Bronze-plated tire bead wire anti-corrosion discoloration packaging system and method

Abstract

The invention relates to the technical field of rust-proof treatment of metal products, in particular to a rust-proof discoloration-proof packaging system and method for a bronze-plated tire bead wire. The system sequentially comprises a cleaning unit, a surface treatment unit, a drying box, a film coating device, a cooling unit, a post-treatment unit, a take-up device and a packaging system according to the process. The core of the process method is as follows: the steel wire is immediately coated with a special antirust film coating agent to be cured by using waste heat generated after the steel wire is dried, and the film coating agent comprises water-based resin, a silane coupling agent, a conductive polymer, a nano filler and benzotriazole; during packaging, an intelligent packaging system with a built-in humidity response humidity control bag is adopted, and the humidity control bag can automatically release inert gas and a moisture absorbent when the environment humidity reaches a preset threshold value. Multiple synergistic protection on the surface of the steel wire is achieved, the anti-rust period is remarkably prolonged to 12 months or above through dynamic humidity control, meanwhile, the bonding performance and the retention rate of the steel wire and rubber are improved, and energy conservation and environment protection are achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of anti-rust treatment of metal products, in particular to a bronze-plated bead wire anti-rust and discoloration packaging system and method. BACKGROUND

[0002] Bead wire is a key framework material of radial tire, and its surface is usually plated with bronze layer to enhance the adhesion performance with rubber. However, in the production process, the cleaning liquid, treatment liquid and heat carried on the surface of the steel wire are extremely easy to cause rust and discoloration during storage and transportation, which seriously affects the product quality and subsequent adhesion performance.

[0003] The existing technology usually adopts processes such as cleaning, drying, anti-rust oil coating and vacuum packaging to prolong the storage period of the steel wire. However, these methods have the following defects: the film layer formed by the traditional anti-rust oil or simple anti-rust agent has poor adhesion and is easy to lose, and may affect the subsequent adhesion with rubber. After coating the anti-rust film, an additional heating and curing step is often required, which increases energy consumption. The static vacuum packaging or simple inert gas filling will quickly lose the anti-rust effect once the package appears a slight leakage and the internal humidity rises, and cannot achieve long-term stable rust prevention.

[0004] Therefore, there is an urgent need in the art for a new system and method that can achieve long-term rust prevention, energy saving and environmental protection, and does not harm the adhesion performance of the steel wire with rubber. SUMMARY

[0005] In view of the deficiencies in the above prior art, the purpose of the present application is to provide a bronze-plated bead wire anti-rust and discoloration packaging system, which can significantly prolong the storage period of bronze-plated bead wire, improve its adhesion performance with rubber, and achieve energy-saving production.

[0006] Another purpose of the present application is to provide a bronze-plated bead wire anti-rust and discoloration packaging method, which realizes active and responsive control of the internal humidity of the package through the design of a humidity-responsive humidity control bag. When the humidity exceeds the standard, the humidity control bag automatically releases a dry inert atmosphere, long-term maintains a low-humidity environment inside, breaks through the rust prevention period bottleneck of traditional static packaging, and prolongs the storage period of the steel wire to 12-18 months.

[0007] The present application is implemented by using the following technical solutions: The bronze-plated bead wire anti-rust and discoloration packaging system comprises, in the process flow, the following connected in sequence: A hot water washing tank for hot water immersion cleaning of the copper-plated steel wire; A surface treatment unit comprising a wire rubbing device and a blowing pipe for removing residual moisture on the surface of the steel wire; A drying oven for thoroughly drying the surface of the steel wire and making it carry residual heat; A film coating device is arranged downstream of the outlet of the drying oven and is used to coat the steel wire with a rust-proof film coating agent while the steel wire is still carrying residual heat; A cold air box is used to cool the steel wire after the film coating; A post-processing unit including a guide wheel set and a straightener is used to arrange the steel wire surface; A take-up spool is used to wind the steel wire onto the spool; A packaging system is used to seal and package the steel wire roll; The packaging system includes an inner packaging bag, a gas-phase rust-proof material arranged in the inner packaging bag, and at least one humidity-responsive humidity control bag; The humidity-responsive humidity control bag includes a sealed bag body, a desiccant and an inert gas filled in the bag body, the bag body is provided with a sealing portion made of a humidity-dissolvable material, the sealing portion is configured to dissolve and break when the ambient humidity reaches a preset threshold. The amount of desiccant filled in the humidity-responsive humidity control bag is 5-50 grams.

[0008] The humidity-dissolvable material is polyvinyl alcohol, and different dissolution humidity thresholds are set by controlling the thickness of the polyvinyl alcohol film of the sealing portion. The humidity-responsive humidity control bag includes a sealed bag body, a desiccant and an inert gas filled in the bag body, the bag body is provided with a sealing portion made of a polyvinyl alcohol (PVA) film with a predetermined thickness, the sealing portion is configured to cause mechanical failure due to dissolution when the ambient humidity reaches a preset threshold corresponding to the thickness of the PVA film, thereby releasing the inert gas and the desiccant. The degree of hydrolysis of the polyvinyl alcohol (PVA) film is 86.0-90.0 mol%, and the viscosity of a 4% aqueous solution of the PVA film at 20°C is 28.0-32.0 mPa·s. The thickness of the PVA film is 10 μm, 20 μm or 30 μm, corresponding to a dissolution failure humidity threshold of about 60% RH, 70% RH or 80% RH, respectively.

