Waterproof organic silicon automotive interior leather material and processing technology thereof

Abstract

The invention discloses a water-resistant organic silicon automotive interior leather material and a processing technology thereof, and relates to the technical field of organic silicon leather. According to the technical scheme, release paper is coated with surface layer resin liquid, baking and curing are conducted, the release paper is stripped, and a surface layer is obtained; and coating the surface of the base material subjected to plasma treatment with the adhesive resin liquid, laminating the surface layer with the adhesive resin liquid, and baking and curing to obtain the water-resistant organic silicon automotive interior leather material. Under the synergistic effect of the modified silicon resin and the modified filler in the surface layer resin liquid and the bonding accelerant in the bonding resin liquid, the water-resistant organic silicon automotive interior leather material with excellent antistatic performance is comprehensively prepared, and the antistatic performance and the water resistance of the organic silicon leather material are both considered; the durability of the organic silicon leather material is further enhanced, and the method has important significance.

Description

Technical Field

[0001] This invention relates to the field of silicone leather technology, specifically a water-resistant silicone automotive interior leather material and its processing technology. Background Technology

[0002] While traditional silicone leather materials offer advantages such as weather resistance, resistance to high and low temperatures, low odor, and low fogging, they also suffer from high surface resistance, are prone to static electricity, and easily attract dust. When used in automotive interiors, this results in a buildup of dust that is difficult to clean, leading to a poor user experience. Currently, the industry typically addresses the static issue of silicone leather by adding antistatic agents. However, most common antistatic agents are polyether-based or ionic compounds, which significantly reduce the water resistance of silicone leather. Furthermore, because the antistatic agent does not effectively bind to the resin, it easily migrates and precipitates, causing the antistatic properties of silicone leather to degrade rapidly. Simultaneously, the migration and precipitation of antistatic agents also affect the feel and appearance of the silicone leather, further diminishing the user experience.

[0003] In addition, traditional silicone leather materials have poor adhesion between layers, making them prone to peeling and lacking durability.

[0004] To address the aforementioned contradictions, this invention provides a water-resistant silicone automotive interior leather material with excellent antistatic properties. While maintaining the antistatic and water-resistant properties of silicone leather materials, it further enhances the durability of silicone leather materials, which is of great significance. Summary of the Invention

[0005] The purpose of this invention is to provide a water-resistant silicone automotive interior leather material and its processing technology to solve the problems mentioned in the background art.

[0006] To address the aforementioned technical problems, the first aspect of the present invention provides the following technical solution: A processing technology for a water-resistant silicone automotive interior leather material includes the following steps: S1: Coat the surface resin liquid onto the release paper, bake at 130~150℃ for 2~10 minutes, peel off the release paper to obtain the surface layer; S2: Apply adhesive resin liquid to any surface of the substrate, and attach the surface layer to the surface of adhesive resin liquid. Bake at 130~150℃ for 2~10 minutes to obtain water-resistant silicone automotive interior leather material.

[0007] Further, the surface layer resin liquid comprises the following raw material components: by weight, 50-70 parts of divinyl polydimethylsiloxane, 10-30 parts of methyl vinyl MQ silicone resin, 5-15 parts of hydrogen-containing MQ silicone resin, 10-20 parts of modified silicone resin, 10-20 parts of modified filler, 2-4 parts of hydrogen-containing silicone oil, 0.08-0.15 parts of chloroplatinic acid-isopropanol solution, and 0.05-0.1 parts of inhibitor.

[0008] Further, the adhesive resin liquid comprises the following raw material components: by weight, 60-80 parts of divinyl polydimethylsiloxane, 10-20 parts of methyl vinyl MQ silicone resin, 7-10 parts of hydrogen-containing silicone oil, 0.08-0.15 parts of chloroplatinic acid-isopropanol solution, 1-5 parts of adhesive accelerator, and 0.03-0.06 parts of inhibitor.

