CN105803134B - A kind of process for tanning of sheepskin - Google Patents
A kind of process for tanning of sheepskin Download PDFInfo
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- CN105803134B CN105803134B CN201410833128.6A CN201410833128A CN105803134B CN 105803134 B CN105803134 B CN 105803134B CN 201410833128 A CN201410833128 A CN 201410833128A CN 105803134 B CN105803134 B CN 105803134B
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Abstract
The invention provides a kind of process for tanning of sheepskin, comprise the following steps：A) pending sheepskin is subjected to sour skin working process；B) sheepskin after sour skin working process is subjected to pre-tanning in the presence of the first tanning agent, first tanning agent is modified Researches on Tanning of Oxazolidines；C) sheepskin after pre-tanning is subjected to retanning in the presence of the second tanning agent, obtains the sheepskin after retanning；Second tanning agent is the mixing tanning agent of the modified Researches on Tanning of Oxazolidines, organophosphor tanning agent and vegetable tanning agent.Compared with prior art, the resultant Leather shrinkage temperature that the process for tanning that the present invention is provided is obtained can reach more than 100 DEG C, and tearing strength can reach more than 6.5kgf.
Description
Technical field
It is to be related to a kind of process for tanning of sheepskin more specifically the present invention relates to leather processing technique field.
Background technology
Tanning refer to by tanning agent make rawhide become finished leather physical and chemical process, collagen polypeptide chain can be made by tanning
Between generate cross-bond, increase the stability of collagen structure, improve shrinkage temperature and hydrothermal stability, improve antiacid, alkali, enzyme
Deng the ability of chemicals.At present, conventional process for tanning is especially the most universal with chrome tanning based on metal tannage, but golden
Category tannage can form a large amount of reluctant waste water and solid waste, and the problem of there is heavy metal pollution can be to environment and people
Body is caused than more serious influence.
In recent years, domestic and international experts and scholars develop a series of nonmetallic tannages, wherein, the nonmetallic tannage of a big chunk
All be based on aldehydes tanning agent, obtained product using above exist it is a series of as temperature, pH value limit, with other things
The compatibility of matter is poor and the problems such as finished leather storage colour-change, this all adds difficulty for the large-scale use of aldehydes tanning agent, more
It is important that the use of aldehydes tanning agent is often resulted in, aldehyde in resultant Leather is exceeded, and prospect of the application also allows of no optimist.Another part
Nonmetallic tannage is based on vegetable tanning agent, such as, and Publication No. CN101724719A Chinese patent discloses one kind without gold
Belong to the process for tanning of tanned goat leather for making garment, using the two kinds of non-metal tannage agent combination tannings of vegetable tanning agent and organic phosphine, obtain
Product shrinkage temperature more than 90 DEG C, and with preferable physical and mechanical properties.
But, for goat skin, the ideal material that sheepskin is removed from office as production high-grade clothing has that grain is thin, skin
The features such as plate is soft, because sheepskin fibrage itself is loose, tanning of the process for tanning that above-mentioned patent is provided in sheepskin
There is significant limitation in aspect, tanned resultant Leather generally existing tensile strength is low, tearing strength is poor and shrinkage temperature
It is relatively low, it is extremely difficult to higher physical index.
The content of the invention
In view of this, it is an object of the invention to provide a kind of process for tanning of sheepskin, the tanning side that the present invention is provided
The product shrinkage temperature that method is obtained is high, and tensile strength and tearing strength are high.
The invention provides a kind of process for tanning of sheepskin, comprise the following steps：
A) pending sheepskin is subjected to sour skin working process；
B) sheepskin after sour skin working process is subjected to pre-tanning in the presence of the first tanning agent, first tanning agent is to change
Property Researches on Tanning of Oxazolidines；
C) sheepskin after pre-tanning is subjected to retanning in the presence of the second tanning agent, obtains the sheepskin after retanning；It is described
Second tanning agent is the mixing tanning agent of the modified Researches on Tanning of Oxazolidines, organophosphor tanning agent and vegetable tanning agent.
It is preferred that, the mass ratio of the first tanning agent described in step b) and the sheepskin after sour skin working process is (2~6)：
100。
It is preferred that, the mass ratio of the second tanning agent described in step c) and the sheepskin after pre-tanning is (9~16)：100.
It is preferred that, the mass ratio of modified Researches on Tanning of Oxazolidines, organophosphor tanning agent and vegetable tanning agent described in step c) for (1~
4)：(6~8)：(2~4).
It is preferred that, the process of pre-tanning specifically includes following steps described in step b)：
B1) sheepskin after sour skin working process is carried out to go acid treatment；
B2 the sheepskin after acid treatment) will be gone to carry out the first ungrease treatment；
B3 the sheepskin after the first ungrease treatment) is subjected to tanning in the presence of modified Researches on Tanning of Oxazolidines；
B4 tanned sheepskin) is subjected to neutralisation treatment, the sheepskin after pre-tanning is obtained.
It is preferred that, step b2) described in the first ungrease treatment time be 25min~35min, pH value be 3.5~4.5.
It is preferred that, the process of retanning specifically includes following steps described in step c)：
C1 the sheepskin after pre-tanning) is subjected to the second ungrease treatment；
C2 the sheepskin after the second ungrease treatment) is subjected to tanning in the presence of the second tanning agent；
C3 tanned sheepskin) is subjected to neutralisation treatment, the sheepskin after retanning is obtained.
It is preferred that, the process of sour skin working process specifically includes following steps described in step a)：
Pending sheepskin is sequentially passed through into immersion, fleshing, lime paste preparation depilation, liming, washing, deliming, softening and pickling,
Obtain the sheepskin after sour skin working process.
It is preferred that, the immersion process is specially：
Pending sheepskin is immersed in the water for being dissolved with soaking enzyme；The soaking enzyme is the efficient soaking enzyme of S2 types.
It is preferred that, the step c) also includes：
Sheepskin after retanning is subjected to stuffing, water squeezing, moisture regain, buffing and polishing successively.
