Preparation method of UV-resistant, flame-retardant and waterproof polyurethane resin and high-grade calf leather

Abstract

The application relates to a preparation method of a UV-resistant, flame-retardant and waterproof polyester resin, wherein n-butyl acetate is taken, methyl methacrylate, butyl acrylate, beta-hydroxyethyl methacrylate and acrylic acid are uniformly mixed; polyhydroxy acrylate prepolymer, neopentyl glycol, dimethylol propionic acid and the like are dissolved in water, ethylene glycol butyl ether, diethanolamine and distilled water are added after uniform mixing; pentaerythritol and benzene-1,2,3,4,5,6-hexacarboxylic acid are uniformly mixed, concentrated sulfuric acid is added drop by drop, and the benzene-1,2,3,4,5,6-hexacarboxylic acid is removed by rotary evaporation; titanium nitrate, zirconium nitrate and hyperbranched polycarboxylic acid ligand are dissolved in N,N-dimethylformamide to obtain high-performance fillers; the high-performance fillers, melamine polyphosphate, high-dispersibility polyester resin and the like are used to prepare the UV-resistant, flame-retardant and waterproof polyester resin. The UV-resistant, flame-retardant and waterproof polyester resin has suitable particle size and dispersing capacity, and has good flame retardancy, anti-yellowing property, flame retardancy, waterproofness, physical and mechanical properties and ecological environmental protection performance.

Description

Technical Field

[0001] This invention relates to the field of leather technology, and in particular to a method for preparing a UV-resistant, flame-retardant, and waterproof polyurethane resin and high-grade calfskin. Background Technology

[0002] With economic development, the requirements for leather and leather products are no longer limited to comfort; they now demand multiple functionalities, such as flame retardancy, water resistance, antibacterial properties, and resistance to yellowing. Water resistance, flame retardancy, and resistance to yellowing are the most critical properties, as these three characteristics significantly expand the application areas of leather and enhance the added value of leather and leather products. Therefore, developing coating resin materials with waterproof, flame retardant, and yellowing-resistant properties is of practical significance. Summary of the Invention

[0003] This invention provides a method for preparing UV-resistant, flame-retardant, and waterproof polyurethane resin and high-grade calfskin, in order to overcome the problem that existing leather and leather products have low requirements for waterproof, flame-retardant, and yellowing-resistant properties, which limits the application fields of leather.

[0004] The present invention adopts the following technical solution:

[0005] A method for preparing a UV-resistant, flame-retardant, and waterproof polyester resin includes the following steps:

[0006] Step 1: Take 100 parts of n-butyl acetate, purge oxygen with nitrogen, add 50-150 parts of methyl methacrylate, 200-400 parts of butyl acrylate, 100-300 parts of β-hydroxyethyl methacrylate, and 0-100 parts of acrylic acid, mix evenly, slowly raise the temperature to 100-120℃, add 300 parts of n-butyl acetate and 10-30 parts of azobisisobutyronitrile within 4 hours, and then continue to add 10-50 parts of n-butyl acetate and 1-5 parts of tert-butyl peroxide within 4 hours, keep warm for 2-6 hours, lower the reaction temperature to 68-72℃, add 20-30 parts of ammonia water and 800-1200 parts of deionized water for neutralization, keep warm for 0.5-1 hour after neutralization, and then fractionate the solvent to obtain the polyhydroxy acrylic acid prepolymer;

[0007] Step 2: Dissolve 20-100 parts of polyhydroxy acrylic acid prepolymer, 10-20 parts of neopentyl glycol, 15-40 parts of dimethylolpropionic acid, 10-30 parts of trimethylolpropane, 20-80 parts of cyclohexanedicarboxylic acid, 60-120 parts of adipic acid, 10-30 parts of xylene, and 20-80 parts of ethylene glycol butyl ether in 200 parts of water. After mixing thoroughly, slowly heat to 130-150℃, add 1-5 parts of dibutyltin oxide, and maintain the temperature for 0.5-1 hour. Gradually raise the temperature to 160-180℃ and hold for 1-2 hours, then raise the temperature to 185-195℃ and hold for 2-3 hours, then raise the temperature to 200-210℃ and hold for 1-2 hours, then lower the temperature to 80℃ and add ethylene glycol butyl ether at a solid content of 70-85%. Lower the temperature to 60℃ and add diethanolamine, controlling the acid value to 20-30 mg KOH / g. Finally, cool to room temperature and add distilled water at a solid content of 45-55% to obtain a highly dispersible polyester resin.

