CN116004930B - Manufacturing process of environment-friendly wear-resistant PU (polyurethane) cattle two-layer leather - Google Patents
Manufacturing process of environment-friendly wear-resistant PU (polyurethane) cattle two-layer leather Download PDFInfo
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- CN116004930B CN116004930B CN202310167709.XA CN202310167709A CN116004930B CN 116004930 B CN116004930 B CN 116004930B CN 202310167709 A CN202310167709 A CN 202310167709A CN 116004930 B CN116004930 B CN 116004930B
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- 239000010985 leather Substances 0.000 title claims abstract description 64
- 239000004814 polyurethane Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
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- 229920002635 polyurethane Polymers 0.000 title abstract description 11
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- 238000010438 heat treatment Methods 0.000 claims description 14
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 5
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
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- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
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- 238000007599 discharging Methods 0.000 description 4
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 description 4
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 4
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- FJJMDVGTVROHEL-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl acetate Chemical compound CO[Si](C)(OC)CCCOC(C)=O FJJMDVGTVROHEL-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
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- 238000010521 absorption reaction Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- NATNFHSGWXVQDI-UHFFFAOYSA-N (methoxy-methyl-propylsilyl)oxymethyl acetate Chemical compound CCC[Si](C)(OC)OCOC(C)=O NATNFHSGWXVQDI-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- URJQOOISAKEBKW-UHFFFAOYSA-N Emorfazone Chemical compound C1=NN(C)C(=O)C(OCC)=C1N1CCOCC1 URJQOOISAKEBKW-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention relates to the technical field of leather processing, improves a manufacturing process of environment-friendly wear-resistant PU (polyurethane) two-layer leather, and solves the problems that the existing leather manufacturing process is not environment-friendly, is easy to cause environmental pollution and the manufactured two-layer leather is poor in wear resistance. The method comprises the following steps: (1) rewetting; (2) tanning; (3) neutralization; (4) retanning; (5) dyeing; (6) fatting; (7) post-finishing: the after-finishing comprises the working procedures of squeezing water, stretching, vacuum drying, hanging, vibrating, buffing and coating, wherein the coating working procedure is to coat the PU wear-resistant coating on the surface of crust leather in a spray coating or roller coating mode, and then trimming treatment is carried out to obtain the environment-friendly wear-resistant PU double-layer leather finished product.
Description
Technical Field
The invention relates to the technical field of leather processing, in particular to a manufacturing process of environment-friendly wear-resistant PU (polyurethane) cattle two-layer leather.
Background
The cattle two-layer leather is attractive and fashionable, is cheap and practical, and is very suitable for mass consumers. Tanning and retanning are important procedures of tanning processing, and can be classified into chrome tanning, vegetable tanning, oil tanning, aldehyde tanning and the like according to the tanning method, and the chrome tanning method is dominant in the tanning process due to excellent physical and chemical properties of the chrome tanning. So-called chrome tannage, i.e. the addition of a chrome tanning agent during tanning or retanning, improves the product properties of the leather.
Chinese patent No. CN201711004735.1 discloses a method for producing washable cow leather with two layers, which comprises the following steps: taking a two-layer beef skin blank subjected to processing, squeezing and shaving, and then sequentially carrying out rewetting, primary washing, retanning, neutralization, secondary washing, filling, dyeing, fatliquoring, acid fixing, tertiary washing, fixing, quaternary washing, drying, hanging and airing, vibrating and softening, buffing and breaking. The washable cattle two-layer leather prepared by the method has good washability, and the washable cattle two-layer leather has higher leather yield. The retanning method comprises the following specific steps: according to the mass percentage of the skin blank, 120-150% of water, 0.25-0.35% of formic acid and 2.5-3.5% of chromium oxide are added into a rotary drum, the pH is regulated to 3.5-3.8, the liquid is discharged after 90-120 min is operated, and the water temperature is 24-26 ℃. The method takes chromium oxide as a chrome tanning agent, can not be completely absorbed by skin collagen fibers when being used for retanning, and generates a large amount of chromium-containing waste liquid which can cause serious harm to human beings and the environment if being directly discharged; if the waste is treated before being discharged, the production cost is increased intangibly due to the large treatment difficulty and high cost. Meanwhile, trivalent chromium in the chrome tanning agent can be converted into toxic and harmful hexavalent chromium under certain conditions. Therefore, a novel environment-friendly cattle two-layer leather production process is developed, leather products with excellent comprehensive performance and no chromium dissolution phenomenon are produced, and the novel cattle two-layer leather production process is one of the problems to be solved in the field.
In addition, the ox two-layer leather is mainly close to a net layer of leather and is formed by weaving thick collagen fiber bundles in a three-dimensional space, and the collagen fiber bundles are loosely woven, so that the ox two-layer leather has poor wear resistance and short service life.
In view of the above problems, the present applicant has conducted intensive studies and has proposed the present invention.
