High-adhesion automotive trim surface treating agent and preparation method thereof

Abstract

The invention relates to the technical field of preparation of polysiloxane surface treating agents, and discloses a high-adhesion automotive interior surface treating agent and a preparation method thereof. Comprising the following raw materials in parts by mass: 80-100 parts of acrylic acid modified polysiloxane resin, 5-10 parts of polydimethylsiloxane, 5-8 parts of reinforcing filler, 2-5 parts of an amino silane coupling agent, 0.1-0.5 part of a flatting agent and 1-2 parts of a thickening agent. According to the present invention, the acrylic acid modified polysiloxane resin is adopted as the matrix, and the polydimethylsiloxane, the reinforcing filler, the amino silane coupling agent, the leveling agent and the thickening agent are compounded, such that the prepared automobile interior surface treatment agent has high adhesion, can improve the wear resistance of the automobile interior after being sprayed on the surface of the automobile interior, and further has the good wear resistance, the added reinforcing filler can be uniformly dispersed in a polysiloxane surfactant system, so that the adhesive force and the wear resistance of the polysiloxane surfactant are improved.

Description

Technical Field

[0001] This invention relates to the field of polysiloxane surface treatment agent preparation technology, specifically to a high-adhesion automotive interior surface treatment agent and its preparation method. Background Technology

[0002] Automotive interiors are typically made of materials such as polypropylene, acrylonitrile-butadiene-styrene copolymer, polycarbonate, and thermoplastic polyolefins. While these materials have good mechanical and processing properties, their surfaces often lack a pleasant tactile feel and are prone to accumulating dust. Currently, automotive interior surface treatment agents are often used to clean, polish, and protect automotive interiors, improving their surface performance by removing stains and applying a glossy layer.

[0003] Surface treatment agents are often used to improve the surface properties of interior parts. Polysiloxanes are widely used in such treatment agents due to their unique flexibility, resistance to high and low temperatures, weather resistance, and ability to provide an excellent smooth feel. However, polysiloxane surface treatment agents have a high Si-O bond content and inorganic hybrid characteristics. The film formed is close to an inorganic system and is easy to peel off from the automotive interior, resulting in poor adhesion. Summary of the Invention

[0004] This invention provides a high-adhesion automotive interior surface treatment agent and its preparation method, which solves the problem that polysiloxane surface treatment agents have inorganic hybrid characteristics, and the film-forming material is close to an inorganic system, making it easy to peel off from automotive interiors and resulting in poor adhesion.

[0005] The technical solution of the present invention:

[0006] A high-adhesion automotive interior surface treatment agent, comprising the following raw materials in parts by weight: 80-100 parts of acrylic modified polysiloxane resin, 5-10 parts of polydimethylsiloxane, 5-8 parts of reinforcing filler, 2-5 parts of aminosilane coupling agent, 0.1-0.5 parts of leveling agent, and 1-2 parts of thickener;

[0007] The reinforcing filler is obtained by surface-treating potassium titanate whiskers with silane coupling agent and then reacting them with carboxyl-polyethylene glycol-carboxyl and hydroxyl-terminated polydimethylsiloxane.

[0008] Composite potassium titanate whiskers are obtained by synthesizing a porous carbon layer on the surface of potassium titanate whiskers, and then reacting it with zirconium oxychloride octahydrate and ammonia.

[0009] A method for preparing a high-adhesion automotive interior surface treatment agent includes the following preparation steps:

[0010] Acrylic-modified polysiloxane resin and polydimethylsiloxane are mixed and stirred at 800-1000 r / min for 10-15 min. Reinforcing filler, aminosilane coupling agent, leveling agent and thickener are added and stirred at 50-60℃ and 2500-3000 r / min for 15-20 min to obtain automotive interior surface treatment agent.

[0011] Furthermore, the temperature of the twin-screw extruder is 125-135℃ in zone one, 145-155℃ in zone two, 160-170℃ in zone three, 165-175℃ in the die head, and the screw speed is 30-40 rpm.

[0012] Furthermore, the aminosilane coupling agent is selected from any one of γ-aminopropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, and N-β(aminoethyl)-γ-aminopropyltriethoxysilane.

[0013] Furthermore, the leveling agent is selected from any one of the leveling agents BYK-320, BYK-354, and FL2028.

[0014] Furthermore, the thickener is selected from any one of methylcellulose, hydroxypropyl methylcellulose, sodium carboxymethylcellulose, and hydroxyethylcellulose.

[0015] Furthermore, the reinforcing filler is specifically prepared by the following steps:

[0016] A1. After mixing potassium titanate whiskers, tannic acid and ethanol evenly, glucose is added, stirred, removed and dried, placed in a tube furnace, potassium hydroxide solution is added, nitrogen gas is introduced, carbonized at 800-900℃ for 4-5 hours, cooled to room temperature, removed, washed and dried to obtain modified potassium titanate whiskers.

[0017] A2. After mixing zirconium oxychloride octahydrate, modified potassium titanate whiskers and deionized water evenly, ammonia, glycine and potassium chloride are added, stirred evenly, placed in a reaction vessel, and subjected to hydrothermal reaction at 170-190℃ for 20-22h. After cooling to room temperature, the mixture is filtered, washed and dried to obtain composite potassium titanate whiskers.

[0018] A3. Mix the composite potassium titanate whiskers, ethanol and deionized water evenly, add silane coupling agent, stir the reaction, cool to room temperature, filter, wash and dry to obtain epoxidized composite potassium titanate whiskers.

[0019] A4. Add the epoxidized composite potassium titanate whiskers to ethanol, stir well, add hydrochloric acid, stir, filter, and collect the solid;

[0020] Hydroxyl-terminated polydimethylsiloxane, carboxyl-polyethylene glycol-carboxyl, and toluene were mixed and stirred until homogeneous. P-toluenesulfonic acid was added, and nitrogen gas was introduced. The mixture was stirred and reacted at 100-110℃ for 3-4 hours. The solid was added, and the reaction was continued for 1-2 hours. After cooling, triethylamine was added to neutralize the p-toluenesulfonic acid. The temperature was then raised again, and toluene was removed under reduced pressure to obtain the reinforcing filler.