[0008] Step 3: Take 100 parts of pentaerythritol and 450-600 parts of benzoic acid and mix them evenly. Under nitrogen protection, slowly raise the temperature to 60-90℃ and add 5-20 parts of concentrated sulfuric acid dropwise over 1 hour. Then continue to keep warm for 1-5 hours and slowly lower the temperature to room temperature. Then remove excess benzoic acid by rotary evaporation to obtain an acid-impregnating agent with pentaerythritol as the core.

[0009] Step 4: Dissolve 100-160 parts of titanium nitrate, 50-80 parts of zirconium nitrate, 60-140 parts of hyperbranched polycarboxylic acid ligand, 10-50 parts of 2,3-pyrazine dicarboxylic acid (CAS: 89-01-0), 20-40 parts of 7-azaindole-3-carboxylic acid, 10-30 parts of benzotriazolyl organic compound, and 10-20 parts of nitric acid in 3000-5000 parts of N,N-dimethylformamide. React at 120-140℃ for 24-48 hours, then slowly cool to room temperature. Add 1000 parts of N,N-dimethylformamide and continue the reaction for 12 hours. Finally, filter to obtain filter residue. Transfer the filter residue to an ethanol solution (10% by weight of ethanol) and add 0.1% sodium hydroxide. Soak at room temperature for 6 hours, then filter. Wash the filter residue repeatedly with N,N-dimethylformamide and vacuum dry to obtain the high-performance packing material.

[0010] Step 5: Take 200-1000 parts of high-performance filler, 50-500 parts of melamine polyphosphate, 1000 parts of highly dispersible polyester resin, 5-10 parts of γ-glycidyl etheroxypropyltrimethoxysilane, 20-50 parts of ethylene glycol monobutyl ether, and 0-5 parts of benzotriazole organic compound, wherein the amount of melamine polyphosphate is not higher than that of the high-performance filler. Disperse strongly for 60-120 minutes to obtain UV-resistant, flame-retardant, and waterproof polyester resin.

[0011] Further improvements are made to the above-mentioned benzotriazole organic compounds, which are one or more of 2,(2'-hydroxy-5'-methylphenyl)benzotriazole, 2,(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2,(2'4'-dihydroxyphenyl)benzotriazole, and 2-(2'-hydroxy-4'-aminophenyl)benzotriazole.

[0012] A method for preparing a UV-resistant, flame-retardant, and waterproof polyester resin for use in high-grade calfskin shoe uppers includes the following steps:

[0013] Raw leather → Tumbling and softening (1-3 hours) → Stretching and softening (level 5-6) → Spraying base coating (8.0 g / sf) 2 → Apply primer coating (8.0g / sf) 2 → Burnishing (120℃ / 50kg / 9.3m·min) -1 → Spray the intermediate coating (12.0g / sf) 2 → Spray the intermediate coating (12.0g / sf) 2 → Texture roller (100℃ / 80kg / 9.3m·min) -1 → Spray the intermediate coating (12.0g / sf) 2 → Burnishing (130℃ / 30kg / 9.3m·min) -1 → Spray the intermediate coating (12.0g / sf) 2 → Spray on the top coating (8.0g / sf) 2 → Spray on the top coating (8.0g / sf) 2 → Burnishing (130℃ / 30kg / 9.3m·min) -1 → Vibration softening (level 5-6) → Spraying a feel layer (2.0g / sf) 2 → Burnishing (130℃ / no pressure / 9.3m·min) -1 → Finished product;

[0014] The base coating comprises the following raw materials: 200-300 parts water, 80-120 parts adhesive resin, 30-80 parts UV-resistant, flame-retardant and waterproof polyester resin, 30-50 parts polyurethane resin, 10-30 parts acrylic resin, and 30-80 parts penetrant.

[0015] The intermediate coating consists of the following raw materials: 400-500 parts water, 80-120 parts composite resin, 80-120 parts UV-resistant, flame-retardant and waterproof polyester resin, 50-80 parts polyurethane resin, 30-50 parts acrylic resin, 0-30 parts softening agent, 40-60 parts release wax, 30-80 parts oil wax additive, and 20-60 parts casein.

