Preparation method of basalt mineral fiber interface enhanced environment-friendly marine silk synthetic leather

Abstract

The invention discloses a preparation method of basalt mineral fiber interface enhanced environment-friendly marine silk synthetic leather. The preparation method comprises the following steps: blending marine silk fibers and polyester fibers to prepare a non-woven fabric; the non-woven fabric is subjected to impregnation, pre-solidification, ironing and surface coating material scraping, and is sent into a three-turn-back solidification tank for solidification, water washing, pre-ironing, drying, cooling and rolling, and the environment-friendly marine silk synthetic leather is obtained. The coating material is prepared from second bio-based polyurethane resin, dimethylformamide, basalt mineral fibers, porous silicon dioxide, a nonionic active agent, a fluoride-free hydrolysis-resistant auxiliary agent and color paste. According to the invention, the synthetic leather is prepared through a synergistic composite system of'marine silk base cloth ', 'an impregnation material adopts bio-based polyurethane resin' and'a coating material introduces basalt mineral fibers and porous silicon dioxide as fillers', so that not only is high environmental protection realized, but also the interface bonding force between the resin and the base cloth is remarkably enhanced, an effective stress buffer network is constructed, and the service life of the synthetic leather is prolonged. The long-acting physical properties such as hydrolysis resistance and low-temperature folding resistance of the synthetic leather are greatly improved.

Description

Technical Field

[0001] This invention relates to the field of synthetic leather technology, specifically to a method for producing environmentally friendly marine silk synthetic leather reinforced with basalt mineral fiber interfaces. Background Technology

[0002] With the deepening of environmental protection concepts, the development of green synthetic leather using recycled fibers and bio-based materials has become an important industry trend. Among these, combining "marine silk" nylon fibers made from recycled marine fishing nets with bio-based polyurethane resin derived from renewable resources is considered a technological path that combines resource recycling and low-carbon advantages. However, in actual research and application, it has been found that the combination of these two environmentally friendly materials has significant limitations: due to the inherent interfacial compatibility and stress buffering defects between the molecular chain structure, polarity, and crystallization behavior of bio-based polyurethane resin and recycled nylon fibers, the interfacial bonding force between the two is relatively weak. When synthetic leather prepared in this way is applied to fields such as sports footwear materials that require dynamic bending and humid and hot environments, under long-term repeated stress, stress easily concentrates at the resin-fiber interface, inducing microcracks. The formation and propagation of these microcracks directly lead to the rapid decline of key long-term physical properties of synthetic leather products, such as hydrolysis resistance and low-temperature flexural strength, resulting in a service life far below the requirements of high-end applications.

[0003] Currently, the industry commonly uses the addition of conventional inorganic fillers (such as calcium carbonate and talc) or organic fillers (such as wood flour) to improve the performance of synthetic leather. However, these conventional filling methods mainly focus on reducing costs or making limited adjustments to the physical feel. They do not provide effective solutions for the deep interfacial bonding and stress buffering problems related to product durability caused by the inherent differences in materials. Therefore, developing an innovative technology that can fundamentally strengthen the interface and improve dynamic durability has urgent market demand and significant technological value. Summary of the Invention

[0004] To address the problems of weak interfacial bonding between bio-based polyurethane resin and marine silk fiber and insufficient long-term durability of synthetic leather in existing technologies, this invention provides an environmentally friendly marine silk synthetic leather manufacturing method with basalt mineral fiber interface reinforcement. By designing a composite system that synergistically integrates "marine silk base fabric", "impregnating material using bio-based polyurethane resin", and "coating material incorporating basalt mineral fiber and porous silica as fillers", the synthetic leather is prepared, significantly improving its environmental friendliness, hydrolysis resistance, folding resistance, and mechanical strength.

[0005] To achieve the above objectives, the present invention provides the following technical solution: a method for producing environmentally friendly marine silk synthetic leather reinforced with basalt mineral fiber interfaces, comprising the following steps: S1: Nonwoven fabric made from a blend of marine silk fiber and polyester fiber; S2: The nonwoven fabric is impregnated with an impregnating material containing a first bio-based polyurethane resin to obtain an impregnated base fabric; S3: After the impregnated base fabric undergoes pre-coagulation and ironing processes, a coating material is scraped onto the surface to form a fabric layer; the coating material is made of a second bio-based polyurethane resin, dimethylformamide, basalt mineral fiber, porous silica, nonionic surfactant, fluorine-free hydrolysis-resistant additive, and color paste in a ratio of 100:(35-45):(4-6):(2-4):(0.4-0.6):(0.6-1):(1-3); S4: The base fabric with the fabric layer is then sent into the three-fold coagulation tank for coagulation, so that the base fabric has a dense pore structure. S5: After washing, pre-ironing, drying, cooling and rolling, the desired environmentally friendly marine silk synthetic leather is obtained.

[0006] Furthermore, in S1, the ratio of marine silk fiber to polyester fiber is (45-55%):(45-55%).

[0007] Furthermore, in S1, the marine silk fiber is produced by a physical method, which includes the processes of recycling waste fishing nets, sorting and cleaning, slicing, and spinning.

[0008] Furthermore, in S2, the first bio-based polyurethane resin has a solid content of 30%, a bio-based content of 30%, a 100% modulus of 55-65, and a viscosity range of 130,000-160,000 cps.