[0021] Furthermore, in the above A1 reaction process, tannic acid contains a large number of phenolic hydroxyl groups, which have good adhesion and act as a linker, allowing the carbon precursor glucose to be coated onto the surface of potassium titanate whiskers through tannic acid. After high-temperature carbonization, the glucose decomposes to form a dense carbon layer. Potassium hydroxide acts as an activator, forming channels on the surface of the dense carbon layer, thereby achieving the coating of a porous carbon layer on the surface of potassium titanate whiskers and obtaining modified potassium titanate whiskers.

[0022] Furthermore, during the A2 reaction process described above, the modified potassium titanate whisker surface contains a large number of porous structures, which can adsorb zirconium ions from zirconium oxychloride octahydrate onto the modified potassium titanate whisker surface. Ammonia water, as a precipitant, can react with the zirconium ions adsorbed into the pores on the modified potassium titanate whisker surface to form zirconium hydroxide precipitate. After hydrothermal reaction, the formed zirconium hydroxide precipitate decomposes to form zirconium oxide crystals. Glycine and potassium chloride can regulate the crystal phase of zirconium dioxide, thereby forming nano-zirconium dioxide on the surface and in the pores of the modified potassium titanate whisker, resulting in composite potassium titanate whiskers.

[0023] Furthermore, during the A3 reaction process described above, the silanol groups generated by the hydrolysis of the silane coupling agent can chemically bond with the hydroxyl groups on the surface of the composite potassium titanate whiskers, thereby grafting the silane coupling agent onto the surface of the composite potassium titanate whiskers to obtain epoxidized composite potassium titanate whiskers.

[0024] Furthermore, during the A4 reaction process described above, the epoxidized composite potassium titanate whiskers undergo ring-opening under acidic conditions, which is beneficial for the epoxidized composite potassium titanate whiskers to participate in the polycondensation reaction of carboxyl-polyethylene glycol-carboxyl and hydroxyl-terminated polydimethylsiloxane.

[0025] The carboxyl group of carboxyl-polyethylene glycol-carboxyl undergoes a polycondensation reaction with the hydroxyl group of hydroxyl-terminated polydimethylsiloxane to form a polyether segment modified polysiloxane. During the reaction, the hydroxyl groups generated by the ring opening of the epoxy groups in the epoxidized composite potassium titanate whiskers can also participate in the reaction, thereby forming a polyether segment modified polysiloxane on the surface of the composite potassium titanate whiskers and obtaining a reinforcing filler.

[0026] Further, in step A1, the mass ratio of potassium titanate whiskers, tannic acid, ethanol, glucose and potassium hydroxide solution is (4-5):(0.5-1):(180-220):(2.5-3):(1.5-2).

[0027] Further, in step A2, the mass ratio of zirconium oxychloride octahydrate, modified potassium titanate whiskers, deionized water, ammonia, glycine, and potassium chloride is (2-2.4):(4.5-5):(150-170):(1.5-2):(0.3-0.5):(0.7-0.9).

[0028] Further, in step A3, the mass ratio of composite potassium titanate whiskers, ethanol, deionized water and silane coupling agent is (4-4.5):(120-130):(40-50):(1-1.2).

[0029] Further, in step A4, the mass ratio of epoxidized composite potassium titanate whiskers, ethanol and hydrochloric acid is (4-4.5):(20-30):(1-2).

[0030] Further, in step A4, the mass ratio of hydroxyl-terminated polydimethylsiloxane, carboxyl-polyethylene glycol-carboxyl, toluene, p-toluenesulfonic acid, and solids is (9-15):(1-1.5):(20-25):(0.3-0.8):(4-4.2).

[0031] The present invention has the following beneficial effects:

[0032] (1) In the technical solution of the present invention, a porous carbon layer is synthesized on the surface of potassium titanate whiskers. On the one hand, the surface roughness of potassium titanate whiskers is improved, the contact area between potassium titanate whiskers and polysiloxane resin is enhanced, and the porous carbon has a three-dimensional network pore structure with high adsorption performance. It can be adsorbed on the surface of automotive interior and enhance the adhesion of polysiloxane surfactant on the surface of automotive interior. On the other hand, potassium titanate whiskers have a high aspect ratio and can be randomly dispersed in the polysiloxane surfactant system to form a micro-skeleton in the surfactant matrix, absorb and weaken the energy generated by external force, and improve the wear resistance of the paint film.

[0033] (2) In the technical solution of the present invention, nano-zirconia is formed on the surface and in the channels of modified potassium titanate whiskers. On the one hand, the synthesized nano-zirconia, as a wear-resistant aggregate, can improve the wear resistance of polysiloxane surfactant. Moreover, the surface of nano-zirconia contains a large number of hydroxyl groups, which can be adsorbed on the surface of automotive interior and enhance the adhesion of polysiloxane surfactant to the surface of automotive interior. On the other hand, the modified potassium titanate whiskers, as a carrier of nano-zirconia, have nano-zirconia agglomerate on the surface, which affects the adhesion and wear resistance of polysiloxane surfactant. In addition, during the process of polysiloxane surfactant forming a paint film on the surface of automotive interior, nano-zirconia can fill the gaps in the paint film, improve the density of the paint film, and enhance the adhesion of polysiloxane surfactant to the surface of automotive interior.

[0034] (3) In the technical solution of this invention, the composite potassium titanate whiskers are surface-treated with a silane coupling agent to impart reactive functional groups (epoxy groups) to the composite potassium titanate whiskers. This facilitates the synthesis of polyether segment-modified polysiloxanes on the surface of the composite potassium titanate whiskers, allowing the composite potassium titanate whiskers to be uniformly dispersed in the polysiloxane surfactant system, thereby enhancing the wear resistance and adhesion of the polysiloxane surfactant. The epoxidized composite potassium titanate whiskers are mixed and reacted with carboxyl-polyethylene glycol-carboxyl and hydroxyl-terminated polydimethylsiloxane to achieve the formation of polyether segment-modified polysiloxanes on the surface of the composite potassium titanate whiskers. On the one hand, the polyether segment modified polysiloxane formed by carboxyl-polyethylene glycol-carboxyl and hydroxyl-terminated polydimethylsiloxane contains a large number of long-chain aliphatic structures, which can effectively reduce the crosslinking density of the polysiloxane surfactant film and improve the adhesion of the polysiloxane surfactant to the automotive interior. On the other hand, the polyether segment modified polysiloxane contains a large number of siloxane bonds, which have good compatibility with the polysiloxane surfactant matrix, so that the composite potassium titanate whiskers are uniformly dispersed in the polysiloxane surfactant system, enhancing the wear resistance and adhesion of the polysiloxane surfactant.

