CN107312896A - A kind of animal hide fiber unstructured approach acted on based on zytase - Google Patents
A kind of animal hide fiber unstructured approach acted on based on zytase Download PDFInfo
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- CN107312896A CN107312896A CN201710574969.3A CN201710574969A CN107312896A CN 107312896 A CN107312896 A CN 107312896A CN 201710574969 A CN201710574969 A CN 201710574969A CN 107312896 A CN107312896 A CN 107312896A
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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
- C14C1/06—Facilitating unhairing, e.g. by painting, by liming
- C14C1/065—Enzymatic unhairing
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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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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention discloses a kind of animal hide fiber unstructured approach acted on based on zytase, it is related to leather and Qiu Ge production field.The method have the characteristics that in the processes such as immersion, softening and the pickling of the processes such as the immersion of process hides, depilation, softening and pickling or fur coat processed, addition zytase is used as the loose auxiliary agent of hide fiber.This method efficiently can not only be destroyed exclusively has the components such as the proteoglycan and glycosaminoglycan of cementation to hide fiber in Animal Skin, and does not have destruction to hide collagen composition.This method has wide applicability, is suitable for the manufacturing process of the various uses leather or Qiu Ge using various Animal Skins as raw material, reaches that promotion hide fiber is loose, improves the effect of the pliability, feel and physical and mechanical properties of resultant Leather.Used in leather making process, the use of polluter such as lime and vulcanized sodium can be substantially reduced, promote hair removal effect.
Description
Technical field
The present invention relates to the leather using Animal Skin as raw material or Qiu Ge manufacture field, and in particular to one kind uses xylan
Enzyme carries out loose method to animal hide fiber.
Background technology
Hide fiber it is appropriate be loosely one of main purpose of process hides and fur coat beam house processed.The loose journey of animal hide fiber
Degree directly affect the infiltration of material in rear process and and collagenous fibres on active group combination, and then have influence on the softness of finished leather
Property, fullness, elasticity, grain state, physical and mechanical properties and area yield of leather etc..When particularly producing soft leather, fiber is loose
Degree directly determines the quality and class of resultant Leather.
Tanning production mainly uses the corium layer segment of Animal Skin, especially with collagen component therein, its
He is required for being removed in beam house non-collagen tissue such as interfibrillar substance, fat, blood stains, elastin laminin and reticulin
Appropriate removing is also required to, is that the combination of the materials such as tanning, dyeing, stuffing and collagenous fibres opens passage and fully exposes reaction
Group.
Qiu Ze processed is mainly using corium and the animal hair being attached on skin corium, except should be noted to protect in production process
Protect outside fleece, remaining is substantially similar to the principle of process hides, it is also desirable to which appropriate carry out fiber is loose, to obtain plentiful soft fur coat
Skin.
Play the proteoglycans in the mainly gelatinous interfibrillar substance of fibres bond in Animal Skin（Also referred to as glue egg
In vain）.This kind of material tool is highly hydrophilic, can keep connective tissue moisture, have very strong swelliong power, be transferred to from weak solution
Desiccation, volume contraction is up to more than 1000 times, and this can cause after transepidermal water loss drying, and fibre compact is sticked together.Skin
In proteoglycans wide variety, content at most be dermatan sulphate proteoglycan（DSPG）, DSPG is by one or two
High-molecular compound formed by glycosaminoglycan and core protein covalent bond, including glue decorations proteoglycans（Decorin）, egg-pair
White glycan（Biglycan）.Pass through three sugar units between sugar chain and core protein（Galactolipin-the β -1,4 of β -1,3- galactolipins-β -1,3
Xylose）It is connected with serine or threonine with O-glycosides key, in addition, also passing through N- glycosidic bonds on the aspartic acid on core protein
It is connected with 2-3 bar oligonucleotide chains.Glycosaminoglycan（glycosaminoglycan,GAG）Also referred to as mucopolysaccharide, acidic polysaccharose or amino are more
Sugar, the long-chain that the disaccharide unit being made up of aminohexose-hexuronic acid is combined to form by glycosidic bond not branching compound.Root
According to the difference of the Nomenclature Composition and Structure of Complexes of monose, hyaluronic acid, dermatan sulfate, chondroitin sulfate, keratan sulfate, heparin can be divided into
With the type of Heparan sulfate 6.Sulphation does not occur typically for the sugar unit of hyaluronic acid, and molecular weight is up to 600KD polysaccharide.
