JP2022105324A - Process for manufacturing flame-retardant, wear-resistant, anti-sticking and low-voc leather for car seats - Google Patents

Abstract

To provide a process for manufacturing flame-retardant, wear-resistant, anti-sticking and low-voc leather for car seats.SOLUTION: The invention discloses a process for manufacturing flame-retardant, wear-resistant, anti-sticking and low-VOC leather for car seats, comprising a deashing step, a retanning step, a neutralizing step, a fat liquoring step and a finishing step. According to the invention, a nitrogen-phosphorus intumescent flame retardant modifies wear-resistant polyurethane to be used in the finishing step, and an anti-adhesion material reduces the adhesion of the coating. The prepared leather for car seats has better wear resistance and lower VOC on the basis of keeping better flame retardance and low fogging performance, allows further improvement to the absorptivity of a fat liquoring agent, and solves the problem of adhesion of a grain surface layer in the process of static storage of the finished leather.SELECTED DRAWING: None

Description

The present invention relates to a process for manufacturing leather for car seats, and more particularly to a process for manufacturing leather for car seats having flame retardancy, abrasion resistance, adhesive resistance, and low VOC.

Currently, China is the world's largest automobile consumer market, and in 2019, China's automobile production and sales reached 2,5721 thousand units and 257,691,000 units, respectively. The production and sales volume continues to be the highest in the world, of which 20% are equipped with genuine leather seats. The market demand for genuine leather for automobiles is very large, and with the prosperity of the automobile market, more and more leather companies are paying attention to the business opportunities for automobile leather making. According to the report of the annual meeting of the China Leather Association at the end of 2017, even in an environment where the profits of all products in the leather industry nationwide are generally declining, only the profits of automotive leather continue to grow. Has been pointed out.

Yantai University's Leather and Protein Laboratory has long been involved in the research and development of automotive leather and ancillary chemicals. Patent Document 1 of Yantai University relates to an antifouling property, ultra-low TVOC emission, and abrasion resistance leather manufacturing process for cowhide car seats. Undercoat paints include water-based pigment pastes, light-resistant paints, light-resistant acrylic resin paints, light-resistant water-resistant polyurethanes, flame-retardant paints and cationic oils, and intermediate paints include matte polyurethanes, glossy polyurethanes and cross-linking agents. , Material B, abrasion resistant polyurethanes, carbodiimides, PTFE emulsions and smoke control materials, topcoats include finishes and cationic oils. The prepared cowhide car seat leather further improved antifouling property and wear resistance and reduced the amount of TVOC emission based on maintaining flame retardancy, light resistance and low fogging property. Since the leather for automobiles is in close contact with humans, the coating film is easily peeled off due to the wear of the human body, and the standards of existing automobile manufacturers for the leather for automobiles are different, so that the wear resistance of the leather for automobiles is further improved. There is a need.

Patent Document 2 discloses a process for manufacturing leather for cowhide car seats, which has flame retardancy, yellowing resistance, and low fogging property. By replacing decalcification with ammonium chloride in the production process with ammonium chloride-less decalcification, the amount of fogging generated in the seat leather is suppressed by high-temperature water washing, and retanning, greasing, and finishing are carried out step by step to make the leather flame-retardant. This is a leather process for car seats that improves the light resistance and improves the light resistance of the coating film with a light resistant material. In this process, roller coating is selected instead of spray coating to reduce the amount of leather chemicals used. According to the research and development of high-performance automobile interior leather products with flame retardancy, low fogging resistance, light resistance, heat resistance, and yellowing resistance, there is a wide market outlook. As a conventional index for evaluating flame retardancy, the oxygen index is 32, the afterburn time is 5 s, the flameless combustion time is 3 s, and the smoke density is 29.7. Car fires are a low-probability event, but they have not lowered automakers' standards for flame retardancy. Patent Document 3 discloses a leather manufacturing process for flame-retardant, light-resistant, low-fogging, and degradable cowhide car seats. Replacing ammonium chloride decalcification with ammonium chlorideless decalcification, tetrakis (hydroxymethyl) phosphonium sulfate, flame-retardant starch-based leather surfactant is selected as the leather tanning agent instead of the conventional chromium tanning agent. However, the amount of fogging of the seat leather is suppressed by high-temperature water washing, retanning, greasing, and finishing are carried out in stages to improve the flame retardancy of the leather, and the light-resistant material improves the light resistance of the coating film. Choose roller coating instead of spray coating to reduce the amount of leather chemicals used. The oxygen index is 32, the afterburn time is 5s, and the flameless combustion time is 5s, indicating that there is still room for improvement.

Greasing is one of the important processes in the production of leather for automobiles, which determines the flexibility, abundance and elasticity of the finished leather, and the physical and mechanical properties such as strength and elongation of the finished leather, and the finished leather. Affects hygiene properties such as water absorption, breathability and water vapor permeability. Furthermore, by adding grease, it is possible to give the finished leather special properties such as waterproofness, oil resistance, antifouling property, and antifog property. As a conventional leather processing process, only 60 to 70% of the oils and fats during the leather processing for sofas are absorbed by the leather. Greasing is one of the processes that use the most chemicals in leather, and the unabsorbed greasing agent gets into the wastewater, which not only wastes the chemicals but also in the wastewater. The COD and BOD indicators were raised, and the wastewater treatment cost was increasing. Therefore, auxiliary materials are needed to improve the water treatment of the leather industry. In Patent Document 1, a binding flame-retardant greasing agent is used, and a starch-based surfactant is used to promote uniform permeation of fats and oils to clarify the bath liquid and absorb fats and oils. It also reached 95%, and because it was firmly bonded to the leather fiber, the generation of free fats and oils was clearly reduced, but it is stated that there is still room for improvement in this index.

