Automobile interior ceiling repairing adhesive and preparation method thereof

Abstract

The invention provides an automobile interior ceiling repairing adhesive and a preparation method thereof. The automobile interior ceiling repairing adhesive comprises the following components in parts by weight: 25-35 parts of a grafting solution, 5-10 parts of chloroprene rubber, 5-15 parts of phenolic resin powder, 0.8-1.2 parts of magnesium oxide, 3-8 parts of chlorinated rubber, 40-70 parts of an environment-friendly solvent mixed solution and 1-3 parts of a composite anti-aging agent, the chloroprene rubber is chloroprene rubber; the environment-friendly solvent mixed solution is a mixed solution of cyclohexane, methyl acetate, acetone and propylene glycol methyl ether acetate; the compound type anti-aging agent is formed by compounding BHT (butylated hydroxytoluene), 1010, 168 and disteaxyl thiodipropionate. Aiming at normal-temperature bonding of the automobile ceiling interior, the adhesive is easy to spray and construct, and the bonded adhesive layer is good in high and low temperature resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of automobile interior adhesives, focusing on applications in automobile ceiling modification and repair scenarios, and in particular to an automobile interior ceiling repair adhesive that can be sprayed and a preparation method thereof. Background Art

[0002] With the significant improvement of people's living standards and the rapid progress of automobile industry production technology, cars have evolved from a simple means of transportation to an important embodiment of people's pursuit of comfort in life. At present, major automobile manufacturers and automobile modification markets attach great importance to improving the overall quality of the cockpit, not only focusing on environmental protection, striving to reduce the emission of volatile organic compounds (VOC) in the car, and ensuring the health of drivers and passengers, but also paying attention to the ornamental value of the interior, and meeting the personalized needs of different consumers through diversified interior design and modification.

[0003] In the process of car interior modification, especially for the car roof, which is a large and irregularly shaped part, the bonding and repair of its interior materials put forward higher requirements for adhesives. Although the existing adhesives on the market can achieve a certain degree of bonding function, there are many shortcomings. On the one hand, the construction performance of some adhesives is poor under normal temperature (5-35°C). Either it is difficult to spray evenly, resulting in low construction efficiency and uneven repair effect; or the adhesive layer after bonding has poor high and low temperature resistance. In the high temperature exposure in summer or the low temperature environment in winter, the adhesive layer is prone to cracking and debonding, affecting the stability and service life of the car ceiling interior. On the other hand, the environmental performance of many adhesives does not meet the increasingly stringent in-vehicle air quality standards, and the volatile harmful gases may endanger the health of drivers and passengers in the long term.

[0004] In view of the limitations of the above-mentioned existing technologies, there is an urgent need to develop a repair glue specifically for automobile ceiling interiors, which can not only meet good construction performance at room temperature, but also have excellent high and low temperature resistance and environmental protection properties, so as to meet the actual needs of automobile modification factories and after-sales maintenance markets for high-quality automobile ceiling interior processing. Summary of the invention

[0005] Aiming at the problems existing in the existing automobile ceiling adhesive, the present invention provides an automobile interior ceiling repair adhesive and a preparation method thereof.

[0006] A car interior ceiling repair adhesive, the components by weight are: 25-35 parts of grafting liquid, 5-10 parts of chloroprene rubber, 5-15 parts of phenolic resin powder, 0.8-1.2 parts of magnesium oxide, 3-8 parts of chlorinated rubber, 40-70 parts of environmentally friendly solvent mixture, 1-3 parts of composite antioxidant; the chloroprene rubber is chloroprene rubber; the environmentally friendly solvent mixture is a mixture of cyclohexane, methyl acetate, acetone and propylene glycol methyl ether acetate (PMA); the composite antioxidant is compounded by BHT, 1010, 168 and distearyl thiodipropionate (DSTDP). In the present invention, the grafting liquid in the adhesive system can not only significantly improve the heat resistance of the adhesive, but also enhance the interface bonding between it and different ceiling interior materials, thereby improving the overall bonding effect. The unique molecular structure and crystallization characteristics of the chloroprene rubber enable it to act as the main structural framework in the adhesive, providing a solid support for the entire adhesive layer. It also has good initial adhesion and cohesive strength, ensuring the initial adhesion of the adhesive to the ceiling surface and its stability during subsequent long-term use. As an important auxiliary agent, magnesium oxide plays multiple roles in the adhesive system, including regulating pH, promoting cross-linking reactions, and improving the hardness and heat resistance of the adhesive layer. It works in synergy with other ingredients to optimize the comprehensive performance of the adhesive layer. The relative molecular mass of the chlorinated rubber is precisely controlled at 20,000 ± 1,000. Through its special chemical structure and physical properties, it can not only significantly improve the bonding strength of the adhesive, but also improve the flexibility and chemical corrosion resistance of the adhesive layer, so that it can better adapt to the complex use environment of the car roof. The propylene glycol methyl ether acetate introduced into the environmentally friendly solvent mixture has extremely low volatility, good solubility and excellent compatibility with other solvent components. This mixed solvent system can not only effectively dissolve the components, ensure the uniformity and fluidity of the adhesive, and facilitate spraying construction, but also greatly reduce the VOC content of the entire repair glue, so that it meets the strict environmental protection requirements in the car and creates a healthy air environment in the car. The composite antioxidant can more comprehensively and efficiently capture and remove free radicals generated by heat, oxygen, light and other factors during the use of the adhesive through the synergistic effect of the various components, greatly improve the aging resistance of the adhesive, slow down the aging rate of the adhesive layer, and ensure the long-term stability of the repair effect of the car ceiling interior.