Other glycosaminoglycans sulphation on the hydroxyl generally on 3,4 or 6 carbon, therefore with a large amount of negative electrical charges.Some albumen gather
Core protein on sugar can be connected by the way that the spherical plot structures of N- ends is non-covalent with hyaluronic acid, form proteoglycan aggregation
Body.Additionally, there may be connection albumen prevents aggregation depolymerization.
Decorin controls the formation of collagenous fibril, by controlling aggregation and constraint between collagenous fibres molecule to influence
The diameter of fiber.Hyaluronic acid plays a part of lubricating under physiological status can be fine by collagen after collagenous fibres, but rawhide drying
Dimension bonds, and skin is lost flexibility, hardened to be hardened.Therefore, fiber loosely needs to remove these materials.
Traditional fiber is loosely mainly completed by liming and softening process.Using lime in strong basicity in liming process
Under the conditions of long duration of action can remove glycosaminoglycan and some Aci dic proteinpolysaccharides that most of electrovalent bond is combined, moreover, calcium from
Son has peptization, and this method raw material is easy to get, simple to operate, fiber favorable loosening effect, but lime solubility is low, actually makes
Consumption is far more than theoretical amount, reaches the 3%-15% of raw hide weight, causes great waste of material and environmental pollution, and process hides is given up
50%-70% BOD and COD, 15%-20% total solid matters in water（TS）Come from liming process.And in fur production process, be
Protection fleece, it is impossible to handle fur using overbased materials.
Protease is added in softening process suitably to destroy collagen and remove connection albumen and core protein, but due to making
Protease preparation is impure, complicated components, there is complex operation, to hide glue original structure excess destruction, cause the empty pine of finished leather and
The danger of grain damage, further, since protective effect of the long chain polysaccharides chain to core protein around proteoglycan, protease pair
The destruction of core protein is weaker.Therefore in real process still with lime it is loose based on.
To solve the pollution problem of lime, the engineer and expert of this area have developed ashless/few grey expansion process, lead to
Cross and use the inorganic bases or organic amine etc. such as sodium hydroxide, silicate part to substitute lime in skin alkali swelling, also to a certain extent
Obtain industrial applications.One subject matter of these methods is, the degrees of expansion of skin, state and the loose effect of fiber and lime
Liming skin still has a certain distance, can influence the flexibility and fullness of the performance, particularly leather of the operation of piece graywall and finished leather
Deng still there is a certain distance.
Find that the removal of mucin is loosely relevant with depilation and fiber with Ba Bajinna et al., it is believed that pectase, hyalomitome
Sour enzyme etc. can promote depilation and the loose effect of fiber.Alexander research shows the loose and intracutaneous albumen of materials with hide glue fibril
The removal of polysaccharide and hyaluronic acid is closely related.
At present, due to amylase to collagen without destruction, be only capable of the glucide destroyed in interfibrillar substance, people
Begin to use amylase promote fiber it is loose.（Diversiform-leaved poplar, the green hide fiber based on biological enzyme formulation is separated in loose technology
State's leather, 2013（15）：16-22；Thanikaivelan P, Integrated hair removal and fiber
opening process using mixed enzymes.CleanTechnologiesandEnvironmentalPolicy,
2007,9(1):61-68）.But it is due to glycoside hydrolase huge number, Various Functions, to the selectivity of glycosyl, there is also obvious
Difference, wherein amylase mainly act on α-Isosorbide-5-Nitrae-glycosidic bond, and the selectivity to β-glycosidic bond is not strong.
As it was previously stated, passing through three sugar units between sugar chain and core protein in intracutaneous proteoglycans（β -1,3- galactolipins -
The xyloses of β -1,3 galactolipins-β -1,4）It is connected with serine or threonine with O-glycosides key.Zytase can hydrolyze xylose glycosidic bond,
Therefore glycosidic bond between xylose-O- serine/threonines that can be by destroying connection core protein and glycosaminoglycan, makes macromolecular sugar
Chain is separated with core protein, so that it is in the proteoglycan structure that sheath shape is surrounded to destroy collagenous fibres surrounding molecules, makes collagen fine
Tie up beam loose, the increase of fiber spacing.
