CN101463397B - Method for manufacturing chromium-free tanning environment protection pigskin shoes - Google Patents
Method for manufacturing chromium-free tanning environment protection pigskin shoes Download PDFInfo
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- CN101463397B CN101463397B CN2009100366337A CN200910036633A CN101463397B CN 101463397 B CN101463397 B CN 101463397B CN 2009100366337 A CN2009100366337 A CN 2009100366337A CN 200910036633 A CN200910036633 A CN 200910036633A CN 101463397 B CN101463397 B CN 101463397B
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- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000005554 pickling Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 34
- 230000001105 regulatory effect Effects 0.000 claims description 26
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 17
- 235000019253 formic acid Nutrition 0.000 claims description 17
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- AKXUUJCMWZFYMV-UHFFFAOYSA-M tetrakis(hydroxymethyl)phosphanium;chloride Chemical compound [Cl-].OC[P+](CO)(CO)CO AKXUUJCMWZFYMV-UHFFFAOYSA-M 0.000 claims description 6
- 235000018553 tannin Nutrition 0.000 claims description 4
- 229920001864 tannin Polymers 0.000 claims description 4
- 239000001648 tannin Substances 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 210000003746 feather Anatomy 0.000 claims description 3
- 239000004519 grease Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims 1
- 239000010985 leather Substances 0.000 abstract description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 11
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract description 2
- 239000010977 jade Substances 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention provides a method for manufacturing chrome-free tanning environment-friendly pigskin shoe inner leather. The method adopts an organophosphorus salt chrome-free tanning agent, and during the process of producing environment-friendly chrome-free tanning pigskin, the method comprises the steps as follows: softening, pickling, primary tanning, remoistening, oxidizing, neutralizing, tanning again and removing aldehyde. Pigskin leather produced by the method has white leather which is as white as polished jade and color leather which is brighter and more colorful; finished leather has good flame retardancy, noncorrosibility and very high tensile strength and tearing strength; the finished leather has good natural degradability and does not cause pollution to the environment; and the finished leather and waste material can not produce hexavalent chrome toxicity and the problem of formaldehyde pollution.
Description
[technical field]
The present invention relates to the leather tanning field, relate in particular to a kind of environmental protection chrome-free tanning lining leather of pigskin shoes.
[background technology]
Curriery is the important traditional light industry industry of China; It also is one of comparatively serious industry of blowdown; Have more than 100 year historical traditional chromic tanning at present and remain the main process for tanning of China's curriery; But environmental protection, the health perception of Along with people's progressively strengthen, and material such as sexavalent chrome and formaldehyde has caused society and the increasing concern of the public to the harm that human body and environment caused in the chromic tanning.And, successively formulated multinomial technology barriers in recent years to sexavalent chrome and formaldehyde and total chrome content as European Union of one of main trade partners of China.How to reduce the pollution and the discharging of chromium, become the significant problem of current leather technology circle.
As far back as the eighties in 20th century, experts and scholars have just done unremitting effort in the research aspect the Chrome-free leather tanning both at home and abroad, have developed a series of no chromic tannings.Like iron tannage, zirconium tanning, aluminum tanning, aldehyde tannage, organic synthesis multiple tannage such as tan.But still there are some defectives in above-mentioned technology, for example: can not biodegrade; Environment is produced pollution, and the white leather whiteness that chromic tanning produces is not enough, and color is low and deep partially; And the colored leather color of tanning is vivid inadequately attractive in appearance; The tradition chromic tanning can produce trivalent chromium, and the trivalent chromium instability can be converted into sexavalent chrome, and human body and environment are all caused very big potentially dangerous.We can say that present chrome-free tanning technology still is not mature enough and perfect, and advanced technology promote product performance and quality more than needing badly more.
[summary of the invention]
For the technical problem that solves present existence the method that a kind of production environmental protection does not have the chrome tanning pigskin has been proposed; The chrome-free tanning agent main component that the present invention adopts is a THP salt; Its chemical formula is that the concrete steps of
said method are following: wherein raw materials used metering by weight
(1) softening: the pelt note with after expanding heavily is 100; Pelt after will losing hair or feathers earlier carries out skimming treatment; Softening process determines whether needs degreasing once more according to the grease situation that contains of pelt, and its pH value of softening process is controlled at 7.0-7.5, and temperature is controlled at 36 ℃-38 ℃; The softening time generally was controlled at 6-8 hour, carried out water-washing step then;
(2) pickling: add 80-100 part normal-temperature water and 8-10 part Industrial Salt, rotated 3-7 minute, with the vitriol oil of 0.9-1.3 part and the formic acid dipping pelt of 0.4-0.6 part, its PH is 2.6-3.2, and temperature is controlled at 20 ℃-28 ℃, and the operation required time is 2.5-3 hour.