[0035] (4) In the technical solution of the present invention, the automotive interior surface treatment agent prepared by using acrylic modified polysiloxane resin as the matrix and compounding polydimethylsiloxane, reinforcing filler, aminosilane coupling agent, leveling agent and thickener has high adhesion and can improve the wear resistance of automotive interior when sprayed on the surface of automotive interior. In addition, the added reinforcing filler can be uniformly dispersed in the polysiloxane surfactant system to improve the adhesion and wear resistance of polysiloxane surfactant. Detailed Implementation

[0036] 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.

[0037] The raw materials used in the embodiments of this invention are shown below, and all reagents used are analytical grade.

[0038] Among them, the acrylic modified polysiloxane resin, with a viscosity of 350 mPa·s, was purchased from Shanghai Huarong Chemical Co., Ltd.

[0039] The polydimethylsiloxane, catalog number D849784, was purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0040] The aminosilane coupling agent is γ-aminopropyltriethoxysilane, the leveling agent is leveling agent BYK-320, and the thickener is methylcellulose.

[0041] Potassium titanate whiskers, product number: P790560 The sample has a diameter of 0.3 μm and a length of 5 μm and was purchased from Shanghai McLean Biochemical Technology Co., Ltd.

[0042] The silane coupling agent is KH560 (γ-glycidoxypropyltrimethoxysilane).

[0043] Hydroxyl-terminated polydimethylsiloxane, industrial grade, with a hydroxyl mass fraction greater than 6%, purchased from Shanghai Resin Factory Co., Ltd.

[0044] Carboxyl-polyethylene glycol with a molecular weight of 2000 was purchased from Chongqing Yusi Pharmaceutical Technology Co., Ltd.

[0045] Example 1

[0046] A high-adhesion automotive interior surface treatment agent comprises the following raw materials in parts by weight: 80 parts of acrylic modified polysiloxane resin, 5 parts of polydimethylsiloxane, 5 parts of reinforcing filler, 2 parts of γ-aminopropyltriethoxysilane, 0.1 parts of leveling agent BYK-320, and 1 part of methylcellulose;

[0047] A method for preparing a high-adhesion automotive interior surface treatment agent includes the following preparation steps:

[0048] Acrylic-modified polysiloxane resin and polydimethylsiloxane were mixed and stirred at 800 r / min for 10 min. Reinforcing filler, γ-aminopropyltriethoxysilane, leveling agent BYK-320 and methylcellulose were added and stirred at 50℃ and 2500 r / min for 15 min to obtain an automotive interior surface treatment agent.

[0049] The reinforcing filler is prepared by the following steps:

[0050] A1. After mixing potassium titanate whiskers, tannic acid, and ethanol evenly, glucose was added, and the mixture was stirred at 70°C for 30 min. The mixture was then removed and dried in an oven at 70°C for 20 min. The mixture was placed in a tube furnace, and a 30% (w / w) potassium hydroxide solution was added. Nitrogen gas was introduced, and the mixture was carbonized at 800°C for 4 h. After cooling to room temperature, the mixture was removed, washed three times with deionized water, and dried in an oven at 70°C for 10 min to obtain modified potassium titanate whiskers. The mass ratio of potassium titanate whiskers, tannic acid, ethanol, glucose, and potassium hydroxide solution was 4:0.5:180:2.5:1.5.

[0051] A2. Zirconium oxychloride octahydrate, modified potassium titanate whiskers, and deionized water were mixed evenly, and then ammonia, glycine, and potassium chloride were added. The mixture was stirred evenly and placed in a reaction vessel. The mixture was subjected to a hydrothermal reaction at 170°C for 20 hours. After cooling to room temperature, the mixture was filtered, washed three times with deionized water, and dried in an oven at 80°C for 10 minutes to obtain composite potassium titanate whiskers. The mass ratio of zirconium oxychloride octahydrate, modified potassium titanate whiskers, deionized water, ammonia, glycine, and potassium chloride was 2:4.5:150:1.5:0.3:0.7.

[0052] A3. Mix the composite potassium titanate whiskers, ethanol, and deionized water evenly, add KH560, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain epoxidized composite potassium titanate whiskers; the mass ratio of composite potassium titanate whiskers, ethanol, deionized water, and KH560 is 4:120:40:1.

[0053] A4. Add the epoxidized composite potassium titanate whiskers to ethanol, stir evenly, add 36% hydrochloric acid by mass, stir at 70℃ for 30 min, filter and collect the solid; the mass ratio of epoxidized composite potassium titanate whiskers, ethanol and hydrochloric acid is 4:20:1.

[0054] Hydroxyl-terminated polydimethylsiloxane, carboxyl-polyethylene glycol-carboxyl, and toluene were mixed and stirred until homogeneous. P-toluenesulfonic acid was added, and nitrogen gas was introduced. The mixture was stirred at 100°C for 3 hours. A solid was added, and the reaction was continued for 1 hour. The temperature was lowered to 60°C, and triethylamine was added to neutralize the p-toluenesulfonic acid. The temperature was then raised to 130°C, and toluene was removed under reduced pressure to obtain the reinforcing filler. The mass ratio of hydroxyl-terminated polydimethylsiloxane, carboxyl-polyethylene glycol-carboxyl, toluene, p-toluenesulfonic acid, and solid was 9:1:20:0.3:4.

