Organic silicon polyurethane synthetic leather with high cohesiveness and wear resistance and preparation method of organic silicon polyurethane synthetic leather

Abstract

The invention relates to the technical field of organic silicon synthetic leather, and discloses organic silicon polyurethane synthetic leather with high cohesiveness and wear resistance and a preparation method of the organic silicon polyurethane synthetic leather. According to the method, different vinyl long-side-chain hydroxyl vinyl silicone oil (PDMS), diisocyanate, trihydroxyl micromolecules and a chain extender are subjected to a polymerization reaction; and the organosilicon polyurethane surface layer slurry with fixed crosslinking density is ingeniously formed. And then uniformly coating release paper with the surface layer slurry, curing, and then blade-coating the surface of the release paper with a high-strength organic silicon bonding layer. Finally, the finished product is prepared through the steps of base cloth attaching, curing, stripping and the like. According to the synthetic leather prepared by the invention, the side chain vinyl is introduced into the surface layer, so that the adhesive property is excellent, the synthetic leather has ultrahigh wear resistance and excellent hydrolysis resistance, the hand feeling is fine and smooth, the antifouling property is excellent, and the comprehensive performance is remarkably improved.

Description

Technical Field

[0001] The invention relates to the technical field of organosilicon synthetic leather, and in particular to organosilicon polyurethane synthetic leather with high adhesion and wear resistance and a preparation method thereof. Background Art

[0002] With the rapid development of society and the significant improvement in people's living standards, the demand for synthetic leather products has continued to rise. In many fields such as sofas, automotive interiors, clothing, and luggage, synthetic leather products, with their unique properties and diverse designs, have shown broad application prospects and become one of the indispensable materials in modern life.

[0003] However, although traditional polyurethane synthetic leather has good flexibility and processability and can meet basic usage needs, there are still some problems that need to be solved in practical applications. For example, its wear resistance is insufficient, and it is easy to cause wear, scratches and other problems during frequent use and friction, affecting the appearance and service life of the product. In addition, the surface of traditional polyurethane synthetic leather is easy to be sticky, especially in high temperature and humid environments. This phenomenon is more obvious, which not only reduces the user experience, but also increases the difficulty of cleaning and maintenance. More importantly, its resistance to moisture and heat is poor. When it is in contact with moisture for a long time or in a high humidity environment, it is prone to breakage, peeling and other phenomena, which seriously affect the overall performance and quality stability of the product.

[0004] To address these issues, numerous studies have attempted to improve the performance of synthetic leather by modifying polyurethane or other additives. However, these approaches often only achieve limited improvements in a single property, making it difficult to achieve a balanced optimization of overall performance. Therefore, developing a synthetic leather preparation method that simultaneously achieves high adhesion, superior wear resistance, moisture and heat stability, antifouling properties, and excellent surface feel is of great practical significance and market value. Summary of the Invention

[0005] The present invention aims to provide a silicone polyurethane synthetic leather with high adhesion and wear resistance and a preparation method thereof, so as to solve the problems of poor adhesion between existing synthetic leather and silicone, unstable wear resistance, moisture resistance and heat resistance, and lack of antifouling property.

[0006] To achieve the above-mentioned purpose, the present invention adopts the following technical scheme: a highly adhesive and wear-resistant silicone polyurethane synthetic leather, comprising a composite adhesive layer, a base fabric, a release paper, and a highly adhesive and ultra-wear-resistant silicone polyurethane synthetic leather surface slurry coated on the release paper. The raw materials of the highly adhesive and ultra-wear-resistant silicone polyurethane synthetic leather surface slurry include: different vinyl long side chain hydroxyl vinyl silicone oils, diisocyanates, solvents, catalysts, trihydroxy small molecules, and chain extenders. Preferably, as an improvement, the vinyl content of the different vinyl long side chain hydroxy vinyl silicone oil is 0.5-4%wt; the molecular formula of the different vinyl long side chain hydroxy vinyl silicone oil is as shown in formula (I): Formula (I) In formula (I), n is 5 to 20, m is 3 to 10, and p is 0 to 15.

