CN110004254B - Method for processing soft shoe upper leather of sturgeon skin of Yangtze river sturgeon and Chinese sturgeon - Google Patents
Method for processing soft shoe upper leather of sturgeon skin of Yangtze river sturgeon and Chinese sturgeon Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
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- C14B1/00—Manufacture of leather; Machines or devices therefor
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- C14B1/00—Manufacture of leather; Machines or devices therefor
- C14B1/40—Softening or making skins or leather supple, e.g. by staking, boarding, or crippling machines, by dry mills
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- C14—SKINS; HIDES; PELTS; LEATHER
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- C14B1/00—Manufacture of leather; Machines or devices therefor
- C14B1/44—Mechanical treatment of leather surfaces
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- C14B—MECHANICAL TREATMENT OR PROCESSING OF SKINS, HIDES OR LEATHER IN GENERAL; PELT-SHEARING MACHINES; INTESTINE-SPLITTING MACHINES
- C14B1/00—Manufacture of leather; Machines or devices therefor
- C14B1/44—Mechanical treatment of leather surfaces
- C14B1/54—Ironing
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- C14—SKINS; HIDES; PELTS; LEATHER
- C14B—MECHANICAL TREATMENT OR PROCESSING OF SKINS, HIDES OR LEATHER IN GENERAL; PELT-SHEARING MACHINES; INTESTINE-SPLITTING MACHINES
- C14B1/00—Manufacture of leather; Machines or devices therefor
- C14B1/58—Drying
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- 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
- C14C1/04—Soaking
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- 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
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- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C15/00—Apparatus for chemical treatment or washing of hides, skins, or leather
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- 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
- C14C3/06—Mineral tanning using chromium compounds
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- 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
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- 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
- C14C3/28—Multi-step processes
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- 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
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
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Abstract
The invention belongs to the field of leather processing, and particularly relates to a method for processing sturgeon leather soft shoe upper leather of Changjiang sturgeons and Chinese sturgeons.
Description
Technical Field
The invention belongs to the field of leather processing, and particularly relates to a method for processing sturgeon leather soft vamp leather of Yangtze river sturgeons and Chinese sturgeons.
Background
The sturgeon leather is a high-end high-quality leather developed in recent years, can be used for manufacturing high-grade sturgeon leather products such as belts, cases, leather shoes and the like, particularly sturgeon leather shoes made of sturgeon leather, has unique patterns and is three-dimensional and natural, and a brand-new material is provided for manufacturing high-end luxury leather shoes.
Because the surface of the sturgeon leather is distributed with 5 rows of natural bone plates, the conventional softening technology is difficult to meet the requirement of the shoe upper leather, the invention emphatically solves the technical problem in the processing process of the sturgeon shoe upper leather, and the processed sturgeon shoe upper leather is soft, full and tear-resistant and is a high-quality material for manufacturing high-grade leather shoes.
Disclosure of Invention
The invention aims to provide a method for processing sturgeon leather soft shoe upper leather of Yangtze river sturgeons and Chinese sturgeons.
In order to achieve the purpose, the invention adopts the following technical measures:
the method for processing the soft shoe upper leather of the sturgeon skin of the Yangtze river sturgeons and the Chinese sturgeons comprises the following steps:
degreasing and tanning sturgeon skin
1. Drum soaking and pre-degreasing
(1) Selecting salt-wet skins of Yangtze river sturgeons or Chinese sturgeons, fully washing the sturgeon skins with water, and weighing after the washing is finished;
(2) weighing 0.51% of water-soaking agent, 1-2% of bactericide, 1-2% of degreasing agent (brother chemical H900) and 200-300% of water by weight of the sturgeon skin obtained in the step (1);
(3) soaking: putting sturgeon skin and water into a rotary drum, adjusting the temperature to be 20-22 ℃, then adding a soaking agent, a bactericide and a degreasing agent, rotating the rotary drum at the speed of 2-4 revolutions per minute for 10-20 minutes, stopping for 40-50 minutes, stopping for 36-48 hours after the self-rotation of the rotary drum from the feeding, then washing with running water in the rotary drum, and controlling water after the rotary drum is discharged;
2. mechanical degreasing
(1) The skin and flesh surfaces of the sturgeons soaked in water are upward, fins are removed, and fish and fat are removed by a steel wire brush or a nylon brush;
(2) cleaning sturgeon skin with meat and fat removed with warm water, and controlling water.