During the use of car seat cushions, the movement of small molecule compounds in the leather causes a special odor. Since the released gas contains compounds such as formaldehyde, acetaldehyde, benzene and toluene, it was necessary to reduce the odor of automobile leather.

In leather processing, the particle surface and the particle surface, and the meat surface and the meat surface are stacked one on top of the other in the aging process. When the coating films on the surfaces adhere to each other, there is a possibility that a part of the coating film may be peeled off or the color may be discolored.

Summarizing the above, we propose new technical means for more prominent technical issues including wear resistance, flame retardancy and absorption of greasing agents, further optimize and improve these indicators, domestic automobiles. The overall quality of the leather needs to be further improved.

Chinese Patent No. CN201910405405.6 Chinese Patent No. CN201510694401.6 Chinese Patent No. CN201510694403.5

GBT 4689.8-1984, QB / T 3812.5-1999 Leather analysis and inspection technology published in June 2005 September 2001 periodical Chinese leather Effect of Phosphorus Flame Retardant on Leather Flame Retardant [J], Chinese Leather, August 2012; TS-INT-002-2008 TVOC emission measurement method for automotive materials and parts

The present invention provides better wear resistance and lower VOC, and further improves grease absorption, based on the prepared car seat leather having better flame retardancy, lower fogging properties. The technical challenge is to provide a flame-retardant, wear-resistant, adhesive-resistant, low-VOC leather manufacturing process for car seats that solves the problem of grain surface layer adhesion during the static storage process of finished leather. And.

The technical means of the present invention are as follows.
It is a flame-retardant, wear-resistant, adhesive-resistant, low-VOC leather manufacturing process for car seats, which includes a decalcification process, a retanning process, a neutralization process, a greasing process, and a finishing process. A process for manufacturing leather for car seats, which is flame-retardant, wear-resistant, adhesive-resistant, and has low VOC, which comprises the following steps.
The finishing process includes an undercoat, an intermediate coat, and a topcoat that are sequentially performed. Roller coating is used for finishing, the temperature of the roller coating is 101 to 105 ° C, the undercoat is applied three times, and the intermediate coating is applied twice. The coating and top coating are one-time coatings, and the paints in each layer are as follows.
(A), Undercoat paint blending ratio: 0.7 to 2.5 parts of water-based pigment paste, 32 parts of water, 0.2 to 0.5 parts of cationic oil;
(B), Mixing ratio of intermediate coating paint: 30 parts of water, 20 to 70 parts of matte polyurethane, 7 to 18 parts of glossy polyurethane, 6 to 13 parts of cross-linking agent, 7 to 14 parts of wear-resistant polyurethane, 0.4 parts of carbodiimide. ~ 0.7 parts, nitrogen-phosphorus expandable flame retardant 1.2 ~ 2.6 parts, film formation accelerator 1.3 ~ 2.6 parts;
Here, a method for preparing an abrasion-resistant polyurethane: 43 parts of a polycarbonate diol, 12.2 to 13.9 parts of isophorone diisocyanate, and 0.18 to 0.45 parts of dibutyltin dilaurate are placed in a reaction vessel, and 1 at 75 to 90 ° C. The reaction is carried out with stirring for ~ 2 hours to obtain a polyurethane prepolymer;
Polyurethane prepolymer containing 0.9 to 3.4 parts of dimethylol propionic acid, a hydrophilic chain extender, 2.2 to 3.4 parts of a nitrogen-phosphorus expandable flame retardant, and 12.5 to 16.5 parts of an acetone solvent. The mixture is added and reacted at 70 to 80 ° C. with stirring for 1 to 2 hours, then 3.0 to 5.0 parts of triethylamine and 100 to 150 parts of water are added and emulsified for 20 to 60 minutes, and then emulsified. Add 1 to 2 parts of substance A and 0.2 to 0.6 parts of epoxy-terminated polyether silicone oil, adjust the pH to 6.5, and react at 70 to 80 ° C. for 1 to 2 hours with stirring for abrasion resistance. Get polyurethane;
Preparation method of the substance A: Add 3 parts of aluminum sulfate and 2 to 3 parts of chromium sulfate to 10 parts of water to adjust the pH to 3.8 to 4.2, and then add citric acid 1.1 to 2.3. Add 1.2 to 3.2 parts of sodium citrate and 0.2 to 0.3 parts of maltohexaose, and react at 60 to 70 ° C. with stirring for 1 to 2 hours, and then further (3-glyci). Sidoxypropyl) 0.3 to 0.6 part of methyldimethoxysilane and 0.3 to 0.6 part of substance B are added and reacted at 70 to 80 ° C. for 1 to 2 hours to obtain substance A;
Preparation method of substance B: Add 1 to 4 parts of sulfamic acid and 0.2 to 0.4 parts of sodium dodecylbenzene sulfonate to 7 parts of perfluoropolyether acylfluoride, and react at 40 to 50 ° C. for 1 to 2 hours. After that, 0.6 to 0.8 part of 2,4-diamino-6-hydroxypyrimidine is added and reacted at 45 to 55 ° C. for 1 to 2 hours to obtain substance B;
Preparation method of nitrogen-phosphorus-based expandable flame retardant: Add sodium methoxydo, which is a base catalyst in an amount of 1 to 4% by mass based on the mass of dimethyl phosphite, to 1 mol of dimethyl phosphite, and then acrylamide 1.1 to 1 Add 2 mol and react at 70-80 ° C for 1-5 hours to obtain 3-dimethoxyphosphorylpropionamide as an intermediate product, lower the temperature of the intermediate product to 50 ° C-55 ° C, and trimethylchlorosilane 0.1- 0.2 mol and 0.1 mol of cyanuric acid chloride are added and reacted at 60 to 80 ° C. with stirring for 2 to 5 hours to adjust the pH of the solution to 6.5 to 7.0 in the stirring process, and then 1 , 3-Propanidithiol 1.6 to 2.7 g and MOFs 0.2 to 0.4 g are added, and the mixture is reacted at 60 to 80 ° C. with stirring for 1 to 3 hours and concentrated until the solid content becomes 80% or more. Obtain a nitrogen-phosphorus expandable flame retardant;
Preparation method of MOFs (metal-organic frameworks, metal-organic frameworks): 1 part of ammonium tetramolybate, 2 to 3 parts of sodium 4-acetamide salicylate, 1 to 2 parts of zirconium sulfate, 1.2 to 1.6 of diethylaluminum chloride Add 1 part and 15 parts of deionized water, stir at 55-60 ° C for 40-60 minutes, adjust the pH to 7.2, add 1-3 parts of ethyl 2-acetylvalerate, and then at 180-190 ° C. The reaction is carried out with stirring for 1 to 2 hours, and the mixture is filtered, washed with water and dried to obtain MOFs;
Preparation method of film-forming accelerator: 6 parts of polyethyleneimine and 8.2-9.4 parts of 2-acetoxyisobutyryl chloride were reacted at 50 to 60 ° C. for 1 to 2 hours with stirring, and then salicylic acid 1.1. ~ 1.4 parts and 1.1 to 2.3 parts of semicarbazide are added in order and reacted at 50 to 70 ° C. for 30 to 90 minutes to obtain a film forming accelerator;
(C), Topcoat paint blending ratio: 14 parts of water, 1.3 to 1.9 parts of adhesive, 5 to 7 parts of finishing agent and 0.2 to 0.3 parts of cationic oil;
Here, a method for preparing an adhesive resistant agent: 6 to 9 parts of 1,2-benzenediol and 12 parts of water are added to 12 parts of trifluoroacetamide, and the mixture is reacted at 50 to 60 ° C. for 1 to 2 hours with stirring and dried. After that, 2.1 to 3.8 parts of phenylphosphoryldichloride and 13 parts of benzene were added, and the mixture was reacted at 60 to 65 ° C. with stirring for 1 hour, and then the remaining benzene was distilled off and the residue was dried. Obtain an adhesive resistant agent.

