阅读说明：本技术 阻燃、耐磨耗、防粘着、低voc的汽车坐垫革制造工艺 (Manufacturing process of flame-retardant, wear-resistant, anti-sticking and low-VOC (volatile organic compound) automobile cushion leather ) 是由 段宝荣 王全杰 唐志海 翁永根 祝妙凤 赵佳 王琦研 于 2020-12-31 设计创作，主要内容包括：本发明公开了一种阻燃、耐磨耗、防粘着、低VOC的汽车坐垫革制造工艺,包括脱灰工序,复鞣工序中和工序,加脂工序和涂饰工序。本发明用氮磷膨胀型阻燃剂改性耐磨性聚氨酯,用于涂饰工序,并且利用防粘结材料降低涂层的粘着性。所制备的汽车坐垫革在保持较好的阻燃、低雾化性能的基础上,具有更好的耐磨耗性能和更低的VOC,进一步提高了加脂剂吸收率,并解决了涂饰皮革陈化过程中的粒面层黏连问题。(The invention discloses a manufacturing process of flame-retardant, wear-resistant, anti-sticking and low-VOC (volatile organic compounds) automobile cushion leather. The invention uses nitrogen and phosphorus intumescent flame retardant to modify wear-resistant polyurethane for coating process, and uses anti-adhesion material to reduce the adhesion of coating. The prepared automobile cushion leather has better wear-resisting performance and lower VOC (volatile organic compounds) on the basis of keeping better flame-retardant and low-fogging performance, further improves the absorptivity of the fatting agent, and solves the problem of grain layer adhesion in the aging process of coating leather.)

1. The process for manufacturing the flame-retardant, wear-resistant, anti-sticking and low-VOC automobile cushion leather comprises a deliming procedure and a retanning procedure

A neutralization step, a fatliquoring step and a coating step, wherein the method comprises the following steps: the coating process comprises the following steps of base coating, intermediate coating and top coating in sequence, wherein the coating is roll coating, the roll coating temperature is 101-105 ℃, the base coating is roll-rolled for three times, the intermediate coating is roll-rolled for two times, and the top coating is roll-rolled for one time, and each layer of coating comprises the following components:

(a) the base coating comprises the following components in parts by weight: 0.7-2.5 parts of water-based pigment paste, 32 parts of water and 0.2-0.5 part of cationic oil;

(b) the middle coating comprises the following components in parts by weight: 30 parts of water, 20-70 parts of extinction polyurethane, 7-18 parts of bright polyurethane, 6-13 parts of a crosslinking agent, 7-14 parts of wear-resistant polyurethane, 0.4-0.7 part of carbodiimide, 1.2-2.6 parts of a nitrogen-phosphorus intumescent flame retardant and 1.3-2.6 parts of a film forming promoter;

the preparation method of the wear-resistant polyurethane comprises the following steps: adding 43 parts of polycarbonate diol, 12.2-13.9 parts of isophorone diisocyanate and 0.18-0.45 part of dibutyltin dilaurate into a reaction container, and stirring at 75-90 ℃ for reaction for 1-2 hours to obtain a polyurethane prepolymer;

adding 0.9-3.4 parts of hydrophilic chain extender dimethylolpropionic acid, 2.2-3.4 parts of nitrogen-phosphorus intumescent flame retardant and 12.5-16.5 parts of acetone solvent into the polyurethane prepolymer, and stirring and reacting for 1-2 hours at the temperature of 70-80 ℃; adding 3.0-5.0 parts of triethylamine and 100-150 parts of water, emulsifying for 20-60 min, adding 1-2 parts of the substance A and 0.2-0.6 part of epoxy-terminated polyether silicone oil, adjusting the pH value to 6.5, and stirring at 70-80 ℃ for reacting for 1-2h to obtain wear-resistant polyurethane;

the preparation method of the substance A comprises the following steps: adding 3 parts of aluminum sulfate and 2-3 parts of chromium sulfate into 10 parts of water, adjusting the pH value to 3.8-4.2, adding 1.1-2.3 parts of gallic acid, 1.2-3.2 parts of sodium citrate and 0.2-0.3 part of malt hexaose, stirring and reacting for 1-2 hours at the temperature of 60-70 ℃, adding 0.3-0.6 part of 3-glycidyl ether oxypropyl methyldimethoxysilane and 0.3-0.6 part of substance B, and reacting for 1-2 hours at the temperature of 70-80 ℃ to obtain a substance A;

the preparation method of the substance B comprises the following steps: adding 1-4 parts of sulfamic acid and 0.2-0.4 part of sodium dodecyl benzene sulfonate into 7 parts of perfluoropolyether acyl fluoride, reacting for 1-2 hours at 40-50 ℃, adding 0.6-0.8 part of 2, 4-diamino-6-hydroxypyrimidine, and reacting for 1-2 hours at 45-55 ℃ to obtain a substance B;

the preparation method of the nitrogen-phosphorus intumescent flame retardant comprises the following steps: adding a basic catalyst sodium methoxide with the mass of 1-4% of dimethyl phosphite into 1mol of dimethyl phosphite, adding 1.1-1.2 mol of acrylamide, reacting at 70-80 ℃ for 1-5 h to obtain 3-dimethoxyphosphoryl propionamide as an intermediate A, reducing the temperature of the intermediate product to 50-55 ℃, adding 0.1-0.2 mol of trimethylchlorosilane and 0.1mol of cyanuric chloride, stirring and reacting at 60-80 ℃ for 2-5 h, adjusting the pH of the solution to 6.5-7.0 in the stirring process, adding 1.6-2.7 g of 1, 3-propanedithiol and 0.2-0.4 g of MOFs, stirring and reacting at 60-80 ℃ for 1-3 h, and concentrating until the solid content reaches more than 80% to obtain the nitrogen-phosphorus intumescent flame retardant;