[0007] Preferably, as an improvement, the diisocyanate is one or a combination of two of isophorone diisocyanate, 4,4-diphenylmethane diisocyanate, and toluene diisocyanate; the solvent is at least one of DMAc, N,N-dimethylformamide (DMF), ethyl acetate, and butyl acetate; the catalyst is an organic bismuth catalyst; the trihydroxy small molecule is trimethylolpropane; and the chain extender is one or a combination of two of isophorone diamine, pentaethylenetetramine, and a small molecule polyester polyol.

[0008] Preferably, as an improvement, a method for preparing a silicone polyurethane synthetic leather with high adhesion and wear resistance comprises the following steps: S1. Dehydrating hydroxyl vinyl silicone oils with different vinyl long side chains, and then fully reacting them with diisocyanate, solvent, and catalyst in a constant temperature environment to obtain isocyanate-terminated vinyl silicone oil prepolymers; S2. Adding trihydroxy small molecules to the isocyanate-terminated vinyl silicone oil prepolymer to cap the isocyanate and construct a tetrafunctional organosiloxane segment; S3, introducing diisocyanate and chain extender into the reaction system in sequence to prepare a polymer slurry; S4. The polymer slurry is evenly coated on the surface of the release paper, and after drying, it is laminated with the composite adhesive layer and the base fabric, and then subjected to aging and peeling in sequence to obtain a highly adhesive and super wear-resistant silicone polyurethane synthetic leather.

[0009] Preferably, as an improvement, in step S1, the molar ratio of different vinyl long side chain hydroxy vinyl silicone oils to diisocyanate is 1:2-1:3, the reaction temperature is 75-85° C., and the reaction time is 1-3 h.

[0010] Preferably, as an improvement, in step S2, the amount of trihydroxy small molecules added is 5%-15% of the mass of PDMS.

[0011] Preferably, as an improvement, in step S2, the molecular formula of the tetrafunctional organosiloxane segment is as follows: Formula (II) In formula (II), n is 5 to 20, m is 3 to 10, and p is 0 to 15.

[0012] Preferably, as an improvement, in step S3, the molar ratio of the diisocyanate added for the second time to the trihydroxy small molecule is 1:1-1:3; the molar ratio of the diisocyanate added for the second time to the chain extender is 2:1-4:1.

[0013] Preferably, as an improvement, in step S4, the drying temperature is 130-150° C., and the curing time is 3-5 min; the aging temperature is 130-150° C., and the aging time is 3-5 min.

[0014] Preferably, as an improvement, a highly adhesive and super wear-resistant organosilicon polyurethane synthetic leather is used in furniture and automobile interior decoration.

[0015] The principles and advantages of this solution are as follows: In practical application, this technical solution addresses the existing problems in the preparation of organosilicon polyurethane synthetic leather by comprehensively optimizing the raw materials and preparation process. Hydroxyvinyl silicone oil (PDMS) reacts with diisocyanate in the presence of a solvent and a catalyst at 75-85°C to form an isocyanate-terminated prepolymer. During this step, the hydroxyl (-OH) groups of the PDMS react with isocyanate (-NCO) groups to form urethane bonds, paving the way for subsequent crosslinking. Furthermore, this technical solution features a unique modified organosiloxane design: by capping hydroxyvinyl silicone oils with varying side chain vinyl groups, tetrafunctional organosiloxane segments are constructed and embedded within the polyurethane network. The hydrosilylation reaction of the side chain vinyl groups with the organosilicon binder forms a strong chemical bond, significantly improving the adhesive properties of the synthetic leather. By precisely controlling the dosage of chain extenders and crosslinkers, as well as the reaction conditions, the polyurethane network structure is optimized, significantly enhancing the wear resistance, hydrolysis resistance, and mechanical strength of the synthetic leather. The secondary addition of diisocyanate and chain extender modulates the prepolymer molecular weight through chain extension reactions while also controlling the spatial distribution of crosslinking points. The chain extender reacts with the isocyanate to extend the molecular chain, while precise control of the crosslink density balances the material's mechanical properties and processing characteristics.