3. Liming and degreasing
(1) Step 2, weighing sturgeon skin obtained after mechanical degreasing and cleaning;
(2) weighing 1.0-1.5% of sodium hydrosulfide particles (effective content 60-80%), 10-15% of lime, 0.5-1% of liming auxiliary agent, 1-2% of degreasing agent and 300-400% of water by weight of the sturgeon skin in the step 3 (1);
(3) putting prepared sturgeon skin and water into a rotary drum, setting the temperature to be 20-24 ℃, the rotating speed to be 4-6 r/min, adding a degreasing agent and sodium hydrosulfide, and rotating for 1 h; adding the liming auxiliary agent and lime, rotating for 5-15 minutes, stopping for 40-60 minutes, rotating at the drum speed of 2-3 revolutions per minute, and calculating the total time from feeding to 48-60 hours;
the end point is that the expansion of the sturgeon skin is uniform, and the ph of the solution with firm skin is more than 12;
washing, namely washing sturgeon skin with running water at normal temperature by using the rotary drum;
(4) secondary mechanical fleshing and fat removing;
4. deashing and degreasing
(1) Step 3, weighing the sturgeon skin treated in the step;
(2) weighing 1-1.5% of ammonium sulfate, 1-1.5% of degreasing agent, 100-200% of water and 0.5-1% of deliming auxiliary agent in the weight of the sturgeon skin in the step 4 (1);
(3) putting sturgeon skin and water into a rotary drum, setting the temperature to be 33-36 ℃, adding ammonium sulfate, a degreasing agent and a deliming auxiliary agent, rotating the rotary drum at the speed of 2-4 r/min for 1-2h,
(4) end point phenolphthalein indicator showed cuts 1/5-1/6 hearts,
(5) washing with water, namely fully washing the rotary drum with warm water;
5. softening
(1) Step 4, weighing the treated sturgeon skin;
(2) weighing 200% of 100-; (3) putting sturgeon skin and water into a rotary drum, setting the water temperature to be 35-37 ℃, adding pancreatin and ammonium sulfate, rotating the rotary drum at the speed of 4-6 r/min for 1-1 h;
(4) the end point is that the grain surface is smooth and white, the finger is pressed with fingerprint, and the skin is flexible and compact
(5) Washing with warm water;
6. pickling
(1) Step 5, weighing the treated sturgeon skin;
(2) weighing 100-200% of water, 10-16% of salt, 1-2% of acetic acid, 2-2.5% of concentrated sulfuric acid and 1-2% of nonionic degreasing agent in the weight of the sturgeon skin in the step 6 (1);
(3) putting sturgeon skin and water into a rotary drum, setting the temperature to be 21-23 ℃, adding salt and a non-ionic degreasing agent, rotating the rotary drum for 1-2 revolutions per minute, and rotating for 25-35 minutes; adding equivalent diluted acetic acid for 2-3 times, and rotating for 25-35 min and 4 r/min each time; then adding diluted concentrated sulfuric acid in 3-5 times in equal amount, rotating for 25-45 minutes each time at a rotating speed of 4-6 revolutions per minute, setting the rotary drum to stop rotating for 40-60 minutes at 5-15 minutes after finishing the rotation at a rotating speed of 2-4 revolutions per minute, and totaling for 24-36 hours from the beginning of feeding to the end of the rotation of the rotary drum;
(4) at the end point, the skin surface is astringent, the skin body is flexible and compact, and the pH value of the solution is 2.0-3.0;
(5) degreasing, namely taking the sturgeon skin out in a pickled skin state, degreasing mechanically, weighing the sturgeon skin, and then putting the sturgeon skin into the original pickling solution;
7. tanning
(1) Weighing 2-4% of modified glutaraldehyde, 1-1.5% of aluminum tanning agent, 8-10% of white tannin extract, 1-1.5% of sodium formate, 1.5-2% of baking soda and 1-1.5% of mildew preventive in the weight of the sturgeon skin in the step 6;
(2) operation of
The preparation method comprises the following steps of (1) carrying out the steps in an original pickling solution, setting the temperature to be 22-24 ℃, adding diluted modified glutaraldehyde, rotating for 1-1.5h, and rotating at 4-6 r/min; adding aluminum tanning agent, rotating for 1-2h, and rotating the drum for 4-6 r/min; adding white tannin and white tannin extract, and rotating for 4h and 4-6 revolutions per minute; stopping the drum and standing for 18-32 hours from the beginning of feeding to the end of standing.
(3) Standing, adding sodium formate and a mildew preventive, and rotating for 1-2 hours at a speed of 4-6 rpm; adding diluted beefsteak in 5-8 times at an interval of 30-50 minutes every time, and rotating the drum at 4-6 revolutions per minute; when ph is detected to be 4.0, continuing to rotate for 2-3h, and rotating the rotary drum for 4-6 revolutions per minute; then the water temperature in the rotary drum is raised to 40-45 ℃, the rotation is carried out for 2-3h, and the rotation speed of the rotary drum is 4-6 r/min; and (3) detecting the shrinkage temperature by boiling water to be more than 80 ℃, stopping the drum and standing, and taking 18-32 hours from the beginning of feeding to the end of standing.
(4) Rotating for 1-2h, and rotating for 2-4 r/min; washing with flowing water in the drum at normal temperature, and discharging from the drum;
8. degreasing
(1) Step 7, weighing the treated sturgeon skin;
(2) weighing 300-400% of water and 3-4% of high-temperature resistant non-ionic degreasing agent by weight of the sturgeon skin in the step 8 (1);
(3) putting sturgeon skin and water into a rotary drum, setting the temperature at 60-70 ℃, adding a degreasing agent, rotating for 4-6 hours at 4-6 rpm, cleaning with hot water at 55-60 ℃, and discharging from the drum for water control;
9. retanning
(1) Step 8, weighing the treated sturgeon skin;
(2) weighing 9(1) 100-200% of water, 0.3-0.6% of formic acid, 2-4% of acrylic acid retanning agent, 4-8% of white tannin, 2-4% of anionic fatliquor and 0.5-1% of baking soda by weight of sturgeon skin;
(3) putting sturgeon skin and water into a rotary drum, setting the temperature at 42-44 ℃, adding diluted formic acid, and rotating for 20-40 minutes; adding the white tannin, turning for 1-3h, adding the acrylic acid retanning agent and the anionic fatting agent, turning for 1-3h, adding the diluted sodium bicarbonate in 3-4 times and the like, turning for 30-50 minutes each time, wherein the rotating speed of a rotating drum is 4-6 revolutions per minute, stopping the drum, standing, and the total time from the beginning of feeding to the end of standing is 18-32 hours;
(4) standing, and rotating for 1-2h at 4-6 rpm; when the pH value of the solution is detected to be 4.0, fully washing with water, and discharging and controlling water;
10. neutralization
(1) Step 9, weighing the sturgeon skin processed;
(2) weighing 200% of water, 2-4% of neutralized tannin, 1-2% of tannin extract, 1-2% of sodium formate and 0.5-1% of baking soda, wherein the weight of the sturgeon skin is 100-;
(3) putting sturgeon skin and water into a rotary drum, setting the temperature at 42-44 ℃, adding neutral tannin, rotating for 20-40 minutes, adding tannin essence, and rotating for 20-40 minutes; adding sodium formate, and rotating for 20-40 min; adding the diluted baking soda for 3-4 times, and rotating for 20-40 minutes each time; the rotating speed of the rotary drum is 2-4 r/min.