the preparation method of the MOFs comprises the following steps: adding 1 part of ammonium tetramolybdate and 2-3 parts of 4-acetaminosalicylate into 1-2 parts of zirconium sulfate, 1.2-1.6 parts of diethyl aluminum chloride and 15 parts of deionized water, stirring at 55-60 ℃ for 40-60 min, adjusting the pH value to 7.2, adding 1-3 parts of 2-propyl ethyl acetoacetate, reacting and stirring at 180-190 ℃ for 1-2h, filtering, washing with water, and drying to obtain MOFs;

the preparation method of the film forming accelerant comprises the following steps: stirring 6 parts of polyethyleneimine and 8.2-9.4 parts of 2-acetoxyisobutyryl chloride to react for 1-2 hours at 50-60 ℃, sequentially adding 1.1-1.4 parts of salicylic acid and 1.1-2.3 parts of semicarbazide, and reacting for 30-90 minutes at 50-70 ℃ to obtain a film forming promoter;

(c) the top coating comprises the following components in parts by weight: 14 parts of water, 1.3-1.9 parts of an anti-bonding material, 5-7 parts of a hand feeling agent and 0.2-0.3 part of cationic oil;

the preparation method of the anti-bonding material comprises the following steps: adding 6-9 parts of 1, 2-benzenediol and 12 parts of water into 12 parts of trifluoroacetamide, stirring and reacting for 1-2h at 50-60 ℃, drying, adding 2.1-3.8 parts of phenylphosphoryl dichloride and 13 parts of benzene, stirring and reacting for 1h at 60-65 ℃, distilling and removing the residual benzene, and drying the residual to obtain the anti-bonding material.

2. The process for manufacturing flame retardant, abrasion resistant, tack-free, low VOC automobile seat cushion leather according to claim 1, wherein the deliming process comprises a pre-deliming process and a main deliming process; pre-deliming: taking the weight of the ash-soaked bare skin after trimming as a weight base, applying 0.3-1.4% of magnesium lactate and 0.2% of 2-hydroxypropionic acid for pre-deliming, wherein the bath liquid ratio is 100-200%, the bath liquid pH is 9.0-10.0, the bath liquid temperature is controlled at 18-22 ℃, and the rotation is carried out for 60-90 min; the main deliming procedure comprises the following steps: the bath liquid ratio is 100-120%, the bath liquid temperature is 18-22 ℃, 0.3-0.7% of 4-methyl salicylic acid is added, the pH value is 9.0-10.0, and the rotation is carried out for 60-90 min.

3. The process of making flame retardant, abrasion resistant, tack free, low VOC automobile seat cushion leather according to claim 1, wherein the retanning step is: the bath liquid ratio is 100-200%, the bath liquid temperature is 40 ℃, 2-4% of tetrakis hydroxymethyl phosphonium sulfate is added, the rotation is 30-50 min, 0.2-0.6% of sodium formate is added, the rotation is 30min, then sodium bicarbonate is added to adjust the pH value to 5.0, the rotation is 40min, the washing is carried out twice by 50 ℃ water, 10min each time, and the liquid is discharged.

4. The process of making flame retardant, abrasion resistant, tack free, low VOC automobile seat cushion leather of claim 1, wherein the neutralization step: taking the weight of the shaved skin after trimming as the weight base, the bath lotion weight ratio is 120%, the bath lotion temperature is 34-36 ℃, sodium formate is added for 0.8-1.0%, the operation is carried out for 30-50 min, sodium carbonate is added for 0.4-0.8%, the operation is carried out for 40-70 min, and the water is washed twice by water with the temperature of 55-60 ℃ and drained.

5. The process of making flame retardant, abrasion resistant, tack free, low VOC automobile seat cushion leather of claim 1 wherein the fatliquoring step comprises: taking the weight of the shaved skin after trimming as the weight base, 80% of bath lotion, 38-42 ℃ of bath lotion temperature, 5-7% of fatting agent SE, 1-2% of phosphorylated grease, 1-2% of BUXOM BP and material for promoting fatting agent absorption, turning for 30-60 min, adding 100% of water, adjusting the bath lotion temperature to 48-52 ℃, turning for 60-90 min, adding 1.5-2.0% of formic acid, turning for 60-90 min, washing twice with 62-65 ℃ water, and draining.

6. The process for preparing the flame-retardant, wear-resistant, anti-sticking and low-VOC automobile cushion leather as claimed in claim 5, wherein the fatliquoring agent absorption promoting material is prepared by the following steps: adding starch treated by a standard sieve with more than 60 meshes into water with the mass of 80% of the starch, stirring and gelatinizing the starch at the temperature of 70-80 ℃ for 20-40 min, adding sodium dodecyl benzene sulfonate with the mass of 0.3-2% of the starch and phosphorus trichloride with the mass of 20-40% of the starch, stirring and reacting the mixture at the temperature of 40-60 ℃ for 1-2h, adding oleamide with the mass of 10-20% of the starch and maleic anhydride with the mass of 30-40% of the starch, and adding 30% of sodium hydroxide to adjust the pH value to 7.5 to obtain the fat-liquoring agent absorption promoting material.

Technical Field

The invention relates to a manufacturing process of automobile cushion leather, in particular to a manufacturing process of flame-retardant, wear-resistant, anti-sticking and low-VOC automobile cushion leather.

Background

China is the largest automobile consumption market in the world at present, the production and sale of Chinese automobiles in 2019 respectively reach 2572.1 ten thousands and 2576.9 thousands, the production and sale amount continues to be the first of China in the world, 20% of the China is provided with leather seats, the demand of the market for leather for automobiles is very large, and with the prosperity of the automobile market, the business opportunity of automobile leather making is concerned by more and more leather enterprises. By the end of 2017, the annual meeting report of the leather association in china mentions that the profit of the automobile leather alone remains increasing in the environment of a general decline in the profits of all articles in the leather industry in the country.