[0009] The ambient humidity penetrates into the PVA film through diffusion, when it reaches the critical dissolution humidity, the hydrogen bonds between the PVA molecular chains are broken by water molecules, causing the mechanical strength of the film to drop sharply, and under the action of the gas pressure in the inner bag, tearing or forming a broken hole occurs at the thinnest part of the film (the sealing area), thereby achieving the release of the contents.

[0010] The inert gas pressure in the humidity-responsive humidity control bag is higher than atmospheric pressure.

[0011] The method for preventing rust and discoloration of the bronze-plated steel wire includes the following steps: (1) Hot water immersion cleaning of the steel wire after copper plating; (2) Steel wire rubbing and blowing to remove surface moisture after cleaning; (3) The steel wire is sent into a drying oven for drying, so that the surface is completely dry and carries residual heat; (4) Surface film: after the steel wire is output from the drying box, a rust-proof film agent is immediately coated on the surface of the steel wire by using the residual heat carried by the steel wire, and the rust-proof film agent is solidified to form a rust-proof film layer; (5) Cooling the steel wire after coating the film; (6) Passing the cooled steel wire through a guide wheel and a straightener for treatment; (7) Rolling the steel wire into a spool and naturally cooling the steel wire; (8) Packaging: sealing the steel wire spool and a gas-phase rust-proof material in an inner packaging bag, and placing at least one humidity-responsive humidity control bag in the inner packaging bag, the humidity control bag being configured to automatically release inert gas and a moisture absorbent in the humidity control bag when the internal environment humidity reaches a preset threshold.

[0012] In the step (4), the surface temperature of the steel wire when output from the drying box is 130-150°C.

[0013] The rust-proof film agent is a water-based inorganic / organic hybrid composite coating, and includes the following components in percentage by weight: Water-based resin: 40%-60%; Silane coupling agent: 1%-8%; Conductive polymer: 5%-20%; Nano filler: 0.5%-5%; Copper corrosion inhibitor: 0.1%-2%; Auxiliary agent: 0.1%-2%; Deionized water: the balance.

[0014] The water-based resin is at least one of a water-based acrylic resin, a water-based epoxy resin, or a water-based polyurethane resin; and the silane coupling agent is at least one of aminopropyl triethoxysilane or γ-glycidoxypropyl trimethoxysilane.

[0015] The water-based resin serves as a basic film-forming material and forms a continuous physical barrier. The water-based acrylic resin, the water-based epoxy resin, or the water-based polyurethane resin is selected. Preferably, the water-based modified acrylic resin is used because it has excellent film-forming property, flexibility, adhesion, and compatibility with other components.

[0016] The silane coupling agent serves as a key bridge for inorganic / organic hybridization and significantly enhances the adhesion of the coating to the steel wire substrate. The aminopropyl triethoxysilane (KH-550) or the γ-glycidoxypropyl trimethoxysilane (KH-560) is selected. Preferably, the KH-550 is used, which can effectively accelerate the hydrolysis and condensation reaction under the condition of 150°C residual heat and form a firm Si-O-Me covalent bond with the substrate.

[0017] The conductive polymer is a water dispersion of poly(3,4-ethylenedioxythiophene):polystyrene sulfonate; the nano-filler includes at least one of zinc oxide nanoparticles, silicon dioxide nanoparticles, and reduced graphene oxide; and the copper corrosion inhibitor is at least one of benzotriazole and methylbenzotriazole.

[0018] The conductive polymer provides an electrochemical anodic protection function to passivate the metal surface. Polyaniline, polypyrrole, and polythiophene conductive polymers are selected. Preferably, a water dispersion of poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is used due to its excellent environmental stability, high conductivity, and low toxicity. The mass ratio of PEDOT to PSS is 1:2.5.

[0019] The nano-filler is used to synergistically enhance the physical barrier effect and corrosion inhibition of the coating. At least one of zinc oxide nanoparticles, silicon dioxide nanoparticles, montmorillonite, and reduced graphene oxide is selected. More preferably, zinc oxide nanoparticles and reduced graphene oxide are used synergistically. The zinc oxide nanoparticles can prolong the penetration path of the corrosion medium and provide Zn 2+ corrosion-inhibiting ions, and the sheet structure of the reduced graphene oxide can provide extreme physical shielding and synergistically construct a perfect conductive corrosion protection network with PEDOT.

[0020] The copper corrosion inhibitor forms an insoluble protective film by chelating with copper ions. Benzotriazole (BTA) and methylbenzotriazole (TTAA) are selected. Preferably, benzotriazole (BTA) is used, which has a high and stable corrosion inhibition effect on copper and copper alloys.

[0021] The adjuvants include wetting dispersants and defoaming agents. The wetting dispersants are polyether-modified polysiloxane compounds, and the defoaming agents are mineral oil or silicone defoaming agents.

[0022] The adjuvants are used to improve the processing and application performance of the coating agent. The main components include: wetting dispersants are used to promote the dispersion of nano-filler and the like in the system and prevent sedimentation. Polyether-modified polysiloxane compounds (BYK-3455) are selected. Defoaming agents are used to inhibit and eliminate foam during production and use. Mineral oil or silicone defoaming agents (BYK-024) are selected.

[0023] Deionized water is used as an environmentally friendly solvent to adjust the system to a suitable application viscosity.

[0024] In step (8), after the steel wire coil is placed in the inner packaging bag, inert gas is directly filled into the bag to expel air, and then the bag is sealed. The copper-plated steel wire product prepared by the method has a composite rust-proof film layer formed by solidification of the residual heat of the steel wire itself on the surface, and the steel wire product is sealed in a package containing the humidity-responsive humidity control bag.