(3) main tanning: in pickling solution, add grease-removing agent, its deal is 0.8-1.0 part, and pH value is 3.0, rotated 20-40 minute, and the sodium bicarbonate that adds 0.3-0.5 part again, regulating pH value is 3.5, rotates 20-40 minute; The synthetic tanning agent that adds the acidproof fatting agent of 0.6-1.0 part and 2.0-4.0 part, regulating pH value is 3.6, rotates 20-40 minute, adds 3.5-5.0 part organophosphorated salt chrome-free tanning agent (THPC), regulating pH value is 3.5, rotates 120-180 minute; Dividing the sodium bicarbonate that adds 0.2-0.3 part respectively 6-8 time, rotated 20 minutes at every turn, is 4.3 up to regulating pH value at last; Rotated again 120-180 minute, and stopped drum and spend the night, look into Ts (shrinkage temperature)＞77 ℃ next day; Go out drum and take horse, water squeezing shaving, weigh (as the foundation of following operation materials);
(4) return wet: add the water of 30 ℃-40 ℃ of 200-300 parts, handle with grease-removing agent of 0.5-0.7 part and the formic acid mixtures of 0.3-0.5 part, the adjusting pH value is 3.4-3.8, draining wash water 4-6 minute;
(5) oxidation: add the water of 30 ℃-40 ℃ of 200-300 parts, the industrial ydrogen peroxide 50 of 1.8-2.2 part, regulating pH value is 3.6, rotates draining wash water 10 minutes 40-50 minute;
(6) neutralization: add the water of 30 ℃-40 ℃ of 200-250 parts, with bicarbonate of ammonia of 1.5-2.5 part and the sodium formiate of 1.5-2.5 part, regulating pH value is 5.5, rotates draining wash water 5 minutes 40-80 minute;
(7) retanning: add 25 ℃ of-35 ℃ of water of 80-120 part, the white tannin of 4.0-8.0 part, regulating pH value is 5.5; Rotated 50-70 minute, and added 6.0-8.0 part fatting agent of anti-the xanthochromia again, rotated 50-70 minute; Adding formic acid adjusting pH value at last is 3.8; The component that adds formic acid is 1.0-2.0 part, and the time 15-35 of rotation minute, the draining wash water was 5 minutes then.
(8) full gear: add 30 ℃ of-50 ℃ of warm water 200-300 parts, formic acid 0.5-0.7 part, regulating pH value is 3.2, rotates 5 minutes, adds the formaldehyde-trapping agent of 1.5-3.0 part; The pH value of this moment reaches 4.2 naturally, rotates 30-50 minute, adds 0.4-0.6 part formic acid, and regulating pH value is 3.6; Rotated 10 minutes, draining wash water 3-5 time was respectively 5 minutes at every turn, went out drum; Extension dries in the air, shake soft, toggling, gage.
Adopting the leather of THP salt tanning among the present invention is white, and dyestuff is had good dissemination, can make the white leather whiter; Colored leather is bright-coloured more beautiful, and finished leather can be degraded, and therefore is considered to the tanning material of tool potentiality in this century; With the leather of the independent tanning of THP salt, its shrinkage temperature can reach more than 80 ℃, and tensile strength reaches 18MPa; Tear strength reaches more than the 135N/mm, and has fire-retardant, anticorrosion; Characteristics such as low pollutions, if be used in combination with tannin extract then shrinkage temperature can reach more than 95 ℃, so this product is by the acceptance of increasing tannery.
Compare with traditional chrome tanning agent; The leather of producing with organophosphorated salt chrome-free tanning agent (THPC) has following characteristic: the white leather of production is as white as polished jade; The colour leather of producing is bright-coloured more beautiful, and finished leather has excellent flame-retardant performance, preservative property and very high tensile strength, tearing toughness, and finished leather has good natural degradation property; Can not pollute environment, finished leather and waste material can not produce sexavalent chrome toxicity and formaldehyde pollution problems.
[embodiment]
In order to further specify the concrete technological process of the present invention; Preferred embodiment is proposed; Unintelligible is qualification to protection scope of the present invention; For adjustment that does not exceed technical scheme of the present invention and the change that the engineering personnel in this field do according to present embodiment, should think and drop in protection scope of the present invention.
