Formula and preparation method of universal TBR steel wire adhesive glue

Abstract

The invention provides a general type TBR steel wire adhesive formula and a preparation method, and relates to the technical field of tire rubber materials. According to the formula, a pyrolysis carbon black and furnace black synergetic reinforcing and nickel boroacylate long-acting bonding system is adopted, and a three-step feeding and banburying process is matched, so that synergetic optimization of the hardness, the bonding performance and the processing efficiency of the rubber material is realized. A core formula comprises 100 parts of natural rubber, 26 parts of reclaimed rubber, 36 parts of N375 carbon black, 34 parts of cracked carbon black, 0.9 part of nickel boroacylate, a composite vulcanization system and the like, and according to the preparation method, the carbon black and a vulcanization auxiliary agent are added in stages, the internal mixing temperature and time are controlled, and it is ensured that materials are evenly dispersed. The bonding tension of the finished rubber material and a steel wire cord is stabilized at 600-700N, the rubber adhesion rate is 100%, the Mooney viscosity at 100 DEG C meets the industrial production requirement, the heat generation of the rubber material is reduced by more than 30% compared with that of a traditional formula, the high-speed and durability of a tire are remarkably improved, and the rubber material is suitable for key parts such as a belted layer of an all-steel radial tire and is high in universality and cost performance.

Description

Technical Field

[0001] This invention relates to the field of tire rubber materials technology, specifically a general-purpose TBR steel wire adhesive formulation and preparation method, which is suitable for key parts such as tire belt layers and carcass cords that require high-strength bonding with steel wire cords, and can be widely used in the industrial production of various all-steel radial tires. Background Technology

[0002] The steel cord adhesive in TBR tires is the core material connecting the steel cords to the rubber matrix. Its adhesive properties, heat generation characteristics, and processing performance directly determine the tire's service life and safety performance. Traditional steel cord adhesives have several technical drawbacks: The contradiction between carbon black dispersion and heat generation: In order to ensure the hardness and tensile stress of the rubber compound, a large amount of carbon black (50-60 parts) is required. However, traditional furnace blacks (such as HAF and ISAF) are difficult to disperse and are prone to agglomeration, resulting in uneven mixing of the rubber compound and a significant increase in heat generation. Especially when driving at high speed, excessive heat generation will accelerate the aging of the rubber compound and reduce the adhesion durability. Insufficient long-term performance of the adhesive system: Traditionally, cobalt salts are used as tackifiers. Although the initial adhesion effect is good, the adhesive tensile strength decreases significantly after long-term use (such as in humid or high-temperature environments), which affects the service life of the tire. Low production efficiency: Existing mixing processes mostly involve one-time feeding, resulting in insufficient mixing of carbon black and rubber matrix, requiring multiple re-mixing processes, which leads to long production cycles and high energy consumption; Poor versatility: The adhesive formulations for different tire specifications vary significantly and require individual adjustments, increasing production and management costs.

[0003] In existing technologies, although attempts have been made to use silica and carbon black together or to optimize the sulfidation system, the problems of synergistic effects of carbon black dispersion, heat generation and long-term adhesion have not been fundamentally solved, and there is a lack of efficient preparation processes suitable for industrial production.

[0004] Therefore, developing a TBR steel wire adhesive formulation and preparation method that is low in heat generation, high in adhesion, uniformly dispersed, and highly versatile has become an urgent problem to be solved in the industry. Summary of the Invention

[0005] (a) Technical problems to be solved To address the shortcomings of existing technologies, this invention provides a general-purpose TBR steel wire adhesive formulation and preparation method, which solves the problem that, although attempts have been made to use silica and carbon black together or to optimize the vulcanization system, the synergistic issues of carbon black dispersion, heat generation, and long-term adhesion have not been fundamentally resolved.

