Imitation leather material for automotive trim and preparation method of imitation leather material
By modifying polyurethane resin and composite silk fibroin fiber, the breathability and strength of the polyurethane imitation leather material are improved, and flexibility, wear resistance and antistatic properties are imparted, and the problem of difficulty in taking into account both breathability and strength in the prior art is solved.
Patent Information
- Application Number
- CN202510744552.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-05
- Publication Date
- 2025-08-12
AI Technical Summary
Existing polyurethane imitation leather materials are difficult to take into account both breathability and strength, and the improvement of breathability will lead to a decrease in mechanical strength.
By modifying the polyurethane resin and compositeing the modified polymer resin and silk fibre fiber, the cross-linking and tensile structure of the silk fibre fiber are used to improve flexibility, the polyurethane resin forms a host-guest interaction with cyclodextrin to improve mechanical properties, and urethane groups and polar groups are introduced into the polymer resin to improve compatibility and antistatic properties.
The polyurethane imitation leather material has good strength, flexibility, wear resistance and anti-static characteristics while maintaining breathability, solving the problems of both breathability and strength.
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Abstract
Description
Technical Field
[0001] The invention relates to the technical field of artificial leather material preparation, in particular to an imitation leather material for automobile interior decoration and a preparation method thereof. Background Art
[0002] Imitation leather is a man-made synthetic material used to simulate genuine leather or animal hide. It is also called artificial leather and is primarily made of polyurethane (PU) and polyvinyl chloride (PVC) or other polymers. The resin is made into a slurry and then applied to a base fabric. The resin gradually solidifies to form a microporous surface layer, which is then dry-laminated and formed. After post-processing processes such as embossing and spraying, various types of patterns and effects are produced to simulate the appearance and texture of genuine leather. Among them, PVC imitation leather, although cheaper, is harder and less wear-resistant, easily deformed, and less durable than polyurethane imitation leather. Polyurethane imitation leather is the most common imitation leather material, with a soft, wear-resistant texture and the texture of genuine leather. It is widely used in areas such as automotive interiors. Although imitation leather can simulate the texture of genuine leather in appearance, it still cannot compare with genuine leather in terms of feel and breathability.
[0003] As the most common imitation leather material, polyurethane imitation leather material has breathability, mechanical strength and flexibility as its core performance indicators. Reducing the density of polyurethane imitation leather material can increase the porosity, allowing more air circulation and improving the breathability of polyurethane imitation leather. At the same time, for every 10% increase in porosity, the mechanical strength will decrease by an average of 40%-60%. Summary of the Invention
[0004] In view of the above problems, the present invention provides an imitation leather material for automobile interior decoration and a preparation method thereof.
[0005] The purpose of the present invention is achieved by adopting the following technical solutions: A method for preparing an imitation leather material for automobile interior decoration comprises the following steps: (1) Weigh [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide, 2-[[(butylamino)-carbonyl]oxy]ethyl 2-acrylate and vinyl cyclodextrin respectively and dissolve them in N,N-dimethylformamide, add initiator, pass nitrogen through the mixed system to deoxygenate, and then stir and react at 60-80°C for 12-24 hours. After the reaction is completed, add deionized water to dilute and cool the reaction system, separate the precipitate, wash and dry to obtain a polymer resin; (2) The polyurethane prepolymer, the silk fibroin fiber, the polymer resin and the foaming agent are mixed in a stirrer in proportion and stirred, a cross-linking agent, an organic tin catalyst and an auxiliary agent are added, and the mixture is stirred again to obtain a mixed slurry, the mixed slurry is coated on a release paper, and the mixture is kept warm at 60-160° C. for 5-30 minutes to obtain a product; The cross-linking agent includes a modified polyol, and the preparation method of the modified polyol includes the following steps: 3,3-bis(4-hydroxyphenyl)-2-phenylpropan-1-one and 3-chloro-1,2-propylene glycol are weighed separately and dissolved in toluene, and a base and a catalyst are added. The mixture is stirred and heated at 80-100°C for 2-10 hours. After the reaction is completed, the mixture is washed with water, dried, and the solvent is evaporated to obtain the product.