[0016] During the technical research and development phase, this technical solution introduced silicone oil blocks to improve the material's antifouling and adhesion properties. However, this also led to a secondary technical problem specific to this solution: the introduction of silicone oil blocks reduced the strength of the polyurethane, which in turn affected the material's feel, wear resistance, and strength. Based on this, this technical solution optimized the types and ratios of raw materials to design a suitable silicone oil block structure, enabling the product to achieve both antifouling properties, adhesion, good feel, and excellent wear resistance. Furthermore, silicone and polyurethane have poor compatibility. This solution, through the selection of solvents and process optimization, synthesized a prepolymer with the desired structure, thus resolving this issue.

[0017] In summary, the beneficial effects of this technical solution are: 1. In this technical solution, the organosilicon segment (PDMS) gives the material low surface energy properties, making it anti-fouling and skin-friendly; the polyurethane segment provides mechanical strength and flexibility. The two synergistically optimize the overall performance. The improvement in overall performance is specifically reflected in the following aspects: ① High Adhesion: The vinyl side chains undergo a hydrosilylation reaction with the adhesive, forming chemical crosslinks that significantly enhance peel strength. Experimental results show that the peel strength reaches 50-62 N / cm, 1.5-12 times higher than the control (5-32 N / cm).

[0018] ② Superior wear resistance: The three-dimensional cross-linked network structure enhances the interaction between molecular chains, resisting structural damage caused by friction. Experiments show that the Martindale wear resistance is >200,000 times, while the control sample only has 10,000-60,000 times.

[0019] ③ Hydrolysis Resistance: The chemical stability of the organosiloxane chain segments inhibits hydrolysis, and the cross-linked network prevents water molecules from penetrating. Experiments show that after 5 days of boiling in 85°C, the leather surface shows no whitening or cracking, and its hydrolysis resistance reaches Level 1. ④ Antifouling performance: The low surface energy of silicone reduces stain adhesion, making stains easy to clean. Experiments show that the antifouling level reaches level 4 (no residual stains).

[0020] ⑤ Hand feel and folding resistance: The flexibility of the silicone segments and the toughness of the cross-linked network synergistically improve tactile feel and fatigue resistance. Experiments show that the synthetic leather produced with this solution has a smooth hand feel (Grade 1) and withstands 100,000 folds without cracking.

[0021] 2. This technical solution breaks through the defects of traditional synthetic leather, solves the problems of traditional polyurethane synthetic leather such as insufficient wear resistance, poor adhesion, and low moisture and heat stability, and achieves simultaneous optimization of multiple performances.

[0022] 3. This technical solution has strong process controllability. By precisely controlling the molar ratio of PDMS to diisocyanate (1:2-1:3), the amount of trihydroxy small molecule added (5%-15% of the PDMS mass) and the reaction temperature (75-85°C), high-performance materials can be repeatedly prepared.

[0023] 4. The synthetic leather of this technical solution has a wide range of applications and is suitable for high-frequency usage scenarios such as furniture and car interiors, meeting the requirements of durability, comfort and aesthetics, such as sofa seats and car seat fabrics. DETAILED DESCRIPTION

[0024] The following is further described in detail through specific embodiments, but the embodiments of the present invention are not limited thereto. Unless otherwise specified, the technical means used in the following embodiments are conventional means well known to those skilled in the art; the experimental methods used are all conventional methods; and the materials, reagents, etc. used are all commercially available.

[0025] Program Overview: A highly adhesive and wear-resistant silicone polyurethane synthetic leather comprises a composite adhesive layer, a base fabric, a release paper, and a highly adhesive and ultra-wear-resistant silicone polyurethane synthetic leather surface slurry coated on the release paper. The raw materials of the highly adhesive and ultra-wear-resistant silicone polyurethane synthetic leather surface slurry include: different vinyl long side chain hydroxyl vinyl silicone oils (PDMS), diisocyanates, solvents, catalysts, trihydroxy small molecules, and chain extenders.

