CN109576409B - Method for making glittering sturgeon skin leather - Google Patents
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- C—CHEMISTRY; METALLURGY
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- 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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- C—CHEMISTRY; METALLURGY
- 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
- C14B1/02—Fleshing, unhairing, samming, stretching-out, setting-out, shaving, splitting, or skiving skins, hides, or leather
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- C—CHEMISTRY; METALLURGY
- 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
- C14B1/40—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
- 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
- C14B1/46—Fluffing, buffing, or sanding
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- C—CHEMISTRY; METALLURGY
- 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
- C14B1/44—Mechanical treatment of leather surfaces
- C14B1/54—Ironing
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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
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
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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
- C14C15/00—Apparatus for chemical treatment or washing of hides, skins, or leather
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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
- C14C3/04—Mineral tanning
- C14C3/06—Mineral tanning using chromium compounds
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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
- C14C3/08—Chemical tanning by organic agents
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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
- C14C3/28—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
- C14C5/00—Degreasing leather
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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 discloses a method for manufacturing flash sturgeon leather belt leather.
Description
Technical Field
The invention belongs to the field of leather processing, and particularly relates to a method for manufacturing glittering sturgeon skin leather.
Background
Because the surface of the leather of the flash sturgeon (A. stellatus) is distributed with 5 rows of natural bone plates, the flash sturgeon is slender, the bone plates are regularly arranged, the bone plates are relatively smaller, the leather sheet is thinner, and the flash sturgeon is suitable for producing high-grade belts and luxury watchbands, for the leather of the belts and watchbands, water resistance, moisture resistance and sweat resistance are needed, and the conventional tanning technology is difficult to meet the requirements of luxury product production.
Disclosure of Invention
The invention aims to provide a method for manufacturing the leather belt of the flash sturgeon skin, the leather of the flash sturgeon processed by the method is waterproof, moistureproof, soft, plumpy and tear-resistant, and is a high-quality material for manufacturing luxury belts and watchbands.
In order to achieve the purpose, the invention adopts the following technical measures:
the method for manufacturing the glittering sturgeon skin leather comprises the following steps:
1. drum soaking and pre-degreasing
(1) Selecting materials: fully washing the glittering sturgeon skin with water, and weighing after the washing is finished;
(2) weighing 1-1.5% of soaking agent, 1-2% of bactericide, 2-4% of degreasing agent and 200-300% of water in the weight of the flash 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, starting from feeding until the rotary drum rotates for 12-24 hours, then washing with running water in the rotary drum, and discharging the rotary drum for water control;
2. liming and degreasing
(1) Step 1, weighing sturgeon skin obtained after cleaning;
(2) weighing 1.0-2.0% of sodium hydrosulfide particles (effective content 60-80%), 8-12% of lime, 0.5-1% of liming auxiliary agent, 2-4% of degreasing agent and 300-400% of water by weight of the sturgeon skin in the step 2 (1);
(3) putting prepared sturgeon skin and water into a rotary drum, setting the temperature to be 22-24 ℃, rotating the rotary drum at the rotating speed of 1-3 revolutions per minute, adding a degreasing agent, dissolving the sodium hydrosulfide in the water, and rotating for 25-35 minutes; adding the liming auxiliary agent and lime, rotating for 5-15 minutes, stopping for 45-55 minutes, rotating at the rotating speed of the rotary drum of 2-4 revolutions per minute, and finishing the rotation of the rotary drum for 12-24 hours from the feeding start;
(4) 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.