The invention provides a kind of process for tanning of sheepskin, comprise the following steps：A) pending sheepskin is carried out
Sour skin working process；B) sheepskin after sour skin working process is subjected to pre-tanning, first tan in the presence of the first tanning agent
Agent is modified Researches on Tanning of Oxazolidines；C) sheepskin after pre-tanning is subjected to retanning in the presence of the second tanning agent, obtained after retanning
Sheepskin；Second tanning agent is the mixing tanning agent of the modified Researches on Tanning of Oxazolidines, organophosphor tanning agent and vegetable tanning agent.The present invention
The process for tanning of offer carries out pre-tanning by modified Researches on Tanning of Oxazolidines to the sheepskin after sour skin working process first, after processing
Sheepskin shrinkage temperature control more than 80 DEG C；Pass through the modified Researches on Tanning of Oxazolidines, organophosphor tanning agent and vegetable tanning again
The mixing tanning agent of agent carries out retanning to the sheepskin after pre-tanning, further increases shrinkage temperature, while improving the anti-tensile of product
Intensity and tearing strength.Compared with prior art, the resultant Leather shrinkage temperature that the process for tanning that the present invention is provided is obtained can reach
To more than 100 DEG C, tearing strength can reach more than 6.5kgf with.
Embodiment
Below in conjunction with the embodiment of the present invention, technical scheme is clearly and completely described, it is clear that institute
The embodiment of description is only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention,
The every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, belongs to this hair
The scope of bright protection.
The invention provides a kind of process for tanning of sheepskin, comprise the following steps：
A) pending sheepskin is subjected to sour skin working process；
B) sheepskin after sour skin working process is subjected to pre-tanning in the presence of the first tanning agent, first tanning agent is to change
Property Researches on Tanning of Oxazolidines；
C) sheepskin after pre-tanning is subjected to retanning in the presence of the second tanning agent, obtains the sheepskin after retanning；It is described
Second tanning agent is the mixing tanning agent of the modified Researches on Tanning of Oxazolidines, organophosphor tanning agent and vegetable tanning agent.
In the present invention, pending sheepskin is carried out into sour skin to handle.The present invention does not have to the source of the sheepskin
It is specifically limited, using the sheepskin rawhide well known to those skilled in the art for tanning.In the present invention, the sour skin
The purpose of processing is sheepskin rawhide is mainly left the web being made up of collagen, is that follow-up tannery is prepared.It is described
The process of sour skin working process preferably specifically includes following steps：
Pending sheepskin is sequentially passed through into immersion, fleshing, lime paste preparation depilation, liming, washing, deliming, softening and pickling,
Obtain the sheepskin after sour skin working process.
In the present invention, pending sheepskin is soaked.The immersion process is preferably specially：
Pending sheepskin is immersed in the water for being dissolved with soaking enzyme；The soaking enzyme is the efficient soaking enzyme of S2 types.
In the present invention, the efficient soaking enzyme of S2 types can accelerate immersion, and contribute to degreasing.The present invention is to the soaking enzyme
Source is not particularly limited, using the commercial goods of the above-mentioned efficient soaking enzyme of S2 types known to art personnel.
In the present invention, the mass ratio of the soaking enzyme and pending sheepskin is preferably (0.3~0.5)：100, more preferably 0.4：
100。
In the present invention, described be dissolved with the water of soaking enzyme preferably also includes bactericide and sodium carbonate；The bactericide
Preferably 830B types bactericide.The present invention is not particularly limited to the source of the bactericide and sodium carbonate, using this area skill
The commercial goods of 830B types bactericide and sodium carbonate known to art personnel.In the present invention, the bactericide and pending
The mass ratio of sheepskin be preferably (0.2~0.4)：100, more preferably 0.3：100；The sodium carbonate and pending sheep
The mass ratio of skin is preferably (0.4~0.6)：100, more preferably 0.5：100.
In the present invention, the immersion process is carried out preferably in rotary drum, is specially：
The water for being dissolved with soaking enzyme, bactericide and sodium carbonate is added in the rotary drum, by the pending sheepskin
It is immersed in above-mentioned water, turns after 30min, sets rotary drum for automatic rotation, draining after certain time completes the immersion process；
The automatic rotation preferably turns 10min~15min, more preferably 10min per hour.In the present invention, the temperature of the immersion
Degree is preferably 20 DEG C~30 DEG C, more preferably 25 DEG C；The time of the immersion is preferably 11h~13h, more preferably 12h.At this
In invention, the rotary drum is the equipment well known to those skilled in the art for leather processing, and the present invention does not have special limit to this
System.
Complete after the immersion, the sheepskin after immersion is carried out fleshing by the present invention.In the present invention, the mesh of the fleshing
Be to remove the sheepskin head after the immersion and the uneven part of afterbody immersion.The present invention does not have to the equipment of the fleshing
It is specifically limited, using CM fleshing machines well known to those skilled in the art.After the completion of the fleshing, preferably also include fleshing
Sheepskin afterwards carries out control water, and the time of the control water is preferably 2h~3h, more preferably 2h.
Complete after the fleshing, the sheepskin after fleshing is carried out lime paste preparation depilation by the present invention.In the present invention, the lime paste preparation
Epilation process is preferably specially：
Sheepskin after fleshing is placed in lime paste preparation passage and carries out lime paste preparation, then the sheepskin after lime paste preparation is taken off
Hair.Lime paste preparation is carried out present invention preferably employs vulcanized sodium；The concentration of the vulcanized sodium is preferably 16 ° of B é~17 ° B é.In the present invention
In, the preferred 2 row's shower nozzles of opening of the lime paste preparation passage carry out lime paste preparation；The rotating speed of sheepskin is preferably 210r/ in the lime paste preparation passage
Min~230r/min, more preferably 220r/min.The present invention is not particularly limited to the equipment of the depilation, using this area
Depilator known to technical staff.In the present invention, the lime paste preparation process carries out lime paste preparation only with vulcanized sodium, it is to avoid make
The pollution problem caused with lime.
Complete after the lime paste preparation depilation, the sheepskin after the present invention loses hair or feathers lime paste preparation carries out liming.In the present invention, it is described
Liming process is carried out preferably in rotary drum, is specially：
Sodium sulfide solution is added in the rotary drum, it is molten that the sheepskin after the lime paste preparation is lost hair or feathers is immersed in above-mentioned vulcanized sodium
Liquid, turns after 30min, sets rotary drum for automatic rotation, draining after certain time completes the liming process；The automatic rotation
Preferably turn 3min~5min, more preferably 3min per hour.In the present invention, the concentration of the sodium sulfide solution is preferably
14g/L~16g/L, more preferably 15g/L.In the present invention, the temperature of the liming is preferably 20 DEG C~25 DEG C, more preferably
22℃；The time of the liming is preferably 19h~21h, more preferably 20h.In the present invention, the liming process is only with sulphur
Change sodium and carry out liming, it is to avoid the pollution problem caused using lime, while liming liquid energy enough carries out waste liquid circulation reduction discharge
Amount, reduces pollution.
