Multi-element synergistic flame-retardant artificial leather and preparation method thereof

Abstract

The invention relates to the field of PVC artificial leather, and particularly discloses multi-element synergistic flame-retardant artificial leather and a preparation method thereof.The multi-element synergistic flame-retardant artificial leather comprises a surface layer, a foaming layer and a base cloth layer from top to bottom, and the surface layer is prepared from, by mass, 90-100 parts of PVC, 8-10 parts of stabilizer, 5-6 parts of lubricant and 30-50 parts of plasticizer; the foaming layer comprises the following raw materials in parts by mass: 80-100 parts of PVC resin, 2-12 parts of a foaming agent and 8-12 parts of a modified flame retardant; the base cloth layer comprises one or more of knitted cloth, woven cloth or spunlace cloth; the modified flame retardant comprises silicon dioxide aerogel fibers coated with a polyvinyl alcohol modified flame retardant, and the flame retardant comprises antimony trioxide. According to the artificial leather prepared by the invention, doping of the flame-retardant material is completed by utilizing refined and reasonable coating, and stable and efficient flame retardance of the artificial leather under a high-power fire source is realized.

Description

Technical Field

[0001] This application relates to the field of PVC artificial leather, and more specifically, to a multi-component synergistic flame-retardant artificial leather and its preparation method. Background Technology

[0002] PVC artificial leather is widely used in various fields due to its environmental friendliness, durability, and versatility, such as automotive interiors, furniture, footwear, and protective clothing. Typically, antimony halide (SbCl3) is generated by adding Sb2O3 flame retardant to capture H· and OH· free radicals from the combustion chain reaction in the gas phase, inhibiting the chain reaction and achieving a flame-retardant effect. However, Sb2O3 is a micron-sized powder, which easily agglomerates in PVC paste resin, requiring high shear force dispersion, increasing energy consumption and production costs. Furthermore, Sb2O3 alone has low flame-retardant efficiency and must be combined with halogenated flame retardants such as chlorinated paraffin. Halogenated systems themselves suffer from poor thermal stability and easy precipitation. While Sb2O3 mainly inhibits gas-phase combustion by capturing free radicals, its flame-retardant effect is limited and difficult to handle high-power fire sources (such as automotive interior fires). Therefore, considering these issues, this paper proposes a method for reducing Sb2O3 dosage and using a multi-element synergistic approach to achieve a more stable and efficient flame-retardant effect in PVC artificial leather. This method is of great value in improving the stable flame retardancy of artificial leather under high-power fire sources. Summary of the Invention

[0003] To address the issue of insufficient flame retardant effect in PVC artificial leather, this application provides a multi-element synergistic flame retardant artificial leather and its preparation method.

[0004] In a first aspect, this application provides a multi-component synergistic flame-retardant artificial leather, comprising, from top to bottom, a surface layer, a foam layer, and a base fabric layer. The surface layer comprises the following raw materials in parts by weight: 90-100 parts PVC, 8-10 parts stabilizer, 5-6 parts lubricant, and 30-50 parts plasticizer. The foam layer comprises the following raw materials in parts by weight: 80-100 parts PVC resin, 2-12 parts foaming agent, and 8-12 parts flame retardant. The base fabric layer comprises one or more of knitted fabric, woven fabric, or spunlace fabric. The flame retardant comprises polyvinyl alcohol-modified antimony trioxide-coated silica aerogel fiber.

[0005] By adopting the above technical solution, the raw material settings for the surface layer, foam layer, and base fabric layer are relatively simple. The raw material settings for the surface layer and foam layer are similar, and the connection is relatively tight. By adding a certain mass of polyvinyl alcohol modified flame retardant to the foam layer to coat silica gel fibers, especially polyvinyl alcohol modified antimony trioxide to coat silica gel fibers, the flame retardant is more evenly dispersed, reducing agglomeration and better exerting the flame retardant effect. At the same time, while silica gel fibers provide good heat insulation effect, the porous structure increases the surface area for flame retardant reaction, promotes the formation of flame retardant gas and char layer, and enhances the flame retardant's ability to capture free radicals in the artificial leather system, resulting in better flame retardant and heat insulation effects.

[0006] In one specific implementation, the flame retardant further includes a halogenated flame retardant, nano-aluminum hydroxide, and diethylaluminum hypophosphite. The halogenated flame retardant includes one or more of decabromodiphenyl ether and octabromodiphenyl ether. The mass ratio of the halogenated flame retardant, nano-aluminum hydroxide, diethylaluminum hypophosphite, and polyvinyl alcohol-modified antimony trioxide-coated silica aerogel fiber is (3-4):1:(2.2-2.4):(1.5-2.1).