The decalcification step includes a preliminary decalcification step and a main decalcification step.
Preliminary decalcification step: Based on the weight of lime-pickled bare skin after trimming, magnesium lactate 0.3-1.4% and 2-hydroxypropionic acid 0.2% are added to pre-decalcify, and the bath ratio is 100. % To 200%, the pH of the bath is 9.0 to 10.0, the bath temperature is controlled to 18 to 22 ° C., and the mixture is rotated for 60 to 90 minutes.
Main decalcification step: The bath ratio is 100% to 120%, the bath temperature is 18 to 22 ° C., 4-methylsalicylic acid 0.3 to 0.7% is added, and the pH is 9.0 to 10.0. Rotate for 60-90 minutes.

The retanning step: the bath ratio is 100 to 200%, the bath temperature is 40 ° C., tetrakis (hydroxymethyl) phosphonium sulfate 2% to 4% is added, and the mixture is rotated for 30 to 50 minutes, and sodium formate 0.2 to 0.2 to Add 0.6% and rotate for 30 minutes, then add sodium hydrogen carbonate to adjust the pH to 5.0, rotate for another 40 minutes, wash twice with water at 50 ° C for 10 minutes each time, and drain the liquid. do.

The neutralization step: based on the weight of the shaving skin after trimming, the bath ratio is 120%, the bath temperature is 34 to 36 ° C., sodium formate 0.8 to 1.0% is added, and 30 to 50 is added. Rotate for 1 minute, add 0.4% to 0.8% sodium carbonate, further rotate for 40 to 70 minutes, wash twice with water at 55 to 60 ° C., and drain.

The greasing step: based on the weight of the shaving skin after trimming, the bath ratio is 80%, the bath temperature is 38 to 42 ° C., the greasing agent SE 5 to 7%, the phosphorylated oil 1-2%, Add BUXOM BP, 1-2% greasing agent absorption accelerator, rotate for 30 to 60 minutes, add 100% water, adjust the bath temperature to 48 to 52 ° C., rotate for 60 to 90 minutes, and rotate for 60 to 90 minutes. Add 5 to 2.0%, rotate for 60 to 90 minutes, wash twice with water at 62 to 65 ° C., and drain.

Preparation method of greasing agent absorption promoting material: Steel treated with a standard sieve of 60 mesh or more is added to 80% of the mass of water, stirred and gelatinized at 70 to 80 ° C. for 20 to 40 minutes, and then the starch is prepared. Add 0.3 to 2% by mass of sodium dodecylbenzenesulfonate and 20 to 40% by mass of phosphorus trichloride with respect to the mass of starch, and react at 40 to 60 ° C. with stirring for 1 to 2 hours. Next, 10 to 20% by mass of oleic acid amide with respect to the mass of starch, 30 to 40% by mass of maleic anhydride and 30% by mass of sodium hydroxide to the mass of starch were added, and the pH was adjusted to 7. Adjust to 5 to obtain the greasing agent absorption promoting material.

