A water-based steel cord drawing fluid composition and its preparation method

Abstract

This invention relates to the field of drawing fluid technology, and discloses a water-based steel cord drawing fluid composition and its preparation method. The raw materials for preparing the water-based steel cord drawing fluid composition include: water, base oil, oiliness agent, extreme pressure anti-wear agent, surfactant, alkali, rust inhibitor, defoamer, carboxylic acid complexing agent, and organophosphonate complexing agent. The carboxylic acid complexing agent is at least one of tetrasodium glutamate diacetate and trisodium methylglycine diacetate; the organophosphonate complexing agent is at least one of tetrasodium aminotrimethylene phosphonate and butane-1,2,4-tricarboxylic acid 2-phosphonate. This invention, by using a combination of carboxylic acid complexing agent and organophosphonate complexing agent, solves the technical problem of easy dissociation of complexes and the inability to maintain the stability of the drawing fluid composition when only carboxylic acid complexing agent is used to replace ethylenediamine and its derivatives. This further ensures the long-term stability of the drawing fluid system under high-speed steel cord drawing conditions, ensuring that the core performance of the drawing fluid, such as lubrication and rust prevention, remains unchanged.

Description

Technical Field

[0001] This invention relates to the field of drawing fluid technology, and in particular to a water-based steel cord drawing fluid composition and its preparation method. Background Technology

[0002] Steel cord is a fine-gauge steel wire strand or rope made from high-quality high-carbon steel. Its diameter is approximately 0.15–0.8 mm, and it is plated with a brass layer. It is a specialized wire material mainly used as the skeleton material for passenger car tires, light truck tires, heavy truck tires, construction machinery tires, and aircraft tires. It can also be used as a reinforcing material for other rubber products. Steel cord drawing fluid is a specialized metalworking fluid used in the high-speed drawing of fine-gauge high-carbon steel wires during steel cord production. It is mostly water-based and its main functions are to provide efficient lubrication, rapid cooling, cleaning, and rust prevention during the drawing process; reduce friction and drawing force between the steel wire and the die; reduce die wear and wire breakage; ensure the surface quality of the steel wire; and adapt to the high-speed drawing process requirements of steel cord.

[0003] To ensure the stability of the steel cord drawing fluid system and improve its lubrication performance, traditional water-based steel cord drawing fluids often use ethylenediamine and its derivatives as complexing agents. However, ethylenediamine has respiratory sensitization properties, and its related derivatives also pose similar health risks due to their raw material or structural associations. Therefore, some researchers have sought alternative complexing agents with lower health risks to replace ethylenediamine and its derivatives. For example, Chinese patent document CN116987543A discloses a steel cord wet drawing lubricant composition. This composition uses tetrasodium glutamate diacetate and tetrasodium aspartate diacetate as preferred complexing agents to control the brass component content in the lubricant emulsion during processing, ensuring the stability of the lubricant composition, guaranteeing the lubricant's processing performance, and improving its service life. However, tetrasodium glutamate diacetate and tetrasodium aspartate diacetate are carboxylic acid complexing agents, and their complexation constants for metal ions such as copper and zinc are low. The complexes formed are still easily dissociated in the water-based steel cord drawing fluid system, which cannot keep the components in the water-based steel cord drawing fluid stable for a long time, thus affecting the lubrication and other properties of the drawing fluid. Summary of the Invention

[0004] The purpose of this invention is to provide a water-based steel cord drawing fluid composition and its preparation method, aiming to solve the problem that the composition of existing steel cord drawing fluids that do not use ethylenediamine and its derivatives cannot maintain stability for a long time.

[0005] To address the aforementioned technical problems, the first aspect of this invention provides a water-based steel cord drawing fluid composition, the raw materials for which, by weight, are: Water 20-72 parts, base oil 5-20 parts, oiliness agent 5-15 parts, extreme pressure anti-wear agent 10-20 parts, surfactant 5-10 parts, alkali 1-5 parts, rust inhibitor 0.5-2 parts, defoamer 0.1-0.5 parts, and carboxylic acid complexing agent and organophosphonate complexing agent totaling 2-5 parts; Among them, the carboxylic acid complexing agent is at least one of tetrasodium glutamate diacetate and trisodium methylglycine diacetate; The organophosphonate complexing agent is at least one of aminotrimethylenephosphonate tetrasodium and 2-phosphonobutane-1,2,4-tricarboxylic acid.

[0006] In the water-based steel cord drawing fluid composition, the carboxylic acid complexing agent and the organophosphonate complexing agent are mixed in a weight ratio of (1-2):1.

[0007] In the water-based steel cord drawing fluid composition, the base oil is a mixture of mineral oil and vegetable oil; the mineral oil and vegetable oil are mixed in a weight ratio of (5-10):1.

[0008] In the water-based steel cord drawing fluid composition, the mineral oil is at least one of mineral oil 10N, mineral oil 15N, mineral oil 22N, mineral oil 32N, mineral oil 100SN, mineral oil 150SN, mineral oil 200SN, No. 15 white oil, and No. 26 white oil; and the vegetable oil is at least one of castor oil, coconut oil, and soybean oil.

[0009] In the water-based steel cord drawing fluid composition, the oiling agent is a mixture of fatty acid esters and fatty acids; the ratio of the fatty acid esters and fatty acids by weight is (1-2):1.

[0010] In the water-based steel cord drawing fluid composition, the fatty acid ester is at least one of pentaerythritol glyceryl ester, isooctyl isostearate, trimethylolpropane trioctanoate, polyglycerol-4 oleate, and neopentyl glycol diheptanoate; the fatty acid is at least one of ricinoleic acid, palmitic acid, stearic acid, 9-octadecenoic acid, lauric acid, and isopalmitic acid.

[0011] In the water-based steel cord drawing fluid composition, the extreme pressure anti-wear agent is a phosphorus-based extreme pressure anti-wear agent.

[0012] In the water-based steel cord drawing fluid composition, the alkali is at least one of diethanolamine, triethanolamine, isopropanolamine, and methyldiethanolamine.

[0013] In the water-based steel cord drawing fluid composition, the rust inhibitor is at least one of benzotriazole, imidazoline oleate, and 5-methylbenzotriazole.

