CN108285937A - A method of based on biological enzyme oxidation vegetable extract and its for leather tanning - Google Patents
A method of based on biological enzyme oxidation vegetable extract and its for leather tanning Download PDFInfo
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- CN108285937A CN108285937A CN201810337805.3A CN201810337805A CN108285937A CN 108285937 A CN108285937 A CN 108285937A CN 201810337805 A CN201810337805 A CN 201810337805A CN 108285937 A CN108285937 A CN 108285937A
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- vegetable extract
- tanning
- biological enzyme
- vegetable
- leather
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- 235000013311 vegetables Nutrition 0.000 title claims abstract description 84
- 239000000284 extract Substances 0.000 title claims abstract description 74
- 239000010985 leather Substances 0.000 title claims abstract description 58
- 102000004190 Enzymes Human genes 0.000 title claims abstract description 43
- 108090000790 Enzymes Proteins 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000003647 oxidation Effects 0.000 title claims description 27
- 238000007254 oxidation reaction Methods 0.000 title claims description 27
- 108010031396 Catechol oxidase Proteins 0.000 claims abstract description 14
- 102000030523 Catechol oxidase Human genes 0.000 claims abstract description 14
- 108010029541 Laccase Proteins 0.000 claims abstract description 14
- 108010001336 Horseradish Peroxidase Proteins 0.000 claims abstract description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
- 241000196324 Embryophyta Species 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000009738 saturating Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000002255 enzymatic effect Effects 0.000 claims description 2
- 108090000854 Oxidoreductases Proteins 0.000 claims 3
- 102000004316 Oxidoreductases Human genes 0.000 claims 3
- 244000025797 Castanea pumila Species 0.000 claims 1
- 235000007763 Castanea pumila Nutrition 0.000 claims 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 11
- 239000000835 fiber Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000000704 physical effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 230000013011 mating Effects 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 229940088598 enzyme Drugs 0.000 description 22
- 235000018553 tannin Nutrition 0.000 description 11
- 229920001864 tannin Polymers 0.000 description 11
- 239000001648 tannin Substances 0.000 description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 235000013824 polyphenols Nutrition 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 244000269722 Thea sinensis Species 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 235000009508 confectionery Nutrition 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000008442 polyphenolic compounds Chemical class 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 108010059892 Cellulase Proteins 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 229940106157 cellulase Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- 241000283707 Capra Species 0.000 description 1
- -1 EC1.10.3.2) Proteins 0.000 description 1
- 241001553774 Euphorbia punicea Species 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 108700020962 Peroxidase Proteins 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 102000003425 Tyrosinase Human genes 0.000 description 1
- 108060008724 Tyrosinase Proteins 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/10—Vegetable tanning
- C14C3/12—Vegetable tanning using purified or modified vegetable tanning agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a kind of using biological enzyme vegetable extract and its applied to the method for leather tanning, more particularly to biological enzyme increases substantially vegetable extract and generates multiple spot covalent cross-linking with rawhide collagenous fiber network, and mating quick tanning system is applied to leather tanning process, in the tanning step multiple spot covalent cross-linking is generated using laccase, polyphenol oxidase, horseradish peroxidase enzyme catalytic vegetable extract and rawhide collagenous fiber network, the covalent cross-linking degree for promoting vegetable extract and collagenous fibres, to the hydrothermal stability for promoting finished leather and other physical mechanical properties.Interim tanning charging is carried out in a manner of high concentration quick tannage by the vegetable extract of biological enzyme, and the tanning time of vegetable extract is greatly shortened.The process for tanning of the present invention uses nontoxic, harmless, environmental-friendly biological enzyme and renewable, natural vegetable extract for basic material, promotes the hydrothermal stability and physical property of vegetable tanned leather so that finished leather physical property is good, soft, vegetable tanning sense is low.
Description
Technical field
The present invention relates to leather tanning technical field, more particularly to a kind of vegetable extract and its use based on biological enzyme
In the method for leather tanning.
Background technology
China is the processing big country of World Leather Industry, and processing capacity, export volume occupy first place in the world long, but leather processing mistake
Generated serious pollution is the main problem of leather industry sustainable development in journey, the reason is that being used in leather processing procedure
A large amount of harmful Leather Chemicals, seriously polluted ecological environment.Therefore by degradable, environment amenable biomass leather
It is the emphasis that home and abroad colleagues study that chemical materials, which is applied to leather processing procedure,.Vegetable tanning agent be it is a kind of it is natural, can be again
Raw, free of contamination sustainable leather retanning agent, but vegetable tanning agent tan at leather have shrinkage temperature is low, physical mechanical property not
The defects of foot, application range limitation, so the application in leather industry is limited to a certain extent.