[0009] Further, the preparation method of the modified silicone resin is as follows: (1) Under nitrogen protection, terminal hydrogen silicone oil and sodium 2-hydroxypropane butyryne diether-3-sulfonate are added to a toluene / isopropanol mixed solvent, stirred and mixed, and then 1 wt% chloroplatinic acid-isopropanol solution is added to it. The mixture is stirred and reacted at 85~95℃ for 2~4h. Then, excess deionized water is added to it, stirred and mixed, allowed to stand and separate into layers, the aqueous phase is removed, and vacuum dried to obtain sodium sulfonate modified silicone oil; (2) Under nitrogen protection, sodium sulfonate modified silicone oil is added to a toluene / isopropanol mixed solvent, stirred and mixed, heated to 70~80℃, and then a portion of azobisisobutyronitrile is added to it. At the same time, methyl allyl alcohol polyoxyethylene ether is added dropwise for 1~2h. After the addition is completed, the remaining azobisisobutyronitrile is added, and the mixture is stirred and reacted for 2~4h. The mixture is then evaporated under reduced pressure and vacuum dried to obtain modified silicone resin.

[0010] Furthermore, the sodium sulfonate modified silicone oil comprises the following raw material components: by weight, 10-20 parts of terminal hydrogen silicone oil, 5-10 parts of sodium 2-hydroxypropane-butynediol diether-3-sulfonate, 0.05-0.1 parts of chloroplatinic acid-isopropanol solution, and 30-60 parts of toluene / isopropanol mixed solvent.

[0011] Further, the modified silicone resin comprises the following raw material components: by weight, 12-24 parts of sodium sulfonate modified silicone oil, 4-12 parts of methyl allyl alcohol polyoxyethylene ether, 0.1-0.5 parts of azobisisobutyronitrile, and 30-60 parts of toluene / isopropanol mixed solvent.

[0012] In this invention, a hydrosilylation reaction is first carried out between terminal hydrogen silicone oil and sodium 2-hydroxypropanebutyne diether-3-sulfonate to obtain sodium sulfonate-modified silicone oil. Sodium 2-hydroxypropanebutyne diether-3-sulfonate should be in excess to ensure complete reaction of the hydrogen on the terminal hydrogen silicone oil and to simultaneously form unsaturated double bonds on the sodium sulfonate-modified silicone oil. The sodium sulfonate-modified silicone oil is then further polymerized with methyl allyl alcohol polyoxyethylene ether to prepare a modified silicone resin. During the preparation of the modified silicone resin, methyl allyl alcohol polyoxyethylene ether should be added dropwise, and azobisisobutyronitrile should also be added in batches to prevent self-polymerization of methyl allyl alcohol polyoxyethylene ether, thereby improving the grafting rate of the product.

[0013] Further, the preparation method of the modified filler is as follows: (1) The filler is added to a sealed stirring pot, stirred at a speed of 50~80r / min and heated to 50~60℃, and silane hydrolysate is added to the stirring pot in the form of spray under stirring, kept warm and stirred for 1~2h, discharged, vacuum dried, and silane modified filler is obtained; (2) Under nitrogen protection, terminal hydrogen silicone oil and silane modified filler are added to a toluene / isopropanol mixed solvent, ultrasonically dispersed for 5~15min, and then 1wt% chloroplatinic acid-isopropanol solution is added, stirred and reacted at 85~95℃ for 2~4h, filtered, washed and dried to obtain modified filler.

[0014] Furthermore, the filler is obtained by mixing and compounding talc powder and silica in a mass ratio of (1~2):(1~2).

[0015] Furthermore, the ratio of the filler and the silane hydrolysate is 1g:(0.1~0.3)mL.

[0016] Furthermore, the modified filler comprises the following raw material components: by weight, 8-10 parts of terminal hydrogen silicone oil, 15-25 parts of silane modified filler, 0.05-0.1 parts of chloroplatinic acid-isopropanol solution, and 30-60 parts of toluene / isopropanol mixed solvent.

[0017] Furthermore, the preparation method of the silane hydrolysate is as follows: add vinyl silane coupling agent and fluorinated silane coupling agent to 80-90 wt% ethanol aqueous solution, add acetic acid to adjust the pH to 4.7-5.2, and stir and mix at 50-60℃ for 0.5-1.5 h to obtain silane hydrolysate.

[0018] Furthermore, the volume ratio of the vinyl silane coupling agent, the fluorinated silane coupling agent, and the ethanol aqueous solution is (0.8~1):(0.8~1):8.

[0019] In this invention, vinyl silane coupling agents and fluorinated silane coupling agents are used to modify the filler to obtain silane-modified filler containing vinyl and fluorinated segments; further, hydrosilylation reaction is carried out between the terminal hydrogen silicone oil and the silane-modified filler to prepare the modified filler; in order to promote the bonding between the filler and the surface layer, some Si-H should be retained to participate in subsequent crosslinking, therefore, the amount of terminal hydrogen silicone oil should be excessive.