The advantageous effects of the present invention are as follows.
(1) In the present invention, a polycarbonate diol is used as an abrasion-resistant polyurethane to react with isophorone diisocyanate, and a substance A and an epoxy-terminated polyether silicone oil are used to reduce the flexibility of the polyurethane by cross-linking the substance A. , Improves the defect that the plate is rigid. Hydrolyzed with aluminum sulfate and chromium sulfate in an environment of pH 3.8 to 4.2, the hydrolyzate is used as a complexing agent, and glutinous acid, sodium citrate, and maltohexaose are added to the metal. React with the complexing agent. Here, the reactive group of glutinous acid is a hydroxyl group and a carboxyl group, and the reactive group of sodium citrate is a sodium carboxylate and a hydroxyl group. Although widely used in medicine, malthexaose has a large number of hydroxyl groups and their cyclic structure. The cyclic structure is used to increase the rigidity of polyurethane, and the hydroxyl group is used to react with the above-mentioned aluminum sulfate and chromium sulfate in a complex reaction, and aluminum sulfate and chromium sulfate are used to form the carboxylate and hydroxyl group on the polyurethane chain. To form a polyurethane with a spatial network structure. In order to reduce the flexibility of polyurethane due to the network structure, the present invention reacts with the amino group of sulfamic acid using the fluoride acyl of perfluoropolyether acylfluoride to form the flexible group of perfluoropolyether acylfluoride. Introduce and fill the network spacing distributed in the space with flexible groups. In this way, the frictional force of the mutual direct chain movement of the polyurethane is reduced and the flexibility is improved, and at the same time, 2,4-diamino-6-hydroxypyrimidine is used to increase the flexible rigidity and the abrasion resistance of the polyurethane is improved. Improve overall.

(2) Carboxylic acid anion anion of ammonium tetramolybate and sodium 4-acetamide salicylate binds electrically negatively, and zirconium sulfate is further added to form a complex ion in a hydrolyzed environment. Diethylaluminum chloride bonds with the amino group of sodium 4-acetamide salicylate and reacts to introduce organic aluminum, and at the same time, the zirconium complex and molybdenum compound bond with the carboxylic acid ion of ethyl 2-acetylvalerate in an alkaline environment. Then, a branched compound is introduced to widen the spatial interval of MOFs, and the binding between MOFs and the expandable flame retardant becomes easy.

(3) The MOFs system is dispersed in the flexible and rigid chain segments of polyurethane to enhance the flame retardancy and smoke suppression characteristics of polyurethane, and at the same time expand under the heat receiving conditions of the expandable flame retardant material, and the expansion layer becomes MOFs. The char layer formed in the heat receiving environment, which is dispersed in the loose space of MOFs and filled in the mesh space of MOFs, is dense and thick to prevent the emission of smoke.

(4) Polyethyleneimine and 2-acetoxyisobutyryl chlorideimine react with the acid chloride to introduce salicylic acid and semicarbazide to improve the film-forming property and wear resistance of polyurethane.

(5) Trifluoroacetamide reacts with 1,2-benzenediol in an aqueous system, reacts with a phenolic hydroxyl group using the amino group of the amide, and then undergoes a modification reaction with phenylphosphoryl dichloride in the benzene system to be applied. Obtain an adhesive resistant agent for preventing film adhesion.

(6) The present invention uses starch gelatinization to react with phosphorus trichloride to introduce P-Cl chemical bonds into the system and then react with oleic acid amides to introduce amide bonds into the compound. This compound, which undergoes a ring-opening reaction by further adding maleic anhydride, has a powerful effect of improving the absorption of fats and oils in the fattening process, can reduce the residual fat and oil of the system to less than 2%, and makes leather fats and oils. The water in the process is more clarified.

The present invention will be further described below in conjunction with embodiments.

The manufacturing process of the embodiment of the present invention is as follows.

(1), Preliminary water pickling: Using the weight of the raw leather as the standard for the amount of material used and the bath ratio in step (1), a disinfectant (Badericides 72, manufactured by Hueiing Enterprise Co., Ltd.) 0 .10%, water pickling aid (Humectan RDL, manufactured by Hueiing Enterprise Co., Ltd.) 0.18%, soda ash 0.2% added, bath ratio controlled to 400% The bath temperature is 20 to 22 ° C., the bath pH is 8.8 to 9.2, and the degree of sterilization is 8, the rotation is performed every 60 minutes for 5 minutes for a total of 18 hours, and then the lining and trimming are performed. , Weighing is carried out in sequence and used as a reference for the amount of material used and the bath ratio in steps (2) to (3).

Actual measurement data of hydration: 55% of water is replenished to the loose part of the rawhide, and 25% to 30% of water is replenished to the tight part.

(2), Honshu-zuke: Fungicide (Baderidies 72, manufactured by Hueiing Enterprise Co., Ltd.) 0.4%, Water-pickled aid (Humectan RDL, Kitaka Kogyo Leather Co., Ltd.) (Made by Hueiing Enterprise Co., Ltd.) 0.4% and 0.3% soda ash are added to control the bath ratio to 700%, the bath temperature is 18 to 20 ° C, and the bath pH is 9.8 to. 10.2, the degree of bokeh is 3 to 4, and the main is to immerse in the bath liquid, the rotation is subordinate, and the rotation is performed every 60 minutes for 5 minutes for a total of 20 hours.

Actual measurement data of hydration: 80% of water is replenished to the loose part of the rawhide, and 60% of water is replenished to the tight part.

(3), Lime soaking: Lime soaking aid 0.6% (manufactured by DERMOLLANAR, Hueiing Enterprise Co., Ltd.), sodium hydrogen sulfide 0.4%, sodium sulfide 1.5% (Add in 3 portions), add 1.4% lime, bath ratio is 90%, bath temperature is 24 ° C, rotation time is 180 minutes, bath pH is 11, the drum is stopped overnight. Next, lining, trimming, and weighing are performed to use the amount of material used and the bath ratio in steps (4) to (8) as a reference.