[0006] In some preferred embodiments, the mass ratio of the [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide to the 2-[[(butylamino)-carbonyl]oxy]ethyl 2-acrylate, the vinyl cyclodextrin, and the initiator in step (1) is 1:(0.8-2.4):(0.5-1.2):(0.001-0.005).
[0007] In some preferred embodiments, the initiator in step (1) is one or more of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, dibenzoyl peroxide, methyl ethyl ketone peroxide, and dicarbonate peroxide.
[0008] In some preferred embodiments, the mass ratio of the polyurethane prepolymer to the silk fibroin fiber, the polymer resin, the foaming agent, the cross-linking agent, the organotin catalyst, and the auxiliary agent in step (2) is 10: (0.5-1.8): (1-3.2): (0.05-0.1): (1-2): (0.01-0.03): (0-3).
[0009] In some preferred embodiments, the foaming agent is one or more of azodicarbonamide, N-dodecylethanolamine, 4,4-oxodibenzenesulfonylhydrazide ether, and dodecyldimethylammonium chloride.
[0010] In some preferred embodiments, the crosslinking agent is a mixture of modified polyol and polyether polyol or polyester polyol, the polyether polyol is sucrose polyether polyol, the polyester polyol is aromatic dibasic acid polyol, and the mass fraction of the modified polyol in the crosslinking agent is 24-60wt%.
[0011] In some preferred embodiments, in the method for preparing the modified polyol, the mass ratio of the 3,3-bis(4-hydroxyphenyl)-2-phenylpropan-1-one to the 3-chloro-1,2-propanediol, the base, and the catalyst is 1:(0.5-0.64):(0.7-0.86):(0.005-0.01).
[0012] In some preferred embodiments, the base is sodium hydroxide or potassium hydroxide, and the catalyst is tetrabutylammonium bromide.
[0013] In some preferred embodiments, the method for preparing the polyurethane prepolymer comprises the following steps: In a dry and anhydrous container, polyether polyol and organotin catalyst are added dropwise to diisocyanate, and after the addition is completed, the mixture is stirred until uniform, and the temperature is raised to 60-80° C. and stirred for reaction for 4-6 hours to obtain the polyurethane prepolymer.
[0014] In some preferred embodiments, the organotin catalyst is dibutyltin dilaurate or stannous octoate.
[0015] In some preferred embodiments, the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, dicyclohexylmethane diisocyanate, and xylyl-4,4 diisocyanate.
[0016] The mass ratio of the polyether polyol to the organic tin catalyst and the diisocyanate is 1: (0.001-0.005): (1.5-2.8).
[0017] In some preferred embodiments, the method for preparing the silk fibroin fiber comprises the following steps: The silk fibroin solution is freeze-dried and then dissolved with formic acid, glycerol is added and stirred to obtain a mixed solution, the mixed solution is electrospun into fibers, and the fibers are cut to obtain silk fibroin fibers with a length of 5-500 mm.
[0018] In some preferred embodiments, the mass ratio of the solid content of the silk fibroin solution to the formic acid and the glycerol is 1:(1-6):(0.5-2).
[0019] In some preferred embodiments, the diameter of the silk fibroin fiber is 0.1-1 μm.
[0020] In some preferred embodiments, the auxiliary agent is one or more of a foaming auxiliary agent, a dispersant, an antioxidant, and a colorant.
[0021] In some preferred embodiments, the foaming aid is one or more of zinc stearate, calcium stearate, and stearic acid; the dispersant is one or more of polyethylene glycol, polyvinyl pyrrolidone, alkylphenol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether; the antioxidant is one or more of antioxidants 2103, 1076, 1035, 1010, 626, 168, and 164, and the colorant is selected as needed.
[0022] Another aspect of the present invention is to provide an imitation leather material for automobile interior trim prepared by the above preparation method.