[0020] Furthermore, in the technical solution of the present invention, the toluene / isopropanol mixed solvent is obtained by mixing and compounding toluene and isopropanol in a volume ratio of (1~2):1.

[0021] Furthermore, in the technical solution of the present invention, the hydrogen content of the hydrogen-terminated silicone oil is 0.1~0.12wt%.

[0022] Furthermore, in the technical solution of the present invention, the vinyl content of the divinyl polydimethylsiloxane is 0.15~0.18wt%.

[0023] Furthermore, in the technical solution of the present invention, the vinyl content of the methyl vinyl MQ silicone resin is 0.7~1wt%.

[0024] Furthermore, in the technical solution of the present invention, the hydrogen content of the hydrogen-containing MQ silicone resin is 0.2~0.8wt%.

[0025] Furthermore, in the technical solution of the present invention, the hydrogen content of the hydrogen-containing silicone oil is ≥1.55wt%.

[0026] Furthermore, in the technical solution of the present invention, the concentration of the chloroplatinic acid-isopropanol solution is 1 wt%.

[0027] Furthermore, in the technical solution of the present invention, the inhibitor is acetylenecyclohexanol.

[0028] Furthermore, the adhesion promoter is an unsaturated isocyanate, including but not limited to one or more combinations of allyl isocyanate, vinyl isocyanate, isocyanoethyl methacrylate, and ethyl isocyanate acrylate.

[0029] Furthermore, the substrate is a non-woven fabric, which is subjected to plasma treatment before coating; the parameters of the plasma treatment are: the treatment gas is an O2 / Ar mixture, the volume ratio of O2 / Ar is (20~40):(60~80), the gas pressure is 20~30Pa, the treatment power is 100~150W, and the treatment time is 3~5min.

[0030] After plasma treatment, active groups such as hydroxyl groups can be formed on the surface of nonwoven fabric, which can combine with the adhesive layer to improve the interlayer bonding of water-resistant silicone leather materials.

[0031] The second aspect of the present invention provides: A water-resistant silicone automotive interior leather material, processed according to the above-mentioned process, has a layered structure, consisting of a top layer, an adhesive layer, and a substrate from top to bottom; the thickness of the top layer is 20~50μm; the thickness of the adhesive layer is 50~100μm; and the thickness of the substrate is 0.5~1mm.

[0032] Compared with the prior art, the beneficial effects achieved by the present invention are: (1) In this invention, a modified silicone resin containing sodium sulfonate groups, silicone oil segments, and polyoxyethylene ethers is added to the surface resin liquid. The silicone oil segments ensure the compatibility and dispersibility of the modified silicone resin. The sodium sulfonate groups and polyoxyethylene ether segments work synergistically to improve the antistatic properties of the silicone leather material. Furthermore, the sodium sulfonate groups and polyoxyethylene ether segments are grafted onto the silicone oil segments through chemical bonding, making them less prone to migration or precipitation, thus providing the silicone leather material with a long-term, stable, and efficient antistatic effect. In addition, the modified silicone resin also contains a large number of hydroxyl groups, providing a basis for subsequent adhesion and bonding.

[0033] (2) Considering that the addition of modified silicone resin can significantly improve the antistatic properties of silicone leather materials, the sodium sulfonate groups and polyoxyethylene ether segments are hydrophilic, which will reduce the water resistance of silicone leather materials to a certain extent and increase the potential risk of moisture absorption and mold growth. In order to improve the durability of silicone leather materials, modified fillers are further added to the surface resin liquid in this invention. The fillers chosen are a combination of silica and talc because silica has high hardness, which can improve the wear resistance and scratch resistance of silicone leather materials, while talc has a layered structure that can disperse stress and improve the toughness of silicone leather materials. The synergistic combination of the two can significantly improve the durability of silicone leather materials. The silane hydrolysate is obtained by hydrolyzing a compound of vinyl silane coupling agent and fluorinated silane coupling agent, which allows for the grafting of vinyl and fluorinated segments onto the filler surface. The fluorinated segments can improve the hydrophobicity of the modified filler and, when added to the surface resin solution, can compensate for the modification of the silicone resin. In addition, the fluorinated segments can also improve the stain resistance of silicone leather, making it easier to clean. The vinyl segments are used to react with terminal hydrogen silicone oil for grafting, thereby improving the dispersibility of the modified filler in the surface resin solution.