(4) Preliminary decalcification: Preliminary decalcification was carried out by adding 0.6% magnesium lactate and 0.2% 2-hydroxypropionic acid, the bath ratio was 150%, and the pH of the bath was 9.5. The bath temperature is controlled to 22 ° C. and rotated for 60 minutes.

(5) Main decalcification: The bath ratio is 100%, the bath temperature is 20 ° C., 0.6% of 4-methylsalicylic acid is added, the pH is 9.0, and the mixture is rotated for 90 minutes.

(6), Softening: The bath ratio is 0.3, the temperature is 28 ° C., Dermascal ASB 1.0% (replaceable with a similar manufacturer's product) is added, and glacial acetic acid 0.2 from the shaft of the rotating drum during rotation. % (Diluted with 10-fold cold water in advance), rotate for 40 minutes, measure pH 8.5, sodium metabisulfate 0.1%, Oropon OO pancreatin preparation (Derui Leather Technology (Qingdao) Co., Ltd.) (Manufactured by Together for Leather China Ltd.) 1.5% was added, the mixture was rotated for 240 minutes, washed twice with water, and the bath ratio was 100% each time.

(7), Acid immersion: Bath ratio is 70%, bath temperature is 19 to 20 ° C, salt is added, and the mixture is rotated for 40 minutes to adjust the Baume degree to 8 to 10, sodium formate 0.9%, and sulfuric acid. Add 4.2%, rotate for 90 minutes, pH is 2.5, discard two-thirds of the bath solution and proceed to step (8).

(8), Tanning: Add 4.2% of HLS high-absorption chrome tanning agent (manufactured by Brother Enterprises Holding Co., Ltd.), rotate for 2 hours, and add 0.9% baking soda at 20-minute intervals. The mixture was added 3 times and rotated for 6 hours after the addition, and the measured pH was 4.2 to 4.5.

(9), Standing storage (aging): Cowhide was taken out from the drum and stored statically (aged) for 48 hours.

(10), water squeezing, shaving: Shaving to a thickness of 1.8 to 2.0 mm, squeezing out water to 60%, weighing and measuring, the standard of material usage and bath ratio in steps (11) to (14). And.

(11), Rewetting: The bath ratio is 250%, the bath temperature is 35 ° C, formic acid 0.2%, degreasing agent FA 0.5% (Clariant Chemicals (China) Ltd. ) Was added, and the mixture was rotated for 40 minutes, drained at a pH of 3.5, washed twice for 10 minutes each time, and drained.

(12), Retanning: The bath ratio is 200%, the bath temperature is 40 ° C., 2% of tetrakis (hydroxymethyl) phosphonium sulfate is added, the mixture is rotated for 50 minutes, 0.4% of sodium formate is added, and 30 minutes. After rotation, sodium hydrogen carbonate was added to adjust the pH to 5.0, and the mixture was further rotated for 40 minutes, washed twice with water at 50 ° C. for 10 minutes each time, and drained.

(13), Neutralization: The bath ratio is 120%, the bath temperature is 35 ° C., 0.9% sodium formate is added, the mixture is rotated for 40 minutes, 0.4% to 0.8% sodium carbonate is added, and further. The mixture was rotated for 50 minutes to adjust the pH to 5.2, washed twice with water at 55 ° C. for 10 minutes each time, and drained.

(14), greasing: The bath ratio is 80%, the bath temperature is 40 ° C., the greasing agent SE 7% (manufactured by Shanghai Leather Co., Ltd.) is added, and the mixture is rotated for 60 minutes. Phosphoric oil (BUXOM SP Shandong Leahou Light Industrial of New Material Co., Ltd.) 2%, BUXOM BP (Shandong Leahou Light) (Made by Industrial of New Material Co., Ltd.)) Add 1% and 1% greasing agent absorption promoter, rotate for 1 hour, add 100% water, adjust the bath temperature to 50 ° C, and rotate for 60 minutes. , 1.5% formic acid was added, and the mixture was rotated for 60 minutes, washed twice with water at 65 ° C. for 10 minutes, drained, and vacuum-dried under a reduced pressure of 1 atm.

Preparation method of the greasing agent absorption promoting material: Starch treated with a standard sieve of 60 mesh or more is added to 80% of the mass of water, stirred and gelatinized at 70 ° C. for 40 minutes, and then the mass of the starch is increased. To 2% by mass of sodium dodecylbenzenesulfonate and 40% by mass of phosphorus trichloride with respect to the mass of starch, the reaction was carried out at 60 ° C. with stirring for 2 hours, and then 20% by mass with respect to the mass of starch. 35% by mass of maleic anhydride and 30% by mass of sodium hydroxide are added to the mass of oleic acid amide and starch to adjust the pH to 7.5 to obtain the greasing agent absorption promoting material.

(15), hanging, drying, seasoning: This is a conventional manufacturing process.