The content of the invention
The purpose of the present invention is to provide a kind of fiber loose new method for the deficiency of the loose technology of existing fiber, to drop
The pollution of lime and akali sulphide in low traditional liming process, makes up the grain that existing protease depilation and the loose technology of fiber are caused
Surface damage, the deficiency of the empty pine of finished leather, overcome other without sulphur without the loose not enough shortcoming of fiber in gray technology.
Novelty of the invention is that the albumen that intracutaneous cementation is efficiently exclusively acted on using zytase is gathered
The xylose between core protein and glycosaminoglycan-O-glycosides key in sugared structure, and intracutaneous collagen structure is not damaged.
The basic characteristics of the present invention are the structures for the main component proteoglycan that interfibrillar substance is destroyed using zytase, are beaten
Constraint between broken collagenous fiber bundle, reaches the purpose of loose fiber.
The process hides and hide fiber unstructured approach in Qiu Jiagong processed that above-mentioned purpose of the present invention can be achieved at least contain following methods
In a process, each operation operating procedure material therefor is in parts by mass.
Method 1：The loose method of hide fiber that zytase promotes in leather making process at least contains one in following process
Individual process, each operation operating procedure material therefor is according to mass parts meter；
（1）Immersion：By 100 parts of addition rotary drums of raw material skin, add water 100-500 parts, 18-25 DEG C of temperature adds zytase 0.01-
2.0 parts, rotate after 30-240min, then routinely immersion technique carries out subsequent operation；
（2）Depilation：
Enzymatic depilation：100 parts of addition rotary drums of Animal Skin after being handled through immersion or after immersion ungrease treatment, add water 30-500 parts, adjust
Temperature is to 20-40 DEG C, and pH value 6-10 adds 0.01-2 parts of zytase, rotates 0-180min, adds depilation enzyme, then by enzymatic depilation
Technique carries out follow-up epilation operation；
Grey alkaline process depilation：100 parts of input rotary drums of Animal Skin after being handled through immersion or after immersion ungrease treatment, add water 30-500
Part, temperature adjustment is to 18-25 DEG C, pH value 6-8, adds after 0.01-2 part of zytase, rotation 30-240min, routinely ruin hair or
Protect hair dehairing process and add the follow-up epilation operation of the epilatory material such as vulcanized sodium and lime progress；
（3）Softening：By 100 parts of input rotary drums of Animal Skin after deliming, add water 30-100 parts, temperature adjustment to 25-40 DEG C, pH value 6-
9,0.01-2.0 parts of zytase of addition, intermittent rotary 0-180min, routinely the progress of softening process addition macerating enzyme is follow-up soft
Change operation；
（4）Pickling：By 100 parts of input rotary drums of Animal Skin after softened processing, add water 20-100 parts, temperature adjustment to 18-25 DEG C, plus
Enter 0.01-2.0 parts of zytase, rotate after 30-240min, routinely soak salt-free pickling procedure operation；
By the skin of above-mentioned processing, routinely technique carries out subsequent operation again.
Method 2：Zytase promotes the loose method of fiber to comprise at least in following process at least during fur coat processed
One process, each operation material therefor is according to mass parts meter：
（1）Fur soaks：By water, 1000-2000 parts add in paddle-tumble or rotary drum, 18-25 DEG C of temperature, and adding zytase makes bath
The concentration of enzyme reaches 0.01-5g/L in liquid, adds 100 parts of raw material skin after stirring evenly, and stroke or rotates after 30-240min, then by normal
Rule immersion technique carries out follow-up immersion operation；
（2）Fur softens：By water, 800-2000 parts add in paddle-tumble or rotary drum, and 25 DEG C -40 DEG C of temperature, pH value 6-9 adds wood poly-
Carbohydrase makes the concentration of enzyme in body lotion reach 0.01-5g/L, after stirring evenly throw 100 parts of skin, stroke or rotate 0-60min, it is routinely soft
Chemical industry skill carries out follow-up softening operation；
（3）Fur pickling：By water, 1000-2000 parts add in paddle-tumble or rotary drum, 18-25 DEG C of temperature, and adding zytase makes bath
The concentration of enzyme reaches 0.01-5g/L in liquid, adds 100 parts of raw material skin after stirring evenly, and stroke or rotates after 30-240min, routinely
Pickling or salt-free pickling technique carry out follow-up pickling procedure operation；
By the skin of above-mentioned processing, routinely technique carries out subsequent operation again.
