CN101718007B - Production method of regenerated silk protein fiber - Google Patents
Production method of regenerated silk protein fiber Download PDFInfo
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- CN101718007B CN101718007B CN2009101548559A CN200910154855A CN101718007B CN 101718007 B CN101718007 B CN 101718007B CN 2009101548559 A CN2009101548559 A CN 2009101548559A CN 200910154855 A CN200910154855 A CN 200910154855A CN 101718007 B CN101718007 B CN 101718007B
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- 239000000835 fiber Substances 0.000 title claims abstract description 63
- 108090000623 proteins and genes Proteins 0.000 title claims abstract description 34
- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 238000009987 spinning Methods 0.000 claims abstract description 43
- 239000002699 waste material Substances 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012047 saturated solution Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 102000008186 Collagen Human genes 0.000 claims abstract 4
- 108010035532 Collagen Proteins 0.000 claims abstract 4
- 229920001436 collagen Polymers 0.000 claims abstract 4
- 239000011550 stock solution Substances 0.000 claims abstract 4
- 235000021190 leftovers Nutrition 0.000 claims abstract 2
- 230000007062 hydrolysis Effects 0.000 claims description 27
- 238000006460 hydrolysis reaction Methods 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 239000004627 regenerated cellulose Substances 0.000 claims description 3
- 239000011555 saturated liquid Substances 0.000 claims 3
- 239000003242 anti bacterial agent Substances 0.000 claims 1
- 239000003205 fragrance Substances 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 108010022355 Fibroins Proteins 0.000 abstract description 63
- 239000000463 material Substances 0.000 abstract description 13
- 238000002156 mixing Methods 0.000 abstract description 10
- 238000005406 washing Methods 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 7
- 229920000297 Rayon Polymers 0.000 abstract description 6
- 238000002166 wet spinning Methods 0.000 abstract description 3
- 239000004753 textile Substances 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 23
- 229920001971 elastomer Polymers 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 230000001112 coagulating effect Effects 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 238000005554 pickling Methods 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 235000008708 Morus alba Nutrition 0.000 description 2
- 240000000249 Morus alba Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000010364 biochemical engineering Methods 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000017854 proteolysis Effects 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- WFXRJNDIBXZNJK-KVVVOXFISA-N azanium;(z)-octadec-9-enoate Chemical compound N.CCCCCCCC\C=C/CCCCCCCC(O)=O WFXRJNDIBXZNJK-KVVVOXFISA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000003531 protein hydrolysate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000009366 sericulture Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention discloses a production method and equipment of regenerated silk protein fibers, and belongs to the technical field of textiles. The method comprises the following steps: washing and drying a silk raw material, then putting the silk material into an alkali liquor, hydrolyzing to obtain a regenerated silk protein stock solution, and drying to obtain regenerated silk protein powder; adding water into the prepared regenerated fibroin powder and stirring to obtain a regenerated fibroin saturated solution; mixing the regenerated fibroin saturated solution, the regenerated collagen solution and the auxiliary agent according to the proportion of 10-50 percent, 85-45 percent and 5 percent, uniformly mixing and spinning to obtain the regenerated fibroin fiber. The invention takes silk waste silk, silk leftovers, waste spinning, silk spinning waste silk and other non-spinnable protein materials as raw materials, prepares regenerated silk protein powder, and then cooperates with viscose and auxiliary agent to regenerate a novel silk protein fiber by wet spinning, and the invention has excellent performance, is healthy and comfortable, and solves the problem of secondary utilization of the waste protein materials on the other hand.
Description
Technical field
The present invention relates to a kind of production method of fiber, more specifically relate to a kind of production method of regenerated fibroin fiber.
Background technology
China is the native place of silk, and silk is the rarity of China.The existing history more than 5000 of China's silk silk fabric production, planting mulberry, sericulture, filature, knitting silk fabric is the greatness invention of Ancient Chinese for the people, is the major contribution to the mankind, and one page of radiance is arranged on world's civilized history.Silk is as a kind of natural fabric with premium properties, always as high-grade fabric.But because the restriction of output, natural silk fiber is limited; Therefore; Regenerated fibroin fiber arises at the historic moment, and at present, the main production technology of regenerated fibroin fiber is following: adopt the Biochemical Engineering technology; From silk cocoon, extract fibroin like lithium bromide water solution, and then adopt electrostatic spinning to be spun into and use regenerated fibroin fiber.