[0007] By employing the above technical solution, halogenated flame retardants react with antimony trioxide to generate gaseous antimony halide, which suppresses flames by capturing and isolating oxygen through gaseous free radicals. Nano-aluminum hydroxide decomposes, absorbs heat, and releases water vapor for cooling. Diethylaluminum hypophosphite promotes char formation and inhibits combustion, and can also decompose at high temperatures to generate PO· free radicals, which capture and quench H· and HO· free radicals in the combustion chain reaction, further interrupting flame propagation. It can also achieve relatively uniform coating of silica aerogel fibers, and the good heat insulation effect of silica aerogel fibers delays the temperature rise inside the artificial leather. The curve, while providing heat insulation and flame retardancy, shifts the heating curve to the right. Nano-aluminum hydroxide first decomposes, absorbs heat, and releases water vapor. Halogenated flame retardants and antimony trioxide then release antimony halides, successively forming char and generating airflow. Together, they allow the compound flame retardants to reach their decomposition temperatures sequentially. At high temperatures, the flame retardants and the airflow generated by the decomposition within the system are at a suitable speed. The competition between the self-volatilization and deethylation of aluminum diethylphosphite is also suitable, allowing for more effective free radical capture and quenching. With less solid residue, it contributes more to the flame retardant effect, resulting in better flame retardant performance of the artificial leather.

[0008] In one specific implementation, the preparation steps of polyvinyl alcohol-modified flame retardant-coated silica aerogel fibers include: S1: Tetraethyl orthosilicate is mixed with ethanol and water, dilute hydrochloric acid is added, the mixture is heated and stirred, then polyvinyl alcohol is added, the mixture is heated and stirred, electrospun, and then dried under supercritical CO2 conditions to form silica aerogel fibers. S2: Immerse silica aerogel in dopamine Tris buffer solution, stir, then immerse in an aqueous solution of antimony nitrate and urea, and react in a water bath to obtain flame retardant coated silica aerogel fibers. S3: Immerse flame-retardant-coated silica aerogel fibers in a polyvinyl alcohol aqueous solution, add boric acid, heat and impregnate, and then heat to cure to obtain polyvinyl alcohol-modified flame-retardant-coated silica aerogel fibers.

[0009] By adopting the above technical solution, the preparation steps are relatively simple. The aerogel fiber has a high specific surface area and low density. The fiber is continuous and uniform, and the porous structure is not easy to collapse. It can attach flame retardants well. Dopamine activation provides abundant hydroxyl and amino groups. After hydrolysis reaction, it is uniformly coated with antimony trioxide nanoparticles, resulting in good flame retardant effect.

[0010] In one specific implementation, S3 further includes the following steps: adding the remaining flame retardant to a polyvinyl alcohol aqueous solution, stirring, and ultrasonically dispersing.

[0011] In one specific embodiment, polyvinyl alcohol comprises polyvinyl alcohol 1000, and the concentration of the aqueous polyvinyl alcohol solution is 9-12 wt%.

[0012] By adopting the above technical solution, the polyvinyl alcohol has a suitable viscosity, resulting in a good coating effect for flame retardants. The halogenated flame retardant, nano-aluminum hydroxide, and diethylaluminum hypophosphite are uniformly dispersed in the polyvinyl alcohol solution, preventing agglomeration and growth, resulting in small particle size and a higher oxygen index in the product. Simultaneously, the coating effect on modified antimony trioxide-coated silica aerogel fibers is good, further enhancing the synergistic effect of the flame retardants.

[0013] In one specific implementation, the preparation steps also include post-treatment: heating and stretching the polyvinyl alcohol modified flame retardant-coated silica aerogel fibers at a temperature of 185-195°C and a stretching ratio of 1.5-2.5 times.

[0014] By adopting the above technical solutions, the orientation and dimensional stability of the fibers are improved, and the flame retardant and heat insulation components are more stably distributed in the artificial leather system.

[0015] In one specific implementation, the silica aerogel fibers in S1 include coarse silica aerogel fibers and fine silica aerogel fibers in a mass ratio of 1:(1.0-2.0).

[0016] By adopting the above technical solution, coarse and fine silica aerogel fibers are interwoven in the artificial leather. The coarse silica aerogel fibers have a higher heat insulation effect, while the fine silica aerogel fibers contribute a better flame retardant effect. The combined effect makes the temperature rise curve of the artificial leather more suitable for the composition settings of this application, and the resulting artificial leather has a better flame retardant effect.

[0017] In one specific implementation, the spinning voltage of coarse silica aerogel fibers is 25-30kV and the spinning solution flow rate is 0.4-0.6mL / h, while the spinning voltage of fine silica aerogel fibers is 30-35kV and the spinning solution flow rate is 0.2-0.4mL / h.