[0055] Example 2

[0056] A high-adhesion automotive interior surface treatment agent comprises the following raw materials in parts by weight: 90 parts of acrylic modified polysiloxane resin, 8 parts of polydimethylsiloxane, 6 parts of reinforcing filler, 3 parts of γ-aminopropyltriethoxysilane, 0.3 parts of leveling agent BYK-320, and 1.5 parts of methylcellulose;

[0057] A method for preparing a high-adhesion automotive interior surface treatment agent includes the following preparation steps:

[0058] Acrylic-modified polysiloxane resin and polydimethylsiloxane were mixed and stirred at 900 r / min for 13 min. Reinforcing filler, γ-aminopropyltriethoxysilane, leveling agent BYK-320 and methylcellulose were added and stirred at 55℃ and 2800 r / min for 18 min to obtain an automotive interior surface treatment agent.

[0059] The reinforcing filler is prepared by the following steps:

[0060] A1. Potassium titanate whiskers, tannic acid, and ethanol were mixed evenly, and then glucose was added. The mixture was stirred at 70°C for 30 min, removed, and dried in a 70°C oven for 20 min. The mixture was then placed in a tube furnace, and a 30% potassium hydroxide solution was added. Nitrogen gas was introduced, and the mixture was carbonized at 850°C for 4.5 h. After cooling to room temperature, the mixture was removed, washed three times with deionized water, and dried in a 70°C oven for 10 min to obtain modified potassium titanate whiskers. The mass ratio of potassium titanate whiskers, tannic acid, ethanol, glucose, and potassium hydroxide solution was 4.5:0.8:200:2.8:1.8.

[0061] A2. Zirconium oxychloride octahydrate, modified potassium titanate whiskers, and deionized water were mixed evenly, and then ammonia, glycine, and potassium chloride were added. The mixture was stirred evenly and placed in a reaction vessel. The mixture was subjected to a hydrothermal reaction at 180°C for 21 hours. After cooling to room temperature, the mixture was filtered, washed three times with deionized water, and dried in an oven at 80°C for 10 minutes to obtain composite potassium titanate whiskers. The mass ratio of zirconium oxychloride octahydrate, modified potassium titanate whiskers, deionized water, ammonia, glycine, and potassium chloride was 2.2:4.8:160:1.8:0.4:0.8.

[0062] A3. Mix the composite potassium titanate whiskers, ethanol, and deionized water evenly, add KH560, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain epoxidized composite potassium titanate whiskers; the mass ratio of composite potassium titanate whiskers, ethanol, deionized water, and KH560 is 4.3:125:45:1.1;

[0063] A4. Add the epoxidized composite potassium titanate whiskers to ethanol, stir evenly, add 36% hydrochloric acid by mass, stir at 70℃ for 30 min, filter, and collect the solid; the mass ratio of epoxidized composite potassium titanate whiskers, ethanol and hydrochloric acid is 4.3:25:1.5.

[0064] Hydroxyl-terminated polydimethylsiloxane, carboxyl-polyethylene glycol-carboxyl, and toluene were mixed and stirred until homogeneous. P-toluenesulfonic acid was added, and nitrogen gas was introduced. The mixture was stirred at 105°C for 3.5 hours. A solid was added, and the reaction was continued for another 1.5 hours. The temperature was lowered to 60°C, and triethylamine was added to neutralize the p-toluenesulfonic acid. The temperature was then raised to 130°C, and toluene was removed under reduced pressure to obtain the reinforcing filler. The mass ratio of hydroxyl-terminated polydimethylsiloxane, carboxyl-polyethylene glycol-carboxyl, toluene, p-toluenesulfonic acid, and solid was 12:1.3:23:0.5:4.1.

[0065] Example 3

[0066] A high-adhesion automotive interior surface treatment agent comprises the following raw materials in parts by weight: 100 parts of acrylic modified polysiloxane resin, 10 parts of polydimethylsiloxane, 8 parts of reinforcing filler, 5 parts of γ-aminopropyltriethoxysilane, 0.5 parts of leveling agent BYK-320, and 2 parts of methylcellulose.

[0067] A method for preparing a high-adhesion automotive interior surface treatment agent includes the following preparation steps:

[0068] Acrylic-modified polysiloxane resin and polydimethylsiloxane were mixed and stirred at 1000 r / min for 15 min. Reinforcing filler, γ-aminopropyltriethoxysilane, leveling agent BYK-320 and methylcellulose were added and stirred at 60℃ and 3000 r / min for 20 min to obtain an automotive interior surface treatment agent.

[0069] The reinforcing filler is prepared by the following steps:

[0070] A1. After mixing potassium titanate whiskers, tannic acid, and ethanol evenly, glucose was added, and the mixture was stirred at 70°C for 30 min. The mixture was then removed and dried in a 70°C oven for 20 min. It was then placed in a tube furnace, and a 30% potassium hydroxide solution was added. Nitrogen gas was introduced, and the mixture was carbonized at 900°C for 5 h. After cooling to room temperature, the mixture was removed, washed three times with deionized water, and dried in a 70°C oven for 10 min to obtain modified potassium titanate whiskers. The mass ratio of potassium titanate whiskers, tannic acid, ethanol, glucose, and potassium hydroxide solution was 5:1:220:3:2.

[0071] A2. Zirconium oxychloride octahydrate, modified potassium titanate whiskers, and deionized water were mixed evenly, and then ammonia, glycine, and potassium chloride were added. The mixture was stirred evenly and placed in a reaction vessel. The mixture was subjected to a hydrothermal reaction at 190℃ for 22 hours. After cooling to room temperature, the mixture was filtered, washed three times with deionized water, and dried in an oven at 80℃ for 10 minutes to obtain composite potassium titanate whiskers. The mass ratio of zirconium oxychloride octahydrate, modified potassium titanate whiskers, deionized water, ammonia, glycine, and potassium chloride was 2.4:5:170:2:0.5:0.9.

[0072] A3. Mix the composite potassium titanate whiskers, ethanol, and deionized water evenly, add KH560, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain epoxidized composite potassium titanate whiskers; the mass ratio of composite potassium titanate whiskers, ethanol, deionized water, and KH560 is 4.5:130:50:1.2.