Complete after the liming, the present invention is washed the sheepskin after liming.In the present invention, the mesh of the washing
Be to after liming sheepskin carry out deliming.In the present invention, the water-washing process is carried out preferably in rotary drum, is specially：
Sheepskin after liming is placed in rotary drum, is rinsed 3 times with water repeatedly, 10min is rinsed every time；Then at described turn
Added in drum and be dissolved with the water of deliming agent and turn after 10min, rotary drum is set turned 30min again to stop 30min and stop 30min again, control pH
It is worth for 8.5；Finally above-mentioned sheepskin is rinsed 2 times with water repeatedly, 10min is rinsed every time.In the present invention, the deliming agent is excellent
Elect ASB type deliming agents as.The present invention is not particularly limited to the source of the deliming agent, using well known to those skilled in the art
The commercial goods of above-mentioned ASB types deliming agent.In the present invention, the mass ratio of the deliming agent and sheepskin be preferably (5~
7)：100, more preferably 6：100.In the present invention, the temperature of the washing is preferably 18 DEG C~22 DEG C, more preferably 20 DEG C.
After sheepskin after liming is washed, in addition to by the sheepskin progress fleshing after washing, remove the water
Sheepskin head and the uneven part of afterbody washing after washing, complete water-washing process.The present invention does not have to the equipment of the fleshing
It is specifically limited, using CM fleshing machines well known to those skilled in the art.
In the present invention, the sheepskin after washing is softened.The softening process is carried out preferably in rotary drum, specifically
For：
The water of 30 DEG C of addition, the sheepskin after the washing is immersed in above-mentioned water, turns 10min in the rotary drum
Afterwards, draining；Then 40 DEG C of water is added in the rotary drum, macerating enzyme, degreasing agent and wood powder is added, turns 2.5h, is controlled
Rotary drum temperature is 38 DEG C；Finally above-mentioned sheepskin is rinsed 3 times repeatedly with 20 DEG C of water, it is 22 DEG C to control rotary drum temperature.At this
In invention, the macerating enzyme is preferably CH type macerating enzymes, and the degreasing agent is preferably VLC-3 type degreasing agents.The present invention is to described
The source of macerating enzyme, degreasing agent and wood powder is not particularly limited, and is softened using above-mentioned CH types well known to those skilled in the art
The commercial goods of enzyme, VLC-3 types degreasing agent and wood powder.In the present invention, the silk floss after the macerating enzyme and the washing
The mass ratio of sheepskin is preferably (0.04~0.06)：100, more preferably 0.05：100；After the degreasing agent and the washing
The mass ratio of sheepskin is preferably (0.2~0.4)：100, more preferably 0.3：100；Silk floss after the wood powder and the washing
The mass ratio of sheepskin is preferably (0.06~0.08)：100, more preferably 0.07：100.
Complete after the softening, the sheepskin after softening is carried out pickling by the present invention, obtains the silk floss after sour skin working process
Sheepskin.In the present invention, the pickling process is carried out preferably in rotary drum, is specially：
The salt solution that concentration is 7 ° of B é~8 ° B é is added in the rotary drum, the sheepskin after the softening is immersed in above-mentioned
In salt solution, turn 30min；Then 20 DEG C of sulfuric acid solution and mould inhibitor is added in the rotary drum, is turned after 2h, draining.In this hair
In bright, the salt solution is the aqueous solution of sodium chloride well known to those skilled in the art, and it is not specifically limited to this by the present invention.At this
In invention, the mould inhibitor is preferably BK-55 type mould inhibitors.The present invention is to the source of the mould inhibitor and sulfuric acid solution without spy
Different limitation, using the commercial goods of above-mentioned BK-55 types mould inhibitor and sulfuric acid solution well known to those skilled in the art.At this
In invention, the mass ratio of the sheepskin after the mould inhibitor and the softening is preferably (0.04~0.06)：100, more preferably
0.05：100；The mass ratio of sheepskin after the sulfuric acid solution and the softening is preferably (1.5~1.7)：100, more preferably
For 1.6：100.
Obtain after the sheepskin after sour skin working process, the present invention is by the sheepskin after the sour skin working process first
Pre-tanning is carried out in the presence of tanning agent；First tanning agent is modified Researches on Tanning of Oxazolidines.In the present invention, the modified oxazolidine tan
Agent is the oxazolidine that β ethoxys are modified with acrylic resin, with low toxicity, reacts the excellent spies such as activity is good, reaction range is wide
Property.The present invention is not particularly limited to the source of the modified Researches on Tanning of Oxazolidines, using β hydroxyls second well known to those skilled in the art
The oxazolidine TWE commercial goods that base is modified with acrylic resin.In the present invention, first tanning agent with sour skin processing
The mass ratio of sheepskin after reason is preferably (2~6)：100, more preferably 4：100.
In the present invention, the process of the pre-tanning preferably specifically includes following steps：
B1) sheepskin after sour skin working process is carried out to go acid treatment；
B2 the sheepskin after acid treatment) will be gone to carry out the first ungrease treatment；
B3 the sheepskin after the first ungrease treatment) is subjected to tanning in the presence of modified Researches on Tanning of Oxazolidines；
B4 tanned sheepskin) is subjected to neutralisation treatment, the sheepskin after pre-tanning is obtained.
In the present invention, the sheepskin after the sour skin working process is carried out going acid treatment.It is described to go acid treatment process
It is preferred that being carried out in rotary drum, it is specially：
The salt solution that concentration is 6 ° of B é~7 ° B é is added in the rotary drum, the sheepskin after the sour skin working process is soaked
Stain adds sodium acetate in above-mentioned salt solution.In the present invention, the salt solution is sodium chloride well known to those skilled in the art
The aqueous solution, it is not specifically limited to this by the present invention.In the present invention, the sheep after the sodium acetate and the sour skin working process
The mass ratio of skin is preferably (1~2)：100, more preferably 1：100.In the present invention, it is described go acid treatment temperature be preferably
25 DEG C~35 DEG C, more preferably 30 DEG C.
Gone described in completing after acid treatment, the present invention will go the sheepskin after acid treatment to carry out the first ungrease treatment.Described
The purpose of one ungrease treatment is the fiber of the scattered sheepskin gone after acid treatment, the combination of pretanning agent during increase pre-tanning
Point.In the present invention, the first ungrease treatment process is preferably specially：
The sheepskin gone after acid treatment is handled under conditions of the first degreasing agent.In the present invention, it is described
First degreasing agent is preferably VLC-3 type degreasing agents.The present invention is not particularly limited to the source of first degreasing agent, using this
The commercial goods of above-mentioned VLC-3 types degreasing agent known to art personnel.In the present invention, first degreasing agent and
The mass ratio of the sheepskin gone after acid treatment is preferably (4~6)：100, more preferably 5：100.In the present invention, it is described
The time of first ungrease treatment is preferably 25min~35min, more preferably 30min；The pH value of first ungrease treatment is preferred
For 3.5~4.5, more preferably 3.5~4.