In the above-mentioned technical solutions, the zytase be bacterium, actinomyces, fungi and yeasts production zytase in
At least one.The type of the zytase be endo-type β -1,4- zytases, circumscribed-type β -1,4- zytases, β -1,
At least one of the zytase such as 3- zytases, xylobiase family.
Preferably, the use pH value of zytase is 4-10, and the use pH value of preferred zytase is 5-8.
Preferably, the temperature in use of zytase is 18-45 DEG C.
This method is suitable for the loose process of fiber of various Animal Skins.
This method is suitable for the process of all kinds purposes leather or fur.
The invention has the advantages that
The invention provides the method that hide fiber during a kind of process hides or fur coat processed is loose, using zytase, can exclusively it make
For the junction of sugar chain and core protein in intracutaneous proteoglycan, sugar chain is effectively discharged, without destroying intracutaneous collagen
The structural proteins such as albumen, safe operation.
The present invention can effectively reduce the consumption of lime and sulfide, suspension in sludge and waste water in reduction process hides, total
Nitrogen, COD are equivalent, reduce wastewater treatment difficulty, nontoxic, advantageously reduce the pollution of process hides generation.
This method is used before enzymatic depilation, can open intracutaneous passage, improves the seepage velocity of protease, reduction enzyme is in grain
The action time in face, accelerate the speed of enzymatic depilation and reduce destruction of the protease to grain, so as to improve the peace of enzymatic depilation
The quality of full property and finished leather.
The process compatibility of this method is good, can be according to leather or fur the need for, be widely used in process hides or fur coat processed production
During each process, including immersion, depilation, softening and fur immersion, softening and pickling etc..
The fiber that the present invention is suitable for such as various Animal Skins of pigskin, sheepskin, goat skin, ox-hide, rabbit is loose, and suitable
Together in various types of leather making processes（Such as clothing leather, upper leather, sofa artificial leather, shoe lining leather, suede, automobile cushion leather
Deng）, the more excellent resultant Leather of more soft, physical and mechanical properties can be obtained.
Embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that, embodiment is served only for
The present invention is further described, it is impossible to be interpreted as limiting the scope of the invention, the person skilled in the art in the field
Some nonessential modifications and adaptations can be made according to the content of the invention described above.
1-yellow cow sofa leather of embodiment soaks
After salted cattlehide 100kg, washing, pre- immersion and fleshing, add rotary drum, add water 200kg, temperature adjustment to about 22 DEG C, plus
Enter zytase（Jinan Jigang Design Inst.）0.1kg, after rotating 60 minutes, adds soda ash 0.5kg, permeates
Agent JFC0.2kg, bactericide 0.2kg, are rotated 60 minutes, intermittent rotary, are rotated 5 minutes per hour, total soaking time about 22 is small
When.
The result of proteoglycan and total reducing sugar is as shown in table 1 in waste liquid after immersion.In the cattle hide for adding zytase immersion
The proteoglycan and total reducing sugar being removed are apparently higher than blank group, test result indicates that it is loose to add the group fiber of zytase loosely
Degree is more preferable.
Proteoglycan and total sugar content in the immersion waste liquid of table 1（mg/L）
The leather depilation of 2-cow leather upper of embodiment
Ox-hide 100kg after immersion, adds rotary drum, add water 50kg, and temperature adjustment adjusts the pH value 6-7 of skin, zytase to about 25 DEG C
（Shandong Longke Enzyme Co., Ltd.）0.1kg, after rotating 4 hours, adds 1398 proteinase-10 .15kg, 3h is rotated, to only
Small Mao is remained, lime 1kg is added, turns 40min, vulcanized sodium 0.5kg is added, turns 40min, hair adds expanding agent CAS after purifying（Sichuan reaches
Prestige Science and Technology Co., Ltd.）0.25kg, water 30kg, turn 20min and stop 20min, plus CAS0.25kg, water 25kg turns 20min and stopped
After 20min, the 50kg that adds water, turn to stop bulging stay overnight after 30min.Deliming pelt is not required to enzyme bating after split, deliming, is directly entered
Pickling procedure, is carried out according still further to conventional footwear upper leather technique afterwards.