Disclosure of Invention
Therefore, aiming at the above, the invention provides a manufacturing process of environment-friendly wear-resistant PU (polyurethane) two-layer leather, which solves the problems that the existing leather manufacturing process is not environment-friendly, is easy to cause environmental pollution and the manufactured two-layer leather is poor in wear resistance.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
the process for manufacturing the environment-friendly wear-resistant PU cattle two-layer leather comprises the following steps of:
(1) Placing blue wet skin in a rotary drum, taking the weight of the blue wet skin as a reference, adding 190-220% of water, 0.45-0.65% of rewetting agent L-CC, 0.6-0.9% of degreasing agent TJ-A124, 0.5-0.8% of formic acid into the rotary drum, running 80-100 min, adding 1.2-1.8% of oxalic acid, 4-8% of modified glutaraldehyde, 0.9-1.5% of softening enzyme TJ-A489, running 120-150 min, then adjusting the pH value to 3.0-3.3, draining liquid and washing with water;
(2) Based on the weight of blue wet skin, 120% water with the water temperature of 33-36 ℃, 2-3% tanning agent HT, 0.8-1.6% protein filler TJ-R957, 0.1-0.2% mildew preventive TJ-A2239, 60-80 min, 5-8% chrome-free tanning agent TWLZ, 20-40 min, 0.4-0.6% formic acid, 30min, pH value adjustment to 3.8-4.0 and liquid discharge are added into a rotary drum;
(3) Based on the weight of blue wet skin, adding 100-150% of water with the water temperature of 28-32 ℃, 1.8-3% of neutralized tannin FAK, 1.2-2% of sodium formate into a rotary drum, running for 20-40 min, adding 0.9-1.5% of sodium bicarbonate, and adjusting the pH value to 5.0-5.5;
(4) Based on the weight of blue wet skin, adding 3-6% of chestnut tannin extract TCR, 3-5% of synthetic white tannin extract TJ-R2330, 1-3% of acrylic polymer TJ-R5520, 1.2-2.5% of dispersed tannin TJ-R369, 2-4% of fatty aldehyde tanning agent CRS09, 1-2% of sulfited fish oil TJ-F283 into a rotary drum, and operating for 90-120 min;
(5) Based on the weight of blue wet skin, 1.5-2.5% of dispersed tannin TJ-R369 and 0.8-2% of dye are added into a rotary drum, 90-120 min is operated, 2-4% of formic acid is added, the formic acid is added in two times, 20-30 min is operated after each addition, and finally liquid is discharged and water is washed;
(6) Based on the weight of blue wet skin, 120-160% of water with the water temperature of 42-48 ℃, 2.8-4.5% of animal fat FOW, 0.9-1.8% of synthetic fatting agent L-28C, 0.8-1.5% of synthetic fatting agent KR-96S, 2-4% of acrylic polymer TJ-R5218, 0.1-0.3% of antistatic agent, running 60-90 min, adding 1.2-2% of formic acid, running 30-50 min, adjusting the pH value to 3.8-4.0, discharging liquid, washing, discharging out of the drum, and standing;
(7) Performing after-finishing on crust leather treated in the step (6), wherein the after-finishing comprises the steps of squeezing water, stretching, vacuum drying, hanging and airing, vibrating and softening, buffing and finishing, and the specific process of the finishing step is as follows: coating PU wear-resistant paint on the surface of crust leather in a spray coating or roller coating mode, and then trimming to obtain an environment-friendly wear-resistant PU two-layer leather finished product.
The further improvement is that: the PU wear-resistant paint is prepared by the following method: firstly, adding a polyol I, a polyol II and an organotin catalyst into a reaction kettle, heating to 50-60 ℃ under the nitrogen atmosphere, adding diphenylmethane diisocyanate and modified talcum powder, heating to 75-85 ℃, and stirring for reacting for 2-4 h; then tartaric acid and diethylene glycol are added for continuous reaction for 1-3 h; cooling to below 40 ℃, regulating the pH value to 7-8, adding water, carrying out emulsification reaction for 0.5-1.5 h, finally adding an auxiliary agent, and uniformly mixing to obtain the PU wear-resistant coating, wherein the polyol I has the following structural formula:
wherein x is an integer of 2 to 6, y is an integer of 2 to 6, z is an integer of 10 to 20, and R is-CH 2 CH 2 CH 2 -。
The further improvement is that: the polyol II is polypropylene oxide ether dihydric alcohol, the functionality is 2, and the molecular weight is 2000-3000.
The further improvement is that: the PU wear-resistant paint is prepared by reacting the following raw materials in parts by weight: 42 to 56 parts of polyol I, 18 to 32 parts of polyol II, 0.05 to 0.2 part of organotin catalyst, 10 to 20 parts of diphenylmethane diisocyanate, 16 to 30 parts of modified talcum powder, 4 to 8 parts of tartaric acid, 2 to 4 parts of diethylene glycol, 100 to 160 parts of water and 0.8 to 2 parts of auxiliary agent.
The further improvement is that: the auxiliary agent is formed by mixing any one or more than two of a leveling agent, a thickening agent and a defoaming agent in any ratio.
The further improvement is that: the modified talcum powder is prepared by the following method: adding nano talcum powder and hexamethylene diisocyanate into toluene solvent, stirring and reacting for 4-6 hours at 65-75 ℃, filtering, washing and drying after the reaction is finished, thus obtaining the modified talcum powder.
