³ are not particularly limited as long as they are monovalent substituents or halogen elements. Examples of monovalent substituents include alkoxy groups, alkyl groups, and carboxyl groups. Group, acyl group, aryl group and the like. Among these, an alkoxy group is particularly preferable in that the viscosity of the lubricant liquid can be reduced. R ^{1 to} R ³ may all be the same type of substituent, and some of them may be different types of substituents.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and alkoxy-substituted alkoxy groups such as a methoxyethoxy group and a methoxyethoxyethoxy group. Among these, it is preferable that all of R ^{1 to} R ³ are methoxy group, ethoxy group, methoxyethoxy group, or methoxyethoxyethoxy group, from the viewpoint of compatibility with the lubricant liquid. Particularly preferred is an ethoxy group or a methoxyethoxyethoxy group.

  Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group and the like. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group.

  The hydrogen element in these substituents is preferably substituted with a halogen element.

In the general formula (1), examples of the group represented by Y ¹ , Y ² , and Y ³ include CH ₂ group, oxygen, sulfur, selenium, nitrogen, boron, aluminum, scandium, gallium, yttrium, Indium, lanthanum, thallium, carbon, silicon, titanium, tin, germanium, zirconium, lead, phosphorus, vanadium, arsenic, niobium, antimony, tantalum, bismuth, chromium, molybdenum, tellurium, polonium, tungsten, iron, cobalt, nickel, etc. Among these, a CH ₂ group and a group containing oxygen, sulfur, selenium, and nitrogen are preferable. In particular, when Y ¹ , Y ² , and Y ³ contain sulfur and selenium elements, it is preferable because the heat resistance of the lubricant is significantly improved. Y ^{1 to} Y ³ may all be the same type, or some of them may be different from each other.

  In the general formula (1), X includes an organic compound containing at least one element selected from the group consisting of carbon, silicon, nitrogen, phosphorus, oxygen, and sulfur from the viewpoint of consideration of toxicity, environment, and the like. Group is preferable, and an organic group having a structure represented by the following general formula (3) is more preferable.

但し、一般式（３）において、Ｒ^５〜Ｒ^９は、一価の置換基又はハロゲン元素を表す。Ｙ^５〜Ｙ^９は、二価の連結基、二価の元素、又は単結合を表し、Ｚは二価の基又は二価の元素を表す。 General formula (3),

However, in the general formula ^(3), R 5 ~R ⁹ represents a monovalent substituent or a halogen element. Y ^{5 to} Y ⁹ represent a divalent linking group, a divalent element, or a single bond, and Z represents a divalent group or a divalent element.

In the general formula (3), as R ^{5 to} R ⁹ , any of the same monovalent substituents and halogen elements as those described for R ^{1 to} R ³ in the general formula (1) can be preferably used. Moreover, these may be the same kind in the same organic group, and some may be different kinds. R ⁵ and R ⁶ , and R ⁸ and R ⁹ may be bonded to each other to form a ring. In the general formula (3), examples of the group represented by Y ^{5 to} Y ⁹ include a divalent linking group or a divalent group similar to those described for Y ^{1 to} Y ³ in the general formula (1). Similarly, sulfur and selenium elements are particularly preferable because the heat resistance of the lubricant is remarkably improved. These may be the same type in the same organic group, or some of them may be different types. In the general formula (3), as Z, for example, a CH ₂ group, CHR (R represents an alkyl group, an alkoxyl group, a phenyl group, etc .; the same shall apply hereinafter) group, an NR group, oxygen, sulfur, selenium. , Boron, aluminum, scandium, gallium, yttrium, indium, lanthanum, thallium, carbon, silicon, titanium, tin, germanium, zirconium, lead, phosphorus, vanadium, arsenic, niobium, antimony, tantalum, bismuth, chromium, molybdenum, tellurium , Polonium, tungsten, iron, cobalt, nickel, and the like. Among these, oxygen, sulfur, and selenium are preferable in addition to the CH ₂ group, CHR group, and NR group. In particular, sulfur and selenium elements are preferable because the heat resistance of the lubricant is significantly improved.

By appropriately selecting R ^{1 to} R ⁹ , Y ^{1 to} Y ³ , Y ^{5 to} Y ⁹ , and Z in the general formulas (1) to (3), it is possible to have more suitable viscosity, solubility, and the like. It becomes. These phosphazene derivatives may be used alone or in combination of two or more.

  Next, in the wire drawing method of the present invention, the above-described lubricant of the present invention is added to water to form an aqueous solution, and the brass-plated steel wire is wet-drawn in this aqueous solution.

