CN115216565A - Integrative chrome-free tanning method for Tan lamb fur leather - Google Patents
Integrative chrome-free tanning method for Tan lamb fur leather Download PDFInfo
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- 239000010985 leather Substances 0.000 title claims abstract description 68
- 235000019687 Lamb Nutrition 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 76
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000005554 pickling Methods 0.000 claims abstract description 8
- DNEHKUCSURWDGO-UHFFFAOYSA-N aluminum sodium Chemical group [Na].[Al] DNEHKUCSURWDGO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920013724 bio-based polymer Polymers 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 84
- 238000002791 soaking Methods 0.000 claims description 44
- 238000006748 scratching Methods 0.000 claims description 43
- 230000002393 scratching effect Effects 0.000 claims description 43
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 30
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 claims description 21
- 238000005237 degreasing agent Methods 0.000 claims description 20
- 239000013527 degreasing agent Substances 0.000 claims description 19
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- 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 15
- 235000019253 formic acid Nutrition 0.000 claims description 15
- 210000004209 hair Anatomy 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- 210000002268 wool Anatomy 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052755 nonmetal Inorganic materials 0.000 claims description 10
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 108091005508 Acid proteases Proteins 0.000 claims description 6
- 230000000844 anti-bacterial effect Effects 0.000 claims description 6
- 239000003899 bactericide agent Substances 0.000 claims description 6
- 239000003599 detergent Substances 0.000 claims description 6
- 241000283903 Ovis aries Species 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- -1 aluminum trimethyl sulfate Chemical compound 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 238000007920 subcutaneous administration Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 238000009991 scouring Methods 0.000 claims description 3
- HSEYYGFJBLWFGD-UHFFFAOYSA-N 4-methylsulfanyl-2-[(2-methylsulfanylpyridine-3-carbonyl)amino]butanoic acid Chemical compound CSCCC(C(O)=O)NC(=O)C1=CC=CN=C1SC HSEYYGFJBLWFGD-UHFFFAOYSA-N 0.000 claims description 2
- 229940103272 aluminum potassium sulfate Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 4
- 238000004043 dyeing Methods 0.000 abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004040 coloring Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 229910052804 chromium Inorganic materials 0.000 abstract 3
- 239000011651 chromium Substances 0.000 abstract 3
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 102000004190 Enzymes Human genes 0.000 description 7
- 108090000790 Enzymes Proteins 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 3
- 239000003139 biocide Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 235000018553 tannin Nutrition 0.000 description 3
- 229920001864 tannin Polymers 0.000 description 3
- 239000001648 tannin Substances 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- 241000283973 Oryctolagus cuniculus Species 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 235000017399 Caesalpinia tinctoria Nutrition 0.000 description 1
- 241000283707 Capra Species 0.000 description 1
- 241000102542 Kara Species 0.000 description 1
- 241000282339 Mustela Species 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 241000388430 Tara Species 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention provides an integrated chrome-free tanning method for Tanbai fur leather, which comprises the processes of pickling softening, tanning and retanning, and the method takes a non-metallic salt tanning agent of which the main component is sodium aluminum silicate as a main tanning agent, takes an aluminum salt and a bio-based polymer synthesized retanning agent as a retanning agent, can fundamentally eliminate the problem of pollutant discharge in the tanning process and the ecological safety problem of a terminal product because the main tanning agent does not contain harmful metals such as chromium and the like, and does not contain formaldehyde and can be degraded, thereby solving the problems that the prior art for integrally tanning fur leather adopts an aldehyde tanning agent to cause the discharge of a chromium-containing compound and chromium-containing waste liquid in the product, adopts an organic phosphine tanning agent to cause the overproof free formaldehyde in the product, and adopts a tanning extract to cause the coloring of fur. The tan lamb fur leather tanned by the method has the advantages that the color of the fur quilt is white, no pollution is caused, the fur plate is easy to rub down, the fluff is uniform, the color is light, the dyeing is easy, and the quality of a fur and leather integrated product is improved.
Description
Technical Field
The invention belongs to the field of fur leather tanning, and relates to a beach lamb fur leather integrated chromium-free tanning method.