[0026] A method for preparing a highly adhesive and wear-resistant organosilicon polyurethane synthetic leather comprises the following steps: (Steps S1-S3 are steps for preparing a highly adhesive and wear-resistant organosilicon polyurethane synthetic leather surface slurry) S1. Dehydrate hydroxyl vinyl silicone oil (PDMS) with different vinyl long side chains, then fully react with diisocyanate, solvent (10-20 ml), and catalyst at a constant temperature of 75-85°C for 1-3 hours to accurately prepare isocyanate-terminated vinyl silicone oil prepolymer; the molar ratio of hydroxyl vinyl silicone oil (PDMS) with different vinyl long side chains to diisocyanate is 1:2-1:3; Wherein, the diisocyanate is one or a combination of two of isophorone diisocyanate, 4,4-diphenylmethane diisocyanate, and toluene diisocyanate; The solvent is at least one of DMAc, N,N-dimethylformamide (DMF), ethyl acetate and butyl acetate; The catalyst is an organic bismuth catalyst; the amount of the catalyst is 0.05%-0.3% of the total mass of the diisocyanate and the polyol; The vinyl content of hydroxy vinyl silicone oils with different vinyl length side chains is 0.5~4% (mass fraction), and the side chain length can be adjusted to meet different performance requirements. The molecular formula of hydroxy vinyl silicone oils with different vinyl length side chains is as follows: Formula (I) In formula (I), n is 5 to 20, m is 3 to 10, and p is 0 to 15.

[0027] S2. Precisely add trihydroxy small molecules to the prepolymer, with the added amount accounting for 5%-15% of the PDMS mass. Utilize the trihydroxy small molecules to react with the prepolymer to achieve isocyanate end-capping, thereby constructing tetrafunctional organosiloxane segments. This innovative structure significantly enhances the crosslinking density of the polymer network and the interfacial bonding strength, laying a key foundation for the excellent performance of the final product. Among them, the trihydroxy small molecule is trimethylolpropane; The molecular formula of the tetrafunctional organosiloxane segment is as follows: Formula (II) In formula (II), n is 5 to 20, m is 3 to 10, and p is 0 to 15.

[0028] S3. Based on S2, a secondary precise addition is carried out, and diisocyanate and chain extender with specific ratios are introduced into the reaction system in sequence. The molecular weight of the prepolymer and the spatial distribution of cross-linking points are regulated by chemical reactions, and the mechanical properties and processing properties of the polymer are cleverly balanced to successfully prepare a highly adhesive and ultra-wear-resistant silicone polyurethane synthetic leather surface slurry.

[0029] The molar ratio of the secondary added diisocyanate to the trihydroxy small molecule is 1:1-1:3; the molar ratio of the secondary added diisocyanate to the chain extender is 2:1-4:1; and the chain extender is one or a combination of two of isophorone diamine, pentaethylenetetramine and small molecule polyester polyol.

[0030] S4. The prepared slurry is evenly coated on the surface of the release paper and dried under strictly controlled process conditions. The drying temperature is controlled at 130-150°C and the curing time is 3-5 min. It is then laminated with the composite adhesive layer and the base fabric, and then subjected to aging and peeling processes in sequence. The aging temperature is 130-150°C and the aging time is 3-5 min. Finally, a highly adhesive and super wear-resistant silicone polyurethane synthetic leather is obtained.

[0031] The adhesive used in step S4 is a two-component silicone adhesive, including component A which is hydrogen-containing silicone oil and component B which is a mixture of vinyl silicone oil and a catalyst.

[0032] The above-mentioned high-adhesion and super-wear-resistant silicone polyurethane synthetic leather is used in furniture and automobile interior decoration.

[0033] Example 1 A method for preparing a highly adhesive and ultra-wear-resistant silicone polyurethane synthetic leather surface slurry comprises the following steps: Step S1: Dehydrate long-side-chain double-terminated hydroxypropyl silicone oil (PDMS-2000) with a vinyl content of 1.0% at 130°C for 1 h. Then, 6 g of PDMS-2000 and 1.58 g of 4,4-diisocyanate dicyclohexylmethane (HMDI) were added to a reactor, and 10 mL of N,N-dimethylacetamide (DMAc) and 0.0136 g of an organic bismuth catalyst were added. The mixture was stirred at 75°C for 1 h at a speed of 350 r / min.