[0018] By adopting the above technical solution, the coarse and fine silica aerogel fiber structure is relatively uniform, without obvious beaded structure, and will not split or break, and the size is suitable for the artificial leather system of this application.

[0019] Secondly, this application provides a method for preparing multi-component synergistic flame-retardant artificial leather, comprising the following steps: weighing and mixing the raw materials of the surface layer and foam layer in the indicated mass fractions, then heating and calendering the foam layer and bonding it to the intermediate product on the base fabric layer, and then heating and calendering the surface layer and bonding it to one side of the foam layer of the intermediate product to obtain multi-component synergistic flame-retardant artificial leather.

[0020] By adopting the above technical solution, the preparation method is simple, suitable for the component settings of this application, has good interlayer bonding effect, and the flame retardant and heat insulation fiber are evenly distributed in the artificial leather, so that the artificial leather can achieve a stable flame retardant effect.

[0021] In summary, this application has the following beneficial effects: This application involves adding a certain mass of polyvinyl alcohol modified flame retardant to PVC artificial leather to coat silica aerogel fibers, and further adding a certain mass proportion of halogen flame retardant, nano aluminum hydroxide, and diethyl aluminum hypophosphite. This allows the composite flame retardant to have good char formation, free radical capture, and quenching effects. At the same time, through the heat insulation of the fibers, the temperature rise curve inside the artificial leather is shifted to the right, so that different decomposition temperatures and gas release rates are matched, resulting in better flame retardant effect.

[0022] By limiting the process parameters, post-treatment, and mass ratio of two sizes of silica aerogel fibers, the thermal insulation and flame retardant contributions of polyvinyl alcohol-modified antimony trioxide-coated silica aerogel fibers in vivo are balanced. By further limiting the type and mass of polyvinyl alcohol, the viscosity is suitable for the flame retardant of this application, and the flame retardant achieves more uniform dispersion and smaller particle size, resulting in a better flame retardant effect in the artificial leather. Attached Figure Description

[0023] Figure 1 Schematic diagram of the structure of a multi-component synergistic flame-retardant artificial leather product.

[0024] Explanation of reference numerals in the attached figures: 1. Top layer; 2. Foam layer; 3. Base fabric layer. Detailed Implementation

[0025] The present application will be further described in detail below with reference to embodiments and comparative examples.

[0026] To further aid in understanding the technical solution of the present invention, several specific embodiments are provided to describe the technical solution of the present invention in more detail. All described embodiments are only some embodiments of the present invention, not all of them; embodiments can be combined with each other, and the same or similar concepts or processes may not be repeated in some embodiments. The following embodiments are further illustrations of the present invention, but the present invention is not limited thereto.

[0027] Unless otherwise specified, the chemical reagents used in the examples and comparative examples are commercially available conventional reagents.

[0028] The stabilizer was purchased from Yingzheng New Materials (calcium stearate), the lubricant was purchased from Havis TF-3500EL, the plasticizer was purchased from Shuanghong SH-DEDB, and the foaming agent was purchased from Ya Yang CCR308.

[0029] Preparation Example Preparation Example 1: Polyvinyl alcohol modified antimony trioxide coated fine silica aerogel fibers S1: Mix 100ml of tetraethyl orthosilicate with 400ml of ethanol and 100ml of water, adjust the pH to 3 with dilute hydrochloric acid, stir at 60℃ for 3 hours, then add 10g of polyvinyl alcohol 1000, heat to 80℃ and stir, electrospin with voltage 32kV, receiving distance 15cm, spinning solution flow rate 0.3mL / h, and then dry under supercritical CO2 conditions to form fine silica aerogel fibers; S2: The fine silica aerogel fibers were immersed in a Tris buffer solution containing 2 mg / mL dopamine and stirred at room temperature for 12 hours. Then, they were immersed in an aqueous solution of 0.1 mol / L antimony nitrate and 0.2 mol / L urea and reacted in a water bath at 80°C for 4 hours to obtain fine silica aerogel fibers coated with antimony trioxide. S3: 9.2g of antimony trioxide-coated fine silica aerogel fiber was immersed in 400ml of 10wt% polyvinyl alcohol 1000 aqueous solution, 2g of boric acid was added, and the fiber was soaked at 60℃ for 2 hours. Then it was dried and cured by hot air at 120℃ to obtain polyvinyl alcohol modified antimony trioxide-coated fine silica aerogel fiber.