  In the wire drawing method of the present invention, the concentration of the phosphazene derivative compound in the aqueous solution is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 5.0% by mass. If this concentration is less than 0.01% by mass, the desired effect of the phosphazene derivative compound will not be exhibited. On the other hand, if it exceeds 10.0% by mass, the viscosity will increase and good lubricating performance will not be exhibited.

  Further, in the wire drawing method of the present invention, a slip-type multistage wire drawing machine having a die for a brass-plated steel wire and a drive capstan for drawing the steel wire that has passed through the die is preferably used. However, it is sufficient if the lubricant satisfies the above conditions, and other conditions related to the wire drawing process, such as wire speed, slip speed in a slip type multi-stage wire drawing machine, die shape, etc. There is no particular limitation. Moreover, the wire drawing method of the present invention is not particularly limited as long as the steel wire is drawn by wet drawing, and may be either single wire drawing or continuous wire drawing.

  A steel cord obtained by twisting a plurality of filaments of steel wire obtained by the above-described wire drawing method can be suitably used for reinforcement in various rubber articles such as tires and conveyor belts.

Hereinafter, the present invention will be described based on examples.
Examples 1 to 4, Reference Examples 1 to 4 and Comparative Example After high-carbon steel wire having a diameter of about 5.5 mm was repeatedly dry-drawn until the diameter was about 1.6 mm, patenting treatment and brass plating were performed. About the wire material which prepared by adding a process, the wet wire-drawing process was performed. In the comparative example, the conventional lubricant is used, and in the example, the lubricant is blended with the phosphazene derivative compounds shown in Table 1 and Table 2 below, and the diameter is about 0.20 mm. A slip-type multistage drawing was performed. At this time, the content and structure of the phosphazene derivative compound in the aqueous solution of the lubricant in wet wire drawing were varied as shown in Tables 1 and 2 below. In the table, “cyclic” and “chain” of the phosphazene derivative compound have the following structures.

(Annular 1)
It is a cyclic phosphazene derivative (in the general formula (2), R ⁴ is an ethoxy group, and n is 3).
(Annular 2)
A cyclic phosphazene derivative (in the general formula (2), R ⁴ is a methoxyethoxyethoxy group, and n is 3).
(Chain 1)
A chain phosphazene derivative (in the general formula (1), X is the structure of the organic group (A) represented by the general formula (3), and Y ^{1 to} Y ³ and Y ^{5 to} Y ⁶ are all And R ^{1 to} R ³ and R ^{5 to} R ⁶ are all ethoxy groups, and Z is oxygen).
(Chain 2)
A chain phosphazene derivative (in the general formula (1), X is the structure of the organic group (A) represented by the general formula (3), and Y ^{1 to} Y ³ and Y ^{5 to} Y ⁶ are all And R ^{1 to} R ³ and R ^{5 to} R ⁶ are all methoxyethoxyethoxy groups, and Z is oxygen).

  A repeated twist test was performed on the steel wires obtained in Examples 1 to 4, Reference Examples 1 to 4 and Comparative Example. The test was performed by repeatedly applying clockwise and counterclockwise rotations and counting the number of repetitions until a crack was generated. Evaluation is expressed as an index value with the comparative example being 100, and the higher the numerical value, the better the ductility. The obtained results are shown in Tables 1 and 2 below.

  From the results shown in Table 1 and Table 2, it was confirmed that the steel wire of any of the examples had an improved repeated twist test value and an improved ductility value compared to the steel wire of the comparative example.

It is a schematic diagram which shows a slip type multistage wire drawing machine.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Steel wire 10 Slip type multi-stage wire drawing machine 11 Lubricant for wet wire drawing 12 Lubricating liquid tank 13A, 13B Drive capstan 14 Die 15 Drive capstan 16 Final die

Claims (4)

A wet drawing lubricant used for wet drawing of a brass-plated steel wire, comprising a phosphazene derivative compound , wherein the phosphazene derivative compound is a chain compound. Lubricant for wire drawing. Claim 1 Symbol placing wet drawing lubricant were added into the water solution and without, in the aqueous solution, for reinforcing a rubber article steel wire the steel wire which is brass-plated, characterized in that wet-drawing Wet wire drawing method. The wet wire drawing method according to claim 2, wherein the concentration of the phosphazene derivative compound in the aqueous solution is 0.01 to 10.0% by mass. The wet-drawn wire according to claim 2 or 3, wherein the brass-plated steel wire is wet-drawn using a slip-type multi-stage wire drawing machine including a die and a drive capstan that pulls out the steel wire that has passed through the die. Wet wire drawing method.

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