[0016] The top coating comprises the following raw materials: 100-200 parts water, 30-50 parts UV-resistant, flame-retardant and waterproof polyester resin, 50-100 parts polyurethane resin, 5-10 parts crosslinking agent, and 0-10 parts silicone hand feel agent.

[0017] The tactile layer comprises the following ingredients: 100-150 parts water and 10-30 parts tactile agent.

[0018] As can be seen from the above description of the present invention, compared with the prior art, the present invention has the following advantages:

[0019] 1. First, a polyhydroxy acrylic prepolymer is synthesized using methyl methacrylate, butyl acrylate, β-hydroxyethyl methacrylate, and acrylic acid. This prepolymer serves as the hydroxyl structure for synthesizing polyester materials. It is then combined with neopentyl glycol, dimethylolpropionic acid, trimethylolpropane, cyclohexanedicarboxylic acid, and adipic acid to synthesize a polyester resin with excellent waterproof properties. Furthermore, the synthesis of hyperbranched polycarboxylic acid ligands effectively immobilizes the introduced benzotriazole (UV resistant agent). By using a light metal coordination coupling polycarboxylic acid ligand with multiple coordination orbitals (free of heavy metals), polycarboxylic acid-containing materials, and benzotriazole, 7-azaindole-3-carboxylic acid is primarily used for closed-end coordination, regulating the coordination ability of benzotriazole with the cation center. This enhances the reactivity of each ligand while better limiting the particle size of the high-performance filler, thus improving particle size and distribution.

[0020] 2. In addition to excellent UV resistance, high-performance fillers, due to the large number of carboxyl groups on their surface, can improve the compatibility between polyester resin segments. When dispersed in polyester resin, they can effectively crosslink the polyester, forming a dense film and thus enhancing the waterproofing effect of the polyester resin. Simultaneously, high-performance fillers are high in nitrogen and carbon, possessing good flame-retardant properties, and can synergistically enhance the flame-retardant performance of coatings with melamine polyphosphate.

[0021] 3. UV Resistance Principle: The mechanism of action of benzotriazole UV absorbers is to convert absorbed light energy into heat or other lower energies through molecular tautomerism. Initially, the molecule exists in the form of a lipid compound. After absorbing ultraviolet light, the electron cloud density shifts from the oxygen atom to the nitrogen atom of the triazole ring, making the nitrogen atom basic. Protons then transfer to the nitrogen atom, forming an unstable tautomer. Because the tautomer is in an unstable state, it releases the absorbed energy as heat or other lower energies, returning to its stable ground state.

[0022] 4. Flame retardant principle: When high-performance fillers and melamine polyphosphate are heated, they decompose to form disproportionation products such as phenoxy radicals and phosphoric acid and other phosphorus oxides. Phenoxy radicals can capture gaseous free radicals generated during combustion and block the chain reaction of combustion. Phosphoric acid oxides can effectively promote the char formation of polyurethane substrate and synergistically form a composite carbon layer of phosphorus, nitrogen, carbon and oxygen with polyester resin, thereby improving the flame retardant performance of the coating.

[0023] 5. The UV-resistant, flame-retardant, and waterproof polyester resin has a suitable particle size and dispersion ability. A 2% concentration UV-resistant, flame-retardant, and waterproof polyester resin dispersion has a particle size of 1800-3000 nm, a particle size distribution coefficient of 0.250-0.500, and a light transmittance of ≥50%.

[0024] 6. The UV-resistant, flame-retardant, and waterproof polyester resin has good hydrolysis resistance. After film formation, when soaked in water for 30 minutes, the swelling rate is ≤20% and the mass loss rate is ≤5%. It also has good solvent resistance, with a mass loss rate of ≤5% in ethanol and ≤2% in acetone.

[0025] 7. UV-resistant, flame-retardant, and waterproof polyester resin has good flame-retardant properties. After film formation, the flame retardant rating is V-2, and the limiting oxygen index is ≥30%.

[0026] 8. Leather coated with UV-resistant, flame-retardant, and waterproof polyester resin has good resistance to yellowing, flame retardancy, and waterproofing. Yellowing resistance is ≥4, dynamic waterproofing cycles are ≥20,000, static waterproofing absorption is ≤20% after 2 hours, limiting oxygen index is ≥30%, and burning speed is ≤60mm / min.