[0025] A method for preparing a rust-proof film-forming agent, comprising the following steps: I. Silane pre-hydrolysis In a clean reaction kettle equipped with a stirrer, add about two-thirds of the formula amount of deionized water. Turn on the stirring and control the speed at 300-500 rpm. Slowly and evenly add the formula amount of aminopropyl triethoxysilane (KH-550). Continue stirring at this speed for 40-60 minutes to allow the KH-550 to fully hydrolyze in water, forming a uniform and clear pre-hydrolysis solution.

[0026] II. Preparation and dispersion of nano-filler slurry Add the formula amount of wetting dispersant to the above pre-hydrolysis solution. Under moderate stirring at 400-600 rpm, slowly add the formula amount of zinc oxide nanoparticles (ZnONPs) and reduced graphene oxide (rGO) dispersion. Quickly increase the stirring speed to high speed for high shear dispersion: shear rate: ≥2000 rpm dispersion time: 30-45 minutes III. Mixing of main resin and functional components Reduce the stirring speed to moderate speed of 500-700 rpm. Slowly add the formula amount of water-based resin (water-based modified acrylic resin), PEDOT:PSS water dispersion, and benzotriazole (BTA) to the system in sequence. After each material is added, stir for 5-10 minutes to mix them uniformly, and then add the next one.

[0027] IV. Defoaming and viscosity adjustment Add the formula amount of defoaming agent. Rinse the containers containing each material with the remaining deionized water, and add all the rinse water to the reaction kettle to adjust the system to the appropriate application viscosity. Continue stirring at a speed of 500-700 rpm for 30 minutes or more to ensure uniform mixing of the entire system.

[0028] V. Maturation and filtration Stop stirring and let the prepared film-forming agent stand for at least 2 hours for maturation. This process helps to eliminate air bubbles introduced during stirring and allows the components in the system to fully interact and reach a stable state. Filter the matured film-forming agent using a 100-200 mesh filter to remove any possible small amount of gel particles or impurities, and the final product is obtained.

[0029] Specific structure of humidity-responsive humidity control bag: Bag structure: Bag material: polyethylene or polypropylene film with a thickness of 0.05-0.08 mm. It has good flexibility, strength and certain gas barrier property, which can ensure that the bag body is not easily damaged during storage and transportation, and the internal gas can maintain a certain pressure.

[0030] Sealing part: heat sealing with wet sol film. The wet sol film is made by coating polyvinyl alcohol (PVA) aqueous solution on the substrate and drying.

[0031] Content: Inert gas: high-purity nitrogen (N2) is filled, the pressure is slightly higher than atmospheric pressure, and is controlled at 1.1-1.3 atm (absolute pressure). The pressurized gas ensures that when the sealing film is broken, the contents can be "sprayed out" and diffuse to the packaging space.

[0032] Hygroscopic agent: powder, 100% silica gel (particle size 50-100 μm) or a mixture of silica gel and molecular sieve (silica gel:molecular sieve = 7:3) is selected.

[0033] Wet sol film thickness setting and rupture threshold: By accurately controlling the thickness of the PVA sealing film, the dissolution and rupture time of the film in different relative humidity environments can be set, thereby realizing different humidity response thresholds. The specific corresponding relationship is as follows:

[0034] Setting principle: In the packaging system, usually 2 or 3 humidity control bags with different thicknesses (i.e. different rupture thresholds) are put in at the same time. For example, put in one 10 μm, one 20 μm and one 30 μm humidity control bag, which can form a three-level humidity response defense system. This setting ensures that the internal humidity of the packaging can be dynamically and staged controlled at a low level (<40% RH) throughout the storage life, thereby realizing a rust prevention period far exceeding traditional methods. For a packaging with a free space of about 100L, put in three humidity control bags, and the PVA film thicknesses are 10 μm, 20 μm and 30 μm (corresponding to rupture thresholds of about 60%, 70% and 80% RH), and the internal hygroscopic agent loading amounts are set to 15g, 20g and 25g respectively.

[0035] The working principle of the present application is: The present application combines physical and chemical methods through hot water washing and wire wiping and blowing to completely remove contaminants, residual liquid and moisture on the surface of steel wire, providing a clean and activated substrate for subsequent film coating. A clean surface is a prerequisite for high-quality film adhesion. The approximately 150℃ residual heat carried by the steel wire after drying is used as a free and immediate energy source to trigger the curing process of the film coating agent. The mechanism of action includes: rapidly evaporating the water in the water-based film coating agent; the high temperature greatly accelerates the hydrolysis-condensation reaction of the silane coupling agent, forming a strong Si-O-Me covalent bond with the steel wire substrate and hybrid cross-linking with the resin, significantly enhancing adhesion and density; heat promotes polymer molecular chain movement and rearrangement, and facilitates the formation of a more uniform and dense composite network structure of nanofiller (ZnO, rGO) and conductive polymer (PEDOT) in the film layer. Finally, before the steel wire cools to room temperature, a strong composite rust-proof film with physical barrier, chemical corrosion inhibition and electrochemical protection is formed.