[0030] Preparation Example 2: Polyvinyl alcohol modified flame retardant coated with fine silica aerogel fibers S1: Mix 100ml of tetraethyl orthosilicate with 400ml of ethanol and 100ml of water, adjust the pH to 3 with dilute hydrochloric acid, stir at 60℃ for 3 hours, then add 10g of polyvinyl alcohol 1000, heat to 80℃ and stir, electrospin with voltage 32kV, receiving distance 15cm, spinning solution flow rate 0.3mL / h, and then dry under supercritical CO2 conditions to form fine silica aerogel fibers; S2: The fine silica aerogel fibers were immersed in a Tris buffer solution containing 2 mg / mL dopamine and stirred at room temperature for 12 hours. Then, they were immersed in an aqueous solution of 0.1 mol / L antimony nitrate and 0.2 mol / L urea and reacted in a water bath at 80°C for 4 hours to obtain fine silica aerogel fibers coated with antimony trioxide. S3: Add 4g decabromodiphenyl ether, 1g nano aluminum hydroxide, and 2.2g diethyl aluminum hypophosphite to 400ml of 10wt% polyvinyl alcohol aqueous solution, and ultrasonically disperse at 300W for 30 minutes. Immerse 2g antimony trioxide-coated fine silica aerogel fibers in the solution, add 2g boric acid, and impregnate at 60℃ for 2 hours. Then, dry and cure with hot air at 120℃ to obtain polyvinyl alcohol modified flame retardant-coated fine silica aerogel fibers.

[0031] Preparation Example 3: Polyvinyl alcohol modified flame retardant coated with fine silica aerogel fibers S1: Mix 100ml of tetraethyl orthosilicate with 400ml of ethanol and 100ml of water, adjust the pH to 3 with dilute hydrochloric acid, stir at 60℃ for 3 hours, then add 10g of polyvinyl alcohol 1000, heat to 80℃ and stir, electrospin with voltage 32kV, receiving distance 15cm, spinning solution flow rate 0.3mL / h, and then dry under supercritical CO2 conditions to form fine silica aerogel fibers; S2: The fine silica aerogel fibers were immersed in a Tris buffer solution containing 2 mg / mL dopamine and stirred at room temperature for 12 hours. Then, they were immersed in an aqueous solution of 0.1 mol / L antimony nitrate and 0.2 mol / L urea and reacted in a water bath at 80°C for 4 hours to obtain fine silica aerogel fibers coated with antimony trioxide. S3: Add 4g of decabromodiphenyl ether and 3.2g of nano aluminum hydroxide to 400ml of 10wt% polyvinyl alcohol 1000 aqueous solution, ultrasonically disperse at 300W for 30 minutes, immerse 2g of antimony trioxide-coated fine silica aerogel fiber, add 2g of boric acid, impregnate at 60℃ for 2 hours, and then dry and cure with hot air at 120℃ to obtain polyvinyl alcohol modified flame retardant-coated fine silica aerogel fiber.

[0032] Preparation Example 4: Polyvinyl alcohol modified flame retardant coated with fine silica aerogel fibers S1: Mix 100ml of tetraethyl orthosilicate with 400ml of ethanol and 100ml of water, adjust the pH to 3 with dilute hydrochloric acid, stir at 60℃ for 3 hours, then add 10g of polyvinyl alcohol 1000, heat to 80℃ and stir, electrospin with voltage 32kV, receiving distance 15cm, spinning solution flow rate 0.3mL / h, and then dry under supercritical CO2 conditions to form fine silica aerogel fibers; S2: The fine silica aerogel fibers were immersed in a Tris buffer solution containing 2 mg / mL dopamine and stirred at room temperature for 12 hours. Then, they were immersed in an aqueous solution of 0.1 mol / L antimony nitrate and 0.2 mol / L urea and reacted in a water bath at 80°C for 4 hours to obtain fine silica aerogel fibers coated with antimony trioxide. S3: Add 4g decabromodiphenyl ether, 1g nano aluminum hydroxide, and 2.2g diethyl aluminum hypophosphite to 400ml of 14wt% polyvinyl alcohol 1000 aqueous solution, and ultrasonically disperse at 300W for 30 minutes. Immerse 2g antimony trioxide-coated fine silica aerogel fibers in the solution, add 2g boric acid, and impregnate at 60℃ for 2 hours. Then, dry and cure with hot air at 120℃ to obtain polyvinyl alcohol modified flame retardant-coated fine silica aerogel fibers.

