Silicone synthetic leather for automobiles and preparation method thereof

Abstract

This application discloses an automotive silicone synthetic leather and its preparation method. The silicone synthetic leather includes a base fabric, an adhesive layer, and a top layer. By weight, the top layer contains the following components: silicone base adhesive: 20-50 parts; crosslinked hydrosilicone oil: 1-24 parts; boron-hybridized vinyl silicone resin: 5-45 parts; polysilazane: 1-15 parts; platinum catalyst: 0.001-0.05 parts. The crosslinked hydrosilicone oil is a polysiloxane having at least three hydrogen atoms bonded to silicon atoms. The polysilazane includes at least one of perhydropolysilazane and vinyl polysilazane, with each molecule of vinyl polysilazane having at least one vinyl group bonded to a silicon atom. The synthetic leather of this application not only possesses the basic performance requirements for automotive synthetic leather, such as excellent wear resistance, heat resistance, yellowing resistance, UV resistance, hydrolysis resistance, and stain resistance, but also exhibits excellent flexural strength and seam fatigue strength.

Description

Technical Field

[0001] This application relates to the field of silicone synthetic leather, and in particular to a silicone synthetic leather for automobiles and its preparation method. Background Technology

[0002] Silicone synthetic leather is a product made by coating a base fabric with silicone resin. Both sides of the synthetic leather closely resemble leather, and it has excellent breathability. It can mimic the composition and structure of natural leather and can be used as a substitute material. It is widely used in the manufacture of products in furniture, medical, decorative, and outdoor industries.

[0003] On the one hand, due to the unique -Si-O-Si- structure of silicone resin, it combines the properties of inorganic and organic materials, exhibiting excellent high and low temperature resistance, weather resistance, low surface tension, physiological inertness, and good film-forming properties, breathability, hydrophobicity, and flame retardancy. On the other hand, compared with natural leather, silicone synthetic leather performs worse in mechanical properties such as abrasion resistance and scratch resistance, especially its lower seam fatigue strength, which makes it prone to pinhole cracking at the seams during use, thus limiting its application. Summary of the Invention

[0004] To improve the wear resistance, scratch resistance, and pinhole crack resistance of silicone synthetic leather, this application provides a silicone synthetic leather for automobiles and its preparation method.

[0005] In a first aspect, this application provides an automotive silicone synthetic leather, comprising a base fabric, an adhesive layer, and a top layer, wherein the top layer comprises the following components by weight:

[0006] Silicone-based adhesive: 20-50 parts;

[0007] Crosslinked hydrosilicone oil: 1-24 parts;

[0008] Boron-hybridized vinyl silicone resin: 5-45 parts;

[0009] Polysilazane: 1-15 parts;

[0010] Platinum catalyst: 0.001–0.05 parts;

[0011] The crosslinked hydrosilicone oil is a polysiloxane having at least three hydrogen atoms bonded to silicon atoms;

[0012] The polysilazane includes at least one of perhydropolysilazane and vinyl polysilazane, wherein one molecule of vinyl polysilazane has at least one vinyl group bonded to a silicon atom.

[0013] As a silicone synthetic leather, the surface layer and adhesive layer of this application are both silicone materials, which are obtained by addition polymerization of vinyl silicone oil and hydrogen-containing silicone oil as the main raw materials in a platinum catalyst. By adding boron-hybridized vinyl silicone resin and polysilazane to the surface layer of this application, the structural strength, heat resistance, and adhesion strength between the surface layer and adjacent layers of the silicone material can be significantly improved, thereby improving the abrasion resistance, scratch resistance, flexural resistance, and seam fatigue strength of the synthetic leather, especially enhancing the low-temperature flexural properties of the synthetic leather.

[0014] Specifically, boron-hybrid vinyl silicone resin contains a boron-silicon hybrid crosslinking network structure, which enhances the structural strength and heat resistance of the base resin; at the same time, the introduction of boron atoms enhances its adhesive properties. The -Si-NH-Si backbone of polysilazane contains polar groups, and nitrogen atoms readily form intramolecular hydrogen bonds, increasing molecular bonding strength. Furthermore, it can react with polar functional groups in adjacent layers, significantly improving the wear resistance of the surface layer. The combination of hydrogen-containing silicone oil and a platinum catalyst can promote the crosslinking of side-chain fluorinated vinyl silicone resin with polysilazane, improving the overall mechanical strength of synthetic leather.

[0015] Furthermore, when the polysilazane in this application is vinyl polysilazane, under the action of a platinum catalyst, one coordinate bond of the platinum atom breaks and coordinates with the boron-hybridized vinyl silicone resin, and the other coordinate bond breaks and coordinates with the vinyl polysilazane, causing the two base resins to approach each other. Then, crosslinking is achieved by reacting the two resins with crosslinked hydrogen silicone oil, forming a crosslinked network structure, which significantly improves the structural strength of the surface layer.

[0016] It should be noted that the silicone silicone in this application is a polysiloxane having at least two vinyl groups bonded to silicon atoms, namely, end-chain vinyl silicone oil and / or dual-end-chain vinyl silicone oil. To improve production efficiency, this application uses a mixture of vinyl silicone oil and silica, more preferably a mixture of vinyl silicone oil and silica in a mass ratio of (10-35):(65-90), wherein the vinyl silicone oil is a polysiloxane having at least two vinyl groups bonded to silicon atoms.

[0017] In practical applications, single-component vinyl silicone oil and silica can also be used. The aforementioned vinyl silicone oil is a polysiloxane having at least two vinyl groups bonded to silicon atoms, i.e., base-terminal / side-chain vinyl silicone oil.

[0018] The crosslinked hydrosilicone oils in this application are all polysiloxanes having at least three hydrogen atoms bonded to silicon atoms, with the hydrogen atoms located at the end chain and / or side chain. In actual production applications, chain-extended hydrosilicone oils, i.e., polysiloxanes having two end chain hydrogen atoms bonded to silicon atoms, can be added to the surface layer composition according to product performance requirements.

[0019] Preferably, the viscosity of the polysilazane is 100–2000 mPa·s.

[0020] Preferably, in the surface layer composition, based on the content of 1 mol of vinyl groups bonded to silicon atoms, there are 1.05 to 1.1 mol of hydrogen atoms bonded to silicon atoms.

[0021] The content (hydrogen content) of hydrogen atoms bonded to silicon atoms in the crosslinked hydrosilicone oil of this application is preferably 0.3-1.6%.