The performance of resultant Leather is as shown in table 2.
The physical and mechanical properties table of leather after the stuffing of table 2
As a result showing the physical and mechanical properties of the resultant Leather after xylanase treatment can match in excellence or beauty in the leather of conventional lime processing,
And the former is more soft.
3-pig leather for making garment of embodiment softens
Routinely pig pelt 100kg is added after rotary drum, deliming after technique liming, split, and add water 40kg, and temperature adjustment is added to 35 DEG C
Macerating enzyme DOWELLZYMBM（Protease, Sichuan Dowell Technology Co., Ltd.）1.5kg and zytase（Shandong Long Kete
Enzyme preparation Co., Ltd）0.05kg, is rotated after 90min, intermittent rotary, and 5min clocks, common 4h are rotated per 30min.
By the skin of above-mentioned processing, routinely technique carries out subsequent operation again.
4-sheepskin of embodiment fur soaks
Sheep wet salted hide 100kg is added in paddle-tumble, and add water 2000kg, sodium chloride 40kg, zytase（Shandong Long Kete enzyme preparations
Co., Ltd）After 1kg, stroke 30min, interval stroke, per 1h strokes 10min, common 20h.
By the skin of above-mentioned processing, routinely technique carries out subsequent operation again.
5-fox of embodiment fur pickling/softening
Water 1000kg is added in paddle-tumble, 25 DEG C of temperature, add zytase 3kg, the raw fox skin 100 added after stirring evenly after degreasing
Part, after stroke 30min, gap stroke, per 1h strokes 10min, common 3h.Sodium sulphate 80kg is added, sulfuric acid 2kg, stroke is added
After 30min, add prolease activity in acid protease 537, body lotion and reach after 10000U/L, stroke 30min, gap stroke,
Per 1h strokes 10min, common 3h.Sulfuric acid 2-3kg is added, body lotion pH value 2.0-2.6, gap stroke, per 1h strokes is adjusted
10min, common 15-30h.
By the skin of above-mentioned processing, routinely technique carries out subsequent operation again.
Claims (6)
1. a kind of animal hide fiber unstructured approach acted on based on zytase, it is characterised in that its specific implementation method is as follows：
Method 1：Zytase promotes the loose method of hide fiber in leather making process, it is characterised in that this method comprise at least with
At least one process in lower process, each operation operating procedure material therefor is according to mass parts meter；
（1）Immersion：By 100 parts of addition rotary drums of raw material skin, add water 100-500 parts, 18-25 DEG C of temperature adds zytase 0.01-
2.0 parts, rotate after 30-240min, then routinely immersion technique carries out follow-up immersion operation；
（2）Depilation：
Enzymatic depilation：100 parts of addition rotary drums of Animal Skin after being handled through immersion or after immersion ungrease treatment, add water 30-500 parts, adjust
Temperature is to 20-40 DEG C, and regulation pH value to 6-10 adds 0.01-2 parts of zytase, rotates after 0-180min, adds depilation enzyme, then
Follow-up epilation operation is carried out by enzymatic depilation technique；
Grey alkaline process depilation：100 parts of addition rotary drums of Animal Skin after being handled through immersion or after immersion ungrease treatment, add water 30-500
Part, temperature adjustment is to 18-25 DEG C, pH value 6-8, adds after 0.01-2 part of zytase, rotation 30-240min, routinely ruin hair or
Protect hair dehairing process and add the follow-up epilation operation of the epilatory material such as sulfide and lime progress；
（3）Softening：By 100 parts of input rotary drums of Animal Skin after dealkalize, add water 30-100 parts, temperature adjustment controls pH to 25-40 DEG C
Value 6-9, adds 0.01-2.0 parts of zytase, intermittent rotary 0-180min, after routinely softening process addition macerating enzyme is carried out
Continuous softening operation；
（4）Pickling：By 100 parts of input rotary drums of Animal Skin after softened processing, add water 20-100 parts, temperature adjustment to 18-25 DEG C, plus