[0033] Preparation Example 5: Polyvinyl alcohol modified flame retardant coated with fine silica aerogel fibers S1: Mix 100ml of tetraethyl orthosilicate with 400ml of ethanol and 100ml of water, adjust the pH to 3 with dilute hydrochloric acid, stir at 60℃ for 3 hours, then add 10g of polyvinyl alcohol 1000, heat to 80℃ and stir, electrospin with voltage 32kV, receiving distance 15cm, spinning solution flow rate 0.3mL / h, and then dry under supercritical CO2 conditions to form fine silica aerogel fibers; S2: The fine silica aerogel fibers were immersed in a Tris buffer solution containing 2 mg / mL dopamine and stirred at room temperature for 12 hours. Then, they were immersed in an aqueous solution of 0.1 mol / L antimony nitrate and 0.2 mol / L urea and reacted in a water bath at 80°C for 4 hours to obtain fine silica aerogel fibers coated with antimony trioxide. S3: Add 4g decabromodiphenyl ether, 1g nano aluminum hydroxide, and 2.2g diethyl aluminum hypophosphite to 400ml of 10wt% polyvinyl alcohol 1000 aqueous solution, ultrasonically disperse at 300W for 30 minutes, immerse 2g antimony trioxide-coated fine silica gel fiber, add 2g boric acid, impregnate at 60℃ for 2 hours, and then dry and cure with hot air at 120℃. S4: Heated to 190 degrees Celsius and stretched to twice its original size, resulting in polyvinyl alcohol-modified flame retardant-coated fine silica aerogel fibers.

[0034] Preparation Example 6: Polyvinyl alcohol modified flame retardant coated coarse silica aerogel fibers S1: Mix 100ml of tetraethyl orthosilicate with 400ml of ethanol and 100ml of water, adjust the pH to 3 with dilute hydrochloric acid, stir at 60℃ for 3 hours, then add 10g of polyvinyl alcohol 1000, heat to 80℃ and stir, electrospin, voltage 25kV, receiving distance 15cm, spinning solution flow rate 0.5mL / h, and then dry under supercritical CO2 conditions to form coarse silica aerogel fibers; S2: The crude silica aerogel fiber was immersed in a Tris buffer solution of 2 mg / mL dopamine and stirred at room temperature for 12 hours. Then it was immersed in an aqueous solution of 0.1 mol / L antimony nitrate and 0.2 mol / L urea and reacted in a water bath at 80°C for 4 hours to obtain antimony trioxide coated crude silica aerogel fiber. S3: Add 4g decabromodiphenyl ether, 1g nano aluminum hydroxide, and 2.2g diethyl aluminum hypophosphite to 400ml of 10wt% polyvinyl alcohol 1000 aqueous solution, ultrasonically disperse at 300W for 30 minutes, immerse 2g antimony trioxide-coated coarse silica gel fiber, add 2g boric acid, impregnate at 60℃ for 2 hours, and then dry and cure with hot air at 120℃. S4: Heating to 190 degrees Celsius and stretching to twice its original size yields polyvinyl alcohol-modified flame retardant-coated coarse silica aerogel fibers.

[0035] Preparation Example 7: Fine silica aerogel fibers S1: Mix 100ml of tetraethyl orthosilicate with 400ml of ethanol and 100ml of water, adjust the pH to 3 with dilute hydrochloric acid, stir at 60℃ for 3 hours, then add 10g of polyvinyl alcohol 1000, heat to 80℃ and stir, electrospin with voltage 32kV, receiving distance 15cm, spinning solution flow rate 0.3mL / h, and then dry under supercritical CO2 conditions to form fine silica aerogel fibers; Example

[0036] Example 1 The raw materials used in this embodiment are as follows: Top layer: PVC 100g, stabilizer 9g, lubricant 5g, plasticizer 30g; The foaming layer comprises the following raw materials by weight: 100g of PVC resin, 8g of foaming agent, and 10g of polyvinyl alcohol modified antimony trioxide coated fine silica aerogel fiber obtained in Preparation Example 1. Base fabric: woven cotton fabric.

[0037] The raw materials for the surface layer and the foam layer are weighed and mixed evenly according to their weight. Then, the foam layer is heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to the base fabric layer to obtain the intermediate product. The surface layer is then heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to one side of the foam layer of the intermediate product to obtain the multi-functional synergistic flame-retardant artificial leather.

[0038] Example 2 The raw materials used in this embodiment are as follows: Top layer: PVC 90g, stabilizer 8g, lubricant 6g, plasticizer 40g; The foaming layer comprises the following raw materials by weight: 100g of PVC resin, 8g of foaming agent, and 10g of polyvinyl alcohol modified antimony trioxide coated fine silica aerogel fiber obtained in Preparation Example 1. Base fabric: woven cotton fabric.