[0022] In this application, the platinum catalyst is preferably one or more of the following: isopropanol chloroplatinate solution, tetrahydrofuran chloroplatinate solution, divinyltetramethyldisiloxane chloroplatinate complex, or chloroplatinate-1,3,5,7-tetravinyl-1,3,5,7-tetramethyl-cyclotetrasiloxane and divinyltetramethyldisiloxane chloroplatinate.

[0023] Preferably, the Pt atom content in the platinum catalyst is 300 to 100,000 ppm.

[0024] The surface layer composition of this application may include any one or more of the following, depending on the product requirements: inhibitors, fillers, organic solvents, reactive diluents, flame retardants, antioxidants, colorants, ultraviolet absorbers, light stabilizers, hand feel agents, antistatic agents, matting agents, silica, plasticizers, thickeners, surfactants, and film-forming aids.

[0025] Preferably, the inhibitor is one or more of methylbutyninol, ethynylcyclohexanol, alkynyl-containing maleic acid or its derivatives, and polyvinyl polysiloxane; the inhibitor is used to control the crosslinking speed of the system and improve the workability.

[0026] Preferably, the amount of the inhibitor is 0.0001 to 0.1 parts.

[0027] The filler used in this application is preferably at least one of the following: silicone resin MQ micro powder, silica (silica, including fumed silica, precipitated silica, organosilane treated silica, etc.), calcium carbonate (light, heavy, nano-sized, etc.), alumina, zinc borate, aluminum silicate, glass micro powder, and magnesium oxide; the filler is used for reinforcement to improve the structural strength of the resin material.

[0028] The preferred specific surface area of ​​the silica in this application is 100-300 g / m2.

[0029] The preferred particle size of the filler in this application is 800 to 5000 mesh.

[0030] The organic solvent used in this application is preferably one or more of C5-C30 alkanes and / or aromatics, C5-C30 ethers and / or esters, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane; the reactive diluent used in this application is terminal vinyl silicone oil with a viscosity of 300-10000 mPa·s; the organic solvent and reactive diluent are used to dissolve and dilute the components, reduce the viscosity of the system, and improve the leveling performance.

[0031] The flame retardant used in this application is preferably at least one of aluminum hydroxide, magnesium hydroxide, decabromodiphenyl ethane, and antimony trioxide.

[0032] Preferably, the raw materials for the boron-hybridized vinyl silicone resin include vinyl silicone resin, boric acid derivative and titanium chelate catalyst in a mass ratio of (70-90):1:(0.05-0.1), wherein the boric acid derivative molecule has at least one boric acid group or borate ester group.

[0033] Preferably, the boric acid derivative includes at least one of 4-biphenylboronic acid, boric acid, n-butylboronic acid, 3-methoxyphenylboronic acid, trimethyl borate, tributyl borate, and tri-n-propyl borate.

[0034] Preferably, the titanate chelate catalyst comprises at least one of titanium acetylacetonate (acetylacetonate titanate), butyl phosphate titanate, and organoalkoxy titanate.

[0035] Preferably, the vinyl silicone resin has a viscosity of mPa·s and a vinyl content of 0.9-3.0 wt%.

[0036] Preferably, the method for preparing the boron-hybridized vinyl silicone resin includes:

[0037] Vinyl silicone resin and boric acid derivatives are dissolved in an organic solvent, and a titanium chelate catalyst is added. After mixing evenly, the mixture is heated to react. After the reaction is completed, the low-boiling-point substances are removed by vacuuming under reduced pressure.

[0038] Preferably, the temperature of the heating reaction is 40–60°C;

[0039] Preferably, the heating reaction time is 4 to 8 hours.

[0040] The above reaction uses boric acid derivatives as the boron source to copolymerize with difunctional and trifunctional alkoxysilane segments in vinyl silicone resin, introducing boron atoms into the silicone resin and promoting the improvement of resin structural strength. Titanium acetylacetonate acts as a catalytic promoter, enhancing reactivity and promoting the formation of cross-linked network structures.

[0041] Preferably, the surface layer also contains 3 to 28 parts by weight of silane coupling agent modified zirconium oxide.

[0042] Preferably, the silane coupling agent is a vinylsilane coupling agent.

[0043] Preferably, the ratio of zirconium oxide to silane coupling agent is 100:5 to 15.

[0044] Preferably, the modification steps of the modified zirconium oxide include: adding zirconium oxide to n-hexane, ultrasonically dispersing it, adding vinyltriethoxysilane, adding acid to adjust the pH to 4-5, ultrasonically dispersing it, and then filtering, washing, and drying it to obtain the product.

[0045] Zirconia occupies the free volume in the silicone resin, preventing the molecular chains of the matrix material from occupying all the space. The chain segments are fixed to some extent, and the movement of the molecular chains is restricted to a certain degree, which increases the glass transition temperature and thus improves the heat resistance, elastic modulus, rigidity and impact strength of the surface layer and silicone.

[0046] Silane coupling agents can significantly reduce the surface energy of zirconium oxide and inhibit agglomeration and sedimentation. Furthermore, the use of vinylsilane coupling agents can promote crosslinking between the modified zirconium oxide and the matrix resin, further enhancing the structural strength of the surface layer material and reducing the probability of pinhole cracking.

[0047] The side of the surface layer away from the adhesive layer contains a surface treatment layer, which, by weight, comprises the following components:

[0048] Side-chain fluorinated vinyl silicone resin: 40-75 parts;

[0049] Polysilazane: 2-25 parts;

[0050] Crosslinked hydrosilicone oil: 3-20 parts;

[0051] Adhesive: 0.5–18 parts;

[0052] Platinum catalyst: 0.001 to 1 part;

[0053] Filler: 8-40 parts;

[0054] Organic solvent: 30-70 parts;

[0055] The fluorinated vinyl silicone resin with side chains is a silicone resin having fluorinated side chains and vinyl groups bonded to silicon atoms;

[0056] The polysilazane includes at least one of perhydropolysilazane and vinyl polysilazane, wherein one molecule of vinyl polysilazane has at least one vinyl group bonded to a silicon atom.

[0057] Preferably, the side-chain fluorinated vinyl silicone resin has a vinyl content of 0.5-2.0% and a fluorine content of 0.1-0.5%.

[0058] By applying a surface treatment layer to the outer side of the surface layer, the stain resistance and self-cleaning effect and surface gloss of silicone synthetic leather can be significantly improved. At the same time, the combination of the surface treatment layer and the surface layer can enhance the wear resistance, scratch resistance and pinhole crack resistance of silicone synthetic leather while ensuring the bonding strength of each layer.