(5) Washing, namely washing the rotary drum with running water at normal temperature;
3. mechanical defatting and fleshing
(1) Putting sturgeon skin and flesh side up, and brushing grease and fish flesh with a steel wire brush;
(2) washing the degreased sturgeon skin with clear water;
4. deashing and degreasing
(1) Step 3, weighing the sturgeon skin treated in the step;
(2) weighing 1-2% of ammonium sulfate, 1-2% of degreasing agent, 100% of water and 200% of deliming additive 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, and rotating the rotary drum at the rotating speed of 1-3 revolutions per minute for 20-30 minutes;
(4) water washing, namely fully washing with water at the temperature of between 33 and 36 ℃;
5. softening
(1) Step 4, weighing the treated sturgeon skin;
(2) weighing 200% of 100-;
(3) putting the flash 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 1-3 r/min for 20-30 min;
(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 water, namely fully washing with warm water at the temperature of 35-37 ℃ in the rotary drum;
6. pickling
(1) Step 5, weighing the treated sturgeon skin;
(2) weighing 100-200% of water, 10-16% of salt, 2-4% of acetic acid, 1-3% of concentrated sulfuric acid and 2-4% 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 20-24 ℃, adding salt, rotating the rotary drum for 1-3 revolutions per minute and rotating for 20-30 minutes; adding a degreasing agent, adding equivalent diluted acetic acid in 2-3 portions, and rotating for 20-30 minutes and 2-4 revolutions per minute each time; then evenly adding diluted concentrated sulfuric acid for 4-6 times, rotating for 20-30 minutes each time at the rotating speed of 2-4 revolutions per minute, stopping the drum and standing, wherein the total time from feeding to standing is 12-24 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 2.0-3.0;
(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, 1.5-3% of aluminum tanning agent, 10-12% of white tannin extract, 1-2% of sodium formate, 1.5-2.5% of baking soda and 1-2% of mildew preventive, based on the weight of the sturgeon skin in the step 6;
(2) operation of
The method is carried out in the original pickle liquor, the temperature is set to be 22-24 ℃, diluted modified glutaraldehyde is added, and the mixture is rotated for 1-2 hours at 2-4 revolutions per minute; adding aluminum tanning agent, rotating for 1-2h, and rotating the drum for 2-4 r/min; adding white tannin and white tannin extract, rotating for 1-2h and 2-4 r/min, stopping drum and standing, and totally 12-24h from the beginning of feeding to the end of standing;
(3) adding sodium formate and a mildew preventive, and rotating for 1-2h and 2-4 r/min; adding diluted sodium bicarbonate in 5-8 times, rotating for 25-35 min each time, and rotating for 2-4 r/min; when the ph of the solution is detected to be 4.0, continuing rotating for 2-3 h; then, the water temperature in the rotary drum is raised to 38-42 ℃, and the rotary drum is rotated for 2-4 h; when the shrinkage temperature is detected by boiling water and is above 80 ℃, stopping the drum and standing for 12-24 hours from the beginning of feeding to the end of standing.
(4) Washing sturgeon skin with running water in the drum at normal temperature, and taking the sturgeon skin out of the drum for degreasing;
8. degreasing
(1) Step 7, weighing the treated sturgeon skin;
(2) weighing 400-600% of water and 4-6% 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 6-8 r/min, rotating for 6-8 h, 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, 4-6% 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 40-48 ℃, adding diluted formic acid, and rotating for 25-35 minutes; adding white tannin, and rotating for 1-2 h; adding an acrylic acid retanning agent and an anionic fatting agent, and turning for 1-2 h; adding diluted sodium bicarbonate in 3-4 times, rotating for 35-45 min each time, stopping drum, standing, and keeping the total time from feeding to standing for 12-24 hr;
(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 cleaning with water at the temperature of between 35 and 40 ℃, 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, 2-4% 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 42-46 ℃, adding neutral tannin, and rotating for 25-35 minutes; adding tannin essence, and rotating for 25-35 min; adding sodium formate, and rotating for 25-350 min; adding the diluted baking soda in 3-4 times, each time rotating for 25-35 minutes, wherein the rotating speed of the rotary drum is 2-4 revolutions per minute;
(4) detecting the pH value of the solution at the end point of 5.0-6.0;
(5) fully cleaning sturgeon skin with water at 40 ℃, and controlling water after the sturgeon skin is discharged;
11. dyeing and fatliquoring
(1) Step 10, weighing the sturgeon skin processed;
(2) weighing 100-;
(3) putting sturgeon skin and water into a rotary drum, setting the temperature at 48-52 ℃, adding a leveling agent, and rotating for 5-15 minutes; adding dye to rotate for 35-45 minutes; adding neat's foot oil and rotating for 55-65 min; adding phospholipid fatting agent and rotating for 55-65 min; adding waterproof fatting agent and rotating for 55-65 min; adding diluted formic acid in 2-3 times, rotating for 25-35 minutes each time, wherein the rotating speed of the rotating drum in the above procedures is 10-12 revolutions per minute; discharging liquid and controlling water, then washing with normal-temperature water in the rotary drum, and discharging and controlling water;
12. falling soft
Filling the flesh bone lamella with hot melt adhesive, meanwhile, sleeving sturgeon leather into a protection bag, then putting the sturgeon leather into a milling drum for milling for 3 hours, rotating the drum for 12 revolutions per minute, and fully opening fibers of the milled sturgeon skin, thereby being beneficial to the operation of subsequent processes of plate stretching and coating; 13. toggling drying
14. Polishing with abrasive paper
15. 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;
16. and (3) coating the ironed sturgeon leather in different styles according to requirements, and spraying a waterproof agent on the front surface of the sturgeon leather after finishing coating.