[0006] (II) Technical Solution To achieve the above objectives, the present invention provides the following technical solution: A general-purpose TBR steel wire adhesive formulation and preparation method, wherein the formulation comprises, by weight, the following: 90-110 parts natural rubber, 20-30 parts reclaimed rubber, 30-40 parts high-structure abrasion-resistant furnace black N375, 30-38 parts pyrolysis carbon black, 5-9 parts zinc oxide, 0.8-1.2 parts 203 resin, 0.8-1.2 parts antioxidant 4020, 0.8-1.2 parts antioxidant RD, 0.7-1.1 parts borylate nickel, 3-4 parts insoluble sulfur OT20, 2.5-3.5 parts insoluble sulfur 7020, 0.2-0.4 parts accelerator NS, 0.5-0.7 parts accelerator DZ, 0.1-0.2 parts anti-scorching agent, and 0.8-1.2 parts modulus reinforcing agent.

[0007] Further, the formulation preferably comprises, by weight: 100 parts natural rubber, 26 parts reclaimed rubber, 36 parts high-structure abrasion-resistant furnace black N375, 34 parts pyrolysis carbon black, 7 parts zinc oxide, 1 part 203 resin, 1 part antioxidant 4020, 1 part antioxidant RD, 0.9 parts borylated nickel, 3.5 parts insoluble sulfur OT20, 3 parts insoluble sulfur 7020, 0.3 parts accelerator NS, 0.6 parts accelerator DZ, 0.15 parts scorch inhibitor, and 1 part modulus reinforcing agent.

[0008] Furthermore, the pyrolysis carbon black has an iodine absorption value ≥80mg / g, a DBP absorption value ≥100cm3 / 100g, a moisture content ≤1%, and a particle size range of 20-50nm. It synergistically reinforces the N375 carbon black to ensure that the rubber compound has a Shore hardness of 65-75HA.

[0009] Furthermore, the nickel borate has a nickel content of ≥12% and a boron content of ≥3%, exhibits good compatibility with the adhesive at room temperature, and retains ≥95% of the adhesive tensile strength in the later stages of use, which is superior to traditional cobalt salt adhesive systems.

[0010] Furthermore, the reclaimed rubber is tire reclaimed rubber with a Mooney viscosity (ML1+4100℃) of 30-40 and a tensile strength ≥10MPa, which synergistically improves the processing fluidity and cost advantage of the rubber compound when combined with natural rubber.

[0011] Furthermore, a method for preparing a general-purpose TBR steel wire adhesive formulation includes the following steps: Step 1: Initial Mixing Stage Natural rubber, reclaimed rubber, N375 carbon black, 50%-60% pyrolysis carbon black, zinc oxide, 203 resin, antioxidant 4020, antioxidant RD, and nickel borate are put into an internal mixer and mixed for 4-6 minutes at a temperature of 110-120℃ and a rotor speed of 40-50 r / min. After cooling in a cooling open mill, the mixture is transferred to a mixing open mill for a second mixing for 2-3 minutes. Step Two: Mixing Stage The material obtained in step one and the remaining pyrolysis carbon black are fed into an internal mixer and mixed for 3-5 minutes at a temperature of 100-110℃ and a rotor speed of 35-45r / min. After cooling in a cooling open mill, the mixture is continued to be mixed in a mixing open mill for 1-2 minutes. Step 3: Final Mixing Stage The material obtained in step two is put into an internal mixer, and insoluble sulfur OT20, insoluble sulfur 7020, accelerator NS, accelerator DZ, anti-scorching agent, and modulus enhancer are added. The mixture is mixed for 2-4 minutes at a temperature of 80-90℃ and a rotor speed of 30-40 r / min. After discharge, the material is passed through a two-roll mill 3-5 times to obtain TBR steel wire adhesive.

[0012] Furthermore, in step one, the initial feeding sequence of the internal mixer is as follows: first, natural rubber and reclaimed rubber are added, and after plasticizing for 1-2 minutes, the remaining initial mixed materials are added to avoid premature agglomeration of carbon black.

[0013] Furthermore, the final mixing temperature in step three is strictly controlled at 80-90℃ to prevent premature decomposition of insoluble sulfur, ensure uniform dispersion of the sulfidation system, and scorch time ≥8min.

[0014] Furthermore, the performance indicators of the finished adhesive compound are as follows: tensile strength ≥18MPa, tear strength ≥45kN / m, steel wire bonding tensile strength 600-700N, adhesive adhesion rate 100%, Mooney viscosity at 100℃ (1+4) 40-60MU, and heat generation (100℃×20min) ≤60℃.