[0073] A4. Add the epoxidized composite potassium titanate whiskers to ethanol, stir evenly, add 36% hydrochloric acid by mass, stir at 70℃ for 30 min, filter and collect the solid; the mass ratio of epoxidized composite potassium titanate whiskers, ethanol and hydrochloric acid is 4.5:30:2.

[0074] Hydroxyl-terminated polydimethylsiloxane, carboxyl-polyethylene glycol-carboxyl, and toluene were mixed and stirred until homogeneous. P-toluenesulfonic acid was added, and nitrogen gas was introduced. The mixture was stirred at 110°C for 4 hours. A solid was added, and the reaction was continued for another 2 hours. The temperature was lowered to 60°C, and triethylamine was added to neutralize the p-toluenesulfonic acid. The temperature was then raised to 130°C, and toluene was removed under reduced pressure to obtain the reinforcing filler. The mass ratio of hydroxyl-terminated polydimethylsiloxane, carboxyl-polyethylene glycol-carboxyl, toluene, p-toluenesulfonic acid, and solid was 15:1.5:25:0.8:4.2.

[0075] Comparative Example 1

[0076] The only difference between this comparative example and Example 3 is the preparation of the reinforcing filler, as detailed below:

[0077] The reinforcing filler is prepared by the following steps:

[0078] A1. Zirconium oxychloride octahydrate, potassium titanate whiskers, and deionized water were mixed evenly, and then ammonia, glycine, and potassium chloride were added. The mixture was stirred evenly and placed in a reaction vessel. The mixture was subjected to a hydrothermal reaction at 190°C for 22 hours. After cooling to room temperature, the mixture was filtered, washed three times with deionized water, and dried in an oven at 80°C for 10 minutes to obtain composite potassium titanate whiskers. The mass ratio of zirconium oxychloride octahydrate, potassium titanate whiskers, deionized water, ammonia, glycine, and potassium chloride was 2.4:5:170:2:0.5:0.9.

[0079] A2. The composite potassium titanate whiskers, ethanol, and deionized water were mixed evenly, KH560 was added, and the mixture was stirred at 70℃ for 1.5 h. After cooling to room temperature, the mixture was filtered, washed three times with ethanol, and three times with deionized water. The mixture was then dried in an oven at 70℃ for 10 min to obtain epoxidized composite potassium titanate whiskers. The mass ratio of composite potassium titanate whiskers, ethanol, deionized water, and KH560 was 4.5:130:50:1.2.

[0080] A3. Add the epoxidized composite potassium titanate whiskers to ethanol, stir evenly, add 36% hydrochloric acid by mass, stir at 70℃ for 30 min, filter and collect the solid; the mass ratio of epoxidized composite potassium titanate whiskers, ethanol and hydrochloric acid is 4.5:30:2.

[0081] Hydroxyl-terminated polydimethylsiloxane, carboxyl-polyethylene glycol-carboxyl, and toluene were mixed and stirred until homogeneous. P-toluenesulfonic acid was added, and nitrogen gas was introduced. The mixture was stirred at 110°C for 4 hours. A solid was added, and the reaction was continued for another 2 hours. The temperature was lowered to 60°C, and triethylamine was added to neutralize the p-toluenesulfonic acid. The temperature was then raised to 130°C, and toluene was removed under reduced pressure to obtain the reinforcing filler. The mass ratio of hydroxyl-terminated polydimethylsiloxane, carboxyl-polyethylene glycol-carboxyl, toluene, p-toluenesulfonic acid, and solid was 15:1.5:25:0.8:4.2.

[0082] Comparative Example 2

[0083] The only difference between this comparative example and Example 3 is the preparation of the reinforcing filler, as detailed below:

[0084] The reinforcing filler is prepared by the following steps:

[0085] A1. After mixing potassium titanate whiskers, tannic acid, and ethanol evenly, glucose was added, and the mixture was stirred at 70°C for 30 min. The mixture was then removed and dried in a 70°C oven for 20 min. It was then placed in a tube furnace, and a 30% potassium hydroxide solution was added. Nitrogen gas was introduced, and the mixture was carbonized at 900°C for 5 h. After cooling to room temperature, the mixture was removed, washed three times with deionized water, and dried in a 70°C oven for 10 min to obtain modified potassium titanate whiskers. The mass ratio of potassium titanate whiskers, tannic acid, ethanol, glucose, and potassium hydroxide solution was 5:1:220:3:2.

[0086] A2. Mix modified potassium titanate whiskers, ethanol, and deionized water evenly, add KH560, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol, wash 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain epoxidized modified potassium titanate whiskers; the mass ratio of modified potassium titanate whiskers, ethanol, deionized water, and KH560 is 4.5:130:50:1.2.

[0087] A3. Add the epoxidized potassium titanate whiskers to ethanol, stir evenly, add 36% hydrochloric acid by mass, stir at 70℃ for 30 min, filter and collect the solid; the mass ratio of epoxidized potassium titanate whiskers, ethanol and hydrochloric acid is 4.5:30:2.

[0088] Hydroxyl-terminated polydimethylsiloxane, carboxyl-polyethylene glycol-carboxyl, and toluene were mixed and stirred until homogeneous. P-toluenesulfonic acid was added, and nitrogen gas was introduced. The mixture was stirred at 110°C for 4 hours. A solid was added, and the reaction was continued for another 2 hours. The temperature was lowered to 60°C, and triethylamine was added to neutralize the p-toluenesulfonic acid. The temperature was then raised to 130°C, and toluene was removed under reduced pressure to obtain the reinforcing filler. The mass ratio of hydroxyl-terminated polydimethylsiloxane, carboxyl-polyethylene glycol-carboxyl, toluene, p-toluenesulfonic acid, and solid was 15:1.5:25:0.8:4.2.