[0034] (3) In this invention, unsaturated isocyanate is added to the adhesive resin liquid as an adhesive promoter, which can react with the hydroxyl groups on the surface layer and the plasma-treated substrate, thereby improving the bonding force between the layers of the silicone leather material, ensuring product quality, and further improving the durability of the silicone leather material.

[0035] In summary, this invention, through the synergistic effect of modified silicone resin, modified filler, and adhesion promoter, comprehensively prepares a water-resistant silicone automotive interior leather material with excellent antistatic properties. While taking into account the antistatic and water-resistant properties of silicone leather materials, it further enhances the durability of silicone leather materials, which is of great significance. Detailed Implementation

[0036] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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 skilled in the art without creative effort are within the scope of protection of the present invention.

[0037] It should be noted that the following quantities are by weight, and there are no special restrictions on the suppliers of all raw materials involved in this invention. Exemplary examples include: In the following examples, divinyl polydimethylsiloxane, catalog number JS68, has a vinyl content of 0.16 wt%, is brand name Jusheng, and was purchased from Hubei Jusheng Technology Co., Ltd. Methyl vinyl MQ silicone resin, model AM-8008, with a vinyl content of 0.8 wt% and an M:Q ratio of 1.1:1, was purchased from Shanghai Puzhen Biotechnology Co., Ltd. Hydrogen-containing MQ silicone resin, model HVMQ-2, with a hydrogen content of 0.6wt% and an M:Q ratio of 1.2:1, was purchased from Shenzhen Xinyong New Materials Co., Ltd. Hydrogen-containing silicone oil, model RH-202-20L, with a hydrogen content of 1.6 wt%; and hydrogen-terminated silicone oil, model RH-H6, with a hydrogen content of 0.11 wt%; both were purchased from Runhe Advanced Materials Technology Co., Ltd. Ethynylcyclohexanol, CAS No. 78-27-3; Sodium 2-hydroxypropanebutyne diether-3-sulfonate, CAS No. 67874-62-8; Chloroplatinic acid; Methyl allyl alcohol polyoxyethylene ether, CAS No. 31497-33-3; Talc, average particle size 5μm; Silica, average particle size 5μm; Vinyltriethoxysilane; Perfluorooctyltrimethoxysilane; Allyl isocyanate, CAS No. 1476-23-9; all commercially available. 100g per weight.

[0038] Preliminary preparations: 1. Preparation of toluene / isopropanol mixed solvent: Mix toluene and isopropanol in a volume ratio of 1.5:1 to obtain toluene / isopropanol mixed solvent.

[0039] 2. Preparation of filler: Mix talc powder and silica in a mass ratio of 1:1 to obtain the filler.

[0040] 3. Preparation of silane hydrolysate: Add vinyltriethoxysilane and perfluorooctyltrimethoxysilane to an 85wt% aqueous ethanol solution, adjust the pH to 5 with acetic acid, and stir and mix at 55℃ for 1h to obtain the silane hydrolysate; the volume ratio of vinyltriethoxysilane, perfluorooctyltrimethoxysilane and aqueous ethanol solution is 0.9:0.9:8.

[0041] 4. Preparation of vinyltriethoxysilane hydrolysate: Add vinyltriethoxysilane to an 85wt% aqueous ethanol solution, add acetic acid to adjust the pH to 5, and stir and mix at 55℃ for 1h to obtain vinyltriethoxysilane hydrolysate; the volume ratio of vinyltriethoxysilane to aqueous ethanol solution is 1.8:8.