The further improvement is that: the mass ratio of the nano talcum powder to the hexamethylene diisocyanate is 1:1.2-1.5.
The further improvement is that: the preparation method of the polyol I comprises the following steps: adding octamethyl cyclotetrasiloxane, propyl methyl dimethoxy silane and acetoxy propyl methyl dimethoxy silane into a container, stirring and mixing uniformly, heating to 90-100 ℃, adding tetramethyl ammonium hydroxide, reacting for 2-4 h, then adding 1, 3-di (3-hydroxypropyl) -1, 3-tetramethyl disiloxane, and continuing to react for 8-15 h to obtain the polyol I.
By adopting the technical scheme, the invention has the beneficial effects that:
1. in the step (1) of the production process provided by the invention, the rewetting agent L-CC, the degreasing agent TJ-A124, the modified glutaraldehyde and the softening enzyme TJ-A489 are compounded for use, so that the leather billet can be endowed with good softness, and the permeation and absorption of various subsequent tanning agents and fatliquoring agents are promoted. In the step (2), the combination of the chromium-free complex tanning agent TWLZ, the protein filler TJ-R957 and the tanning agent HT can endow leather with good fullness and elasticity, gently disperse collagen fibers and improve the permeation uniformity of various reagents; meanwhile, the filling effect on the abdomen and the part between the two bones is obvious, the position difference can be effectively solved, and the leather is endowed with uniform and consistent hand feeling. In the step (3), the addition of the neutralized tannin can gently neutralize leather, promote the penetration of various tanning agents in the subsequent process, and improve the compactness and the fineness of the finished grain surface. The step (4) adopts chromium-free retanning, reduces chromium pollution, reduces waste liquid treatment cost, improves production environment protection, and particularly, adopts the compound of chestnut tannin extract TCR, synthetic Bai Kaojiao TJ-R2330, acrylic polymer TJ-R5520, dispersed tannin TJ-R369, fatty aldehyde tanning agent CRS09 and sulfited fish oil TJ-F283, thereby improving the bonding capability with fibers, endowing leather with excellent softness and fullness, effectively reducing position difference and enabling leather grain surfaces to be flat, thin and compact; the leather is also enabled to have excellent heat resistance and perspiration resistance, and simultaneously the lubricating effect of the collagen fiber is improved. In the step (5), the addition of the dispersed tannin TJ-R369 can promote better dispersion and permeation of the dye, and is favorable for realizing more excellent dispersion and absorption effects in the subsequent fatting process. In the step (6), the animal fat FOW, the synthetic fatting agent L-28C, the synthetic fatting agent KR-96S and the acrylic polymer TJ-R5218 are compounded, so that the stability of the system is improved, the finished leather is plump and soft, and the grain surface of the leather is clean and has high flatness.
2. In order to improve the wear resistance of the two-layer leather, it is common practice to paint polyurethane paint on the leather surface. However, the traditional solvent type polyurethane coating has high content of volatile organic compounds, severely pollutes the environment in the manufacturing and construction processes, and has certain limit on application. The water-based polyurethane coating uses water as a dispersion medium, has the advantages of no toxicity, environmental friendliness and the like, but when the water-based polyurethane coating is used as a coating material, the surface is easy to be physically damaged after the water-based polyurethane coating is subjected to external forces such as friction, collision and the like due to the general wear resistance, so that the coating is damaged, and the service life is greatly shortened. According to the invention, through the optimal design, the synthesized water-based polyurethane coating meets the requirements of environmental protection, and the raw material components generate a synergistic effect, so that the prepared water-based polyurethane coating has excellent performances of wear resistance, adhesive force and the like. Specifically, first, the polyol I and the polyol II react with the diisocyanate to form a prepolymer with a crosslinked network structure, wherein the molecular structure of the polyol I contains acyloxy and siloxane groups, the molecular structure of the polyol II contains ether bonds and epoxy groups, and the specific functional groups are introduced to remarkably improve the wear resistance, the impact resistance and the like of the coating. Then tartaric acid is used as a chain extender, diethylene glycol is used as a cross-linking agent, and the cross-linking density of the system is further improved through the combination of the tartaric acid and the diethylene glycol, so that the wear resistance of the coating is improved. The nano talcum powder has large surface area, high surface energy and high chemical activity, is easy to aggregate to reach a stable state, and has poor compatibility with an organic phase, so that the due performance is difficult to fully play. According to the invention, nano talcum powder is modified, a-NCO group in a hexamethylene diisocyanate molecular structure is utilized to react with hydroxyl on the surface of talcum powder, high-activity isocyanate is introduced on the surface of nano talcum powder, and then the nano talcum powder reacts with polyol I and polyol II, so that the dispersibility in a system and the compatibility with other organic polymers are improved, and the prepared aqueous polyurethane emulsion has good stability. The modification of talcum powder is also helpful for the exertion of nanometer effect, and improves the mechanical property and heat resistance of the coating film.