[0014] In the water-based steel cord drawing fluid composition, the surfactant is at least one of isomeric tridecyl alcohol polyoxyethylene ether, cocoamine polyoxyethylene ether, ethoxylated fatty acid methyl ester, and C12-14 fatty alcohol polyoxyethylene ether phosphonate.

[0015] A second aspect of the present invention provides a method for preparing a water-based steel cord drawing fluid composition, which is used to prepare the above-mentioned water-based steel cord drawing fluid composition, comprising the following steps: S1. Mix water, alkali, and oiling agent, and stir well; S2. Add extreme pressure anti-wear agent to the mixed solution obtained in step S1, and stir to mix evenly; S3. Add defoamer, rust inhibitor, carboxylic acid complexing agent, organophosphonate complexing agent and surfactant to the mixed solution obtained in step S2, and stir evenly to obtain the water-based steel cord drawing fluid composition.

[0016] The beneficial effects of this invention are: The first aspect of this invention provides a water-based steel cord drawing fluid composition. This drawing fluid composition, through the compounding of base oil, oiliness agent, extreme pressure anti-wear agent, surfactant, alkali, rust inhibitor, and complexing agent, achieves high lubricity, surface brightness, and low die wear, meeting the requirements of high-speed steel cord drawing. Furthermore, by compounding carboxylic acid complexing agents and organophosphonate complexing agents, it solves the technical problem of easy complex dissociation and unstable drawing fluid composition when only carboxylic acid complexing agents are used to replace ethylenediamine and its derivatives. Simultaneously, the excellent metal surface corrosion inhibition and film-forming properties, particle dispersion and scale inhibition, and adaptability to high-temperature and high-alkali environments of organophosphonate complexing agents further ensure the long-term stability of the drawing fluid system under high-speed steel cord drawing conditions, guaranteeing the preservation of the core performance of the drawing fluid, such as lubrication and rust prevention.

[0017] The second aspect of this invention provides a method for preparing a water-based steel cord drawing fluid composition. The preparation method is simple, the quality is controllable, and it can quickly produce a water-based steel cord drawing fluid composition, which is conducive to the large-scale, industrial, and market-oriented application of the water-based steel cord drawing fluid composition. Attached Figure Description

[0018] Figure 1 This is a photograph of the water-based steel cord drawing fluid composition provided by the present invention.

[0019] Figure 2 This is a flowchart of the preparation method of the water-based steel cord drawing fluid composition provided by the present invention. Detailed Implementation

[0020] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0021] like Figure 1 As shown, the first aspect of the present invention provides a water-based steel cord drawing fluid composition, the raw materials for which, by weight, are: The composition comprises 20-72 parts water (deionized water), 5-20 parts base oil, 5-15 parts oiliness agent, 10-20 parts extreme pressure anti-wear agent, 5-10 parts surfactant, 1-5 parts alkali, 0.5-2 parts rust inhibitor, 0.1-0.5 parts defoamer, and 2-5 parts total of carboxylic acid complexing agent and organophosphonate complexing agent. The water-based steel cord drawing fluid composition, by combining carboxylic acid complexing agent and organophosphonate complexing agent, can leverage the carboxylic acid complexing agent's effect on alkaline earth metal ions (Ca... 2+ Mg 2+ The high-efficiency chelating effect of organic phosphonate complexing agents, combined with their stronger complexing stability for transition metal ions such as iron, copper, and zinc, solves the technical problems of easy dissociation of complexes and the inability to maintain the stability of drawing fluid components when only carboxylic acid complexing agents are used to replace ethylenediamine and its derivatives. At the same time, the excellent metal surface corrosion inhibition and film-forming properties, particle dispersion and scale inhibition properties, and adaptability to high temperature and high alkalinity environments of organic phosphonate complexing agents can further ensure the long-term stability of the drawing fluid system under high-speed steel cord drawing conditions, and ensure that the core performance of the drawing fluid, such as lubrication and rust prevention, does not decline.

[0022] To ensure that the water-based steel cord drawing fluid composition provided by this invention possesses stronger copper and zinc ion complexation stability, superior metal surface corrosion inhibition film-forming properties, higher adaptability to high-temperature and high-alkali environments, and a longer service life, and to enable the drawing fluid composition to meet the requirements of high-speed and high-precision steel cord drawing processes, in a preferred embodiment, the organophosphonate complexing agent is at least one of tetrasodium aminotrimethylenephosphonate and 2-phosphonobutane-1,2,4-tricarboxylic acid.

[0023] Among them, tetrasodium aminotrimethylene phosphonate is an anionic, multidentate chelating agent with polyphosphonate groups. In alkaline drawing fluid compositions, tetrasodium aminotrimethylene phosphonate can completely dissociate, and the multiple dissociated phosphonate groups can simultaneously donate lone pairs of electrons to copper and zinc ions, forming stable polycyclic chelates. This effectively binds metal ions within the drawing fluid composition, preventing them from reacting with other components to form precipitates. Secondly, by occupying the coordination active sites of copper and zinc ions, tetrasodium aminotrimethylene phosphonate can effectively inhibit the catalytic oxidative degradation of lubricating components in the drawing fluid composition by metal ions, thus preventing demulsification, aging, and deterioration of the drawing fluid composition, thereby extending its cycle life. Furthermore, because copper and zinc ions can be stably chelated in the drawing fluid composition, metal ions cannot escape to the surface of the steel wire and die, thus preventing the deposition and adhesion of metal ions at the source, ensuring the surface finish of the steel cord, and reducing die wear, meeting the requirements of high-speed, high-precision drawing of steel cord. In addition, the phosphonate anions generated by the hydrolysis of sodium aminotrimethylene phosphonate can form a weakly coordinated adsorption film on the surface of the steel wire. This adsorption film can physically isolate the steel wire surface from the corrosive media in the water-based drawing fluid composition, preventing electrochemical corrosion (rusting, blackening, pitting) of the iron substrate and brass plating of the steel cord, thus achieving an auxiliary corrosion inhibition effect. Furthermore, the rust inhibitor forms a synergistic effect, which can improve the overall rust prevention performance.