[0027] 9. Leather coated with UV-resistant, flame-retardant, and waterproof polyester resin has good physical and mechanical properties. The coating has a dry / wet rubbing resistance of ≥4, an abrasion resistance of ≥4, and a bending resistance of ≥50,000 times at room temperature.

[0028] 10. Leather coated with UV-resistant, flame-retardant, and waterproof polyester resin also has good ecological and environmental protection performance: VOC≤100μg / g, heavy metals arsenic≤100ppm, lead≤100ppm, cadmium≤100ppm, soluble arsenic≤1ppm, soluble antimony≤30ppm. Detailed Implementation

[0029] Example 1:

[0030] A method for preparing a UV-resistant, flame-retardant, and waterproof polyester resin includes the following steps:

[0031] Step 1: Take 100 parts of n-butyl acetate, purge with nitrogen to remove oxygen, add 50 parts of methyl methacrylate, 350 parts of butyl acrylate, and 200 parts of β-hydroxyethyl methacrylate and mix evenly. Slowly raise the temperature to 100℃, add 300 parts of n-butyl acetate and 30 parts of azobisisobutyronitrile within 4 hours, and then add 40 parts of n-butyl acetate and 4 parts of tert-butyl peroxide within another 4 hours. Keep the temperature for 5 hours, lower the reaction temperature to 70℃, add 26 parts of ammonia and 940 parts of deionized water to neutralize, keep the temperature for 1 hour after neutralization, and then fractionate the solvent to obtain the polyhydroxy acrylic acid prepolymer.

[0032] Step 2: Dissolve 20 parts of polyhydroxy acrylic acid prepolymer, 20 parts of neopentyl glycol, 35 parts of dimethylolpropionic acid, 25 parts of trimethylolpropane, 60 parts of cyclohexanedicarboxylic acid, 60 parts of adipic acid, 30 parts of xylene, and 30 parts of ethylene glycol butyl ether in 200 parts of water. After mixing evenly, slowly raise the temperature to 130°C, add 5 parts of dibutyltin oxide, and keep warm for 1 hour. Then gradually raise the temperature to 160°C and keep warm for 2 hours. Then raise the temperature to 185°C and keep warm for 3 hours. Then raise the temperature to 200°C and keep warm for 2 hours. Then lower the temperature to 80°C and add ethylene glycol butyl ether according to 70% solid content. Lower the temperature to 60°C and add diethanolamine, controlling the acid value to 20-30 mg KOH / g. Finally, cool to room temperature and add distilled water according to 45% solid content to obtain a highly dispersible polyester resin.

[0033] Step 3: Take 100 parts of pentaerythritol and 450 parts of benzoic acid and mix them evenly. Under nitrogen protection, slowly raise the temperature to 85°C and add 6 parts of concentrated sulfuric acid dropwise over 1 hour. Then continue to keep warm for 4 hours and slowly lower the temperature to room temperature. Then remove excess benzoic acid by rotary evaporation to obtain an acid-impregnating agent with pentaerythritol as the core.

[0034] Step 4: Dissolve 100 parts titanium nitrate, 80 parts zirconium nitrate, 120 parts hyperbranched polycarboxylic acid ligand, 30 parts 2,3-pyrazine dicarboxylic acid (CAS: 89-01-0), 25 parts 7-azaindole-3-carboxylic acid, 20 parts 2,(2'4'-dihydroxyphenyl)benzotriazole, 5 parts 2-(2'-hydroxy-4'-aminophenyl)benzotriazole, and 20 parts nitric acid in 5000 parts N,N-dimethylformamide. React at 120℃ for 48 hours, then slowly cool to room temperature. Add 1000 parts N,N-dimethylformamide and continue the reaction for 12 hours. Finally, filter to obtain filter residue. Transfer the filter residue to an ethanol solution (10% by weight of ethanol) and add 0.1% sodium hydroxide. Soak at room temperature for 6 hours, then filter. Wash the filter residue repeatedly with N,N-dimethylformamide and vacuum dry to obtain the high-performance packing material.

[0035] Step 5: Take 200 parts of high-performance filler, 50 parts of melamine polyphosphate, 1000 parts of highly dispersible polyester resin, 5 parts of γ-glycidyl etheroxypropyltrimethoxysilane, and 20 parts of ethylene glycol monobutyl ether, and strongly disperse for 60 minutes to obtain UV-resistant, flame-retardant, and waterproof polyester resin.