The leather protein laboratory of cigarette-desk university is dedicated to the research and development of automobile leather and its matched chemical materials for a long time, the Chinese invention patent with the patent number of CN201910405405.6 relates to a manufacturing process of antifouling, ultralow total carbon emission and wear-resistant cowhide automobile cushion leather, and the primary coating comprises water-based pigment paste, light-resistant coating, light-resistant acrylate resin coating, light-resistant waterborne polyurethane, flame-retardant coating and cationic oil; the intermediate coating comprises delustering polyurethane, bright polyurethane, a cross-linking agent, a material, wear-resistant polyurethane, carbodiimide, PTFE emulsion and a smoke inhibiting material; the top coating includes a hand feel agent and a cationic oil. The prepared cowhide automobile cushion leather further improves antifouling and wear-resisting performances and reduces total carbon emission on the basis of keeping flame retardance, light resistance and low atomization. Because the automobile leather is in close contact with people, the coating of the automobile leather is easy to fall off along with the long-term abrasion of the human body, and the standards of the existing automobile manufacturers for the automobile leather are different, so the abrasion resistance of the automobile leather needs to be further improved.

The Chinese invention patent with the patent number of 201510694401.6 discloses a manufacturing process of flame-retardant, yellowing-resistant and low-fogging cowhide automobile cushion leather, which comprises the production procedures of replacing ammonium salt deashing with ammonium salt deashing, reducing the fogging value of the cushion leather by high-temperature washing, improving the flame retardant property of the leather by the steps of retanning, fatliquoring and finishing and improving the light resistance of a coating with a light-resistant material, selecting roller coating to replace spraying to reduce the using amount of a leather material, developing and developing a flame-retardant, low-fogging, light-resistant, heat-resistant and anti-yellowing high-performance automobile interior leather product, having wide market prospect, and evaluating the conventional index oxygen index of flame retardance to be 32, the afterflame time to be 5s, the smoldering time to be 3s and the smoke density to be 29.7. Although the fire of automobiles is a small-probability event, the standard of flame retardance of various automobile manufacturers is not reduced, the Chinese invention patent with the patent number of 201510694403.5 discloses a manufacturing process of flame-retardant, light-resistant and low-fogging degradable cow leather automobile seat cushion leather, which replaces ammonium salt deliming with ammonium salt deliming, selects tetrakis (hydroxymethyl) phosphonium sulfate and flame-retardant starch type leather surfactant as leather tanning agents to replace the traditional chrome tanning agents, reduces the fogging value of the seat cushion leather by high-temperature washing, improves the flame retardance of the leather by the steps of retanning, fatliquoring and finishing, improves the light resistance of a coating by a light-resistant material, and reduces the using amount of a leather material by selecting roller coating to replace spraying. The oxygen index was 32, the follow on time was 5s, and the smoldering time was 5s, indicating that there is still room for improvement.

The greasing is one of the important processes of automobile leather production, determines the softness, fullness and elasticity of the finished leather, influences the physical and mechanical properties of the finished leather such as strength, elongation and the like and the sanitary properties of the finished leather such as water absorption, air permeability, water vapor permeability and the like, and can even endow the finished leather with special properties of water resistance, oil resistance, pollution resistance, atomization resistance and the like through the greasing. As the leather-making processing technique in the prior art, only 60-70% of grease is absorbed by the leather in the sofa leather processing, the fatliquoring is one of the most chemical materials used in the leather fatliquoring, and the non-absorbed fatliquoring agent enters the wastewater, thereby not only causing the waste of the chemical materials, but also causing the increase of COD and BOD indexes in the wastewater and improving the wastewater treatment cost. Therefore, auxiliary materials are needed to improve the water treatment of leather industry, and Chinese patent with patent number 201910405405.6 mentions that: the combined flame-retardant fatting agent is adopted, the starch-based surfactant is utilized to promote uniform penetration of grease, bath lotion is clear, the grease absorption rate reaches 95%, the combination with leather fibers is firm, the generation of free grease is obviously reduced, and the index still has room for continuous improvement.

In the use process of the automobile seat cushion, the small molecular compounds in the leather migrate to release special odor, and the released gas contains compounds such as formaldehyde, acetaldehyde, benzene, toluene and the like, so that the odor of the automobile leather needs to be reduced.

In leather processing, grain surfaces are arranged opposite to grain surfaces in an aging process, and flesh surfaces are arranged opposite to flesh surfaces, but after the last process of coating, the cohesiveness of the grain surfaces of the leather is enhanced, the grain surfaces and the grain surface coating are mutually adhered in the arrangement process, and the problem that partial coating is separated or the color is inconsistent can be caused.

In summary, it is necessary to provide new technical measures for the outstanding technical problems including abrasion resistance, flame retardancy and absorption rate of the fatting agent, so as to further optimize and improve the indexes and further improve the overall quality of the domestic automobile leather.

Disclosure of Invention

The invention aims to solve the technical problem of providing a manufacturing process of flame-retardant, wear-resistant, anti-sticking and low-VOC automobile cushion leather.