Laccase（Laccase, EC1.10.3.2）, polyphenol oxidase（Polyphenol oxidase, EC
1.10.3.1）, horseradish peroxidase（Horseradish Peroxidase, EC 1.11.1.7）With catalysis oxidation plant
The ability of tannin extract polyphenol tannin composition, the polyphenol tannin in vegetable extract can be oxidized to quinoid structure, while quinoid knot by it
Covalent cross-linking occurs for the amino of structure and rawhide collagenous fiber network.These oxidizing ferment are in neighborhoods such as papermaking, environment, organic syntheses at present
It suffers from and is widely applied.Its essence of the tanning of leather is exactly that tanning agent forms multiple spot crosslinking between rawhide collagenous fiber network, is made
It obtains rawhide and becomes finished leather.The tannin composition of vegetable extract is mostly aldehydes matter, in the catalysed oxidn of biological enzyme, these phenolic materials
Matter is oxidized to quinoid structure and generates multiple spot covalent cross-linking with rawhide collagenous fiber network again, and not oxidized phenolic hydroxyl structure can be with
Continuation is combined with collagenous fibres active group in the form of hydrogen bond so that the hydrothermal stability of vegetable tanned leather increases substantially,
The physicochemical properties such as physical mechanical property are promoted.
Invention content
It is an object of the invention to a kind of methods being applied to leather tanning using biological enzyme vegetable extract, using life
Object enzymatic vegetable extract is used for leather tanning, promotes vegetable tanning leather property.Biological enzyme of the present invention increases substantially
Vegetable extract generates multiple spot covalent cross-linking with rawhide collagenous fiber network, and mating quick tanning system is applied to leather tanning mistake
Journey generates multiple spot covalent cross-linking in the tanning step using Laccase Catalyzed vegetable extract and rawhide collagenous fiber network, promotes plant
The covalent cross-linking degree of tannin extract and collagenous fibres, to the hydrothermal stability for promoting finished leather and other physical mechanical properties.
The technical scheme is that：A method of leather tanning is applied to based on biological enzyme vegetable extract,
Middle biological enzyme increases substantially vegetable extract and generates multiple spot covalent cross-linking degree, and mating quick tanning with rawhide collagenous fiber network
System is applied to leather tanning process, to improve tanning efficiency and promote vegetable leather hydrothermal stability and physical property.
Based on the above technical solution, for the present invention in order to tell on more preferably, application is more abundant, is also equipped with as follows
Attached technical characteristic：
The biological enzyme is the solid powder or liquid preparation of laccase.
The biological enzyme is the solid powder or liquid preparation of polyphenol oxidase.
The biological enzyme is the solid powder or liquid preparation of horseradish peroxidase.
The biological enzyme is that polyphenol oxidase derives from plant or microorganism.
The biological enzyme is that horseradish peroxidase derives from plant or microorganism.
The biological enzyme be laccase, polyphenol oxidase, 50U/g that horseradish peroxidase dosage is vegetable extract dry weight ~
300U/g。
Cellulase treatment vegetable extract technological parameter is as follows：Vegetable extract is dissolved in 8 ~ 15 times（Vegetable extract dry weight）Water
In, wait for that it is completely dissolved, addition biological enzyme 2h ~ for 24 hours.Temperature is about 25 DEG C ~ 55 DEG C, pH 4.0 ~ 7.5.
Leather is common animal's leather, such as pig, ox, sheepskin.
The inventive principle of above-mentioned technical proposal is as follows：The biological enzyme is laccase, polyphenol oxidase, horseradish peroxidase
The tannin composition of enzyme, vegetable extract is mostly aldehydes matter, and in the catalysed oxidn of biological enzyme, these aldehydes matters are oxidized to
The quinoid structure active amino with rawhide collagenous fiber network again（-NH2）Schiff base reaction/Michael addition reaction occurs so that
Vegetable extract polyphenol tannin composition forms firm covalent cross-linking, while not oxidized phenol hydroxyl between rawhide collagenous fiber network
Based structures can continue to be combined in the form of hydrogen bond with collagenous fibres active group so that the hydrothermal stability of vegetable tanned leather is big
The physicochemical properties such as amplitude raising, physical mechanical property are promoted.