Background
The fur-leather integrated product is a very special leather product, not only has the typical fur characteristics of fur, but also has the characteristic of comfortable leather suede, also known as double leather (double face), and the product has the heat retention of fur, and also has the comfortable hand feeling and the fashionable appearance of natural leather. The integral wool and leather product is produced with leather board and through direct jointing, and has natural leather characteristic and beautiful leather jointing line. In recent years, fur-leather integrated products have been expanded to various skins of small animals, such as goat skins, lamb skins, kara sheepskin, swarca lambs, and even skins of small animals, such as rabbits, minks, and the like, and are gradually favored by more and more consumers.
The tanning process of leather-in-one leather involves, in addition to all the steps of the pelt processing, special retanning filling of the pelt board to obtain good sandability, firmness and softness of the pelt board and a uniform consistency in thickness and appearance. Therefore, the tanning process of the existing fur and leather integrated product mostly adopts a chrome tanning method, and then is matched with a plurality of tanning agents or filling materials for retanning and filling (Zhang Yao red, zhuqin, sheep leather and leather integrated product process technical key, western leather, 39 (9): 57-59). For example, CN102002541A discloses an integrated tanning process of tanning with tannin extract, which comprises neutralizing after tanning and then filling with tannin extract as filler, wherein on one hand, tannin extract can easily color the fur quilt, which can affect the natural color of the fur quilt, especially is not suitable for white beach lambskin, and on the other hand, chrome tanning agent is used during tanning, which can lead to the product containing chrome compound and also has the problem of discharging chrome-containing waste liquid; CN112575129A discloses an integrated process of environment-friendly rabbit fur and leather, which avoids the use of aldehyde tanning agent, but uses tara tanning extract or organic phosphine tanning agent during tanning, the organic phosphine tanning agent will release formaldehyde during tanning, which results in the free formaldehyde of the product exceeding standard, and the tanning extract will cause the coloring of fur quilt, which affects the natural color of fur quilt. Therefore, a feasible ecological tanning method of a fur and leather integrated product is urgently needed at present to fundamentally eliminate the pollutant discharge problem in the tanning process and the ecological safety problem of an end product, avoid the adverse effect of tanning on a fur quilt and improve the quality of the fur and leather integrated product.
Disclosure of Invention
The invention provides a chrome-free tanning method for Tanbai lamb fur leather, aiming at solving the problems that the discharge of chrome-containing compounds and chrome-containing waste liquid in products can be caused by adopting a chrome tanning agent in the existing fur leather integrated tanning process, the overproof free formaldehyde in the products can be caused by adopting an aldehyde tanning agent or an organic phosphine tanning agent, and the natural color of the fur quilt can be influenced by adopting tanning extract.
In order to achieve the purpose, the invention adopts the following technical scheme:
a beach lamb fur leather integrated chrome-free tanning method comprises the following steps:
(1) Pickling for softening
Putting the soaked and washed hair velutipes into water in a groove according to the proportion of adding 10-12L of water into each velutipes, adding sodium chloride to 6-6.5 DEG Be', adding a fatting agent until the concentration is 1-1.5 g/L, scratching the groove for 20-40 min, adding formic acid until the pH value of bath liquid is 4.2-4.5, scratching the groove for 20-40 min, adding acid protease until the concentration is 1.6-2 g/L, scratching the groove for 40-60 min, adding formic acid until the concentration is 4-5 g/L, scratching the groove for 20-40 min, then adding sulfuric acid until the pH value of the bath liquid is 2.2-2.5, intermittently scratching the groove for 10-14 h, and discharging the velutipes;
(2) Tanning
Putting acid-soaked and softened beach lambskin into water in a groove according to the proportion of adding 10-12L of water into each beach lambskin, adding a non-metal salt tanning agent with the main component of sodium aluminum silicate until the concentration is 6-12 g/L, scratching the groove for 50-80 min, standing for 50-80 min, continuously scratching the groove for 20-40 min, standing for 20-40 min, then adding baking soda into the groove for multiple times until the pH value of bath liquid is 4.5-4.7, standing for 10-14 h, discharging the skin, and standing the obtained beach lambskin for 24-48 h;
(3) Retanning
According to the proportion of adding 10-12L of water into each Tan lamb skin, putting the Tan lamb skin subjected to tanning treatment into water in a paddle vat, adding an aluminum tanning agent until the concentration is 5-12 g/L, adding a synthetic retanning agent until the concentration is 3-5 g/L, adding a fatting agent until the concentration is 4-8 g/L, stroking the paddle vat for 120-150 min, adding formic acid to adjust the pH value of bath liquid to 3.8-4.0, peeling, standing for controlling water, buffing and finishing; in the step, the temperature of the bath liquid is controlled to be 31-33 ℃.