[0024] The molecular structure of 2-phosphonobutane-1,2,4-tricarboxylic acid contains both phosphonic acid and hydroxyl groups. In the drawing fluid composition, it can dissociate into multi-charged phosphonate anions. These anions, in synergy with the hydroxyl groups, can form multi-site complexes with copper and zinc ions, creating highly stable water-soluble chelates. This completely blocks the catalytic activity of metal ions and inhibits their catalytic oxidative degradation of the lubricating components in the drawing fluid composition, thus maintaining the stability of the drawing fluid system. Secondly, the steel cord surface is coated with brass. During the drawing process, metal friction generates copper-zinc oxide microparticles of wear debris. Phosphonate anions can adsorb onto the surface of these microparticles, making them negatively charged. This prevents particle agglomeration and precipitation, eliminating problems such as mold clogging, steel cord surface scratches, and a sudden increase in the coefficient of friction caused by wear debris agglomeration and ensuring the smoothness of the drawing process. Furthermore, the negatively charged layer formed on the surface of copper-zinc oxide microparticles can maintain the stability of the interfacial potential of the drawing fluid emulsion system, and prevent the drawing fluid composition from demulsifying and flocculating due to metal ions, thereby ensuring the lubrication performance of the drawing fluid composition.

[0025] Different ratios of carboxylic acid complexing agents and organophosphonate complexing agents affect the core properties of water-based steel cord drawing fluid compositions, such as system stability, lubrication durability, and rust and corrosion inhibition. Specifically, when the proportion of carboxylic acid complexing agents is too high, the content of organophosphonate complexing agents is insufficient, significantly reducing the complexing stability for copper and zinc ions. This makes the resulting complexes prone to dissociation under high-temperature and high-alkali drawing conditions. The released metal ions then react with extreme pressure anti-wear agents and other components to form precipitates, causing turbidity and stratification in the drawing fluid composition. Simultaneously, the corrosion inhibition, film-forming, and microparticle dispersion and scale inhibition advantages of organophosphonate complexing agents cannot be fully utilized. This not only leads to decreased lubrication performance and increased die wear after aging of the drawing fluid composition but also reduces the surface brightness of the steel cord, making it prone to defects such as rust and pitting.

[0026] When the proportion of organophosphonate complexing agents is too high, the content of carboxylic acid complexing agents is insufficient, which weakens the chelating ability of alkaline earth metal ions such as calcium and magnesium in water, making it easy to generate scale and cause blockage of pipes and molds. Furthermore, when the proportion of organophosphonate complexing agents is too high, the excessive amount of organophosphonate complexing agents will compete with extreme pressure anti-wear agents for adsorption, weakening the density of the extreme pressure lubricating film and affecting the friction reduction and anti-wear effect of the drawing fluid composition. Based on this, the present invention found that when the carboxylic acid complexing agent and the organophosphonate complexing agent are mixed in a weight ratio of (1-2):1, the carboxylic acid complexing agent can efficiently chelate alkaline earth metal ions, ensuring the compatibility and hard water resistance of the water-based system of the drawing fluid composition. At the same time, the organophosphonate complexing agent can achieve strong complexing stability of transition metal ions such as copper and zinc, exerting its excellent corrosion inhibition, film formation, particle dispersion, and scale inhibition effects. Meanwhile, the carboxylic acid complexing agent and the organophosphonate complexing agent do not compete for adsorption and can form multiple synergies with rust inhibitors and extreme pressure anti-wear agents, so that the drawing fluid composition maintains excellent complexing stability and lubrication and rust prevention effects in both fresh and aged fluid states, thus adapting to the harsh working conditions of high-speed drawing of steel cord.

[0027] To ensure that the drawing fluid composition possesses both long-lasting lubrication and extreme pressure lubrication, while simultaneously improving its stability, in a preferred embodiment, a mixture of mineral oil and vegetable oil is selected as the base oil. The mineral oil may be at least one of mineral oil 10N, mineral oil 15N, mineral oil 22N, mineral oil 32N, mineral oil 100SN, mineral oil 150SN, mineral oil 200SN, No. 15 white oil, and No. 26 white oil; the vegetable oil may be at least one of castor oil, coconut oil, and soybean oil.

[0028] Specifically, mineral oil has a stable molecular chain, which can form a durable oil film on the metal surface, providing basic lubrication. Vegetable oil, on the other hand, contains polar ester and carboxyl groups in its molecular structure, which have a stronger adsorption force on the metal surface of steel cord, and can form a dense extreme pressure lubrication film to resist the high temperature and pressure of high-speed drawing. Therefore, the use of mineral oil and vegetable oil as a base oil can ensure smooth drawing under low load and prevent metal sticking and wire breakage under high load, thus making up for the problems of insufficient extreme pressure of mineral oil alone and poor basic lubrication durability of vegetable oil alone.

[0029] The polar groups of vegetable oil can enhance the binding force between the base oil and the surfactant and aqueous phase in the drawing fluid composition, avoiding problems such as emulsification and separation and oil phase precipitation caused by excessive non-polarity of mineral oil. At the same time, the hydrophobicity of mineral oil can balance the strong polarity of vegetable oil and prevent the base oil from being too hydrophilic and reducing the lubrication effect of the oil film. Therefore, the base oil obtained by compounding can maintain a uniform emulsion state in the water-based drawing fluid composition, so that the drawing fluid composition can be stable for a long time.

[0030] The ratio of mineral oil to vegetable oil determines the polarity balance, emulsification stability, and lubrication synergy of the base oil. When the proportion of vegetable oil is too high, the strong polar ester and carboxyl groups of the vegetable oil will make the overall polarity of the base oil too strong. On the one hand, this will compete with the oiliness agents and extreme pressure anti-wear agents in the drawing oil for adsorption, crowding out lubrication adsorption sites on the metal surface, weakening the density of the composite lubricating film, and thus reducing the friction-reducing and anti-wear capabilities of the drawing fluid composition. Furthermore, during steel cord drawing, problems such as sticking to the die and wire breakage are more likely to occur. On the other hand, excessive vegetable oil will increase the bonding force between the base oil and the aqueous phase, making the lubricating film too hydrophilic. Under the high-temperature friction and water scouring of high-speed drawing, the lubricating film is prone to detachment, losing its long-term lubrication effect.