The present invention has following advantage：
1, the present invention is used for the main tan process of leather of vegetable extract, improves thermal stability, the Physical Mechanical of vegetable tanning leather
Its tanning physical property contrast table of the physicochemical properties such as energy is as shown in table 1, to meet the needs of different purposes are to vegetable tanning leather.
2, the present invention provides it is a kind of using cellulase treatment vegetable extract be applied to leather tanning method, to environment without
Pollution, meet can leather industry sustainable development, increase its application range in the leather tanning of different-style for vegetable extract.
3, the finished leather produced of the present invention has hydrothermal stability height, tissue tight, solid full, good moldability excellent
Point.It is suitble to various Animal Skins such as pigskin, sheepskin, goat skin, cattle hide, buffalo hide, milk ox-hide and the tanning for consuming ox-hide, is suitble to
Various uses is removed from office such as：Vegetable tanning clothing leather, vegetable tanned upper leather, vegetable tanning shoe lining leather, vegetable tanning Napped leather, vegetable tanning automobile cushion leather, vegetable tanning
The manufacturing process of heavy leather.
Specific implementation mode
With reference to embodiment, the present invention is further elaborated, but the present invention is not limited to following embodiment.
1, the preparation of biological enzyme oxidation vegetable extract
Embodiment 1
Catalytic oxidation treatment is carried out to vegetable extract according to the most suitable technique for applying of laccase, process conditions are：25 DEG C of temperature, pH
4.0, laccase dosage 300U/g vegetable extracts, time 2h.Overall process is passed through air with air pump.After obtaining Laccase Catalyzed oxidation
Vegetable extract solution.
Embodiment 2
Catalytic oxidation treatment is carried out to vegetable extract according to the most suitable technique for applying of polyphenol oxidase, process conditions are：Temperature
55 DEG C, pH 7.5, polyphenol oxidase enzyme dosage 50U/g vegetable extracts, the time is for 24 hours.Overall process is passed through air with air pump.It obtains more
Vegetable extract solution after phenol oxidase catalysis oxidation.
Embodiment 3
Catalytic oxidation treatment is carried out to vegetable extract according to the most suitable technique for applying of horseradish peroxidase, process conditions are：
40 DEG C, pH 5.5, dosage 150U/g of temperature, time 12h.Overall process is passed through air with air pump.Obtain horseradish peroxidase
Vegetable extract solution after catalysis oxidation.
2, biological enzyme oxidation vegetable extract is applied to leather tanning
The sweet tea dry hide that following embodiment is provided by specialized leathers factory, liming, deliming, softening, pickling are all made of at common process
Reason.
The vegetable extract is dissolved in 8 ~ 15 times of water, and after catalysis, concentration is still tannin extract:Water is 1:8 ~ 15,
Concentration is no longer altered (as diluted or concentrating)；Specific implementation process is successively increased with being catalyzed tannin extract liquor capacity, also
It is that the tannin extract liquor capacity after catalysis is divided into 10%, 20%, 30%, 40% adds respectively.
The vegetable extract dosage is that 1.5 times of meters 15% ~ 45% of sour tare weight are the leather demand style differences because different,
Its dosage is different.
Embodiment 4
Pickling sweet tea dry hide is in liquor ratio 1.0, pH3.0, anhydrous sodium sulphate 5%（1.5 times of meters of sour tare weight）Under conditions of return acid, use sodium bicarbonate
Bath foam pH is adjusted to 5.5, skin is extracted in drain, then the vegetable extract after Laccase Catalyzed is aoxidized（The 1.5 of 15% ~ 45% sour tare weight
It counts again）Solution adds in four times, respectively：10%（Rotation 30 minutes）, 20%（Rotate 1h）, 30%（Rotate 2h）And add 3% yuan
Bright powder, 40%（It is saturating to turn to leather tan）, washing, the rear process such as dyeing, stuffing is the same as conventional.