[0036] Traditional vacuum or static air packaging is "passive defense", while the packaging system of the present application is "active defense". Initial environment creation: by filling high-purity inert gas and placing gas-phase rust-proof paper, an initial low-oxygen, rust-proof atmosphere environment is created. When the package causes unavoidable micro-leakage, the humidity-responsive humidity control bag starts to work. Its sealing film (hygroscopic sol film) dissolves and breaks when the set humidity threshold is reached. By setting humidity control bags of different thicknesses (i.e. different dissolution thresholds), graded and responsive humidity control is achieved. When the humidity first rises to a lower threshold (60% RH), the first humidity control bag breaks, releasing pressurized dry nitrogen and a moisture absorbent, rapidly reducing the humidity. If the humidity accumulates to a higher threshold (70% RH, 80% RH) due to continuous leakage, subsequent humidity control bags will be activated in turn for the second and third rounds of intervention.

[0037] Compared with the prior art, the present application has the following beneficial effects: (1) Through systematic innovation, the rust-proof storage period of bronze-plated bead wire is significantly extended from 3-5 months in the traditional method to more than 12 months, and the optimal scheme can reach 20 months, solving the long-standing storage problem in the industry. The rust-proof film layer not only prevents rust, but also firmly combines with the steel wire substrate and produces excellent adhesion with the bead rubber, with a high adhesion retention rate of more than 95%, far exceeding customer technical specifications, ensuring the final quality of downstream products.

[0038] (2) The structure of the "humidity response humidity control bag" makes the packaging upgrade from passive defense to active and responsive intelligent protection system, which can effectively resist moisture micro-leakage during storage, providing core protection for achieving ultra-long rust prevention period. Creatively using the waste heat of the drying process to solidify the rust-proof film, it saves additional heating energy and realizes the cascade utilization of energy. At the same time, the water-based environmentally friendly formula is adopted, which eliminates VOC emissions and meets the development trend of green manufacturing. The rust-proof film layer builds a four-way synergistic protection mechanism of "physical barrier + chemical corrosion inhibition + electrochemical protection + nano enhancement", which blocks corrosion from multiple paths and multiple dimensions. The technology is far more advanced and reliable than traditional single mechanism technology. BRIEF DESCRIPTION OF DRAWINGS

[0039] Fig. 1 The structure of the "humidity response humidity control bag" makes the packaging upgrade from passive defense to active and responsive intelligent protection system, which can effectively resist moisture micro-leakage during storage, providing core protection for achieving ultra-long rust prevention period. Creatively using the waste heat of the drying process to solidify the rust-proof film, it saves additional heating energy and realizes the cascade utilization of energy. At the same time, the water-based environmentally friendly formula is adopted, which eliminates VOC emissions and meets the development trend of green manufacturing. The rust-proof film layer builds a four-way synergistic protection mechanism of "physical barrier + chemical corrosion inhibition + electrochemical protection + nano enhancement", which blocks corrosion from multiple paths and multiple dimensions. The technology is far more advanced and reliable than traditional single mechanism technology. Fig. 2 The structure of the "humidity response humidity control bag" makes the packaging upgrade from passive defense to active and responsive intelligent protection system, which can effectively resist moisture micro-leakage during storage, providing core protection for achieving ultra-long rust prevention period. Creatively using the waste heat of the drying process to solidify the rust-proof film, it saves additional heating energy and realizes the cascade utilization of energy. At the same time, the water-based environmentally friendly formula is adopted, which eliminates VOC emissions and meets the development trend of green manufacturing. The rust-proof film layer builds a four-way synergistic protection mechanism of "physical barrier + chemical corrosion inhibition + electrochemical protection + nano enhancement", which blocks corrosion from multiple paths and multiple dimensions. The technology is far more advanced and reliable than traditional single mechanism technology. In the figure: 1, hot water washing tank; 2, wire wiping device; 3, blowing air pipe; 4, drying box; 5, film coating device; 6, cold air box; 7, guide roller group; 8, straightener; 9, take-up spool; 10, packaging system; 11, bronze-plated bead wire; 12, inner packaging bag; 13, humidity response humidity control bag. DETAILED DESCRIPTION

[0040] In order to make the purpose, technical scheme of the present application more clear and understandable, the present application will be further described in detail below.

[0041] Raw material manufacturer: Water-based resin: water-based modified acrylic resin, Zannen Co., Ltd., Germany, SETAPUR® 6701; Silane coupling agent: aminopropyl triethoxysilane (KH-550), Momentive Performance Materials Germany GmbH, SILQUEST® A-1100; Conductive polymer: PEDOT: PSS aqueous dispersion (solid content 1.5%), Heraeus Germany GmbH, Clevios™ PH1000; Nanofiller: zinc oxide nanoparticles (particle size 30-50 nm), Araldite Industrial Corporation, Z135508; Reduced graphene oxide dispersion: solid content 2 mg / mL, Nanjing Xianfeng Nanometer Material Technology Co., Ltd., XFS02; Copper corrosion inhibitor: benzotriazole (BTA), National Pharmaceutical Group Chemical Reagent Co., Ltd., analytical pure, 30072528; Auxiliary agent: wetting and dispersing agent, polyether modified polysiloxane, BYK-Chemie GmbH, BYK-3455; Defoaming agent: silicone, BYK-024, BYK-Chemie Co., Ltd.; Packaging material: gas phase rust-proof paper in accordance with QB / T 1319-2010; Wet sol film: PVA film, Kuraray Co., Ltd., BP-XX series.