In the technical scheme of the above integrative chrome-free tanning method for Tanbai fur leather, the nonmetal tanning agent with the main component of sodium aluminum silicate is MZ 8132.
In the technical scheme of the above integrative chrome-free tanning method for Tanbai fur leather, the aluminum tanning agent is at least one of aluminum sulfate, aluminum trimethyl sulfate, aluminum ammonium sulfate and aluminum potassium sulfate.
In the technical scheme of the integrated chrome-free tanning method for the Tan lamb fur leather, the synthetic retanning agent is a bio-based polymer and comprises SAFETAN MM 002 or SAFETAN BB 003.
In the technical scheme of the above integrative chrome-free tanning method for Tan lamb fur leather, the operations of soaking and wool washing treatment are as follows:
(1) Pre-soaking water
According to the proportion of adding 15-18L of water into each beach lamb skin, putting the salt-cured beach lamb skin into the water in the scratch groove, then adding a water soaking auxiliary agent until the concentration is 0.4-0.6 g/L, soaking for 6-8 h at room temperature, peeling, and scratching the scratch groove at intervals during soaking;
(2) Wool scouring
Putting the beach lambskin subjected to pre-soaking treatment into water in a groove according to the proportion of adding 15-18L of water into each beach lambskin, then adding a wool detergent until the concentration is 1-1.2 g/L, adding a degreasing agent until the concentration is 0.8-1 g/L, adding soda until the concentration is 0.6-0.8 g/L, sliding the groove for 45-60 min, discharging the skin, and carding to remove dirt on a hair quilt; the temperature of bath liquid in the scoring groove is controlled to be 36-38 ℃;
(3) Main soaking water
According to the proportion of adding 15-18L of water into each beach lambskin, putting the beach lambskin subjected to hair washing treatment into the water in the scratch groove, adding a soaking aid until the concentration is 0.5-0.8 g/L, adding a degreasing agent until the concentration is 0.8-1.2 g/L, adding a bactericide until the concentration is 0.1-0.3 g/L, scratching the scratch groove for 45-60 min, then intermittently scratching the scratch groove for 10-14 h, scratching the scratch groove for 10-20 min, removing the skin, and removing the subcutaneous tunica albuginea of the obtained beach lambskin.
Further, the degreasing agent is a degreasing agent DOWELAN FG-C or a degreasing agent LIPADOL DA 112.
Further, in the main soaking step, when the temperature and humidity are relatively high, formaldehyde may be added to the paddle to a concentration of 0.3 to 0.5g/L before the paddle starts to be stroked.
In the technical scheme of the integrated chrome-free tanning method for Tanbai fur leather, the fatting agent is at least one of fatting agent SYNTHOL PD990, fatting agent SYNTHOL MC-K, fatting agent SYNTHOL FL327 and fatting agent SYNTHOL LW.
In the step (2) of the technical scheme of the integrated chrome-free tanning method for the Tan lamb fur leather, if the white tanning agent is added, the scoring groove is scratched for 50-80 min after the white tanning agent is added, the mixture is kept stand for 50-80 min, the scoring groove is scratched for 20-40 min, and then baking soda is added into the scoring groove; if the tanning agent is not added, adding the non-metal salt tanning agent into the scratch groove, scratching the scratch groove for 50-80 min, standing for 50-80 min, continuously scratching the scratch groove for 20-40 min, standing for 20-40 min, and directly adding the baking soda into the scratch groove.
In the technical scheme of the integrative chrome-free tanning method of the Tibet lamb fur leather, the intermittent rowing of the step (1) refers to intermittent rowing in a mode of continuously rowing for 2-5 min every 2 h.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1. the invention provides an integrated chrome-free tanning method for Tanbai fur leather, which takes a non-metallic salt tanning agent with the main component of sodium aluminum silicate as a main tanning agent, and takes an aluminum salt and a bio-based polymer synthesized retanning agent as a retanning agent.