Complete after first ungrease treatment, the present invention is by the sheepskin after the first ungrease treatment in modified Researches on Tanning of Oxazolidines
In the presence of carry out tanning.In the present invention, the time of the tanning is preferably 80min~100min, more preferably 90min.
Complete after the tanning, tanned sheepskin is carried out neutralisation treatment by the present invention, obtains the sheepskin after pre-tanning.
The neutralisation treatment process is carried out preferably in rotary drum, is specially：
The salt solution that concentration is 6 ° of B é~7 ° B é is added in the rotary drum, the tanned sheepskin is immersed in above-mentioned
In salt solution, sodium acetate is added, turns 1h；Then sodium bicarbonate solution is added, turns 6h, control ph is 7.In the present invention,
The salt solution is the aqueous solution of sodium chloride well known to those skilled in the art, and it is not specifically limited to this by the present invention.In the present invention
In, the mass ratio of the sodium acetate and the tanned sheepskin is preferably (1~2)：100, more preferably 1.5：100.
In the present invention, the mass ratio of the sodium bicarbonate solution and the tanned sheepskin is preferably (1~2)：100, more preferably
For 1.6：100.In the present invention, the temperature of the neutralisation treatment is preferably 30 DEG C~40 DEG C, more preferably 35 DEG C.
In the present invention, by the detection of the sheepskin progress shrinkage temperature after pre-tanning, then discharge opeing, with 50 DEG C of water repeatedly
Rinse 5 times, 10min is rotated every time.Testing result shows, the contraction of the sheepskin after the pre-tanning that the method that the present invention is provided is obtained
Temperature is more than 80 DEG C.
Complete after the pre-tanning, the sheepskin after pre-tanning is carried out retanning by the present invention in the presence of the second tanning agent, is obtained
Sheepskin after retanning；Second tanning agent is the mixed tannage of the modified Researches on Tanning of Oxazolidines, organophosphor tanning agent and vegetable tanning agent
Agent.In the present invention, the modified Researches on Tanning of Oxazolidines is identical with above-mentioned technical proposal, will not be repeated here.It is described organic
Phosphorus tanning agent is preferably ALBRITE AD type organophosphor tanning agents and ALBRITE CC type organophosphor tanning agents.The vegetable tanning agent is preferably
The type vegetable tanning agents of BIOTAN TS 801 and the type vegetable tanning agents of BIOTAN TS 808.The present invention is to the organophosphor tanning agent and plant
The source of tanning agent is not particularly limited, using ALBRITE AD type organophosphors tanning agent well known to those skilled in the art, ALBRITE
The commercial goods of CC type organophosphors tanning agent, the type vegetable tanning agents of BIOTAN TS 801 and the type vegetable tanning agents of BIOTAN TS 808 are
Can.In the present invention, the mass ratio of second tanning agent and the sheepskin after pre-tanning is (9~16)：100, more preferably (11~
14)：100.In the present invention, the mass ratio of the modified Researches on Tanning of Oxazolidines, organophosphor tanning agent and vegetable tanning agent be preferably (1~
4)：(6~8)：(2~4), more preferably 2：(6~8)：(3~4).
In the present invention, the process of the retanning preferably specifically includes following steps：
C1 the sheepskin after pre-tanning) is subjected to the second ungrease treatment；
C2 the sheepskin after the second ungrease treatment) is subjected to tanning in the presence of the second tanning agent；
C3 tanned sheepskin) is subjected to neutralisation treatment, the sheepskin after retanning is obtained.
In the present invention, the sheepskin after pre-tanning is subjected to the second ungrease treatment.The second ungrease treatment process is preferred
Specially：
The sheepskin after the pre-tanning is handled under conditions of the second degreasing agent.In the present invention, described second
Degreasing agent is preferably the mixture of white oil and VLC-3 type degreasing agents.The present invention is not special to the source of second degreasing agent
Limitation, using the commercial goods of above-mentioned white oil and VLC-3 type degreasing agent well known to those skilled in the art.In the present invention
In, the mass ratio of the sheepskin after second degreasing agent and the pre-tanning is preferably (2.5~4.5)：100, more preferably
3.5：100.In the present invention, the mass ratio of white oil and VLC-3 the type degreasing agent is preferably (0.5~1.5)：(2~3), more
Preferably 1：2.5.In the present invention, the time of second ungrease treatment is preferably 110min~130min, more preferably
120min。
In the present invention, second ungrease treatment preferably also includes the sheepskin after the second ungrease treatment with 50 DEG C
Water is washed；The number of times of the washing is preferably 4~6 times, more preferably 5 times.
Complete after second ungrease treatment, the present invention by the sheepskin after the second ungrease treatment the second tanning agent effect
Lower carry out tanning.In the present invention, the tannery adds pH adjusting agent before being preferably also included in progress tanning；The pH
Conditioning agent is preferably formic acid.The present invention is not particularly limited to the source of the pH adjusting agent, ripe using those skilled in the art
The commercial goods for the above-mentioned formic acid known.In the present invention, sheepskin after the formic acid and second ungrease treatment
Mass ratio is preferably (0.3~0.5)：100, more preferably 0.4：100.In the present invention, the time of the tanning is preferably 13h
~15h, more preferably 14h.
Complete after the tanning, tanned sheepskin is carried out neutralisation treatment by the present invention, obtains the sheepskin after retanning.
The neutralisation treatment process is carried out preferably in rotary drum, is specially：
The water of 25 DEG C of addition, the tanned sheepskin is immersed in above-mentioned water, first is added in the rotary drum
Sour sodium, control ph is 4.4.In the present invention, the mass ratio of the sodium formate and the tanned sheepskin is preferably (1
~1.4)：100, more preferably 1.2：100.