[0034] Step S2: After the reaction is completed, 0.8 g of trimethylolpropane (TMP) is added and reacted for 0.5 h to form a tetrafunctional organosiloxane molecular chain.

[0035] Step S3: 3.15 g of HMDI and 2.1 g of HDPOL-340 were added to the polymer, and 20 ml of DMAc was added to adjust the viscosity. The reaction was continued at 75° C. for 3 h to form a silicone polyurethane surface layer slurry with a fixed crosslinking density (high-adhesion and ultra-wear-resistant silicone polyurethane synthetic leather surface layer slurry).

[0036] After forming the high-adhesiveness and super-wear-resistant organosilicon polyurethane synthetic leather surface layer slurry, the method for preparing the high-adhesiveness and super-wear-resistant organosilicon polyurethane synthetic leather is the same as the above step S4.

[0037] Example 2 A method for preparing a highly adhesive and ultra-wear-resistant silicone polyurethane synthetic leather surface slurry comprises the following steps: Step S1: Dehydrate long-side-chain double-terminated hydroxypropyl silicone oil (PDMS-2800) with a vinyl content of 2.0% at 130°C for 1 h. Then, 5.28 g of PDMS-2800 and 1.21 g of 4,4-diisocyanate dicyclohexylmethane (HMDI) were added to a reactor. 6 mL of N,N-dimethylacetamide (DMAc), 2 ml of N,N-dimethylformamide (DMF), 1 ml of ethyl acetate, 1 ml of butyl acetate, and 0.0121 g of an organic bismuth catalyst were also added. The mixture was stirred at 75°C for 3 h at a speed of 350 r / min.

[0038] Step S2: After the reaction is completed, 0.74 g of trimethylolpropane (TMP) is added and reacted for 0.5 h to form a tetrafunctional organosiloxane molecular chain.

[0039] Step S3: 2.42 g of diphenylmethane diisocyanate (MDI) and 2.1 g of HDPOL-340 were added to the polymer, and 20 ml of DMAc was added to adjust the viscosity. The reaction was continued at 75°C for 3 h to form a silicone polyurethane surface layer slurry with a fixed crosslinking density (high-adhesion, ultra-wear-resistant silicone polyurethane synthetic leather surface layer slurry).

[0040] After forming the high-adhesiveness and super-wear-resistant organosilicon polyurethane synthetic leather surface layer slurry, the method for preparing the high-adhesiveness and super-wear-resistant organosilicon polyurethane synthetic leather is the same as the above step S4.

[0041] Example 3 A method for preparing a highly adhesive and ultra-wear-resistant silicone polyurethane synthetic leather surface slurry comprises the following steps: Step S1: Dehydrate long-side-chain bi-terminal hydroxypropyl silicone oil (PDMS-3500) with a vinyl content of 0.5% at 130°C for 1 h. Then, 9 g of PDMS-3500 and 1.33 g of isophorone diisocyanate (IPDI) were added to a reactor. 10 mL of N,N-dimethylacetamide (DMAc) and 0.0132 g of an organic bismuth catalyst were also added. The mixture was stirred at 75°C for 1 h at a speed of 350 r / min.

[0042] Step S2: After the reaction is completed, 0.8 g of trimethylolpropane (TMP) is added and reacted for 0.5 h to form a tetrafunctional organosiloxane molecular chain.

[0043] Step S3: 3.4 g of HMDI and 2.1 g of HDPOL-340 were added to the polymer, and 20 ml of DMAc was added to adjust the viscosity. The reaction was continued at 75° C. for 3 h to form a silicone polyurethane surface layer slurry with a fixed crosslinking density (high-adhesion and ultra-wear-resistant silicone polyurethane synthetic leather surface layer slurry).

[0044] After forming the high-adhesiveness and super-wear-resistant organosilicon polyurethane synthetic leather surface layer slurry, the method for preparing the high-adhesiveness and super-wear-resistant organosilicon polyurethane synthetic leather is the same as the above step S4.