(4) Detecting the pH value of the solution at the end point of 5-6;
(5) fully washing sturgeon skin with water, and naturally controlling water;
secondly, soft dyeing is carried out
1. Falling soft
Filling the hollow part of the meat-dough plate with hot melt adhesive, sleeving sturgeon leather into a protection bag, putting the sturgeon leather into a softening drum, and softening for 6-7 hours with 10-15 r/min of the rotary drum;
2. fully washing the softened sturgeon skin with water, and controlling the water;
3. the secondary retanning is carried out,
(1) weighing the sturgeon skin treated in the step 2;
(2) weighing 100-200% of water, 2-4% of acrylic acid retanning agent, 2-4% of polymer resin retanning agent, 4-6% of bark tannin extract (soft) and 1-2% of baking soda in the weight of the sturgeon skin in the step two 3 (1);
(3) putting sturgeon skin and water into a rotary drum, setting the temperature at 42-44 ℃, adding an acrylic acid retanning agent, rotating for 50-70 minutes, adding a resin tanning agent, rotating for 50-70 minutes, adding tannin extract, and rotating for 50-70 minutes, wherein the rotating speed of the rotary drum is 4-6 revolutions per minute; adding diluted sodium bicarbonate 3-4 times, rotating at 4-6 rpm for 20-40 min each time, washing with water when ph is 5.5, and draining;
4. dyeing and fatliquoring
(1) Step two 3, weighing the treated sturgeon skin;
(2) weighing the second step 4(1), 100-
(3) Putting sturgeon skin and water into a rotary drum, setting the temperature at 45-55 ℃, adding a leveling agent, rotating for 8-12 minutes, adding a dye, rotating for 30-50 minutes, adding neat's foot oil, rotating for 50-70 minutes, adding a phospholipid fatting agent, rotating for 50-70 minutes, adding a lanolin fatting agent, rotating for 50-70 minutes, adding diluted formic acid in 2-3 times in average, rotating for 30 minutes each time, wherein the rotary drum rotating speed of the above procedures is 10-15 revolutions per minute, discharging liquid and controlling water, and then fully washing and controlling water in the rotary drum;
7. toggling drying
8. Water spraying softening
Uniformly spraying water on the dried sturgeon leather on the meat surface, and then stacking in a sealing manner for 24-48 h;
9. falling soft
The time for the falling and softening is 2 to 4 hours as the method for the second 1 falling and softening;
10. toggling drying
11. Polishing with abrasive paper
12. High temperature ironing
Ironing by adopting a modified leather embossing machine; the modified leather embossing machine comprises a hot pressing plate and a corresponding bottom plate of the leather embossing machine; the bottom plate is provided with a groove, and the size of the groove is slightly larger than the protrusion of the main bone plate of the sturgeon skin; the contact surface of the hot pressing plate and the leather is provided with a high-temperature resistant felt;
the Chinese sturgeons and the Yangtze river sturgeons are both from artificially cultured populations.
In the above method, preferably, the thickness of the high temperature resistant felt is 2 cm; the length of the groove is 100cm, the depth is 1.5cm, and the width is 5 cm.
In the above method, preferably, the hot press plate has a temperature of 100 ℃, a pressure of 200 kg/cm, and a ironing time of about 2 to 3 seconds.
Compared with the prior art, the invention has the following advantages:
1. the tanned sturgeon leather is soft and plump, the bone plate is intact and has smooth surface;
2. a brand-new environment-friendly chrome-free tanning process is adopted, so that the market popularization is easy;
3. different degreasing agents and degreasing methods are selected for different grease components in different tanning procedures to perform degreasing respectively, and after degreasing, sturgeon skins are cleaner and tidier than the sturgeon skins in the traditional method, so that the subsequent operation is easy;
4. the high-quality product rate of the sturgeon leather tanned by the method reaches over 90 percent, and greatly exceeds the product rate of 30 percent of the traditional tanning method;
5. the connection part of the bone plate and the leather is tightly wrapped, and the requirement of large-angle bending in the leather shoe processing process is completely met.
Drawings
FIG. 1 is a schematic diagram of sturgeon leather that is degreased and unclean;
wherein, a is the degreased clean sturgeon skin embryo by the method of the invention;
b is sturgeon skin embryo treated by the degreasing method in the prior art.
FIG. 2 is a schematic structural diagram of a hot pressing plate and a base plate of the reformed leather embossing machine;
wherein, 1-felt; 2-grooves.
Fig. 3 is the prepared soft shoe upper leather of the sturgeon skin of the sturgeon in Yangtze river.
Fig. 4 is a schematic diagram of sturgeon skin filled with hot melt adhesive in the recesses of the bone plate.
Detailed Description
The technical scheme of the invention is the conventional technology in the field if not particularly stated; the reagents or materials, if not specifically mentioned, are commercially available. The Chinese sturgeons and the Yangtze river sturgeons used in the embodiment of the invention are both from artificially cultured populations.
Example 1:
the method for processing the soft shoe upper leather of the sturgeon skin of the Yangtze river sturgeons and the Chinese sturgeons comprises the following steps:
according to conventional cognition in the field, the weight of the sturgeon skin related to the invention is the wet weight of the sturgeon skin; the percentage addition amount of the raw materials used in each step is based on the weight of the sturgeon skin involved in each step.
Degreasing and tanning sturgeon skin
1. Drum soaking and pre-degreasing
(1) Selecting 20 kg of Yangtze river sturgeon salted and wet skin, fully washing the sturgeon skin with water at the temperature of 18-22 ℃ in a rotary drum, and weighing after the water washing is finished.