[0031] When the proportion of vegetable oil is too low, the base oil becomes too non-polar overall. The polar groups in the vegetable oil are insufficient to enhance the compatibility between the mineral oil and the water-based system, leading to insufficient emulsification between the base oil, surfactants, and the aqueous phase. This results in oil-water separation and oil phase precipitation in the drawing fluid composition, significantly reducing its stability and making it unsuitable for long-term recycling. Furthermore, a small amount of vegetable oil cannot form a dense extreme pressure lubricating film on the metal surface, making it difficult to withstand the high temperature and pressure conditions of high-speed steel cord drawing. Therefore, this invention discovers that when the weight ratio of mineral oil to vegetable oil is (5-10):1, the drawing fluid composition can achieve both long-term lubrication and extreme pressure lubrication, while simultaneously improving its stability.

[0032] To ensure that the drawing fluid composition provides both strong adsorption lubrication and long-lasting stable basic lubrication, in a preferred embodiment, the oiling agent is a mixture of fatty acid esters and fatty acids. The fatty acid ester is at least one selected from pentaerythritol glyceryl ester, isooctyl isostearate, trimethylolpropane trioctyl ester, polyglycerol-4 oleate, and neopentyl glycol diheptanoate; the fatty acid is at least one selected from ricinoleic acid, palmitic acid, stearic acid, 9-octadecenoic acid, lauric acid, and isopalmitic acid.

[0033] Specifically, fatty acids contain carboxyl groups in their molecular structure, which can chemically adsorb onto the metal surface of steel cord, rapidly forming a dense extreme pressure lubricating film. This film can withstand the high temperature, high pressure, and high shear force of high-speed drawing, preventing the steel cord from sticking or breaking. Meanwhile, fatty acid esters have milder polarity and more stable molecular chains, enabling them to form a physical adsorption film on the outside of the extreme pressure lubricating film formed by fatty acids. This provides long-lasting and stable basic lubrication, reducing frictional losses under low loads. Therefore, when fatty acids and fatty acid esters are combined and used as oiling agents, a double-layer composite lubricating film can be formed, meeting the lubrication needs of different loads throughout the entire steel cord drawing process.

[0034] The ratio of fatty acid esters to fatty acids determines the lubrication performance of the drawing fluid composition. When the proportion of fatty acids is too high, the overall polarity of the oiling agent is too strong. The carboxyl groups of the fatty acids will form an excessively thick chemical adsorption film on the steel cord surface. On the one hand, this film competes with rust inhibitors and complexing agents in the drawing fluid composition for adsorption sites on the metal surface, crowding out the formation space of the rust-preventive passivation film and the complexed corrosion inhibitor film, thus weakening the rust-preventive and complexing stabilizing effects of the drawing fluid. On the other hand, the excessive adsorption causes the lubricating film to adhere firmly to the metal surface, preventing normal shedding and regeneration during the friction and shearing of the drawing process, ultimately leading to lubrication failure. Conversely, when the proportion of fatty acid esters is too high, the overall polarity of the oiling agent is too weak. Insufficient fatty acid content prevents the formation of a dense extreme-pressure lubricating film on the metal surface, making it difficult to withstand the high temperature, high pressure, and high shear force of steel cord drawing. Based on this, the present invention found that when the ratio of fatty acid esters and fatty acids by weight is (1-2):1, it can achieve dual protection of basic lubrication and extreme pressure lubrication. The double-layer composite lubricating film formed by the two types of oily agents has the characteristics of high temperature resistance, shear resistance and easy renewal, which can meet the lubrication requirements of different loads throughout the steel cord drawing process.

[0035] Different types of extreme pressure anti-wear agents can affect the synergy between the drawing fluid composition and the complexing agent compound system, as well as the extreme pressure anti-wear effect of high-speed steel cord drawing. Therefore, in a preferred embodiment, a phosphorus-based extreme pressure anti-wear agent is used, which is at least one of phosphite ester, fatty alcohol polyoxyethylene ether phosphate ester, and pentaerythritol phosphate ester. Specifically, the phosphorus-based extreme pressure anti-wear agent and the organophosphonate complexing agent mentioned above are both phosphorus-based functional components. Among them, the passivation film formed by the organophosphonate complexing agent on the metal surface can provide a stable adsorption substrate for the phosphorus-based extreme pressure anti-wear agent; while the phosphate produced by the decomposition of the phosphorus-based extreme pressure anti-wear agent can supplement the composition of the passivation film, forming a dense phosphorus-based composite lubricating extreme pressure film, which can significantly improve the high pressure resistance and shear resistance between the steel cord and the die, reduce the friction coefficient and die wear, and thus adapt to the high temperature and high pressure conditions of high-speed steel cord drawing.

[0036] Different types of alkalis can significantly affect the pH buffering capacity of the drawing fluid composition and its corrosion inhibition effect on the metal surface. Therefore, in a preferred embodiment, the alkali is at least one of diethanolamine, triethanolamine, isopropanolamine, and methyldiethanolamine. All of the above-mentioned alkalis are alkanolamine organic bases, which are mildly alkaline and possess excellent pH buffering capacity. They can stabilize the drawing fluid system within a suitable weak alkaline range, avoiding both excessive alkalinity that could corrode the brass plating of the steel cord and damage the passivation film on the metal surface, and insufficient alkalinity that would prevent the complexing agent and rust inhibitor from functioning properly. Furthermore, these alkanolamine alkalis have good compatibility with the complexing agents, phosphorus-based extreme pressure anti-wear agents, oiling agents, and other functional components in the drawing fluid composition, without causing side reactions that consume effective components. They can also synergistically work with rust inhibitors and complexing agents to help form a dense protective film on the metal surface, further enhancing the corrosion inhibition and rust prevention effect.