[0023] The beneficial effects of the present invention are: In view of the problem that polyurethane imitation leather materials in the prior art are difficult to achieve both air permeability and strength, the present invention provides an imitation leather material. By modifying a polyurethane resin and simultaneously compounding the modified polymer resin and silk fibroin fibers, the polyurethane imitation leather material has good strength while maintaining air permeability, and also has the characteristics of flexibility, wear resistance, and antistatic properties. Specifically, by crosslinking and stretching the sparse crystalline phase of silk fibroin, the resin matrix can effectively disperse local mechanical stress to a larger internal area, effectively achieving stress dispersion in the material and improving flexibility. Glycerol treatment can transform the highly tortuous α-helical amorphous structure in the silk fibroin fibers into highly ordered crystalline β-sheets, thereby further stabilizing and strengthening the silk fibroin fibers. The polyurethane resin is treated with polyols to form a crystalline β-sheet. The invention relates to a modification method in which a guest structure of 3,3-diphenyl-2-phenylpropan-1-one is introduced into a polyurethane side chain to form a host-guest interaction with a cyclodextrin main body in a polymer resin, thereby improving the mechanical properties of the material. At the same time, the 2-acrylate-2-[[(butylamino)-carbonyl]oxy]ethyl ester monomer in the polymer resin has the same carbamate group as the polyurethane main chain, thereby effectively improving the compatibility of the resin. The polyurethane structure of the invention contains many polar groups, which are prone to losing or gaining electrons and generating static electricity during friction or contact. The invention introduces a [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide monomer into the polymer resin to improve the electrical conductivity of the resin, thereby avoiding the possible influence of static electricity on the performance and application of the imitation leather material. DETAILED DESCRIPTION
[0024] The present invention is further described with reference to the following examples.
[0025] Example 1 A method for preparing an imitation leather material for automobile interior decoration comprises the following steps: (1) Preparation of silk fibroin fibers: 10% silk fibroin solution was freeze-dried and then dissolved in formic acid, glycerol was added and stirred to obtain a mixed solution, the mixed solution was electrospun into fibers, and the fibers were cut to obtain silk fibroin fibers with a diameter of 0.6 µm and a length of 100-200 mm, wherein the mass ratio of the solid content of the silk fibroin solution to the formic acid and the glycerol was 1:3.5:1.2; (2) Preparation of polymer resin: [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide, 2-acrylic acid-2-[[(butylamino)-carbonyl]oxy]ethyl ester and vinyl cyclodextrin are weighed and dissolved in N,N-dimethylformamide, azobisisobutyronitrile is added as an initiator, the mixed system is nitrogen-purified to deoxygenate, and the mixture is stirred at 70°C for 15 hours. After the reaction is completed, deionized water is added to dilute the reaction system, the precipitate is separated, washed and dried to obtain the polymer resin; the mass ratio of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide to the 2-acrylic acid-2-[[(butylamino)-carbonyl]oxy]ethyl ester, the vinyl cyclodextrin and the azobisisobutyronitrile is 1:1.5:0.9:0.003; (3) Preparation of polyurethane prepolymer: In a dry and anhydrous container, polyether polyol (R4110, Shanghai Dongda) and dibutyltin dilaurate were added dropwise to a mixture of isophorone diisocyanate and hexamethylene diisocyanate. After the addition was completed, the mixture was stirred until uniform. The mixture was heated to 70°C and stirred for 5 hours to obtain the polyurethane prepolymer. The mass ratio of the polyether polyol to the dibutyltin dilaurate, the isophorone diisocyanate, and the hexamethylene diisocyanate was 1:0.003:1.4:1.1. (4) Preparation of modified polyols: 3,3-bis(4-hydroxyphenyl)-2-phenylpropan-1-one and 3-chloro-1,2-propylene glycol were weighed and dissolved in toluene, sodium hydroxide and tetrabutylammonium bromide were added, and the mixture was stirred at 100°C for 5 hours. After the reaction was completed, the mixture was washed with water, dried, and the solvent was evaporated to obtain the modified polyol; the mass ratio of the 3,3-bis(4-hydroxyphenyl)-2-phenylpropan-1-one to the 3-chloro-1,2-propylene glycol, the sodium hydroxide, and the tetrabutylammonium bromide was 1:0.55:0.82:0.007; (5) Preparation of composite materials: 10 parts of polyurethane prepolymer, 1.2 parts of silk fibroin fiber, 2.5 parts of polymer resin and 0.06 parts of foaming agent are mixed in a blender and stirred; 1.5 parts of cross-linking agent, 0.02 parts of dibutyltin dilaurate and 1 part of antioxidant are added and stirred again to obtain a mixed slurry; the mixed slurry is coated on release paper and kept warm at 120°C for 15 minutes to obtain the imitation leather material for automobile interior decoration; the imitation leather material for automobile interior decoration can be compounded with other materials such as sponge layer and lining cloth layer; the release paper is peeled off and embossed, rubbed and other treatments are performed; and the imitation leather can be obtained by treating the imitation leather with a leather finishing agent to imitate the texture of genuine leather; The foaming agent is azodicarbonamide; The cross-linking agent is a mixture of modified polyol and polyether polyol (R4110, Shanghai Dongda) in a mass ratio of 1:1.