In the present invention, the sheepskin after retanning is carried out to the detection of shrinkage temperature.Testing result shows that the present invention is provided
The obtained retanning of method after sheepskin shrinkage temperature more than 100 DEG C.
In the present invention, complete after the retanning, preferably also include：
Sheepskin after retanning is subjected to stuffing, water squeezing, moisture regain, buffing and polishing successively.
In the present invention, the sheepskin after the retanning is subjected to stuffing.The stuffing process is carried out preferably in rotary drum,
Specially：
Sheepskin after retanning is immersed in the water for being dissolved with fatting agent, turns 1h；Then formic acid is added, described add is completed
Fat process.In the present invention, the fatting agent is preferably INGRASSANTE CH89 types fatting agents and LEDEROLINOR FC2 types
Fatting agent.The present invention is not particularly limited to the source of the fatting agent, using well known to those skilled in the art above-mentioned
The commercial goods of INGRASSANTE CH89 types fatting agents and LEDEROLINOR FC2 type fatting agents.In the present invention, institute
The mass ratio for stating the sheepskin after fatting agent and the retanning is preferably (4~6)：100, more preferably 5：100.In the present invention
In, the mass ratio of the sheepskin after the formic acid and the retanning is preferably (0.5~0.7)：100, more preferably 0.6：100.
In the present invention, the temperature of the stuffing is preferably 60 DEG C~70 DEG C, more preferably 65 DEG C.
Complete after the stuffing, the sheepskin after stuffing is carried out water squeezing by the present invention.In the present invention, the mesh of the water squeezing
Be sheepskin is met normal water squeezing requirement, the present invention is not particularly limited to the method for the water squeezing, can such as use ability
Field technique personnel know water squeezing, vacuum and hang dry-cure.
Complete after the water squeezing, the present invention is got damp again the sheepskin after water squeezing.Method of the present invention to the moisture regain
Be not particularly limited, such as can using standing, shake soft, toggling the step of got damp again.
Complete after the moisture regain, the sheepskin after moisture regain is carried out buffing by the present invention.In the present invention, the mesh of the buffing
Be that dedusting and deburring are carried out to the sheepskin after moisture regain, the present invention is not particularly limited to the equipment of the buffing, can such as adopted
With big buffing machine well known to those skilled in the art.
Complete after the buffing, the sheepskin after buffing is polished by the present invention, obtains resultant Leather.
In the present invention, the tearing strength to the resultant Leather is surveyed according to the ISO 3377-2-2002 methods provided
Examination.Test result shows that the tearing strength for the resultant Leather that the process for tanning that the present invention is provided is obtained can reach more than 6.5kgf.
The invention provides a kind of process for tanning of sheepskin, comprise the following steps：A) pending sheepskin is carried out
Sour skin working process；B) sheepskin after sour skin working process is subjected to pre-tanning, first tan in the presence of the first tanning agent
Agent is modified Researches on Tanning of Oxazolidines；C) sheepskin after pre-tanning is subjected to retanning in the presence of the second tanning agent, obtained after retanning
Sheepskin；Second tanning agent is the mixing tanning agent of the modified Researches on Tanning of Oxazolidines, organophosphor tanning agent and vegetable tanning agent.The present invention
The process for tanning of offer carries out pre-tanning by modified Researches on Tanning of Oxazolidines to the sheepskin after sour skin working process first, after processing
Sheepskin shrinkage temperature control more than 80 DEG C；Pass through the modified Researches on Tanning of Oxazolidines, organophosphor tanning agent and vegetable tanning again
The mixing tanning agent of agent carries out retanning to the sheepskin after pre-tanning, further increases shrinkage temperature, while improving the anti-tensile of product
Intensity and tearing strength.Compared with prior art, the resultant Leather shrinkage temperature that the process for tanning that the present invention is provided is obtained can reach
To more than 100 DEG C, tearing strength can reach more than 6.5kgf.
It is the resultant Leather good hand feeling produced, soft in addition, the process for tanning that provides of the present invention carries out tanning to sheepskin
It is soft, and grain pore is clear, smooth, is the desirable feedstock for producing high-grade clothing and upper leather.
In order to further illustrate the present invention, it is described in detail below by following examples.Following examples of the present invention
Soaking enzyme S2 used is provided by Da Wei Science and Technology Co., Ltd.；Bactericide 830B used reaches the limited public affairs of bright trade by Shanghai
Department provides；ASB types deliming agent used is provided by TFL morals are auspicious；VLC-3 types degreasing agent used is limited by the triumphant fine chemistry industry of section (Shanghai)
Company provides；CH types macerating enzyme used is provided by BASF AG；Modified Researches on Tanning of Oxazolidines TWE used is provided by TFL morals are auspicious；It is used
ALBRITE AD type organophosphor tanning agents and ALBRITE CC type organophosphor tanning agents are had by Luo Diya Hengchang (Zhangjiagang) fine chemistry industry
Limit company provides；The type vegetable tanning agents of BIOTAN TS 801 and the vegetable tanning agents of BIOTAN TS 808 used byCompany provides；INGRASSANTE CH89 types fatting agent used is carried by ALPA companies
For；LEDEROLINOR FC2 type fatting agents used are provided by Kekai Fine Chemical (Shanghai) Co., Ltd..