[0059] Specifically, the fluorinated side chains of the fluorinated vinyl silicone resin can accumulate on the surface of the surface treatment layer, forming a smooth surface structure with strong hydrophobicity and a low coefficient of friction, thus improving the wear resistance, scratch resistance, and dirt resistance of the surface layer. Furthermore, the surface layer, due to its high boron-doped silicone resin content, has poor gloss and feel; by adding a surface treatment layer, the appearance quality of the silicone synthetic leather can be significantly improved. While the adhesion between the surface treatment layer and the silicone material is relatively poor due to the influence of the fluorinated groups, the boron-hybridized vinyl silicone resin in the surface layer allows for good adhesion, ensuring bonding strength. Finally, under the action of a platinum catalyst, the fluorinated vinyl silicone resin with side chains can undergo a cross-linking reaction with polysilazane to form a cross-linked network structure, significantly improving the structural strength of the surface layer and endowing it with excellent wear resistance and resistance to pinhole cracking.

[0060] The above-mentioned surface treatment layer may contain one or more of the following: inhibitors, accelerators, adhesives, fillers, and organic solvents, depending on the product performance requirements.

[0061] Preferably, the amount of inhibitor used in the surface layer is 0.0001 to 0.1 parts;

[0062] Preferably, the accelerator in the surface treatment layer includes at least one of titanate, aluminate, zirconate, zinc isooctanoate, and distin dilaurate; more preferably, the amount of the accelerator is 0.5-10 parts.

[0063] Preferably, the surface treatment layer filler includes at least one of organosilicon elastic microspheres, silica powder, organic matting powder, and tactile powder.

[0064] Preferably, an intermediate layer is provided between the surface layer and the adhesive layer, and the intermediate layer comprises the following components by weight: Component A:

[0065] Silicone-based adhesive: 10-20 parts;

[0066] Vinyl-terminated silicone oil: 5-35 parts, viscosity 300-10000 mPa·s;

[0067] Vinyl MQ resin: 15-30 parts;

[0068] Crosslinked hydrosilicone oil: 1-24 parts;

[0069] Organosilicon core-shell particles: 10–30 parts;

[0070] Inhibitor: 0.001–0.05 parts;

[0071] Component B:

[0072] Silicone-based adhesive: 10-30 parts;

[0073] Vinyl-terminated silicone oil: 5-10 parts, viscosity 300-10000 mPa·s;

[0074] Vinyl MQ resin: 15-30 parts;

[0075] Platinum catalyst: 0.001 to 1 part;

[0076] The terminated vinyl silicone oil is a polysiloxane having two end-chain vinyl groups bonded to silicon atoms.

[0077] Preferably, the vinyl MQ resin has a vinyl content of 0.9 to 3.5 wt%.

[0078] Preferably, the surface layer composition includes 1 to 20 parts by weight of flame retardant and 5 to 30 parts by weight of organic solvent.

[0079] Preferably, the surface layer composition includes 1-10 parts by weight of filler and 5-30 parts by weight of organic solvent.

[0080] Preferably, the intermediate layer also includes 1 to 15 parts of pigment.

[0081] To test the yellowing properties of synthetic leather, the preferred pigment is a white paste made of rutile titanium dioxide, such as Jianxin JS-110.

[0082] The organosilicon core-shell particles of this application have an organosilicon core and an organic polymer shell, preferably made by Wacker Chemie. At least one of P52 and complexed EPX-152.

[0083] The intermediate layer of this application may contain any one or more of the following components, depending on the product requirements: filler, organic solvent, reactive diluent, flame retardant, antioxidant, colorant, ultraviolet absorber, light stabilizer, hand feel agent, antistatic agent, matting agent, silica, plasticizer, thickener, surfactant, and film-forming aid.

[0084] In this application, the intermediate layer serves as both a coloring layer and a muscle layer, showcasing the color of the synthetic leather. Simultaneously, it works in conjunction with the top layer and surface treatment layer to impart excellent weather resistance, flame retardancy, flexural strength, and seam fatigue strength to the synthetic leather. Specifically, the application of organosilicon core-shell particles effectively increases the toughness and structural strength of the intermediate layer, thereby improving the aforementioned properties. The intermediate layer is significantly cheaper than the top layer and is often used to reduce the amount of top layer required, thus lowering the overall manufacturing cost of the organosilicon synthetic leather.

[0085] Preferably, the adhesive layer comprises the following components, based on parts by weight:

[0086] Component A:

[0087] Silicone-based adhesive: 20-30 parts;

[0088] Vinyl-terminated silicone oil: 10-30 parts, viscosity 300-10000 mPa·s;

[0089] Vinyl MQ resin: 5-15 parts;

[0090] Crosslinked hydrosilicone oil: 1-20 parts;

[0091] Organosilicon core-shell particles: 5–25 parts;

[0092] Adhesive: 0.5–25 parts;

[0093] Inhibitor: 0.001–0.05 parts;

[0094] Component B:

[0095] Silicone-based adhesive: 20-30 parts;

[0096] Vinyl-terminated silicone oil: 10-30 parts, viscosity 300-10000 mPa·s;

[0097] Platinum catalyst: 0.001 to 1 part.

[0098] The adhesive layer composition of this application may include any one or more of the following, depending on the product requirements: filler, organic solvent, reactive diluent, flame retardant, antioxidant, colorant, ultraviolet absorber, light stabilizer, hand feel agent, antistatic agent, matting agent, silica, plasticizer, thickener, surfactant, and film-forming aid.

[0099] The adhesive layer serves to connect the base fabric with the intermediate layer or other silicone resin layers, ensuring a strong bond between the synthetic leather and the substrate.

[0100] Preferably, the adhesive comprises one or more of γ-(methacryloyloxy)propyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and tri(2-hydroxyethyl)isocyanurate triacrylate.

[0101] The aforementioned adhesive contains unsaturated groups and hydroxyl groups or active groups that can be hydrolyzed to produce hydroxyl groups; wherein the unsaturated groups can participate in the crosslinking reaction of the hydrosilicone oil, thereby forming a strong connection with the organosilicon interlayer, and the active groups can bond with the active groups in the base fabric to form a connection.

[0102] Secondly, this application provides a method for preparing silicone synthetic leather for automobiles, comprising the following steps:

[0103] Surface layer preparation: Mix the raw materials except for the platinum catalyst evenly according to the formula, add the catalyst, and continue mixing to obtain the surface layer resin; coat the surface layer resin onto the release paper and heat to vulcanize to form the surface layer;

[0104] Intermediate layer preparation: According to the formula, the raw materials of components A and B are mixed separately and set aside. After the components A and B are mixed evenly, they are coated on the surface layer and heated for vulcanization to form the intermediate layer.