[0026] Example 2 A method for preparing an imitation leather material for automobile interior decoration comprises the following steps: (1) Preparation of silk fibroin fibers: 10% silk fibroin solution was freeze-dried and then dissolved in formic acid, glycerol was added and stirred to obtain a mixed solution, the mixed solution was electrospun into fibers, and the fibers were cut to obtain silk fibroin fibers with a diameter of 0.6 µm and a length of 100-200 mm, wherein the mass ratio of the solid content of the silk fibroin solution to the formic acid and the glycerol was 1:6:2; (2) Preparation of polymer resin: [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide, 2-acrylic acid-2-[[(butylamino)-carbonyl]oxy]ethyl ester and vinyl cyclodextrin were weighed and dissolved in N,N-dimethylformamide, and azobisisobutyronitrile was added as an initiator. After nitrogen was passed through the mixed system to deoxygenate, the mixture was stirred at 70°C for 15 hours. After the reaction was completed, deionized water was added to dilute the reaction system, and the precipitate was separated, washed, and dried to obtain the polymer resin; the mass ratio of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide to the 2-acrylic acid-2-[[(butylamino)-carbonyl]oxy]ethyl ester, the vinyl cyclodextrin, and the azobisisobutyronitrile was 1:2.4:1.2:0.003; (3) Preparation of polyurethane prepolymer: In a dry and anhydrous container, polyether polyol (R4110, Shanghai Dongda) and dibutyltin dilaurate are added dropwise to a mixture of isophorone diisocyanate and hexamethylene diisocyanate. After the addition is complete, the mixture is stirred until uniform. The mixture is heated to 70°C and stirred for 5 hours to obtain the polyurethane prepolymer. The mass ratio of the polyether polyol to the dibutyltin dilaurate, the isophorone diisocyanate, and the hexamethylene diisocyanate is 1:0.003:2:1. (4) Preparation of modified polyols: 3,3-bis(4-hydroxyphenyl)-2-phenylpropan-1-one and 3-chloro-1,2-propylene glycol were weighed and dissolved in toluene, sodium hydroxide and tetrabutylammonium bromide were added, and the mixture was stirred at 100°C for 5 hours. After the reaction was completed, the mixture was washed with water, dried, and the solvent was evaporated to obtain the modified polyol; the mass ratio of the 3,3-bis(4-hydroxyphenyl)-2-phenylpropan-1-one to the 3-chloro-1,2-propylene glycol, the sodium hydroxide, and the tetrabutylammonium bromide was 1:0.64:0.7:0.007; (5) Preparation of composite materials: 10 parts of polyurethane prepolymer, 0.5 parts of silk fibroin fiber, 1 part of polymer resin, and 0.06 parts of foaming agent are mixed in a blender and stirred; 1 part of cross-linking agent, 0.02 parts of dibutyltin dilaurate, and 1 part of antioxidant 1010 are added, and the mixture is stirred again to obtain a mixed slurry; the mixed slurry is coated on release paper and kept warm at 120° C. for 15 minutes to obtain the imitation leather material for automobile interior decoration; the imitation leather material for automobile interior decoration can be compounded with other layers such as sponge layer, lining cloth layer, etc.; the release paper is removed and embossing, kneading, etc. are performed, and the imitation leather can be obtained by treating the imitation leather with a leather finishing agent; The foaming agent is 4,4-oxydibenzenesulfonylhydrazide ether; The cross-linking agent is a mixture of modified polyol and polyester polyol (PE-B175, Shandong Yinuowei) in a mass ratio of 1:1.