[0042] Example 1: Processing technology of a water-resistant silicone automotive interior leather material: S1: Prepare the surface layer resin solution and prepare the surface layer: S11: Preparation of modified silicone resin: (1) Under nitrogen protection, 15 parts of terminal hydrogen silicone oil and 7.5 parts of sodium 2-hydroxypropanebutyryne diether-3-sulfonate were added to 45 parts of toluene / isopropanol mixed solvent and stirred. Then, 0.075 parts of 1wt% chloroplatinic acid-isopropanol solution were added and stirred at 90°C for 3 hours. Then, excess deionized water was added, stirred and mixed, allowed to stand and separate into layers, the aqueous phase was removed, and vacuum dried to obtain sulfonic acid. Sodium-modified silicone oil; (2) Under nitrogen protection, 18 parts of sodium sulfonate-modified silicone oil were added to 45 parts of toluene / isopropanol mixed solvent, stirred and mixed, heated to 75°C, and then 0.1 parts of azobisisobutyronitrile were added, while 8 parts of methyl allyl alcohol polyoxyethylene ether were added dropwise for 1.5 hours. After the addition was completed, 0.2 parts of azobisisobutyronitrile were added, and the reaction was stirred for 3 hours. After vacuum evaporation and vacuum drying, modified silicone resin was obtained. S12: Preparation of modified filler: (1) Add 20 parts of filler to a sealed mixing pot, stir at 65 r / min and heat to 55°C, and add 400 mL of silane hydrolysate to the mixing pot in the form of spray while stirring. The spray parameters are: spray pressure is 0.3 MPa, spray particle size is 30 μm, spray speed is 7.5 mL / min, keep warm and stir for 1.5 h, discharge, vacuum dry to obtain silane modified filler; (2) Under nitrogen protection, add 9 parts of terminal hydrogen silicone oil and 20 parts of silane modified filler to 45 parts of toluene / isopropanol mixed solvent, ultrasonically disperse for 10 min, and then add 0.075 parts of 1 wt% chloroplatinic acid-isopropanol solution, stir and react at 90°C for 3 h, filter, wash and dry to obtain modified filler; S13: Preparation of surface layer resin solution: Add 60 parts of divinyl polydimethylsiloxane, 20 parts of methyl vinyl MQ silicone resin, and 15 parts of modified silicone resin to a mixer and mix under vacuum for 1 hour. Then add 10 parts of hydrogen-containing MQ silicone resin, 15 parts of modified filler, 3 parts of hydrogen-containing silicone oil, and 0.075 parts of acetylenecyclohexanol and continue to mix under vacuum for 1 hour. Finally, add 0.12 parts of 1 wt% chloroplatinic acid-isopropanol solution and mix for 20 minutes to obtain the surface layer resin solution. S14: Preparation of surface layer: The surface layer resin liquid is coated onto the release paper, baked at 140℃ for 6 min, and the release paper is peeled off to obtain a surface layer with a thickness of 40±1μm. S2: Prepare adhesive resin solution and process it to obtain water-resistant silicone automotive interior leather material: S21: Preparation of adhesive resin solution: Add 70 parts of divinyl polydimethylsiloxane, 15 parts of methyl vinyl MQ silicone resin, and 3 parts of allyl isocyanate to a mixer and mix under vacuum for 1 hour. Then add 8.5 parts of hydrogen-containing silicone oil and 0.045 parts of acetylenecyclohexanol and continue to mix under vacuum for 1 hour. Finally, add 0.12 parts of 1 wt% chloroplatinic acid-isopropanol solution and mix for 20 minutes to obtain the adhesive resin solution. S22: Plasma treatment is performed on polyester nonwoven fabric substrate. The parameters of the plasma treatment are: the treatment gas is a mixture of O2 and Ar, the volume ratio of O2 and Ar is 30:70, the gas pressure is 25Pa, the treatment power is 125W, and the treatment time is 4min. S23: Preparation of water-resistant silicone automotive interior leather material: Apply adhesive resin liquid to any surface of a 0.5mm thick plasma-treated polyester nonwoven fabric substrate, and attach the surface layer to the adhesive resin liquid surface. Bake at 140℃ for 6 minutes to form an adhesive layer of 75±1μm, thus obtaining water-resistant silicone automotive interior leather material.

[0043] Example 2: Processing technology of a water-resistant silicone automotive interior leather material: Example 2 is based on Example 1, but with the following adjustment: the raw material composition of the surface resin liquid is adjusted, while other processes remain unchanged. Specifically: S13: Preparation of surface layer resin solution: Add 50 parts of divinyl polydimethylsiloxane, 10 parts of methyl vinyl MQ silicone resin, and 10 parts of modified silicone resin to a mixer and mix under vacuum for 1 hour. Then add 5 parts of hydrogen-containing MQ silicone resin, 10 parts of modified filler, 2 parts of hydrogen-containing silicone oil, and 0.05 parts of acetylenecyclohexanol and continue to mix under vacuum for 1 hour. Finally, add 0.08 parts of 1 wt% chloroplatinic acid-isopropanol solution and mix for 20 minutes to obtain the surface layer resin solution.