[0015] Furthermore, this universal TBR steel wire adhesive is suitable for steel wire bonding parts such as the belt layer and carcass cord of all-steel radial tires, and can be adapted to various specifications of TBR tires such as 9.00R20 and 11.00R20, demonstrating strong versatility.

[0016] (III) Beneficial Effects This invention provides a general-purpose TBR steel wire adhesive formulation and preparation method. It has the following beneficial effects: 1. This invention provides a general-purpose TBR steel wire adhesive formulation and preparation method, which uses N375 furnace black and pyrolysis carbon black in a ratio of 36:34. N375 ensures high strength and hardness of the adhesive, while pyrolysis carbon black has good dispersibility and low heat generation, improving processing fluidity and reducing the heat generation of the adhesive by more than 30%, thus solving the contradiction between dispersion and heat generation in traditional single carbon black filling. Furthermore, borosilicate nickel is selected to replace part of the cobalt salt. Although the initial adhesion performance is comparable to that of cobalt salt, the adhesion tensile strength retention rate is ≥95% after long-term use, significantly improving tire durability.

[0017] 2. This invention provides a general-purpose TBR steel wire bonding adhesive formulation and preparation method. By adding carbon black and vulcanization aids in stages through "initial mixing-supplementary mixing-final mixing", carbon black agglomeration and premature sulfur decomposition caused by one-time feeding are avoided. The mixing efficiency is increased by 20%, the uniformity of rubber dispersion is significantly improved, and the formulation is suitable for the steel wire bonding requirements of various specifications of TBR tires. It can be applied to different models of products without major adjustments, thereby reducing production management costs. Detailed Implementation

[0018] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all 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.

[0019] Example 1: This invention provides a general-purpose TBR steel wire adhesive formulation, which preferably comprises, by weight: 100 parts natural rubber, 26 parts reclaimed rubber, 36 parts high-structure abrasion-resistant furnace black N375, 34 parts pyrolysis carbon black, 7 parts zinc oxide, 1 part 203 resin, 1 part antioxidant 4020, 1 part antioxidant RD, 0.9 parts borylate nickel, 3.5 parts insoluble sulfur OT20, 3 parts insoluble sulfur 7020, 0.3 parts accelerator NS, 0.6 parts accelerator DZ, 0.15 parts anti-scorching agent, and 1 part modulus reinforcing agent; The formula includes the following systems: Raw rubber system: 100 parts natural rubber + 26 parts reclaimed rubber; Natural rubber possesses high strength, high elasticity, and excellent adhesion, providing the core mechanical properties for rubber compounds; Reclaimed rubber reduces raw material costs while improving the flowability of rubber processing. The reclaimed rubber selected is tire reclaimed rubber with a Mooney viscosity of 30-40 and a tensile strength of ≥10MPa to avoid performance degradation.

[0020] Reinforcing system: 36 parts N375 carbon black + 34 parts pyrolysis carbon black; N375 is a high-structure abrasion-resistant furnace black with an iodine absorption value of 115 mg / g and a DBP absorption value of 125 cm3 / 100g, providing excellent reinforcing effects and ensuring the hardness and tensile stress of the rubber compound. The pyrolysis carbon black has an iodine absorption value of ≥80mg / g and a DBP absorption value of ≥100cm³ / 100g. It has good dispersibility and low heat generation. It works synergistically with N375 to reduce the heat generation of the rubber compound and improve the uniformity of mixing.

[0021] Adhesive system: 0.9 parts of nickel borate; With a nickel content of ≥12% and a boron content of ≥3%, it forms a stable chemical bond with the surface of the steel wire cord, exhibiting superior long-term adhesion performance compared to traditional cobalt salts, and achieving an adhesive adhesion rate of 100%.

[0022] Vulcanization system: 3.5 parts of insoluble sulfur OT20 + 3 parts of insoluble sulfur 7020 + 0.3 parts of accelerator NS + 0.6 parts of accelerator DZ; Insoluble sulfur prevents blooming; OT20 and 7020 are used together to optimize vulcanization speed; accelerator NS (sulfenamide) extends scorch time to ensure full wetting of rubber compound and steel wire; and accelerator DZ increases crosslinking density of vulcanized rubber.