[0027] Example 3 A method for preparing an imitation leather material for automobile interior decoration comprises the following steps: (1) Preparation of polymer resin: [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide, 2-[[(butylamino)-carbonyl]oxy]ethyl 2-acrylate and vinyl cyclodextrin are weighed and dissolved in N,N-dimethylformamide, azobisisobutyronitrile is added as an initiator, the mixed system is nitrogen-purified to deoxygenate, and the mixture is stirred at 70°C for 15 hours. After the reaction is completed, deionized water is added to dilute the reaction system, the precipitate is separated, washed and dried to obtain the polymer resin; the mass ratio of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide to the 2-[[(butylamino)-carbonyl]oxy]ethyl 2-acrylate, the vinyl cyclodextrin and the azobisisobutyronitrile is 1:1.5:0.9:0.003; (2) Preparation of polyurethane prepolymer: In a dry and anhydrous container, polyether polyol (R4110, Shanghai Dongda) and dibutyltin dilaurate are added dropwise to a mixture of isophorone diisocyanate and hexamethylene diisocyanate. After the addition is complete, the mixture is stirred until uniform. The mixture is heated to 70°C and stirred for 5 hours to obtain the polyurethane prepolymer. The mass ratio of the polyether polyol to the dibutyltin dilaurate, the isophorone diisocyanate, and the hexamethylene diisocyanate is 1:0.003:1.4:1.1. (3) Preparation of modified polyols: 3,3-bis(4-hydroxyphenyl)-2-phenylpropan-1-one and 3-chloro-1,2-propylene glycol were weighed and dissolved in toluene, sodium hydroxide and tetrabutylammonium bromide were added, and the mixture was stirred at 100°C for 5 hours. After the reaction was completed, the mixture was washed with water, dried, and the solvent was evaporated to obtain the modified polyol; the mass ratio of the 3,3-bis(4-hydroxyphenyl)-2-phenylpropan-1-one to the 3-chloro-1,2-propylene glycol, the sodium hydroxide, and the tetrabutylammonium bromide was 1:0.55:0.82:0.007; (4) Preparation of composite materials: 10 parts of polyurethane prepolymer, 2.5 parts of the polymer resin, and 0.06 parts of a foaming agent were mixed in a blender by weight, 1.5 parts of a cross-linking agent, 0.02 parts of dibutyltin dilaurate, and 1 part of an antioxidant were added, and the mixture was stirred and mixed again to obtain a mixed slurry. The mixed slurry was coated on a release paper and kept warm at 120° C. for 15 minutes to obtain the imitation leather material for automotive interior decoration; The foaming agent is azodicarbonamide; The cross-linking agent is a mixture of modified polyol and polyether polyol (R4110, Shanghai Dongda) in a mass ratio of 1:1.