[0036] Example 2:

[0037] A method for preparing a UV-resistant, flame-retardant, and waterproof polyester resin includes the following steps:

[0038] Step 1: Take 100 parts of n-butyl acetate, purge oxygen with nitrogen, add 100 parts of methyl methacrylate, 300 parts of butyl acrylate, 150 parts of β-hydroxyethyl methacrylate, and 50 parts of acrylic acid, mix well, and slowly raise the temperature to 110℃. Add 300 parts of n-butyl acetate and 20 parts of azobisisobutyronitrile within 4 hours, and then add 20 parts of n-butyl acetate and 2 parts of tert-butyl peroxide within another 4 hours. Keep the temperature for 3 hours, lower the reaction temperature to 68℃, add 20 parts of ammonia and 800 parts of deionized water for neutralization, keep the temperature for 0.5 hours after neutralization, and then fractionate the solvent to obtain the polyhydroxy acrylic acid prepolymer.

[0039] Step 2: Dissolve 80 parts of polyhydroxy acrylic acid prepolymer, 20 parts of neopentyl glycol, 15 parts of dimethylolpropionic acid, 30 parts of trimethylolpropane, 80 parts of cyclohexanedicarboxylic acid, 60 parts of adipic acid, 10 parts of xylene, and 70 parts of ethylene glycol butyl ether in 200 parts of water. After mixing evenly, slowly raise the temperature to 140°C, add 3 parts of dibutyltin oxide, and keep warm for 1 hour. Then gradually raise the temperature to 170°C and keep warm for 2 hours. Then raise the temperature to 190°C and keep warm for 3 hours. Then raise the temperature to 205°C and keep warm for 2 hours. Then lower the temperature to 80°C and add ethylene glycol butyl ether according to 80% solid content. Lower the temperature to 60°C and add diethanolamine, controlling the acid value to 20-30 mg KOH / g. Finally, cool to room temperature and add distilled water according to 50% solid content to obtain a highly dispersible polyester resin.

[0040] Step 3: Take 100 parts of pentaerythritol and 520 parts of benzoic acid and mix them evenly. Under nitrogen protection, slowly raise the temperature to 75°C and add 12 parts of concentrated sulfuric acid dropwise over 1 hour. Then continue to keep warm for 3 hours and slowly lower the temperature to room temperature. Then remove excess benzoic acid by rotary evaporation to obtain an acid-impregnating agent with pentaerythritol as the core.

[0041] Step 4: Dissolve 120 parts titanium nitrate, 60 parts zirconium nitrate, 60 parts hyperbranched polycarboxylic acid ligand, 50 parts 2,3-pyrazine dicarboxylic acid (CAS: 89-01-0), 40 parts 7-azaindole-3-carboxylic acid, 10 parts 2,(2'-hydroxy-5'-methylphenyl)benzotriazole, 20 parts 2,(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, and 15 parts nitric acid in 4000 parts N,N-dimethylformamide. React at 130℃ for 36 hours, then slowly cool to room temperature. Add 1000 parts N,N-dimethylformamide and continue the reaction for 12 hours. Finally, filter to obtain filter residue. Transfer the filter residue to an ethanol solution (10% by weight of ethanol) and add 0.1% sodium hydroxide. Soak at room temperature for 6 hours, then filter. Wash the filter residue repeatedly with N,N-dimethylformamide and vacuum dry to obtain the high-performance packing material.

[0042] Step 5: Take 800 parts of high-performance filler, 400 parts of melamine polyphosphate, 1000 parts of highly dispersible polyester resin, 6 parts of γ-glycidyl etheroxypropyltrimethoxysilane, 50 parts of ethylene glycol monobutyl ether, and 5 parts of 2-(2'-hydroxy-4'-aminophenyl)benzotriazole, and strongly disperse for 120 minutes to obtain UV-resistant, flame-retardant, and waterproof polyester resin.