[0009] Furthermore, in S2, the impregnating material is prepared from a first bio-based polyurethane resin, dimethylformamide, tear-resistant agent, fluorine-free hydrolysis-resistant agent, and color paste in a ratio of 100:(300-400):(10-20):(0.8-1.2):(18-22); the viscosity of the impregnating material is 120±10cps.

[0010] Furthermore, in S3, the viscosity of the coating material is 12000±1000cps.

[0011] Furthermore, in the S3 coating process, the coating gap is controlled at 200±5 mils, corresponding to a coating amount of 1.3±0.05 kg / y.

[0012] Furthermore, in the S4 coagulation process, the base fabric enters the three-fold coagulation tank at a 30° angle to the coagulation liquid, the sugar content of the coagulation liquid is 20-22%, and the temperature is 32±2℃; after the base fabric leaves the coagulation tank, its thickness and width are measured.

[0013] Furthermore, in the S5 washing process, the water then enters a washing system consisting of 16 washing tanks. Tanks 1 to 6 are washed at room temperature with a sugar content of 22-15%. After the initial washing, the sugar content of tanks 7 to 16 is 13-0%. Among them, the temperature of tanks 7 to 13 is room temperature, and the temperature of the last three tanks is increased to 60-80℃.

[0014] Furthermore, in the pre-ironing process of S5, the temperature of the ironing rollers is 110±10℃; after pre-ironing, it enters the drying oven. The temperature of the first group of drying ovens is 150℃, the temperature of the second to fourth groups of drying ovens is 160℃, and the temperature of the fifth group of drying ovens is 140℃. After drying, the synthetic leather is cooled by six cooling rollers and finally rolled up. The thickness of the roll is controlled at 1.1-1.2mm, and the effective width is controlled at 140-142cm.

[0015] This invention provides an environmentally friendly method for producing synthetic leather from marine silk reinforced with basalt mineral fiber interfaces, which has the following beneficial effects: 1. The synthetic leather uses environmentally friendly marine silk base fabric and bio-based polyurethane resin. Compared with traditional petroleum-based synthetic leather, this combination not only has excellent biodegradability and high recycling rate, but also inherits the inherent excellent physical properties of raw materials, solves the problem of insufficient physical properties of recycled fibers in the application of space leather, and further implements the concept of green environmental protection, low carbon and sustainable development.

[0016] 2. Through the synergistic effect of marine silk base fabric, specific bio-based polyurethane, and composite filler of basalt mineral fiber and porous silica, the interfacial bonding force between bio-based polyurethane resin and base fabric is significantly enhanced, and an effective stress buffer network is constructed, thereby greatly improving the long-term physical properties of synthetic leather, such as hydrolysis resistance and low-temperature folding resistance.

[0017] 3. This product line uses a fluorine-free formula throughout. No fluorine-containing materials are used in the production process or raw materials, ensuring that the product has no fluorine residue and will not cause fluorine pollution to the ecological environment and human health. It has good environmental protection properties and meets the increasingly stringent environmental protection requirements and green consumption trends worldwide. Compared with traditional fluorine-containing synthetic leather, it is more environmentally friendly.

[0018] 4. The product adopts a three-layer coagulation process, which promotes the formation of a uniform and dense cell structure in the fabric layer. While maintaining the biodegradability and recyclability of the material, this process also endows the product with superior physical properties. Its key indicators such as peel strength and hydrolysis resistance can meet the usage requirements of the entire shoe body and some apparel, achieving a unity of high recyclability and superior physical properties. Detailed Implementation

[0019] 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.

[0020] This invention provides a method for producing environmentally friendly marine silk synthetic leather reinforced with basalt mineral fiber interfaces, comprising the following steps: S1: Nonwoven fabric made from a blend of marine silk fiber and polyester fiber.

[0021] S2: The nonwoven fabric is impregnated with an impregnating material containing a first bio-based polyurethane resin to obtain an impregnated base fabric. The nonwoven fabric is placed upright on a fabric storage rack, and the production line speed is set to 12m / min; then the nonwoven fabric enters the impregnation tank, and the pressure of the extrusion rollers is controlled at 5-5.5Kg during the impregnation process.

[0022] S3: After the impregnated base fabric undergoes pre-coagulation and ironing processes, a coating material is applied to the surface to form a fabric layer. The coating material is prepared by mixing a second bio-based polyurethane resin, dimethylformamide, basalt mineral fiber, porous silica, nonionic surfactant, fluorine-free hydrolysis-resistant additive, and color paste in a ratio of 100:(35-45):(4-6):(2-4):(0.4-0.6):(0.6-1):(1-3). The viscosity of the coating material is 12000±1000cps. The second bio-based polyurethane resin used is XCW-8790ZW bio-based polyurethane resin produced by Asahikawa Chemical. The physical properties of this resin are: solid content 35%, bio-based content 30%, modulus 80-90%, tensile strength >45MPa, elongation ≥500%, and viscosity range 200,000-250,000cps. PU synthetic leather made from this resin also has high peel strength (≥100N / 3CM) and good hydrolysis resistance (peel strength ≥100N / 3CM after soaking in 10% NaOH solution at room temperature for 12 hours).

[0023] S4: The base fabric with the fabric layer is then sent into the three-fold coagulation tank for coagulation, so that the base fabric has a dense pore structure.