[0023] Auxiliary system: 7 parts zinc oxide, activated vulcanization system, 1 part 203 resin to enhance adhesion, antioxidant 4020+RD for synergistic anti-aging, 0.15 parts anti-scorching agent to prevent scorching, 1 part modulus enhancer to improve tensile stress.

[0024] The preparation method includes the following steps: Step 1: Initial Mixing Stage Feeding sequence: First, put 100 parts of natural rubber and 26 parts of reclaimed rubber into the internal mixer, plasticize for 1.5 minutes, temperature 90-100℃, speed 45r / min, so that the raw rubber is fully softened; Mixing operation: Add 36 parts of N375 carbon black, 20 parts of pyrolysis carbon black, 7 parts of zinc oxide, 1 part of 203 resin, 1 part of antioxidant 4020, 1 part of antioxidant RD, and 0.9 parts of nickel borate. Adjust the internal mixer temperature to 115℃ and the speed to 45r / min, and mix for 5 minutes to ensure that the raw rubber and filler are initially integrated. Cooling and secondary mixing: The initial mixed material is discharged, cooled by a cooling open mill, and then transferred to a mixing open mill for two thin passes with a roller gap of 1-2 mm to further disperse the material.

[0025] Step Two: Mixing Stage Feeding and mixing: Add the material obtained in step one and 14 parts of the remaining pyrolysis carbon black into the internal mixer, control the temperature at 105℃ and the speed at 40r / min, and mix for 4 minutes to make the remaining pyrolysis carbon black evenly dispersed in the rubber compound and avoid agglomeration. Cooling treatment: The discharged material is cooled to ≤50℃ in a cooling open mill and then transferred to a mixing open mill for 1.5 minutes to ensure uniform temperature of the rubber compound.

[0026] Step 3: Final Mixing Stage Vulcanization aid feeding: Put the material obtained in step two into a mixer, add 3.5 parts of insoluble sulfur OT20, 3 parts of insoluble sulfur 7020, 0.3 parts of accelerator NS, 0.6 parts of accelerator DZ, 0.15 parts of anti-scorching agent, and 1 part of modulus enhancer. Control the temperature at 85℃ and the speed at 35r / min, and mix for 3min to avoid premature decomposition of sulfur. Discharge and refining: The final mixed material is discharged and passed through a two-roll mill 4 times with a roller gap of 0.8-1.2mm to ensure that the vulcanization aid is evenly dispersed. Then, it is sheeted out to a thickness of 5-8mm to obtain the finished TBR steel wire adhesive.

[0027] Step 4: Vulcanization and Performance Testing After the rubber compound is combined with the steel cord, it is vulcanized at 150℃ for 30 minutes. The adhesive tensile strength, adhesive adhesion rate, physical and mechanical properties and processing performance are tested to ensure that they meet the requirements of industrial production.

[0028] The performance test results are shown in the table below: Application effect The steel wire adhesive prepared using this formula and method was applied to 9.00R20 TBR tires. After indoor mileage testing, the high-speed performance (120km / h) was improved by 12%, the durability performance (cumulative mileage) was improved by 15%, the qualified rate of finished tires reached over 98%, and the production cost was reduced by 18% compared with traditional formulas.

[0029] The following points should be noted in this article: 1. The embodiments disclosed herein only relate to the structures involved in the embodiments disclosed herein; other structures may refer to general designs.

[0030] 2. Where there is no conflict, the embodiments of this disclosure and the features in the embodiments can be combined with each other to obtain new embodiments.

[0031] Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

Claims

1. A general-purpose TBR steel wire adhesive formulation, characterized in that, The formulation, by weight, comprises: 90-110 parts natural rubber, 20-30 parts reclaimed rubber, 30-40 parts high-structure abrasion-resistant furnace black N375, 30-38 parts pyrolysis carbon black, 5-9 parts zinc oxide, 0.8-1.2 parts 203 resin, 0.8-1.2 parts antioxidant 4020, 0.8-1.2 parts antioxidant RD, 0.7-1.1 parts borylate nickel, 3-4 parts insoluble sulfur OT20, 2.5-3.5 parts insoluble sulfur 7020, 0.2-0.4 parts accelerator NS, 0.5-0.7 parts accelerator DZ, 0.1-0.2 parts scorching inhibitor, and 0.8-1.2 parts modulus enhancer.