[0043] Example 3:

[0044] A method for preparing a UV-resistant, flame-retardant, and waterproof polyester resin includes the following steps:

[0045] Step 1: Take 100 parts of n-butyl acetate, purge oxygen with nitrogen, add 150 parts of methyl methacrylate, 200 parts of butyl acrylate, 100 parts of β-hydroxyethyl methacrylate, and 50 parts of acrylic acid, mix evenly, and slowly raise the temperature to 120℃. Add 300 parts of n-butyl acetate and 10 parts of azobisisobutyronitrile within 4 hours, and then add 30 parts of n-butyl acetate and 3 parts of tert-butyl peroxide within another 4 hours. Keep the temperature for 5 hours, lower the reaction temperature to 72℃, add 30 parts of ammonia and 1200 parts of deionized water for neutralization, keep the temperature for 1 hour after neutralization, and then fractionate the solvent to obtain the polyhydroxy acrylic acid prepolymer.

[0046] Step 2: Dissolve 50 parts of polyhydroxy acrylic acid prepolymer, 15 parts of neopentyl glycol, 40 parts of dimethylolpropionic acid, 15 parts of trimethylolpropane, 35 parts of cyclohexanedicarboxylic acid, 85 parts of adipic acid, 20 parts of xylene, and 60 parts of ethylene glycol butyl ether in 200 parts of water. After mixing evenly, slowly raise the temperature to 150°C, add 2 parts of dibutyltin oxide, and keep warm for 0.5 hours. Then gradually raise the temperature to 180°C and keep warm for 1 hour. Then raise the temperature to 195°C and keep warm for 2 hours. Then raise the temperature to 210°C and keep warm for 1 hour. Then lower the temperature to 80°C and add ethylene glycol butyl ether according to 80% solid content. Lower the temperature to 60°C and add diethanolamine, controlling the acid value to 20-30 mg KOH / g. Finally, cool to room temperature and add distilled water according to 55% solid content to obtain a highly dispersible polyester resin.

[0047] Step 3: Take 100 parts of pentaerythritol and 600 parts of benzoic acid and mix them evenly. Under nitrogen protection, slowly raise the temperature to 65°C and add 18 parts of concentrated sulfuric acid dropwise over 1 hour. Then continue to keep warm for 2 hours and slowly lower the temperature to room temperature. Then remove excess benzoic acid by rotary evaporation to obtain an acid-impregnating agent with pentaerythritol as the core.

[0048] Step 4: Dissolve 150 parts titanium nitrate, 50 parts zirconium nitrate, 140 parts hyperbranched polycarboxylic acid ligand, 330 parts 2,3-pyrazine dicarboxylic acid (CAS: 89-01-0), 30 parts 7-azaindole-3-carboxylic acid, 10 parts 2-(2'-hydroxy-4'-aminophenyl)benzotriazole, and 10 parts nitric acid in 3000 parts N,N-dimethylformamide. React at 140℃ for 24 hours, then slowly cool to room temperature. Add 1000 parts N,N-dimethylformamide and continue the reaction for 12 hours. Finally, filter to obtain filter residue. Transfer the filter residue to an ethanol solution (10% by weight of ethanol) and add 0.1% sodium hydroxide. Soak at room temperature for 6 hours, then filter. Wash the filter residue repeatedly with N,N-dimethylformamide and vacuum dry to obtain the high-performance packing material.

[0049] Step 5: Take 580 parts of high-performance filler, 220 parts of melamine polyphosphate, 1000 parts of highly dispersible polyester resin, 8 parts of γ-glycidyl etheroxypropyltrimethoxysilane, 40 parts of ethylene glycol monobutyl ether, and 3 parts of 2,(2'4'-dihydroxyphenyl)benzotriazole, and strongly disperse for 90 minutes to obtain UV-resistant, flame-retardant, and waterproof polyester resin.

[0050] The basic properties, stability, and flame retardant properties of the UV-resistant, flame-retardant, and waterproof polyester resins obtained in Examples 1, 2, and 3 were experimentally tested, and the experimental data are shown in Table 1 below.

[0051] Table 1

[0052]

[0053] Example 4:

[0054] A method for preparing a UV-resistant, flame-retardant, and waterproof polyester resin for use in high-grade calfskin shoe uppers includes the following steps: raw leather → tumbling and softening (3 hours) → stretching and softening (level 6) → spraying a base coating (8.0 g / sf). 2 → Apply primer coating (8.0g / sf) 2 → Burnishing (120℃ / 50kg / 9.3m·min) -1 → Spray the intermediate coating (12.0g / sf) 2 → Spray the intermediate coating (12.0g / sf) 2 → Texture roller (100℃ / 80kg / 9.3m·min) -1 → Spray the intermediate coating (12.0g / sf) 2 → Burnishing (130℃ / 30kg / 9.3m·min) -1 → Spray the intermediate coating (12.0g / sf) 2 → Spray on the top coating (8.0g / sf) 2 → Spray on the top coating (8.0g / sf) 2 → Burnishing (130℃ / 30kg / 9.3m·min) -1 → Vibration softening (level 6) → Spraying a feel layer (2.0g / sf) 2 → Burnishing (130℃ / no pressure / 9.3m·min) -1 → Finished product;