[0105] Preparation of adhesive layer: Mix the raw materials of components A and B separately according to the ratio and set aside. After mixing components A and B evenly, coat them onto the intermediate layer to form an adhesive layer.

[0106] Base fabric lamination: The base fabric is laminated onto the adhesive layer, and the adhesive layer is heated to vulcanize;

[0107] Preparation of surface treatment layer: According to the formula, the raw materials except for the platinum catalyst are mixed evenly, then the platinum catalyst is added and the mixing is continued to obtain the surface treatment layer resin. The surface treatment layer resin is applied to the surface layer by printing or coating process, and then heated and dried to form the surface treatment layer, thus obtaining the silicone synthetic leather.

[0108] In this application, the thickness of the surface layer is preferably 0.01–0.15 mm; the thickness of the intermediate layer is preferably 0.01–0.15 mm; the thickness of the intermediate layer is preferably 0.1–0.4 mm; the thickness of the adhesive layer is preferably 0.1–0.5 mm; and the thickness of the surface treatment layer is preferably 10–100 g / m². 2 The vulcanization temperatures described in this application are all between 80 and 150°C.

[0109] In summary, this application has the following beneficial effects:

[0110] 1. This application significantly enhances the structural strength of the surface layer silicone resin by adding polysilazane and boron hybrid vinyl silicone resin, thereby endowing it with excellent wear resistance, scratch resistance, flexural resistance, temperature resistance, and joint fatigue strength.

[0111] 2. By employing a combination of a top layer and a surface treatment layer, this application can improve the surface gloss and stain resistance of synthetic leather while ensuring the bonding strength between the top layer, surface treatment layer and other layers, and further improve the abrasion resistance, flexural resistance and seam fatigue strength of synthetic leather. Detailed Implementation

[0112] Preparation example of boron-hybridized vinyl silicone resin

[0113] Preparation Example 1-1: A boron-hybridized vinyl silicone resin was prepared according to the following method:

[0114] 3336g of vinyl silicone resin, 42g of 4-biphenylboronic acid, and acetone were added sequentially to a reaction flask and stirred until completely dissolved. Then, 2.6g of titanium acetylacetone was added and stirred until homogeneous. The mixture was heated to 50℃ and reacted for 6 hours. After that, the mixture was vacuumed (0.6-0.8MPa) to remove low-boiling substances. The vacuuming operation lasted for 60 minutes to obtain boron-hybridized vinyl silicone resin.

[0115] Preparation Examples 1-2: A boron-hybridized vinyl silicone resin was prepared according to the following method:

[0116] 3600g of vinyl silicone resin, 42g of 4-biphenylboronic acid, and acetone were added sequentially to a reaction flask and stirred until completely dissolved. Then, 4.0g of titanium acetylacetone was added and stirred until homogeneous. The mixture was heated to 50℃ and reacted for 6 hours. After that, the low-boiling substances were removed by vacuuming (0.6-0.8MPa) for 60 minutes to obtain boron-hybridized vinyl silicone resin.

[0117] Preparation Examples 1-3, a boron-hybridized vinyl silicone resin, differs from Preparation Example 1-1 in that an equal amount of trimethyl borate is used instead of 4-biphenylboronic acid.

[0118] Preparation Examples 1-4: A boron-hybridized vinyl silicone resin, which differs from Preparation Example 1-1 in that a titanate chelate (titanium acetylacetonate) is not added.

[0119] Example of modified zirconium oxide preparation

[0120] Preparation Example 2-1: A modified zirconia was prepared by adding 100g of zirconia to 200g of n-hexane, ultrasonically dispersing for 30min, adding 10g of vinyltriethoxysilane, adjusting the pH to 4-5 by adding hydrochloric acid, ultrasonically dispersing for 8h, filtering, washing, and drying to obtain vinyl-modified zirconia.

[0121] Preparation Example 2-2: A modified zirconia was prepared by adding 100g of zirconia to 200g of n-hexane, ultrasonically dispersing at 3.5 for 30min, adding 5g of epoxytriethoxysilane, adjusting the pH to 4-5 by adding hydrochloric acid, ultrasonically dispersing for 8h, filtering, washing, and drying to obtain epoxy-modified zirconia.

[0122] Example

[0123] Example 1: An automotive silicone synthetic leather was prepared according to the following steps:

[0124] 1. Surface layer preparation

[0125] 1-1. According to the surface layer ratio, add boron-hybridized vinyl silicone resin (Preparation Example 1-1), vinyl polysilazane (viscosity 1000 mPa·s), organosilicon-based adhesive (carbon black content 20 wt%), modified zirconium oxide (Preparation Example 2-1), and organic solvent (150# solvent oil) to the reaction vessel. After stirring at 1500 rpm for 30 min with a high-speed disperser, add inhibitor (3-methyl-1-butyn-3-ol) and crosslinked hydrosilicone oil (hydrogen content 1.5%). Continue stirring at 1500 rpm for 30 min to obtain the hydrogen-containing component for later use.

[0126] 1-2. Before use, add platinum catalyst (isopropanol solution of H2PtCl6·6H2O) to the hydrogen-containing component and stir at 1500 rpm for 20 min to obtain the surface resin.

[0127] 1-3. Coat the surface of the release paper with the top layer resin to a thickness of 0.01 mm, and then place it in a vulcanizing environment at 120°C for 3 minutes to form the top layer.

[0128] 2. Preparation of the intermediate layer

[0129] 2-1. Add the silicone-based adhesive (20wt% carbon black content), vinyl-terminated silicone oil (850mPa.s), inhibitor, and organic solvent (150# solvent oil) to a stainless steel container. Stir with a planetary mixer for 15 minutes. Then add the crosslinking hydrosilicone oil, vinyl MQ resin (1.7wt% vinyl content), and silicone core-shell particles (Wacker). P52), flame retardant (1250 mesh aluminum hydroxide), silane-treated silica (150 mesh) 2 Mix (g), stir for 15 minutes; then add pigment paste to adjust the color, and obtain component A.

[0130] 2-2. Add the silicone-based adhesive (carbon black content 20wt%), vinyl-terminated silicone oil (850mPa.s), vinyl MQ resin (vinyl content 2.3wt%), platinum catalyst (isopropanol solution of H2PtCl6·6H2O), and 150# solvent oil to a stainless steel container, and add silane-treated silica (specific surface area 150m²). 2 The mixture (g) was dispersed in a planetary mixer for 20 minutes to obtain component B.

[0131] 2-3. Add components A and B to a stainless steel bucket according to the ratio, disperse with a planetary mixer for 20 minutes, mix evenly, filter, and obtain the intermediate layer slurry for later use.