(2) Weighing 1% of water soaking agent (Pasteur Eusaponn W), 1% of bactericide (Langshan CISMOLLAN AN 90), 2% of degreasing agent (brother chemical H900) and 200% of water in the weight of the sturgeon skin obtained in the step (1);
(3) soaking in water to pre-degrease the skin of the sturgeon, mainly removing surface grease, and preparing for liming working section
Putting sturgeon skin and water into a rotary drum, adjusting the temperature to be 22 ℃, then adding a soaking agent, a bactericide and a degreasing agent, rotating the rotary drum at the rotating speed of 2 revolutions per minute, rotating for 15 minutes and stopping for 45 minutes, wherein the rotating speed cannot be too high so as to prevent the sturgeon skin from being excessively rubbed and damaging patterns on the surface of the sturgeon skin, and the total 48 hours is counted from feeding to finishing the rotation of the rotary drum. Then the water in the rotary drum is washed for 20 minutes, and the water is discharged from the rotary drum and controlled.
2. Mechanical degreasing
(1) The sturgeon skin and flesh surfaces soaked with water are upward and fixed on a panel, fish fins are removed by scissors, and fish and fat are removed by high-speed rotation of an electric 80-mesh steel brush or an 80-mesh nylon brush.
(2) Cleaning sturgeon skin with meat and fat removed with warm water, and controlling water.
3. Liming and degreasing
(1) Step 2, weighing sturgeon skin obtained after mechanical degreasing and cleaning;
(2) weighing 1.0% of sodium hydrosulfide (the content is 70%, 70% refers to the effective content of sodium hydrosulfide and flaky particles), 10% of lime, 0.5% of liming auxiliary agent (Langsheng CISMALOLLAN BH-C), 2% of degreasing agent (brother chemical H900) and 300% of water in the weight of the sturgeon skin in the step 3 (1);
(3) putting prepared sturgeon skin and water into a rotary drum, setting the temperature to be 20 ℃, rotating the rotary drum at the rotating speed of 4 revolutions per minute, adding a degreasing agent, dissolving the dissolved sodium hydrosulfide in the water, and rotating for 1 hour; and adding the liming auxiliary agent and lime, rotating for 10 minutes, stopping for 50 minutes, rotating at the rotating speed of the rotary drum of 2 revolutions per minute, and counting the total time from the feeding to the finishing of the rotation of the rotary drum for 48 hours.
The end point is that the expansion of the sturgeon skin is uniform, and the pH of the solution for keeping the skin stiff is more than 12.
And (4) washing, namely washing the rotary drum with running water at normal temperature for 2 times and 10 minutes each time at 4 revolutions per minute.
(4) And (5) removing meat and fat for the second time (the method is the same as 2).
4. Deashing and degreasing
(1) Step 3, weighing the sturgeon skin treated in the step;
(2) weighing 1% of ammonium sulfate, 1% of degreasing agent (Pasteur Eusapon OC), 100% of water and 0.5% of deliming auxiliary agent (Pasteur) based on the weight of the sturgeon skin in the step 4(1)
(3) Putting sturgeon skin and water into a rotary drum, setting the temperature at 33 ℃, adding ammonium sulfate, a degreasing agent and a deliming auxiliary agent, rotating the rotary drum at the speed of 2 r/min for 2h,
(4) end point phenolphthalein indicator showed cuts 1/5-1/6 hearts,
(5) and (4) water washing, namely fully washing the glass substrate with drum warm water (33-36 ℃) for 2 times, 20 minutes each time and 4 revolutions per minute. After cleaning, the surface of the fish skin is clean, tidy and soft, and the solid grease on the surface is basically removed.
5. Softening
(1) Step 4, weighing the treated sturgeon skin;
(2) weighing 100% of water, 1% of pancreatin and 0.5% of ammonium sulfate by weight of the sturgeon skin in the step 5 (1);
(3) putting sturgeon skin and water into a rotary drum, setting the water temperature to be 35-37 ℃, adding pancreatin and ammonium sulfate, rotating the rotary drum at the speed of 4 r/min for 1 h;
(4) the end point is that the grain surface is smooth and white, the finger is pressed with fingerprint, and the skin is flexible and compact
(5) And (3) water washing, namely fully washing the inner part of the rotary drum with warm water at the temperature of between 35 and 37 ℃ for 10 minutes, washing the inner part of the rotary drum with water at the normal temperature of between 20 and 24 ℃ for 10 minutes, and rotating the rotary drum at 2 revolutions per minute.
6. Pickling
(1) Step 5, weighing the treated sturgeon skin;
(2) weighing 100% of water, 16% of salt, 2% of acetic acid, 2% of concentrated sulfuric acid and 2% of nonionic degreasing agent (Pasteur Eusapon OE) in the weight of the sturgeon skin obtained in the step 6 (1);
(3) putting sturgeon skin and water into a rotary drum, setting the temperature to be 21 ℃, adding salt and a non-ionic degreasing agent, rotating the rotary drum for 1 r/min and 30 min; adding equivalent diluted acetic acid (the acetic acid is diluted by water with the weight being 10 times of that of the acetic acid) in two times, and rotating for 30 minutes and 4 revolutions per minute each time; then adding diluted concentrated sulfuric acid (diluted by 10 times of water) in 4 times of equal amount, wherein the rotation speed is 4 r/min and 30 min each time; after the completion, the rotary drum is set to rotate for 10 minutes and stop for 50 minutes, the rotating speed is 2 revolutions per minute, and the total time from the beginning of feeding to the end of rotation is 36 hours;
(4) at the end point, the skin surface is astringent, the skin body is flexible and compact, and the pH value of the solution is 2.5;
(5) degreasing, namely taking the sturgeon skin out in a sour skin state, removing solid fat on a dried panel again (the method is the same as 2), weighing the sturgeon skin, and then putting the sturgeon skin into the original pickling liquid;
7. tanning
(1) Weighing 2% of modified glutaraldehyde, 1.5% of aluminum tanning agent, 10% of white tannin extract, 1% of sodium formate, 1.5% of baking soda and 1% of mildew preventive in the weight of the sturgeon skin obtained in the step 6;
(2) operation of
The method is carried out in the original pickle liquor, the temperature is set to be 24 ℃, modified glutaraldehyde is added (the weight ratio is 1:5, the material-water ratio is 1: 5), and the mixture is rotated for 1.5h at 4 revolutions per minute; adding an aluminum tanning agent, rotating for 1h, and rotating a drum for 4 revolutions per minute; adding white tannin and white tannin extract, and rotating for 4h and 4 revolutions per minute; stopping the drum and standing for 24 hours from the beginning of feeding to the end of standing.