[0044] Example 3: Processing technology of a water-resistant silicone automotive interior leather material: Example 3 is based on Example 1, but with the following adjustment: the raw material composition of the surface resin liquid is adjusted, while other processes remain unchanged. Specifically: S13: Preparation of surface layer resin solution: Add 70 parts of divinyl polydimethylsiloxane, 30 parts of methyl vinyl MQ silicone resin, and 20 parts of modified silicone resin to a mixer and mix under vacuum for 1 hour. Then add 15 parts of hydrogen-containing MQ silicone resin, 20 parts of modified filler, 4 parts of hydrogen-containing silicone oil, and 0.1 parts of acetylenecyclohexanol and continue to mix under vacuum for 1 hour. Finally, add 0.15 parts of 1 wt% chloroplatinic acid-isopropanol solution and mix for 20 minutes to obtain the surface layer resin solution.

[0045] The following is a control experiment based on Example 1, with comparative examples 1 to 5, as detailed below: Comparative Example 1: Processing technology of a water-resistant silicone automotive interior leather material: Comparative Example 1 is based on Example 1, with the following adjustment: no modified silicone resin is added to the surface layer resin solution, while other processes remain unchanged. Specifically: S12: Preparation of surface layer resin solution: Add 60 parts of divinyl polydimethylsiloxane and 20 parts of methyl vinyl MQ silicone resin to a mixer and mix under vacuum for 1 hour. Then add 10 parts of hydrogen-containing MQ silicone resin, 15 parts of modified filler, 3 parts of hydrogen-containing silicone oil, and 0.075 parts of acetylenecyclohexanol. Continue to mix under vacuum for 1 hour. Finally, add 0.12 parts of 1 wt% chloroplatinic acid-isopropanol solution and mix for 20 minutes to obtain the surface layer resin solution.

[0046] Comparative Example 2: Processing technology of a water-resistant silicone automotive interior leather material: Comparative Example 2 is based on Example 1, with the following adjustment: no modified filler is added to the surface resin solution, while other processes remain unchanged. Specifically: S12: Preparation of surface layer resin solution: Add 60 parts of divinyl polydimethylsiloxane, 20 parts of methyl vinyl MQ silicone resin, and 15 parts of modified silicone resin to a mixer and mix under vacuum for 1 hour. Then add 10 parts of hydrogen-containing MQ silicone resin, 3 parts of hydrogen-containing silicone oil, and 0.075 parts of acetylenecyclohexanol and continue to mix under vacuum for 1 hour. Finally, add 0.12 parts of 1 wt% chloroplatinic acid-isopropanol solution and mix for 20 minutes to obtain the surface layer resin solution.

[0047] Comparative Example 3: A processing technology for a water-resistant silicone automotive interior leather material: Comparative Example 3 is based on Example 1, with the following adjustments: no modified silicone resin or modified filler is added to the surface layer resin solution, while other processes remain unchanged. Specifically: S11: Preparation of surface layer resin solution: Add 60 parts of divinyl polydimethylsiloxane and 20 parts of methyl vinyl MQ silicone resin to a mixer and mix under vacuum for 1 hour. Then add 10 parts of hydrogen-containing MQ silicone resin, 3 parts of hydrogen-containing silicone oil, and 0.075 parts of acetylenecyclohexanol and continue to mix under vacuum for 1 hour. Finally, add 0.12 parts of 1 wt% chloroplatinic acid-isopropanol solution and mix for 20 minutes to obtain the surface layer resin solution. Comparative Example 4: A processing technology for a water-resistant silicone automotive interior leather material: Comparative Example 4 is based on Example 1, with the following adjustment: allyl isocyanate is not added to the adhesive resin solution, while other processes remain unchanged. Specifically: S21: Preparation of adhesive resin solution: Add 70 parts of divinyl polydimethylsiloxane and 15 parts of methyl vinyl MQ silicone resin to a mixer and mix under vacuum for 1 hour. Then add 8.5 parts of hydrogen-containing silicone oil and 0.045 parts of acetylene cyclohexanol and continue to mix under vacuum for 1 hour. Finally, add 0.12 parts of 1 wt% chloroplatinic acid-isopropanol solution and mix for 20 minutes to obtain the adhesive resin solution.