In conclusion, the raw material components or operation parameters adopted in each link of the tanning process are adjusted and optimized, and the crust leather is coated with the specific aqueous polyurethane coating, so that the finished leather prepared by the method has excellent comprehensive performance, the production is improved to be environment-friendly, and the discharged waste liquid has little pollution to the environment.
Detailed Description
The following describes embodiments of the present invention in detail with reference to specific examples, so as to solve the technical problem by applying the technical means to the present invention, and the implementation process for achieving the technical effect can be fully understood and implemented accordingly.
Unless otherwise indicated, the technical means employed in the examples are conventional means well known to those skilled in the art, and the reagents and products employed are also commercially available. The sources of the reagents used, the trade names and the members of the list of constituents which are necessary are all indicated at the first occurrence.
Example 1
The process for manufacturing the environment-friendly wear-resistant PU cattle two-layer leather comprises the following steps of:
(1) Placing blue wet skin in a rotary drum, adding 190% of water, 0.45% of rewetting agent L-CC (manufactured by Lin Rui New Material Co., ltd.), 0.6% of degreasing agent TJ-A124 (manufactured by Guangdong Demei fine chemical Co., ltd., hereinafter abbreviated as Demei fine chemical), 0.5% of formic acid, running 80min, adding 1.2% of oxalic acid, 4% of modified glutaraldehyde (manufactured by Wuhan Ji Ye L chemical Co., ltd.), 0.9% of softening enzyme TJ-A489 (manufactured by Demei fine chemical Co., ltd.), running 120min, then adjusting pH value to 3.0-3.3, draining and washing with water;
(2) Based on the weight of blue wet skin, 120% water with the water temperature of 33 ℃, 2% tanning agent HT (Demei fine chemical production), 0.8% protein filler TJ-R957 (Demei fine chemical production), 0.1% mildew preventive TJ-A2239 (Demei fine chemical production), 60 min, then 5% chrome-free tanning agent TWLZ (Demei fine chemical production), 20min, 0.4% formic acid, 30min, pH value adjustment to 3.8-4.0 and liquid discharge are added into a rotary drum;
(3) Based on the weight of blue wet skin, adding 100% water with water temperature of 28 ℃, 1.8% neutralized tannin FAK (produced by Beijing Panbo chemistry Co., ltd.), 1.2% sodium formate, running for 20min, adding 0.9% sodium bicarbonate, and adjusting pH to 5.0-5.5;
(4) Based on the weight of blue wet skin, adding 3% of chestnut tannin extract TCR (Demei fine chemical production), 3% of synthetic white tannin extract TJ-R2330 (Demei fine chemical production), 1% of acrylic polymer TJ-R5520 (Demei fine chemical production), 1.2% of dispersed tannin TJ-R369 (Demei fine chemical production), 2% of fatty aldehyde tanning agent CRS09 (Sichuan da Wired technology Co., ltd.), 1% of sulfited fish oil TJ-F283 (Demei fine chemical production) into a rotary drum, and operating for 90 min;
(5) Based on the weight of blue wet skin, 1.5% of dispersed tannin TJ-R369 (produced by Demei fine chemical industry) and 0.8% of dye are added into a rotary drum, 90min is operated, 2% of formic acid is added, the formic acid is added in two times, 20min is operated after each addition, and finally liquid is discharged and water is washed;
(6) Based on the weight of blue wet skin, 120% water with the water temperature of 42 ℃, 2.8% animal fat FOW (manufactured by Nandron chemical Co., ltd.), 0.9% synthetic fatting agent L-28C (manufactured by Lin Rui New Material Co., ltd.), 0.8% synthetic fatting agent KR-96S (manufactured by Qingdao Kogyo biological technology Co., ltd.), 2% acrylic polymer TJ-R5218 (manufactured by Demei fine chemical Co., ltd.), 0.1% antistatic agent, running 60 min, further adding 1.2% formic acid, running 30min, adjusting the pH value to 3.8-4.0, discharging liquid, washing with water, discharging out of the drum, and standing;
(7) Performing after-finishing on crust leather treated in the step (6), wherein the after-finishing comprises the steps of squeezing water, stretching, vacuum drying, hanging and airing, vibrating and softening, buffing and finishing, and the specific process of the finishing step is as follows: coating PU wear-resistant paint on the surface of crust leather in a spray coating or roller coating mode, and then trimming to obtain an environment-friendly wear-resistant PU cattle two-layer leather finished product, wherein the PU wear-resistant paint is prepared by reacting the following raw materials in parts by weight: 42 parts of polyol I, 18 parts of polypropylene oxide ether dihydric alcohol (with the functionality of 2 and the molecular weight of 2000), 0.05 part of dibutyl tin dilaurate, 10 parts of diphenylmethane diisocyanate, 16 parts of modified talcum powder, 4 parts of tartaric acid, 2 parts of diethylene glycol, 100 parts of water and 0.8 part of flatting agent, wherein the polyol I has the following structural formula:
wherein x is an integer of 2 to 6, y is an integer of 2 to 6, z is an integer of 10 to 20, and R is-CH 2 CH 2 CH 2 -. The preparation method of the polyol I comprises the following steps: adding octamethyl cyclotetrasiloxane, propyl methyl dimethoxy silane and acetoxypropyl methyl dimethoxy silane into a container, stirring and mixing uniformly, heating to 90 ℃, adding tetramethyl ammonium hydroxide, reacting for 2 hours, then adding 1, 3-bis (3-hydroxypropyl) -1, 3-tetramethyl disiloxane, and continuing to react for 15 hours to obtain the polyol I.