The existing shortcoming of this technology is, the one, adopt dissolving silks such as lithium bromide water solution, and obtain the fibroin aqueous solution; With this as spinning solution; Carry out electrostatic spinning again, processing step is required with equipment requirements higher, easy restricted and can't carry out the heavy industrialization volume production; The 2nd, adopt above-mentioned technology to obtain the regenerated fibroin fiber structural instability, cause the serviceability of product not good.
Summary of the invention
The objective of the invention is to solve the defective of above-mentioned prior art, main purpose of the present invention provides a kind of suitable suitability for industrialized production and function admirable, the production method of the regenerated fibroin fiber that health is comfortable.
The technical scheme that the present invention takes is following, and a kind of production method of regenerated fibroin fiber is characterized in that, may further comprise the steps:
(1), preparation regenerated fibroin powder: with silk raw material washing back oven dry; Then above-mentioned silk raw material is put into the alkali lye of concentration 3-5%; Under the 60-70 ℃ of temperature hydrolysis 3-5 hour; Hydrolysis is intact filters, and gets regenerated fibroin stoste, and the oven dry of regenerated fibroin stoste is made regenerated fibroin powder;
(2), preparation regenerated fibroin fiber: step 1 is made regenerated fibroin powder add water and stir and to obtain the regenerated fibroin saturated solution; With the regenerated fibroin saturated solution: reclaimed rubber stoste: auxiliary agent is pressed 10-50%: 85-45%: 5% mixed mixes the back wet spinning and makes regenerated fibroin fiber.
Of the present inventionly further be set to:
Any one or a few of the protein material that silk material choice silk waste silk, silk offcut and waste spinning, silk spinning waste silk etc. can not spin.
During the hydrolysis of silk raw material, the silk raw material: the weight ratio of alkali lye is 1: 50.
The preparation regenerated fibroin fiber comprises, earlier regenerated fibroin powder is put in the water, is stirred to saturatedly, obtains the regenerated fibroin saturated solution; Filter filtering particle and mechanical admixture undissolved or partly dissolving through filter; Then with the regenerated fibroin saturated solution: reclaimed rubber stoste: auxiliary agent is in 10-50%: 85-45%: 5% ratio static mixing, fully stir to make between two kinds of stostes and mix; And stored standing and defoaming 24 hours, and blend spinning solution is sent into filament spinning component and is carried out spinning, and fibre forming is after be finished product after the desulfurization, bleaching, pickling washing, oven dry.
Reclaimed rubber stoste is the regenerated cellulose class; Auxiliary agent is any one of antiseptic, aromatic, anti ultraviolet agent etc.
Secondary objective of the present invention provides a kind of production equipment of regenerated fibroin fiber; Comprise the mixing arrangement, device for spinning, the coiler device that are streamline and set successively; Wherein mixing arrangement comprises dissolution kettle, filter, middle bucket and the pulp storing barrel that links to each other successively; Device for spinning comprises successively measuring pump, filter, the spinning head that links to each other, and coiler device comprises coagulating bath, receives roll dies, stretch bath, draw roll, washing bath and take up roll are formed.
The present invention is a raw material with the protein material that silk waste silk, silk offcut and waste spinning, silk spinning waste silk etc. can not spin; Utilize the Biochemical Engineering technology therefrom to extract protein liquid, process regenerated fibroin powder after, cooperate viscose glue and auxiliary agent; Adopt a kind of novel fibroin fiber of wet spinning regeneration; Function admirable, healthy comfortable, one side has solved the second use problem of waste protein materials such as can not spinning discarded silk waste silk, silk spinning leftover bits and pieces; Simultaneously can be suitable for large-scale industrial production, have active operation significance.
Below in conjunction with the accompanying drawing and the specific embodiment the present invention is described further.
Description of drawings
Fig. 1 is a process chart of the present invention.