[0007] Preferably, the grafting liquid component is a mixture of 50-60 parts of cyclohexane, butanone, and dimethyl carbonate solvent, 10-15 parts of chloroprene rubber, 10-15 parts of methyl methacrylate, and 0.2-0.4 parts of calcium cyclohexane and titanium trichloride composite catalyst. The use of calcium cyclohexane and titanium trichloride composite catalyst can significantly improve the efficiency and selectivity of the grafting reaction, make the structure of the grafted product more stable, enhance the cohesive strength and heat resistance of the adhesive, and thus slow down the aging process to a certain extent. In addition, the reasonable selection of the environmentally friendly solvent mixture not only ensures the construction performance and environmental performance of the adhesive, but also reduces the degradation of the adhesive performance caused by solvent volatilization or reaction with other components, and further improves its aging resistance.

[0008] Further preferably, the preparation method of the grafting liquid comprises the following steps: step 1, adding a mixed solution of cyclohexane, butanone and dimethyl carbonate solvent into a reactor equipped with a high-precision temperature control system, an efficient stirring device and a dropping device, turning on the stirring device, and setting the stirring speed to 280-320r / min; step 2, adding chloroprene rubber into the reactor, and continuously stirring to pre-dissolve the chloroprene rubber film for 2-3h. During this process, the solvent temperature is monitored in real time by a temperature sensor to keep it at room temperature to achieve the chloroprene rubber. Uniform dispersion; Step 3, heating the reactor to 85°C at a rate of 1.5-2°C per minute, stirring continuously during the heating process, and when the set temperature of 85°C is reached, methyl methacrylate is slowly added to the reactor, and at the same time, calcium cyclohexaneate and titanium trichloride composite catalyst are uniformly added to the reactor through a dropping device within 20-30min, and the reaction is continued. During this period, the viscosity change of the reaction system is monitored in real time by an online viscosity monitoring device. When the viscosity reaches 3000-3500cps / 85°C, the reaction is immediately terminated to obtain a grafting liquid.

[0009] Preferably, in the construction of the solvent system of the grafting liquid, the volume ratio of cyclohexane, butanone, and dimethyl carbonate is limited to one of 3:2:2, 2:3:3, and 3:2:1. The organic solvent will undergo thermal expansion at the reaction temperature, and its volume will increase significantly compared to the normal temperature state. Based on this characteristic, the full cylinder design is adopted and the solvent ratio is made according to the volume ratio, which can accurately control the amount of solvent, effectively avoid the risk of overflow caused by excessive solvent addition, and ensure the safety and stability of the reaction process. In this mixed solvent system, the boiling points of butanone and cyclohexane are relatively low, about 5°C lower than the reaction temperature. When the reaction system heats up, butanone and cyclohexane evaporate first, forming a solvent vapor protection layer above the reaction vessel. This vapor layer can effectively prevent air from entering the reaction system, thereby replacing the traditional nitrogen filling protection method. It not only simplifies the operation process and reduces the use and maintenance costs of gas protection equipment, but also significantly improves the efficiency of the grafting reaction, so that the reaction can be carried out more efficiently and stably. From the practical operation level, the setting of the volume ratio has significant advantages. Production personnel can directly design according to the volume of production equipment, and use volume measurement tools such as metering cylinders and flow meters to quickly and accurately measure the volume of the required mixed solvent. This method is simple and intuitive to operate, greatly reducing the errors caused by human operation and ensuring the high accuracy of solvent ratio.

[0010] Preferably, the environmentally friendly solvent mixture is formed by mixing cyclohexane, methyl acetate, acetone, and propylene glycol methyl ether acetate in a specific volume ratio of 3:2:2:1, 2:3:2:1, or 3:2:1:1. This ratio scheme is determined based on an in-depth study of the solubility of chloroprene sheets and the spraying performance of adhesives. Under this ratio, the chloroprene sheets can be fully dissolved. During the spraying application process, factors such as the volatility and surface tension of the solvent will affect the spraying effect. If the solvent system is not suitable, it may cause the flying silk phenomenon, that is, the glue liquid forms a filament instead of a uniform mist or granular state during spraying, affecting the construction quality and efficiency. By mixing these solvents in a specific ratio, the volatility and surface tension of the mixed solvent can be adjusted, so that the glue filaments are in a point-type granular state, ensuring that they can be evenly dispersed on the surface of the car roof during spraying, and improving the coating uniformity and adhesion of the repair glue. The evaporation rate of the solvent is a key factor affecting the drying time and bonding effect of the adhesive. Different solvents have their own unique volatility characteristics, and these characteristics are closely related to the volume of the solvent. By accurately controlling the volume ratio of each solvent in the environmentally friendly solvent mixture, its overall volatility rate can be finely adjusted. It can make the adhesive dry at an ideal speed after being sprayed on the surface of the automotive interior ceiling. It will not cause the adhesive to fail to fully infiltrate the bonded material due to drying too quickly, thereby affecting the bonding strength; nor will it extend the construction period and reduce construction efficiency due to drying too slowly. This precise control of the volatility rate enables the adhesive to always maintain better drying performance and bonding effects under different environmental conditions, such as different temperature and humidity environments, greatly improving the applicability and reliability of the product.