[0089] Comparative Example 3

[0090] The only difference between this comparative example and Example 3 is the preparation of the reinforcing filler, as detailed below:

[0091] The reinforcing filler is prepared by the following steps:

[0092] A1. After mixing potassium titanate whiskers, tannic acid, and ethanol evenly, glucose was added, and the mixture was stirred at 70°C for 30 min. The mixture was then removed and dried in a 70°C oven for 20 min. It was then placed in a tube furnace, and a 30% potassium hydroxide solution was added. Nitrogen gas was introduced, and the mixture was carbonized at 900°C for 5 h. After cooling to room temperature, the mixture was removed, washed three times with deionized water, and dried in a 70°C oven for 10 min to obtain modified potassium titanate whiskers. The mass ratio of potassium titanate whiskers, tannic acid, ethanol, glucose, and potassium hydroxide solution was 5:1:220:3:2.

[0093] A2. Zirconium oxychloride octahydrate, modified potassium titanate whiskers, and deionized water were mixed evenly, and then ammonia, glycine, and potassium chloride were added. The mixture was stirred evenly and placed in a reaction vessel. The mixture was subjected to a hydrothermal reaction at 190℃ for 22 hours. After cooling to room temperature, the mixture was filtered, washed three times with deionized water, and dried in an oven at 80℃ for 10 minutes to obtain composite potassium titanate whiskers. The mass ratio of zirconium oxychloride octahydrate, modified potassium titanate whiskers, deionized water, ammonia, glycine, and potassium chloride was 2.4:5:170:2:0.5:0.9.

[0094] A3. Add the composite potassium titanate whiskers to ethanol, stir evenly, add hydrochloric acid with a mass fraction of 36%, stir at 70℃ for 30 min, filter and collect the solid; the mass ratio of epoxidized composite potassium titanate whiskers, ethanol and hydrochloric acid is 4.5:30:2.

[0095] Hydroxyl-terminated polydimethylsiloxane, carboxyl-polyethylene glycol-carboxyl, and toluene were mixed and stirred until homogeneous. P-toluenesulfonic acid was added, and nitrogen gas was introduced. The mixture was stirred at 110°C for 4 hours. A solid was added, and the reaction was continued for another 2 hours. The temperature was lowered to 60°C, and triethylamine was added to neutralize the p-toluenesulfonic acid. The temperature was then raised to 130°C, and toluene was removed under reduced pressure to obtain the reinforcing filler. The mass ratio of hydroxyl-terminated polydimethylsiloxane, carboxyl-polyethylene glycol-carboxyl, toluene, p-toluenesulfonic acid, and solid was 15:1.5:25:0.8:4.2.

[0096] Comparative Example 4

[0097] The only difference between this comparative example and Example 3 is the preparation of the reinforcing filler, as detailed below:

[0098] The reinforcing filler is prepared by the following steps:

[0099] A1. After mixing potassium titanate whiskers, tannic acid, and ethanol evenly, glucose was added, and the mixture was stirred at 70°C for 30 min. The mixture was then removed and dried in a 70°C oven for 20 min. It was then placed in a tube furnace, and a 30% potassium hydroxide solution was added. Nitrogen gas was introduced, and the mixture was carbonized at 900°C for 5 h. After cooling to room temperature, the mixture was removed, washed three times with deionized water, and dried in a 70°C oven for 10 min to obtain modified potassium titanate whiskers. The mass ratio of potassium titanate whiskers, tannic acid, ethanol, glucose, and potassium hydroxide solution was 5:1:220:3:2.

[0100] A2. Zirconium oxychloride octahydrate, modified potassium titanate whiskers, and deionized water were mixed evenly, and then ammonia, glycine, and potassium chloride were added. The mixture was stirred evenly and placed in a reaction vessel. The mixture was subjected to a hydrothermal reaction at 190℃ for 22 hours. After cooling to room temperature, the mixture was filtered, washed three times with deionized water, and dried in an oven at 80℃ for 10 minutes to obtain composite potassium titanate whiskers. The mass ratio of zirconium oxychloride octahydrate, modified potassium titanate whiskers, deionized water, ammonia, glycine, and potassium chloride was 2.4:5:170:2:0.5:0.9.

[0101] A3. Mix the composite potassium titanate whiskers, ethanol, and deionized water evenly, add KH560, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain epoxidized composite potassium titanate whiskers; the mass ratio of composite potassium titanate whiskers, ethanol, deionized water, and KH560 is 4.5:130:50:1.2.

[0102] A4. Add the epoxidized composite potassium titanate whiskers to ethanol, stir evenly, add 36% hydrochloric acid by mass, stir at 70℃ for 30 min, filter and collect the solid; the mass ratio of epoxidized composite potassium titanate whiskers, ethanol and hydrochloric acid is 4.5:30:2.

[0103] Carboxyl-polyethylene glycol-carboxyl and toluene were mixed and stirred evenly. p-Toluenesulfonic acid was added, and nitrogen gas was introduced. The mixture was stirred at 110°C for 4 hours. The solid was added, and the mixture was stirred for another 2 hours. The temperature was lowered to 60°C, and triethylamine was added to neutralize the p-toluenesulfonic acid. The temperature was then raised to 130°C, and toluene was removed under reduced pressure to obtain the reinforcing filler. The mass ratio of carboxyl-polyethylene glycol-carboxyl, toluene, p-toluenesulfonic acid, and solid was 16.5:25:0.8:4.2.

[0104] Comparative Example 5

[0105] The only difference between this comparative example and Example 3 is the preparation of the reinforcing filler, as detailed below:

[0106] The reinforcing filler is prepared by the following steps:

[0107] A1. After mixing potassium titanate whiskers, tannic acid, and ethanol evenly, glucose was added, and the mixture was stirred at 70°C for 30 min. The mixture was then removed and dried in a 70°C oven for 20 min. It was then placed in a tube furnace, and a 30% potassium hydroxide solution was added. Nitrogen gas was introduced, and the mixture was carbonized at 900°C for 5 h. After cooling to room temperature, the mixture was removed, washed three times with deionized water, and dried in a 70°C oven for 10 min to obtain modified potassium titanate whiskers. The mass ratio of potassium titanate whiskers, tannic acid, ethanol, glucose, and potassium hydroxide solution was 5:1:220:3:2.