Embodiment 1
(1) tested based on 10 skins：Rawhide weight is 3.5kg/, and 20kg water is added in rotary drum, adds 140g
S2 types soaking enzyme, 105g 830B types bactericide and 175g sodium carbonate, under the conditions of 25 DEG C, turn to turn automatic after 30min, per hour
Turn 10min, total soaking time is 12h, draining, the sheepskin after being soaked；Then after using CM fleshing machines to above-mentioned immersion
Sheepskin head and afterbody respectively remove a knife, then control water 2h, obtain the sheepskin after fleshing；The sheepskin after fleshing is placed again
In lime paste preparation passage, setting rotating speed is 220r/min, opens 2 row's shower nozzles, and lime paste preparation is carried out for 16 ° of B é vulcanized sodium with concentration, it
Depilator unhairing is used afterwards, obtains the sheepskin after lime paste preparation depilation；Then concentration is added in rotary drum molten for 15g/L vulcanized sodium
Liquid, the sheepskin after lime paste preparation is lost hair or feathers is immersed in above-mentioned sodium sulfide solution, under conditions of 22 DEG C, turns to turn automatic after 30min,
Turn 3min per hour, total liming time is 20h, obtains the sheepskin after liming；Sheepskin water flushing 3 times after liming, often
Secondary flushing 10min, afterwards in the rotary drum add be dissolved with supplement 750g ASB type deliming agents water turn 10min after, set
Rotary drum turns 30min to stop 30min and stops 30min again again, and control ph is 8.5, then above-mentioned sheepskin is rinsed 2 times with water repeatedly,
Each 10min, respectively removes a knife, the sheepskin after being washed with CM fleshing machines to above-mentioned sheepskin head and afterbody afterwards；So
30 DEG C of water is added in rotary drum afterwards, is turned after 10min, draining, then 40 DEG C of water is added in the rotary drum, by rotary drum temperature control
System adds 6.25g CH types macerating enzyme, 37.5g VLC-3 types degreasing agents and 12.5g wood powders, turns 2.5h, Zhi Houyong at 38 DEG C
20 DEG C of water is rinsed 3 times repeatedly, and it is 22 DEG C, the sheepskin after being softened to control rotary drum temperature；Finally, added in rotary drum dense
Spend for 7 ° of B é salt solution, turn 30min, add 20 DEG C of 200g sulfuric acid solution and 6.25g BK-55 type mould inhibitors, turn after 2h,
Draining, obtains the sheepskin after sour skin working process.
(2) salt solution that concentration is 6 ° of B é is added in rotary drum, the sheepskin after the processing of sour skin is immersed in above-mentioned salt solution,
Supplement 150g sodium acetates are added, control ph is 3.5~4, adds 625g VLC-3 type degreasing agents, turns 30min, Ran Houjia
Enter 500g and be modified Researches on Tanning of Oxazolidines WTE, turn 90min, add salt solution of the concentration for 6 ° of B é, by rotary drum temperature control at 35 DEG C,
Add 100g sodium acetates and turn 1h, add 215g sodium acid carbonates and turn 6h, control ph is 7, obtains the sheepskin after pre-tanning.
Sheepskin after pre-tanning is carried out to the detection of shrinkage temperature, then discharge opeing rinses 5 times with 50 DEG C of water repeatedly, often
Secondary rotation 10min.Testing result shows, the contraction temperature of the sheepskin after the pre-tanning that the method that the embodiment of the present invention 1 is provided is obtained
Spend for 82 DEG C.
(3) take the sheepskin after pre-tanning to be placed in above-mentioned rotary drum, add 125g white oils and 312g VLC-3 type degreasing agents,
Turn 120min, rinse 5 times repeatedly with 50 DEG C of water, then add 45g formic acid, add 250g be modified Researches on Tanning of Oxazolidines TWE,
250g ALBRITE AD type organophosphors tanning agent, 250g ALBRITE CC type organophosphor tanning agents and the types of 125g BIOTAN TS 801
Vegetable tanning agent, the type vegetable tanning agents of 125g BIOTAN TS 808, rotate after 6h, stop operating, and place 8h, finally add in rotary drum
Enter 25 DEG C of water, add 85g sodium formates, control ph is 4.4, obtains the sheepskin after retanning.
Sheepskin after retanning is carried out to the detection of shrinkage temperature.Testing result shows, the side that the embodiment of the present invention 1 is provided
The shrinkage temperature of sheepskin after the retanning that method is obtained is at 100 DEG C.
(4) added in rotary drum and be dissolved with 250g INGRASSANTE CH89 types fatting agents and 250g LEDEROLINOR
The water of FC2 type fatting agents, the sheepskin after retanning is immersed in above-mentioned water, under the conditions of 65 DEG C, turns 1h, adds 85g first
Acid, completes stuffing process；Above-mentioned sheepskin is subjected to water squeezing, vacuum and hangs dry, 4h, the soft, toggling that shakes is stood and is got damp again, then with big
Buffing machine carries out dedusting and deburring, finally polishes, and obtains removing from office finished product.
Tearing strength to the resultant Leather is tested according to the ISO 3377-2-2002 methods provided.Test result
Show, the tearing strength for the resultant Leather that the process for tanning that the present invention is provided is obtained is 6.5kgf.
Embodiment 2
(1) tested based on 10 skins：Rawhide weight is 3.5kg/, and 20kg water is added in rotary drum, adds 140g
The water of S2 types soaking enzyme, 105g 830B types bactericide and 175g sodium carbonate, under the conditions of 25 DEG C, turns to turn automatic after 30min, often
Hour turns 10min, and total soaking time is 12h, draining, the sheepskin after being soaked；Then with CM fleshing machines to above-mentioned immersion
A knife is respectively removed on sheepskin head and afterbody afterwards, is then controlled water 2h, is obtained the sheepskin after fleshing；Again by the sheepskin after fleshing
It is placed in lime paste preparation passage, setting rotating speed is 220r/min, opens 2 row's shower nozzles, is drenched with concentration for 16 ° of B é vulcanized sodium
Ash, uses depilator unhairing afterwards, obtains the sheepskin after lime paste preparation depilation；Then the vulcanization that concentration is 15g/L is added in rotary drum
Sodium solution, the sheepskin after lime paste preparation is lost hair or feathers is immersed in above-mentioned sodium sulfide solution, under conditions of 22 DEG C, turns to turn after 30min
Automatically, 3min is turned per hour, total liming time is 20h, obtains the sheepskin after liming；Sheepskin after liming rinses 3 with water
It is secondary, 10min is rinsed every time, afterwards in the rotary drum add be dissolved with supplement 750g ASB type deliming agents water turn 10min after,
Set rotary drum to turn 30min again to stop 30min and stop 30min again, control ph is 8.5, then above-mentioned sheepskin is rinsed 2 with water repeatedly
Secondary, each 10min respectively removes a knife, the sheepskin after being washed with CM fleshing machines to above-mentioned sheepskin head and afterbody afterwards；
Then 30 DEG C of water is added in rotary drum, is turned after 10min, draining, then 40 DEG C of water is added in the rotary drum, by rotary drum temperature
Control adds 6.25g CH types macerating enzyme, 37.5g VLC-3 types degreasing agents and 12.5g wood powders, turns 2.5h, afterwards at 38 DEG C
Rinsed repeatedly with 20 DEG C of water 3 times, it is 22 DEG C, the sheepskin after being softened to control rotary drum temperature；Finally, added in rotary drum
Concentration turns 30min for 7 ° of B é salt solution, adds 20 DEG C of 200g sulfuric acid solution and 6.25BK-55 type mould inhibitors, turns after 2h,
Draining, obtains the sheepskin after sour skin working process.