The technical scheme of the invention is as follows:

the process for manufacturing the flame-retardant, wear-resistant, anti-sticking and low-VOC automobile cushion leather comprises a deliming procedure and a retanning procedure

A neutralization step, a fatliquoring step and a coating step, wherein the method comprises the following steps: the coating process comprises the following steps of base coating, intermediate coating and top coating in sequence, wherein the coating is roll coating, the roll coating temperature is 101-105 ℃, the base coating is roll-rolled for three times, the intermediate coating is roll-rolled for two times, and the top coating is roll-rolled for one time, and each layer of coating comprises the following components:

(a) the base coating comprises the following components in parts by weight: 0.7-2.5 parts of water-based pigment paste, 32 parts of water and 0.2-0.5 part of cationic oil;

(b) the middle coating comprises the following components in parts by weight: 30 parts of water, 20-70 parts of extinction polyurethane, 7-18 parts of bright polyurethane, 6-13 parts of a crosslinking agent, 7-14 parts of wear-resistant polyurethane, 0.4-0.7 part of carbodiimide, 1.2-2.6 parts of a nitrogen-phosphorus intumescent flame retardant and 1.3-2.6 parts of a film forming promoter;

the preparation method of the wear-resistant polyurethane comprises the following steps: adding 43 parts of polycarbonate diol, 12.2-13.9 parts of isophorone diisocyanate and 0.18-0.45 part of dibutyltin dilaurate into a reaction container, and stirring at 75-90 ℃ for reaction for 1-2 hours to obtain a polyurethane prepolymer;

adding 0.9-3.4 parts of hydrophilic chain extender dimethylolpropionic acid, 2.2-3.4 parts of nitrogen-phosphorus intumescent flame retardant and 12.5-16.5 parts of acetone solvent into the polyurethane prepolymer, and stirring and reacting for 1-2 hours at the temperature of 70-80 ℃; adding 3.0-5.0 parts of triethylamine and 100-150 parts of water, emulsifying for 20-60 min, adding 1-2 parts of the substance A and 0.2-0.6 part of epoxy-terminated polyether silicone oil, adjusting the pH value to 6.5, and stirring at 70-80 ℃ for reacting for 1-2h to obtain wear-resistant polyurethane;

the preparation method of the substance A comprises the following steps: adding 3 parts of aluminum sulfate and 2-3 parts of chromium sulfate into 10 parts of water, adjusting the pH value to 3.8-4.2, adding 1.1-2.3 parts of gallic acid, 1.2-3.2 parts of sodium citrate and 0.2-0.3 part of malt hexaose, stirring and reacting for 1-2 hours at the temperature of 60-70 ℃, adding 0.3-0.6 part of 3-glycidyl ether oxypropyl methyldimethoxysilane and 0.3-0.6 part of substance B, and reacting for 1-2 hours at the temperature of 70-80 ℃ to obtain a substance A;

the preparation method of the substance B comprises the following steps: adding 1-4 parts of sulfamic acid and 0.2-0.4 part of sodium dodecyl benzene sulfonate into 7 parts of perfluoropolyether acyl fluoride, reacting for 1-2 hours at 40-50 ℃, adding 0.6-0.8 part of 2, 4-diamino-6-hydroxypyrimidine, and reacting for 1-2 hours at 45-55 ℃ to obtain a substance B;

the preparation method of the nitrogen-phosphorus intumescent flame retardant comprises the following steps: adding a basic catalyst sodium methoxide with the mass of 1-4% of dimethyl phosphite into 1mol of dimethyl phosphite, adding 1.1-1.2 mol of acrylamide, reacting at 70-80 ℃ for 1-5 h to obtain 3-dimethoxyphosphoryl propionamide as an intermediate A, reducing the temperature of the intermediate product to 50-55 ℃, adding 0.1-0.2 mol of trimethylchlorosilane and 0.1mol of cyanuric chloride, stirring and reacting at 60-80 ℃ for 2-5 h, adjusting the pH of the solution to 6.5-7.0 in the stirring process, adding 1.6-2.7 g of 1, 3-propanedithiol and 0.2-0.4 g of MOFs, stirring and reacting at 60-80 ℃ for 1-3 h, and concentrating until the solid content reaches more than 80% to obtain the nitrogen-phosphorus intumescent flame retardant;

the preparation method of the MOFs comprises the following steps: adding 1 part of ammonium tetramolybdate and 2-3 parts of 4-acetaminosalicylate into 1-2 parts of zirconium sulfate, 1.2-1.6 parts of diethyl aluminum chloride and 15 parts of deionized water, stirring at 55-60 ℃ for 40-60 min, adjusting the pH value to 7.2, adding 1-3 parts of 2-propyl ethyl acetoacetate, reacting and stirring at 180-190 ℃ for 1-2h, filtering, washing with water, and drying to obtain MOFs;

the preparation method of the film forming accelerant comprises the following steps: stirring 6 parts of polyethyleneimine and 8.2-9.4 parts of 2-acetoxyisobutyryl chloride to react for 1-2 hours at 50-60 ℃, sequentially adding 1.1-1.4 parts of salicylic acid and 1.1-2.3 parts of semicarbazide, and reacting for 30-90 minutes at 50-70 ℃ to obtain a film forming promoter;

(c) the top coating comprises the following components in parts by weight: 14 parts of water, 1.3-1.9 parts of an anti-bonding material, 5-7 parts of a hand feeling agent and 0.2-0.3 part of cationic oil;

the preparation method of the anti-bonding material comprises the following steps: adding 6-9 parts of 1, 2-benzenediol and 12 parts of water into 12 parts of trifluoroacetamide, stirring and reacting for 1-2h at 50-60 ℃, drying, adding 2.1-3.8 parts of phenylphosphoryl dichloride and 13 parts of benzene, stirring and reacting for 1h at 60-65 ℃, distilling and removing the residual benzene, and drying the residual to obtain the anti-bonding material.

The deashing process comprises a pre-deashing process and a main deashing process; pre-deliming: taking the weight of the ash-soaked bare skin after trimming as a weight base, applying 0.3-1.4% of magnesium lactate and 0.2% of 2-hydroxypropionic acid for pre-deliming, wherein the bath liquid ratio is 100-200%, the bath liquid pH is 9.0-10.0, the bath liquid temperature is controlled at 18-22 ℃, and the rotation is carried out for 60-90 min; the main deliming procedure comprises the following steps: the bath liquid ratio is 100-120%, the bath liquid temperature is 18-22 ℃, 0.3-0.7% of 4-methyl salicylic acid is added, the pH value is 9.0-10.0, and the rotation is carried out for 60-90 min.