2. The beach lamb fur leather tanned by the method has white fur quilt color and no contamination, and the fur plate is easy to grind down, has uniform fluff and light color and is easy to dye, thereby improving the comprehensive performance and quality of fur and leather integrated products and solving the problem that the fur quilt is colored and the natural color of the fur quilt is influenced by adopting tanning extract in the existing fur and leather integrated tanning process.
Detailed description of the preferred embodiment
The invention provides a method for tanning Tan lamb fur leather without chrome in one piece through the following embodiments. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make modifications and adaptations of the present invention based on the above disclosure and still fall within the scope of the present invention.
In the following examples, the commercial agents such as degreasing agent, fatting agent, water immersion aid, wool scouring agent, acid protease, bactericide, non-metal tanning agent, synthetic retanning agent and white tanning agent are commercial products of company such as Darwei technology, hengpu Beijing and SMIT, and can be purchased directly from the market. For example:
the wool detergent DOWELLAN SWA is a dabulan SWA wetting and dispersing auxiliary agent, the degreasing agent DOWELLAN FG-C is a dabulan FG-C nonionic degreasing agent, the soaking auxiliary agent SPH is a dabulan SPH soaking auxiliary agent, and the soaking auxiliary agents SAE and FA acid enzyme are commercial products of Skawa Darwei science and technology Limited.
The main components of the non-metal salt tanning agent MZ 8132 are sodium aluminum silicate, fatliquoring agents SYNTHOL PD990, fatliquoring agents SYNTHOL MC-K, fatliquoring agents SYNTHOL FL327, fatliquoring agents SYNTHOL LW, synthetic retanning agents SAFETAN MM 002, synthetic retanning agents SAFETAN BB 003 and degreasing agents LIPID OL DA 112, which are all commercial products of Schmidt (Nanjing) leather chemicals Limited company.
The white tanning agent KASTANO DC is a commercial product of Hempp science and technology Limited liability company of Beijing.
Example 1
In the embodiment, the integrative chrome-free tanning method for the Tan lamb fur leather comprises the following specific steps:
(1) Pre-soaking water
According to the proportion of adding 15L of water into each beach lamb skin, putting the salted beach lamb skin into water in a scratch groove, then adding a water soaking auxiliary agent SPH till the concentration is 0.5g/L, soaking for 8h at room temperature, peeling, and scratching the scratch groove at intervals during the soaking period. In the step, the temperature of bath liquid in the scoring groove is controlled to be 20 ℃.
(2) Hair washing device
According to the proportion of adding 15L of water into each beach lambskin, putting the beach lambskin which is subjected to pre-soaking treatment into water in a groove, then adding a wool detergent DOWELLAN SWA to the concentration of 1g/L, adding a degreasing agent DOWELLAN FG-C to the concentration of 1g/L, adding soda to the concentration of 0.6g/L, sliding the groove for 60min, discharging the skin, and then combing the hair to remove dirt on a hair quilt. In the step, the temperature of bath liquid in the scoring groove is controlled to be 36-38 ℃.
(3) Principal soaking water
Putting the beach lambskins subjected to wool washing treatment into water in a rowing tank according to the proportion of adding 15L of water into each beach lambskin, adding a water soaking auxiliary agent SPH till the concentration is 0.5g/L, adding a degreasing agent LIPID OL DA 112 till the concentration is 1.2g/L, adding a bactericide BIOCIDE B7 till the concentration is 0.1g/L, rowing the rowing tank for 60min, then intermittently rowing the rowing tank for 14h in a manner of continuously rowing the rowing tank for 5min every 2h, then rowing the rowing tank for 15min, and discharging the skin; mechanically fleshing the skin of the Tibet lambs and removing subcutaneous flesh membranes. In this step, the temperature of the bath in the scoring tank was controlled to 25 ℃.
(4) Pickling for softening
According to the proportion of adding 12L of water into each beach lambskin, the beach lambskin after main soaking treatment is put into water in a groove, sodium chloride is added until the concentration is 50g/L (6-6.5 DEG Be'), fat liquor SYNTHOL PD990 is added until the concentration is 1.5g/L, the groove is scratched for 40min, formic acid is added until the pH value of bath liquid is 4.2-4.5, the groove is scratched for 20min, acid protease (FA acid enzyme, enzyme activity 800 unit) is added until the concentration is 2g/L, the groove is scratched for 60min, formic acid is added until the concentration is 5g/L, the groove is scratched for 30min, then sulfuric acid is added until the pH value of the bath liquid is 2.2-2.5, and the groove is scratched intermittently for 12h in a mode of scratching 2min every 2h to produce the skin. In the step, the temperature of bath liquid in the scoring groove is controlled to be 25 ℃.