The PU wear-resistant paint is prepared by the following method: firstly, adding a polyol I, polypropylene oxide ether dihydric alcohol and dibutyl tin dilaurate into a reaction kettle, heating to 50 ℃ under the nitrogen atmosphere, adding diphenylmethane diisocyanate and modified talcum powder, heating to 75 ℃, and stirring for reaction for 4 hours; then tartaric acid and diethylene glycol are added for continuous reaction for 1h; cooling to below 40 ℃, regulating the pH value to 7-8, adding water, and carrying out emulsification reaction for 0.5h to obtain aqueous polyurethane emulsion; and finally adding a leveling agent, and uniformly mixing to obtain the PU wear-resistant coating.
Wherein the modified talcum powder is prepared by the following method: adding nano talcum powder and hexamethylene diisocyanate into toluene solvent according to the mass ratio of 1:1.2, stirring and reacting for 6 hours at 65 ℃, and filtering, washing and drying after the reaction is finished to obtain the modified talcum powder.
Example 2
The process for manufacturing the environment-friendly wear-resistant PU cattle two-layer leather comprises the following steps of:
(1) Placing blue wet skin in a rotary drum, adding 200% of water, 0.55% of rewetting agent L-CC, 0.75% of degreasing agent TJ-A124 and 0.65% of formic acid into the rotary drum based on the weight of the blue wet skin, running 90min, adding 1.5% of oxalic acid, 6% of modified glutaraldehyde and 1.2% of softening enzyme TJ-A489, running 135 min, adjusting the pH value to 3.0-3.3, draining liquid and washing with water;
(2) Based on the weight of blue wet skin, 120% water with the water temperature of 35 ℃, 2.5% tanning agent HT, 1.2% protein filler TJ-R957 and 0.15% mildew preventive TJ-A2239 are added into a rotary drum, 70 min is operated, then 6% chrome-free tanning agent TWLZ is added, 30min is operated, 0.5% formic acid is added, 30min is operated, the pH value is adjusted to 3.8-4.0, and liquid is discharged;
(3) Based on the weight of blue wet skin, adding 120% water with water temperature of 30 ℃, 2.4% neutralized tannin FAK and 1.6% sodium formate into a rotary drum, running for 30min, adding 1.2% sodium bicarbonate, and adjusting the pH value to 5.0-5.5;
(4) Based on the weight of blue wet skin, adding 5% of chestnut tannin extract TCR, 4% of synthetic tannin extract TJ-R2330, 2% of acrylic polymer TJ-R5520, 1.8% of dispersed tannin TJ-R369, 3% of fatty aldehyde tanning agent CRS09 and 1.5% of sulfited fish oil TJ-F283 into a rotary drum, and running for 100 min;
(5) Based on the weight of blue wet skin, adding 2% dispersed tannin TJ-R369 and 1.5% dye into a rotary drum, running for 100min, adding 3% formic acid, running for 25 min after each addition, and finally draining and washing;
(6) Based on the weight of blue wet skin, 140% of water with the water temperature of 45 ℃, 3.6% of animal fat FOW, 1.4% of synthetic fatting agent L-28C, 1.2% of synthetic fatting agent KR-96S, 3% of acrylic polymer TJ-R5218 and 0.2% of antistatic agent are added into a rotary drum, 75 min of formic acid is added, 40min of formic acid is added, the pH value is adjusted to 3.8-4.0, and the rotary drum is discharged after liquid discharge and water washing and is left;
(7) Performing after-finishing on crust leather treated in the step (6), wherein the after-finishing comprises the steps of squeezing water, stretching, vacuum drying, hanging and airing, vibrating and softening, buffing and finishing, and the specific process of the finishing step is as follows: coating PU wear-resistant paint on the surface of crust leather in a spray coating or roller coating mode, and then trimming to obtain an environment-friendly wear-resistant PU cattle two-layer leather finished product, wherein the PU wear-resistant paint is prepared by reacting the following raw materials in parts by weight: 50 parts of polyol I, 25 parts of polypropylene oxide ether dihydric alcohol (with the functionality of 2 and the molecular weight of 2000), 0.12 part of dibutyl tin dilaurate, 15 parts of diphenylmethane diisocyanate, 24 parts of modified talcum powder, 6 parts of tartaric acid, 3 parts of diethylene glycol, 130 parts of water, 0.9 part of flatting agent and 0.5 part of defoamer, wherein the polyol I has the following structural formula:
wherein x is an integer of 2 to 6, y is an integer of 2 to 6, z is an integer of 10 to 20, and R is-CH 2 CH 2 CH 2 -. The preparation method of the polyol I comprises the following steps: adding octamethyl cyclotetrasiloxane, propyl methyl dimethoxy silane and acetoxypropyl methyl dimethoxy silane into a container, stirring and mixing uniformly, heating to 95 ℃, adding tetramethyl ammonium hydroxide, reacting for 3 hours, then adding 1, 3-bis (3-hydroxypropyl) -1, 3-tetramethyl disiloxane, and continuing to react for 12 hours to obtain the polyol I.