(3) Adding sodium formate and a mildew preventive, and rotating for 1h and 4 r/min; adding diluted baking soda (20 times of 35 ℃ water solution by weight) in 8 times of equal amount, rotating for 40 minutes each time, and rotating the drum for 4 revolutions per minute; when ph is detected to be 4.0, continuing to rotate for 2h at 4 revolutions per minute; then the water temperature in the rotary drum is raised to 40 ℃, and the water is rotated for 2h and 4 r/min; and (3) detecting the shrinkage temperature by boiling water to be more than 80 ℃, stopping the drum and standing for 24 hours from the beginning of feeding to the end of standing.
(4) Rotating for 1h and 2 r/min; and (5) washing the drum for 20 minutes by running water at normal temperature, and taking the drum out for degreasing.
8. Degreasing
Because of the particularity of the sturgeon leather, the sturgeon leather is different from common leather, and the grease is difficult to remove completely at one time, so that the step is very critical, the sturgeon leather is not easy to manufacture, and the quality of a final finished product is seriously influenced.
(1) Step 7, weighing the treated sturgeon skin;
(2) weighing 400% of water and 4% of high-temperature-resistant non-ionic degreasing agent (Pasteur Eusapon OC, brother chemical H901 in a mass ratio of 1: 1) by weight of the sturgeon skin obtained in the step 8 (1);
(3) putting sturgeon skin and water into a rotary drum, setting the temperature at 65 ℃, adding a degreasing agent, rotating for 6 hours at 6 revolutions per minute, cleaning for 2 times with hot water at 55-60 ℃ for 10 minutes each time, and discharging from the drum for water control.
The degreased sturgeon leather is uniform light blue white as a in figure 1, leather fibers are completely opened, finger pressure has fluffy feeling, natural grease in the sturgeon leather is basically removed, the leather is firm, no rotten leather exists, the leather surface is clean, and no other pungent taste exists except leather smell. The sturgeon leather is sent to an SGS (SGS) institution for detection, based on a candidate list of high-concern substances for authorization examination published by the European chemical administration on 12, 17 and 2015 (according to REACH regulation No. 1907/2006 of European Union), 168 high-concern Substances (SVHC) are screened and tested, and meanwhile, the lead content is detected, and the detection content and the detection result are as follows:
depending on the particular test range and analytical technique, the test results for high substance of interest concentrations of less than 0.1% lead in the test samples are as follows:
remarking:
1)1mg/kg＝0.0001％
(2) MDL (medium density language) method detection limit
(3) ND is not detected (< MDL)
(4) "-" (not specified)
Lead (Pb)
The test method comprises the following steps: reference US EPA method 3052: 1996, using ICP-OES for analysis.
9. Retanning
(1) Step 8, weighing the treated sturgeon skin;
(2) weighing 9(1) 100 percent of water, 0.3 percent of formic acid, 2 percent of acrylic acid retanning agent, 4 percent of danine, 2 percent of anionic fatliquor and 0.5 percent of baking soda by weight of sturgeon skin;
(3) putting sturgeon skin and water into a rotary drum, setting the temperature at 44 ℃, adding diluted formic acid (diluted by 1: 10 times of water and in weight ratio), and rotating for 30 minutes; adding the white tannin, turning for 2h, adding the acrylic acid retanning agent and the anionic fatting agent, and turning for 2 h; adding diluted baking soda (diluted by water with the weight ratio of 1: 20) in 4 times in equal amount, rotating for 40 minutes each time, wherein the rotating speed of the rotating drum is 4 revolutions per minute, stopping the drum, standing, and the total time from the feeding to the standing is 24 hours;
(4) after standing, rotating for 1h and 4 revolutions per minute; when the pH value of the solution is detected to be 4.0, fully washing the solution for 2 times with water at the temperature of 35-40 ℃, wherein each time lasts for 10 minutes, and discharging the solution for controlling water;
10. neutralization
(1) Step 9, weighing the sturgeon skin processed;
(2) weighing 100% of water, 2% of neutralized tannin, 2% of tannin extract (PAK-N-C Langshan), 1% of sodium formate and 0.5% of baking soda by weight of the sturgeon skin in the step 10 (1);
(3) putting sturgeon skin and water into a rotary drum, setting the temperature at 44 ℃, adding neutral tannin, and rotating for 30 minutes; adding tannin essence and rotating for 30 minutes; adding sodium formate, and rotating for 30 minutes; adding the diluted baking soda (diluted by water with the weight ratio of 1: 20) in 3 times in average, and rotating for 30 minutes each time; the rotating speed of the rotary drum is 2 revolutions per minute.
(4) Detecting the pH value of the solution at the end point of 5.5;
(5) fully cleaning the sturgeon skin for 2 times at 40 ℃, 10 minutes each time, taking out the sturgeon skin, and naturally controlling water for 24 hours to prepare for the next procedure.