(5) Tanning
Putting acid-soaked and softened beach lambskins into water in a groove according to the proportion of adding 12L of water into each beach lambskin, adding a non-metal salt tanning agent MZ 8132 until the concentration is 8g/L, scratching the groove for 60min, stopping scratching the groove, standing for 60min, continuously scratching the groove for 30min, stopping scratching the groove, standing for 30min, adding a white tanning agent KASTANO DC until the concentration is 2g/L, scratching the groove for 60min, standing for 60min, continuously scratching the groove for 30min, then adding baking soda into the groove at intervals of 30min for 4 times until the pH value of bath liquid is 4.5-4.7, standing for 12h, peeling, and standing the obtained beach lambskins for 24h. In this step, the temperature of the bath in the scoring tank was controlled to 25 ℃.
(6) Retanning
According to the proportion of adding 12L of water into each beach lamb skin, putting the tanned beach lamb skin into water in a scoring groove, adding aluminum trimethyl to the concentration of 5g/L, adding a synthetic retanning agent SAFETAN BB 003 to the concentration of 5g/L, adding a fatting agent SYNTHOL MC-K to the concentration of 2g/L and a fatting agent SYNTHOL FL327 to the concentration of 4g/L, scoring for 150min, adding formic acid to adjust the pH value of bath liquid to 3.8-4.0, peeling, standing for controlling water, grinding the skin and finishing; in this step, the temperature of the bath in the scoring tank was controlled to 32 ℃.
The tan lamb fur leather obtained by tanning in the embodiment has white fur quilt color and no contamination, a leather plate is easy to rub down, fluff is uniform, the color is light, and dyeing is easy, and further shrinkage temperature and free formaldehyde content detection are carried out on the tan lamb fur leather, and the result shows that the tan lamb fur leather obtained by tanning in the embodiment has the shrinkage temperature of more than 85 ℃ and the free formaldehyde content of less than 25mg/kg.
Example 2
In the embodiment, the integrative chrome-free tanning method of the Tan lamb fur leather comprises the following specific steps:
(1) Pre-soaking water
According to the proportion of adding 18L of water into each beach lamb skin, putting the salted beach lamb skin into the water in the scratch groove, then adding a water soaking auxiliary agent SPH till the concentration is 0.4g/L, soaking for 8h at room temperature, peeling, and scratching the scratch groove at intervals during the soaking period. In the step, the temperature of bath liquid in the scoring groove is controlled to be 20 ℃.
(2) Hair washing device
Putting the soaked beach lambskin into water in a groove according to the proportion of adding 18L of water into each beach lambskin, then adding a wool detergent DOWELLAN SWA to the concentration of 1g/L, adding a degreasing agent LIPADO 112 to the concentration of 0.8g/L, adding soda to the concentration of 0.6g/L, sliding the groove for 45min, discharging the skin, and combing the hair to remove dirt on the hair quilt. In the step, the temperature of bath liquid in the scoring groove is controlled to be 36-38 ℃.
(3) Principal soaking water
Putting the washed-hair beach lambskin into water in a groove according to the proportion of adding 18L of water into each beach lambskin, adding a soaking auxiliary agent SAE to the concentration of 0.8g/L, adding a degreasing agent LIPADOL DA 112 to the concentration of 0.8g/L, adding a bactericide BIOCIDE B7 to the concentration of 0.3g/L, scratching the groove for 60min, intermittently scratching the groove for 12h in a manner of continuously scratching the groove for 5min every 2h, scratching the groove for 10min, and discharging the skin; mechanically fleshing the skin of the Tibet lambs and removing subcutaneous flesh membranes. In the step, the temperature of bath liquid in the paddle is controlled to be 25 ℃,
(4) Pickling for softening
According to the proportion of adding 12L of water into each beach lambskin, the beach lambskin after main soaking treatment is put into water in a groove, sodium chloride is added until the concentration is 50g/L (6-6.5 DEG Be'), fat liquor SYNTHOL PD990 is added until the concentration is 1g/L, the groove is scratched for 20min, formic acid is added until the pH value of bath liquid is 4.2-4.5, the groove is scratched for 40min, acid protease (FA acid enzyme, enzyme activity 800 unit) is added until the concentration is 1.6g/L, the groove is scratched for 40min, formic acid is added until the concentration is 5g/L, the groove is scratched for 40min, then sulfuric acid is added until the pH value of the bath liquid is 2.2-2.5, and the groove is scratched intermittently for 12h in a mode of scratching every 2h for 2min, and the skin is discharged. In this step, the temperature of the bath in the scoring tank was controlled to 25 ℃.