[0042] Test method: Neutral salt spray test: GB / T10125-2021 "Salt Spray Test for Artificial Atmosphere Corrosion Test"; Color difference ΔE: GB / T 11186-2022 "Paint Film Color Measurement Method", measure the surface color difference after 12 months of natural storage; Wet heat test state: GB / T 1740-2020 "Paint Film Resistance to Wet Heat Test Method", test for 240 hours under the condition of temperature 50℃ and humidity 95%RH, and check the surface state and color difference; Steel wire and rubber adhesion: GB / T33142-2016 "Steel wire rope rubber adhesion test method" (using H type extraction method); Gas phase rust-proof paper: QB / T 1319-2010 "Gas Phase Rust-Proof Paper"; Internal humidity of packaging: GB / T15171-2023 "Soft packaging sealing performance test method" (through built-in sensor or indicator card).

[0043] As shown in Figs. 1-2 The anti-rust and discoloration packaging system for bronze-plated bead wire used in the example includes, according to the process flow, sequentially connected: Hot water washing tank 1 for hot water immersion cleaning of copper-plated steel wire; Surface treatment unit including wire rubbing device 2 and blowing pipe 3 for removing residual water on the surface of the steel wire; Drying box 4 for thoroughly drying the surface of the steel wire and making it carry residual heat; Film coating device 5 arranged downstream of the outlet of the drying box for coating the surface of the steel wire carrying residual heat with rust-proof film coating agent; Cold air box 6 for cooling the coated steel wire; Post-treatment unit including guide roller set 7 and straightener 8 for arranging the surface of the steel wire; Take-up spool 9 for winding the steel wire onto the spool; Packaging system 10 for sealing and packaging the steel wire coil; The packaging system 10 includes inner packaging bag 12, gas phase rust-proof material placed in the inner packaging bag 12, and at least one humidity-responsive humidity control bag 13; the gas phase rust-proof material is gas phase rust-proof paper; The humidity-responsive humidity control bag includes a sealed bag body 13, a desiccant and an inert gas filled in the bag body, and the bag body is provided with a sealing part made of a moisture-soluble material, which is configured to dissolve and rupture when the ambient humidity reaches a preset threshold.

[0044] The inner packaging bag 12 contains bronze-plated tire bead wire 11 and humidity-responsive humidity control bag 13.

[0045] The preparation method of the rust-preventive coating agent includes the following steps: I. Silane pre-hydrolysis In a clean reactor equipped with a stirrer, add approximately two-thirds of the formula volume of deionized water. Turn on the stirrer and control the speed at 400 rpm. Slowly and uniformly add the formula volume of aminopropyltriethoxysilane (KH-550) dropwise. Continue stirring at this speed for 50 minutes to allow KH-550 to fully hydrolyze in water, forming a homogeneous and clear pre-hydrolyzed solution.

[0046] II. Preparation and Dispersion of Nanofiller Slurry Add the prescribed amount of wetting and dispersing agent to the pre-hydrolyzed solution. Slowly add the prescribed amount of nanofiller while stirring at a medium speed of 500 rpm. Rapidly increase the stirring speed to a high speed for high-speed shear dispersion: shear rate: 2000 rpm, dispersion time: 45 minutes.

[0047] III. Mixing of the main resin and functional components Reduce the stirring speed to medium speed of 600 rpm. Slowly add the formulated amounts of conductive polymer, PEDOT:PSS aqueous dispersion, and benzotriazole (BTA) to the system in sequence. After each material is added, stir for 10 minutes to allow for initial homogenization before adding the next.

[0048] IV. Defoaming and Viscosity Adjustment Add the prescribed amount of defoamer. Rinse the containers holding all materials with the remaining deionized water, and add all the rinsing liquid into the reactor to adjust the system to the appropriate application viscosity. Continue stirring at 600 rpm for 40 minutes to ensure the entire system is thoroughly mixed.

[0049] V. Maturation and Filtration Stop stirring and allow the prepared coating agent to stand and mature for 3 hours. This process helps eliminate air bubbles introduced during stirring and allows the components in the system to interact fully and reach a stable state. Filter the matured coating agent through a 200-mesh filter to remove any trace amounts of gel particles or impurities, yielding the final product.

[0050] The specific structure of a humidity-responsive moisture control bag: Bag structure: Bag material: polyethylene or polypropylene film with a thickness of 0.08 mm. It has good flexibility, strength and certain gas barrier property, which can ensure that the bag body is not easily damaged during storage and transportation, and the internal gas can maintain a certain pressure.

[0051] Sealing part: hot sealing with wet sol film. The wet sol film is formed by coating polyvinyl alcohol (PVA) aqueous solution on the substrate and drying.

[0052] Content: Inert gas: high-purity nitrogen (N2) is filled, the pressure is slightly higher than atmospheric pressure, and is controlled at 1.3 atm (absolute pressure). The pressurized gas ensures that when the sealing film is broken, the content can be "sprayed out" and diffused to the packaging space.

[0053] Hygroscopic agent: powder, a mixture of silica gel (particle size 80 μm) and molecular sieve (silica gel:molecular sieve=7:3) is selected. The thickness of the PVA film is 10 μm, 20 μm and 30 μm (corresponding to the breakage threshold of about 60%, 70% and 80% RH), and the internal hygroscopic agent is loaded in an amount of 15 g, 20 g and 25 g respectively.

[0054] Wet sol film thickness setting and breakage threshold: By accurately controlling the thickness of the PVA sealing film, the dissolution and breakage time of the PVA sealing film in different relative humidity environments is set, so as to realize different humidity response thresholds.