[0045] Example 4 A method for preparing a highly adhesive and ultra-wear-resistant silicone polyurethane synthetic leather surface slurry comprises the following steps: Step S1: Dehydrate long-side-chain double-terminated hydroxypropyl silicone oil (PDMS-3000) with a vinyl content of 4.0% at 130°C for 1 h. Then, 7.8 g of PDMS-3000 and 1.57 g of 4,4-diisocyanate dicyclohexylmethane (HMDI) were added to a reactor, and 10 mL of N,N-dimethylacetamide (DMAc) and 0.0132 g of an organic bismuth catalyst were added. The mixture was stirred at 75°C for 1 h at a speed of 350 r / min.

[0046] Step S2: After the reaction is completed, 0.93 g of trimethylolpropane (TMP) is added and reacted for 0.5 h to form a tetrafunctional organosiloxane molecular chain.

[0047] Step S3: 3.2 g of HMDI and 0.52 g of isophorone diamine were added to the polymer, and 20 mL of DMAc was added to adjust the viscosity. The reaction was continued at 75° C. for 1.5 h to form a silicone polyurethane surface layer slurry with a fixed crosslinking density (high-adhesion and ultra-wear-resistant silicone polyurethane synthetic leather surface layer slurry).

[0048] After forming the high-adhesiveness and super-wear-resistant organosilicon polyurethane synthetic leather surface layer slurry, the method for preparing the high-adhesiveness and super-wear-resistant organosilicon polyurethane synthetic leather is the same as the above step S4.

[0049] Example 5 A method for preparing a highly adhesive and ultra-wear-resistant silicone polyurethane synthetic leather surface slurry comprises the following steps: Step S1: Dehydrate long-side-chain double-terminated hydroxypropyl silicone oil (PDMS-3800) with a vinyl content of 3.5% at 130°C for 1 h. Then, 6.2 g of PDMS-3800 and 1.57 g of 4,4-diisocyanate dicyclohexylmethane (HMDI) were added to a reactor, along with 10 mL of N,N-dimethylacetamide (DMAc) and 0.0136 g of an organic bismuth catalyst. The mixture was stirred at 85°C for 1 h at a speed of 350 r / min.

[0050] Step S2: After the reaction is completed, 0.8 g of trimethylolpropane (TMP) is added and reacted for 0.5 h to form a tetrafunctional organosiloxane molecular chain.

[0051] Step S3: 2.7 g of HMDI and 1.2 g of pentaethylenetetramine were added to the polymer, and 20 ml of DMAc was added to adjust the viscosity. The reaction was continued at 85° C. for 3 h to form a silicone polyurethane surface layer slurry with a fixed crosslinking density (high-adhesion and ultra-wear-resistant silicone polyurethane synthetic leather surface layer slurry).

[0052] After forming the high-adhesiveness and super-wear-resistant organosilicon polyurethane synthetic leather surface layer slurry, the method for preparing the high-adhesiveness and super-wear-resistant organosilicon polyurethane synthetic leather is the same as the above step S4.

[0053] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that in this comparative example, the long side chain double-terminated hydroxypropyl silicone oil (PDMS-2000) with a vinyl content of 1.0% is replaced by double-terminated hydroxypropyl silicone oil with a vinyl content of 1.0%.

[0054] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that in this comparative example, the long side chain bi-terminal hydroxypropyl silicone oil (PDMS-2000) with a vinyl content of 1.0% is replaced by bi-terminal hydroxypropyl silicone oil.

[0055] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that in this comparative example, 4,4-diisocyanate dicyclohexylmethane (HMDI) is replaced by hexamethylene diisocyanate (HDI).

[0056] Comparative Example 4 The difference between Comparative Example 4 and Example 1 is that in this comparative example, trimethylolpropane is replaced with 3,4,5-trihydroxybutyl benzoate.

[0057] Comparative Example 5 The difference between Comparative Example 5 and Example 1 is that in this comparative example, HDPOL-340 is replaced with adipic acid dihydrazide of equal molar mass.

[0058] Comparative Example 6 The difference between Comparative Example 6 and Example 1 is that the reaction temperature in step S1 is lowered to 65°C.

[0059] Comparative Example 7 The difference between Comparative Example 7 and Example 1 is that the reaction time of step S3 is reduced to 2 hours.