[0011] Preferably, the composite antioxidant is compounded by BHT, 1010, 168, and distearyl thiodipropionate in a mass ratio of 1:1:1:2, 1:2:1:2 or 2:1:1:1. In the actual use of the adhesive, the adhesive layer will inevitably be affected by various external factors such as light, heat, oxygen, and mechanical stress, thereby gradually becoming sticky, hard, brittle, or cracked. This process in which the physical and mechanical properties gradually decrease over time and the elasticity decreases is called aging. The occurrence of aging phenomena will seriously affect the service life and performance stability of the adhesive. Compounding the antioxidant according to the above mass ratio is intended to fully tap the unique advantages of each component and build a composite antioxidant system with significant synergistic effects. Among them, the addition of the new antioxidant DSTDP (i.e., distearyl thiodipropionate) plays a key role. DSTDP has a unique molecular structure, and the sulfur atoms in its molecules can react with the free radicals generated by the adhesive during the aging process to form stable compounds, thereby interrupting the free radical chain reaction. At the same time, there is a synergistic effect between DSTDP and other antioxidants such as BHT, 1010, and 168. BHT and 1010 can capture free radicals, and 168 can decompose hydroperoxides. They cooperate with DSTDP to inhibit the oxidative aging process of the adhesive from different angles.

[0012] Preferably, the phenolic resin powder has a particle size of 50-80 microns. This particle size range is precisely designed to avoid dust pollution caused by too small particle size during the production process, and to ensure smooth painting during construction and achieve refined detail repair effects, making the repair of the car roof structure more accurate and fitting, effectively filling small gaps and uneven areas, and further enhancing the bonding strength.

[0013] The preparation method of the automobile interior ceiling repair glue described above comprises the following steps: step 1, weighing each component by weight; step 2, adding an environmentally friendly solvent mixture to the grafting liquid, and then adding chloroprene rubber, chlorinated rubber, phenolic resin powder, magnesium oxide and a composite antioxidant in sequence, turning on a high-speed dispersing and stirring device, setting the stirring speed to 1100-1300r / min, and dispersing and stirring for 6-8h. During this process, laser particle size analysis technology and a rheometer are used to monitor the dispersion state of each component in the system and the rheological properties of the glue in real time to ensure that each component is fully and evenly mixed to form a stable glue system; step 3, using a viscosity detection device to detect the viscosity of the glue system obtained in step 2, and fine-tuning the viscosity of the glue system by butanone or acetone to make the viscosity range of the glue system within 400-600cps / 25°C; step 4, filtering the glue prepared in step 3 through a 200-mesh high-precision filter device to remove possible impurity particles, and then packaging to obtain a finished automobile ceiling interior repair glue.

[0014] Beneficial effects of the present invention: (1) Excellent construction performance and high and low temperature resistance: This repair glue is specially designed for normal temperature construction of automobile ceiling interiors. By optimizing the solvent system and the synergistic effect of various components, its viscosity is between 400-600cps / 25℃, which can achieve uniform and smooth spraying operation, greatly improving construction efficiency and repair quality; moreover, the adhesive layer maintains stable bonding performance in a wide temperature range of -30℃ to 85℃. After high and low temperature cycle tests simulating the actual use environment (after no less than 10 cycles), no cracking, debonding and other phenomena occur, ensuring the long-term firmness of automobile ceiling interiors in different seasons and different regional environments. (2) Excellent environmental performance: By introducing PMA environmentally friendly diluent into the environmentally friendly solvent mixture and strictly controlling the preparation process, the VOC content of the repair glue is reduced compared with the existing solvent-based adhesive products, effectively reducing the volatilization of harmful gases in the car, creating a healthy and comfortable car environment for drivers and passengers, and conforming to the current development trend of green environmental protection. (3) Accurate repair effect and good adaptability: Due to the selection of a specific particle size range of phenolic resin powder and the fine preparation of the entire formula, the repair adhesive can perform fine repairs on the interior of the car ceiling. Whether it is large-area lamination or filling and repairing of subtle parts, it can achieve good bonding effects and has excellent adaptability to ceiling interiors of different materials (fabric, plastic, composite materials, etc.). The repaired part is naturally integrated with the surrounding interior from the appearance, with almost no traces of repair, which improves the overall aesthetics and quality of the car ceiling interior. (4) Long-term aging resistance: The addition of the new antioxidant DSTDP in the composite antioxidant significantly enhances the anti-aging ability of the adhesive. After accelerated aging tests (tested in accordance with GMW3172), the aging rate of the repair adhesive of the present invention is slowed down by about 20%-30% compared with the traditional repair adhesive. It can maintain the stability of various properties of the adhesive layer for a long time, reduce the failure of ceiling interior repair caused by aging of the adhesive, reduce the frequency of maintenance, and increase the service life of the car ceiling interior. DETAILED DESCRIPTION

[0015] The specific embodiments of the present invention are described in detail below, but it should be understood that the protection scope of the present invention is not limited by the specific embodiments. Example

[0016] A car interior ceiling repair glue comprises the following components by weight: 30 parts of grafting liquid, 8 parts of chloroprene rubber, 10 parts of phenolic resin powder, 1 part of magnesium oxide, 5 parts of chlorinated rubber, 56 parts of environmentally friendly solvent mixed liquid, and 2 parts of composite antioxidant; the chloroprene rubber is chloroprene rubber; the environmentally friendly solvent mixed liquid is prepared by mixing cyclohexane, methyl acetate, acetone, and PMA environmentally friendly diluent in a volume ratio of 3:2:2:1; the composite antioxidant is prepared by compounding BHT, 1010, 168, and a new antioxidant DSTDP in a mass ratio of 1:1:1:2; and the particle size of the phenolic resin powder is controlled to be 50-80 microns.