(2) salt solution that concentration is 6 ° of B é is added in rotary drum, the sheepskin after pickling is handled is immersed in above-mentioned salt solution,
Supplement 150g sodium acetates are added, control ph is 3.5~4, adds 625g VLC-3 type degreasing agents, turns 30min, Ran Houjia
Enter 750g and be modified Researches on Tanning of Oxazolidines TWE, turn 90min, add salt solution of the concentration for 6 ° of B é, by rotary drum temperature control at 35 DEG C,
Add 100g sodium acetates and turn 1h, add 215g sodium acid carbonates and turn 6h, control ph is 7, obtains the sheepskin after pre-tanning.
Sheepskin after pre-tanning is carried out to the detection of shrinkage temperature, then discharge opeing rinses 5 times with 50 DEG C of water repeatedly, often
Secondary rotation 10min.Testing result shows, the contraction temperature of the sheepskin after the pre-tanning that the method that the embodiment of the present invention 1 is provided is obtained
Spend for 86 DEG C.
(3) take the sheepskin after pre-tanning to be placed in above-mentioned rotary drum, add 125g white oils and 312g VLC-3 type degreasing agents,
Turn 120min, rinse 5 times repeatedly with 50 DEG C of water, then add 45g formic acid, add 375g be modified Researches on Tanning of Oxazolidines TWE,
375g ALBRITE AD type organophosphors tanning agent, 375g ALBRITE CC type organophosphor tanning agents and the types of 175g BIOTAN TS 801
Vegetable tanning agent, the type vegetable tanning agents of 175g BIOTAN TS 808, rotate after 6h, stop operating, and place 8h, finally add in rotary drum
Enter 25 DEG C of water, add 85g sodium formates, control ph is 4.4, obtains the sheepskin after retanning.
Sheepskin after retanning is carried out to the detection of shrinkage temperature.Testing result shows, the side that the embodiment of the present invention 1 is provided
The shrinkage temperature of sheepskin after the retanning that method is obtained is at 105 DEG C.
(4) added in rotary drum and be dissolved with 250g INGRASSANTE CH89 fatting agents and 250g LEDEROLINOR
The water of FC2 type fatting agents, the sheepskin after retanning is immersed in above-mentioned water, under the conditions of 65 DEG C, turns 1h, adds 85g first
Acid, completes stuffing process；Above-mentioned sheepskin is subjected to water squeezing, vacuum and hangs dry, 4h, the soft, toggling that shakes is stood and is got damp again, then with big
Buffing machine carries out dedusting and deburring, finally polishes, and obtains removing from office finished product.
Tearing strength to the resultant Leather is tested according to the ISO 3377-2-2002 methods provided.Test result
Show, the tearing strength for the resultant Leather that the process for tanning that the present invention is provided is obtained is 6.8kgf.
Embodiment 3
(1) tested based on 10 skins：Rawhide weight is 3.5kg/, and 20kg water is added in rotary drum, is added
140g S2 types soaking enzyme, 105g 830B types bactericide and 175g sodium carbonate, under the conditions of 25 DEG C, turn to turn automatic after 30min, often
Hour turns 10min, and total soaking time is 12h, draining, the sheepskin after being soaked；Then with CM fleshing machines to above-mentioned immersion
A knife is respectively removed on sheepskin head and afterbody afterwards, is then controlled water 2h, is obtained the sheepskin after fleshing；Again by the sheepskin after fleshing
It is placed in lime paste preparation passage, setting rotating speed is 220r/min, opens 2 row's shower nozzles, is drenched with concentration for 16 ° of B é vulcanized sodium
Ash, uses depilator unhairing afterwards, obtains the sheepskin after lime paste preparation depilation；Then the vulcanization that concentration is 15g/L is added in rotary drum
Sodium solution, the sheepskin after lime paste preparation is lost hair or feathers is immersed in above-mentioned sodium sulfide solution, under conditions of 22 DEG C, turns to turn after 30min
Automatically, 3min is turned per hour, total liming time is 20h, obtains the sheepskin after liming；Sheepskin after liming rinses 3 with water
It is secondary, 10min is rinsed every time, adds be dissolved with after the water of 750g ASB type deliming agents turns 10min in the rotary drum afterwards, set
Rotary drum turns 30min to stop 30min and stops 30min again again, and control ph is 8.5, then above-mentioned sheepskin is rinsed 2 times with water repeatedly,
Each 10min, respectively removes a knife, the sheepskin after being washed with CM fleshing machines to above-mentioned sheepskin head and afterbody afterwards；So
30 DEG C of water is added in rotary drum afterwards, is turned after 10min, draining, then 40 DEG C of water is added in the rotary drum, by rotary drum temperature control
System adds 6.25g CH types macerating enzyme, 37.5g VLC-3 types degreasing agents and 12.5g wood powders, turns 2.5h, Zhi Houyong at 38 DEG C
20 DEG C of water is rinsed 3 times repeatedly, and it is 22 DEG C, the sheepskin after being softened to control rotary drum temperature；Finally, added in rotary drum dense
Spend for 7 ° of B é salt solution, turn 30min, add 20 DEG C of 200g sulfuric acid solution and 6.25gBK-55 type mould inhibitors, turn after 2h,
Draining, obtains the sheepskin after sour skin working process.
(2) salt solution that concentration is 6 ° of B é is added in rotary drum, the sheepskin after pickling is handled is immersed in above-mentioned salt solution,
Supplement 150g sodium acetates are added, control ph is 3.5~4, adds 625g VLC-3 type degreasing agents, turns 30min, Ran Houjia
Enter 1000g and be modified Researches on Tanning of Oxazolidines TWE, turn 90min, add salt solution of the concentration for 6 ° of B é, by rotary drum temperature control at 35 DEG C,
Add 100g sodium acetates and turn 1h, add 215g sodium acid carbonates and turn 6h, control ph is 7, obtains the sheepskin after pre-tanning.
Sheepskin after pre-tanning is carried out to the detection of shrinkage temperature, then discharge opeing rinses 5 times with 50 DEG C of water repeatedly, often
Secondary rotation 10min.Testing result shows, the contraction temperature of the sheepskin after the pre-tanning that the method that the embodiment of the present invention 1 is provided is obtained
Spend for 88 DEG C.