In the above method, preferably, the length of the groove is 100 cm, the width is about 5 cm, the depth is about 1.5 cm, and the thickness of the high temperature resistant felt is 2 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.
Compared with the prior art, the invention has the following advantages:
1. the tanned flash sturgeon leather is soft and plump, and the bone plate is intact;
2. a brand new 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 the product yield greatly exceeds 30 percent of that of the traditional tanning method.
5. The waterproof and moistureproof effects are excellent, water is dripped on the flesh side and the front side of the flash sturgeon leather through detection, and the anti-seepage time can reach more than 24 hours.
6. The leather produced by processing is environment-friendly, has no peculiar smell, and only has the smell of the leather.
Drawings
Fig. 1 is a schematic diagram of sturgeon skin filled with hot melt adhesive at the recesses of the bone plate.
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 a glittering sturgeon leather belt leather prepared in example 1 of the present invention.
Fig. 4 is a belt prepared using the glittering sturgeon leather prepared in example 1.
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.
Example 1:
the method for manufacturing the glittering sturgeon skin leather 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 total weight of the skin and gill of the sturgeon involved in each step.
1. Drum soaking and pre-degreasing
(1) Selecting materials: the glittering sturgeon skin mainly comprises salt-wet skin of 6 kilograms of glittering sturgeons, the water temperature in the rotary drum is 18-22 ℃, the sturgeon skin is fully washed, and the weight is weighed after the water washing is finished.
(2) Weighing 1% of water soaking agent (Pasteur Eusaponn W), 1% of bactericide (Langshan Cismolan AN 90), 2% of degreasing agent (brother chemical H900) and 200% of water in weight of the flash 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 time is 24 hours from the feeding to the end of 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. Liming and degreasing
(1) Step 1, weighing sturgeon skin obtained after cleaning;
(2) weighing 1.0% of sodium hydrosulfide particles (effective content is 70%), 8% of lime, 0.5% of liming auxiliary agent (Langshan CISMOLLAN BH-C), 2% of degreasing agent (brother chemical H900)3 and 300% of water in the weight of the sturgeon skin in the step 2 (1); (3) putting prepared sturgeon skin and water into a rotary drum, setting the temperature to be 24 ℃, rotating the rotary drum at the rotating speed of 1 r/min, adding a degreasing agent, dissolving the sodium hydrosulfide in the water, rotating for 30 min, adding an liming auxiliary agent and lime, rotating for 10 min, stopping for 50 min, rotating the rotary drum at the rotating speed of 2 r/min, and counting the time from the feeding to the end of the rotation of the rotary drum for 24 h.
(4) 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.
(5) And (4) washing, namely washing the rotary drum with running water at normal temperature for 2 times and 10 minutes each time at 2 revolutions per minute.
3. Mechanical defatting and fleshing
(1) The sturgeon skin and flesh side is upward and fixed on a chopping board, grease and fish are manually brushed away by a 80-mesh steel brush, and the strength cannot be too high when brushing away due to the fact that the glittering sturgeon skin is thin, so that the sturgeon skin is prevented from being damaged;
(2) and washing the degreased sturgeon skin with clear water.
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 to be 33 ℃, adding ammonium sulfate, a degreasing agent and a deliming auxiliary agent, and rotating the rotary drum at the rotating speed of 1 r/min for 30 min;
(4) and (4) water washing, namely fully washing the glass substrate for 2 times by using warm water (33-36 ℃) of a rotary drum, 10 minutes each time and 2 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, 0.5% of pancreatin and 0.5% of ammonium sulfate by weight of the sturgeon skin in the step 5 (1);
(3) putting the flash sturgeon skin and water into a rotary drum, setting the water temperature to be 36 ℃, adding pancreatin and ammonium sulfate, rotating the rotary drum at the speed of 1 r/min for 30 min;
(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 for 10 minutes by warm water at the temperature of 35-37 ℃, washing the inner part of the rotary drum for 10 minutes at the normal temperature of 20-24 ℃, and rotating the rotary drum for 1 r/min.