The retanning procedure comprises the following steps: the bath liquid ratio is 100-200%, the bath liquid temperature is 40 ℃, 2-4% of tetrakis hydroxymethyl phosphonium sulfate is added, the rotation is 30-50 min, 0.2-0.6% of sodium formate is added, the rotation is 30min, then sodium bicarbonate is added to adjust the pH value to 5.0, the rotation is 40min, the washing is carried out twice by 50 ℃ water, 10min each time, and the liquid is discharged.

The neutralization step: taking the weight of the shaved skin after trimming as the weight base, the bath lotion weight ratio is 120%, the bath lotion temperature is 34-36 ℃, sodium formate is added for 0.8-1.0%, the operation is carried out for 30-50 min, sodium carbonate is added for 0.4-0.8%, the operation is carried out for 40-70 min, and the water is washed twice by water with the temperature of 55-60 ℃ and drained.

The step of greasing comprises the following steps: taking the weight of the shaved skin after trimming as the weight base, 80% of bath lotion, 38-42 ℃ of bath lotion temperature, 5-7% of fatting agent SE, 1-2% of phosphorylated grease, 1-2% of BUXOM BP and material for promoting fatting agent absorption, turning for 30-60 min, adding 100% of water, adjusting the bath lotion temperature to 48-52 ℃, turning for 60-90 min, adding 1.5-2.0% of formic acid, turning for 60-90 min, washing twice with 62-65 ℃ water, and draining.

The preparation method of the material for promoting the absorption of the fatting agent comprises the following steps: adding starch treated by a standard sieve with more than 60 meshes into water with the mass of 80% of the starch, stirring and gelatinizing the starch at the temperature of 70-80 ℃ for 20-40 min, adding sodium dodecyl benzene sulfonate with the mass of 0.3-2% of the starch and phosphorus trichloride with the mass of 20-40% of the starch, stirring and reacting the mixture at the temperature of 40-60 ℃ for 1-2h, adding oleamide with the mass of 10-20% of the starch and maleic anhydride with the mass of 30-40% of the starch, and adding 30% of sodium hydroxide to adjust the pH value to 7.5 to obtain the fat-liquoring agent absorption promoting material.

The invention has the positive effects that:

(1) the invention adopts polycarbonate diol as wear-resistant polyurethane to react with isophorone diisocyanate, adopts a substance A and epoxy-terminated polyether silicone oil to increase the defects of reduced flexibility and rigid plate of polyurethane caused by crosslinking of the substance A, adopts aluminum sulfate and chromium sulfate to hydrolyze in the environment of pH3.8-4.2, uses the aluminum sulfate and chromium sulfate as complexing agents, adds gallic acid, sodium citrate and maltohexaose to react with metal complexing agents, wherein the reaction group of gallic acid is hydroxyl and carboxyl, the reaction group of sodium citrate is sodium carboxylate and hydroxyl, maltohexaose is widely applied in medicine, but has a large amount of hydroxyl and cyclic hydroxyl, uses the cyclic enhanced rigidity of polyurethane, uses the hydroxyl to perform complexing reaction with the aluminum sulfate and chromium sulfate, and simultaneously uses the aluminum sulfate, chromium sulfate and carboxylate radical on polyurethane chain, Hydroxyl is complexed to form spatial reticular polyurethane, and the softness of the polyurethane is reduced due to the reticular structure, so that acyl fluoride of perfluoropolyether acyl fluoride is adopted to react with amino of sulfamic acid, a flexible group of the perfluoropolyether acyl fluoride is introduced, and spatially distributed websites are filled with the flexible group at intervals, so that the polyurethane is directly chained to move, the friction force is reduced, the flexibility is enhanced, and meanwhile, the flexible rigidity is increased by adopting 2, 4-diamino-6-hydroxypyrimidine, and the wear resistance of the polyurethane is integrally improved.

(2) Ammonium tetramolybdate is combined with carboxylic acid negative ions of 4-acetamido sodium salicylate in an electronegativity manner, then zirconium sulfate is added to form complex ions in a hydrolysis environment, diethyl aluminum chloride is combined with amino groups of 4-acetamido sodium salicylate to react, organic aluminum is introduced, meanwhile, in an alkaline environment, zirconium complex, molybdenum compound are combined with carboxylic acid ions of 2-propyl ethyl acetoacetate, and branched chain compounds are introduced to increase the space distance of MOFs, so that the MOFs and the intumescent flame retardant are combined conveniently.

(3) The MOFs system is dispersed in the flexible and rigid chain segments of the polyurethane, so that the flame retardance and smoke suppression performance of the polyurethane is improved, the expansion type flame retardant material expands under the heated condition, the expansion layer is dispersed in the loose space of the MOFs and filled in the reticular space of the MOFs, and in the heated environment, the formed carbon layer is compact and large in thickness, and smoke is prevented from being released.

(4) The polyethyleneimine reacts with imine of 2-acetoxy isobutyryl chloride and acyl chloride, and salicylic acid and semicarbazide are introduced to improve the film forming property of polyurethane and improve the wear resistance of the polyurethane.

(5) Reacting trifluoroacetamide and 1, 2-benzenediol in a water system, reacting amino of amide with phenolic hydroxyl, and then carrying out modification reaction with phenyl phosphoryl dichloride in a benzene system to obtain the anti-sticking agent for sticking the coating.

(6) The invention adopts the reaction of starch gelatinization and phosphorus trichloride, introduces a P-Cl chemical bond in the system, then reacts with oleamide, introduces an amido bond into a compound, and then adds maleic anhydride to carry out an amino anhydride ring-opening reaction.

Detailed Description

The invention is further illustrated by the following examples.