[0132] 2-4. Apply the intermediate layer slurry onto the top layer coating film with a coating thickness of 0.2 mm, and then place it in a vulcanizing environment at 130℃ for 5 minutes to form the intermediate layer.

[0133] 3. Preparation of adhesive layer

[0134] 3-1. Add the silicone-based adhesive (10wt% carbon black content), vinyl-terminated silicone oil (850 mPa·s), adhesive (2-(3,4-epoxycyclohexyl)ethyltriethoxysilane), and inhibitor (3-methyl-1-butyn-3-ol) to a stainless steel container and stir with a planetary mixer for 20 min. Then add the vinyl MQ resin (1.5wt% vinyl content), crosslinking hydrogen silicone oil (1.0% hydrogen content), and silicone core-shell particles (WACKER). P52), silane-treated silica (specific surface area 150m²) 2 Add g of [unspecified ingredient] and flame retardant (1250 mesh aluminum hydroxide), and stir for 20 minutes. Then add pigment paste to adjust the color, thus preparing component A.

[0135] 3-2. Add the organosilicon-based adhesive (carbon black content 10wt%), vinyl-terminated silicone oil (2000 mPa·s), and platinum catalyst (isopropanol solution of H2PtCl6·6H2O) to a stainless steel container, and add silane-treated silica (specific surface area 150 m² / g). 2 The mixture (g) was dispersed in a planetary mixer for 20 minutes to obtain component B.

[0136] 3-3. Add components A and B to a stainless steel container according to the specified ratio, disperse in a planetary mixer for 30 minutes, mix evenly, filter and set aside.

[0137] 3-4. Apply the adhesive layer slurry onto the intermediate layer coating film with a coating thickness of 0.3 mm to form the adhesive layer.

[0138] 4. Base fabric composite

[0139] 4-1. Use a pressure roller or a corner roller to smoothly adhere the DSC1610 (Haojili) white weft-knitted fabric to the adhesive layer slurry.

[0140] 4-2. Then place it at 130℃ for 5 minutes to vulcanize.

[0141] 4-3. After cooling, separate the release paper from the surface layer and then roll it up for recycling.

[0142] 5. Preparation of surface treatment layer

[0143] 5-1. Fluorinated vinyl silicone resin (vinyl content 1.0 wt%, fluorine content 0.2 wt%), vinyl polysilazane (1000 mPa·s), crosslinked hydrosilicone oil (hydrogen content 1.5 wt%), organic solvent (dodecyl isocyanate), 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane (adhesive), inhibitor (3-methyl-1-butyn-3-ol), and silane are used to treat silica (specific surface area 150 m² / s). 2Mix (g) at 40°C with stirring at 2000 r / min, then add the accelerator (titanium ester) and platinum catalyst (0.05% tetrahydrofuran chloroplatinate solution), mix thoroughly, and filter through a 200-mesh screen for later use.

[0144] 5-2. Using an 80-200 mesh anilox roller, apply the surface treatment layer to the leather surface by printing or roller coating, with a coating amount of 60g / m². 2 Drying at 140℃ for 3 minutes yields silicone synthetic leather for automobiles.

[0145] Example 2: An automotive silicone synthetic leather was prepared according to the following steps:

[0146] 1. Surface layer preparation

[0147] 1-1. According to the surface layer ratio, add boron-hybridized vinyl silicone resin (Preparation Example 1-2), vinyl polysilazane (viscosity 1000 mPa·s), organosilicon-based adhesive (carbon black content 30 wt%), modified zirconium oxide (Preparation Example 2-1), and organic solvent (150# solvent oil) to the reaction vessel. After stirring at 1500 rpm for 30 min with a high-speed disperser, add inhibitor (3-methyl-1-butyn-3-ol) and crosslinked hydrosilicone oil (hydrogen content 1.0%). Continue stirring at 1500 rpm for 30 min to obtain the hydrogen-containing component for later use.

[0148] 1-2. Before use, add platinum catalyst (isopropanol solution of H2PtCl6·6H2O) to the hydrogen-containing component and stir at 1500 rpm for 20 min to obtain the surface resin.

[0149] 1-3. Coat the surface of the release paper with the top layer resin to a thickness of 0.01 mm, and then place it in a vulcanizing environment at 120°C for 3 minutes to form the top layer.

[0150] 2. Preparation of the intermediate layer

[0151] 2-1. Add the silicone-based adhesive (10wt% carbon black content), vinyl-terminated silicone oil (5000 mPa·s), inhibitor, and organic solvent to a stainless steel container and stir with a planetary mixer for 15 minutes. Then add the crosslinked hydrosilicone oil, vinyl MQ resin (1.7wt% vinyl content), and silicone core-shell particles (Wacker). P52), flame retardant (1250 mesh aluminum hydroxide), silane-treated silica (150 mesh) 2 Mix (g), stir for 15 minutes; then add pigment paste to adjust the color, and obtain component A.

[0152] 2-2. Add the organosilicon-based adhesive (carbon black content 10wt%), vinyl-terminated silicone oil (850 mPa.s), vinyl MQ resin (vinyl content 1.8wt%), platinum catalyst (isopropanol solution of H2PtCl6·6H2O), and 150# solvent oil to a stainless steel container, and add silane-treated silica (specific surface area 150 m² / s). 2 The mixture (g) was dispersed in a planetary mixer for 20 minutes to obtain component B.

[0153] 2-3. Add components A and B to a stainless steel bucket according to the ratio, disperse with a planetary mixer for 20 minutes, mix evenly, filter, and obtain the intermediate layer slurry for later use.

[0154] 2-4. Apply the intermediate layer slurry onto the top layer coating film with a coating thickness of 0.2 mm, and then place it in a vulcanizing environment at 130℃ for 5 minutes to form the intermediate layer.

[0155] 3. Preparation of adhesive layer

[0156] 3-1. Add the silicone-based adhesive (20wt% carbon black content), vinyl-terminated silicone oil (5000 mPa·s), γ-(methacryloyloxy)propyltrimethoxysilane (adhesive), and inhibitor (3-methyl-1-butyn-3-ol) to a stainless steel container and stir with a planetary mixer for 20 minutes. Then add vinyl MQ resin (1.5wt% vinyl content), crosslinked hydrogen silicone oil (1.2% hydrogen content), and silicone core-shell particles (Wacker). P52), silane-treated silica (specific surface area 150m²) 2 Add g of [unspecified ingredient] and flame retardant (1250 mesh aluminum hydroxide), and stir for 20 minutes. Then add pigment paste to adjust the color, thus preparing component A.