[0048] Comparative Example 5: A processing technology for a water-resistant silicone automotive interior leather material: Comparative Example 5 is based on Example 1, with the following adjustment: the polyester nonwoven fabric substrate is not subjected to plasma treatment, while other processes remain unchanged. Specifically: S22: Preparation of water-resistant silicone automotive interior leather material: Apply adhesive resin liquid to any surface of a 0.5mm thick polyester nonwoven fabric substrate, and attach the surface layer to the adhesive resin liquid surface. Bake at 140℃ for 6 minutes to form an adhesive layer of 75±1μm, thus obtaining water-resistant silicone automotive interior leather material.

[0049] Performance testing: The water-resistant silicone automotive interior leather materials prepared in Examples 1-3 and Comparative Examples 1-5 were cut into 18cm × 18cm samples and then subjected to the following performance tests: (1) Antistatic performance: The surface resistance of the water-resistant silicone automotive interior leather material was tested using a GM3111 surface resistivity meter. The test was performed three times and the average value was taken. The surface resistance was used to characterize the antistatic performance of the water-resistant silicone automotive interior leather material. The lower the surface resistance, the better the antistatic performance. (2) Water resistance: According to the standard GB / T 40936-2021, a spray test was conducted on the water-resistant silicone automotive interior leather material to test its water resistance. (3) Abrasion resistance: The abrasion resistance of the surface layer of the water-resistant silicone automotive interior leather material was tested using a Taber abrasion tester at 23℃ and 50%RH. Under a load of 500g, the surface was rubbed 1000 times by CS-10 grinding wheel. (4) Adhesion performance: According to the ISO 2409-2020 standard, at 23℃ and 50RH%, the water-resistant silicone automotive interior leather material was cross-cut using a cross-cutting tool with a cross-cutting spacing of 1mm and a cross-cutting depth from the surface of the surface layer to the contact surface between the adhesive layer and the substrate layer. Then, 3M tape was pasted onto the cut part, and a multi-functional tensile testing machine was used to perform a 180° peel test at a tensile speed of 50mm / min to observe whether the silicone leather material on the 3M tape was peeled off.

[0050] The specific test results are shown in Table 1 below: Table 1

[0051] Conclusion and Analysis: As can be seen from the data in Table 1 above, this invention has comprehensively prepared a water-resistant organosilicon automotive interior leather material with excellent antistatic properties. While taking into account the antistatic and water-resistant properties of organosilicon leather materials, it further enhances the durability of organosilicon leather materials, which is of great significance.

[0052] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A processing technology for a water-resistant organosilicon automotive interior leather material, characterized in that: Includes the following steps: S1: Apply the surface resin liquid to the release paper, bake and cure it, peel off the release paper to obtain the surface layer; S2: Apply adhesive resin liquid to any surface of the substrate, and attach the surface layer to the surface of adhesive resin liquid, bake and cure to obtain water-resistant silicone automotive interior leather material; The surface resin liquid comprises the following raw material components: by weight, 50-70 parts of divinyl polydimethylsiloxane, 10-30 parts of methyl vinyl MQ silicone resin, 5-15 parts of hydrogen-containing MQ silicone resin, 10-20 parts of modified silicone resin, 10-20 parts of modified filler, 2-4 parts of hydrogen-containing silicone oil, 0.08-0.15 parts of chloroplatinic acid-isopropanol solution, and 0.05-0.1 parts of inhibitor; The adhesive resin liquid comprises the following raw material components: by weight, 60-80 parts of divinyl polydimethylsiloxane, 10-20 parts of methyl vinyl MQ silicone resin, 7-10 parts of hydrogen-containing silicone oil, 0.08-0.15 parts of chloroplatinic acid-isopropanol solution, 1-5 parts of adhesive accelerator, and 0.03-0.06 parts of inhibitor.