[0024] S5: After washing, pre-ironing, drying, cooling and rolling, the desired environmentally friendly marine silk synthetic leather is obtained.

[0025] In S1, the ratio of marine silk fiber to polyester fiber is (45-55%):(45-55%). Preferably, it is 50:50. Synthetic leather produced using this ratio can guarantee high-standard physical properties while also possessing high environmental value. The marine silk fiber is obtained using a physical method, which includes recycling waste fishing nets, sorting and cleaning, slicing, and spinning processes. Conventional synthetic leather for sports shoes primarily uses chemically synthesized all-polyester nonwoven fabric as its base fabric, characterized by high peel strength, high tear strength, and high tensile load. This invention, without reducing the performance of ordinary polyester nonwoven fabric, uses recycled marine fishing net fiber (100% nylon) blended with conventional polyester fiber to produce an environmentally friendly nonwoven fabric. Marine silk fiber can usually be obtained through physical and chemical methods. Marine silk fiber produced by chemical methods has a higher purity than that produced by physical methods, but the cost also increases accordingly. This invention uses a physical method to obtain marine silk fiber.

[0026] Preferably, the nonwoven fabric has a thickness of 0.75 mm and a basis weight of 200 g / m²; physical property standard: burst strength ≥ 18 kgf / cm². 2 Tensile load ≥350N / 3cm, elongation 40%-90%, tear strength ≥55N / 5cm.

[0027] In S2, the impregnating material is prepared by mixing a first bio-based polyurethane resin, dimethylformamide, tear-resistant agent, fluorine-free hydrolysis-resistant agent, and color paste in a ratio of 100:(300-400):(10-20):(0.8-1.2):(18-22); the viscosity of the impregnating material is 120±10cps.

[0028] The first bio-based polyurethane resin has a solid content of 30%, a bio-based content of 30%, a 100% modulus of 55-65, and a viscosity range of 130,000-160,000 cps. To implement the concept of "green, low-carbon, and environmentally friendly," a renewable, recyclable, and hydrolysis-resistant bio-based polyurethane resin is selected to replace the petroleum-based polyurethane used in traditional processes. This choice achieves material sustainability at the source, making the synthetic leather products more compliant with green and environmentally friendly requirements. Preferably, the first bio-based polyurethane resin uses XCW-65NFD bio-based polyurethane resin produced by Asahikawa Chemicals, which not only maintains high performance but also possesses biodegradable and recyclable characteristics, significantly improving environmental friendliness.

[0029] The tear-resistant agent is selected from polyurethane elastomer micropowder, rubber toughening agent, or polyurethane (35% solid content, 1000 cps viscosity) to enhance the tear resistance of synthetic leather. In this invention, polyurethane (35% solid content, 1000 cps viscosity) is preferred as the tear-resistant agent.

[0030] In S3, the nonionic surfactant can be a polyoxyethylene ether surfactant, such as fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether; in this invention, the nonionic surfactant is purchased from Shanghai Rido Polymer Materials Co., Ltd. (Rido Chemical) as S-8I additive, which is used to improve the wettability and dispersibility of the coating material.

[0031] In S3, the main chemical component of the fluorine-free hydrolysis-resistant additive is a hydrophobic compound without fluorinated carbon chains (CF bonds). In this invention, the fluorine-free hydrolysis-resistant additive is preferably a fluorine-free polycarbodiimide hydrolysis-resistant additive, used to improve the durability of synthetic leather in humid and hot environments. The additives described above are all commonly used in the art, and other commercially available models with similar functions can also be used as substitutes.

[0032] In stage S3, the sugar content of the pre-coagulated liquid is tested using an Abbe refractometer and maintained within the range of 30-33%. Sugar content corresponds to the concentration of dimethylformamide aqueous solution. During this stage, the pressure of the pre-coagulation hydraulic roller is also controlled at 5-5.5 kg to squeeze out excess coagulated liquid. After passing through a six-roller ironing device, it enters the coating station, where the coating material is applied to the impregnated base fabric using a forward-facing doctor blade. The gap between the doctor blade and the impregnated base fabric is a key parameter for controlling the coating thickness; the gap is controlled between 200±5 mils, corresponding to a coating weight of 1.3±0.05 kg / y. During production, the coating surface condition must be continuously monitored, and any abnormalities should be addressed promptly.

[0033] In the S4 coagulation process, the base fabric enters the triple-fold coagulation tank at a 30° angle to the coagulation liquid. The coagulation liquid has a sugar content of 20-22% and a temperature of 32±2℃. After the base fabric leaves the coagulation tank, its thickness and width are measured. Surface coagulation has the advantages of effectively avoiding cavitation caused by a thicker coating layer and increasing production line speed. The triple-fold coagulation tank design extends the travel path of the base fabric in the coagulation tank, increasing the effective coagulation time of the coating and resulting in a denser cell structure. This design integrates coating cell structure, formulation, and production process, producing a product that meets both physical properties and tactile requirements.

[0034] In the S5 washing process, the water then enters a washing system consisting of 16 washing tanks. Tanks 1 to 6 are washed at room temperature with a sugar content of 22-15%. After the initial washing, the sugar content of tanks 7 to 16 is 13-0%. Among them, the temperature of tanks 7 to 13 is room temperature, and the temperature of the last three tanks is increased to 60-80℃.