The PU wear-resistant paint is prepared by the following method: firstly, adding a polyol I, polypropylene oxide ether dihydric alcohol and dibutyl tin dilaurate into a reaction kettle, heating to 55 ℃ under the nitrogen atmosphere, adding diphenylmethane diisocyanate and modified talcum powder, heating to 80 ℃, and stirring for reaction for 3 hours; then tartaric acid and diethylene glycol are added for continuous reaction for 2 hours; cooling to below 40 ℃, regulating the pH value to 7-8, adding water, and performing emulsification reaction for 1h to obtain aqueous polyurethane emulsion; and finally, adding a leveling agent and a defoaming agent, and uniformly mixing to obtain the PU wear-resistant coating.
Wherein the modified talcum powder is prepared by the following method: adding nano talcum powder and hexamethylene diisocyanate into toluene solvent according to the mass ratio of 1:1.35, stirring and reacting for 5 hours at 70 ℃, and filtering, washing and drying after the reaction is finished to obtain the modified talcum powder.
Example 3
The process for manufacturing the environment-friendly wear-resistant PU cattle two-layer leather comprises the following steps of:
(1) Placing blue wet skin in a rotary drum, adding 220% of water, 0.65% of rewetting agent L-CC, 0.9% of degreasing agent TJ-A124 and 0.8% of formic acid into the rotary drum based on the weight of the blue wet skin, running 100min, adding 1.8% of oxalic acid, 8% of modified glutaraldehyde and 1.5% of softening enzyme TJ-A489, running 150min, adjusting the pH value to 3.0-3.3, draining liquid and washing with water;
(2) Based on the weight of blue wet skin, 120% of water with the water temperature of 36 ℃, 3% of tanning agent HT, 1.6% of protein filler TJ-R957 and 0.2% of mildew inhibitor TJ-A2239 are added into a rotary drum, 80min is operated, then 8% of chrome-free tanning agent TWLZ is added, 40min is operated, 0.6% of formic acid is added, 30min is operated, the pH value is adjusted to 3.8-4.0, and liquid is discharged;
(3) Based on the weight of blue wet skin, 150% water with the water temperature of 32 ℃, 3% neutralized tannin FAK and 2% sodium formate are added into a rotary drum, the operation is 40min, and then 1.5% sodium bicarbonate is added, so that the pH value is adjusted to 5.0-5.5;
(4) Based on the weight of blue wet skin, adding 6% of chestnut tannin extract TCR, 5% of synthetic tannin extract TJ-R2330, 3% of acrylic polymer TJ-R5520, 2.5% of dispersed tannin TJ-R369, 4% of fatty aldehyde tanning agent CRS09 and 2% of sulfited fish oil TJ-F283 into a rotary drum, and running for 120min;
(5) Based on the weight of blue wet skin, adding 2.5% of dispersed tannin TJ-R369 and 2% of dye into a rotary drum, running for 120min, adding 4% of formic acid, running for 30min after each addition, and finally draining liquid and washing with water;
(6) Based on the weight of blue wet skin, 160% of water with the water temperature of 48 ℃, 4.5% of animal fat FOW, 1.8% of synthetic fatting agent L-28C, 1.5% of synthetic fatting agent KR-96S, 4% of acrylic polymer TJ-R5218 and 0.3% of antistatic agent are added into a rotary drum, 90min is operated, 2% of formic acid is added, 50min is operated, the pH value is adjusted to 3.8-4.0, and the liquid is discharged and washed out of the drum for standing;
(7) Performing after-finishing on crust leather treated in the step (6), wherein the after-finishing comprises the steps of squeezing water, stretching, vacuum drying, hanging and airing, vibrating and softening, buffing and finishing, and the specific process of the finishing step is as follows: coating PU wear-resistant paint on the surface of crust leather in a spray coating or roller coating mode, and then trimming to obtain an environment-friendly wear-resistant PU cattle two-layer leather finished product, wherein the PU wear-resistant paint is prepared by reacting the following raw materials in parts by weight: 56 parts of polyol I, 32 parts of polypropylene oxide ether dihydric alcohol (with the functionality of 2 and the molecular weight of 3000), 0.2 part of dibutyl tin dilaurate, 20 parts of diphenylmethane diisocyanate, 30 parts of modified talcum powder, 8 parts of tartaric acid, 4 parts of diethylene glycol, 160 parts of water, 0.8 part of flatting agent, 0.8 part of thickening agent and 0.4 part of defoaming agent, wherein the polyol I has the following structural formula:
wherein x is an integer of 2 to 6, y is an integer of 2 to 6, z is an integer of 10 to 20, and R is-CH 2 CH 2 CH 2 -. The preparation method of the polyol I comprises the following steps: adding octamethyl cyclotetrasiloxane, propyl methyl dimethoxy silane and acetoxypropyl methyl dimethoxy silane into a container, stirring and mixing uniformly, heating to 100 ℃, adding tetramethyl ammonium hydroxide, reacting for 4 hours, then adding 1, 3-bis (3-hydroxypropyl) -1, 3-tetramethyl disiloxane, and continuing to react for 8 hours to obtain the polyol I.