[0017] The grafting liquid component is a mixed solution of 56 parts of cyclohexane, butanone, and dimethyl carbonate solvent, 12 parts of chloroprene rubber, 12 parts of methyl methacrylate, and 0.2 parts of a composite catalyst of calcium cyclohexane and titanium trichloride, wherein the volume ratio of the cyclohexane, butanone, and dimethyl carbonate solvent is 3:2:2; in the composite catalyst of calcium cyclohexane and titanium trichloride, the mass ratio of calcium cyclohexane and titanium trichloride is 1:1; the preparation method of the grafting liquid comprises the following steps: step 1, adding a mixed solution of cyclohexane, butanone, and dimethyl carbonate solvent into a reactor equipped with a high-precision temperature control system, a high-efficiency stirring device, and a dropping device, turning on the stirring device, and setting the stirring speed to 300r / min; step 2, Add chloroprene rubber into the reactor and continue stirring to pre-dissolve the chloroprene rubber film for 2.5 hours. During this process, the temperature of the solvent is monitored in real time by a temperature sensor to keep it at room temperature (20°C) to achieve uniform dispersion of the chloroprene rubber. Step three, heat the reactor to 85°C at a rate of 2°C per minute, and continue stirring during the heating process. When the set temperature is reached, methyl methacrylate is slowly added to the reactor. At the same time, calcium cyclohexaneate and titanium trichloride composite catalyst are uniformly added to the reactor through a dropping device within 20 minutes. Continue the reaction. During this period, the viscosity change of the reaction system is monitored in real time by an online viscosity monitoring device. When the viscosity reaches 3500cps / 85°C, the reaction is immediately terminated to obtain a grafting liquid.

[0018] The preparation method of the above-mentioned automobile interior ceiling repair glue comprises the following steps: step 1, weighing each component by weight; step 2, adding an environmentally friendly solvent mixture to the grafting liquid, and then adding chloroprene rubber, chlorinated rubber, phenolic resin powder, magnesium oxide and a composite antioxidant in sequence, turning on a high-speed dispersing and stirring device, setting the stirring speed to 1200r / min, and dispersing and stirring for 7 hours. During this process, laser particle size analysis technology and a rheometer are used to monitor the dispersion state of each component in the system and the rheological properties of the glue in real time to ensure that each component is fully and evenly mixed to form a stable glue system; step 3, using a viscosity detection device to detect the viscosity of the glue system obtained in step 2, and fine-tuning the viscosity of the glue system to 500cps / 25°C by butanone; step 4, filtering the glue prepared in step 3 through a 200-mesh high-precision filter device to remove possible impurity particles, and then packaging to obtain a finished automobile ceiling interior repair glue.

[0019] The performance test of the automobile interior ceiling repair adhesive obtained in this embodiment was carried out. A vehicle with a fabric interior ceiling was selected. There was a spot on the ceiling surface with an area of ​​about 100 cm 2 For the damaged and debonded areas and multiple minor scratches, the prepared repair glue was sprayed with a spray gun at room temperature of 25°C and relative humidity of 50%. Example

[0020] A car interior ceiling repair glue comprises the following components by weight: 25 parts of grafting liquid, 8 parts of chloroprene rubber, 12 parts of phenolic resin powder, 1.1 parts of magnesium oxide, 6 parts of chlorinated rubber, 40 parts of environmentally friendly solvent mixed liquid, and 1 part of composite antioxidant; the chloroprene rubber is chloroprene rubber; the environmentally friendly solvent mixed liquid is prepared by mixing cyclohexane, methyl acetate, acetone, and PMA environmentally friendly diluent in a volume ratio of 2:3:2:1; the composite antioxidant is prepared by compounding BHT, 1010, 168, and a new antioxidant DSTDP in a mass ratio of 1:2:1:2; and the particle size of the phenolic resin powder is controlled to be 50-80 microns.

[0021] The grafting liquid components of this embodiment are a mixture of 60 parts of cyclohexane, butanone, and dimethyl carbonate solvent, 10 parts of chloroprene rubber, 11 parts of methyl methacrylate, and 0.3 parts of a composite catalyst of calcium cyclohexane and titanium trichloride, wherein the volume ratio of the cyclohexane, butanone, and dimethyl carbonate solvent is 2:3:3; in the composite catalyst of calcium cyclohexane and titanium trichloride, the mass ratio of calcium cyclohexane and titanium trichloride is 2:1; the preparation method of the grafting liquid comprises the following steps: step 1, adding a mixture of cyclohexane, butanone, and dimethyl carbonate solvent into a reactor equipped with a high-precision temperature control system, a high-efficiency stirring device, and a dropping device, turning on the stirring device, and setting the stirring speed to 280r / min; step 2, Add chloroprene rubber into the reactor and continue stirring to pre-dissolve the chloroprene rubber film for 2.8 hours. During this process, the solvent temperature is monitored in real time by a temperature sensor to keep it at room temperature (24°C) to achieve uniform dispersion of the chloroprene rubber. Step three, heat the reactor to 85°C at a rate of 1.5°C per minute, and continue stirring during the heating process. When the set temperature is reached, methyl methacrylate is slowly added to the reactor. At the same time, calcium cyclopentaneate and titanium trichloride composite catalyst are uniformly added to the reactor through a dropping device within 30 minutes. The reaction is continued. During this period, the viscosity change of the reaction system is monitored in real time by an online viscosity monitoring device. When the viscosity reaches 3200cps / 85°C, the reaction is immediately terminated to obtain a grafting liquid.