[0060] The silicone polyurethane surface layer slurries of Examples 1-5 and Comparative Examples 1-7 were applied to release paper using a conventional blade coating process, with the coating thickness controlled to between 0.1 and 0.5 mm. The surface layer was then cured at 130°C (preferably for 3-5 minutes) to obtain the surface layer. A high-strength silicone adhesive was then applied to the surface layer (with a coating gap of 1 mm) and cured at 130°C (preferably for 3-5 minutes). The high-strength adhesive was then applied again (with a coating gap of 2 mm), and the surface layer was bonded to the base fabric. The surface layer was then cured in an oven at 130°C (preferably for 3-5 minutes). After the release paper cooled, it was peeled off to obtain the synthetic leather surface layer.

[0061] Performance test: The organosilicon polyurethane synthetic leathers prepared in Examples 1-5 and Comparative Examples 1-7 were subjected to relevant performance tests. The test indicators and test methods are as follows, and the test results are shown in Table 1.

[0062] 1. Hydrolysis resistance test Place the synthetic leather in 85°C water for 5 days and observe whether the leather surface turns white, cracks or delaminates.

[0063] Grade 1: leather surface is normal; Level 2: leather surface turns white; Level 3: Leather surface cracking; Level 4: Leather surface delamination.

[0064] 2. Antifouling test The experiment was conducted according to ASTM D1308-02, using oil-based pens, chili oil, beverages, and ballpoint pens to test antifouling performance. The test time was 15 minutes, 1 hour, 2 hours, 8 hours, and 24 hours. The evaluation criteria are as follows: Level 1: The stain is not removed at all; Level 2: The stain is almost still there; Level 3: slight stains; Level 4: No residual stains.

[0065] 3. Hand feel test Touch the treated leather surface with your hands to judge the feel. The evaluation criteria are as follows: Level 1: smooth; Level 2: relatively smooth; Level 3: General; Level 4: Poor.

[0066] 4. Folding fastness The test is carried out according to the method specified in QB / T 2714 to test the folding fastness and check whether the leather surface is powdering or cracking. The highest number of folding times without cracking or powdering is recorded, and the test is up to 100,000 times.

[0067] 5. Peel strength 200 mm × 25 mm synthetic leather strips were bonded with hot melt adhesive. One end of the substrate was fixed and the other end was stretched at a rate of 100 mm / min. The strip was peeled off from the fixed surface at an angle of 180° and the peel force was recorded.

[0068] Table 1

[0069] As can be clearly seen from the data in Table 1, the silicone polyurethane leather successfully prepared in the examples of this application demonstrates excellent performance across multiple key performance indicators. It exhibits exceptional wear resistance, maintaining the integrity of the surface layer even after high-intensity friction. It also exhibits excellent hydrolysis resistance, maintaining a stable chemical structure and properties even in long-term humid environments, making it less susceptible to degradation due to hydrolysis. It also exhibits excellent folding resistance, maintaining its original flexibility and shape after repeated folding without cracking. Furthermore, the surface layer has a smooth and delicate feel, a pleasant touch, and excellent anti-fouling properties, resisting the adhesion of liquid stains and making it easy to clean. Furthermore, its adhesion to the base fabric is excellent, maintaining a tight bond with the base fabric even after external forces or prolonged use, without peeling or loosening. Consequently, the silicone polyurethane surface layer prepared in this application perfectly meets the durability, comfort, and aesthetic requirements of materials for products such as sofas and chairs. It can be widely used as a high-quality material in related product manufacturing, providing a strong guarantee for the performance and quality of products such as sofas and chairs.

[0070] The above is only an embodiment of the present invention, and the common knowledge such as the specific technical solutions and / or characteristics in the solution are not described in detail here. It should be pointed out that for those skilled in the art, without departing from the technical solution of the present invention, several variations and improvements can be made, which should also be regarded as the scope of protection of the present invention, and these will not affect the effect of the implementation of the present invention and the practicality of the patent. The scope of protection required by this application shall be based on the content of its claims, and the specific implementation methods and other records in the description can be used to interpret the content of the claims.