[0035] In the pre-ironing process of S5, the temperature of the ironing rollers is 110±10℃. After pre-ironing, the material enters the drying oven. The temperature of the first group of drying ovens is 150℃, the temperature of the second to fourth groups of drying ovens is 160℃, and the temperature of the fifth group of drying ovens is 140℃. After drying, the synthetic leather is cooled by six cooling rollers and finally rolled up. The thickness of the roll is controlled at 1.1-1.2mm, and the effective width is controlled at 140-142cm.

[0036] The shape-retaining marine silk synthetic leather produced by the above method has the following advantages: 1. The synthetic leather uses environmentally friendly marine silk base fabric and bio-based polyurethane resin. Compared with traditional petroleum-based synthetic leather, this combination not only has excellent biodegradability and high recycling rate, but also inherits the inherent excellent physical properties of raw materials, solves the problem of insufficient physical properties of recycled fibers in the application of space leather, and further implements the concept of green environmental protection, low carbon and sustainable development.

[0037] 2. Through the synergistic effect of marine silk base fabric, specific bio-based polyurethane, and composite filler of basalt mineral fiber and porous silica, the interfacial bonding force between the resin and the base fabric is significantly enhanced, and an effective stress buffer network is constructed, thereby greatly improving the long-term physical properties of synthetic leather, such as hydrolysis resistance and low-temperature folding resistance.

[0038] 3. This product line uses a fluorine-free formula throughout. No fluorine-containing materials are used in the production process or raw materials, ensuring that the product has no fluorine residue and will not cause fluorine pollution to the ecological environment and human health. It has good environmental protection properties and meets the increasingly stringent environmental protection requirements and green consumption trends worldwide. Compared with traditional fluorine-containing synthetic leather, it is more environmentally friendly.

[0039] 4. The product adopts a three-layer coagulation process, which promotes the formation of a uniform and dense cell structure in the fabric layer. While maintaining the biodegradability and recyclability of the material, this process also endows the product with superior physical properties. Its key indicators such as peel strength and hydrolysis resistance can meet the usage requirements of the entire shoe body and some apparel, achieving a unity of high recyclability and superior physical properties.

[0040] The beneficial effects of the present invention’s environmentally friendly marine silk synthetic leather production method are illustrated below through several examples and comparative examples. Example 1

[0041] This example provides a method for producing environmentally friendly marine silk synthetic leather reinforced with basalt mineral fiber interfaces, including the following steps: S1: Nonwoven fabric is made by blending marine silk fiber and polyester fiber in a 50:50 ratio; the parameters of the nonwoven fabric are measured.

[0042] S2: The nonwoven fabric is impregnated to obtain the impregnated base fabric; the impregnating material is made of a first bio-based polyurethane resin, dimethylformamide, tear-resistant agent, fluorine-free hydrolysis-resistant agent, and color paste in a ratio of 100:350:15:1:20, and the viscosity of the impregnating material is 120cps.

[0043] S3: After the impregnated base fabric undergoes pre-solidification and ironing processes, a coating material is scraped onto the surface to form a fabric layer; the coating gap is controlled at 200 mils, corresponding to a coating amount of 1.3 kg / y; the coating material is made of second bio-based polyurethane resin, dimethylformamide, basalt mineral fiber, porous silica, nonionic surfactant, fluorine-free hydrolysis resistant additive, and color paste in a ratio of 100:40:5:3:0.5:0.8:2, and the viscosity of the coating material is 12000 cps.

[0044] S4: The base fabric with the fabric layer is then sent into the three-fold coagulation tank for coagulation to give the base fabric a dense pore structure. The base fabric enters the three-fold coagulation tank at a 30° angle with the coagulation liquid. The sugar content of the coagulation liquid is 20-22%, and the temperature is 32±2℃. After the base fabric leaves the coagulation tank, its thickness and width are measured.

[0045] S5: After washing, pre-ironing, drying, cooling and rolling, the desired environmentally friendly marine silk synthetic leather is obtained. Example 2

[0046] This example provides a method for producing environmentally friendly marine silk synthetic leather reinforced with basalt mineral fiber interfaces, including the following steps: S1: Nonwoven fabric is made by blending marine silk fiber and polyester fiber in a ratio of 45:55; the parameters of the nonwoven fabric are measured.

[0047] S2: The nonwoven fabric is impregnated to obtain the impregnated base fabric; the impregnating material is made of a first bio-based polyurethane resin, dimethylformamide, tear-resistant agent, fluorine-free hydrolysis-resistant agent, and color paste in a ratio of 100:350:15:1:20, and the viscosity of the impregnating material is 120cps.

[0048] S3: After the impregnated base fabric undergoes pre-solidification and ironing processes, a coating material is scraped onto the surface to form a fabric layer; the coating gap is controlled at 200 mils, corresponding to a coating amount of 1.3 kg / y; the coating material is made of second bio-based polyurethane resin, dimethylformamide, basalt mineral fiber, porous silica, nonionic surfactant, fluorine-free hydrolysis resistant additive, and color paste in a ratio of 100:40:5:3:0.5:0.8:2, and the viscosity of the coating material is 12000 cps.

[0049] S4: The base fabric with the fabric layer is then sent into the three-fold coagulation tank for coagulation to give the base fabric a dense pore structure. The base fabric enters the three-fold coagulation tank at a 30° angle with the coagulation liquid. The sugar content of the coagulation liquid is 20-22%, and the temperature is 32±2℃. After the base fabric leaves the coagulation tank, its thickness and width are measured.