6. Pickling
(1) Step 5, weighing the treated sturgeon skin;
(2) weighing 100% of water, 16% of salt, 2% of acetic acid, 1% 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, rotating the rotary drum for 1 r/min and 30 min, adding a degreasing agent, adding equivalent diluted acetic acid (the acetic acid is diluted by 10 times of water by weight) twice, rotating for 30 min and 2 r/min each time, then adding diluted concentrated sulfuric acid (diluted by 10 times of water) 4 times averagely, rotating for 30 min each time, rotating for 2 r/min and then stopping the drum for standing, wherein the total time from the beginning of feeding to the end of standing is 24 h;
(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 again on a dried panel (the method is the same as 3), 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 (diluted by water with the weight ratio of 1: 5) is added, and the mixture is rotated for 1h and rotated for 2 r/min; adding an aluminum tanning agent, rotating for 1h, and rotating a drum for 2 revolutions per minute; adding the white tannin and the white tannin extract, rotating for 2 hours and 2 revolutions per minute, stopping the drum and standing, and totally 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 2 r/min; adding diluted baking soda (20 times of 35 ℃ water solution by weight) in 8 times of equal amount, rotating for 30 minutes each time, and rotating the drum for 2 revolutions per minute; when the ph of the solution is detected to be 4.0, continuing rotating for 2 hours; then, the water temperature in the rotary drum is raised to 40 ℃, and the rotary drum is rotated for 2 hours; when the shrinkage temperature is detected by boiling water and is above 80 ℃, stopping the drum and standing for 24 hours from the beginning of feeding to the end of standing.
(4) Rotating at the speed of 2 r/min, washing with flowing water in a rotating drum at normal temperature for 20 min, and taking out of the drum to prepare 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 Eusapono OC, brother chemical H901 in a 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, leather fibers are completely opened, finger pressure has fluffy feeling, natural grease in the sturgeon leather is basically removed completely, the leather is firm, rotten leather does not exist, 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 white tannin, 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 (1: 10 times of water for dilution, weight ratio), and rotating for 30 minutes; adding white tannin and rotating for 2 h; adding an acrylic acid retanning agent and an anionic fatting agent, and turning for 2 hours; 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 between 35 and 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) into the reactor evenly for 3 times, wherein the rotation speed of the rotary drum is 2 revolutions per minute for 30 minutes each time;
(4) detecting the pH value of the solution at the end point of 5.5;
(5) fully washing sturgeon skin for 2 times with water at 40 ℃, 10 minutes each time, taking out of the drum, and naturally controlling water for 24 hours to prepare for the next procedure.
11. Dyeing and fatliquoring
(1) Step 10, weighing the sturgeon skin processed;
(2) weighing step 11(1) 100% water, 4% phospholipid fatliquor, 2% neatsfoot oil (brother chemical), 1% waterproof fatliquor (us 3M), 1% levelling agent (basf FR-DE), 1% formic acid, 1% dye by weight of sturgeon skin;
(3) putting sturgeon skin and water into a rotary drum, setting the temperature at 50 ℃, adding a leveling agent, and rotating for 10 minutes; adding a dye, and rotating for 40 minutes; adding neat's foot oil and rotating for 60 minutes; adding phospholipid fatting agent and rotating for 60 minutes; adding waterproof fatting agent and rotating 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, and rotating the drum at the speed of 10 revolutions per minute in the above procedures; draining liquid and controlling water, then washing twice with normal-temperature water in the rotary drum for 10 minutes each time, discharging the drum and stacking, and controlling water for 24 hours.
12. Falling soft
The method is characterized in that the inner side (meat surface) of a main bone plate in the middle of the tanned and degreased sturgeon leather is empty, the bone plate is easy to break by direct milling, the meat surface bone plate is filled with hot melt adhesive (figure 1), meanwhile, the sturgeon leather is sleeved with a protection bag, then the sturgeon leather is put into a milling drum to be milled for 3 hours, the rotating drum rotates for 12 revolutions per minute, fibers of the sturgeon leather after milling are fully opened, and the operation of subsequent plate stretching and coating processes is facilitated;
13. toggling drying
14. 1000 mesh German import warrior sand paper polishing
15. 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;
the length of the groove is 100 cm, the width of the groove is about 5 cm, the depth of the groove is about 1.5 cm, and the groove is basically consistent with the width of the main bone plate on the back of the sturgeon leather.
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.
16. And (3) coating the ironed sturgeon leather in different styles such as high gloss, matte and the like according to requirements, spraying a waterproof agent on the front surface of the sturgeon leather after finishing coating, and enhancing the waterproof and moistureproof effects of the flash sturgeon leather.