[0039] The raw materials for the surface layer and the foam layer are weighed and mixed evenly according to their weight. Then, the foam layer is heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to the base fabric layer to obtain the intermediate product. The surface layer is then heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to one side of the foam layer of the intermediate product to obtain the multi-functional synergistic flame-retardant artificial leather.

[0040] Example 3 The raw materials used in this embodiment are as follows: Top layer: PVC 90g, stabilizer 8g, lubricant 6g, plasticizer 40g; The foamed layer comprises the following raw materials by weight: 100g of PVC resin, 8g of foaming agent, and 10g of fine silica aerogel fibers coated with polyvinyl alcohol modified flame retardant obtained in Preparation Example 2. Base fabric: woven cotton fabric.

[0041] The raw materials for the surface layer and the foam layer are weighed and mixed evenly according to their weight. Then, the foam layer is heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to the base fabric layer to obtain the intermediate product. The surface layer is then heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to one side of the foam layer of the intermediate product to obtain the multi-functional synergistic flame-retardant artificial leather.

[0042] Example 4 The raw materials used in this embodiment are as follows: Top layer: PVC 90g, stabilizer 8g, lubricant 6g, plasticizer 40g; The foamed layer comprises the following raw materials by weight: 100g of PVC resin, 8g of foaming agent, and 10g of fine silica aerogel fibers coated with polyvinyl alcohol modified flame retardant obtained in Preparation Example 3. Base fabric: woven cotton fabric.

[0043] The raw materials for the surface layer and the foam layer are weighed and mixed evenly according to their weight. Then, the foam layer is heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to the base fabric layer to obtain the intermediate product. The surface layer is then heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to one side of the foam layer of the intermediate product to obtain the multi-functional synergistic flame-retardant artificial leather.

[0044] Example 5 The raw materials used in this embodiment are as follows: Top layer: PVC 90g, stabilizer 8g, lubricant 6g, plasticizer 40g; The foamed layer comprises the following raw materials by weight: 100g of PVC resin, 8g of foaming agent, and 10g of fine silica aerogel fibers coated with polyvinyl alcohol modified flame retardant prepared in Preparation Example 4. Base fabric: woven cotton fabric.

[0045] The raw materials for the surface layer and the foam layer are weighed and mixed evenly according to their weight. Then, the foam layer is heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to the base fabric layer to obtain the intermediate product. The surface layer is then heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to one side of the foam layer of the intermediate product to obtain the multi-functional synergistic flame-retardant artificial leather.

[0046] Example 6 The raw materials used in this embodiment are as follows: Top layer: PVC 90g, stabilizer 8g, lubricant 6g, plasticizer 40g; The foamed layer comprises the following raw materials by weight: 100g of PVC resin, 8g of foaming agent, and 10g of fine silica aerogel fibers coated with polyvinyl alcohol modified flame retardant obtained in Preparation Example 5. Base fabric: woven cotton fabric.

[0047] The raw materials for the surface layer and the foam layer are weighed and mixed evenly according to their weight. Then, the foam layer is heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to the base fabric layer to obtain the intermediate product. The surface layer is then heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to one side of the foam layer of the intermediate product to obtain the multi-functional synergistic flame-retardant artificial leather.

[0048] Example 7 The raw materials used in this embodiment are as follows: Top layer: PVC 90g, stabilizer 8g, lubricant 6g, plasticizer 40g; The foamed layer comprises the following raw materials by weight: 100g of PVC resin, 8g of foaming agent, 5g of fine silica aerogel fibers coated with polyvinyl alcohol modified flame retardant obtained in Preparation Example 5, and 5g of coarse silica aerogel fibers coated with polyvinyl alcohol modified flame retardant obtained in Preparation Example 6. Base fabric: woven cotton fabric.

[0049] The raw materials for the surface layer and the foam layer are weighed and mixed evenly according to their weight. Then, the foam layer is heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to the base fabric layer to obtain the intermediate product. The surface layer is then heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to one side of the foam layer of the intermediate product to obtain the multi-functional synergistic flame-retardant artificial leather.

[0050] Example 8 The raw materials used in this embodiment are as follows: Top layer: PVC 90g, stabilizer 8g, lubricant 6g, plasticizer 40g; The foamed layer comprises the following raw materials by weight: 100g of PVC resin, 8g of foaming agent, 6.6g of fine silica aerogel fibers coated with polyvinyl alcohol modified flame retardant obtained in Preparation Example 5, and 3.3g of coarse silica aerogel fibers coated with polyvinyl alcohol modified flame retardant obtained in Preparation Example 6. Base fabric: woven cotton fabric.

[0051] The raw materials for the surface layer and the foam layer are weighed and mixed evenly according to their weight. Then, the foam layer is heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to the base fabric layer to obtain the intermediate product. The surface layer is then heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to one side of the foam layer of the intermediate product to obtain the multi-functional synergistic flame-retardant artificial leather.