[0055] The base coat comprises the following raw materials: 200 parts water, 80 parts bonding resin (AP39, Stahl), 60 parts UV-resistant, flame-retardant, and waterproof polyester resin, 40 parts polyurethane resin (3910, Stahl), 20 parts acrylic resin (17, Stahl), and 50 parts penetrant (ethylene glycol monobutyl ether); the intermediate coat comprises the following raw materials: 400 parts water, 80 parts composite resin (78-555, Stahl), 120 parts UV-resistant, flame-retardant, and waterproof polyester resin, 80 parts polyurethane resin (3910, Stahl), 40 parts acrylic resin (17, Stahl), 20 parts softening agent (43-055, Stahl), 50 parts release wax (946, Pierre Carr), 50 parts oil and wax additives (MC, Haowei Chemical), and 50 parts casein (C30, Tompler).

[0056] The top coating comprises the following raw materials: 150 parts water, 50 parts UV-resistant, flame-retardant, and waterproof polyester resin, 100 parts polyurethane resin (LN.A, Stahl), 5 parts crosslinking agent (AKU, Stahl), and 10 parts silicone hand-feel agent (5230, Stahl); the hand-feel layer comprises the following raw materials: 150 parts water and 15 parts hand-feel agent (5230, Stahl). This embodiment uses the UV-resistant, flame-retardant, and waterproof polyester resin prepared in Example 1.

[0057] Example 5: The preparation method of UV-resistant, flame-retardant and waterproof polyester resin applied to high-grade calfskin shoe upper leather in this example is basically the same as that in Example 4. The difference is that this example uses the UV-resistant, flame-retardant and waterproof polyester resin obtained in Example 2.

[0058] Example 6: The preparation method of UV-resistant, flame-retardant and waterproof polyester resin applied to high-grade calfskin shoe upper leather in this example is basically the same as that in Example 4. The difference is that this example uses the UV-resistant, flame-retardant and waterproof polyester resin obtained in Example 3.

[0059] The shoe upper leathers obtained in Examples 4, 5, and 6 were subjected to experimental testing, and the experimental data are shown in Table 2 below:

[0060] Table 2

[0061]

[0062]

[0063] The above are merely specific embodiments of the present invention, but the design concept of the present invention is not limited thereto. Any non-substantial modifications made to the present invention using this concept shall be considered as infringing upon the protection scope of the present invention.