[0055] All examples and part of the comparative examples (comparative examples 3, 4 and 5) are placed with gas phase rust prevention paper meeting the standard of QB / T 1319-2010 in the packaging. Its role is to build a basic and continuous all-around rust prevention atmosphere environment.

[0056] Example 1 The method of the bronze-plated bead wire rust and discoloration packaging system comprises the following steps: (1) hot water immersion cleaning of the copper-plated steel wire; (2) wiping and blowing the cleaned steel wire to remove surface moisture; (3) feeding the steel wire into a drying oven for drying, so that the surface is completely dried and carries residual heat; (4) surface coating: after the steel wire is output from the drying oven, immediately coat a rust-proof coating agent on the surface of the steel wire by using the residual heat carried by the steel wire, so that the coating agent is solidified to form a rust-proof film layer; (5) cooling the coated steel wire; (6) passing the cooled steel wire through a guide wheel and a straightener for treatment; (7) winding the steel wire into a spool and naturally cooling; (8) Packaging: The steel wire coil is wrapped with gas phase rust prevention paper or layered with gas phase rust prevention paper, and 2 humidity response humidity control bags (threshold values are 70 / 80%RH respectively) are placed in the inner packaging bag. The humidity control bag is configured to automatically release the inert gas and moisture absorber inside when the internal environment humidity reaches the preset threshold value.

[0057] In step (4), the surface temperature of the steel wire when it comes out of the drying oven is 130°C. In step (8), after the steel wire coil is placed in the inner packaging bag, inert gas is directly filled into the bag to expel air, and then it is sealed.

[0058] The rust-proof coating agent is a water-based inorganic / organic hybrid composite coating, which includes the following components by weight percentage: Water-based acrylic resin: 50%: KH-550: 5%: PEDOT: PSS: 15%: ZnO: 2%: rGO: 1%: BTA: 1%: BYK-3455: 1%: BYK-024: 1%: deionized water: balance.

[0059] Example 2 The method of the bronze-plated bead steel wire anti-rust discoloration packaging system includes the following steps: (1) Hot water immersion cleaning of the copper-plated steel wire; (2) Steel wire scrubbing and blowing after cleaning to remove surface moisture; (3) The steel wire is sent into a drying oven for drying, so that its surface is completely dried and carries residual heat; (4) Surface coating: after the steel wire comes out of the drying oven, a rust-proof coating agent is immediately coated on its surface using the residual heat it carries, so that the coating agent solidifies to form a rust-proof film layer; (5) Cooling of the coated steel wire; (6) The cooled steel wire is processed through guide rollers and straighteners; (7) The steel wire is wound onto a spool and naturally cooled; (8) Packaging: The steel wire coil is wrapped with gas phase rust prevention paper or layered with gas phase rust prevention paper, and 2 humidity response humidity control bags (threshold values are 70 / 80%RH respectively) are placed in the inner packaging bag. The humidity control bag is configured to automatically release the inert gas and moisture absorber inside when the internal environment humidity reaches the preset threshold value.

[0060] In step (4), the surface temperature of the steel wire when it comes out of the drying oven is 130°C. In step (8), after the steel wire coil is placed in the inner packaging bag, inert gas is directly filled into the bag to expel air, and then it is sealed.

[0061] The rust-proof coating agent is a water-based inorganic / organic hybrid composite coating, which includes the following components by weight percentage: Water-based acrylic resin: 45%; KH-550: 4%; PEDOT: PSS: 20%; ZnO: 1.5%; BTA: 1%; BYK-3455: 0.2%; BYK-024: 1%, deionized water: the balance.

[0062] Example 3 The method of the bronze-plated bead wire anti-corrosion discoloration packaging system comprises the following steps: (1) hot water immersion cleaning of the copper-plated steel wire; (2) wire wiping and blowing of the cleaned steel wire to remove surface moisture; (3) sending the steel wire into a drying oven for drying, so that the surface is completely dried and carries residual heat; (4) surface film coating: immediately after the steel wire is output from the drying oven, a rust-proof film forming agent is coated on the surface of the steel wire by using the residual heat carried by the steel wire, so that the rust-proof film forming agent is solidified to form a rust-proof film layer; (5) cooling of the coated steel wire; (6) passing the cooled steel wire through a guide wheel and a straightener for processing; (7) winding the steel wire onto a spool and naturally cooling; (8) packaging: wrapping the steel wire roll with gas phase rust-proof paper or interleaving with gas phase rust-proof paper, and putting 3 humidity response humidity control bags (threshold values are 60 / 70 / 80%RH) into the inner packaging bag, the humidity control bag is configured to automatically release the inert gas and moisture absorber in the bag when the internal environment humidity reaches the preset threshold value.

[0063] In the step (4), the surface temperature of the steel wire when it is output from the drying oven is 130°C. In the step (8), after the steel wire roll is put into the inner packaging bag, inert gas is directly filled into the bag to expel air, and then the bag is sealed.

[0064] The rust-proof film forming agent is a water-based inorganic / organic hybrid composite coating, which comprises the following components by weight percentage: Water-based acrylic resin: 48%; KH-550: 8%; PEDOT: PSS 8%; ZnO: 1%; BTA: 1.5%; BYK-3455: 0.2%; BYK-024: 0.5%, deionized water: the balance.