[0050] S5: After washing, pre-ironing, drying, cooling and rolling, the desired environmentally friendly marine silk synthetic leather is obtained. Example 3

[0051] This example provides a method for producing environmentally friendly marine silk synthetic leather reinforced with basalt mineral fiber interfaces, including the following steps: S1: Nonwoven fabric is made by blending marine silk fiber and polyester fiber in a ratio of 55:45; the parameters of the nonwoven fabric are measured.

[0052] S2: The nonwoven fabric is impregnated to obtain the impregnated base fabric; the impregnating material is made of a first bio-based polyurethane resin, dimethylformamide, tear-resistant agent, fluorine-free hydrolysis-resistant agent, and color paste in a ratio of 100:350:15:1:20, and the viscosity of the impregnating material is 120cps.

[0053] S3: After the impregnated base fabric undergoes pre-solidification and ironing processes, a coating material is scraped onto the surface to form a fabric layer; the coating gap is controlled at 200 mils, corresponding to a coating amount of 1.3 kg / y; the coating material is made of second bio-based polyurethane resin, dimethylformamide, basalt mineral fiber, porous silica, nonionic surfactant, fluorine-free hydrolysis resistant additive, and color paste in a ratio of 100:40:5:3:0.5:0.8:2, and the viscosity of the coating material is 12000 cps.

[0054] S4: The base fabric with the fabric layer is then sent into the three-fold coagulation tank for coagulation to give the base fabric a dense pore structure. The base fabric enters the three-fold coagulation tank at a 30° angle with the coagulation liquid. The sugar content of the coagulation liquid is 20-22%, and the temperature is 32±2℃. After the base fabric leaves the coagulation tank, its thickness and width are measured.

[0055] S5: After washing, pre-ironing, drying, cooling and rolling, the desired environmentally friendly marine silk synthetic leather is obtained. Example 4

[0056] This example provides a method for producing environmentally friendly marine silk synthetic leather reinforced with basalt mineral fiber interfaces, including the following steps: S1: Nonwoven fabric is made by blending marine silk fiber and polyester fiber in a 50:50 ratio; the parameters of the nonwoven fabric are measured.

[0057] S2: The nonwoven fabric is impregnated to obtain the impregnated base fabric; the impregnating material is made of a first bio-based polyurethane resin, dimethylformamide, tear-resistant agent, fluorine-free hydrolysis-resistant agent, and color paste in a ratio of 100:350:15:1:20, and the viscosity of the impregnating material is 120cps.

[0058] S3: After the impregnated base fabric undergoes pre-solidification and ironing processes, a coating material is scraped onto the surface to form a fabric layer; the coating gap is controlled at 200 mils, corresponding to a coating amount of 1.3 kg / y; the coating material is made of second bio-based polyurethane resin, dimethylformamide, basalt mineral fiber, porous silica, nonionic surfactant, fluorine-free hydrolysis resistant additive, and color paste in a ratio of 100:35:4:2:0.4:0.6:1, and the viscosity of the coating material is 11000 cps.

[0059] S4: The base fabric with the fabric layer is then sent into the three-fold coagulation tank for coagulation to give the base fabric a dense pore structure. The base fabric enters the three-fold coagulation tank at a 30° angle with the coagulation liquid. The sugar content of the coagulation liquid is 20-22%, and the temperature is 32±2℃. After the base fabric leaves the coagulation tank, its thickness and width are measured.

[0060] S5: After washing, pre-ironing, drying, cooling and rolling, the desired environmentally friendly marine silk synthetic leather is obtained. Example 5

[0061] This example provides a method for producing environmentally friendly marine silk synthetic leather reinforced with basalt mineral fiber interfaces, including the following steps: S1: Nonwoven fabric is made by blending marine silk fiber and polyester fiber in a 50:50 ratio; the parameters of the nonwoven fabric are measured.

[0062] S2: The nonwoven fabric is impregnated to obtain the impregnated base fabric; the impregnating material is made of a first bio-based polyurethane resin, dimethylformamide, tear-resistant agent, fluorine-free hydrolysis-resistant agent, and color paste in a ratio of 100:350:15:1:20, and the viscosity of the impregnating material is 120cps.

[0063] S3: After the impregnated base fabric undergoes pre-solidification and ironing processes, a coating material is scraped onto the surface to form a fabric layer; the coating gap is controlled at 200 mils, corresponding to a coating amount of 1.3 kg / y; the coating material is made of second bio-based polyurethane resin, dimethylformamide, basalt mineral fiber, porous silica, nonionic surfactant, fluorine-free hydrolysis resistant additive, and color paste in a ratio of 100:45:6:4:0.6:1:3, and the viscosity of the coating material is 13000 cps.

[0064] S4: The base fabric with the fabric layer is then sent into the three-fold coagulation tank for coagulation to give the base fabric a dense pore structure. The base fabric enters the three-fold coagulation tank at a 30° angle with the coagulation liquid. The sugar content of the coagulation liquid is 20-22%, and the temperature is 32±2℃. After the base fabric leaves the coagulation tank, its thickness and width are measured.

[0065] S5: After washing, pre-ironing, drying, cooling and rolling, the desired environmentally friendly marine silk synthetic leather is obtained.