[0037] Different types of rust inhibitors can affect the lubrication and rust prevention performance of the drawing fluid composition. Therefore, in a preferred embodiment, at least one of benzotriazole, imidazoline oleate, and 5-methylbenzotriazole is used as a rust inhibitor. The rust inhibitors described above can meet the dual rust prevention requirements of the high-carbon steel substrate and the brass plating of the steel cord. Among them, benzotriazole and 5-methylbenzotriazole have targeted complexation ability for copper and zinc ions, which can form a dense passivation film on the surface of the brass plating, effectively preventing the plating from oxidizing, turning black, and pitting. Imidazoline oleate can form a strong adsorption film on the surface of the high-carbon steel substrate, isolating the corrosive medium and achieving long-term rust prevention. Moreover, all three are compatible with the complexing agent, phosphorus extreme pressure anti-wear agent, and other components used in this invention, and there is no competitive adsorption. They will not affect the lubrication and complexation core performance of the drawing fluid composition, so that the rust prevention effect of the drawing fluid composition is stable and does not decrease under the high temperature and high alkalinity conditions of high-speed drawing of steel cord.

[0038] Different types of defoamers can affect the system compatibility of water-based steel cord drawing fluid compositions. Therefore, in a preferred embodiment, vegetable oil-derived polyethers are used as defoamers. Vegetable oil-derived polyethers exhibit good system compatibility with water-based steel cord drawing fluid compositions, preventing stratification and precipitation. This avoids instability in the drawing fluid system caused by defoamer incompatibility. Furthermore, the defoaming and foam-suppressing effects of vegetable oil-derived polyethers are gentle and long-lasting, effectively eliminating foam generated during drawing processes due to high-speed stirring and metal friction.

[0039] Different types of surfactants can affect the emulsification stability of the drawing fluid composition. Therefore, in a preferred embodiment, at least one of the following surfactants is used: isomeric tridecyl alcohol polyoxyethylene ether, cocoamine polyoxyethylene ether, ethoxylated fatty acid methyl ester, and C12-14 fatty alcohol polyoxyethylene ether phosphonate. The surfactants described above can emulsify and disperse base oil, oiliness agents, and other oil-phase components, ensuring the homogeneity of the water-oil phase and the stability for long-term cyclic use of the drawing fluid. Simultaneously, surfactants can assist various lubricating and rust-preventing components in spreading evenly on the steel cord surface, optimizing the film-forming effect.

[0040] like Figure 2 As shown, a second aspect of the present invention provides a method for preparing a water-based steel cord drawing fluid composition, used to prepare the above-mentioned water-based steel cord drawing fluid composition, comprising the following steps: S1. Mix water, alkali and oiling agent, and stir at 60°C for 1 hour; S2. Add the extreme pressure anti-wear agent to the mixed solution obtained in step S1 and stir for 20 min. S3. Add defoamer, rust inhibitor, carboxylic acid complexing agent, organophosphonate complexing agent and surfactant to the mixed solution obtained in step S2, and stir evenly to obtain the water-based steel cord drawing fluid composition.

[0041] The preparation method described is simple and the quality is controllable. It can quickly produce a composition suitable for water-based steel cord drawing fluid, which is conducive to the large-scale, industrial and market application of water-based steel cord drawing fluid composition.

[0042] The present invention will be further illustrated by the following examples and comparative examples. Some of the raw materials used in the examples and comparative examples are from the following sources: Mineral oil 150SN: Jinan Xinhuihuang Chemical Co., Ltd.; Coconut oil: Xi'an Huilin Biotechnology Co., Ltd.; Trimethylolpropane trioctyl ester (fatty acid ester): Jiangsu Pulesi Biotechnology Co., Ltd.; Palmitoleic acid (fatty acid): Jinan Jinyu Chemical Co., Ltd.; Fatty alcohol polyoxyethylene ether phosphate (extreme pressure anti-wear agent): Wuhan Jixin Yibang Biotechnology Co., Ltd.; Isomeric tridecyl alcohol polyoxyethylene ether (surfactant): Jinan Daorong Chemical Co., Ltd.; Diethanolamine (alkali): Shandong Lanxing New Materials Co., Ltd.; Isopropanolamine (base): Hubei Langbowan Biomedical Co., Ltd.; Benzotriazole (rust inhibitor): Jinan Yuno Chemical Co., Ltd.; Defoamer: Castor oil polyether from Hai'an, Jiangsu; Carboxylic acid complexing agent (tetrasodium diglutamate): Changzhou Deye Chemical Co., Ltd. Organophosphonate complexing agent (tetrasodium aminotrimethylenephosphonate): Xuzhou Yihuiyang New Materials Co., Ltd.; 5-Methylbenzotriazole: Zhongshan Dixing Chemical Co., Ltd.; Polyether-modified polysiloxane: Hubei Xinyuhong Biomedical Technology Co., Ltd.; Ethylenediamine: Jinan Liyang Chemical Co., Ltd.; Dihydroxyethyl ethylenediamine: Shanghai Baoyang Baoxin Biotechnology Co., Ltd.; Disodium ethylenediaminetetrapropionate: Guangdong Yuanfeng Chemical Reagent Co., Ltd.; Laureth polyoxyethylene ether: Sanda Chemical (Nantong) Co., Ltd.; Cocamidopropyl Betaine: Shandong Junning Chemical Technology Co., Ltd.; Isooctyl phosphate: Shandong Huling New Materials Co., Ltd.; Ethylenediamine phosphate: Hubei Xinghengye Technology Co., Ltd.; Flaxseed oil: Jinan Yuno Chemical Co., Ltd.; Pentaerythritol tetraoleate: Jinan Yuno Chemical Co., Ltd.; Ammonium stearate: Jinan Huijinchuan Trading Co., Ltd.; Isobutylene sulfide: Jinan Jinyu Chemical Co., Ltd.

[0043] Example 1 This embodiment provides a water-based steel cord drawing fluid composition, the raw materials of which, by weight, include: 47.7 parts water, 12 parts base oil, 10 parts oiliness agent, 15 parts extreme pressure anti-wear agent (fatty alcohol polyoxyethylene ether phosphate), 8 parts surfactant (isotridecyl alcohol polyoxyethylene ether), 3 parts alkali (diethanolamine), 1.0 part rust inhibitor (benzotriazole), 0.3 parts defoamer, and a total of 3 parts carboxylic acid complexing agent and organophosphonate complexing agent.