(5) Tanning
According to the proportion of adding 12L of water into each beach lamb skin, putting the beach lamb skin subjected to pickling softening treatment into water in a rowing tank, adding a non-metal salt tanning agent MZ 8132 until the concentration is 12g/L, rowing the rowing tank for 80min, stopping rowing, standing for 80min, continuing rowing the rowing tank for 20min, stopping rowing, standing for 20min, then adding baking soda into the rowing tank for 4 times at intervals of 30min every time until the pH value of bath liquid is 4.5-4.7, standing for 14h, peeling, and standing the obtained beach lamb skin for 48h. In the step, the temperature of bath liquid in the scoring groove is controlled to be 25 ℃.
(6) Retanning
According to the proportion of adding 12L of water into each Tan lamb skin, putting the Tan lamb skin after tanning treatment into water in a scoring groove, adding aluminum sulfate until the concentration is 10g/L, adding a synthetic retanning agent SAFETAN MM 002 until the concentration is 4g/L, adding a fatting agent SYNTHOL LW until the concentration is 4g/L, adding a fatting agent SYNTHOL FL327 until the concentration is 4g/L, scoring the groove for 120min, adding formic acid to adjust the pH value of bath liquid to 3.8-4.0, peeling, standing, controlling water, grinding the skin and finishing; in the step, the temperature of bath liquid in the scoring groove is controlled to be 31 ℃.
The tan lamb fur leather obtained by tanning in the embodiment has white fur quilt color and no contamination, a leather plate is easy to rub down, fluff is uniform, the color is light, and dyeing is easy, and further shrinkage temperature and free formaldehyde content detection are carried out on the tan lamb fur leather, and the result shows that the tan lamb fur leather obtained by tanning in the embodiment has the shrinkage temperature of more than 70 ℃ and the free formaldehyde content of less than 20mg/kg.
Example 3
In the embodiment, the integrative chrome-free tanning method of the Tan lamb fur leather comprises the following specific steps:
(1) Pre-soaking water
According to the proportion of adding 15L of water into each beach lamb skin, putting the salted beach lamb skin into water in a scratch groove, then adding a water soaking auxiliary agent SPH till the concentration is 0.6g/L, soaking for 6h at room temperature, peeling, and scratching the scratch groove at intervals during the soaking period. In the step, the temperature of bath liquid in the scoring groove is controlled to be 20 ℃.
(2) Hair washing device
According to the proportion of adding 15L of water into each beach lambskin, putting the beach lambskin subjected to pre-soaking treatment into water in a groove, then adding a wool detergent DOWELLAN SWA to the concentration of 1.2g/L, adding a degreasing agent LIPIDOL DG 118 to the concentration of 1g/L, adding soda to the concentration of 0.6g/L, sliding the groove for 45min, then taking out the skin, and then combing the hair to remove dirt on a hair quilt. In the step, the temperature of bath liquid in the scoring groove is controlled to be 36-38 ℃.
(3) Main soaking water
Putting washed hair processed beach lambskins into water in a groove according to the proportion of adding 15L of water into each beach lambskin, adding a water soaking auxiliary agent SPH till the concentration is 0.5g/L, adding a degreasing agent LIPADOL 112 till the concentration is 1g/L, adding a bactericide BIOCIDE B7 till the concentration is 0.1g/L, adding formaldehyde till the concentration is 0.5g/L, scratching the groove for 60min, intermittently scratching the groove for 10h in a mode of continuously scratching the groove for 5min every 2h, then scratching the groove for 20min, and discharging the skin; mechanically fleshing the skin of the Tibet lambs and removing subcutaneous flesh membranes. In this step, the temperature of the bath solution in the scoring groove is controlled to be 25 ℃.