The process steps of the embodiment of the invention are as follows:

(1) and pre-soaking: weighing the raw skin as the base number of the material dosage and the bath lotion ratio in the step (1), applying 0.10% of a bactericide (Badericids 72, Humicon Xingxing leather Co., Ltd.), 0.18% of a water immersion aid (Humectan RDL, Humicon Xingxing leather Co., Ltd.), 0.2% of soda ash, controlling the bath lotion ratio at 400%, controlling the bath lotion temperature at 20-22 ℃, controlling the bath lotion pH at 8.8-9.2, controlling the baume degree at 8, rotating for 5min every 60min, running for 18h in total, and then sequentially carrying out fleshing, trimming and weighing as the material dosage and the base number of the bath lotion ratio in the steps (2) to (3).

Actually measured water filling data: 55% of water is filled in the loose part of the raw hide and 25% -30% of water is filled in the tight part of the raw hide.

(2) Main soaking: applying 0.4% of bactericide (Badericids 72, lyre leather Co., Ltd.), 0.4% of water immersion assistant (Humectan RDL, lyre leather Co., Ltd.), 0.3% of soda ash, controlling the bath liquid ratio at 700%, the bath liquid temperature at 18-20 ℃, the bath liquid pH at 9.8-10.2, the baume degree at 3-4, mainly immersing and rotating in the bath liquid, and rotating for 5min every 60min for 20 h.

Actually measured water filling data: the loose part is filled with water by 80 percent, and the tight part is filled with water by 60 percent.

(3) And liming: applying 0.6% liming aid (Dermollanar, shineagon, leather Co., Ltd.), 0.4% sodium hydrosulfide, 1.5% sodium sulfide (added in three batches), 1.4% lime, 90% bath solution ratio, 24 ℃ bath solution temperature, 180min rotation time, 11 bath solution pH, stopping the drum overnight, then fleshing, trimming, weighing as the material usage amount and bath solution ratio base number of the steps (4) to (8).

(4) Pre-deliming: 0.6 percent of magnesium lactate and 0.2 percent of 2-hydracrylic acid are applied for pre-deliming, the bath liquid ratio is 150 percent, the bath liquid pH is 9.5, the bath liquid temperature is controlled at 22 ℃, and the rotation is carried out for 60 min.

(5) Main deliming: the bath liquid ratio is 100%, bath temperature is 20 deg.C, 4-methyl salicylic acid 0.6%, pH is 9.0, and rotation is carried out for 90 min.

(6) Softening: the liquid ratio is 0.3, the internal temperature is 28 ℃, then Dermascale ASB1.0 percent (products of the same manufacturer can be replaced) is added, glacial acetic acid 0.2 percent (diluted by 10 times of cold water in advance) is added from the air of a rotating drum shaft in the rotating process, the rotating process is carried out for 40min, the pH value is measured to be 8.5, sodium metabisulfite 0.1 percent and Oropon OO pancreatin (Delhi company) 1.5 percent are added, the rotating process is carried out for 240min, and the water washing process is carried out for 2 times, wherein the liquid ratio of.

(7) And pickling: the bath liquid ratio is 70%, the bath temperature is 19-20 ℃, the salt is 9%, the rotation is 40min, the baume degree is adjusted to 8-10, 0.9% of sodium formate and 4.2% of sulfuric acid are added, the rotation is 90min, the pH is 2.5, two thirds of the bath liquid is poured out, and the step (8) is carried out.

(8) Tanning: HLS high absorption chrome tanning agent 4.2% (brother chemical limited company), rotate 2h, add baking soda 0.9%, add in three times, interval 20min, add and rotate 6h, found: the pH value is 4.2-4.5.

(9) And (3) aging: and (5) taking out the cowhide from the drum, and aging for 48 h.

(10) Squeezing water and shaving evenly: shaving the materials to a thickness of 1.8-2.0 mm, and weighing the materials as the base numbers of the material dosage and bath liquid ratio in the steps (11) to (14) when the water content is 60%.

(11) And (3) rewetting: the bath liquid ratio is 250%, the bath temperature is 35 ℃, 0.2% of formic acid and 0.5% of degreasing agent FA (Clainen chemical Co., Ltd.) are added, the temperature is 40min, the pH is 3.5, and the liquid is discharged after being washed twice for 10min each time.

(12) Retanning: the bath liquid ratio is 200%, bath temperature is 40 deg.C, tetrakis (hydroxymethyl) phosphonium sulfate is added 2%, rotation is carried out for 50min, sodium formate is added 0.4%, rotation is carried out for 30min, then sodium bicarbonate is added to adjust pH to 5.0, rotation is carried out for 40min, washing is carried out twice with 50 deg.C water, each time is 10min, and liquid discharge is carried out.

(13) And neutralizing: the bath lotion is 120%, the bath lotion temperature is 35 ℃, sodium formate is added at 0.9%, the bath lotion is rotated for 40min, sodium carbonate is added at 0.4-0.8%, the bath lotion is rotated for 50min, the pH is adjusted to 5.2, the bath lotion is washed twice with water at 55 ℃ for 10min each time, and the liquid is discharged.

(14) And fat liquoring: the bath lotion is 80%, the bath lotion temperature is 40 ℃, the fatting agent SE7% (Shanghai leather chemical plant) is added, the operation is carried out for 60min, the phosphated grease (BUXOM SP new material) is 2%, BUXOM BP (new material) is 1%, the fatting agent absorption promoting material is 1%, the operation is carried out for 1h, the water is added for 100%, the bath lotion temperature is adjusted to 50 ℃, the operation is carried out for 60min, the formic acid is added for 1.5%, the operation is carried out for 60min, the bath lotion is washed twice with 65 ℃ water, the operation is carried out for 10min each time, the liquor is drained, and the vacuum drying is.