[0052] Example 9 The raw materials used in this embodiment are as follows: Top layer: PVC 90g, stabilizer 8g, lubricant 6g, plasticizer 40g; The foamed layer comprises the following raw materials by weight: 100g of PVC resin, 8g of foaming agent, 7.5g of fine silica aerogel fibers coated with polyvinyl alcohol modified flame retardant obtained in Preparation Example 5, and 2.5g of coarse silica aerogel fibers coated with polyvinyl alcohol modified flame retardant obtained in Preparation Example 6. Base fabric: woven cotton fabric.

[0053] The raw materials for the surface layer and the foam layer are weighed and mixed evenly according to their weight. Then, the foam layer is heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to the base fabric layer to obtain the intermediate product. The surface layer is then heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to one side of the foam layer of the intermediate product to obtain the multi-functional synergistic flame-retardant artificial leather.

[0054] Comparative Example Comparative Example 1 The ingredients are as follows: Top layer: PVC 90g, stabilizer 8g, lubricant 6g, plasticizer 40g; The foaming layer comprises the following raw materials by weight: 100g PVC resin, 8g foaming agent, and 10g antimony trioxide; Base fabric: woven cotton fabric.

[0055] The raw materials for the surface layer and the foam layer are weighed and mixed evenly according to their weight. Then, the foam layer is heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to the base fabric layer to obtain the intermediate product. The surface layer is then heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to one side of the foam layer of the intermediate product to obtain the multi-functional synergistic flame-retardant artificial leather.

[0056] Comparative Example 2 The ingredients are as follows: Top layer: PVC 90g, stabilizer 8g, lubricant 6g, plasticizer 40g; The foamed layer comprises the following raw materials by weight: 100g of PVC resin, 8g of foaming agent, 5g of antimony trioxide, and the fine silica aerogel fiber obtained in Preparation Example 7. Base fabric: woven cotton fabric.

[0057] The raw materials for the surface layer and the foam layer are weighed and mixed evenly according to their weight. Then, the foam layer is heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to the base fabric layer to obtain the intermediate product. The surface layer is then heated and rolled to 0.5 mm at a heating temperature of 120°C for 3 minutes. While still hot, it is bonded to one side of the foam layer of the intermediate product to obtain the multi-functional synergistic flame-retardant artificial leather.

[0058] Performance Testing Test 1: Referencing GB8410-2006 "Combustion Characteristics of Automotive Interior Materials," test the horizontal flame retardancy rating of the sample. Expose the sample to a flame for 15 seconds. If the flame extinguishes within the first mark, the result is recorded as A - 0 mm / min; if it extinguishes within 60 seconds and the burning distance is no greater than 50 mm, the result is recorded as B; if the flame extinguishes within two measurement marks, record the burning time and distance, calculate the speed V, and record the result as C - burning speed V mm / min; if the flame reaches the second mark, record the burning time and distance, and record the result as D - burning speed V mm / min; if the flame ignites and burns within 15 seconds and reaches the first mark, the result is recorded as E.

[0059] Test 2: The sample was subjected to artificial climate aging test according to GB / T29631-2013, and then Test 1 was repeated to test the flame retardant stability.

[0060] Test 3: Determine the oxygen index of the test sample for combustion behavior according to GB / T2406.1-2008 Oxygen Index Method for Plastics.

[0061] The test results are shown in Table 1.

[0062] Table 1 Flame retardant rating (mm / min) Flame retardancy rating after aging (mm / min) Oxygen Index % Example 1 C-28 C-31 28.1 Example 2 C-30 C-32 28.7 Example 3 B B 32.4 Example 4 B C-15 31.7 Example 5 B C-16 31.4 Example 6 B B 32.8 Example 7 A-0 A-0 33.5 Example 8 A-0 A-0 33.6 Example 9 A-0 B 33.6 Comparative Example 1 C-120 C-175 26.0 Comparative Example 2 C-135 C-172 25.7 In conjunction with Examples 1-2, Comparative Examples 1-2, and Table 1, this application improves the flame retardant properties of artificial leather by adding a certain mass of polyvinyl alcohol-modified antimony trioxide-coated silica aerogel fibers to the artificial leather. This makes the antimony trioxide finer and more evenly distributed in the system, and the combined effect of heat insulation and flame retardancy enhances the flame retardant properties of the artificial leather.

[0063] In conjunction with Examples 2-6 and Table 1, this application further improves the flame retardancy of the product by adding a certain mass of decabromodiphenyl ether, nano aluminum hydroxide, and diethyl aluminum hypophosphite, and by limiting the post-treatment and process parameters, making the competition between the volatilization and decomposition of flame retardants more reasonable.