2. The general-purpose TBR steel wire adhesive formulation according to claim 1, characterized in that, The preferred formulation, by weight, comprises: 100 parts natural rubber, 26 parts reclaimed rubber, 36 parts high-structure abrasion-resistant furnace black N375, 34 parts pyrolysis carbon black, 7 parts zinc oxide, 1 part 203 resin, 1 part antioxidant 4020, 1 part antioxidant RD, 0.9 parts borylated nickel, 0.5 parts insoluble sulfur OT203, 3 parts insoluble sulfur 7020, 0.3 parts accelerator NS, 0.6 parts accelerator DZ, 0.15 parts scorch inhibitor, and 1 part modulus enhancer.

3. The general-purpose TBR steel wire adhesive formulation according to claim 1, characterized in that, The pyrolysis carbon black has an iodine absorption value ≥80mg / g, a DBP absorption value ≥100cm3 / 100g, a moisture content ≤1%, and a particle size range of 20-50nm. It works synergistically with N375 carbon black to ensure that the rubber compound has a Shore hardness of 65-75HA.

4. The general-purpose TBR steel wire adhesive formulation and preparation method according to claim 1, characterized in that, The nickel borate has a nickel content of ≥12% and a boron content of ≥3%. It has good compatibility with the adhesive at room temperature, and the adhesive tensile strength retention rate of the adhesive in the later stage of use is ≥95%.

5. The general-purpose TBR steel wire adhesive formulation according to claim 1, characterized in that, The reclaimed rubber is tire reclaimed rubber with a Mooney viscosity of 30-40 and a tensile strength of ≥10MPa. It works synergistically with natural rubber to improve the processing fluidity and cost advantages of the rubber compound.

6. A method for preparing a general-purpose TBR steel wire adhesive formulation, characterized in that, Includes the following steps: Step 1: Initial Mixing Stage Natural rubber, reclaimed rubber, N375 carbon black, 50%-60% pyrolysis carbon black, zinc oxide, 203 resin, antioxidant 4020, antioxidant RD, and nickel borate are put into an internal mixer and mixed for 4-6 minutes at a temperature of 110-120℃ and a rotor speed of 40-50 r / min. After cooling in a cooling open mill, the mixture is transferred to a mixing open mill for a second mixing for 2-3 minutes. Step Two: Mixing Stage The material obtained in step one and the remaining pyrolysis carbon black are fed into an internal mixer and mixed for 3-5 minutes at a temperature of 100-110℃ and a rotor speed of 35-45r / min. After cooling in a cooling open mill, the mixture is continued to be mixed in a mixing open mill for 1-2 minutes. Step 3: Final Mixing Stage The material obtained in step two is put into an internal mixer, and insoluble sulfur OT20, insoluble sulfur 7020, accelerator NS, accelerator DZ, anti-scorching agent, and modulus enhancer are added. The mixture is mixed for 2-4 minutes at a temperature of 80-90℃ and a rotor speed of 30-40 r / min. After discharge, the material is passed through a two-roll mill 3-5 times to obtain TBR steel wire adhesive.

7. The preparation method of a general-purpose TBR steel wire adhesive formulation according to claim 6, characterized in that, In step one, the initial feeding sequence of the internal mixer is as follows: first, add natural rubber and reclaimed rubber, and then add the remaining initial mixed materials after plasticizing for 1-2 minutes to avoid premature agglomeration of carbon black.

8. The preparation method of a general-purpose TBR steel wire adhesive formulation according to claim 6, characterized in that, The final mixing temperature in step three is strictly controlled at 80-90℃ to prevent premature decomposition of insoluble sulfur, ensure uniform dispersion of the sulfidation system, and scorch time ≥8min.

9. The preparation method of a general-purpose TBR steel wire adhesive formulation according to claim 6, characterized in that, The performance indicators of the finished rubber compound are as follows: tensile strength ≥18MPa, tear strength ≥45kN / m, steel wire bonding tensile strength 600-700N, adhesive adhesion rate 100%, Mooney viscosity at 100℃ 40-60MU, and heat generation ≤60℃.

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