The chrome-free tanning agent staple that the present invention adopts is organophosphorated salt (THPC), and its chemical formula is:
The concrete steps of said technology are following: the wherein raw materials used component umber of pressing measures,
Embodiment 1:
(1) softening: the pelt note with after expanding heavily is 100; Pelt after will losing hair or feathers earlier carries out skimming treatment; Softening process determines whether needs degreasing once more according to the grease situation that contains of pelt, and its pH value of softening process is controlled at 7.0-7.5, and this moment, temperature was controlled at 36 ℃-38 ℃; The softening time generally was controlled at 6-8 hour, carried out water-washing step then;
(2) pickling: add 90 parts of normal-temperature water and 9 parts of Industrial Salts, rotated 5 minutes, with the formic acid dipping pelt of 1.1 parts the vitriol oils and 0.5 part, its PH is 2.6-3.2, and temperature is controlled at 20 ℃-28 ℃, and the operation required time is 2.5-3 hour;
(3) main tanning: in pickling solution, add grease-removing agent, its deal is 1.0 parts, and regulating pH value is 3.0, rotates 30 minutes, adds 0.4 part sodium bicarbonate again, and regulating pH value is 3.5, rotates 30 minutes; The synthetic tanning agent that adds 0.6 part of acidproof fatting agent and 2.0 parts, regulating pH value is 3.6, rotates 30 minutes, adds 4.0 parts of organophosphorated salt chrome-free tanning agents (THPC), the adjusting pH value is 3.5, rotates 150 minutes; Dividing the sodium bicarbonate that adds 0.3 part for 6 times respectively, rotated 20 minutes at every turn, is 4.3 up to regulating pH value at last, rotates 150 minutes again, stops drum and spends the night, and looks into Ts (shrinkage temperature)＞77 ℃ next day, goes out drum and takes horse, water squeezing shaving, weigh (as following operation materials foundation);
(4) return wet: adds 250 parts 35 ℃ water, handle with the formic acid mixtures of 0.6 part grease-removing agent and 0.4 part, the adjusting pH value is 3.6, draining wash water 5 minutes;
(5) oxidation: add 150 parts 35 ℃ water, 2.0 parts of industrial ydrogen peroxide 50, regulating pH value is 3.6, rotates draining wash water 15 minutes 45 minutes;
(6) neutralization: adds 200 parts 35 ℃ water, with the sodium formiate of 2.0 parts bicarbonate of ammonia and 2.0 parts, the adjusting pH value is 5.5, rotates draining wash water 5-8 minute 60 minutes;
(7) retanning: add 100 parts of 30 ℃ of water, 6.0 parts of white tannin, regulating pH value is 5.5; Rotated 60 minutes, and added 5.0 parts of fatting agents of anti-the xanthochromia again, rotated 60 minutes; Adding formic acid adjusting pH value at last is 3.8; The component that adds formic acid is 1.5 parts, the 20 minutes time of rotation, draining wash water 5-8 minute then;
(8) full gear: add 250 parts in 40 ℃ of warm water, 0.6 part in formic acid, regulating pH value is 3.2, rotates 5 minutes, adds 2.5 parts formaldehyde-trapping agent; This moment, pH value reached 4.2 naturally, rotated 40 minutes, added 0.6 part of formic acid, and regulating pH value is 3.6; Rotated 15 minutes, draining wash water 3-5 time was respectively 5 minutes at every turn, went out drum; Extension dries in the air, shake soft, toggling, gage.
Embodiment only is a preferred optimum implementation of the present invention in sum; Unintelligible is that protection scope of the present invention is limited; For technical work personnel present embodiment is done according to the present invention the adjustment that does not exceed technical scheme of the present invention and the change in this field, should think and drop in protection scope of the present invention.