Label among the figure: 1, dissolution kettle; 2, filter; 3, middle bucket; 4, pulp storing barrel; 5, measuring pump; 6, filter; 7, spinning head; 8, coagulating bath; 9, receive roll dies; 10, stretch bath; 11, draw roll; 12, washing bath; 13, take up roll.
The specific embodiment
In conjunction with shown in Figure 1, the production method of regenerated fibroin fiber of the present invention may further comprise the steps:
1, material choice
The protein material of selecting silk waste silk, silk offcut and waste spinning, silk spinning waste silk etc. to spin.
2, preparation regenerated fibroin powder
Silk waste silk, silk offcut and waste spinning, silk spinning waste silk etc. used water washing, and oven dry is weighed under the room temperature then, then above-mentioned silk material is put into the alkali lye that concentration is 3-5% (percentage by weight) (NaOH); In the silk material: alkali lye (weight ratio) is 1: 50 ratio, and under the 60-70 ℃ of temperature hydrolysis 3-5 hour, hydrolysis is intact filtered; Remove alkali lye and impurity; Get regenerated fibroin stoste,, promptly make regenerated fibroin powder through 100 ℃ of oven dry down.
2.1, hydrolysis temperature is to the influence of regenerated fibroin hydrolysis
Temperature directly affects the efficient of regenerated fibroin hydrolysis.Higher temperature can make the silk hydrolysis rate accelerate, and hydrolysis degree is high, and the efficient of hydrolysis is also high; But water evaporates is also many, and higher temperature is unfavorable for the production industrialization; The hydrolysis in the same time of lower temperature is incomplete; Even the minimum part of hydrolysis, hydrolysis efficiency is low, is unfavorable for that enterprise produces in enormous quantities.Therefore, the hydrolysis temperature that control is suitable can obtain regenerated fibroin hydrolyzate preferably, simultaneously, helps the industrialization of enterprise production.Can find out by this paper experiment, the hydrolysis temperature of regenerated fibroin be controlled at 60-70 ℃ more suitable.Reaction time below 60 ℃ is oversize, is unfavorable for industrialization production, and the color to the regenerated fibroin hydrolysis more than 70 ℃ has certain influence.
2.2, concentration of lye is to the influence of regenerated fibroin hydrolysis
The size of concentration of lye directly influence the efficient of silk hydrolysis, and warp is tested, and regenerated fibroin hardly can hydrolysis under acidity or neutrallty condition, hydrolysis fast under alkali condition.So, regenerated fibroin be chosen in hydrolysis under the diluted alkaline condition, generally speaking, concentration of lye is high more to help hydrolysis more, the regenerated fibroin hydrolysis rate is fast more, efficient is high more.So, can find out through experiment and top data, during the regenerated fibroin hydrolysis, generally adopt the concentration of lye of 3-5% more suitable.
Comprehensive above-mentioned consideration; Influence the factor of proteolysis efficient and hydrolysis quality in silk waste silk, silk offcut and waste spinning, the silk spinning waste silk; The proteolysis temperature is selected 60-70 ℃ in silk waste silk, silk offcut and waste spinning, the silk spinning waste silk, and concentration of lye is selected 3-5%.
3, preparation regenerated fibroin fiber
Spinning technique flow process: dissolving-static mixing-filtration-deaeration-metering spinning-plasticizing drawing-off-cut-out-desulfurization-bleaching-pickling-wash-oil (ammonia soap)-dehydration-oven dry.
In conjunction with shown in Figure 1; The production equipment of regenerated fibroin fiber of the present invention; Comprise the mixing arrangement, device for spinning, the coiler device that are streamline and set successively; Wherein mixing arrangement comprises successively dissolution kettle 1, filter 2, middle bucket 3 and the pulp storing barrel 4 that links to each other, and device for spinning comprises measuring pump 5, filter 6, the spinning head 7 that links to each other successively, and coiler device comprises coagulating bath 8, receives roll dies 9, stretch bath 10, draw roll 11, washing bath 12 and take up roll 13 are formed.