Claims

1. A silicone polyurethane synthetic leather with high adhesion and wear resistance, characterized by: It includes a composite adhesive layer, a base fabric, a release paper and a high-adhesion, super-wear-resistant silicone polyurethane synthetic leather surface slurry coated on the release paper. The raw materials of the high-adhesion, super-wear-resistant silicone polyurethane synthetic leather surface slurry include: different vinyl long side chain hydroxyl vinyl silicone oils, diisocyanate, solvent, catalyst, trihydroxy small molecules and chain extender.

2. The highly adhesive and wear-resistant organosilicon polyurethane synthetic leather according to claim 1, characterized in that: The vinyl content of the different vinyl long side chain hydroxy vinyl silicone oil is 0.5-4%wt; the molecular formula of the different vinyl long side chain hydroxy vinyl silicone oil is as shown in formula (I): Formula (I) In formula (I), n is 5 to 20, m is 3 to 10, and p is 0 to 15.

3. The highly adhesive and wear-resistant organosilicon polyurethane synthetic leather according to claim 2, characterized in that: The diisocyanate is one or a combination of two of isophorone diisocyanate, 4,4-diphenylmethane diisocyanate, and toluene diisocyanate; the solvent is at least one of DMAc, N,N-dimethylformamide (DMF), ethyl acetate, and butyl acetate; the catalyst is an organic bismuth catalyst; the trihydroxy small molecule is trimethylolpropane; and the chain extender is one or a combination of two of isophorone diamine, pentaethylenetetramine, and a small molecule polyester polyol.

4. The method for preparing a highly adhesive and wear-resistant organosilicon polyurethane synthetic leather according to any one of claims 1 to 3, characterized in that: The steps include: S1. Dehydrating hydroxyl vinyl silicone oils with different vinyl long side chains, and then fully reacting them with diisocyanate, solvent, and catalyst in a constant temperature environment to obtain isocyanate-terminated vinyl silicone oil prepolymers; S2. Adding trihydroxy small molecules to the isocyanate-terminated vinyl silicone oil prepolymer to cap the isocyanate and construct a tetrafunctional organosiloxane segment; S3, introducing diisocyanate and chain extender into the reaction system in sequence to prepare a polymer slurry; S4. The polymer slurry is evenly coated on the surface of the release paper, and after drying, it is laminated with the composite adhesive layer and the base fabric, and then subjected to aging and peeling in sequence to obtain a highly adhesive and super wear-resistant silicone polyurethane synthetic leather.

5. The method for preparing a highly adhesive and wear-resistant organosilicon polyurethane synthetic leather according to claim 4, characterized in that: In step S1, the molar ratio of different vinyl long side chain hydroxy vinyl silicone oils to diisocyanate is 1:2-1:3, the reaction temperature is 75-85° C., and the reaction time is 1-3 h.

6. The method for preparing a silicone polyurethane synthetic leather with high adhesion and wear resistance according to claim 5, characterized in that: In step S2, the amount of trihydroxy small molecules added is 5%-15% of the mass of PDMS.

7. The method for preparing a silicone polyurethane synthetic leather with high adhesion and wear resistance according to claim 6, characterized in that: In step S2, the molecular formula of the tetrafunctional organosiloxane segment is as follows: Formula (II) In formula (II), n is 5 to 20, m is 3 to 10, and p is 0 to 15.

8. The organic silicone polyurethane synthetic leather with high adhesion and wear resistance and the preparation method thereof according to claim 7, characterized in that: In step S3, the molar ratio of the diisocyanate added for the second time to the trihydroxy small molecule is 1:1-1:3; the molar ratio of the diisocyanate added for the second time to the chain extender is 2:1-4:

1.

9. The method for preparing a silicone polyurethane synthetic leather with high adhesion and wear resistance according to claim 8, characterized in that: In step S4, the drying temperature is 130-150° C., and the curing time is 3-5 min; the aging temperature is 130-150° C., and the aging time is 3-5 min.

10. Use of the highly adhesive and ultra-wear-resistant organosilicon polyurethane synthetic leather according to any one of claims 1 to 3 in furniture and automobile interiors.

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