Claims (1)
1. the method for manufacture of a chromium-free tanning environment protection pigskin shoes, it is characterized in that: said chrome-free tanning agent staple is organophosphorated salt chrome-free tanning agent THPC, may further comprise the steps, wherein raw materials used metering by weight,
(1) softening: the pelt note with after expanding heavily is 100; Pelt after will losing hair or feathers earlier carries out skimming treatment; Softening process determines whether needs degreasing once more according to the grease situation that contains of pelt, and its pH value of softening process is controlled at 7.0-7.5, and temperature is controlled at 36 ℃-38 ℃; The softening time was controlled at 6-8 hour, carried out water-washing step then;
(2) pickling: add 75-100 part normal-temperature water and 8-10 part Industrial Salt, rotated 4-7 minute, with the vitriol oil of 0.9-1.3 part and the formic acid dipping pelt of 0.4-0.6 part, its pH is 2.6-3.2, and temperature is controlled at 20 ℃-28 ℃, and the operation required time is 2.5-3 hour;
(3) main tanning agent: in pickling solution, add grease-removing agent, its deal is 0.8-1.0 part, and the pH value is 3.0, rotated 20-45 minute, and the sodium bicarbonate that adds 0.3-0.5 part again, regulating the pH value is 3.5, rotates 20-45 minute; The synthetic tanning agent that adds the acidproof fatting agent of 0.6-1.0 part and 2.0-4.0 part, regulating the pH value is 3.6, rotates 20-40 minute, adds 3.5-5.0 part organophosphorated salt chrome-free tanning agent THPC, regulating the pH value is 3.5, rotates 120-180 minute; Dividing the sodium bicarbonate that adds 0.2-0.3 part respectively 6-8 time, rotated 20 minutes at every turn, is 4.3 up to regulating the pH value at last, rotates 120-180 minute again, stops drum and spends the night, and looks into Ts (shrinkage temperature)＞77 ℃ next day, goes out drum and takes horse, and the water squeezing shaving is weighed;
(4) return wet: add the water of 30 ℃-40 ℃ of 200-300 parts, handle with grease-removing agent of 0.5-0.7 part and the formic acid mixtures of 0.3-0.5 part, adjusting pH value is 3.4-3.8, draining wash water 4-7 minute;
(5) oxidation: add the water of 30 ℃-40 ℃ of 200-300 parts, the industrial ydrogen peroxide 50 of 1.8-2.2 part, regulating the pH value is 3.6, rotates draining wash water 15 minutes 40-50 minute;
(6) neutralization: add the water of 30 ℃-40 ℃ of 200-250 parts, with bicarbonate of ammonia of 1.5-2.5 part and the sodium formiate of 1.5-2.5 part, regulating the pH value is 5.5, rotates draining wash water 5-8 minute 40-80 minute;
(7) retanning: add 25 ℃ of-35 ℃ of water of 80-120 part, the white tannin of 4.0-8.0 part, regulating the pH value is 5.5; Rotated 50-70 minute, and added 6.0-8.0 part fatting agent of anti-the xanthochromia again, rotated 50-70 minute; Adding the first acid for adjusting pH value at last is 3.8; The component that adds formic acid is 1.0-2.0 part, the time 15-35 of rotation minute, and draining wash water 5-8 minute then;
(8) full gear: add 30 ℃ of-50 ℃ of warm water 200-300 parts, formic acid 0.5-0.7 part, regulating the pH value is 3.2, rotates 5 minutes, adds the formaldehyde-trapping agent of 1.5-3.0 part; The pH value of this moment reaches 4.2 naturally, rotates 30-50 minute, adds 0.4-0.6 part formic acid, and regulating the pH value is 3.6; Rotated 15 minutes, draining wash water 3-5 time was respectively 5 minutes at every turn, went out drum; Extension dries in the air, shake soft, toggling, gage.
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| CN2009100366337A CN101463397B (en) | 2009-01-14 | 2009-01-14 | Method for manufacturing chromium-free tanning environment protection pigskin shoes |
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| CN101463397B true CN101463397B (en) | 2012-07-11 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105506196A (en) * | 2016-01-26 | 2016-04-20 | 湖州长城皮业有限公司 | Preparation process for pig skin top layer instep leather free of chrome tanning |
| CN105543424A (en) * | 2016-01-26 | 2016-05-04 | 湖州长城皮业有限公司 | Preparation process of chrome tanning-free pigskin top-layer shoe lining leather |
| CN105543425A (en) * | 2016-01-26 | 2016-05-04 | 湖州长城皮业有限公司 | Preparation process of chrome tanning-free goat skin clothing leather |
| CN105567885A (en) * | 2016-01-26 | 2016-05-11 | 湖州长城皮业有限公司 | Chrome-free tanned pigskin two-layer shoe lining leather preparation technology |
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| CN101613771B (en) * | 2009-07-15 | 2012-09-26 | 天津市雄冠科技发展有限公司 | Fur tanning method capable of removing residual formaldehyde in fur product |
| ES2400883B1 (en) * | 2011-09-27 | 2014-02-19 | Inescop Instituto Tecnológico De Calzado Y Conexas | PROCEDURE FOR CURTITION, RECURTITION AND FINAL CONDITIONING OF SKIN THROUGH OXAZOLIDINE E. |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105506196A (en) * | 2016-01-26 | 2016-04-20 | 湖州长城皮业有限公司 | Preparation process for pig skin top layer instep leather free of chrome tanning |
| CN105543424A (en) * | 2016-01-26 | 2016-05-04 | 湖州长城皮业有限公司 | Preparation process of chrome tanning-free pigskin top-layer shoe lining leather |
| CN105543425A (en) * | 2016-01-26 | 2016-05-04 | 湖州长城皮业有限公司 | Preparation process of chrome tanning-free goat skin clothing leather |
| CN105567885A (en) * | 2016-01-26 | 2016-05-11 | 湖州长城皮业有限公司 | Chrome-free tanned pigskin two-layer shoe lining leather preparation technology |
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| CN101463397A (en) | 2009-06-24 |
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