(3) take the sheepskin after pre-tanning to be placed in above-mentioned rotary drum, add 125g white oils and 312g VLC-3 type degreasing agents,
Turn 120min, rinsed repeatedly with 50 DEG C of water 5 times, then add 45g formic acid, add 500g and be modified Researches on Tanning of Oxazolidines TWE, mend
Fill 500g ALBRITE AD type organophosphors tanning agent, 500g ALBRITE CC organophosphors tanning agents and the types of 250g BIOTAN TS 801
Vegetable tanning agent, the type vegetable tanning agents of 250g BIOTAN TS 808, rotate after 6h, stop operating, and place 8h, finally add in rotary drum
Enter 25 DEG C of water, add supplement g sodium formates, control ph is 4.4, obtains the sheepskin after retanning.
Sheepskin after retanning is carried out to the detection of shrinkage temperature.Testing result shows, the side that the embodiment of the present invention 1 is provided
The shrinkage temperature of sheepskin after the retanning that method is obtained is at 110 DEG C.
(4) added in rotary drum and be dissolved with 300g INGRASSANTE CH89 types fatting agents and 500g LEDEROLINOR
The water of FC2 type fatting agents, the sheepskin after retanning is immersed in above-mentioned water, under the conditions of 65 DEG C, turns 1h, adds 85g first
Acid, completes stuffing process；Above-mentioned sheepskin is subjected to water squeezing, vacuum and hangs dry, 4h, the soft, toggling that shakes is stood and is got damp again, then with big
Buffing machine carries out dedusting and deburring, finally polishes, and obtains removing from office finished product.
Tearing strength to the resultant Leather is tested according to the ISO 3377-2-2002 methods provided.Test result
Show, the tearing strength for the resultant Leather that the process for tanning that the present invention is provided is obtained is 7.5kgf.
The described above of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.It is right
A variety of modifications of these embodiments will be apparent for those skilled in the art, and as defined herein one
As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will
It will not be intended to be limited to the embodiments shown herein, and be to fit to consistent with principles disclosed herein and features of novelty
Most wide scope.
Claims (9)
1. a kind of process for tanning of sheepskin, it is characterised in that comprise the following steps：
A) pending sheepskin is subjected to sour skin working process；
B) sheepskin after sour skin working process is subjected to pre-tanning in the presence of the first tanning agent, first tanning agent is disliked to be modified
Oxazolidine tanning agent；
C) sheepskin after pre-tanning is subjected to retanning in the presence of the second tanning agent, obtains the sheepskin after retanning；Described second
Tanning agent is the mixing tanning agent of the modified Researches on Tanning of Oxazolidines, organophosphor tanning agent and vegetable tanning agent；The modified Researches on Tanning of Oxazolidines, have
The mass ratio of machine phosphorus tanning agent and vegetable tanning agent is (1~4)：(6~8)：(2~4).
2. process for tanning according to claim 1, it is characterised in that at the first tanning agent described in step b) and sour skin processing
The mass ratio of sheepskin after reason is (2~6)：100.
3. process for tanning according to claim 1, it is characterised in that the second tanning agent described in step c) and the silk floss after pre-tanning
The mass ratio of sheepskin is (9~16)：100.
4. process for tanning according to claim 1, it is characterised in that the process of pre-tanning described in step b) specifically include with
Lower step：
B1) sheepskin after sour skin working process is carried out to go acid treatment；
B2 the sheepskin after acid treatment) will be gone to carry out the first ungrease treatment；
B3 the sheepskin after the first ungrease treatment) is subjected to tanning in the presence of modified Researches on Tanning of Oxazolidines；
B4 tanned sheepskin) is subjected to neutralisation treatment, the sheepskin after pre-tanning is obtained.
5. process for tanning according to claim 4, it is characterised in that step b2) described in the first ungrease treatment time
For 25min~35min, pH value is 3.5~4.5.
6. process for tanning according to claim 1, it is characterised in that the process of retanning described in step c) specifically include with
Lower step：
C1 the sheepskin after pre-tanning) is subjected to the second ungrease treatment；
C2 the sheepskin after the second ungrease treatment) is subjected to tanning in the presence of the second tanning agent；
C3 tanned sheepskin) is subjected to neutralisation treatment, the sheepskin after retanning is obtained.
7. process for tanning according to claim 1, it is characterised in that the process tool of sour skin working process described in step a)
Body comprises the following steps：
Pending sheepskin is sequentially passed through into immersion, fleshing, lime paste preparation depilation, liming, washing, deliming, softening and pickling, obtained
Sheepskin after sour skin working process.
8. process for tanning according to claim 7, it is characterised in that the immersion process is specially：
Pending sheepskin is immersed in the water for being dissolved with soaking enzyme；The soaking enzyme is the efficient soaking enzyme of S2 types.
9. process for tanning according to claim 1, it is characterised in that the step c) also includes：
Sheepskin after retanning is subjected to stuffing, water squeezing, moisture regain, buffing and polishing successively.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB790933A (en) * | 1954-08-13 | 1958-02-19 | Boehme Fettchemie Gmbh | Tanning, retanning and filling processes |
| CN1760377A (en) * | 2005-11-04 | 2006-04-19 | 四川大学 | Composition of tanning agent containing modified tara mimosa extract, and bating method without chrome |
| CN101367773A (en) * | 2008-10-07 | 2009-02-18 | 四川大学 | Bicyclo oxazolidine tanning agent and method of preparing the same |
-
2014
- 2014-12-29 CN CN201410833128.6A patent/CN105803134B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB790933A (en) * | 1954-08-13 | 1958-02-19 | Boehme Fettchemie Gmbh | Tanning, retanning and filling processes |
| CN1760377A (en) * | 2005-11-04 | 2006-04-19 | 四川大学 | Composition of tanning agent containing modified tara mimosa extract, and bating method without chrome |
| CN101367773A (en) * | 2008-10-07 | 2009-02-18 | 四川大学 | Bicyclo oxazolidine tanning agent and method of preparing the same |
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| CN105803134A (en) | 2016-07-27 |
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Effective date of registration: 20220908 Address after: No. 5, Mengzhou Industrial Cluster District, Jiaozuo City, Henan Province, 454750 Patentee after: Longfeng Gelemei Fashion Co.,Ltd. Address before: 454791 No.5, West Industrial Zone, Mengzhou City, Jiaozuo City, Henan Province Patentee before: HENAN PROSPER SKINS & LEATHER ENTERPRISE Co.,Ltd. |