[0065] Example 4 The method of the bronze-plated bead wire anti-corrosion discoloration packaging system comprises the following steps: (1) hot water immersion cleaning of the copper-plated steel wire; (2) wire wiping and blowing of the cleaned steel wire to remove surface moisture; (3) The steel wire is sent into a drying box for drying, so that its surface is completely dried and carries residual heat; (4) Surface coating: after the steel wire is output from the drying box, a rust-proof coating agent is immediately coated on the surface of the steel wire by using the residual heat carried by the steel wire, so that the rust-proof coating agent is solidified to form a rust-proof film layer; (5) The steel wire after coating is cooled; (6) The cooled steel wire is processed through a guide wheel and a straightener; (7) The steel wire is wound onto a spool and naturally cooled; (8) Packaging: the steel wire roll is wrapped with a gas-phase rust-proof paper or is layered with a gas-phase rust-proof paper as a spacer, and a humidity-responsive humidity control bag (threshold value is 80% RH) is put into the inner packaging bag. The humidity control bag is configured to automatically release inert gas and a moisture absorbent in the bag when the internal environment humidity reaches a preset threshold value.

[0066] In the step (4), the surface temperature of the steel wire when it is output from the drying box is 130°C. In the step (8), after the steel wire roll is put into the inner packaging bag, inert gas is directly filled into the bag to expel air, and then the bag is sealed.

[0067] The rust-proof coating agent is a water-based inorganic / organic hybrid composite coating, which includes the following components by weight percentage: Water-based acrylic resin: 55%; KH-550: 3%; PEDOT: PSS: 5%; ZnO: 3%; BTA: 1.5%; BYK-3455: 1%; BYK-024: 0.5%, deionized water: balance.

[0068] Example 5 The method of the bronze-plated bead wire rust-proof and discoloration packaging system includes the following steps: (1) The steel wire after copper plating is immersed in hot water for cleaning; (2) The cleaned steel wire is wiped and blown to remove surface moisture; (3) The steel wire is sent into a drying box for drying, so that its surface is completely dried and carries residual heat; (4) Surface coating: after the steel wire is output from the drying box, a rust-proof coating agent is immediately coated on the surface of the steel wire by using the residual heat carried by the steel wire, so that the rust-proof coating agent is solidified to form a rust-proof film layer; (5) The steel wire after coating is cooled; (6) The cooled steel wire is processed through a guide wheel and a straightener; (7) The steel wire is wound onto a spool and naturally cooled; (8) Packaging: The steel wire coil is wrapped with gas phase rust prevention paper or layered with gas phase rust prevention paper as spacer, and 4 humidity response humidity control bags (threshold values are 60 / 70 / 80 / 80%RH respectively) are put into the inner packaging bag. The humidity control bag is configured to automatically release the inert gas and moisture absorber inside when the internal environment humidity reaches the preset threshold.

[0069] In the step (4), the surface temperature of the steel wire when it comes out of the drying oven is 130℃. In the step (8), after the steel wire coil is put into the inner packaging bag, inert gas is directly filled into the bag to expel air, and then it is sealed.

[0070] The rust prevention film forming agent is a water-based inorganic / organic hybrid composite coating, which includes the following components by weight percentage: Water-based acrylic resin: 50%; KH-550: 5%; PEDOT: PSS: 15%; ZnO: 2%; rGO: 1%; BTA: 1%; BYK-3455: 1%; BYK-024: 1%, deionized water: the balance.

[0071] Comparative Example 1: The difference from Example 1 is that solvent-based rust prevention oil is used for coating, and ordinary packaging is used, which is ordinary plastic woven bag or polyethylene bag, and no gas phase rust prevention material (including gas phase rust prevention paper and humidity control bag) is used inside.

[0072] Comparative Example 2: The difference from Example 1 is that after drying, the steel wire is cooled to 50℃ and coated with gum rosin benzene solution, and ordinary nitrogen charging packaging is used, but no gas phase rust prevention paper and humidity control bag is used inside the packaging.

[0073] Comparative Example 3: The difference from Example 1 is that when packaging, the steel wire coil is wrapped with gas phase rust prevention paper, sealed after filling with nitrogen, but no humidity response humidity control bag is put in.

[0074] Comparative Example 4: The difference from Example 1 is that the film forming agent does not contain PEDOT: PSS, and the share is replaced by acrylic resin.

[0075] Comparative Example 5: The difference from Example 1 is that the film forming agent does not contain KH-550, and the share is replaced by acrylic resin.

[0076] The test data of Examples 1-5 and Comparative Examples 1-5 are shown in Table 1.

[0077] Table 1: Test data of Examples 1-5 and Comparative Examples 1-5

[0078] From Table 1, it can be seen that the rust prevention period of Example 1 is more than 3 times that of Comparative Examples 1 and 2, and the adhesion retention rate (>95%) is also significantly higher. This proves that the overall technical scheme of the present application has a revolutionary advantage in rust prevention ability and adhesion retention performance compared with traditional rust-proof oil and existing technologies such as coumarone resin. The ΔE value of the example is less than 1.5, indicating that the rust-proof film effectively inhibits surface discoloration, while the ΔE value of the comparative example is larger, showing obvious discoloration. This is due to the synergistic effect of the rust-proof film forming agent in the example, and the surface state of the example is good after the wet heat test, without obvious rusting, while the comparative example shows rusting and discoloration. This proves the stability of the system in a high temperature and high humidity environment, and the dynamic humidity control mechanism of the humidity responsive control bag plays a key role. Under the condition that the film forming process is completely the same, the rust prevention performance of Example 1 using the humidity control bag is much better than that of Comparative Example 3 which does not use it. The internal humidity of the packaging of Comparative Example 3 lost control in the later stage, resulting in failure of rust prevention. This strongly proves that the "humidity responsive control bag" this innovative structure is indispensable to achieve long-term and stable rust prevention effect, and its active humidity control mechanism is much better than that of static air-filled packaging. Comparative Example 4, which lacks PEDOT conductive polymer, has significantly lower rust prevention performance than Example 1, proving that the electrochemical anode protection provided by PEDOT is an important part of the composite protection mechanism of the present application. Comparative Example 5, which lacks silane coupling agent, has a significant decrease in rust prevention performance and the most critical adhesion retention rate. This proves that the silane coupling agent plays a decisive role in enhancing the adhesion of the film layer, and firm adhesion is the basis for the film layer to provide long-term effective protection. The film forming agent of the present application is a synergistic system, and silane coupling agent, PEDOT (electrochemical protection), BTA and nano filler are indispensable, which together constitute the core technology to achieve an ultra-long rust prevention period. By simplifying the formula and packaging, a more economical option is provided while ensuring the core advantages. By enhancing the packaging configuration, it is shown that the rust prevention period can be further prolonged to more than 20 months, proving the scalability and high upper limit of the performance of the present application scheme.