[0044] The carboxylic acid complexing agent is tetrasodium glutamate diacetate; the organophosphonate complexing agent is tetrasodium aminotrimethylenephosphonate. The ratio of the carboxylic acid complexing agent to the organophosphonate complexing agent by weight is 2:1.

[0045] The base oil is a mixture of mineral oil 150SN and coconut oil, with a weight ratio of 5:1. The oiliness agent is a mixture of trimethylolpropane trioctanoate and palmitoleic acid, with a weight ratio of 1:1.

[0046] This embodiment also provides a method for preparing a water-based steel cord drawing fluid composition, including the following steps: S1. Mix water, alkali and oiling agent, and stir at 60°C for 1 hour; S2. Add the extreme pressure anti-wear agent to the mixed solution obtained in step S1 and stir for 20 min. S3. Add defoamer, rust inhibitor, carboxylic acid complexing agent, organophosphonate complexing agent and surfactant to the mixed solution obtained in step S2, and stir evenly to obtain the water-based steel cord drawing fluid composition.

[0047] Example 2 This embodiment provides a water-based steel cord drawing fluid composition, the raw materials of which, by weight, include: 51.4 parts water, 15 parts base oil, 15 parts oiliness agent, 10 parts extreme pressure anti-wear agent (fatty alcohol polyoxyethylene ether phosphate), 5 parts surfactant (isotridecyl alcohol polyoxyethylene ether), 1 part alkali (diethanolamine), 0.5 parts rust inhibitor (benzotriazole), 0.1 parts defoamer, and a total of 2 parts carboxylic acid complexing agent and organophosphonate complexing agent.

[0048] The carboxylic acid complexing agent is tetrasodium glutamate diacetate; the organophosphonate complexing agent is tetrasodium aminotrimethylenephosphonate. The carboxylic acid complexing agent and the organophosphonate complexing agent are mixed in a weight ratio of 1:1.

[0049] The base oil is a mixture of mineral oil 150SN and coconut oil, with a weight ratio of 9:1. The oiliness agent is a mixture of trimethylolpropane trioctanoate and palmitoleic acid, with a weight ratio of 1:1.

[0050] This embodiment also provides a method for preparing a water-based steel cord drawing fluid composition, which is the same as the preparation method provided in Example 1.

[0051] Example 3 This embodiment provides a water-based steel cord drawing fluid composition, the raw materials of which, by weight, include: 22.5 parts water, 20 parts base oil, 15 parts oiliness agent, 20 parts extreme pressure anti-wear agent (fatty alcohol polyoxyethylene ether phosphate), 10 parts surfactant (isotridecyl alcohol polyoxyethylene ether), 5 parts alkali (diethanolamine), 2.0 parts rust inhibitor (benzotriazole), 0.5 parts defoamer, and a total of 5 parts carboxylic acid complexing agent and organophosphonate complexing agent. The carboxylic acid complexing agent is tetrasodium glutamate diacetate; the organophosphonate complexing agent is tetrasodium aminotrimethylenephosphonate. The carboxylic acid complexing agent and the organophosphonate complexing agent are mixed in a weight ratio of 1:1.

[0052] The base oil is a mixture of mineral oil 150SN and coconut oil, with a weight ratio of 7:1. The oiliness agent is a mixture of trimethylolpropane trioctanoate and palmitoleic acid, with a weight ratio of 2:1.

[0053] This embodiment also provides a method for preparing a water-based steel cord drawing fluid composition, which is the same as the preparation method provided in Example 1.

[0054] Comparative Example 1 This comparative example provides a water-based steel cord drawing fluid composition, the raw materials of which, by weight, include: Water 44.6 parts, base oil 18.25 parts, oiliness agent 10.5 parts, extreme pressure anti-wear agent 10 parts, surfactant 6.2 parts, rust inhibitor (5-methylbenzotriazole) 0.6 parts, defoamer (polyether modified polysiloxane) 0.3 parts, alkali 4 parts, ethylenediamine 3.6 parts, dihydroxyethylethylenediamine 3 parts, disodium ethylenediaminetetrapropionate 2.5 parts.

[0055] The surfactant is a mixture of lauryl polyoxyethylene ether (3 parts) and cocamidopropyl betaine (3.2 parts). The extreme pressure anti-wear agent is a mixture of isooctyl phosphate (6 parts) and ethylenediamine phosphate (4 parts). The base oil is a mixture of 32N mineral oil (16 parts) and linseed oil (2.25 parts); the oiliness agent is a mixture of pentaerythritol tetraoleate (7 parts) and ammonium stearate (3.5 parts); and the alkali is a mixture of diethanolamine (2 parts) and isopropanolamine (2 parts).

[0056] This comparative example also provides a method for preparing a water-based steel cord drawing fluid composition, which is the same as the preparation method provided in Example 1.

[0057] Comparative Example 2 This comparative example provides a water-based steel cord drawing fluid composition, which differs from Example 1 only in that... The ratio of carboxylic acid complexing agent to organophosphonate complexing agent by weight is 3:1.

[0058] This comparative example also provides a method for preparing a water-based steel cord drawing fluid composition, which is the same as the preparation method provided in Example 1.

[0059] Comparative Example 3 This comparative example provides a water-based steel cord drawing fluid composition, which differs from Example 1 only in that... The ratio of carboxylic acid complexing agent to organophosphonate complexing agent by weight is 2:3.

[0060] This comparative example also provides a method for preparing a water-based steel cord drawing fluid composition, which is the same as the preparation method provided in Example 1.

[0061] Comparative Example 4 This comparative example provides a water-based steel cord drawing fluid composition, which differs from Example 1 only in that... The ratio of mineral oil 150SN to coconut oil by weight is 11:1.

[0062] This comparative example also provides a method for preparing a water-based steel cord drawing fluid composition, which is the same as the preparation method provided in Example 1.

[0063] Comparative Example 5 This comparative example provides a water-based steel cord drawing fluid composition, which differs from Example 1 only in that... The ratio of mineral oil 150SN to coconut oil by weight is 10:5.

[0064] This comparative example also provides a method for preparing a water-based steel cord drawing fluid composition, which is the same as the preparation method provided in Example 1.