[0022] The preparation method of the above-mentioned automobile interior ceiling repair glue comprises the following steps: step 1, weighing each component by weight; step 2, adding an environmentally friendly solvent mixture to the grafting liquid, and then adding chloroprene rubber, chlorinated rubber, phenolic resin powder, magnesium oxide and a composite antioxidant in sequence, turning on a high-speed dispersing and stirring device, setting the stirring speed to 1100r / min, and dispersing and stirring for 8 hours. During this process, laser particle size analysis technology and a rheometer are used to monitor the dispersion state of each component in the system and the rheological properties of the glue in real time to ensure that the components are fully and evenly mixed to form a stable glue system; step 3, using a viscosity detection device to detect the viscosity of the glue system obtained in step 2, and fine-tuning the viscosity of the glue system to 450cps / 25°C through butanone; step 4, filtering the glue prepared in step 3 through a 200-mesh high-precision filter device to remove possible impurity particles, and then packaging to obtain a finished automobile ceiling interior repair glue.

[0023] The performance test of the automobile interior ceiling repair adhesive obtained in this example was carried out on a vehicle whose ceiling interior was made of plastic and had local aging and debonding and small area damage. The repair adhesive was sprayed on the area to be repaired using a spray gun in an environment of 25°C and relative humidity of 45%, and various performance tests were carried out. Example

[0024] A car interior ceiling repair glue comprises the following components by weight: 35 parts of grafting liquid, 10 parts of chloroprene rubber, 5 parts of phenolic resin powder, 1.2 parts of magnesium oxide, 8 parts of chlorinated rubber, 42 parts of environmentally friendly solvent mixed liquid, and 1.5 parts of composite antioxidant; the chloroprene rubber is chloroprene rubber; the environmentally friendly solvent mixed liquid is prepared by mixing cyclohexane, methyl acetate, acetone, and PMA environmentally friendly diluent in a volume ratio of 3:2:1:1; the composite antioxidant is prepared by compounding BHT, 1010, 168, and a new antioxidant DSTDP in a mass ratio of 2:1:1:1; and the particle size of the phenolic resin powder is controlled to be 50-80 microns.

[0025] The grafting liquid components of this embodiment are 54 parts of a mixed solution of cyclohexane, butanone, and dimethyl carbonate solvent, 13 parts of chloroprene rubber, and 0.2 parts of a composite catalyst of calcium cyclohexane and titanium trichloride, wherein the volume ratio of the cyclohexane, butanone, and dimethyl carbonate solvent is 3:2:1; in the composite catalyst of calcium cyclohexane and titanium trichloride, the mass ratio of calcium cyclohexane and titanium trichloride is 1:2; the preparation method of the grafting liquid comprises the following steps: step 1, adding a mixed solution of cyclohexane, butanone, and dimethyl carbonate solvent into a reactor equipped with a high-precision temperature control system, a high-efficiency stirring device, and a dropping device, turning on the stirring device, and setting the stirring speed to 320 r / min; step 2, adding chloroprene rubber Add to the reactor and continue stirring to pre-dissolve the chloroprene rubber film for 2 hours. During this process, the solvent temperature is monitored in real time by a temperature sensor to keep it at room temperature (25°C) to achieve uniform dispersion of the chloroprene rubber; Step three, heat the reactor to 85°C at a rate of 1.5°C per minute, and continue stirring during the heating process. When the set temperature is reached, methyl methacrylate is slowly added to the reactor. At the same time, calcium cyclohexaneate and titanium trichloride composite catalyst are uniformly added to the reactor through a dropping device within 25 minutes. Continue the reaction. During this period, the viscosity change of the reaction system is monitored in real time by an online viscosity monitoring device. When the viscosity reaches 3000cps / 85°C, the reaction is immediately terminated to obtain a grafting liquid.

[0026] The preparation method of the above-mentioned automobile interior ceiling repair glue comprises the following steps: step 1, weighing each component by weight; step 2, adding an environmentally friendly solvent mixture to the grafting liquid, and then adding chloroprene rubber, chlorinated rubber, phenolic resin powder, magnesium oxide and a composite antioxidant in sequence, turning on a high-speed dispersing and stirring device, setting the stirring speed to 1200r / min, and dispersing and stirring for 6.5 hours. During this process, laser particle size analysis technology and a rheometer are used to monitor the dispersion state of each component in the system and the rheological properties of the glue in real time to ensure that the components are fully and evenly mixed to form a stable glue system; step 3, using a viscosity detection device to detect the viscosity of the glue system obtained in step 2, and fine-tuning the viscosity of the glue system to 600cps / 25°C through acetone; step 4, filtering the glue prepared in step 3 through a 200-mesh high-precision filter device to remove possible impurity particles, and then packaging to obtain a finished automobile ceiling interior repair glue.

[0027] The performance test of the automobile interior ceiling repair adhesive obtained in this example was carried out. A vehicle whose interior ceiling was made of composite material (including a combination of fabric and plastic) and had multiple damages and gaps of varying degrees was selected for repair work. At room temperature (28°C and relative humidity of 55%), the repair adhesive was sprayed on the repaired area using a spray gun, and the performance test was carried out. Example

[0028] A car interior ceiling repair glue comprises the following components by weight: 30 parts of grafting liquid, 5 parts of chloroprene rubber, 8 parts of phenolic resin powder, 1 part of magnesium oxide, 4 parts of chlorinated rubber, 70 parts of environmentally friendly solvent mixed liquid, and 3 parts of composite antioxidant; the chloroprene rubber is chloroprene rubber; the environmentally friendly solvent mixed liquid is prepared by mixing cyclohexane, methyl acetate, acetone, and PMA environmentally friendly diluent in a volume ratio of 3:2:2:1; the composite antioxidant is prepared by compounding BHT, 1010, 168, and a new antioxidant DSTDP in a mass ratio of 1:1:1:2; and the particle size of the phenolic resin powder is controlled to be 50-80 microns.