Enter 0.01-2.0 parts of zytase, rotate after 30-240min, routinely pickling or salt-free pickling technique carry out follow-up pickling procedure
Operation；
By the skin of above-mentioned processing, routinely technique carries out subsequent operation again；
Method 2：Zytase promotes the loose method of hide fiber during fur coat processed, it is characterised in that this method comprise at least with
At least one process in lower process, each operation operating procedure material therefor is according to mass parts meter；
（1）Fur soaks：By water, 1000-2000 parts add in paddle-tumble or rotary drum, 18-25 DEG C of temperature, and adding zytase makes bath
The concentration of enzyme reaches 0.01-5g/L in liquid, adds 100 parts of raw material skin after stirring evenly, and stroke or rotates after 30-240min, then by normal
Rule immersion technique carries out follow-up immersion operation；
（2）Fur softens：By water, 800-2000 parts add in paddle-tumble or rotary drum, and 25-40 DEG C of temperature, pH value 6-9 adds xylan
Enzyme makes the concentration of enzyme in body lotion reach 0.01-5g/L, and 100 parts of skin, stroke or rotation 0-60min are thrown after stirring evenly, is routinely softened
Technique adds macerating enzyme and carries out follow-up softening operation；
（3）Fur pickling：By water, 800-2000 parts add in paddle-tumble or rotary drum, 18-25 DEG C of temperature, and adding zytase makes body lotion
The concentration of middle enzyme reaches 0.01-5g/L, and 100 parts of skin is added after stirring evenly, and stroke or rotation are rotated after 30-240min, routinely soaked
Sour or salt-free pickling technique carries out follow-up pickling procedure operation；
By the skin of above-mentioned processing, routinely technique carries out subsequent operation again.
2. according to a kind of animal hide fiber unstructured approach acted on based on zytase described in claim 1, it is characterised in that
Zytase is at least one of bacterium, actinomyces, the zytase of fungi and yeasts production.
3. according to a kind of animal hide fiber unstructured approach acted on based on zytase described in claim 1, it is characterised in that
Zytase is endo-type β -1,4- zytases, circumscribed-type β -1,4- zytases, β -1,3 zytases, xylobiase
At least one of.
4. according to a kind of animal hide fiber unstructured approach acted on based on zytase described in claim 1, its feature is in wood
The suitable action pH value of dextranase is 4-10, and suitable operative temperature is 18-45 DEG C.
5. according to a kind of animal hide fiber unstructured approach acted on based on zytase described in claim 1, it is characterised in that
This method is suitable for the process hides of various Animal Skins and the process of fur coat processed.
6. according to a kind of animal hide fiber unstructured approach acted on based on zytase described in claim 1, it is characterised in that
This method is suitable for the process of all kinds purposes leather or fur.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1900321A (en) * | 2006-07-27 | 2007-01-24 | 四川大学 | Method for ash-free and no-sulfurizing alkaline liming treatment for making pigskin leather |
| CN101235421A (en) * | 2008-02-02 | 2008-08-06 | 四川大学 | Animal fur clean depilation and fur fiber loosing method for preparing leather and application thereof |
| CN102344975A (en) * | 2010-07-30 | 2012-02-08 | 隆昌县阳州制革有限公司 | Clean tanning hair removal expansion method |
-
2017
- 2017-07-14 CN CN201710574969.3A patent/CN107312896B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1900321A (en) * | 2006-07-27 | 2007-01-24 | 四川大学 | Method for ash-free and no-sulfurizing alkaline liming treatment for making pigskin leather |
| CN101235421A (en) * | 2008-02-02 | 2008-08-06 | 四川大学 | Animal fur clean depilation and fur fiber loosing method for preparing leather and application thereof |
| CN102344975A (en) * | 2010-07-30 | 2012-02-08 | 隆昌县阳州制革有限公司 | Clean tanning hair removal expansion method |
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