The PU wear-resistant paint is prepared by the following method: firstly, adding a polyol I, polypropylene oxide ether dihydric alcohol and dibutyl tin dilaurate into a reaction kettle, heating to 60 ℃ under the nitrogen atmosphere, adding diphenylmethane diisocyanate and modified talcum powder, heating to 85 ℃, and stirring for reaction for 2 hours; then tartaric acid and diethylene glycol are added for continuous reaction for 3 hours; cooling to below 40 ℃, regulating the pH value to 7-8, adding water, and carrying out emulsification reaction for 1.5h to obtain aqueous polyurethane emulsion; and finally, adding a leveling agent, a thickening agent and a defoaming agent, and uniformly mixing to obtain the PU wear-resistant coating.
Wherein the modified talcum powder is prepared by the following method: adding nano talcum powder and hexamethylene diisocyanate into toluene solvent according to the mass ratio of 1:1.5, stirring and reacting for 4 hours at 75 ℃, and filtering, washing and drying after the reaction is finished to obtain the modified talcum powder.
Comparative example 1
The PU abrasion-resistant paint differs from example 1 in that: the polypropylene oxide ether glycol was replaced with polyether polyol PTMG-2000, and the other components and the contents thereof were the same as those in example 1.
Comparative example 2
The PU abrasion-resistant paint differs from example 1 in that: polyol I was replaced with polycarbonate diol, and the other components and the contents thereof were the same as in example 1.
Comparative example 3
The PU abrasion-resistant paint differs from example 1 in that: the nano talcum powder is not modified, nano talcum powder and hexamethylene diisocyanate are directly added, and other components and the content thereof are the same as those in the example 1.
Comparative example 4
The PU abrasion-resistant paint differs from example 1 in that: the tartaric acid was replaced with 1, 4-butanediol, and the other components and their contents were the same as in example 1.
Comparative example 5
The PU abrasion-resistant paint differs from example 1 in that: diethylene glycol was replaced with trimethylolpropane and the other components and their contents were the same as in example 1.
The PU abrasion-resistant coatings prepared in examples 1 to 3 were coated on the surface of a substrate to form a paint film (thickness: 25.+ -. 2 μm), the performances of the paint film were examined in various aspects, and the stability of the aqueous polyurethane emulsion obtained was also examined, and the results of the examination are shown in Table 1. Wherein, the emulsion stability is tested according to GB/T6753.3-1986, the specific condition is that the emulsion is stored for 6 months in natural environment, and whether sedimentation, delamination and the like occur or not is observed. The abrasion resistance (mass loss) of the paint film was tested according to GB/T1768-2006; the hardness of the paint film is determined according to GB/T6739-2006; the adhesion of the paint films was determined according to GB/T9286-1998.
TABLE 1
The above description is illustrative of the embodiments using the present teachings, and is not intended to limit the scope of the present teachings to any particular modification or variation of the present teachings by those skilled in the art.
Claims (7)
1. The manufacturing process of the environment-friendly wear-resistant PU cattle two-layer leather is characterized by comprising the following steps of: the method comprises the following steps:
(1) Placing blue wet skin in a rotary drum, taking the weight of the blue wet skin as a reference, adding 190-220% of water, 0.45-0.65% of rewetting agent L-CC, 0.6-0.9% of degreasing agent TJ-A124 and 0.5-0.8% of formic acid into the rotary drum, running for 80-100 min, adding 1.2-1.8% of oxalic acid, 4-8% of modified glutaraldehyde and 0.9-1.5% of softening enzyme TJ-A489, running for 120-150 min, then adjusting the pH value to 3.0-3.3, draining and washing;
(2) Based on the weight of blue wet skin, 120% water with the water temperature of 33-36 ℃, 2-3% tanning agent HT, 0.8-1.6% protein filler TJ-R957, 0.1-0.2% mildew preventive TJ-A2239, running for 60-80 min, then 5-8% chrome-free tanning agent TWLZ, running for 20-40 min, then 0.4-0.6% formic acid, running for 30min, adjusting the pH value to 3.8-4.0, and draining;
(3) Based on the weight of blue wet skin, adding 100-150% of water with the water temperature of 28-32 ℃, 1.8-3% of neutralized tannin FAK, 1.2-2% of sodium formate into a rotary drum, running for 20-40 min, adding 0.9-1.5% of sodium bicarbonate, and adjusting the pH value to 5.0-5.5;
(4) Based on the weight of blue wet skin, adding 3-6% of chestnut tannin extract TCR, 3-5% of synthetic white tannin extract TJ-R2330, 1-3% of acrylic polymer TJ-R5520, 1.2-2.5% of dispersed tannin TJ-R369, 2-4% of fatty aldehyde tanning agent CRS09 and 1-2% of sulfited fish oil TJ-F283 into a rotary drum, and running for 90-120 min;