[0108] A2. Zirconium oxychloride octahydrate, modified potassium titanate whiskers, and deionized water were mixed evenly, and then ammonia, glycine, and potassium chloride were added. The mixture was stirred evenly and placed in a reaction vessel. The mixture was subjected to a hydrothermal reaction at 190℃ for 22 hours. After cooling to room temperature, the mixture was filtered, washed three times with deionized water, and dried in an oven at 80℃ for 10 minutes to obtain composite potassium titanate whiskers. The mass ratio of zirconium oxychloride octahydrate, modified potassium titanate whiskers, deionized water, ammonia, glycine, and potassium chloride was 2.4:5:170:2:0.5:0.9.

[0109] A3. Mix the composite potassium titanate whiskers, ethanol, and deionized water evenly, add KH560, stir and react at 70℃ for 1.5h, cool to room temperature, filter, wash 3 times with ethanol and 3 times with deionized water, and dry in an oven at 70℃ for 10min to obtain epoxidized composite potassium titanate whiskers; the mass ratio of composite potassium titanate whiskers, ethanol, deionized water, and KH560 is 4.5:130:50:1.2.

[0110] A4. Add the epoxidized composite potassium titanate whiskers to ethanol, stir evenly, add 36% hydrochloric acid by mass, stir at 70℃ for 30 min, filter and collect the solid; the mass ratio of epoxidized composite potassium titanate whiskers, ethanol and hydrochloric acid is 4.5:30:2.

[0111] Hydroxyl-terminated polydimethylsiloxane and toluene were mixed and stirred evenly. p-Toluenesulfonic acid was added, and nitrogen gas was introduced. The mixture was stirred at 110°C for 4 hours. The solid was added, and the mixture was stirred for another 2 hours. The temperature was lowered to 60°C, and triethylamine was added to neutralize the p-toluenesulfonic acid. The temperature was then raised to 130°C, and toluene was removed under reduced pressure to obtain the reinforcing filler. The mass ratio of hydroxyl-terminated polydimethylsiloxane, toluene, p-toluenesulfonic acid, and solid was 16.5:25:0.8:4.2.

[0112] The performance of the automotive interior surface treatment agents prepared in Examples 1-3 and Comparative Examples 1-5 was then tested.

[0113] The PP automotive interior was placed at 70°C for 10 minutes to remove surface moisture, and then flame-treated with a neutral flame (flame speed of 3 cm / s) to obtain activated PP automotive interior. The automotive interior surface treatment agent prepared above was sprayed onto the surface of the activated PP automotive interior to obtain automotive interior with automotive interior surface treatment agent sprayed on, which was used for adhesion and abrasion resistance testing.

[0114] The adhesion of automotive interior surface treatment agents was determined according to GB / T 9286-2021 "Cross-cut test of paint and varnish film".

[0115] The automotive interior surfaces coated with automotive interior surface treatment agent were placed on the TABER abrasion tester for testing. 1 kg of the agent was used for 4000 abrasion cycles, and the samples were rated, with the highest rating being 5.

[0116] As shown in Table 1 below.

[0117] Table 1 Performance testing of automotive interior surface treatment agents prepared in Examples 1-3 and Comparative Examples 1-5

[0118] project Adhesion / Grade Abrasion resistance / grade Example 1 0 5 Example 2 0 5 Example 3 0 5 Comparative Example 1 2 3 Comparative Example 2 3 2 Comparative Example 3 2 3 Comparative Example 4 2 3 Comparative Example 5 2 3

[0119] As can be seen from the data in Table 1, the automotive interior surface treatment agents prepared in Examples 1-3 have high adhesion and wear resistance.

[0120] Comparative Example 1 showed that when modified potassium titanate whiskers were replaced with reinforcing fillers prepared from potassium titanate whiskers and added to an automotive interior surface treatment agent, the adhesion and wear resistance decreased. This demonstrates that synthesizing a porous carbon layer on the surface of potassium titanate whiskers can improve the surface roughness of potassium titanate whiskers and enhance the contact area between potassium titanate whiskers and polysiloxane resin. Potassium titanate whiskers have a high aspect ratio and can be randomly dispersed in the polysiloxane surfactant system, forming a microskeleton in the surfactant matrix. This absorbs and weakens the energy generated by external forces, improving the wear resistance of the paint film. Furthermore, the porous carbon has a three-dimensional network pore structure and high adsorption performance, enabling it to adsorb onto the automotive interior surface and enhance the adhesion of the polysiloxane surfactant to the automotive interior surface.

[0121] Comparative Example 2 showed that when composite potassium titanate whiskers were replaced with reinforcing fillers prepared from modified potassium titanate whiskers and added to an automotive interior surface treatment agent, the adhesion and wear resistance decreased. This demonstrates that nano-zirconia synthesized on the surface and in the channels of modified potassium titanate whiskers, as a wear-resistant aggregate, can improve the wear resistance of polysiloxane surfactants. Furthermore, the nano-zirconia surface contains a large number of hydroxyl groups, which can be adsorbed onto the automotive interior surface, enhancing the adhesion of polysiloxane surfactants to the automotive interior surface. In addition, during the formation of a paint film on the automotive interior surface by polysiloxane surfactants, nano-zirconia can fill the gaps in the paint film, increasing the density of the paint film and enhancing the adhesion of polysiloxane surfactants to the automotive interior surface.

[0122] Comparative Example 3 showed that when the epoxidized composite potassium titanate whiskers were replaced with the reinforcing filler prepared from composite potassium titanate whiskers and added to the automotive interior surface treatment agent, the adhesion and wear resistance decreased. This demonstrates that surface treatment of composite potassium titanate whiskers with silane coupling agents imparts reactive functional groups (epoxy groups) to the composite potassium titanate whiskers, which is beneficial for the synthesis of polyether segment modified polysiloxanes on the surface of the composite potassium titanate whiskers. This allows the composite potassium titanate whiskers to be uniformly dispersed in the polysiloxane surfactant system, thereby enhancing the wear resistance and adhesion of the polysiloxane surfactant.