[0028] Example 4 A method for preparing an imitation leather material for automobile interior decoration comprises the following steps: (1) Preparation of silk fibroin fibers: 10% silk fibroin solution was freeze-dried and then dissolved in formic acid, glycerol was added and stirred to obtain a mixed solution, the mixed solution was electrospun into fibers, and the fibers were cut to obtain silk fibroin fibers with a diameter of 0.6 µm and a length of 100-200 mm, wherein the mass ratio of the solid content of the silk fibroin solution to the formic acid and the glycerol was 1:3.5:1.2; (2) Preparation of polyurethane prepolymer: In a dry and anhydrous container, polyether polyol (R4110, Shanghai Dongda) and dibutyltin dilaurate are added dropwise to a mixture of isophorone diisocyanate and hexamethylene diisocyanate. After the addition is complete, the mixture is stirred until uniform. The mixture is heated to 70°C and stirred for 5 hours to obtain the polyurethane prepolymer. The mass ratio of the polyether polyol to the dibutyltin dilaurate, the isophorone diisocyanate, and the hexamethylene diisocyanate is 1:0.003:1.4:1.1. (3) Preparation of modified polyols: 3,3-bis(4-hydroxyphenyl)-2-phenylpropan-1-one and 3-chloro-1,2-propylene glycol were weighed and dissolved in toluene, sodium hydroxide and tetrabutylammonium bromide were added, and the mixture was stirred at 100°C for 5 hours. After the reaction was completed, the mixture was washed with water, dried, and the solvent was evaporated to obtain the modified polyol; the mass ratio of the 3,3-bis(4-hydroxyphenyl)-2-phenylpropan-1-one to the 3-chloro-1,2-propylene glycol, the sodium hydroxide, and the tetrabutylammonium bromide was 1:0.55:0.82:0.007; (4) Preparation of composite materials: 10 parts of polyurethane prepolymer, 1.2 parts of silk fibroin fiber, and 0.06 parts of foaming agent were mixed in a blender by weight, 1.5 parts of cross-linking agent, 0.02 parts of dibutyltin dilaurate, and 1 part of antioxidant 1010 were added, and the mixture was stirred and mixed again to obtain a mixed slurry. The mixed slurry was coated on release paper and kept warm at 120° C. for 15 minutes to obtain the imitation leather material for automotive interior decoration; The foaming agent is azodicarbonamide; The cross-linking agent is a mixture of modified polyol and polyether polyol (R4110, Shanghai Dongda) in a mass ratio of 1:1.
[0029] Example 5 A method for preparing an imitation leather material for automobile interior decoration comprises the following steps: (1) Preparation of silk fibroin fibers: 10% silk fibroin solution was freeze-dried and then dissolved in formic acid, glycerol was added and stirred to obtain a mixed solution, the mixed solution was electrospun into fibers, and the fibers were cut to obtain silk fibroin fibers with a diameter of 0.6 µm and a length of 100-200 mm, wherein the mass ratio of the solid content of the silk fibroin solution to the formic acid and the glycerol was 1:3.5:1.2; (2) Preparation of polymer resin: [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide, 2-acrylic acid-2-[[(butylamino)-carbonyl]oxy]ethyl ester and vinyl cyclodextrin are weighed and dissolved in N,N-dimethylformamide, azobisisobutyronitrile is added as an initiator, the mixed system is nitrogen-purified to deoxygenate, and the mixture is stirred at 70°C for 15 hours. After the reaction is completed, deionized water is added to dilute the reaction system, the precipitate is separated, washed and dried to obtain the polymer resin; the mass ratio of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide to the 2-acrylic acid-2-[[(butylamino)-carbonyl]oxy]ethyl ester, the vinyl cyclodextrin and the azobisisobutyronitrile is 1:1.5:0.9:0.003; (3) Preparation of polyurethane prepolymer: In a dry and anhydrous container, polyether polyol (R4110, Shanghai Dongda) and dibutyltin dilaurate were added dropwise to a mixture of isophorone diisocyanate and hexamethylene diisocyanate. After the addition was completed, the mixture was stirred until uniform. The mixture was heated to 70°C and stirred for 5 hours to obtain the polyurethane prepolymer. The mass ratio of the polyether polyol to the dibutyltin dilaurate, the isophorone diisocyanate, and the hexamethylene diisocyanate was 