(5) Based on the weight of blue wet skin, 1.5-2.5% of dispersed tannin TJ-R369 and 0.8-2% of dye are added into a rotary drum, the operation is carried out for 90-120 min, 2-4% of formic acid is added, the formic acid is added in two times, the operation is carried out for 20-30 min after each addition, and finally liquid draining and water washing are carried out;
(6) Based on the weight of blue wet skin, 120-160% of water with the water temperature of 42-48 ℃, 2.8-4.5% of animal fat FOW, 0.9-1.8% of synthetic fatting agent L-28C, 0.8-1.5% of synthetic fatting agent KR-96S, 2-4% of acrylic polymer TJ-R5218 and 0.1-0.3% of antistatic agent are added into a rotary drum, the rotary drum is operated for 60-90 min, then 1.2-2% of formic acid is added, the rotary drum is operated for 30-50 min, the pH value is adjusted to 3.8-4.0, and the rotary drum is discharged after liquid discharge and water washing and is placed still;
(7) Performing after-finishing on crust leather treated in the step (6), wherein the after-finishing comprises the steps of squeezing water, stretching, vacuum drying, hanging and airing, vibrating and softening, buffing and finishing, and the specific process of the finishing step is as follows: coating PU wear-resistant paint on the surface of crust leather in a spray coating or roller coating mode, and then trimming to obtain an environment-friendly wear-resistant PU two-layer leather finished product.
2. The process for manufacturing the environment-friendly wear-resistant PU two-layer leather according to claim 1, which is characterized in that: the PU wear-resistant paint is prepared by the following method: firstly, adding a polyol I, a polyol II and an organotin catalyst into a reaction kettle, heating to 50-60 ℃ under the nitrogen atmosphere, adding diphenylmethane diisocyanate and modified talcum powder, continuously heating to 75-85 ℃, and stirring for reaction for 2-4 h; then tartaric acid and diethylene glycol are added for continuous reaction for 1-3 h; cooling to below 40 ℃, regulating the pH value to 7-8, adding water, carrying out emulsification reaction for 0.5-1.5 h, finally adding an auxiliary agent, and uniformly mixing to obtain the PU wear-resistant coating, wherein the polyol I has the following structural formula:
wherein x is an integer of 2 to 6, y is an integer of 2 to 6, z is an integer of 10 to 20, and R is-CH 2 CH 2 CH 2 -。
3. The process for manufacturing the environment-friendly wear-resistant PU two-layer leather as claimed in claim 2, which is characterized in that: the polyol II is polypropylene oxide ether dihydric alcohol, the functionality is 2, and the molecular weight is 2000-3000.
4. The process for manufacturing the environment-friendly wear-resistant PU two-layer leather as claimed in claim 2, which is characterized in that: the PU wear-resistant paint is prepared by reacting the following raw materials in parts by weight: 42 to 56 parts of polyol I, 18 to 32 parts of polyol II, 0.05 to 0.2 part of organotin catalyst, 10 to 20 parts of diphenylmethane diisocyanate, 16 to 30 parts of modified talcum powder, 4 to 8 parts of tartaric acid, 2 to 4 parts of diethylene glycol, 100 to 160 parts of water and 0.8 to 2 parts of auxiliary agent.
5. The process for manufacturing the environment-friendly wear-resistant PU two-layer leather as claimed in claim 4, which is characterized in that: the auxiliary agent is formed by mixing any one or more than two of a leveling agent, a thickening agent and a defoaming agent in any ratio.
6. The process for manufacturing the environment-friendly wear-resistant PU two-layer leather as claimed in claim 2, which is characterized in that: the modified talcum powder is prepared by the following method: adding nano talcum powder and hexamethylene diisocyanate into toluene solvent, stirring and reacting for 4-6 hours at 65-75 ℃, filtering, washing and drying after the reaction is finished, thus obtaining the modified talcum powder.
7. The process for manufacturing the environment-friendly wear-resistant PU two-layer leather as claimed in claim 6, which is characterized in that: the mass ratio of the nano talcum powder to the hexamethylene diisocyanate is 1:1.2-1.5.
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| WO2017153505A1 (en) * | 2016-03-10 | 2017-09-14 | Holupelli Consult Gmbh | Method for finishing leather |
| CN107502685A (en) * | 2017-10-25 | 2017-12-22 | 漳州香洲皮革有限公司 | The preparation method of water-fastness cow split leather |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017153505A1 (en) * | 2016-03-10 | 2017-09-14 | Holupelli Consult Gmbh | Method for finishing leather |
| CN107502685A (en) * | 2017-10-25 | 2017-12-22 | 漳州香洲皮革有限公司 | The preparation method of water-fastness cow split leather |
| CN110938716A (en) * | 2019-12-13 | 2020-03-31 | 漳州香洲皮革有限公司 | Method for manufacturing cow double-layer waterproof leather |
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