[0065] Comparative Example 6 This comparative example provides a water-based steel cord drawing fluid composition, which differs from Example 1 only in that... The ratio of trimethylolpropane trioctanoate to palmitoleic acid by weight is 3:1.

[0066] This comparative example also provides a method for preparing a water-based steel cord drawing fluid composition, which is the same as the preparation method provided in Example 1.

[0067] Comparative Example 7 This comparative example provides a water-based steel cord drawing fluid composition, which differs from Example 1 only in that... The ratio of trimethylolpropane trioctanoate to palmitoleic acid by weight is 2:3.

[0068] This comparative example also provides a method for preparing a water-based steel cord drawing fluid composition, which is the same as the preparation method provided in Example 1.

[0069] Comparative Example 8 This comparative example provides a water-based steel cord drawing fluid composition, which differs from Example 1 only in that the phosphorus-based extreme pressure anti-wear agent is replaced with sulfurized isobutylene.

[0070] This comparative example also provides a method for preparing a water-based steel cord drawing fluid composition, which is the same as the preparation method provided in Example 1.

[0071] The water-based steel cord drawing fluid compositions provided in the above embodiments and comparative examples were tested. The test items included extreme pressure performance test, lubrication performance test, friction and wear performance test (wear track width), wear volume and surface roughness test, and copper and zinc ion complexation test.

[0072] The extreme pressure performance test method is conducted according to the standard GB / T 12583-1998 "Determination of Extreme Pressure Properties of Lubricants (Four-Ball Method)" to test the maximum non-seize load (P). B ) and sintering point (P D Test instrument model: Xiamen Tianji MS-10A.

[0073] The lubrication performance was tested using an RCP oscillating friction and wear tester. The test method was as follows: the dedicated control software for the oscillating friction and wear tester was opened, the frequency was adjusted to 0.67Hz, the load was adjusted to 4.5kg, the cycle time was 15s, and 4 cycles were performed; the predetermined temperature of 45℃ was set, and after heating to the predetermined temperature, 10% diluted solution was dropped onto the surface of the YG8 steel ball to start the test; the coefficient of friction between the YG8 steel ball and the brass plate was measured (see Table 1 below), and the data was recorded by computer.

[0074] The tribological wear performance (wear track width) test was conducted according to the standard "NB / SH / T 0847-2010 Determination of Tribological Wear Performance of Extreme Pressure Lubricating Oils - SRV Testing Machine Method". Test conditions: test time 5 min, test frequency 20 Hz, test temperature 50℃, test load 100 N. After the test, a white light interferometer was used to measure the wear volume and surface roughness of the lower plate.

[0075] The copper and zinc ion complexation test was conducted in accordance with the provisions of the standard GB / T13173-2021 Test Methods for Surfactants and Detergents.

[0076] The test results are shown in Tables 1, 2, and 3 below.

[0077] Table 1

[0078] As shown in Table 1, the extreme pressure and lubrication properties of the water-based steel cord drawing fluid compositions provided in Examples 1 to 3 are close to those of the water-based steel cord drawing fluid composition using ethylenediamine and its derivatives in Comparative Example 1, and some examples even outperform Comparative Example 1. This demonstrates that the water-based steel cord drawing fluid compositions provided by this invention can replace traditional water-based steel cord drawing fluids.

[0079] Furthermore, comparing Comparative Example 4 with Example 1, it was found that the extreme pressure performance and lubrication performance of the water-based steel cord drawing fluid composition provided in Comparative Example 4 were lower than those in Example 1. This is because the base oil used in Comparative Example 4 had too high a proportion of mineral oil and too low a proportion of vegetable oil, which could not form a dense extreme pressure lubricating film on the metal surface, resulting in a decrease in extreme pressure performance. At the same time, the base oil was too non-polar and had poor emulsification compatibility with the water-based system, which significantly reduced lubricity and increased the coefficient of friction.

[0080] Furthermore, a comparison between Comparative Example 5 and Example 1 revealed that the extreme pressure performance and lubrication performance of the water-based steel cord drawing fluid composition provided in Comparative Example 5 were lower than those in Example 1. This is because the base oil used in Comparative Example 5 had an excessively high proportion of vegetable oil, whose strong polar groups competed with the oiliness agent and extreme pressure anti-wear agent for adsorption sites on the metal surface, weakening the density of the composite lubricating film and resulting in a decrease in extreme pressure lubrication performance (Pb). In addition, the base oil was too hydrophilic, making the lubricating film prone to detachment under high-temperature friction, thus reducing lubrication.

[0081] Furthermore, comparing Comparative Example 6 with Example 1, it was found that the maximum non-seize load (Pb) of the water-based steel cord drawing fluid composition provided in Comparative Example 6 decreased slightly. This is because the proportion of fatty acid oiling agent in the oiling agent used in Comparative Example 6 is insufficient, which makes it impossible to form a dense chemically adsorbed extreme pressure lubricating film, resulting in a slight decrease in extreme pressure performance (Pb). In addition, the double-layer composite lubricating film structure is incomplete, which weakens the synergy between basic lubrication and extreme pressure lubrication and reduces lubricity.

[0082] Furthermore, comparing Comparative Example 7 with Example 1, it was found that the maximum non-seize load (Pb) of the water-based steel cord drawing fluid composition provided in Comparative Example 7 decreased slightly. This is because the proportion of fatty acid oiling agent in the oiling agent used in Comparative Example 7 was too high, resulting in an excessively thick chemical adsorption film that hindered the normal shedding and regeneration of the lubricating film. In addition, the fatty acid oiling agent competed with the rust inhibitor and complexing agent for adsorption sites, leading to a decrease in the stability of the lubricating film, a slight decrease in extreme pressure performance (Pb), and a reduction in lubricity.

[0083] Furthermore, a comparison of Comparative Example 8 with Example 1 revealed that the extreme pressure performance and lubrication performance of the water-based steel cord drawing fluid composition provided in Comparative Example 8 were significantly reduced. This is because Comparative Example 8 replaced the phosphorus-based extreme pressure anti-wear agent with sulfurized isobutylene, which resulted in the loss of the phosphorus-based synergistic effect with the organophosphonate complexing agent, leading to a significant decrease in the density of the extreme pressure lubricating film and a significant deterioration in both extreme pressure performance and lubrication performance.