Claims

1. A tarnish and discoloration resistant packaging system for bronze plated bead wire, characterized by, According to the process flow, sequentially connected are: a hot water washing tank (1) for hot water immersion cleaning of the steel wire after copper plating; a surface treatment unit including a wire rubbing device (2) and a blowing pipe (3) for removing residual water on the surface of the steel wire; a drying box (4) for completely drying the surface of the steel wire and making it carry residual heat; a film coating device (5) arranged downstream of the outlet of the drying box for coating a rust-proof film agent on the surface of the steel wire carrying residual heat; a cold air box (6) for cooling the steel wire after film coating; a post-treatment unit including a guide roller set (7) and a straightener (8) for arranging the surface of the steel wire; a take-up spool (9) for winding the steel wire onto the spool; a packaging system (10) for sealing and packaging the steel wire roll; the packaging system (10) includes an inner packaging bag (12), a gas phase rust-proof material placed in the inner packaging bag (12), and at least one humidity-responsive humidity control bag (13); the humidity-responsive humidity control bag includes a sealed bag body, a desiccant and an inert gas filled in the bag body, the bag body is provided with a sealing part made of a humidity-dissolving material, and the sealing part is configured to dissolve and break when the ambient humidity reaches a preset threshold.

2. The tarnish and discoloration resistant packaging system for bronze plated cord steel wires according to claim 1, characterized in that, The humidity-dissolving material is polyvinyl alcohol, and different dissolution humidity thresholds are set by controlling the thickness of the polyvinyl alcohol film of the sealing part.

3. The tarnish and discoloration resistant packaging system for bronze plated cord steel wires according to claim 1, characterized in that, The inert gas pressure in the humidity-responsive humidity control bag is higher than the atmospheric pressure.

4. A method of preventing tarnishing and discoloration of the bronze-coated bead wire according to any one of claims 1 to 3, characterized in that, The process includes the following steps: (1) hot water immersion cleaning of the steel wire after copper plating; (2) rubbing and blowing the cleaned steel wire to remove surface moisture; (3) sending the steel wire into the drying box for drying, so that the surface of the steel wire is completely dried and carries residual heat; (4) surface film coating: after the steel wire is output from the drying box, a rust-proof film agent is immediately coated on the surface of the steel wire using the residual heat carried by the steel wire, so that the film agent is solidified to form a rust-proof film layer; (5) cooling the steel wire after film coating; (6) passing the cooled steel wire through the guide roller and the straightener for treatment; (7) winding the steel wire onto the spool and naturally cooling; (8) packaging: sealing the steel wire roll and the gas phase rust-proof material in the inner packaging bag, and placing at least one humidity-responsive humidity control bag in the inner packaging bag, the humidity control bag is configured to automatically release the inert gas and the desiccant in the bag when the internal environment humidity reaches a preset threshold.

5. The method of claim 4, wherein, In step (4), the surface temperature of the steel wire when it is output from the drying box is 130-150℃.

6. The method of claim 4, wherein, The rust-proof film agent is a water-based inorganic / organic hybrid composite coating, which includes the following components by weight percentage: water-based resin: 40%-60%; silane coupling agent: 1%-8%; conductive polymer: 5%-20%; nanofiller: 0.5%-5%; copper corrosion inhibitor: 0.1%-2%; auxiliary agent: 0.1%-2%; deionized water: the balance.

7. The method of claim 6, wherein, The water-based resin is at least one of a water-based acrylic resin, a water-based epoxy resin or a water-based polyurethane resin; the silane coupling agent is at least one of aminopropyl triethoxysilane and γ-glycidyl ether propyl trimethoxysilane.

8. The method of claim 6, wherein, The conductive polymer is a water dispersion of poly (3, 4-ethylenedioxythiophene) : polystyrene sulfonate; the nano filler includes at least one of zinc oxide nanoparticles, silicon dioxide nanoparticles and reduced graphene oxide; and the copper corrosion inhibitor is at least one of benzotriazole and methylbenzotriazole.

9. The method of claim 6, wherein, The auxiliary agent includes a wet dispersant and an antifoaming agent; the wet dispersant is a polyether-modified polysiloxane compound, and the antifoaming agent is a mineral oil or a silicone antifoaming agent.

10. The method of claim 4, wherein, In step (8), after the steel wire coil is put into the inner packaging bag, inert gas is directly filled into the bag to discharge air, and then the bag is sealed.

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