[0029] The grafting liquid components of this embodiment are a mixture of 56 parts of cyclohexane, butanone, and dimethyl carbonate solvent, 15 parts of chloroprene rubber, 10 parts of methyl methacrylate, and 0.4 parts of a composite catalyst of calcium cyclohexane and titanium trichloride, wherein the volume ratio of the cyclohexane, butanone, and dimethyl carbonate solvent is 3:2:2; in the composite catalyst of calcium cyclohexane and titanium trichloride, the mass ratio of calcium cyclohexane and titanium trichloride is 1:1.5; the preparation method of the grafting liquid comprises the following steps: step 1, adding a mixture of cyclohexane, butanone, and dimethyl carbonate solvent into a reactor equipped with a high-precision temperature control system, a high-efficiency stirring device, and a dropping device, turning on the stirring device, and setting the stirring speed to 300r / min; step 2, Step 2. Add chloroprene rubber into the reactor and continue stirring to pre-dissolve the chloroprene rubber film for 3 hours. During this process, the solvent temperature is monitored in real time by a temperature sensor to keep it at room temperature (30°C) to achieve uniform dispersion of the chloroprene rubber. Step 3. Heat the reactor to 85°C at a rate of 1.8°C per minute and continue stirring during the heating process. When the set temperature is reached, methyl methacrylate is slowly added to the reactor. At the same time, calcium cyclohexaneate and titanium trichloride composite catalyst are uniformly added to the reactor through a dropping device within 30 minutes. Continue the reaction. During this period, the viscosity change of the reaction system is monitored in real time by an online viscosity monitoring device. When the viscosity reaches 3500cps / 85°C, the reaction is immediately terminated to obtain a grafting liquid.

[0030] The preparation method of the above-mentioned automobile interior ceiling repair glue comprises the following steps: step 1, weighing each component by weight; step 2, adding an environmentally friendly solvent mixture to the grafting liquid, and then adding chloroprene rubber, chlorinated rubber, phenolic resin powder, magnesium oxide and a composite antioxidant in sequence, turning on a high-speed dispersing and stirring device, setting the stirring speed to 1150r / min, and dispersing and stirring for 7 hours. During this process, laser particle size analysis technology and a rheometer are used to monitor the dispersion state of each component in the system and the rheological properties of the glue in real time to ensure that each component is fully and evenly mixed to form a stable glue system; step 3, using a viscosity detection device to detect the viscosity of the glue system obtained in step 2, and fine-tuning the viscosity of the glue system to 400cps / 25°C through acetone; step 4, filtering the glue prepared in step 3 through a 200-mesh high-precision filter device to remove possible impurity particles, and then packaging to obtain a finished automobile ceiling interior repair glue.

[0031] The performance test of the automobile interior ceiling repair adhesive obtained in this embodiment was carried out. A vehicle with a fabric interior ceiling was selected. There was a spot on the ceiling surface with an area of ​​about 100 cm 2 The damaged and debonded areas and multiple minor scratches were repaired by spraying the prepared repair glue with a spray gun at room temperature (23°C) and a relative humidity of 50%, and a performance test was carried out.

[0032] The adhesive strength test of the repaired ceiling was carried out in accordance with GB / T 5210-2006, using the standard pull-out test method, and the relevant results are shown in Table 1. The vehicle was placed in a simulated high and low temperature environment test chamber, and a high and low temperature cycle test from -30°C to 85°C was carried out, with the number of cycles being 20 times, and the relevant appearance observation results are shown in Table 1. The VOC content, appearance effect and spray performance of the repaired ceiling were tested and evaluated, and the relevant results are shown in Table 1. Example

[0033] A car interior ceiling repair glue comprises the following components by weight: 28 parts of grafting liquid, 10 parts of chloroprene rubber, 10 parts of phenolic resin powder, 1.2 parts of magnesium oxide, 3 parts of chlorinated rubber, 64 parts of environmentally friendly solvent mixed liquid, and 1.8 parts of composite antioxidant; the chloroprene rubber is chloroprene rubber; the environmentally friendly solvent mixed liquid is prepared by mixing cyclohexane, methyl acetate, acetone, and PMA environmentally friendly diluent in a volume ratio of 2:3:2:1; the composite antioxidant is prepared by compounding BHT, 1010, 168, and a new antioxidant DSTDP in a mass ratio of 1:2:1:2; and the particle size of the phenolic resin powder is controlled to be 50-80 microns.