[0157] 3-2. Add the silicone-based adhesive (20wt% silica content), vinyl-terminated silicone oil (500 mPa·s), and platinum catalyst (isopropanol solution of H2PtCl6·6H2O) to a stainless steel container, and add silane-treated silica (specific surface area 150 m² / g). 2 The mixture (g) was dispersed in a planetary mixer for 20 minutes to obtain component B.

[0158] 3-3. Add components A and B to a stainless steel container according to the specified ratio, disperse in a planetary mixer for 30 minutes, mix evenly, filter and set aside.

[0159] 3-4. Apply the adhesive layer slurry onto the intermediate layer coating film with a coating thickness of 0.3 mm to form the adhesive layer.

[0160] 4. Base fabric composite

[0161] 4-1. Use a pressure roller or a corner roller to smoothly adhere the DSC1610 (Haojili) white weft-knitted fabric to the adhesive layer slurry.

[0162] 4-2. Then place it at 130℃ for 5 minutes to vulcanize.

[0163] 4-3. After cooling, separate the release paper from the surface layer and then roll it up for recycling.

[0164] 5. Preparation of surface treatment layer

[0165] 5-1. Fluorinated vinyl silicone resin (vinyl content 1.0 wt%, fluorine content 0.2 wt%), vinyl polysilazane (1000 mPa·s), crosslinked hydrosilicone oil (hydrogen content 1.5%), organic solvent (dodecyl isocyanate), tri(2-hydroxyethyl) isocyanurate triacrylate (adhesive), inhibitor (3-methyl-1-butyn-3-ol), and silane are used to treat silica (specific surface area 150 m² / s). 2 Mix (g) at 40°C with stirring at 2000 r / min, then add the accelerator (titanium ester) and platinum catalyst (0.05% tetrahydrofuran chloroplatinate solution), mix thoroughly, and filter through a 200-mesh screen for later use.

[0166] 5-2. Apply the surface treatment layer to the leather surface using a 200-mesh anilox roller by printing or roller coating, with a coating amount of 80g / m². 2 Drying at 140℃ for 3 minutes yields silicone synthetic leather for automobiles.

[0167] Example 3 is an automotive silicone synthetic leather. The difference from Example 1 is that in the surface layer raw material, an equal amount of boron hybrid vinyl silicone resin obtained in Examples 1-3 is used to replace the boron hybrid vinyl silicone resin obtained in Example 1-1, and the raw material ratio is shown in Table 1.

[0168] Table 1. Raw material ratios for Examples 1-3

[0169]

[0170]

[0171]

[0172] Example 4, an organosilicon synthetic leather for automobiles, differs from Example 1 in that, in the surface layer raw material, an equal amount of boron-hybridized vinyl silicone resin obtained in Examples 1-4 is used to replace the boron-hybridized vinyl silicone resin obtained in Examples 1-1, and the raw material ratio is shown in Table 1.

[0173] Example 5, an organosilicon synthetic leather for automobiles, differs from Example 1 in that an equal amount of modified zirconium oxide obtained in Example 2-2 is used instead of the modified zirconium oxide obtained in Example 2-1.

[0174] Example 6: An automotive silicone synthetic leather, differing from Example 1 in that a top layer of equal thickness replaces the intermediate layer in the synthetic leather. Specifically, during the top layer preparation process, the coating thickness is increased to 0.3 mm. Additionally, in steps 3-4 of the adhesive layer preparation, the adhesive layer slurry is applied to the top layer coating.

[0175] Example 7, an automotive silicone synthetic leather, differs from Example 6 in that the surface of the synthetic leather is not coated with a surface treatment layer.

[0176] Example 8, an organosilicon synthetic leather for automobiles, differs from Example 1 in that an equal amount of vinyl silicone resin (vinyl content of 1.5%) is used instead of side-chain fluorinated vinyl silicone resin in the surface treatment layer raw material.

[0177] Example 9, an organosilicon synthetic leather for automobiles, differs from Example 1 in that an equal amount of side-chain fluorinated vinyl silicone resin is used instead of vinyl polysilazane in the surface treatment layer raw material.

[0178] Example 10, an organosilicon synthetic leather for automobiles, differs from Example 1 in that an equal amount of perhydropolysilazane (1000 mPa·s) is used instead of vinyl polysilazane in the surface layer raw material.

[0179] Example 11, an organosilicon synthetic leather for automobiles, differs from Example 1 in that organosilicon core-shell particles are not added to the intermediate layer and adhesive layer.

[0180] Example 12, an automotive silicone synthetic leather, differs from Example 1 in that no adhesive is added to the surface layer and the adhesive layer.

[0181] Comparative Example

[0182] Comparative Example 1, an automotive silicone synthetic leather, differs from Example 7 in that an equal amount of vinyl silicone resin is used instead of boron-hybridized vinyl silicone resin in the surface layer material.

[0183] Comparative Example 2, an automotive silicone synthetic leather, differs from Example 7 in that an equal amount of silicone-based adhesive (20 wt% silica content) is used instead of vinyl polysilazane in the surface layer material.

[0184] Comparative Example 3, an automotive silicone synthetic leather, differs from Example 1 in that its top layer resin is prepared by mixing Dow Chemical's 8600A and 8600B in a 1:1 mass ratio, with a coating thickness of 0.01 mm. The intermediate layer slurry is obtained by mixing Dow Chemical's 8300A and 8300AB in a 1:1 mass ratio, with a coating thickness of 0.2 mm. The adhesive layer slurry is obtained by mixing Dow Chemical's 8420A and 8420B in a 1:1 mass ratio, with a coating thickness of 0.2 mm.

[0185] Comparative Example 4: Preparation of a semi-silicone synthetic leather, comprising the following steps:

[0186] Top / Middle Layer Preparation: Weigh the top layer resin HDA-5035NY / DMF / MEK = 100 / 50 / 30, mix evenly, add 17 parts of 2701 (rutile titanium dioxide) / 0.1 parts of 6609 (iron yellow) / 0.02 parts of 3687 (iron red), mix and stir evenly at 800-1500r / min, and filter with a 150 mesh filter for later use.

[0187] Solvent-free slurry preparation: Weigh 100 parts of HDPM-2110H-A resin, add 2 parts of HDPM-2110-C, stir evenly, add 40 parts of flame retardant (OP935), stir evenly, and filter for later use.