The flash sturgeon leather processed by the process has excellent waterproof and moistureproof effects, water is dripped on the flesh side and the front side of the flash sturgeon leather through detection, the anti-seepage time can reach more than 24 hours, and the tanned flash sturgeon leather is soft and full, and bone plates are intact (figure 3); the high-quality product rate of the leather reaches more than 90 percent, and the yield greatly exceeds 30 percent of that of the traditional tanning method. Can fully meet the strict requirements of luxury leather belt and watchband production, and has high market economic value. The leather produced by the above method was used to produce a belt as shown in FIG. 4.
Claims (2)
1. The method for manufacturing the glittering sturgeon skin leather comprises the following steps:
1. drum soaking and pre-degreasing
(1) Selecting materials: fully washing the glittering sturgeon skin with water, and weighing after the washing is finished;
(2) weighing 1-1.5% of soaking agent, 1-2% of bactericide, 2-4% of degreasing agent and 200-300% of water in the weight of the flash 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, starting from feeding until the rotary drum rotates for 12-24 hours, then washing with running water in the rotary drum, and discharging the rotary drum for water control;
2. liming and degreasing
(1) Step 1, weighing sturgeon skin obtained after cleaning;
(2) weighing 1.0-2.0% of sodium hydrosulfide particles, 8-12% of lime, 0.5-1% of liming auxiliary agent, 2-4% of degreasing agent and 300-400% of water in the weight of the sturgeon skin in the step 2(1), wherein the effective content of the sodium hydrosulfide particles is 60-80%;
(3) putting prepared sturgeon skin and water into a rotary drum, setting the temperature to be 22-24 ℃, rotating the rotary drum at the rotating speed of 1-3 revolutions per minute, adding a degreasing agent, dissolving the sodium hydrosulfide in the water, and rotating for 25-35 minutes; adding the liming auxiliary agent and lime, rotating for 5-15 minutes, stopping for 45-55 minutes, rotating at the rotating speed of the rotary drum of 2-4 revolutions per minute, and finishing the rotation of the rotary drum for 12-24 hours from the feeding start;
(4) the end point is that the expansion of the sturgeon skin is uniform, and the pH value of the solution with firm skin is more than 12;
(5) washing, namely washing the rotary drum with running water at normal temperature;
3. mechanical defatting and fleshing
(1) Putting sturgeon skin and flesh side up, and brushing grease and fish flesh with a steel wire brush;
(2) washing the degreased sturgeon skin with clear water;
4. deashing and degreasing
(1) Step 3, weighing the sturgeon skin treated in the step;
(2) weighing 1-2% of ammonium sulfate, 1-2% of degreasing agent, 100% of water and 200% of deliming additive 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, and rotating the rotary drum at the rotating speed of 1-3 revolutions per minute for 20-30 minutes;
(4) water washing, namely fully washing with water at the temperature of between 33 and 36 ℃;
5. softening
(1) Step 4, weighing the treated sturgeon skin;
(2) weighing 200% of 100-;
(3) putting the flash 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 1-3 r/min for 20-30 min;
(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 water, namely fully washing with warm water at the temperature of 35-37 ℃ in the rotary drum;
6. pickling
(1) Step 5, weighing the treated sturgeon skin;
(2) weighing 100-200% of water, 10-16% of salt, 2-4% of acetic acid, 1-3% of concentrated sulfuric acid and 2-4% 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 20-24 ℃, adding salt, rotating the rotary drum for 1-3 revolutions per minute and rotating for 20-30 minutes; adding a degreasing agent, adding equivalent diluted acetic acid in 2-3 portions, and rotating for 20-30 minutes and 2-4 revolutions per minute each time; then evenly adding diluted concentrated sulfuric acid for 4-6 times, rotating for 20-30 minutes each time at the rotating speed of 2-4 revolutions per minute, stopping the drum and standing, wherein the total time from feeding to standing is 12-24 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 2.0-3.0;
(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, 1.5-3% of aluminum tanning agent, 10-12% of white tannin extract, 1-2% of sodium formate, 1.5-2.5% of baking soda and 1-2% of mildew preventive, based on the weight of the sturgeon skin in the step 6;
(2) operation of
The method is carried out in the original pickle liquor, the temperature is set to be 22-24 ℃, diluted modified glutaraldehyde is added, and the mixture is rotated for 1-2 hours at 2-4 revolutions per minute; adding aluminum tanning agent, rotating for 1-2h, and rotating the drum for 2-4 r/min; adding white tannin and white tannin extract, rotating for 1-2h and 2-4 r/min, stopping drum and standing, and totally 12-24h from the beginning of feeding to the end of standing;