Embodiment 5
Pickling sweet tea dry hide is in liquor ratio 1.0, pH3.0, anhydrous sodium sulphate 5%（1.5 times of meters of sour tare weight）Under conditions of return acid, use sodium bicarbonate
Bath foam pH is adjusted to 5.5, skin is extracted in drain, then by the vegetable extract after polyphenol oxidase catalyzed oxidation（15% ~ 45% sour skin
1.5 times of meters of weight）Solution is being divided into：10%（Rotation 30 minutes）, 20%（Rotate 1h）, 30%（Rotate 2h）And 3% anhydrous sodium sulphate is added,
40%（It is saturating to turn to leather tan）, washing, the rear process such as dyeing, stuffing is the same as conventional.
Embodiment 6
Pickling sweet tea dry hide is in liquor ratio 1.0, pH3.0, anhydrous sodium sulphate 5%（1.5 times of meters of sour tare weight）Under conditions of return acid, use sodium bicarbonate
Bath foam pH is adjusted to 5.5, skin is extracted in drain, then the vegetable extract after horseradish peroxidase enzyme catalytic is aoxidized（15%~45%
1.5 times of meters of sour tare weight）Solution is being divided into：10%（Rotation 30 minutes）, 20%（Rotate 1h）, 30%（Rotate 2h）And add 3% yuan
Bright powder, 40%（It is saturating to turn to leather tan）, washing, the rear process such as dyeing, stuffing is the same as conventional.
3, biological enzyme aoxidizes vegetable extract tan leather performance test
Embodiment 7
By the tanning of Laccase Catalyzed vegetable extract, polyphenol oxidase catalyzed vegetable extract tanning, horseradish peroxidase enzyme catalytic plant
Tannin extract tanning and untreated vegetable extract tanning are divided into laccase group, polyphenol oxidase group, horseradish peroxidase group and not
Processing group, is tested for the property.
The shrinkage temperature of each group sample is measured according to QB/T2713-2005；According to ISO 3376-2011 standard test each groups
The tensile strength of sample, fracture elongation, tear edge；The thickness of leather uses multi-spots way, i.e., equidistant on each sample block
9 points of liftoff selection measure its thickness, its average value, calculating is taken to thicken rate；Each group sample is measured according to QB/T 4870-2015
Pliability.The above test result is summarized, obtains table 1 as a result, table 1 compares for biological enzyme vegetable extract tanning properties
Table：
Table 1 is the results show that the finished leather that the present invention produces has hydrothermal stability height and good physical mechanical property etc. excellent
Point.
The biological enzyme vegetable extract process for tanning of the present invention is in different types of leather and different-style purposes
Vegetable tanned leather all has good applicability.
It, can according to the technique and scheme of the present invention and its hair it is understood that for those of ordinary skills
Bright design is subject to equivalent substitution or change, and all these changes or replacement should all belong to the guarantor of appended claims of the invention
Protect range.
Claims (6)
1. a kind of vegetable extract of biological enzyme oxidation, which is characterized in that by including prepared by following components：
Vegetable extract
50 ~ 300 U/g vegetable extracts of biological enzyme；
The biological enzyme is one or more of laccase, polyphenol oxidase, horseradish peroxidase.
2. the preparation method of the vegetable extract of oxidase catalyzed oxidation described in claim 1, which is characterized in that including following step
Suddenly：
Vegetable extract is dissolved in the water of 8 ~ 15 times of vegetable extract dry weight, waits for that it is completely dissolved, addition biological enzyme, 25 DEG C ~ 55 DEG C,
It is catalyzed 2h ~ for 24 hours under the conditions of pH 4.0 ~ 7.5, obtains the vegetable extract of biological enzyme.
3. the preparation method of the vegetable extract of biological enzyme oxidation according to claim 2, it is characterised in that：Biological enzyme
It is catalyzed during vegetable extract, air is constantly passed through into mixture.
4. the method that the vegetable extract described in claim 1 based on biological enzyme oxidation is used for leather tanning, feature exist
In including the following steps：
By pickled pelts liquor ratio 1.0, pH 3.0 and containing weight be 1.5 times of meters 5% of sour tare weight anhydrous sodium sulphate bath foam in return acid；
Bath foam pH is adjusted to 5.5 with sodium bicarbonate, skin is extracted in drain；The biology that weight is sour 1.5 times of meters 15% ~ 45% of tare weight will be contained
The solution of the vegetable extract of enzymatic oxidation carries out tanning to rawhide, until tan is saturating.