During work, in dissolution kettle 1, regenerated fibroin powder is put in the water earlier, be stirred to saturatedly, obtain the regenerated fibroin saturated solution; Filter filtering particle and mechanical admixture undissolved or partly dissolving through filter 2, to guarantee carrying out smoothly of spin-drawing process; Then in middle bucket 3 with the regenerated fibroin saturated solution: reclaimed rubber stoste: auxiliary agent is in 10-50%: 85-45%: 5% ratio static mixing; Reclaimed rubber stoste is mainly the regenerated cellulose class; Auxiliary agent can be selected according to the fibre property demand; Give the auxiliary agent of specific function such as fiber some are antibiotic, fragranced, uvioresistant etc. like antiseptic, aromatic, anti ultraviolet agent etc., fully stirred then 30 minutes, make to mix between two kinds of stostes; And through pulp storing barrel 4 storage standing and defoaming, in order to guarantee carrying out smoothly of spinning, general time of repose is about 24 hours, makes air bubble content be less than 0.001%; Blend spinning solution is quantitatively sent into filter 6 by measuring pump 5, once more through filter 6 elimination particle impurities, and sends into spinning head 7 assemblies by curved tube and carries out spinning, and spun thread gets into coagulating bath 8, and coagulating bath 8 is formed: H
2SO
4118g/L, Na
2SO
4325g/L, ZnSO
411.0g/L, 48 ℃ of coagulation bath temperatures; Because the fibre machinery poor performance of gained does not almost have any practical value, thus must carry out drawing-off to the fiber of firm shaping, thus significantly improve the fracture strength of fiber and the ABRASION RESISTANCE of fiber; Stretched roller 11 enters into washing bath behind the tensile fiber, need carry out certain post-processing to fiber, and post processing comprises washing, desulfurization, pickling, goes up wet goods, because have sulfuric acid and sulfate etc. on the fiber behind the spinning technique, must wash and remove; Simultaneously must be through bleaching to improve the whiteness of fiber, hydrogen ion and other material in the fiber removed in pickling, oils to reduce the dynamic and static coefficient of friction of fiber, makes fiber softening level and smooth, with the needs of suitable weaving processing; Fiber is wound up on the take up roll 13 through after washing, and is finished product after cutting off and drying.
Fibre forming principle of the present invention: under certain condition with finite concentration protein hydrolysate stoste and reclaimed rubber stoste; Spinning is carried out in proportioning mixing by certain; And desirable regenerated fibroin fiber is processed in the process post processing; Like this peptide bond of protein among fiber (CO-NH-) with cellulose in-OH forms hydrogen bond, produces stronger molecule adhesion, ten minutes is firm.Content of cellulose is similar in protein content in the hydrolyzed protein liquid and the reclaimed rubber stoste; Regenerated fibroin liquid: reclaimed rubber stoste: the mixed proportion of auxiliary agent is 10-50%: 85-45%: 5%, and the regenerated fibroin fiber performance of wherein processing with blend spinning in 30%: 65%: 5% is very superior.
Beneficial effect of the present invention:
(1), the regenerated fibroin fiber performance that adopts the present invention to make is as shown in table 1.
The performance table of the regenerated fibroin fiber of table 1, the present invention's preparation
(2), stretching property is similar with viscose filament yarn by force for regenerated fibroin fiber; Do, wet strength and elongation be between viscose glue and silk; The dry state brute force of regenerated fibroin fiber is powerful greater than hygrometric state; The dried elongation at break of regenerated fibroin fiber is between viscose glue and silk, and wet elongation at break is less than mulberry silk and viscose glue; Initial modulus 22-46cN/dtex.
(3), regenerated fibroin fiber density is 1.49g/cm
3The regain of regenerated fibroin fiber is 12.6%, and is bigger than silk, and hygroscopicity is relatively good; The textiles snugness of fit that this explanation is processed by this fiber is relatively good, and simultaneously, moisture expantion is big; Monofilament and hardware contact area are increased, thus the coefficient of friction of increased fiber.
(4), the mass specific resistance of regenerated fibroin fiber is: 8.86 * 10
7,,, therefore, in spinning process, add some antistatic additive or increase the influence that workshop humidity all can be eliminated static less than most of synthetic fiber greater than natural fabric.