[0066] Comparative Example 1 This example provides a method for producing synthetic leather, including the following steps: S1: Use chemically synthesized all-polyester nonwoven fabric to measure the parameters of the all-polyester nonwoven fabric.

[0067] S2: The nonwoven fabric is impregnated to obtain the impregnated base fabric; the impregnating material is made of a first bio-based polyurethane resin, dimethylformamide, tear-resistant agent, fluorine-free hydrolysis-resistant agent, and color paste in a ratio of 100:350:15:1:20, and the viscosity of the impregnating material is 120cps.

[0068] S3: After the impregnated base fabric undergoes pre-solidification and ironing processes, a coating material is scraped onto the surface to form a fabric layer; the coating gap is controlled at 200 mils, corresponding to a coating amount of 1.3 kg / y; the coating material is made of second bio-based polyurethane resin, dimethylformamide, basalt mineral fiber, porous silica, nonionic surfactant, fluorine-free hydrolysis resistant additive, and color paste in a ratio of 100:40:5:3:0.5:0.8:2, and the viscosity of the coating material is 12000 cps.

[0069] S4: The base fabric with the fabric layer is then sent into the three-fold coagulation tank for coagulation to give the base fabric a dense pore structure. The base fabric enters the three-fold coagulation tank at a 30° angle with the coagulation liquid. The sugar content of the coagulation liquid is 20-22%, and the temperature is 32±2℃. After the base fabric leaves the coagulation tank, its thickness and width are measured.

[0070] S5: After washing, pre-ironing, drying, cooling and rolling, the desired synthetic leather is obtained.

[0071] Comparative Example 2 This example provides a method for producing environmentally friendly marine silk synthetic leather reinforced with basalt mineral fiber interfaces, including the following steps: S1: Nonwoven fabric is made by blending marine silk fiber and polyester fiber in a ratio of 80:20; the parameters of the nonwoven fabric are measured.

[0072] S2: The nonwoven fabric is impregnated to obtain the impregnated base fabric; the impregnating material is made of a first bio-based polyurethane resin, dimethylformamide, tear-resistant agent, fluorine-free hydrolysis-resistant agent, and color paste in a ratio of 100:350:15:1:20, and the viscosity of the impregnating material is 120cps.

[0073] S3: After the impregnated base fabric undergoes pre-solidification and ironing processes, a coating material is scraped onto the surface to form a fabric layer; the coating gap is controlled at 200 mils, corresponding to a coating amount of 1.3 kg / y; the coating material is made of second bio-based polyurethane resin, dimethylformamide, basalt mineral fiber, porous silica, nonionic surfactant, fluorine-free hydrolysis resistant additive, and color paste in a ratio of 100:40:5:3:0.5:0.8:2, and the viscosity of the coating material is 12000 cps.

[0074] S4: The base fabric with the fabric layer is then sent into the three-fold coagulation tank for coagulation to give the base fabric a dense pore structure. The base fabric enters the three-fold coagulation tank at a 30° angle with the coagulation liquid. The sugar content of the coagulation liquid is 20-22%, and the temperature is 32±2℃. After the base fabric leaves the coagulation tank, its thickness and width are measured.

[0075] S5: After washing, pre-ironing, drying, cooling and rolling, the desired environmentally friendly marine silk synthetic leather is obtained.

[0076] Comparative Example 3 This example provides a method for producing environmentally friendly marine silk synthetic leather reinforced with basalt mineral fiber interfaces, including the following steps: S1: Nonwoven fabric is made by blending marine silk fiber and polyester fiber in a 50:50 ratio; the parameters of the nonwoven fabric are measured.

[0077] S2: The nonwoven fabric is impregnated to obtain the impregnated base fabric; the impregnating material is prepared by mixing traditional petroleum-based hydrolysis-resistant polyurethane resin, dimethylformamide, tear-resistant agent, fluorine-free hydrolysis-resistant agent, and color paste in a ratio of 100:350:15:1:20, and the viscosity of the impregnating material is 120 cps. The traditional petroleum-based hydrolysis-resistant polyurethane resin has a solid content of 35%, a 100% modulus of 85-95%, a tensile strength >45MPa, an elongation ≥500%, and a viscosity of 180,000-240,000 cps.

[0078] S3: After the impregnated base fabric undergoes pre-solidification and ironing processes, a coating material is scraped onto the surface to form a fabric layer; the coating gap is controlled at 200 mils, corresponding to a coating amount of 1.3 kg / y; the coating material is made of second bio-based polyurethane resin, dimethylformamide, basalt mineral fiber, porous silica, nonionic surfactant, fluorine-free hydrolysis resistant additive, and color paste in a ratio of 100:40:5:3:0.5:0.8:2, and the viscosity of the coating material is 12000 cps.

[0079] S4: The base fabric with the fabric layer is then sent into the three-fold coagulation tank for coagulation to give the base fabric a dense pore structure. The base fabric enters the three-fold coagulation tank at a 30° angle with the coagulation liquid. The sugar content of the coagulation liquid is 20-22%, and the temperature is 32±2℃. After the base fabric leaves the coagulation tank, its thickness and width are measured.

[0080] S5: After washing, pre-ironing, drying, cooling and rolling, the desired environmentally friendly marine silk synthetic leather is obtained.