[0188] Preparation of surface treatment layer: 75 parts of side-chain fluorinated vinyl silicone resin, 25 parts of vinyl polysilazane, 12 parts of hydrogen-containing silicone oil (silicon hydrogen content 1.5%), 60 parts of dodecyl isoformane, 0.5-10 parts of adhesive 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 0.07 parts of platinum catalyst (0.05% tetrahydrofuran chloroplatinate solution), 2 parts of accelerator (polydimethylsiloxane), 0.02 parts of inhibitor (3-methyl-1-butyn-3-ol), and 25 parts of silane-treated silica. Mix at 40°C and stirring at 800-1500 r / min for 10 min. Then add the accelerator and platinum catalyst, continue stirring and mixing for 20 min, and pass through a 200-mesh sieve for later use.

[0189] S1: Apply the surface layer paste to the release paper in a 0.20±0.02mm diameter layer and dry it in a hot air oven at 80-140℃ for 3-5 minutes;

[0190] S2: Apply a 0.20±0.05mm layer of intermediate slurry to the dry film of the top layer, and dry it in an oven at 80-140℃ for 3-5 minutes with hot air.

[0191] S3: Mix the prepared solvent-free slurry with HDPM-2110H-B at a weight ratio of 140 / 110, coat it onto the intermediate dry film, and bake it in hot air at 100-120℃ for 40-60 seconds. After the surface has initially gelled, attach the base fabric, flatten it with a roller, and then cure it in an oven at 120-130℃ for 6-10 minutes. Cool and peel it off. Cure at room temperature for more than 12 hours.

[0192] S4: Print the prepared surface treatment agent onto the leather surface using a 100-mesh double-coil roller, and dry it with hot air at 130-150℃ for 3-5 minutes to obtain semi-silicone synthetic leather for automobiles.

[0193] Comparative Example 5: Commercially available off-white PVC artificial leather for automobiles.

[0194] Performance testing

[0195] Experiment 1: Basic Performance Test of Organosilicon Synthetic Leather

[0196] 1. Hydrolysis resistance: Six parallel samples of 150mm*150mm were cut from each example and comparative example and tested using the jungle test method. Before the experiment, the peel strength of three sets of parallel samples was tested and the data were recorded. The other three sets of parallel samples were stored at 70℃ and 95% relative humidity for 5 weeks, and then tested for flexural stress (15000 times / (23±2)℃). The presence of cracks on the leather surface was observed and recorded.

[0197] 2. Xenon light resistance: The xenon light resistance level was assessed and recorded using a gray scale with color change, in accordance with EN SAE J2412-2015 standard. Irradiance: (0.55±0.02) W / (m².nm)@340nm;

[0198] Light intensity: 3.8h, blackboard temperature: (89±2.5)℃, chamber temperature: (62±2)℃, relative humidity: (50±10)%.

[0199] Darkness: 1 hour, blackboard temperature: (38±2.5)℃, chamber temperature: (38±3)℃, relative humidity: (95±10)%.

[0200] Filters: Inner filter: Quartz, Outer filter: Boro;

[0201] Total irradiance: 1055 KJ / m2, test time: 672 h;

[0202] Instrument model: Atlas Ci3000+.

[0203] 3. Abrasion Resistance: Following the ASTM D 3884-2009 standard, an Abrasion Tester was used with a CS10 grinding wheel at a speed of 4000 rpm. Abrasion resistance tests were conducted on each example and comparative example, and the results were rated.

[0204] 4. Flexural resistance: According to QB / T 2714-2018, the flexural resistance of the leather is tested using a leather flexural resistance tester of model MK-761, and the presence of cracks on the leather surface is observed.

[0205] 5. Heat resistance: Place the test sample in an oven at 100℃ for 500 hours. After taking it out, observe whether it changes color or becomes sticky.

[0206] 6. Alcohol resistance: Wipe the surface 10 times with a cotton cloth soaked in alcohol (95% concentration) and observe whether the surface turns white.

[0207] 7. Joint fatigue strength: Tested according to QB / T4043-2010, with a constant load of 29.4 N, a test fixture clearance of 120 mm, a reciprocating motion distance of 150 mm, a reciprocating motion frequency of 30 times / min, and 2500 test cycles. At the end of each test, under the condition of maintaining a static load of 29.4 N, the maximum value (mm) of the joint pinhole size is taken to characterize the joint fatigue strength.

[0208] Table 2. Test Results of Experiment 1

[0209]

[0210]

[0211]

[0212] Analysis of experimental results:

[0213] (1) As can be seen from Examples 1-12 and Comparative Examples 1-6 and Table 2, the silicone synthetic leather of this application can significantly improve the structural strength of the synthetic leather by using a surface material prepared from polysilazane and boron hybrid vinyl silicone resin, thereby improving its wear resistance, heat resistance, joint fatigue strength and flexural resistance, especially the flexural resistance under low temperature conditions.

[0214] Test 2: UV resistance test

[0215] The ultraviolet weathering tester (BN-2130) is used to place the sample in the tester and irradiate it for 360 minutes. The color difference before and after irradiation is measured using X-RITECI7100 and the data is recorded.

[0216] Table 3. Test Results of Experiment 2

[0217]

[0218] Examples 1, 6, 7, and Comparative Example 3 are pure white, while Comparative Examples 4 and 5 are off-white.

[0219] Analysis of test results: After 360 minutes of ultraviolet irradiation, Examples 1, 6, and 7, and Comparative Example 3, showed no significant changes in color or gloss, while Comparative Examples 4 and 5 turned noticeably yellow. Compared to Comparative Examples 4 and 5, Examples 1, 6, and 7, and Comparative Example 3, exhibit superior UV resistance and can meet the technical requirements of the automotive market for light-colored products.

[0220] Experiment 3: Heat Resistance Yellowing Test Experimental Method: Cut the sample into strips of 150×50mm, hang them with a small hook and store them in a constant temperature oven at 100℃ for 168h. Use X-RITE CI7100 to measure the color difference before and after irradiation and record the data.

[0221] Table 4. Test Results of Experiment 3

[0222]

[0223] Analysis of test results: The color difference of Examples 1 and 7 and Comparative Example 3 before and after storage does not exceed 0.5, indicating that these samples have excellent heat resistance to yellowing. However, the color difference values ​​of Comparative Examples 1, 2, 4 and 5 are all greater than 1.2, indicating that heat yellowing is more obvious. Therefore, they are not suitable for use in automobiles with high heat resistance requirements.

[0224] Experiment 4: Stain Resistance Test Experimental Method: Two 10*10cm samples were cut from all examples and comparative examples. Stain resistance tests were conducted using a ballpoint pen and coffee. Ballpoint Pen Test: The sample was laid flat, and a line was drawn on it with a ballpoint pen. After standing for 5 minutes, the leather surface was wiped with a white cloth, and the residue on the drawn line was observed to evaluate the stain resistance. Coffee Test: The sample was laid flat, and coffee was poured onto it. After standing for 4 hours, the coffee stains on the surface were wiped off with a cloth, and the coffee stain residue on the sample was observed to evaluate the stain resistance. Score Criteria: 0—Almost no residue, 1—Slight residue, 2—Some residue, 3—Obvious residue, 4—Most residue, 5—Complete residue.