[0084] Table 2

[0085] Note: The average coefficient of friction in Table 2 is obtained from the tribological performance (wear track width) test.

[0086] Based on the test results in Tables 1 and 2, it can be seen that although the extreme pressure performance of the water-based steel cord drawing fluid compositions provided in Comparative Examples 2 and 3 is comparable to that of the drawing fluid composition provided in Example 1, the ratios of the two complexing agents used in Comparative Examples 2 and 3 both exceed the optimal range. This results in a weakened lubricating film protection effect, a slight increase in wear marks, abrasion, and roughness, and a slight increase in the coefficient of friction.

[0087] Table 3

[0088] Note: In Table 3, "1.5 times increase in Example 1" means that the weight ratio of carboxylic acid complexing agent and organophosphonate complexing agent remains 2:1, but the amount of each complexing agent is increased by 1.5 times compared to Example 1, i.e., the amount of carboxylic acid complexing agent is 3 parts and the amount of organophosphonate complexing agent is 1.5 parts. "0.75 times reduction in Example 1" means that the weight ratio of carboxylic acid complexing agent and organophosphonate complexing agent remains 2:1, but the amount of each complexing agent is reduced by 0.75 times compared to Example 1, i.e., the amount of carboxylic acid complexing agent is 1.5 parts and the amount of organophosphonate complexing agent is 0.75 parts.

[0089] Based on the test results in Table 3, it can be seen that when the ratio of carboxylic acid complexing agents and organophosphonate complexing agents is within a suitable range, the amount of complexing agent is linearly positively correlated with the complexing ability of copper and zinc ions. Therefore, the content of copper and zinc ions in the drawing fluid composition can be controlled by adjusting the amount of complexing agent.

[0090] Furthermore, comparing Comparative Example 1 with Example 1 revealed that the complexation constants of ethylenediamine and its derivatives for copper and zinc ions were lower than those of the compound complexing agent of the present invention. Comparing Comparative Example 2 with Example 1 revealed that when the content of organophosphonate complexing agent was insufficient, it lost its strong complexing stability for copper and zinc ions, resulting in a significant decrease in the complexing value of copper and zinc ions. Comparing Comparative Example 3 with Example 1 revealed that when the organophosphonate complexing agent was in excess, its complexing ability for copper and zinc ions was much stronger than that of carboxylic acid complexing agents. Therefore, the complexing property was greatly improved. However, excessive organophosphonates would compete with the extreme pressure anti-wear agent for adsorption, thus affecting the lubrication performance of the drawing fluid composition (the test results in Tables 1 and 2 have been verified).

[0091] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformations made using the contents of the present invention's specification and drawings under the inventive concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A water-based steel cord drawing fluid composition, characterized by, in parts by weight, Its raw materials include: Water 20-72 parts, base oil 5-20 parts, oiliness agent 5-15 parts, extreme pressure anti-wear agent 10-20 parts, surfactant 5-10 parts, alkali 1-5 parts, rust inhibitor 0.5-2 parts, defoamer 0.1-0.5 parts, and carboxylic acid complexing agent and organophosphonate complexing agent totaling 2-5 parts.

2. The water-based steel cord drawing fluid composition according to claim 1, characterized in that, The carboxylic acid complexing agent is at least one of tetrasodium glutamate diacetate and trisodium methylglycine diacetate; the organophosphonate complexing agent is at least one of tetrasodium aminotrimethylene phosphonate and butane-1,2,4-phosphonate.

3. The water-based steel cord drawing fluid composition according to claim 1, characterized in that, The carboxylic acid complexing agent and the organophosphonate complexing agent are mixed in a weight ratio of (1-2):

1.

4. The water-based steel cord drawing fluid composition according to claim 1, characterized in that, The base oil is a mixture of mineral oil and vegetable oil; the mineral oil and vegetable oil are mixed in a weight ratio of (5-10):

1.

5. The water-based steel cord drawing fluid composition according to claim 4, characterized in that, The mineral oil is at least one of mineral oil 10N, mineral oil 15N, mineral oil 22N, mineral oil 32N, mineral oil 100SN, mineral oil 150SN, mineral oil 200SN, No. 15 white oil, and No. 26 white oil; the vegetable oil is at least one of castor oil, coconut oil, and soybean oil.

6. The water-based steel cord drawing fluid composition according to claim 1, characterized in that, The oiliness agent is a mixture of fatty acid esters and fatty acids; the ratio of the fatty acid esters and fatty acids by weight is (1-2):

1.

7. The water-based steel cord drawing fluid composition according to claim 6, characterized in that, The fatty acid ester is at least one of pentaerythritol glyceryl ester, isooctyl isostearate, trimethylolpropane trioctanoate, polyglycerol-4 oleate, and neopentyl glycol diheptanoate; the fatty acid is at least one of ricinoleic acid, palmitic acid, stearic acid, 9-octadecenoic acid, lauric acid, and isopalmitic acid.

8. The water-based steel cord drawing fluid composition according to claim 1, characterized in that, The extreme pressure anti-wear agent is a phosphorus-based extreme pressure anti-wear agent.

9. The water-based steel cord drawing fluid composition according to claim 1, characterized in that, The alkali is at least one of diethanolamine, triethanolamine, isopropanolamine, and methyldiethanolamine; the rust inhibitor is at least one of benzotriazole, imidazoline oleate, and 5-methylbenzotriazole.

10. A method for preparing a water-based steel cord drawing fluid composition, characterized in that, The method for preparing the water-based steel cord drawing fluid composition as described in any one of claims 1-9 comprises the following steps: S1. Mix water, alkali, and oiling agent, and stir well; S2. Add extreme pressure anti-wear agent to the mixed solution obtained in step S1, and stir to mix evenly; S3. Add defoamer, rust inhibitor, carboxylic acid complexing agent, organophosphonate complexing agent and surfactant to the mixed solution obtained in step S2, and stir evenly to obtain the water-based steel cord drawing fluid composition.

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