[0123] Comparative Example 4, in which hydroxyl-terminated polydimethylsiloxane was replaced by an equal mass of carboxyl-polyethylene glycol-carboxyl, and Comparative Example 5, in which carboxyl-polyethylene glycol-carboxyl was replaced by an equal mass of hydroxyl-terminated polydimethylsiloxane, were added to automotive interior surface treatment agents. The resulting decrease in adhesion and abrasion resistance demonstrated that the polyether segment-modified polysiloxane formed by carboxyl-polyethylene glycol-carboxyl and hydroxyl-terminated polydimethylsiloxane contains a large number of long-chain aliphatic structures. These structures effectively reduce the crosslinking density of the polysiloxane surfactant film, improving the adhesion between the polysiloxane surfactant and the automotive interior. Furthermore, the polyether segment-modified polysiloxane contains a large number of siloxane bonds, exhibiting good compatibility with the polysiloxane surfactant matrix. This allows the composite potassium titanate whiskers to be uniformly dispersed in the polysiloxane surfactant system, enhancing the abrasion resistance and adhesion of the polysiloxane surfactant.

[0124] In the description of this specification, the references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0125] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

Claims

1. A high-adhesion automotive interior surface treatment agent, characterized in that, The raw materials include the following parts by weight: 80-100 parts of acrylic modified polysiloxane resin, 5-10 parts of polydimethylsiloxane, 5-8 parts of reinforcing filler, 2-5 parts of aminosilane coupling agent, 0.1-0.5 parts of leveling agent, and 1-2 parts of thickener; The reinforcing filler is obtained by surface-treating composite potassium titanate whiskers with silane coupling agent and then reacting them with carboxyl-polyethylene glycol-carboxyl and hydroxyl-terminated polydimethylsiloxane. The composite potassium titanate whiskers are obtained by synthesizing a porous carbon layer on the surface of potassium titanate whiskers, followed by a reaction with zirconium oxychloride octahydrate and ammonia.

2. The high-adhesion automotive interior surface treatment agent according to claim 1, characterized in that, The reinforcing filler is specifically prepared by the following steps: A1. After mixing potassium titanate whiskers, tannic acid and ethanol evenly, glucose is added, stirred, removed and dried, placed in a tube furnace, potassium hydroxide solution is added, nitrogen gas is introduced, carbonized at 800-900℃ for 4-5 hours, cooled to room temperature, removed, washed and dried to obtain modified potassium titanate whiskers. A2. After mixing zirconium oxychloride octahydrate, modified potassium titanate whiskers and deionized water evenly, ammonia, glycine and potassium chloride are added, stirred evenly, placed in a reaction vessel, and subjected to hydrothermal reaction at 170-190℃ for 20-22h. After cooling to room temperature, the mixture is filtered, washed and dried to obtain composite potassium titanate whiskers. A3. Mix the composite potassium titanate whiskers, ethanol and deionized water evenly, add silane coupling agent, stir the reaction, cool to room temperature, filter, wash and dry to obtain epoxidized composite potassium titanate whiskers. A4. Add the epoxidized composite potassium titanate whiskers to ethanol, stir well, add hydrochloric acid, stir, filter, and collect the solid; Hydroxyl-terminated polydimethylsiloxane, carboxyl-polyethylene glycol-carboxyl, and toluene were mixed and stirred until homogeneous. P-toluenesulfonic acid was added, and nitrogen gas was introduced. The mixture was stirred and reacted at 100-110℃ for 3-4 hours. The solid was added, and the reaction was continued for 1-2 hours. After cooling, triethylamine was added to neutralize the p-toluenesulfonic acid. The temperature was then raised again, and toluene was removed under reduced pressure to obtain the reinforcing filler.

3. The high-adhesion automotive interior surface treatment agent according to claim 2, characterized in that, In step A1, the mass ratio of potassium titanate whiskers, tannic acid, ethanol, glucose and potassium hydroxide solution is (4-5):(0.5-1):(180-220):(2.5-3):(1.5-2).

4. The high-adhesion automotive interior surface treatment agent according to claim 2, characterized in that, In step A2, the mass ratio of zirconium oxychloride octahydrate, modified potassium titanate whiskers, deionized water, ammonia, glycine, and potassium chloride is (2-2.4):(4.5-5):(150-170):(1.5-2):(0.3-0.5):(0.7-0.9).

5. The high-adhesion automotive interior surface treatment agent according to claim 2, characterized in that, In step A3, the mass ratio of the composite potassium titanate whiskers, ethanol, deionized water and silane coupling agent is (4-4.5):(120-130):(40-50):(1-1.2).

6. The high-adhesion automotive interior surface treatment agent according to claim 2, characterized in that, In step A4, the mass ratio of the epoxidized composite potassium titanate whiskers, ethanol, and hydrochloric acid is (4-4.5):(20-30):(1-2); In step A4, the mass ratio of the hydroxyl-terminated polydimethylsiloxane, carboxyl-polyethylene glycol-carboxyl, toluene, p-toluenesulfonic acid and solid is (9-15):(1-1.5):(20-25):(0.3-0.8):(4-4.2).

7. The high-adhesion automotive interior surface treatment agent according to claim 1, characterized in that, The aminosilane coupling agent is selected from any one of γ-aminopropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, and N-β(aminoethyl)-γ-aminopropyltriethoxysilane.

8. The high-adhesion automotive interior surface treatment agent according to claim 1, characterized in that, The leveling agent is selected from any one of the following: leveling agent BYK-320, leveling agent BYK-354, and leveling agent FL2028.

9. The high-adhesion automotive interior surface treatment agent according to claim 1, characterized in that, The thickener is selected from any one of methylcellulose, hydroxypropyl methylcellulose, sodium carboxymethylcellulose, and hydroxyethylcellulose.

10. A method for preparing a high-adhesion automotive interior surface treatment agent according to any one of claims 1-9, characterized in that, The preparation steps include the following: Acrylic-modified polysiloxane resin and polydimethylsiloxane are mixed and stirred at 800-1000 r / min for 10-15 min. Reinforcing filler, aminosilane coupling agent, leveling agent and thickener are added and stirred at 50-60℃ and 2500-3000 r / min for 15-20 min to obtain automotive interior surface treatment agent.