[0034] The grafting liquid components of this embodiment are a mixture of 50 parts of cyclohexane, butanone, and dimethyl carbonate solvent, 10 parts of chloroprene rubber, 15 parts of methyl methacrylate, and 0.2 parts of a composite catalyst of calcium cyclohexane and titanium trichloride, wherein the volume ratio of the cyclohexane, butanone, and dimethyl carbonate solvent is 2:3:2; in the composite catalyst of calcium cyclohexane and titanium trichloride, the mass ratio of calcium cyclohexane and titanium trichloride is 1:1; the preparation method of the grafting liquid comprises the following steps: step 1, adding a mixture of cyclohexane, butanone, and dimethyl carbonate solvent into a reactor equipped with a high-precision temperature control system, a high-efficiency stirring device, and a dropping device, turning on the stirring device, and setting the stirring speed to 280 r / min; step 2 , add chloroprene rubber to the reactor, and continue stirring to pre-dissolve the chloroprene rubber film for 2.5 hours. During this process, the solvent temperature is monitored in real time by a temperature sensor to keep it at room temperature (35°C) to achieve uniform dispersion of the chloroprene rubber; Step three, heat the reactor to 85°C at a rate of 2°C per minute, and continue stirring during the heating process. When the set temperature is reached, methyl methacrylate is slowly added to the reactor. At the same time, calcium cyclohexaneate and titanium trichloride composite catalyst are uniformly added to the reactor through a dropping device within 30 minutes. Continue the reaction. During this period, the viscosity change of the reaction system is monitored in real time by an online viscosity monitoring device. When the viscosity reaches 3000cps / 85°C, the reaction is immediately terminated to obtain a grafting liquid.

[0035] The preparation method of the above-mentioned automobile interior ceiling repair glue comprises the following steps: step 1, weighing each component by weight; step 2, adding an environmentally friendly solvent mixture to the grafting liquid, and then adding chloroprene rubber, chlorinated rubber, phenolic resin powder, magnesium oxide and a composite antioxidant in sequence, turning on a high-speed dispersing and stirring device, setting the stirring speed to 1300r / min, and dispersing and stirring for 6 hours. During this process, laser particle size analysis technology and a rheometer are used to monitor the dispersion state of each component in the system and the rheological properties of the glue in real time to ensure that the components are fully and evenly mixed to form a stable glue system; step 3, using a viscosity detection device to detect the viscosity of the glue system obtained in step 2, and fine-tuning the viscosity of the glue system to 450cps / 25°C through acetone; step 4, filtering the glue prepared in step 3 through a 200-mesh high-precision filter device to remove possible impurity particles, and then packaging to obtain a finished automobile ceiling interior repair glue.

[0036] The performance test of the automobile interior ceiling repair adhesive obtained in this example was conducted on a vehicle whose ceiling interior was made of plastic and had local aging and debonding and small area damage. The repair adhesive was sprayed on the area to be repaired using a spray gun at room temperature (25°C) and relative humidity of 45%, and the performance test was conducted. The results are shown in Table 1.

[0037] The automotive interior ceiling repair adhesive prepared in Examples 1 to 5 was tested for bonding strength in different application scenarios according to GB / T 5210-2006, using a standard pull-out test method, and the relevant results are shown in Table 1. The vehicle was placed in a simulated high and low temperature environment test chamber, and a high and low temperature cycle test from -30°C to 85°C was performed, with 20 cycles, and the relevant appearance observation results are shown in Table 1. The VOC content, appearance effect and spray performance of the repaired ceiling were tested and evaluated, and the relevant results are shown in Table 1. The performance indicators of various aspects are analyzed as follows: 1. Bonding strength: The bonding strength of each embodiment is close to or reaches 1.5MPa, which meets the actual use requirements. This shows that the proportion of grafting liquid solvent, the proportion of environmentally friendly solvent mixed liquid, and the proportion of antioxidant compound designed by the present invention can provide good bonding performance for the adhesive under the overall formulation system.

[0038] 2. High and low temperature resistance: After 20 high and low temperature cycles from -30°C to 85°C, the adhesive layers of all examples remained in good condition without cracking or debonding. This shows that the ingredients in the formula have good stability under different temperature environments, and the composite antioxidant effectively inhibits the aging and performance degradation of the adhesive under high and low temperature environments, ensuring the long-lasting bonding ability of the adhesive under different temperature conditions.

[0039] 3. Total VOC content: The total VOC content of each example is far lower than the relevant standard requirements, and the eight restricted solvents are not detected (the restricted solvent standard requirements are shown in Table 2), which meets the environmental protection requirements. This shows that the selection and use of environmentally friendly solvents in the formula are properly controlled, reducing the volatilization of harmful substances from the source, while ensuring the performance of the adhesive, reducing the impact on the air quality in the car.

[0040] 4. Appearance: The appearance of the ceiling after repair in each embodiment is good, and the repaired area blends naturally with the surrounding area, and almost no trace of repair is visible. This is due to the good fluidity of the adhesive and the flatness after drying, which enables it to perfectly fill the damaged area and form a consistent appearance with the surrounding materials.

[0041] 5. Spraying performance: The adhesives in the embodiments all showed good performance during the spraying process, and the spraying was uniform and smooth without sagging. This is related to the viscosity control of the adhesive and the volatilization rate of the solvent. The appropriate viscosity and volatilization rate ensure that the adhesive can be evenly covered on the ceiling surface during spraying, and will not cause sagging due to drying too fast or too slow. Different solvent ratios can meet the requirements of spraying construction while ensuring overall performance.