(3) adding sodium formate and a mildew preventive, and rotating for 1-2h and 2-4 r/min; adding diluted sodium bicarbonate in 5-8 times, rotating for 25-35 min each time, and rotating for 2-4 r/min; when the pH value of the solution is detected to be 4.0, continuing rotating for 2-3 h; then, the water temperature in the rotary drum is raised to 38-42 ℃, and the rotary drum is rotated for 2-4 h; when the shrinkage temperature detected by boiling water is above 80 ℃, stopping the drum and standing for 12-24 hours from the beginning of feeding to the end of standing;
(4) washing sturgeon skin with running water in the drum at normal temperature, and taking the sturgeon skin out of the drum for degreasing;
8. degreasing
(1) Step 7, weighing the treated sturgeon skin;
(2) weighing 400-600% of water and 4-6% 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 6-8 r/min, rotating for 6-8 h, 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, 4-6% 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 40-48 ℃, adding diluted formic acid, and rotating for 25-35 minutes; adding white tannin, and rotating for 1-2 h; adding an acrylic acid retanning agent and an anionic fatting agent, and turning for 1-2 h; adding diluted sodium bicarbonate in 3-4 times, rotating for 35-45 min each time, stopping drum, standing, and keeping the total time from feeding to standing for 12-24 hr;
(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 cleaning with water at the temperature of 35-40 ℃, 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, 2-4% 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 42-46 ℃, adding neutral tannin, and rotating for 25-35 minutes; adding tannin essence, and rotating for 25-35 min; adding sodium formate, and rotating for 25-350 min; adding the diluted baking soda in 3-4 times, each time rotating for 25-35 minutes, wherein the rotating speed of the rotary drum is 2-4 revolutions per minute;
(4) detecting the pH value of the solution at the end point of 5.0-6.0;
(5) fully cleaning sturgeon skin with water at 40 ℃, and controlling water after the sturgeon skin is discharged;
11. dyeing and fatliquoring
(1) Step 10, weighing the sturgeon skin processed;
(2) weighing 100-;
(3) putting sturgeon skin and water into a rotary drum, setting the temperature at 48-52 ℃, adding a leveling agent, and rotating for 5-15 minutes; adding dye to rotate for 35-45 minutes; adding neat's foot oil and rotating for 55-65 min; adding phospholipid fatting agent and rotating for 55-65 min; adding waterproof fatting agent and rotating for 55-65 min; adding diluted formic acid in 2-3 times, rotating for 25-35 minutes each time, wherein the rotating speed of the rotating drum in the above procedures is 10-12 revolutions per minute; discharging liquid and controlling water, then washing with normal-temperature water in the rotary drum, and discharging and controlling water;
12. falling soft
Filling the flesh bone lamella with hot melt adhesive, meanwhile, sleeving sturgeon leather into a protection bag, then putting the sturgeon leather into a milling drum for milling for 3 hours, rotating the drum for 12 revolutions per minute, and fully opening fibers of the milled sturgeon skin, thereby being beneficial to the operation of subsequent processes of plate stretching and coating;
13. toggling drying
14. Polishing with abrasive paper
15. 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;
16. and (3) coating the ironed sturgeon leather in different styles according to requirements, and spraying a waterproof agent on the front surface of the sturgeon leather after finishing coating.
2. The method of claim 1, wherein: the length of the groove is 100 cm, the width of the groove is 5 cm, the depth of the groove is 1.5 cm, and the thickness of the high-temperature resistant felt is 2 cm; when ironing treatment is carried out, 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 kilograms per square centimeter, and the ironing time is 2-3 seconds.
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| CN102199675A (en) * | 2011-04-12 | 2011-09-28 | 王学川 | Clean process for producing leather by using sturgeon skin |
| CN102199676A (en) * | 2011-04-12 | 2011-09-28 | 王学川 | Sturgeon skin chrome tanning leather production process |
| CN102796832A (en) * | 2012-08-30 | 2012-11-28 | 陕西科技大学 | Production process for leather for painting |
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| CN102199675A (en) * | 2011-04-12 | 2011-09-28 | 王学川 | Clean process for producing leather by using sturgeon skin |
| CN102199676A (en) * | 2011-04-12 | 2011-09-28 | 王学川 | Sturgeon skin chrome tanning leather production process |
| CN102796832A (en) * | 2012-08-30 | 2012-11-28 | 陕西科技大学 | Production process for leather for painting |
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