[0081] Comparative Example 4 This example provides a method for producing environmentally friendly marine silk synthetic leather reinforced with basalt mineral fiber interfaces, including the following steps: S1: Nonwoven fabric is made by blending marine silk fiber and polyester fiber in a 50:50 ratio; the parameters of the nonwoven fabric are measured.

[0082] S2: The nonwoven fabric is impregnated to obtain the impregnated base fabric; the impregnating material is made of a first bio-based polyurethane resin, dimethylformamide, tear-resistant agent, fluorine-free hydrolysis-resistant agent, and color paste in a ratio of 100:350:10:1:20, and the viscosity of the impregnating material is 120cps.

[0083] S3: After the impregnated base fabric undergoes pre-solidification and ironing processes, a coating material is scraped onto the surface to form a fabric layer; the coating gap is controlled at 200 mils, corresponding to a coating amount of 1.3 kg / y; the coating material is made of second bio-based polyurethane resin, dimethylformamide, basalt mineral fiber, porous silica, nonionic surfactant, fluorine-free hydrolysis resistant additive, and color paste in a ratio of 100:40:5:3:0.5:0.8:2, and the viscosity of the coating material is 12000 cps.

[0084] S4: The base fabric with the fabric layer is then sent into the three-fold coagulation tank for coagulation to give the base fabric a dense pore structure. The base fabric enters the three-fold coagulation tank at a 30° angle with the coagulation liquid. The sugar content of the coagulation liquid is 20-22%, and the temperature is 32±2℃. After the base fabric leaves the coagulation tank, its thickness and width are measured.

[0085] S5: After washing, pre-ironing, drying, cooling and rolling, the desired environmentally friendly marine silk synthetic leather is obtained.

[0086] Comparative Example 5 This example provides an environmentally friendly method for producing synthetic leather from marine silk, including the following steps: S1: Nonwoven fabric is made by blending marine silk fiber and polyester fiber in a 50:50 ratio; the parameters of the nonwoven fabric are measured.

[0087] S2: The nonwoven fabric is impregnated to obtain the impregnated base fabric; the impregnating material is made of a first bio-based polyurethane resin, dimethylformamide, tear-resistant agent, fluorine-free hydrolysis-resistant agent, and color paste in a ratio of 100:350:15:1:20, and the viscosity of the impregnating material is 120cps.

[0088] S3: After the impregnated base fabric undergoes pre-solidification and ironing processes, a coating material is scraped onto the surface to form a fabric layer; the coating gap is controlled at 200 mils, corresponding to a coating amount of 1.3 kg / y; the coating material is made of second bio-based polyurethane resin, dimethylformamide, porous silica, nonionic surfactant, fluorine-free hydrolysis-resistant additive, and color paste in a ratio of 100:40:10:0.5:1:2, and the viscosity of the coating material is 12000 cps.

[0089] S4: The base fabric with the fabric layer is then sent into the three-fold coagulation tank for coagulation to give the base fabric a dense pore structure. The base fabric enters the three-fold coagulation tank at a 30° angle with the coagulation liquid. The sugar content of the coagulation liquid is 20-22%, and the temperature is 32±2℃. After the base fabric leaves the coagulation tank, its thickness and width are measured.

[0090] S5: After washing, pre-ironing, drying, cooling and rolling, the desired environmentally friendly marine silk synthetic leather is obtained.

[0091]

[0092] As can be seen from Table 1: 1. Examples 1-3 show that the nonwoven fabrics prepared by blending marine silk fibers and polyester fibers in a ratio of (45-55):(55-45) exhibit superior key physical properties such as burst strength, tensile load, and tear strength compared to all-polyester nonwoven fabrics (Comparative Example 1). Furthermore, the elongation is more stable than that of nonwoven fabrics with an excessively high proportion of marine silk fibers (Comparative Example 2). This demonstrates that using the preferred ratio of this invention (marine silk:polyester = 50:50) can significantly improve the comprehensive mechanical properties and processing stability of nonwoven fabrics while maintaining environmental friendliness.

[0093] 2. Comparative Example 1: The synthetic leather produced using all-polyester nonwoven fabric has high basic physical properties and strength, but because it originates from non-renewable petroleum resources and has a stable main molecular structure, it is difficult to degrade in the natural environment. Comparative Example 2: The higher marine silk fiber content, while providing better environmental performance and recyclability, affects the basic physical properties and feel of the nonwoven fabric. The nonwoven fabric produced by blending marine silk fiber and polyester fiber in a 50:50 ratio in Example 1 can maintain high standard physical properties while also possessing high environmental value.

[0094]

[0095]

[0096] Comparing Table 2 and Table 3, we can see that: 1. Examples 1-5 (prepared using the method of this invention) are significantly superior to the comparative examples in terms of hydrolysis resistance, flexural strength, tear strength, and interfacial bonding strength, specifically as follows: Hydrolysis resistance: After 12 hours of hydrolysis, the peel strength of the example remained ≥98N / 3cm, which was significantly better than that of Comparative Examples 1, 2, 4 and 5, and on par with Comparative Example 3 (petroleum-based), but with better environmental performance.

[0097] Flexural strength: The examples showed no cracks in both low-temperature and room-temperature bending tests, while Comparative Examples 1, 2, 4, and 5 all showed varying degrees of cracking.

[0098] Mechanical properties: The tear strength of the trousers in the embodiment (≥58N / 5cm) is better than that of comparative examples 1, 2, 4 and 5, indicating that the basalt mineral fiber effectively enhances the resin-fiber interface and improves the tear resistance and stress concentration resistance.