(4) Pickling for softening
According to the proportion of adding 10L of water into each beach lambskin, putting the beach lambskin subjected to main soaking treatment into water in a groove, adding sodium chloride until the concentration is 50g/L (6-6.5 DEG Be'), adding a fatting agent SYNTHOL PD990 until the concentration is 1.2g/L, cutting the groove for 30min, adding formic acid until the pH value of bath liquid is 4.2-4.5, cutting the groove for 30min, adding acid protease (FA acid enzyme, enzyme activity 800 unit) until the concentration is 1.8g/L, cutting the groove for 45min, adding formic acid until the concentration is 4g/L, cutting the groove for 20min, then adding sulfuric acid until the pH value of the bath liquid is 2.2-2.5, and cutting the groove for 14h intermittently in a mode of cutting the groove for 2min every 2h to obtain the skin. In this step, the temperature of the bath in the scoring tank was controlled to 25 ℃.
(5) Tanning
According to the proportion of adding 10L of water into each beach lamb skin, putting the beach lamb skin subjected to pickling softening treatment into water in a groove, adding a non-metal salt tanning agent MZ 8132 until the concentration is 6g/L, sliding the groove for 50min, stopping sliding the groove, standing for 50min, continuing to slide the groove for 40min, stopping sliding the groove, standing for 40min, adding a white tanning agent KASTANO DC until the concentration is 4g/L, sliding the groove for 80min, standing for 50min, continuing to slide the groove for 40min, then adding baking soda into the groove at intervals of 30min for 4 times until the pH value of bath liquid is 4.5-4.7, standing for 10h, discharging the skin, and standing the obtained beach lamb skin for 48h. In this step, the temperature of the bath in the scoring tank was controlled to 25 ℃.
(6) Retanning
Putting tanned beach lambskins into water in a scoring groove according to the proportion of adding 10L of water into each beach lambskin, adding aluminum trimethyl sulfate to the concentration of 4g/L and ammonium aluminum sulfate to the concentration of 8g/L, adding a synthetic retanning agent SAFETAN BB 003 to the concentration of 3g/L, adding a fatting agent SYNTHOL LW to the concentration of 3g/L and a fatting agent SYNTHOL FL327 to the concentration of 2g/L, scoring the scoring groove for 120min, adding formic acid to adjust the pH value of bath liquid to 3.8-4.0, peeling, standing for controlling water, grinding the skin and finishing; in this step, the temperature of the bath in the scoring tank was controlled to 33 ℃.
The fur of the Tan lamb fur leather obtained by tanning in the embodiment is white in color and free from contamination, the leather plate is easy to abrade, the fluff is uniform, the color is light, and the leather plate is easy to dye, and further the shrinkage temperature and the free formaldehyde content of the Tan lamb fur leather are detected, and the result shows that the shrinkage temperature of the Tan lamb fur leather obtained by tanning in the embodiment is more than 85 ℃, and the free formaldehyde content is lower than 75mg/kg.
Claims (10)
1. The integrative chrome-free tanning method of the Tan lamb fur leather is characterized by comprising the following steps:
(1) Pickling for softening
Putting the soaked and washed hair velutipes into water in a groove according to the proportion of adding 10-12L of water into each velutipes, adding sodium chloride to 6-6.5 DEG Be', adding a fatting agent until the concentration is 1-1.5 g/L, scratching the groove for 20-40 min, adding formic acid until the pH value of bath liquid is 4.2-4.5, scratching the groove for 20-40 min, adding acid protease until the concentration is 1.6-2 g/L, scratching the groove for 40-60 min, adding formic acid until the concentration is 4-5 g/L, scratching the groove for 20-40 min, then adding sulfuric acid until the pH value of the bath liquid is 2.2-2.5, intermittently scratching the groove for 10-14 h, and discharging the velutipes;
(2) Tanning
Putting acid-soaked and softened beach lambskin into water in a groove according to the proportion of adding 10-12L of water into each beach lambskin, adding a non-metal salt tanning agent of which the main component is sodium aluminum silicate until the concentration is 6-12 g/L, scratching the groove for 50-80 min, standing for 50-80 min, continuously scratching the groove for 20-40 min, standing for 20-40 min, adding a white tanning agent until the concentration is 0-4 g/L, then adding baking soda into the groove for multiple times until the pH value of bath liquid is 4.5-4.7, standing for 10-14 h, discharging the skin, and standing the obtained beach lambskin for 24-48 h;
(3) Retanning
According to the proportion of adding 10-12L of water into each Tan lamb skin, putting the Tan lamb skin subjected to tanning treatment into water in a paddle vat, adding an aluminum tanning agent until the concentration is 5-12 g/L, adding a synthetic retanning agent until the concentration is 3-5 g/L, adding a fatting agent until the concentration is 4-8 g/L, stroking the paddle vat for 120-150 min, adding formic acid to adjust the pH value of bath liquid to 3.8-4.0, peeling, standing for controlling water, buffing and finishing; in the step, the temperature of the bath liquid is controlled to be 31-33 ℃.