Secondly, soft dyeing is carried out
1. Falling soft
The main bone plate in the middle of the tanned and degreased sturgeon leather is empty, the bone plate is easy to crack by direct milling, the hollow part of the meat bone plate is filled with hot melt adhesive (figure 4), meanwhile, the sturgeon leather is sleeved with a protection bag, then the sturgeon leather is put into a milling drum to be milled for 6 hours, the rotating drum rotates for 12 r/min, and the fibers of the sturgeon leather after milling are fully opened, thereby being beneficial to filling of subsequent materials;
2. fully cleaning the flaked sturgeon leather with water at the temperature of 35-40 ℃, controlling water and weighing
3. The secondary retanning is carried out,
(1) weighing the sturgeon skin treated in the step 2;
(2) weighing 100% of water, 2% of acrylic acid retanning agent (basf), 2% of polymer resin retanning agent (basf), 4% of bark tannin extract (soft) and 1% of baking soda, wherein the weight of the water, the acrylic acid retanning agent (basf), the polymer resin retanning agent (basf) and the baking soda are the weight of sturgeon skin in the step two 3 (1);
(3) putting sturgeon skin and water into a rotary drum, setting the temperature at 44 ℃, adding an acrylic acid retanning agent, turning for 60 minutes, adding a resin retanning agent, turning for 60 minutes, adding tannin extract, turning for 60 minutes, wherein the rotating speed of the rotary drum is 4 revolutions per minute; adding diluted sodium bicarbonate (diluted by warm water with the ratio of 1: 20 times, parts by weight) in 3 times on average, rotating 30 minutes each time and 4 revolutions per minute, when ph is detected to be 5.5, then washing for 20 minutes in a rotating drum with normal temperature running water, discharging the drum, controlling water and weighing.
4. Dyeing and fatliquoring
(1) Step two 3, weighing the treated sturgeon skin;
(2) weighing 100% of water, 4% of phospholipid fatliquor, 2% of neatsfoot oil (brother chemical industry), 6% of lanolin fatliquor (Langsheng), 1% of leveling agent (Pasteur FR-DE), 1% of formic acid and 1% of dye by weight of sturgeon skin in the second step (1);
(3) putting sturgeon skin and water into a rotary drum, setting the temperature at 50 ℃, adding a leveling agent for 10 minutes, adding a dye for 40 minutes, adding neat's foot oil for 60 minutes, adding a phospholipid fatting agent for 60 minutes, adding a lanolin fatting agent for 60 minutes, adding diluted formic acid (diluted by water with the weight ratio of 1: 10 times) for two times on average, rotating for 30 minutes each time, rotating the rotary drum at 10 revolutions per minute in the above procedures, discharging and controlling water, then washing the rotary drum twice with normal-temperature water for 10 minutes each time, discharging and stacking, and controlling water for 24 hours.
7. Toggling drying
8. Water spraying softening
Uniformly spraying water (the water amount is about 30% of the weight of the dried sturgeon leather) on the meat surface of the dried sturgeon leather, and then stacking the sturgeon leather in a sealing manner for 24-48 h;
9. falling soft
The time for the breaking is 3 hours as the method for the second 1 breaking.
10. Toggling drying
11. 1000 mesh German import warrior sand paper polishing
12. High temperature ironing
Ironing the sturgeon leather is an indispensable link in the sturgeon leather coating process, and ironing adopts a modified leather embossing machine (RG-SY);
the modified leather embossing machine comprises a hot pressing plate and a corresponding bottom plate of the leather embossing machine; the bottom plate is provided with a groove, and the size of the groove is slightly larger than the protrusion of the main bone plate of the sturgeon skin; the contact surface of the hot pressing plate and the leather is provided with a high-temperature resistant felt, and the thickness of the felt is 2 cm;
in view of the size of the bone plate of the sturgeon in Yangtze river to be treated, the length of the groove is 100cm, the depth is 1.5cm, and the width is 5 cm.
When ironing, the bulges of the main bone plate of the sturgeon leather are arranged at the grooves of the bottom plate, the temperature of the hot pressing plate is 100 ℃, the pressure is 200 kg/square centimeter, and the ironing time is about 2-3 seconds.
13. The ironed sturgeon leather is coated in different styles according to the requirements, such as high gloss, matte and the like, so that the requirements of different shoe upper leathers are met (figure 3), and as can be seen from figure 3, the sturgeon leather treated by the method provided by the invention has complete leather surface, can be bent freely, has excellent flexibility and is suitable for being used as the shoe upper leather.