[0099] Balancing environmental protection and performance: Although Comparative Example 3 has some physical properties similar to the Example, it uses petroleum-based resin, which is non-degradable and highly polluting; Comparative Example 5 did not add basalt mineral fibers, and its flexural strength and hydrolysis resistance decreased significantly, indicating that basalt mineral fibers play a key role in improving the long-term durability of synthetic leather.

[0100] 2. This invention prepares synthetic leather through a composite system of three components: "marine silk base fabric", "impregnating material using bio-based polyurethane resin", and "coating material incorporating basalt mineral fibers and porous silica as fillers". While achieving high environmental friendliness, it significantly enhances the interfacial bonding force between the resin and the base fabric (i.e., the bonding performance between the fabric layer and the base fabric) and constructs an effective stress buffer network, thereby greatly improving the long-term physical properties of synthetic leather, such as hydrolysis resistance and low-temperature folding resistance.

[0101] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for producing environmentally friendly marine silk synthetic leather reinforced with basalt mineral fiber interfaces, characterized in that: Includes the following steps: S1: Nonwoven fabric made from a blend of marine silk fiber and polyester fiber; S2: The nonwoven fabric is impregnated with an impregnating material containing a first bio-based polyurethane resin to obtain an impregnated base fabric; S3: After the impregnated base fabric undergoes pre-coagulation and ironing processes, a coating material is scraped onto the surface to form a fabric layer; the coating material is made of a second bio-based polyurethane resin, dimethylformamide, basalt mineral fiber, porous silica, nonionic surfactant, fluorine-free hydrolysis-resistant additive, and color paste in a ratio of 100:(35-45):(4-6):(2-4):(0.4-0.6):(0.6-1):(1-3); S4: The base fabric with the fabric layer is then sent into the three-fold coagulation tank for coagulation, so that the base fabric has a dense pore structure. S5: After washing, pre-ironing, drying, cooling and rolling, the desired environmentally friendly marine silk synthetic leather is obtained.

2. The method for producing environmentally friendly marine silk synthetic leather with basalt mineral fiber interface reinforcement according to claim 1, characterized in that: In S1, the ratio of marine silk fiber to polyester fiber is (45-55%):(45-55%).

3. The method for producing environmentally friendly marine silk synthetic leather with basalt mineral fiber interface reinforcement according to claim 2, characterized in that... In S1, the marine silk fiber is produced by a physical method, which includes the processes of recycling waste fishing nets, sorting and cleaning, slicing, and spinning.

4. The method for producing environmentally friendly marine silk synthetic leather with basalt mineral fiber interface reinforcement according to claim 1, characterized in that: In S2, the first bio-based polyurethane resin has a solid content of 30%, a bio-based content of 30%, a 100% modulus of 55-65, and a viscosity range of 130,000-160,000 cps.

5. The method for producing environmentally friendly marine silk synthetic leather with basalt mineral fiber interface reinforcement according to claim 4, characterized in that: In S2, the impregnating material is prepared by mixing a first bio-based polyurethane resin, dimethylformamide, tear-resistant agent, fluorine-free hydrolysis-resistant agent, and color paste in a ratio of 100:(300-400):(10-20):(0.8-1.2):(18-22); the viscosity of the impregnating material is 120±10cps.

6. The method for producing environmentally friendly marine silk synthetic leather with basalt mineral fiber interface reinforcement according to claim 1, characterized in that: In S3, the viscosity of the coating material is 12000±1000cps.

7. The method for producing environmentally friendly marine silk synthetic leather with basalt mineral fiber interface reinforcement according to claim 6, characterized in that: In the S3 coating process, the coating gap is controlled at 200±5 mils, corresponding to a coating amount of 1.3±0.05 kg / y.

8. The method for producing environmentally friendly marine silk synthetic leather with basalt mineral fiber interface reinforcement according to claim 7, characterized in that: In the S4 coagulation process, the base fabric enters the three-fold coagulation tank at a 30° angle to the coagulation liquid. The sugar content of the coagulation liquid is 20-22%, and the temperature is 32±2℃. After the base fabric leaves the coagulation tank, its thickness and width are measured.

9. The method for producing environmentally friendly marine silk synthetic leather with basalt mineral fiber interface reinforcement according to claim 8, characterized in that: In the S5 washing process, the water then enters a washing system consisting of 16 washing tanks. Tanks 1 to 6 are washed at room temperature with a sugar content of 22-15%. After the initial washing, the sugar content of tanks 7 to 16 is 13-0%. Among them, the temperature of tanks 7 to 13 is room temperature, and the temperature of the last three tanks is increased to 60-80℃.

10. The method for producing environmentally friendly marine silk synthetic leather with basalt mineral fiber interface reinforcement according to claim 9, characterized in that: In the pre-ironing process of S5, the temperature of the ironing rollers is 110±10℃. After pre-ironing, the material enters the drying oven. The temperature of the first group of drying ovens is 150℃, the temperature of the second to fourth groups of drying ovens is 160℃, and the temperature of the fifth group of drying ovens is 140℃. After drying, the synthetic leather is cooled by six cooling rollers and finally rolled up. The thickness of the roll is controlled at 1.1-1.2mm, and the effective width is controlled at 140-142cm.

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