(5), the present invention has been owing to adopted regenerated fibroin liquid oven dry has been become silk fibroin powder, is more suitable for suitability for industrialized production.Its raw material adopts waste protein materials such as silk waste silk, silk offcut and waste spinning, silk spinning waste silk; Realize effectively utilizing once more; The regenerated fibroin fiber of its production is a staple fibre, can be processed into cotton type, wool type, medium length type and various natural fabric and chemical fibre blending as required; Develop all kinds of lining various in style, have a extensive future.
Claims (5)
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| CN2009101548559A CN101718007B (en) | 2009-11-26 | 2009-11-26 | Production method of regenerated silk protein fiber |
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| CN2009101548559A CN101718007B (en) | 2009-11-26 | 2009-11-26 | Production method of regenerated silk protein fiber |
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| CN101718007B true CN101718007B (en) | 2012-05-02 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101962822B (en) * | 2010-11-05 | 2011-12-07 | 四川省宜宾惠美线业有限责任公司 | Method for manufacturing wood pupa protein viscose filament yarns |
| CN102134757B (en) * | 2011-01-14 | 2012-08-29 | 东华大学 | A kind of preparation method of regenerated silk fibroin fiber and its products |
| CN102505170B (en) * | 2011-10-26 | 2013-12-18 | 阜宁澳洋科技有限责任公司 | Method for preparing silk protein composite cellulose fibers |
| CN102584430B (en) * | 2012-01-10 | 2013-07-24 | 广西工学院 | Method for manufacturing amino-acid fishpond fertilizer water aqua by waste bave protein |
| CN103305990A (en) * | 2013-06-09 | 2013-09-18 | 江苏华信亚麻纺织有限公司 | Method for spinning spun silk fine yarn |
| CN103549692B (en) * | 2013-09-25 | 2015-11-18 | 桐乡市中龙纺业有限责任公司 | The production method of fibroin foreign fiber fabric |
| CN106435818A (en) * | 2016-09-21 | 2017-02-22 | 东莞市联洲知识产权运营管理有限公司 | Gelatin-based regenerated silk protein fibers and preparation method thereof |
| CN115772725A (en) * | 2022-11-03 | 2023-03-10 | 苏州经贸职业技术学院 | Preparation of functional fullerene fiber blended silk fabric |
| CN115852529A (en) * | 2022-11-06 | 2023-03-28 | 苏州经贸职业技术学院 | Application of acidified modified fullerene dispersion property |
| CN117488459A (en) * | 2023-12-07 | 2024-02-02 | 江苏恋轩服饰有限公司 | Preparation process of environment-friendly regenerated fiber fabric |
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| CN101445546A (en) * | 2008-12-31 | 2009-06-03 | 苏州大学 | Preparation for tussore silk fibroin solution and concentration method thereof |
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| CN86107142A (en) * | 1986-10-11 | 1988-04-20 | 山东省烟台桑蚕原种场 | A kind of method of from broken silkworm cocoon, extracting silk fibroin powder |
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Effective date of registration: 20180710 Address after: 312000 two, floor 91, No. two, Song Wan Road, Shaoxing, Zhejiang. Patentee after: SHAOXING BAIFENG TEXTILE Co.,Ltd. Address before: 312000 Song Wan Road, Shaoxing New District, Zhejiang Province, No. 91 Patentee before: ZHEJIANG BAIKAI TEXTILE Co.,Ltd. |
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Denomination of invention: A production method of regenerated silk protein fiber Effective date of registration: 20230105 Granted publication date: 20120502 Pledgee: Zhejiang Shaoxing Ruifeng Rural Commercial Bank Co.,Ltd. Xincheng Sub branch Pledgor: SHAOXING BAIFENG TEXTILE Co.,Ltd. Registration number: Y2023980030327 |
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Granted publication date: 20120502 Pledgee: Zhejiang Shaoxing Ruifeng Rural Commercial Bank Co.,Ltd. Xincheng Sub branch Pledgor: SHAOXING BAIFENG TEXTILE Co.,Ltd. Registration number: Y2023980030327 |