(16), Finishing: Undercoating, intermediate coating, and topcoating are performed in sequence, and roller coating is used for finishing, the temperature of the roller coating is 101 to 105 ° C, the undercoating is applied three times, the intermediate coating is applied twice, and the topcoating is applied. Is a one-time coating, and the paint in each layer is as follows.
(A), Undercoat paint blending ratio: Aqueous pigment paste NEOSAN 2000 (Clariant Chemicals (China) Ltd.) 1.8 parts, 32 parts of water, Euderm oil as a cationic oil KWO-C (Cation, manufactured by Lanxess Chemicals (China) Ltd.) 0.4 copies;
(B), Mixing ratio of intermediate coating paint: 30 parts of water, matte polyurethane MATT 200 (manufactured by WenZhou GSB Macromole Material Co., Ltd.) 60 parts, glossy polyurethane HPV- 15 parts of C (manufactured by Cytec, USA), 13 parts of cross-linking agent XL-701 (manufactured by Stahl, USA), 11 parts of abrasion-resistant polyurethane, 0.5 parts of carbodiimide, nitrogen-phosphorus expandable flame retardant. 2.6 parts, film formation accelerator 2.6 parts;
Here, a method for preparing an abrasion-resistant polyurethane: 43 parts of polycarbonate diol, 13.9 parts of isophorone diisocyanate, and 0.45 parts of dibutyltin dilaurate are placed in a reaction vessel and reacted at 75 ° C. for 1 hour with stirring to make a polyurethane prepolymer. Get;
3. Add 3.4 parts of the hydrophilic chain extender dimethylolpropionic acid and 12.5 to 16.5 parts of the acetone solvent to the polyurethane prepolymer, react with stirring at 80 ° C. for 2 hours, and then further triethylamine. Add 0 parts and 150 parts of water and emulsify for 60 minutes, then add 1 part of substance A and 0.2 parts of epoxy-terminated polyether silicone oil to adjust the pH to 6.5, and at 80 ° C. for 1 to 2 hours. React with stirring to obtain abrasion resistant polyurethane;
Preparation method of the substance A: Add 3 parts of aluminum sulfate and 3 parts of chromium sulfate to 10 parts of water to adjust the pH to 3.8 to 4.2, then 1.1 parts of gallic acid and 1 part of sodium citrate. . Add 2 parts and 0.3 part of maltohexaose and react at 70 ° C. with stirring for 2 hours, and then add 0.6 part of (3-glycidoxypropyl) methyldimethoxysilane and 0.3 part of substance B. In addition, it is reacted at 70 ° C. for 1 hour to obtain substance A;
Preparation method of substance B: 4 parts of sulfamic acid and 0.4 parts of sodium dodecylbenzenesulfonate were added to 7 parts of perfluoropolyether acylfluoride, and the mixture was reacted at 50 ° C. for 2 hours and then 2,4-diamino-6. -Add 0.6 parts of hydroxypyrimidine and react at 55 ° C. for 2 hours to give substance B;
Preparation method of nitrogen-phosphorus expandable flame retardant: Add sodium methoxydo, which is a base catalyst of 4% by mass based on the mass of dimethyl phosphite, to 1 mol of dimethyl phosphite, and then add 1.1 mol of acrylamide to 70. The reaction was carried out at ° C. for 5 hours to obtain 3-dimethoxyphosphorylpropionamide as an intermediate product, the temperature of the intermediate product was lowered to 55 ° C., 0.1 mol of trimethylchlorosilane and 0.1 mol of cyanuric acid chloride were added, and 5 at 80 ° C. The reaction is carried out with stirring for hours, the pH of the solution is adjusted to 6.5 to 7.0 during the stirring process, then 2.7 g of 1,3-propanedithiol and 0.4 g of MOFs are added, and the mixture is stirred at 80 ° C. for 3 hours. The reaction is carried out while concentrating until the solid content becomes 80% or more to obtain a nitrogen-phosphorus-based expandable flame retardant;
Preparation method of MOFs: Add 1 part of ammonium tetramolybate, 3 parts of sodium 4-acetamide salicylate, 2 parts of zirconium sulfate and 1.2 parts of diethyl aluminum chloride to 15 parts of deionized water, stir at 55 ° C. for 40 minutes, and pH. Is adjusted to 7.2, and after adding 1 part of ethyl 2-acetylvalerate, the reaction is carried out at 180 ° C. at 180 ° C. for 1 hour with stirring, and the mixture is filtered, washed with water and dried to obtain MOFs;
Preparation method of film-forming accelerator: After reacting 6 parts of polyethyleneimine and 8.2 parts of 2-acetoxyisobutyryl chloride at 50 ° C. with stirring for 1 hour, 1.1 parts of salicylic acid and 1.1 to 2 parts of semicarbazide. . Add 3 parts in sequence and react at 50 ° C. for 30 minutes to obtain a film formation accelerator;
(C), Topcoat paint blending ratio: 14 parts of water, 6 parts of finishing agent 2229W (manufactured by Shandong Chuanze Trading Co., Ltd.), Eudermoil KWO-C (cation) as a cationic oil , Made by Lanxess Chemicals (China) Ltd.) 0.2 parts, Adhesive resistant agent 1.9 parts.

Here, a method for preparing an adhesive resistant agent: 9 parts of 1,2-benzenediol and 12 parts of water are added to 12 parts of trifluoroacetamide, and the mixture is reacted at 50 ° C. for 1 hour with stirring, dried, and then phenylphosphoryl dichloride 2 . 1 part and 13 parts of benzene are added and reacted at 65 ° C. for 1 hour with stirring, and then the remaining benzene is distilled off and the residue is dried to obtain the adhesive resistant agent.

Chemicals that do not specify a manufacturer involved in the embodiment of the present invention can be exchanged for similar products of Hueiing Enterprise Co., Ltd. For moist heat stability, refer to Non-Patent Document 1, tensile strength and elongation at maximum cutting, dyed friction fastness in a dry state, dyed friction fastness in a wet state, coating film adhesive fastness, leather fogging property, leather. For the measurement of abrasion resistance and light resistance, refer to (Non-Patent Document 2) by Tadashi Tadashi, Ran Ding, and Yuki Sonne; for the measurement of drying and heat shrinkage temperature, refer to Non-Patent Document 3 of Liu Zhao and Katsuyu Yu. For the oxygen index, vertical combustion method, and smoke density, refer to the academic papers published by Dan Hoei or (Non-Patent Document 4 by Dan Hoei et al.). In addition, when the standard is unclear or not specified, the test may be carried out with reference to the light industry standard or the test method for automobiles, and Patent Document 2 may be referred to.