1:0.003:1.4:1.1. (4) Preparation of modified polyols: 3,3-bis(4-hydroxyphenyl)-2-phenylpropan-1-one and 3-chloro-1,2-propylene glycol were weighed and dissolved in toluene, sodium hydroxide and tetrabutylammonium bromide were added, and the mixture was stirred at 100°C for 5 hours. After the reaction was completed, the mixture was washed with water, dried, and the solvent was evaporated to obtain the modified polyol; the mass ratio of the 3,3-bis(4-hydroxyphenyl)-2-phenylpropan-1-one to the 3-chloro-1,2-propylene glycol, the sodium hydroxide, and the tetrabutylammonium bromide was 1:0.55:0.82:0.007; (5) Preparation of composite materials: 10 parts of polyurethane prepolymer, 1.2 parts of silk fibroin fiber, 2.5 parts of polymer resin and 0.06 parts of foaming agent were mixed in a blender and stirred; 1.5 parts of cross-linking agent, 0.02 parts of dibutyltin dilaurate and 1 part of antioxidant were added and stirred again to obtain a mixed slurry; the mixed slurry was coated on release paper and kept warm at 120°C for 15 minutes to obtain the imitation leather material for automobile interior decoration; the imitation leather material for automobile interior decoration can be compounded with other materials such as sponge layer and lining cloth layer; the release paper was peeled off and embossed, rubbed and other treatments were performed; and the imitation leather was obtained by treating with leather finishing agent; The foaming agent is azodicarbonamide; The cross-linking agent is polyether polyol (R4110, Shanghai Dongda).
[0030] Example 6 A method for preparing an imitation leather material for automobile interior decoration comprises the following steps: (1) Preparation of polyurethane prepolymer: In a dry and anhydrous container, polyether polyol (R4110, Shanghai Dongda) and dibutyltin dilaurate are added dropwise to a mixture of isophorone diisocyanate and hexamethylene diisocyanate. After the addition is complete, the mixture is stirred until uniform. The mixture is heated to 70°C and stirred for 5 hours to obtain the polyurethane prepolymer. The mass ratio of the polyether polyol to the dibutyltin dilaurate, the isophorone diisocyanate, and the hexamethylene diisocyanate is 1:0.003:1.4:1.1. (2) Preparation of composite materials: 10 parts of polyurethane prepolymer and 0.06 parts of foaming agent were mixed in a stirrer by weight, 1.5 parts of cross-linking agent, 0.02 parts of dibutyltin dilaurate, and 1 part of antioxidant 1010 were added, and the mixture was stirred and mixed again to obtain a mixed slurry. The mixed slurry was coated on release paper and kept warm at 120° C. for 15 minutes to obtain the imitation leather material for automotive interior; The foaming agent is azodicarbonamide; The cross-linking agent is polyether polyol (R4110, Shanghai Dongda).
[0031] The performance indicators of the imitation leather materials prepared in Examples 1-6 were tested, among which the tests of elongation at break and folding fastness (25°C, 35,000 times) were carried out in accordance with QB / T4046-2010; the tear strength test method was as follows: a 10 cm × 4 cm test piece was cut from the imitation leather sheet, and a 5 cm slit was cut in the center of the short side of the test piece parallel to the long side. A tensile testing machine was used to clamp each slice with the chuck of the fixture, and the SS curve was measured at a tensile speed of 10 cm / min. The value obtained by dividing the maximum load by the unit area weight of the test piece calculated in advance was taken as the average value. The tear strength per 1mm thickness is evaluated; the feel is evaluated on a scale of 1-10, with 10 being the best and 1 being the worst; the softness test is conducted in accordance with GB / T39371-2020; the wear resistance test is conducted using a rubber alcohol abrasion tester with a load of 1kg, with the appearance of obvious wear on the test surface as the test endpoint. The test results are divided into levels 1-3, with level 1 being abrasion resistance >1000 times, level 2 being 500-1000 times, and level 3 being <500 times; the air permeability test is conducted in accordance with GB / T5453-1997; the test results are shown in the following table:
[0032] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.