[0042] Table 1 Summary of performance test data of Examples 1-5 after application to automobile ceiling Example Bond Strength High and low temperature resistance (-30℃ to 85℃, after 20 cycles) Total VOC content Appearance Spraying performance 1 1.5MPa The adhesive layer is firm, without cracking or debonding <![CDATA[30mg / m 3 ]]> Blending naturally with the surroundings, with almost no signs of repair Spray evenly and smoothly without dripping 2 1.4MPa The adhesive layer is complete without obvious defects <![CDATA[28mg / m 3 ]]> The repair is natural and not easy to detect Smooth spraying without sagging and clogging 3 1.5MPa No cracking or debonding <![CDATA[32mg / m 3 ]]> Overall beauty, repairs are not obvious Spray smoothly without any abnormality 4 1.45MPa The adhesive layer is firm, without debonding or cracking <![CDATA[29mg / m 3 ]]> Coordinate with the surrounding area, no obvious difference Even spraying without sagging problem 5 1.5MPa Keep good and no bad situation <![CDATA[31mg / m 3 ]]> Good appearance and high integration Good spraying effect, no sagging Table 2 Control requirements for eight restricted solvents in GB / T 27630-2011 Concentration requirement unit <![CDATA[mg / m 3 ]]> benzene ≤0.11 Toluene ≤1.10 Xylene ≤1.50 Ethylbenzene ≤1.50 Styrene ≤0.26 formaldehyde ≤0.10 Acetaldehyde ≤0.05 Acrolein ≤0.05

Claims

1. A car interior ceiling repair adhesive, characterized in that: The components are as follows by weight: 25-35 parts of grafting liquid, 5-10 parts of chloroprene rubber, 5-15 parts of phenolic resin powder, 0.8-1.2 parts of magnesium oxide, 3-8 parts of chlorinated rubber, 40-70 parts of environmentally friendly solvent mixed liquid, and 1-3 parts of composite antioxidant; the chloroprene rubber is chloroprene rubber; the environmentally friendly solvent mixed liquid is a mixed liquid of cyclohexane, methyl acetate, acetone and propylene glycol methyl ether acetate; the composite antioxidant is compounded by BHT, 1010, 168 and distearyl thiodipropionate.

2. The automotive interior ceiling repair adhesive according to claim 1, characterized in that: The grafting liquid is prepared from a mixed liquid of 50-60 parts of cyclohexane, butanone and dimethyl carbonate solvent, 10-15 parts of chloroprene rubber, 10-15 parts of methyl methacrylate and 0.2-0.4 parts of a composite catalyst of calcium naphthenate and titanium trichloride.

3. The automotive interior ceiling repair adhesive according to claim 2, characterized in that: The preparation method of the grafting liquid comprises the following steps: step 1, adding a mixed solution of cyclohexane, butanone and dimethyl carbonate solvent into a reaction kettle equipped with a high-precision temperature control system, a high-efficiency stirring device and a dropping device, turning on the stirring device, and setting the stirring speed to 280-320 r / min; step 2, adding chloroprene rubber into the reaction kettle, and continuously stirring to pre-dissolve the chloroprene rubber film for 2-3 hours. During this process, the temperature of the solvent is monitored in real time by a temperature sensor to keep the solvent at room temperature so as to achieve uniform dispersion of the chloroprene rubber. Step 3: Heat the reactor to 85°C at a rate of 1.5-2°C per minute, and continue stirring during the heating process. When the set temperature of 85°C is reached, methyl methacrylate is slowly added to the reactor. At the same time, calcium cyclohexaneate and titanium trichloride composite catalyst are uniformly added to the reactor through a dropping device within 20-30 minutes. The reaction is continued. During this period, the viscosity change of the reaction system is monitored in real time through an online viscosity monitoring device. When the viscosity reaches 3000-3500cps / 85°C, the reaction is immediately terminated to obtain a grafting liquid.

4. The automotive interior ceiling repair adhesive according to claim 2, characterized in that: The volume ratio of cyclohexane, butanone and dimethyl carbonate solvent in the grafting liquid is one of 3:2:2, 2:3:3 and 3:2:

1.

5. The automotive interior ceiling repair adhesive according to claim 1, characterized in that: The environmentally friendly solvent mixture is prepared by mixing cyclohexane, methyl acetate, acetone, and propylene glycol methyl ether acetate in a volume ratio of 3:2:2:1 or 2:3:2:1 or 3:2:1:

1.

6. The automobile interior ceiling repair adhesive according to claim 1, characterized in that: The composite antioxidant is prepared by compounding BHT, 1010, 168 and distearyl thiodipropionate in a mass ratio of 1:1:1:2 or 1:2:1:2 or 2:1:1:

1.

7. The automotive interior ceiling repair adhesive according to claim 1, characterized in that: The particle size of the phenolic resin powder is 50-80 microns.

8. A method for preparing an automobile interior ceiling repair adhesive according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: step 1, weighing each component by weight; step 2, adding an environmentally friendly solvent mixture to the grafting liquid, and then sequentially adding chloroprene rubber, chlorinated rubber, phenolic resin powder, magnesium oxide and a composite antioxidant, starting a high-speed dispersing and stirring device, setting the stirring speed to 1100-1300 r / min, and dispersing and stirring for 6-8 hours, during which a laser particle size analysis technology and a rheometer are used to monitor the dispersion state of each component in the system and the rheological properties of the adhesive solution in real time, so as to ensure that each component is fully and evenly mixed to form a stable adhesive solution system; step 3, using a viscosity detection device to detect the viscosity of the adhesive solution system obtained in step 2, and fine-tuning the viscosity of the adhesive solution system by using butanone or acetone to make the viscosity range of the adhesive solution system within 400-600 cps / 25°C; step 4, filtering the adhesive solution prepared in step 3 through a 200-mesh high-precision filter device to remove possible impurity particles, and then packaging to obtain a finished automobile ceiling interior repair adhesive.