Claims

1. A method for preparing a UV resistant, flame retardant, and water repellent polyester resin, characterized by, Comprising the following steps: Step 1, take 100 parts of n-butyl acetate, oxygen is driven by nitrogen, add 50-150 parts of methyl methacrylate, 200-400 parts of butyl acrylate, 100-300 parts of methyl methacrylate-β-hydroxyethyl, 0-100 parts of acrylic acid are mixed uniformly, then slowly increase the temperature to 100-120°C, add 300 parts of n-butyl acetate and 10-30 parts of azobisisobutyronitrile within 4h, then continue to add 10-50 parts of n-butyl acetate and 1-5 parts of tert-butyl peroxy-2-ethylhexanoate within 4h, keep warm for 2-6h, reduce the reaction temperature to 68-72°C, add 20-30 parts of ammonia water and 800-1200 parts of deionized water for neutralization, keep warm for 0.5-1h after neutralization, then fractionate the solvent to obtain a polyhydroxy acrylic acid prepolymer; Step 2, take 20-100 parts of polyhydroxy acrylic acid prepolymer, 10-20 parts of neopentyl glycol, 15-40 parts of dimethylol propionic acid, 10-30 parts of trimethylolpropane, 20-80 parts of cyclohexane dicarboxylic acid, 60-120 parts of adipic acid, 10-30 parts of dimethylbenzene, 20-80 parts of ethylene glycol butyl ether are dissolved in 200 parts of water, mix uniformly, then slowly heat to 130-150°C, add 1-5 parts of dibutyl tin oxide, keep warm for 0.5-1h, then gradually heat to 160-180°C, keep warm for 1-2h, then heat to 185-195°C, keep warm for 2-3h, then heat to 200-210°C, keep warm for 1-2h, then cool to 80°C, add ethylene glycol butyl ether according to 70-85% solid content, add diethanolamine when the temperature is 60°C, control the acid value to be 20-30mgKOH / g, finally cool to room temperature, add distilled water according to 45-55% solid content, to obtain a high dispersion polyester resin; Step 3, take 100 parts of pentaerythritol and 450-600 parts of mellitic acid, mix uniformly, slowly increase the temperature to 60-90°C under nitrogen protection, add 5-20 parts of concentrated sulfuric acid drop by drop within 1h, then continue to keep warm for 1-5h, slowly reduce the temperature to room temperature, then remove the excess mellitic acid by rotary evaporation to obtain a hyperbranched polycarboxylic acid ligand; Step 4, take 100-160 parts of titanium nitrate, 50-80 parts of zirconium nitrate, 60-140 parts of hyperbranched polycarboxylic acid ligand, 10-50 parts of 2,3-pyrazine dicarboxylic acid, 20-40 parts of 7-azaindole-3-carboxylic acid, 10-30 parts of benzotriazol-based organic matter, 10-20 parts of nitric acid are dissolved in 3000-5000 parts of N, N-dimethylformamide, react at 120-140°C for 24-48h, then slowly cool to room temperature, add 1000 parts of N, N-dimethylformamide and continue to react for 12h, finally filter to obtain a filter residue, transfer the filter residue into an ethanol solution, the filter residue is 10% based on the weight of ethanol, 0.1% of sodium hydroxide, soak for 6h at room temperature, filter, wash the filter residue repeatedly with N, N-dimethylformamide, and vacuum dry to obtain a high-performance filler; Step 5, take 200-1000 parts of high performance filler, 50-500 parts of melamine polyphosphate, 1000 parts of high dispersibility polyester resin, 5-10 parts of gamma-glycidoxypropyltrimethoxysilane, 20-50 parts of ethylene glycol monobutyl ether, 0-5 parts of benzotriazole-based organic matter, wherein the amount of melamine polyphosphate is not higher than the high performance filler, and the strong dispersion is 60-120 minutes, to obtain the UV-resistant, flame-retardant and waterproof polyester resin.

2. The method for preparing a UV-resistant, flame-retardant, and waterproof polyester resin as described in claim 1, characterized in that: The benzotriazole-based organic matter is one or more of 2, (2'-hydroxy-5'-methylphenyl) benzotriazole, 2, (2'-hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2, (2'4'-dihydroxyphenyl) benzotriazole, and 2- (2'-hydroxy-4'-aminophenyl) benzotriazole.

3. A process for the preparation of high grade calfskin upper leather using UV resistant flame retardant water proof polyester resin as claimed in claim 1 wherein, The process comprises the following steps: ​ Crust leather → softening → softening → spraying bottom coating → spraying bottom coating → rolling → spraying middle coating → spraying middle coating → rolling pore roller → spraying middle coating → rolling → spraying middle coating → spraying upper coating → spraying upper coating → rolling → oscillation softening → spraying feel layer → rolling → finished product; The bottom coating comprises the following raw materials: water 200-300 parts, binder resin 80-120 parts, UV-resistant, flame-retardant and waterproof polyester resin 30-80 parts, polyurethane resin 30-50 parts, acrylic resin 10-30 parts, and penetrating agent 30-80 parts; The middle coating comprises the following raw materials: water 400-500 parts, comprehensive resin 80-120 parts, UV-resistant, flame-retardant and waterproof polyester resin 80-120 parts, polyurethane resin 50-80 parts, acrylic resin 30-50 parts, softening aid 0-30 parts, off-plate wax 40-60 parts, oil wax aid 30-80 parts, and casein 20-60 parts; The upper coating comprises the following raw materials: water 100-200 parts, UV-resistant, flame-retardant and waterproof polyester resin 30-50 parts, polyurethane resin 50-100 parts, crosslinking agent 5-10 parts, and silicone feel agent 0-10 parts; The feel layer comprises the following raw materials: water 100-150 parts and feel agent 10-30 parts.

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