Claims
1. A method for preparing an imitation leather material for automobile interior, characterized in that: The following steps are involved: (1) Weigh [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide, 2-[[(butylamino)-carbonyl]oxy]ethyl 2-acrylate and vinyl cyclodextrin respectively and dissolve them in N,N-dimethylformamide, add initiator, pass nitrogen through the mixed system to deoxygenate, and then stir and react at 60-80°C for 12-24 hours. After the reaction is completed, add deionized water to dilute and cool the reaction system, separate the precipitate, wash and dry to obtain a polymer resin; (2) The polyurethane prepolymer, the silk fibroin fiber, the polymer resin and the foaming agent are mixed in a stirrer in proportion and stirred, a cross-linking agent, an organic tin catalyst and an auxiliary agent are added, and the mixture is stirred again to obtain a mixed slurry, the mixed slurry is coated on a release paper, and the mixture is kept warm at 60-160° C. for 5-30 minutes to obtain a product; The cross-linking agent includes a modified polyol, and the preparation method of the modified polyol includes the following steps: 3,3-bis(4-hydroxyphenyl)-2-phenylpropan-1-one and 3-chloro-1,2-propylene glycol are weighed separately and dissolved in toluene, and a base and a catalyst are added. The mixture is stirred and heated at 80-100°C for 2-10 hours. After the reaction is completed, the mixture is washed with water, dried, and the solvent is evaporated to obtain the product.
2. The method for preparing an imitation leather material for automobile interior according to claim 1, wherein: The mass ratio of the [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfonic acid propyl)ammonium hydroxide, the 2-acrylic acid-2-[[(butylamino)-carbonyl]oxy]ethyl ester, the vinyl cyclodextrin, and the initiator in step (1) is 1:(0.8-2.4):(0.5-1.2):(0.001-0.005).
3. The method for preparing an imitation leather material for automobile interior according to claim 1, wherein: The mass ratio of the polyurethane prepolymer to the silk fibroin fiber, the polymer resin, the foaming agent, the cross-linking agent, the organic tin catalyst, and the auxiliary agent in step (2) is 10: (0.5-1.8): (1-3.2): (0.05-0.1): (1-2): (0.01-0.03): (0-3).
4. The method for preparing an imitation leather material for automobile interior according to claim 1, wherein: The mass ratio of the 3,3-bis(4-hydroxyphenyl)-2-phenylpropan-1-one to the 3-chloro-1,2-propanediol, the base, and the catalyst is 1:(0.5-0.64):(0.7-0.86):(0.005-0.01).
5. The method for preparing an imitation leather material for automobile interior according to claim 1, wherein: The preparation method of the polyurethane prepolymer comprises the following steps: In a dry and anhydrous container, polyether polyol and an organotin catalyst are dropwise added to diisocyanate, and after the dropwise addition is completed, the mixture is stirred and mixed until uniform, and the temperature is raised to 60-80° C. and kept stirred for reaction for 4-6 hours to prepare the polyurethane prepolymer; the mass ratio of the polyether polyol to the organotin catalyst and the diisocyanate is 1: (0.001-0.005): (1.5-2.8).
6. The method for preparing an imitation leather material for automobile interior according to claim 1, wherein: The preparation method of the silk fibroin fiber comprises the following steps: The silk fibroin solution is freeze-dried and then dissolved with formic acid, glycerol is added and stirred to obtain a mixed solution, the mixed solution is electrospun into fibers, and the fibers are cut to obtain silk fibroin fibers with a length of 5-500 mm.
7. The method for preparing an imitation leather material for automobile interior according to claim 6, characterized in that: The mass ratio of the solid content of the silk fibroin solution to the formic acid and the glycerol is 1:(1-6):(0.5-2).
8. The method for preparing an imitation leather material for automobile interior according to claim 1, wherein: The foaming agent is one or more of azodicarbonamide, N-dodecylethanolamine, 4,4-oxodibenzenesulfonylhydrazide ether, and dodecyldimethylammonium chloride.
9. The method for preparing an imitation leather material for automobile interior according to claim 1, wherein: The auxiliary agent is one or more of a foaming auxiliary agent, a dispersant, an antioxidant, and a colorant.
10. An imitation leather material for automobile interior, characterized in that: Prepared according to the preparation method according to any one of claims 1 to 9.