[0064] In conjunction with Examples 2, 7-9 and Table 1, this application improves the thermal stability of the system by limiting the coating of silica aerogel fibers with polyvinyl alcohol modified flame retardant at different sizes and by limiting the mass ratio, making the components less prone to precipitation and the flame retardant performance more stable.

[0065] The specific embodiments described herein are merely illustrative of this application and are not intended to limit it. Those skilled in the art can make modifications to these embodiments without contributing any inventive step after reading this specification, 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 multi-component synergistic flame-retardant artificial leather, characterized in that: From top to bottom, it includes a surface layer, a foam layer, and a base fabric layer. The surface layer includes the following raw materials in parts by weight: 90-100 parts PVC, 8-10 parts stabilizer, 5-6 parts lubricant, and 30-50 parts plasticizer. The foam layer includes the following raw materials in parts by weight: 80-100 parts PVC resin, 2-12 parts foaming agent, and 8-12 parts flame retardant. The base fabric layer includes one or more of knitted fabric, woven fabric, or spunlace fabric. The flame retardant includes polyvinyl alcohol modified antimony trioxide coated silica aerogel fiber.

2. The multi-component synergistic flame-retardant artificial leather according to claim 1, characterized in that: The flame retardant also includes halogen flame retardant, nano aluminum hydroxide, and diethyl aluminum hypophosphite. The halogen flame retardant includes one or more of decabromodiphenyl ether and octabromodiphenyl ether. The mass ratio of the halogen flame retardant, nano aluminum hydroxide, diethyl aluminum hypophosphite, and polyvinyl alcohol modified antimony trioxide coated silica aerogel fiber is (3-4):1:(2.2-2.4):(1.5-2.1).

3. The multi-component synergistic flame-retardant artificial leather according to claim 1, characterized in that: The preparation steps of the polyvinyl alcohol modified flame retardant coated silica aerogel fiber include: S1: Tetraethyl orthosilicate is mixed with ethanol and water, dilute hydrochloric acid is added, the mixture is heated and stirred, then polyvinyl alcohol is added, the mixture is heated and stirred, electrospun, and then dried under supercritical CO2 conditions to form silica aerogel fibers. S2: Immerse silica aerogel in dopamine Tris buffer solution, stir, then immerse in an aqueous solution of antimony nitrate and urea, and react in a water bath to obtain flame retardant coated silica aerogel fibers. S3: Immerse flame-retardant-coated silica aerogel fibers in a polyvinyl alcohol aqueous solution, add boric acid, heat and impregnate, and then heat to cure to obtain polyvinyl alcohol-modified flame-retardant-coated silica aerogel fibers.

4. The multi-component synergistic flame-retardant artificial leather according to claim 3, characterized in that: The S3 further includes the following steps: adding the remaining flame retardant to a polyvinyl alcohol aqueous solution, stirring, and ultrasonically dispersing.

5. The multi-component synergistic flame-retardant artificial leather according to claim 4, characterized in that: The polyvinyl alcohol includes polyvinyl alcohol 1000, and the concentration of the polyvinyl alcohol aqueous solution is 9-12 wt%.

6. The multi-component synergistic flame-retardant artificial leather according to claim 3, characterized in that: The preparation steps also include post-treatment: heating and stretching the polyvinyl alcohol modified flame retardant-coated silica aerogel fiber at a temperature of 185-195℃ and a stretching ratio of 1.5-2.5 times.

7. The multi-component synergistic flame-retardant artificial leather according to claim 3, characterized in that: The silica aerogel fibers in S1 include coarse silica aerogel fibers and fine silica aerogel fibers in a mass ratio of 1:(1.0-2.0).

8. The multi-component synergistic flame-retardant artificial leather according to claim 1, characterized in that: The spinning voltage of the coarse silica aerogel fiber is 25-30kV, and the spinning solution flow rate is 0.4-0.6mL / h. The spinning voltage of the fine silica aerogel fiber is 30-35kV, and the spinning solution flow rate is 0.2-0.4mL / h.

9. A method for preparing a multi-component synergistic flame-retardant artificial leather according to any one of claims 1-8, characterized in that: Includes the following steps: The raw materials for the surface layer and the foam layer are weighed and mixed evenly according to their respective weight proportions. Then, the foam layer is heated and calendered, and then bonded to the intermediate product on the base fabric layer. The surface layer is then heated and calendered, and then bonded to one side of the foam layer of the intermediate product to obtain multi-functional synergistic flame-retardant artificial leather.

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