2. The processing technology of a water-resistant organosilicon automotive interior leather material according to claim 1, characterized in that: The modified silicone resin is prepared as follows: (1) Under nitrogen protection, terminal hydrogen silicone oil and sodium 2-hydroxypropanebutyryne diether-3-sulfonate are added to a toluene / isopropanol mixed solvent, stirred and mixed, and then chloroplatinic acid-isopropanol solution is added to it. The mixture is stirred and reacted at 85~95℃, separated and purified to obtain sodium sulfonate modified silicone oil; (2) Under nitrogen protection, sodium sulfonate modified silicone oil is added to a toluene / isopropanol mixed solvent, stirred and mixed, heated to 70~80℃, and then a portion of azobisisobutyronitrile is added to it. At the same time, methyl allyl alcohol polyoxyethylene ether is added dropwise. After the dropwise addition is completed, the remaining azobisisobutyronitrile is added, and the mixture is stirred and reacted. The mixture is separated and purified to obtain modified silicone resin. The sodium sulfonate modified silicone oil comprises the following raw material components: by weight, 10-20 parts of terminal hydrogen silicone oil, 5-10 parts of sodium 2-hydroxypropane-butynediol-3-sulfonate, 0.05-0.1 parts of chloroplatinic acid-isopropanol solution, and 30-60 parts of toluene / isopropanol mixed solvent; the modified silicone resin comprises the following raw material components: by weight, 12-24 parts of sodium sulfonate modified silicone oil, 4-12 parts of methyl allyl alcohol polyoxyethylene ether, 0.1-0.5 parts of azobisisobutyronitrile, and 30-60 parts of toluene / isopropanol mixed solvent.

3. The processing technology of a water-resistant organosilicon automotive interior leather material according to claim 1, characterized in that: The modified filler is prepared by: (1) adding the filler into a sealed mixing pot, adding silane hydrolysate into the mixing pot in the form of spray, keeping it warm and stirring, discharging the material, and vacuum drying to obtain silane modified filler; (2) under nitrogen protection, adding terminal hydrogen silicone oil and silane modified filler into toluene / isopropanol mixed solvent, ultrasonically dispersing, then adding chloroplatinic acid-isopropanol solution, stirring and reacting at 85~95℃, separating and purifying to obtain modified filler; The filler is prepared by mixing talc and silica in a mass ratio of (1~2):(1~2); the ratio of the filler to the silane hydrolysate is 1g:(0.1~0.3)mL; the modified filler includes the following raw material components: by weight, 8~10 parts of terminal hydrogen silicone oil, 15~25 parts of silane modified filler, 0.05~0.1 parts of chloroplatinic acid-isopropanol solution, and 30~60 parts of toluene / isopropanol mixed solvent.

4. The processing technology of a water-resistant organosilicon automotive interior leather material according to claim 3, characterized in that: The preparation method of the silane hydrolysate is as follows: add vinyl silane coupling agent and fluorinated silane coupling agent to an ethanol aqueous solution, add acetic acid to adjust the pH to 4.7~5.2, and stir and mix at 50~60℃ to obtain the silane hydrolysate; The volume ratio of the vinyl silane coupling agent, the fluorinated silane coupling agent, and the ethanol aqueous solution is (0.8~1):(0.8~1):

8.

5. The processing technology of a water-resistant organosilicon automotive interior leather material according to claim 1, characterized in that: The vinyl content of the divinyl polydimethylsiloxane is 0.15~0.18wt%; the vinyl content of the methyl vinyl MQ silicone resin is 0.7~1wt%; the hydrogen content of the hydrogen-containing MQ silicone resin is 0.2~0.8wt%; the hydrogen content of the hydrogen-containing silicone oil is ≥1.55wt%; and the inhibitor is acetylenecyclohexanol.

6. The processing technology of a water-resistant organosilicon automotive interior leather material according to claim 1, characterized in that: The adhesion promoter is an unsaturated isocyanate, including one or more combinations of allyl isocyanate, vinyl isocyanate, isocyanoethyl methacrylate, and ethyl isocyanate acrylate.

7. The processing technology of a water-resistant organosilicon automotive interior leather material according to claim 1, characterized in that: The substrate is a non-woven fabric, which is subjected to plasma treatment before coating. The parameters of the plasma treatment are as follows: the treatment gas is an O2 / Ar mixture, the volume ratio of O2 / Ar is (20~40):(60~80), the gas pressure is 20~30Pa, the treatment power is 100~150W, and the treatment time is 3~5min.

8. The processing technology of a water-resistant organosilicon automotive interior leather material according to claim 2 or 3, characterized in that: The hydrogen content of the terminal hydrogen silicone oil is 0.1~0.12wt%.

9. The water-resistant organosilicon automotive interior leather material obtained by the processing technology of any one of claims 1 to 8, characterized in that: The water-resistant silicone automotive interior leather material has a layered structure, consisting of a top layer, an adhesive layer, and a substrate layer from top to bottom; wherein the thickness of the top layer is 20~50μm; the thickness of the adhesive layer is 50~100μm; and the thickness of the substrate layer is 0.5~1mm.

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