The preparation method of the fat liquor absorption promoting material comprises the following steps: adding starch treated by a standard sieve with more than 60 meshes into water with the mass of 80 percent of the starch, stirring and gelatinizing the starch at 70 ℃ for 40min, adding sodium dodecyl benzene sulfonate with the mass of 2 percent of the starch and phosphorus trichloride with the mass of 40 percent of the starch, stirring and reacting the mixture at 60 ℃ for 2h, adding oleamide with the mass of 20 percent of the starch and maleic anhydride with the mass of 35 percent of the starch, and adding sodium hydroxide with the mass of 30 percent to adjust the pH value to 7.5 to obtain the material for promoting the absorption of the fatting agent.

(15) Hanging and airing, drying and dampening: carrying out a conventional process;

(16) and coating: and sequentially carrying out base coating, intermediate coating and top coating, wherein the coating adopts roller coating, the roller coating temperature is 102 ℃, the base coating is rolled for three times, the intermediate coating is rolled for two times, and the top coating is rolled for one time. The coatings of each layer were as follows:

(a) and (3) priming coating: the paint comprises the following components in parts by weight: aqueous pigment paste NEOSAN 2000 (clariant chemical limited), 1.8 parts, water 32 parts, Euderm oil KWO-C0.4 parts as a cationic oil (cationic, langson chemical);

(b) and intermediate coating: the paint comprises the following components in parts by weight: 30 parts of water, 60 parts of extinction polyurethane MATT 200 (Wenzhou national Shibang high polymer material Co., Ltd.), 15 parts of bright polyurethane HPV-C (Cyte corporation, USA), 13 parts of a crosslinking agent XL-701 (Starer, USA), 11 parts of wear-resistant polyurethane, 0.5 part of carbodiimide, 2.6 parts of nitrogen-phosphorus intumescent flame retardant and 2.6 parts of a film forming accelerant;

the preparation method of the wear-resistant polyurethane comprises the following steps: adding 43 parts of polycarbonate diol, 13.9 parts of isophorone diisocyanate and 0.45 part of dibutyltin dilaurate into a reaction container, and stirring at 75 ℃ for reaction for 1h to obtain a polyurethane prepolymer;

adding 3.4 parts of hydrophilic chain extender dimethylolpropionic acid and 12.5-16.5 parts of acetone solvent into the polyurethane prepolymer, and stirring and reacting for 2 hours at the temperature of 80 ℃; adding 5.0 parts of triethylamine and 150 parts of water, emulsifying for 60min, adding 1 part of substance A and 0.2 part of epoxy-terminated polyether silicone oil, adjusting the pH value to 6.5, and stirring and reacting for 1-2h at 80 ℃ to obtain abrasion-resistant polyurethane;

the preparation method of the substance A comprises the following steps: adding 3 parts of aluminum sulfate and 3 parts of chromium sulfate into 10 parts of water, adjusting the pH value to 3.8-4.2, adding 1.1 parts of gallic acid, 1.2 parts of sodium citrate and 0.3 part of maltohexaose, stirring and reacting at 70 ℃ for 2 hours, adding 0.6 part of 3-glycidyl ether oxypropyl methyldimethoxysilane and 0.3 part of substance B, and reacting at 70 ℃ for 1 hour to obtain a substance A;

wherein the substance B is prepared by the following steps: adding 4 parts of sulfamic acid and 0.4 part of sodium dodecyl benzene sulfonate into 7 parts of perfluoropolyether acyl fluoride, reacting for 2 hours at 50 ℃, adding 0.6 part of 2, 4-diamino-6-hydroxypyrimidine, and reacting for 2 hours at 55 ℃ to obtain a substance B.

The preparation method of the nitrogen-phosphorus intumescent flame retardant comprises the following steps: adding a basic catalyst sodium methoxide with the mass of 4% of dimethyl phosphite into 1mol of dimethyl phosphite, adding 1.1mol of acrylamide, reacting for 5 hours at 70 ℃ to obtain 3-dimethoxyphosphoryl propionamide as an intermediate product, cooling the intermediate product to 55 ℃, adding 0.1mol of trimethylchlorosilane and 0.1mol of cyanuric chloride, stirring for reacting for 5 hours at 80 ℃, adjusting the pH of the solution to 6.5-7.0 during stirring, adding 2.7g of 1, 3-propanedithiol and 0.4g of MOFs, stirring for reacting for 3 hours at 60 ℃, and concentrating until the solid content reaches more than 80%, thereby obtaining the nitrogen-phosphorus intumescent flame retardant;

the preparation method of the MOFs comprises the following steps: adding 1 part of ammonium tetramolybdate, 3 parts of 4-acetamido sodium salicylate, 2 parts of zirconium sulfate and 1.2 parts of diethyl aluminum chloride into 15 parts of deionized water, stirring for 40min at 55 ℃, adjusting the pH value to 7.2, adding 1 part of 2-propyl ethyl acetoacetate, reacting and stirring for 1h at 180 ℃, filtering, washing with water, and drying to obtain the MOFs.

The preparation method of the film forming accelerant comprises the following steps: stirring 6 parts of polyethyleneimine and 8.2 parts of 2-acetoxyisobutyryl chloride at 50 ℃ for reaction for 1 hour, then sequentially adding 1.1 parts of salicylic acid and 1.1 parts of semicarbazide, and reacting at 50 ℃ for 30 minutes to obtain a film-forming promoter;

(c) and top coating: the coating material proportion is as follows: 14 parts of water, 6 parts of a hand feeling agent 2229W (Shandong Chuan commercial Co., Ltd.), 0.2 part of Euderm oil KWO-C (cationic, Langsheng chemical) as a cationic oil, and 1.9 parts of an anti-adhesive material.

The preparation method of the anti-bonding material comprises the following steps: adding 9 parts of 1, 2-benzenediol and 12 parts of water into 12 parts of trifluoroacetamide, stirring and reacting for 1h at 50 ℃, drying, adding 2.1 parts of phenyl phosphoryl dichloride and 13 parts of benzene, stirring and reacting for 1h at 65 ℃, distilling and removing residual benzene, and drying the residual to obtain the anti-adhesion material.