The flame-retardant, wear-resistant, adhesive-resistant, low VOC car seat leather prepared in the embodiment of the present invention and the conventional leather for car seats of the same type were tested. The test data are shown in Table 1.

As the comparative example, the data of the examples of Patent Document 1 was used for comparison. VOCs are represented by ultra-low TVOC emissions. For the mutual non-adhesiveness of the coating film, three skilled finishing engineers confirmed the particle surface adhesion probability of the leather from 100 cowhide sheets, calculated the average value of the adhesive probability, and the mutual non-adhesiveness of the coating film of the comparative example was Previous measurement data from our team.

As can be seen from Table 2, the characteristics when the above-mentioned partial materials were not added were deteriorated. The fact that some materials are not added means that the data test is performed with no specific material added and other materials added.

The test criteria for fats and oils were tested by the extraction method, the sample was dried, and the test was performed by the Soxhlet extraction method of Non-Patent Document 2.

As can be seen from Table 3, the residual amount of fats and oils in the bath liquid to which the greasing agent absorption promoting material of the present invention is added is significantly reduced, and when the greasing agent absorption promoting material is not added, the residual amount of fats and oils in the bath liquid is increased. It goes up significantly.

The model number of the epoxy-terminated polyether silicone oil used in the present invention is IOTA-EO11000, which was purchased from Anhui Co., Ltd.

All parts described in the present invention mean parts by mass.

Claims (6)