2. The method of the Tan lamb fur leather integral chrome-free tanning according to claim 1, wherein the non-metal tanning agent with the main component of sodium aluminum silicate is MZ 8132.
3. The integrated chrome-free tanning method for Tan lambs fur leather according to claim 1, wherein the aluminum tanning agent is at least one of aluminum sulfate, aluminum trimethyl sulfate, aluminum ammonium sulfate and aluminum potassium sulfate.
4. The integrated chrome-free tan of Tan lamb fur leather according to claim 1, wherein the syntan retanning agent is a bio-based polymer including SAFETAN MM 002 or SAFETAN BB 003.
5. The integrated chrome-free tanning method for Tanbo fur leather according to claim 1, characterized in that the operations of soaking and washing treatment are as follows:
(1) Pre-soaking water
According to the proportion of adding 15-18L of water into each beach lamb skin, putting the salt-cured beach lamb skin into the water in the scratch groove, then adding a water soaking auxiliary agent until the concentration is 0.4-0.6 g/L, soaking for 6-8 h at room temperature, peeling, and scratching the scratch groove at intervals during soaking;
(2) Wool scouring
According to the proportion of adding 15-18L of water into each beach lambskin, putting the beach lambskins subjected to pre-soaking treatment into water in a groove, then adding a wool detergent until the concentration is 1-1.2 g/L, adding a degreasing agent until the concentration is 0.8-1 g/L, adding soda until the concentration is 0.6-0.8 g/L, sliding the groove for 45-60 min, discharging the skin, and combing to remove dirt on a hair quilt; the temperature of bath liquid in the scoring groove is controlled to be 36-38 ℃;
(3) Main soaking water
According to the proportion of adding 15-18L of water into each beach lambskin, putting the beach lambskin subjected to wool washing treatment into water in a groove, adding a water soaking auxiliary agent until the concentration is 0.5-0.8 g/L, adding a degreasing agent until the concentration is 0.8-1.2 g/L, adding a bactericide until the concentration is 0.1-0.3 g/L, scratching the groove for 45-60 min, intermittently scratching the groove for 10-14 h, scratching the groove for 10-20 min, discharging the skin, and removing the subcutaneous tunica albuginea of the obtained beach lambskin.
6. The integrated chrome-free tanning method for Tanbai fur leather according to claim 5, characterized in that the degreasing agent is a degreasing agent DOWELAN FG-C or a degreasing agent LIPADOL DA 112.
7. The integrated chrome-free tanning method for Tanbo fur leather according to claim 5, wherein in the main soaking step, before starting to scratch the scratch groove, formaldehyde is added into the scratch groove to a concentration of 0.3-0.5 g/L.
8. The beach lamb fur leather integral chrome-free tanning method of any one of claims 1 to 7, wherein the fatliquor is at least one of fatliquor SYNTHOL PD990, fatliquor SYNTHOL MC-K, fatliquor SYNTHOL FL327 and fatliquor SYNTHOL LW.
9. The integrated chrome-free tanning method for Tanbai fur leather as claimed in any one of claims 1 to 7, wherein in the step (2), if the white tanning agent is added, the scoring groove is scratched for 50-80 min after the addition of the white tanning agent, the mixture is kept still for 50-80 min, the scoring groove is scratched for 20-40 min, and baking soda is added into the scoring groove.
10. The beach lamb fur leather integrated chrome-free tanning method of any one of claims 1 to 7, wherein the intermittent rowing groove means intermittent rowing for 2-5 min per 2h of continuous rowing groove.
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