The chemical materials of unspecified factories related to the embodiment of the invention can be replaced by the similar products of leather Limited company of shineagle, and the wet heat stability is determined by GBT 4689.8-1984, QB/T3812.5-1999, tensile strength and maximum elongation at break, dry friction color fastness, wet friction color fastness, coating adhesion fastness, leather atomization performance, leather wear resistance and light resistance, see Shu from Zhengshaolan and Sunjun (leather analysis and inspection technology, published in 2005 for 6 months); the dry heat shrinkage temperature is shown in Liujie, Tang Ke Yong, China leather in periodicals, 9 months 2001, oxygen index, vertical combustion valve and smoke density, which can be referred to the Laobao series published academic papers or (Laobao and the like, influence of phosphorus flame retardant on the flame retardant property of leather [ J ], China leather, 2012, 8 months; TS-INT-002 + 2008 vehicle material and part total carbon emission determination method), and other conditions such as unclear standards or no description, please refer to the light industry standard or the detection method of the automobile for testing, and also refer to the leather analysis and inspection technology, published in 2005, 6 months.

The flame-retardant, wear-resistant, anti-sticking and low-VOC automobile cushion leather prepared according to the embodiment of the invention and the existing similar automobile cushion leather are respectively detected, and the detection data are shown in Table 1.

TABLE 1 flame-retardant, abrasion-resistant, anti-sticking, low VOC automobile cushion leather manufacturing process

Item	Detection result of automobile cushion leather prepared by the invention	Automobile seat cushion leather detection result of comparison file
			Moist Heat stability/. degree.C	95	94
Tensile strength/MPa	17.2	16.7
			Maximum elongation at break/%)	46	43
Dry rub colour fastness/grade	4.5	4.5
			Wet rub colour fastness/grade	4.5	4.5
Coating adhesion fastness/(N/10 mm)	7.6	7.3
			Dry heat shrinkage temperature/. degree.C	162	155
Light resistance/grade	4.5	4~5
			Atomization value per m parts	2.8	3.1
Oxygen index/%	32.6	32
			Duration of continuous combustion/s	2	3
Smoldering time/s	0.2	0.1
			Tobacco density/%	11.6	12.4
Ultra low total carbon emission/μ gC/g	29.69	31.25
			Abrasion resistance (CS-10,1000g,500 times)	No obvious damage and peeling	No obvious damage and peeling
Coating mutual adhesion (%)	97.6	45.2

The comparison document uses the example data of 201910405405.6, where VOC is expressed as ultra low total carbon emissions, and the coating mutual adhesion is the average of the probability of grain adhesion determined by 3 skilled finishing engineers from 100 pieces of cowhide upholstery leather, and the coating mutual adhesion of the comparison document is a previous measurement by this team.

TABLE 2 Properties of the materials without addition of parts

Item	Detection result of automobile cushion leather prepared by the invention	Without addition of part of material
			Abrasion resistance (CS-10,1000g,500 times)	More damage and peeling	Polyurethane without abrasion resistance
Abrasion resistance (CS-10,1000g,500 times)	Less damage and flaking	Adding abrasion-resistant polyurethane without adding substance A
			Abrasion resistance (CS-10,1000g,500 times)	Less damage and flaking	Adding abrasion-resistant polyurethane, adding substance A and not adding substance B
Coating mutual adhesion (%)	51.3	Without addition of anti-adhesive material
			Coating mutual adhesion (%)	62.1	The adhesion preventing material is added without adding trifluoroacetamide
Coating mutual adhesion (%)	78.3	The bonding preventing material is added without adding phenyl phosphoryl dichloride
			Ultra low total carbon emission/. mu.part C/part	65.4	Non-addition film accelerator
Ultra low total carbon emission/. mu.part C/part	38.7	Adding film forming promoter without adding 2-acetoxy isobutyryl chloride
			Ultra low total carbon emission/. mu.part C/part	39.7	Without addition of 2, 4-diamino-6-hydroxypyrimidine
Oxygen index/%	28.6	Intumescent flame retardant without adding nitrogen and phosphorus
			Tobacco density/%	39.8	Intumescent flame retardant without adding nitrogen and phosphorus
Oxygen index/%	29.8	Expansion type fire retardant with nitrogen and phosphorusWithout addition of MOFs
			Tobacco density/%	34.6	Adding nitrogen phosphorus intumescent flame retardant without adding MOFs
Oxygen index/%	30.8	Adding nitrogen phosphorus intumescent flame retardant, adding MOFs, and not adding 2-propyl ethyl acetoacetate
			Tobacco density/%	29.5	Adding nitrogen phosphorus intumescent flame retardant, adding MOFs, and not adding 2-propyl ethyl acetoacetate

As can be seen from Table 2, the performance of the material without adding the above-mentioned part is reduced, and the data test is carried out without adding a certain material and adding other materials.

TABLE 3 bath Properties

Item	Step of fat liquoring
		Amount of bath oil/%)	1
Amount of oil in bath lotion/% (no material for promoting absorption of fat-liquoring agent)	45.8
		Amount of oil in bath lotion/% (without oil acid amide)	24.8

The grease test standard is that an extraction method is used for testing, a sample can be dried, and the test is carried out by a soxhlet drawer method published in 6 months 2005 by using a leather analysis and inspection technology.

As can be seen from Table 3, the amount of residual fat in the bath solution containing the material for promoting the absorption of the fatliquoring agent in the present invention was greatly reduced, whereas the amount of residual fat in the bath solution was greatly increased without the material for promoting the absorption of the fatliquoring agent.

The epoxy-terminated polyether silicone oil used in the invention is IOTA-EO11000, and is purchased from Anhui Eyota silicone oil Co.

The parts in the invention are all parts by mass.