It is a flame-retardant, wear-resistant, adhesive-resistant, low-VOC leather manufacturing process for car seats, which includes a decalcification process, a retanning process, a neutralization process, a greasing process, and a finishing process. , A process for manufacturing leather for car seats, which is flame-retardant, wear-resistant, adhesive-resistant, and has low VOC, which comprises the following steps.
The finishing process includes an undercoat, an intermediate coat, and a topcoat that are sequentially performed. Roller coating is used for finishing, the temperature of the roller coating is 101 to 105 ° C, the undercoat is applied three times, and the intermediate coating is applied twice. The coating and top coating are one-time coatings, and the paints in each layer are as follows.
(A), Undercoat paint blending ratio: 0.7 to 2.5 parts of water-based pigment paste, 32 parts of water, 0.2 to 0.5 parts of cationic oil;
(B), Mixing ratio of intermediate coating paint: 30 parts of water, 20 to 70 parts of matte polyurethane, 7 to 18 parts of glossy polyurethane, 6 to 13 parts of cross-linking agent, 7 to 14 parts of wear-resistant polyurethane, 0.4 parts of carbodiimide. ~ 0.7 parts, nitrogen-phosphorus expandable flame retardant 1.2 ~ 2.6 parts, film formation accelerator 1.3 ~ 2.6 parts;
Here, the method for preparing the abrasion-resistant polyurethane: 43 parts of a polycarbonate diol, 12.2 to 13.9 parts of isophorone diisocyanate, and 0.18 to 0.45 parts of dibutyltin dilaurate are placed in a reaction vessel at 75 to 90 ° C. The reaction is carried out with stirring for 1 to 2 hours to obtain a polyurethane prepolymer;
Polyurethane prepolymer containing 0.9 to 3.4 parts of the hydrophilic chain extender dimethylol propionic acid, 2.2 to 3.4 parts of the nitrogen-phosphorus expandable flame retardant, and 12.5 to 16.5 parts of the acetone solvent. The mixture is added and reacted at 70 to 80 ° C. with stirring for 1 to 2 hours, then 3.0 to 5.0 parts of triethylamine and 100 to 150 parts of water are added and emulsified for 20 to 60 minutes, and then emulsified. Add 1 to 2 parts of the substance A and 0.2 to 0.6 parts of the epoxy-terminated polyether silicone oil, adjust the pH to 6.5, and react at 70 to 80 ° C. for 1 to 2 hours with stirring to achieve the wear resistance. Obtain sex polyurethane;
Preparation method of the substance A: Add 3 parts of aluminum sulfate and 2 to 3 parts of chromium sulfate to 10 parts of water to adjust the pH to 3.8 to 4.2, and then add citric acid 1.1 to 2.3. Add 1.2 to 3.2 parts of sodium citrate and 0.2 to 0.3 parts of maltohexaose, and react at 60 to 70 ° C. with stirring for 1 to 2 hours, and then further (3-glyci). Sidoxypropyl) 0.3 to 0.6 part of methyldimethoxysilane and 0.3 to 0.6 part of substance B are added and reacted at 70 to 80 ° C. for 1 to 2 hours to obtain the substance A;
Method for preparing substance B: Add 1 to 4 parts of sulfamic acid and 0.2 to 0.4 parts of sodium dodecylbenzenesulfonate to 7 parts of perfluoropolyether acylfluoride, and react at 40 to 50 ° C. for 1 to 2 hours. After that, 0.6 to 0.8 part of 2,4-diamino-6-hydroxypyrimidine is added and reacted at 45 to 55 ° C. for 1 to 2 hours to obtain the substance B;
Method for preparing the nitrogen-phosphorus expandable flame retardant: Add sodium methoxydo, which is a base catalyst in an amount of 1 to 4% by mass based on the mass of dimethyl phosphite, to 1 mol of dimethyl phosphite, and then acrylamide 1.1 to acrylamide. 1.2 mol was added and reacted at 70 to 80 ° C. for 1 to 5 hours to obtain 3-dimethoxyphosphorylpropionamide as an intermediate product, the temperature of the intermediate product was lowered to 50 ° C. to 55 ° C., and trimethylchlorosilane 0.1. -0.2 mol and 0.1 mol of cyanuric acid chloride are added and reacted at 60 to 80 ° C. with stirring for 2 to 5 hours to adjust the pH of the solution to 6.5 to 7.0 in the stirring process, and then the pH of the solution is adjusted to 6.5 to 7.0. Add 1.6 to 2.7 g of 1,3-propanedithiol and 0.2 to 0.4 g of MOFs, react at 60 to 80 ° C. with stirring for 1 to 3 hours, and concentrate until the solid content becomes 80% or more. To obtain the nitrogen-phosphorus expandable flame retardant;
Method for preparing MOFs: Add 1 part of ammonium tetramolybate, 2 to 3 parts of sodium 4-acetamide salicylate to 1 to 2 parts of zirconium sulfate, 1.2 to 1.6 parts of diethyl aluminum chloride and 15 parts of deionized water. Stir at 55-60 ° C. for 40-60 minutes, adjust the pH to 7.2, add 1-3 parts of ethyl 2-acetylvalerate, and then react at 180-190 ° C. for 1-2 hours with stirring. Filter, wash and dry to obtain the MOFs;
Preparation method of film-forming accelerator: 6 parts of polyethyleneimine and 8.2-9.4 parts of 2-acetoxyisobutyryl chloride were reacted at 50 to 60 ° C. for 1 to 2 hours with stirring, and then salicylic acid 1.1. ~ 1.4 parts and 1.1 to 2.3 parts of semicarbazide are added in order and reacted at 50 to 70 ° C. for 30 to 90 minutes to obtain a film forming accelerator;
(C), Topcoat paint blending ratio: 14 parts of water, 1.3 to 1.9 parts of adhesive, 5 to 7 parts of finishing agent and 0.2 to 0.3 parts of cationic oil;
Here, the method for preparing the pressure-sensitive adhesive: 6 to 9 parts of 1,2-benzenediol and 12 parts of water are added to 12 parts of trifluoroacetamide, and the mixture is reacted at 50 to 60 ° C. for 1 to 2 hours with stirring. After drying, 2.1 to 3.8 parts of phenylphosphoryldichloride and 13 parts of benzene were added, and the mixture was reacted at 60 to 65 ° C. with stirring for 1 hour, and then the remaining benzene was distilled off and the residue was dried. The adhesive resistant agent is obtained.
In addition, all the said parts are mass parts. In the decalcification step, based on the weight of the lime-pickled bare skin after trimming, 0.3 to 1.4% of magnesium lactate and 0.2% of 2-hydroxypropionic acid are added to pre-decalcify, and the bath ratio is The pre-decalcification step of 100% to 200%, the pH of the bath is 9.0 to 10.0, the bath temperature is controlled to 18 to 22 ° C. and rotated for 60 to 90 minutes, and the bath ratio is 100% to 120. %, The bath temperature is 18 to 22 ° C., 4-methylsalicylic acid 0.3 to 0.7% is added, the pH is 9.0 to 10.0, and the main decalcification step is rotated for 60 to 90 minutes. The process for manufacturing leather for car seats, which is flame-retardant, wear-resistant, adhesive-resistant, and has low VOC, according to claim 1, further comprising. The retanning step: the bath ratio is 100 to 200%, the bath temperature is 40 ° C., tetrakis (hydroxymethyl) phosphonium sulfate 2% to 4% is added, and the mixture is rotated for 30 to 50 minutes, and sodium formate 0.2 to 0.2 to Add 0.6% and rotate for 30 minutes, then add sodium hydrogen carbonate to adjust the pH to 5.0, rotate for another 40 minutes, wash twice with water at 50 ° C for 10 minutes each time, and drain. The process for manufacturing leather for car seats, which is flame-retardant, wear-resistant, adhesive-resistant, and has low VOC, according to claim 1. The neutralization step: based on the weight of the shaving skin after trimming, the bath ratio is 120%, the bath temperature is 34 to 36 ° C., sodium formate 0.8 to 1.0% is added, and 30 to 50 is added. 1 The process for manufacturing leather for car seats, which is flame-retardant, wear-resistant, adhesive-resistant, and has low VOC. The greasing step: the bath ratio is 80%, the bath temperature is 38 to 42 ° C., the greasing agent SE 5 to 7%, the phosphorylated oil 1-2%, based on the weight of the shaving skin after trimming. Add BUXOM BP, 1-2% greasing agent absorption accelerator, rotate for 30 to 60 minutes, add 100% water, adjust the bath temperature to 48 to 52 ° C., rotate for 60 to 90 minutes, and rotate for 60 to 90 minutes. The flame retardant and abrasion resistance according to claim 1, wherein 5 to 2.0% is added, the mixture is rotated for 60 to 90 minutes, washed twice with water at 62 to 65 ° C., and drained. , Adhesive resistance, low VOC leather manufacturing process for car seats. Preparation method of the greasing agent absorption promoting material: Starch treated with a standard sieve of 60 mesh or more is added to 80% of the mass of water, stirred and gelatinized at 70 to 80 ° C. for 20 to 40 minutes, and then starch. Add 0.3 to 2% by mass of sodium dodecylbenzenesulfonate and 20 to 40% by mass of phosphorus trichloride to the mass of starch, and react at 40 to 60 ° C. with stirring for 1 to 2 hours. Then, 10 to 20% by mass of oleic acid amide with respect to the mass of starch, 30 to 40% by mass of maleic anhydride with respect to the mass of starch, and 30% by mass of sodium hydroxide were added to adjust the pH to 7. The process for producing leather for car seats, which has flame retardancy, abrasion resistance, adhesive resistance, and low VOC, according to claim 5, wherein the oil is adjusted to 5. to obtain the grease absorption promoting material.