5. the method that the vegetable extract according to claim 4 based on oxidase catalyzed oxidation is used for leather tanning, special
The step of sign is, rawhide tanning is carried out using the vegetable extract of biological enzyme oxidation specifically includes：
The solution of vegetable extract containing the biological enzyme oxidation that weight is sour 1.5 times of meters 15% ~ 45% of tare weight is divided by part
10%, 20%, 30%, the 40% of the vegetable extract solution total amount of biological enzyme oxidation is added by several times.
6. the method that the vegetable extract according to claim 5 based on oxidase catalyzed oxidation is used for leather tanning, special
Sign is that the specific addition manner of the vegetable extract solution of biological enzyme oxidation is：
The vegetable extract solution tanning 30min of the 10% biological enzyme oxidation of total amount of adding；Continue the 20% of total amount of adding
The vegetable extract solution tanning 60min of biological enzyme oxidation；The plant evergreen chinquapin of the 30% biological enzyme oxidation of total amount of adding again
Sol solution, and add the anhydrous sodium sulphate of 1.5 times of meters 3% of sour tare weight, tanning 120min；Finally by 40% biological enzyme of remaining total amount
The vegetable extract solution of catalysis oxidation adds, and tanning is saturating to rawhide tan, stops drum overnight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810337805.3A CN108285937B (en) | 2018-04-16 | 2018-04-16 | Plant tannin extract based on biological enzyme catalytic oxidation and method for tanning leather by using plant tannin extract |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810337805.3A CN108285937B (en) | 2018-04-16 | 2018-04-16 | Plant tannin extract based on biological enzyme catalytic oxidation and method for tanning leather by using plant tannin extract |
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| Publication Number | Publication Date |
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| CN108285937A true CN108285937A (en) | 2018-07-17 |
| CN108285937B CN108285937B (en) | 2020-07-21 |
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| CN201810337805.3A Active CN108285937B (en) | 2018-04-16 | 2018-04-16 | Plant tannin extract based on biological enzyme catalytic oxidation and method for tanning leather by using plant tannin extract |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109593898A (en) * | 2019-01-18 | 2019-04-09 | 陕西科技大学 | It is a kind of based on the biomass-based amphoteric retanning agent and preparation method thereof with reactivity |
| CN110184396A (en) * | 2019-05-20 | 2019-08-30 | 梁生 | A kind of leather tanning agent |
| CN112725550A (en) * | 2020-12-31 | 2021-04-30 | 晋江市永建皮革制品有限公司 | Environment-friendly preparation process of washable oxen two-layer leather |
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|---|---|---|---|---|
| CN102002540A (en) * | 2010-11-11 | 2011-04-06 | 陕西科技大学 | Preparation method of modified Chinese gall tanning extract environmentally-friendly leather tanning agent |
| CN102127605A (en) * | 2010-01-19 | 2011-07-20 | 深圳市绿微康生物工程有限公司 | Leather tanning preparation and application method thereof |
| CN106119440A (en) * | 2016-08-30 | 2016-11-16 | 四川达威科技股份有限公司 | Leather tanning agent |
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- 2018-04-16 CN CN201810337805.3A patent/CN108285937B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127605A (en) * | 2010-01-19 | 2011-07-20 | 深圳市绿微康生物工程有限公司 | Leather tanning preparation and application method thereof |
| CN102002540A (en) * | 2010-11-11 | 2011-04-06 | 陕西科技大学 | Preparation method of modified Chinese gall tanning extract environmentally-friendly leather tanning agent |
| CN106119440A (en) * | 2016-08-30 | 2016-11-16 | 四川达威科技股份有限公司 | Leather tanning agent |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109593898A (en) * | 2019-01-18 | 2019-04-09 | 陕西科技大学 | It is a kind of based on the biomass-based amphoteric retanning agent and preparation method thereof with reactivity |
| CN109593898B (en) * | 2019-01-18 | 2021-07-16 | 陕西科技大学 | Biomass-based reactive amphoteric retanning agent and preparation method thereof |
| CN110184396A (en) * | 2019-05-20 | 2019-08-30 | 梁生 | A kind of leather tanning agent |
| CN112725550A (en) * | 2020-12-31 | 2021-04-30 | 晋江市永建皮革制品有限公司 | Environment-friendly preparation process of washable oxen two-layer leather |
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| CN108285937B (en) | 2020-07-21 |
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