Claims (3)
1. The method for processing the soft shoe upper leather of the sturgeon skin of the Yangtze river sturgeons and the Chinese sturgeons comprises the following steps:
degreasing and tanning sturgeon skin
1. Drum soaking and pre-degreasing
(1) Selecting salt-wet skins of Yangtze river sturgeons or Chinese sturgeons, fully washing the sturgeon skins with water, and weighing after the washing is finished;
(2) weighing 0.51% of water-soaking agent, 1-2% of bactericide, 1-2% of degreasing agent and 200-300% of water by weight of the sturgeon skin obtained in the step (1);
(3) soaking: putting sturgeon skin and water into a rotary drum, adjusting the temperature to be 20-22 ℃, then adding a soaking agent, a bactericide and a degreasing agent, rotating the rotary drum at the speed of 2-4 revolutions per minute for 10-20 minutes for 40-50 minutes, stopping for 36-48 hours from the feeding to the end of the rotation of the rotary drum, then washing with running water in the rotary drum, and discharging and controlling water in the rotary drum;
2. mechanical degreasing
(1) The skin and flesh surfaces of the sturgeons soaked in water are upward, fins are removed, and fish and fat are removed by a steel wire brush or a nylon brush;
(2) cleaning sturgeon skin with meat and fat removed with warm water, and controlling water;
3. liming and degreasing
(1) Step 2, weighing sturgeon skin obtained after mechanical degreasing and cleaning;
(2) weighing 1.0-1.5% of sodium hydrosulfide particles in the weight of the sturgeon skin in the step 3(1), wherein the effective content of the sodium hydrosulfide particles is 60-80%, 10-15% of lime, 0.5-1% of liming auxiliary agent, 1-2% of degreasing agent and 300-400% of water;
(3) putting prepared sturgeon skin and water into a rotary drum, setting the temperature to be 20-24 ℃, the rotating speed to be 4-6 r/min, adding a degreasing agent and sodium hydrosulfide, and rotating for 1 h; adding the liming auxiliary agent and lime, rotating for 5-15 minutes, stopping for 40-60 minutes, rotating at the rotating speed of the rotary drum of 2-3 revolutions per minute, and counting the time from the feeding to the finishing of the rotation of the rotary drum for 48-60 hours;
the end point is that the expansion of the sturgeon skin is uniform, the skin is firm, and the pH value of the solution is more than 12;
washing, namely washing sturgeon skin with running water at normal temperature by using the rotary drum;
(4) secondary mechanical fleshing and fat removing;
4. deashing and degreasing
(1) Step 3, weighing the sturgeon skin treated in the step;
(2) weighing 1-1.5% of ammonium sulfate, 1-1.5% of degreasing agent, 100-200% of water and 0.5-1% of deliming auxiliary agent in the weight of the sturgeon skin in the step 4 (1);
(3) putting sturgeon skin and water into a rotary drum, setting the temperature to be 33-36 ℃, adding ammonium sulfate, a degreasing agent and a deliming auxiliary agent, rotating the rotary drum at the speed of 2-4 r/min for 1-2h,
(4) end point phenolphthalein indicator showed cuts 1/5-1/6 hearts,
(5) washing with water, namely fully washing the rotary drum with warm water;
5. softening
(1) Step 4, weighing the treated sturgeon skin;
(2) weighing 200% of 100-;
(3) putting sturgeon skin and water into a rotary drum, setting the water temperature to be 35-37 ℃, adding pancreatin and ammonium sulfate, rotating the rotary drum at the speed of 4-6 r/min for 1-1 h;
(4) the end point is that the grain surface is smooth and white, the finger is pressed with fingerprint, and the skin is flexible and compact
(5) Washing with warm water;
6. pickling
(1) Step 5, weighing the treated sturgeon skin;
(2) weighing 100-200% of water, 10-16% of salt, 1-2% of acetic acid, 2-2.5% of concentrated sulfuric acid and 1-2% of nonionic degreasing agent in the weight of the sturgeon skin in the step 6 (1);
(3) putting sturgeon skin and water into a rotary drum, setting the temperature to be 21-23 ℃, adding salt and a non-ionic degreasing agent, rotating the rotary drum for 1-2 revolutions per minute, and rotating for 25-35 minutes; adding equivalent diluted acetic acid for 2-3 times, and rotating for 25-35 minutes and 4 revolutions per minute each time; then adding diluted concentrated sulfuric acid in 3-5 times in equal amount, rotating for 25-45 minutes each time at a rotating speed of 4-6 revolutions per minute, setting the rotary drum to rotate for 5-15 minutes and stop for 40-60 minutes after the completion, rotating at a rotating speed of 2-4 revolutions per minute, and totaling 24-36 hours from the beginning of feeding to the end of rotation of the rotary drum;
(4) at the end point, the skin surface is astringent, the skin body is flexible and compact, and the pH value of the solution is 2.0-3.0;
(5) degreasing, namely taking the sturgeon skin out in a pickled skin state, degreasing mechanically, weighing the sturgeon skin, and then putting the sturgeon skin into the original pickling solution;
7. tanning
(1) Weighing 2-4% of modified glutaraldehyde, 1-1.5% of aluminum tanning agent, 8-10% of white tannin extract, 1-1.5% of sodium formate, 1.5-2% of baking soda and 1-1.5% of mildew preventive in the weight of the sturgeon skin in the step 6;
(2) operation of
The preparation method comprises the following steps of (1) carrying out the steps in an original pickling solution, setting the temperature to be 22-24 ℃, adding diluted modified glutaraldehyde, rotating for 1-1.5h, and rotating at 4-6 r/min; adding aluminum tanning agent, rotating for 1-2h, and rotating the drum for 4-6 r/min; adding white tannin and white tannin extract, and rotating for 4h and 4-6 revolutions per minute; stopping the drum and standing for 18-32 hours from the beginning of feeding to the end of standing;
(3) standing, adding sodium formate and mildew preventive, rotating for 1-2h, and rotating for 4-6 r/min; adding diluted sodium bicarbonate in 5-8 times, rotating for 30-50 min each time, and rotating for 4-6 r/min; when the pH value is detected to be 4.0, the rotary drum is continuously rotated for 2 to 3 hours at 4 to 6 revolutions per minute; then the water temperature in the rotary drum is raised to 40-45 ℃, the rotation is carried out for 2-3h, and the rotation speed of the rotary drum is 4-6 r/min; detecting the shrinkage temperature by boiling water to be more than 80 ℃, stopping the drum and standing for 18-32 hours from the beginning of feeding to the end of standing;