[0225] Table 5. Test Results of Experiment 4

[0226]

[0227]

[0228] Analysis of experimental results:

[0229] Examples 1 and 9, and Comparative Examples 3 and 4, showed ideal results in cleaning stains from ballpoint pens, red wine, and juice, achieving virtually no residue or very little residue. However, Comparative Example 5 (commercially available product) and Examples 7 and 8 did not perform well in terms of easy cleaning, and were difficult to remove once contaminated. This indicates that the application of side-chain fluorinated vinyl silicone resin has a significant impact on the stain resistance and self-cleaning properties of the surface layer.

[0230] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A silicone synthetic leather for automobiles, comprising a base fabric, an adhesive layer, and a top layer, characterized in that, The surface layer comprises the following components in parts by weight: Silicone-based adhesive: 20-50 parts; Crosslinked hydrosilicone oil: 1-24 parts; Boron-hybridized vinyl silicone resin: 5-45 parts; Polysilazane: 1-15 parts; Platinum catalyst: 0.001–0.05 parts; 3-28 parts of silane coupling agent modified zirconium oxide; The crosslinked hydrosilicone oil is a polysiloxane having at least three hydrogen atoms bonded to silicon atoms; The raw materials for the boron-hybridized vinyl silicone resin include vinyl silicone resin, boric acid derivative and titanium chelate catalyst in a mass ratio of (70-90):1:(0.05-0.1), wherein the boric acid derivative molecule has at least one boric acid group or borate ester group. The preparation method of the boron-hybridized vinyl silicone resin includes: Vinyl silicone resin and boric acid derivatives are dissolved in an organic solvent, and a titanium chelate catalyst is added. After mixing evenly, the mixture is heated to react. After the reaction is completed, the low-boiling-point substances are removed by vacuuming under reduced pressure. The temperature of the heating reaction is 40–60°C; The heating reaction time is 4–8 hours; The polysilazane includes at least one of perhydropolysilazane and vinyl polysilazane, wherein one molecule of vinyl polysilazane has at least one vinyl group bonded to a silicon atom; The modification steps for modified zirconia include: Zirconia is added to n-hexane and ultrasonically dispersed. Vinyltriethoxysilane is added, and acid is added dropwise to adjust the pH to 4-5. After ultrasonic dispersion, the mixture is filtered, washed, and dried to obtain the final product.

2. The silicone synthetic leather for automobiles according to claim 1, characterized in that, The silane coupling agent is a vinylsilane coupling agent.

3. The silicone synthetic leather for automobiles according to claim 1, characterized in that, The side of the surface layer away from the adhesive layer contains a surface treatment layer, which, by weight, comprises the following components: Side-chain fluorinated vinyl silicone resin: 40-75 parts; Polysilazane: 2-25 parts; Crosslinked hydrosilicone oil: 3-20 parts; Adhesive: 0.5–18 parts; Platinum catalyst: 0.001 to 1 part; Filler: 8-40 parts; Organic solvent: 30-70 parts; The fluorinated vinyl silicone resin with side chains is a silicone resin having fluorinated side chains and vinyl groups bonded to silicon atoms; The polysilazane includes at least one of perhydropolysilazane and vinyl polysilazane, wherein one molecule of vinyl polysilazane has at least one vinyl group bonded to a silicon atom.

4. The silicone synthetic leather for automobiles according to claim 1, characterized in that, An intermediate layer is present between the top layer and the adhesive layer. By weight, the intermediate layer comprises the following components: Component A: Silicone-based adhesive: 10-20 parts; Vinyl-terminated silicone oil: 5-35 parts, viscosity 300-10000 mPa·s; Vinyl MQ resin: 15-30 parts; Crosslinked hydrosilicone oil: 1-24 parts; Organosilicon core-shell particles: 10–30 parts; Inhibitor: 0.001–0.05 parts; Component B: Silicone-based adhesive: 10-30 parts; Vinyl-terminated silicone oil: 5-10 parts, viscosity 300-10000 mPa·s; Vinyl MQ resin: 15-30 parts; Platinum catalyst: 0.001 to 1 part; The terminated vinyl silicone oil is a polysiloxane having two end-chain vinyl groups bonded to silicon atoms.

5. The silicone synthetic leather for automobiles according to claim 1, characterized in that, The adhesive layer comprises the following components in parts by weight: Component A: Silicone-based adhesive: 20-30 parts; Vinyl-terminated silicone oil: 10-30 parts, viscosity 300-10000 mPa·s; Vinyl MQ resin: 5-15 parts; Crosslinked hydrosilicone oil: 1-20 parts; Organosilicon core-shell particles: 5–25 parts; Adhesive: 0.5–25 parts; Inhibitor: 0.001–0.05 parts; Component B: Silicone-based adhesive: 20-30 parts; Vinyl-terminated silicone oil: 10-30 parts, viscosity 300-10000 mPa·s; Platinum catalyst: 0.001 to 1 part.

6. The silicone synthetic leather for automobiles according to claim 3 or 5, characterized in that, The adhesive comprises one or more of γ-(methacryloyloxy)propyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and tri(2-hydroxyethyl)isocyanurate triacrylate.

7. A method for preparing automotive silicone synthetic leather according to any one of claims 1-6, characterized in that, Includes the following steps: Surface layer preparation: Mix the raw materials except for the platinum catalyst evenly according to the formula, add the catalyst, and continue mixing to obtain the surface layer resin; coat the surface layer resin onto the release paper and heat to vulcanize to form the surface layer; Intermediate layer preparation: According to the formula, the raw materials of components A and B are mixed separately and set aside. After the components A and B are mixed evenly, they are coated on the surface layer and heated for vulcanization to form the intermediate layer. Preparation of adhesive layer: Mix the raw materials of components A and B separately according to the ratio and set aside. After mixing components A and B evenly, coat them onto the intermediate layer to form an adhesive layer. Base fabric lamination: The base fabric is laminated onto the adhesive layer, and the adhesive layer is heated to vulcanize; Preparation of surface treatment layer: According to the formula, the raw materials except for the platinum catalyst are mixed evenly, then the platinum catalyst is added and the mixing is continued to obtain the surface treatment layer resin. The surface treatment layer resin is applied to the surface layer by printing or coating process, and then heated and dried to form the surface treatment layer, thus obtaining the silicone synthetic leather.

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