(4) rotating for 1-2h, and rotating for 2-4 r/min; washing with flowing water in the drum at normal temperature, and discharging from the drum;
8. degreasing
(1) Step 7, weighing the treated sturgeon skin;
(2) weighing 300-400% of water and 3-4% of high-temperature resistant non-ionic degreasing agent by weight of the sturgeon skin in the step 8 (1);
(3) putting sturgeon skin and water into a rotary drum, setting the temperature at 60-70 ℃, adding a degreasing agent, rotating for 4-6 hours at 4-6 rpm, cleaning with hot water at 55-60 ℃, and discharging from the drum for water control;
9. retanning
(1) Step 8, weighing the treated sturgeon skin;
(2) weighing 9(1) 100-200% of water, 0.3-0.6% of formic acid, 2-4% of acrylic acid retanning agent, 4-8% of white tannin, 2-4% of anionic fatliquor and 0.5-1% of baking soda by weight of sturgeon skin;
(3) putting sturgeon skin and water into a rotary drum, setting the temperature at 42-44 ℃, adding diluted formic acid, and rotating for 20-40 minutes; adding the white tannin, turning for 1-3h, adding the acrylic acid retanning agent and the anionic fatting agent, turning for 1-3h, adding the diluted sodium bicarbonate in 3-4 times and the like, turning for 30-50 minutes each time, wherein the rotating speed of a rotating drum is 4-6 revolutions per minute, stopping the drum, standing, and the total time from the beginning of feeding to the end of standing is 18-32 hours;
(4) standing, and rotating for 1-2h at 4-6 rpm; when the pH value of the solution is detected to be 4.0, fully washing with water, and discharging and controlling water;
10. neutralization
(1) Step 9, weighing the sturgeon skin processed;
(2) weighing 200% of water, 2-4% of neutralized tannin, 1-2% of tannin extract, 1-2% of sodium formate and 0.5-1% of baking soda, wherein the weight of the sturgeon skin is 100-;
(3) putting sturgeon skin and water into a rotary drum, setting the temperature at 42-44 ℃, adding neutralizing tannin, and rotating for 20-40 minutes, and adding tannin essence and rotating for 20-40 minutes; adding sodium formate, and rotating for 20-40 min; adding the diluted baking soda for 3-4 times at 20-40 min intervals; the rotating speed of the rotary drum is 2-4 revolutions per minute;
(4) detecting the pH value of the solution by 5-6 at the end point;
(5) fully washing sturgeon skin with water, and naturally controlling water;
secondly, soft dyeing is carried out
1. Falling soft
Filling the hollow part of the meat-dough plate with hot melt adhesive, sleeving sturgeon leather into a protection bag, putting the sturgeon leather into a softening drum, and softening for 6-7 hours with 10-15 r/min of the rotary drum;
2. fully washing the softened sturgeon skin with water, and controlling the water;
3. the secondary retanning is carried out,
(1) weighing the sturgeon skin treated in the step 2;
(2) weighing 100-200% of water, 2-4% of acrylic acid retanning agent, 2-4% of polymer resin retanning agent, 4-6% of soft wattle bark tannin extract and 1-2% of baking soda, wherein the weight of the sturgeon skin is calculated in the step two 3 (1);
(3) putting sturgeon skin and water into a rotary drum, setting the temperature at 42-44 ℃, adding an acrylic acid retanning agent, rotating for 50-70 minutes, adding a resin tanning agent, rotating for 50-70 minutes, adding tannin extract, and rotating for 50-70 minutes, wherein the rotating speed of the rotary drum is 4-6 revolutions per minute; adding diluted sodium bicarbonate 3-4 times, rotating at 4-6 rpm for 20-40 min each time, washing with water when pH is 5.5, and draining;
4. dyeing and fatliquoring
(1) Step two 3, weighing the treated sturgeon skin;
(2) weighing 100-;
(3) putting sturgeon skin and water into a rotary drum, setting the temperature at 45-55 ℃, adding a leveling agent, rotating for 8-12 minutes, adding a dye, rotating for 30-50 minutes, adding neat's foot oil, rotating for 50-70 minutes, adding a phospholipid fatting agent, rotating for 50-70 minutes, adding a lanolin fatting agent, rotating for 50-70 minutes, adding diluted formic acid in 2-3 times in average, rotating for 30 minutes each time, wherein the rotary drum rotating speed of the above procedures is 10-15 revolutions per minute, discharging liquid and controlling water, and then fully washing and controlling water in the rotary drum;
7. toggling drying
8. Water spraying softening
Uniformly spraying water on the dried sturgeon leather on the meat surface, and then stacking in a sealing manner for 24-48 h;
9. falling soft
The time for the falling and softening is 2 to 4 hours as the same as the falling and softening method in the step two 1;
10. toggling drying
11. Polishing with abrasive paper
12. High temperature ironing
Ironing by adopting a modified leather embossing machine; the modified leather embossing machine comprises a hot pressing plate and a corresponding bottom plate of the leather embossing machine; the bottom plate is provided with a groove, and the size of the groove is larger than the main bone plate bulge of the sturgeon skin; the contact surface of the hot pressing plate and the leather is provided with a high-temperature resistant felt;
the Chinese sturgeons and the Yangtze river sturgeons are both from artificially cultured populations.
2. The method of claim 1, wherein: the thickness of the high-temperature resistant felt is 2 cm; the length of the groove is 100cm, the depth is 1.5cm, and the width is 5 cm.
3. The method of claim 1, wherein: the temperature of the hot pressing plate is 100 ℃, the pressure is 200 kg/square centimeter, and the ironing time is 2-3 seconds.
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| CN102199676A (en) * | 2011-04-12 | 2011-09-28 | 王学川 | Sturgeon skin chrome tanning leather production process |
| CN102839236A (en) * | 2012-09-29 | 2012-12-26 | 桐乡市雄鹰皮草有限公司 | Dual-purpose modification process for native breed sheepskin leather |
| CN104774980A (en) * | 2015-03-23 | 2015-07-15 | 浙江金鑫皮革有限公司 | Goat instep leather manufacturing technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102199676A (en) * | 2011-04-12 | 2011-09-28 | 王学川 | Sturgeon skin chrome tanning leather production process |
| CN102839236A (en) * | 2012-09-29 | 2012-12-26 | 桐乡市雄鹰皮草有限公司 | Dual-purpose modification process for native breed sheepskin leather |
| CN104774980A (en) * | 2015-03-23 | 2015-07-15 | 浙江金鑫皮革有限公司 | Goat instep leather manufacturing technology |
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