CN1811020A - Mixed soybean protein-viscose fiber - Google Patents
Mixed soybean protein-viscose fiber Download PDFInfo
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- CN1811020A CN1811020A CN 200510111710 CN200510111710A CN1811020A CN 1811020 A CN1811020 A CN 1811020A CN 200510111710 CN200510111710 CN 200510111710 CN 200510111710 A CN200510111710 A CN 200510111710A CN 1811020 A CN1811020 A CN 1811020A
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Abstract
The present invention is one kind of soybean protein-viscose blend fiber and its production process and use. The blend fiber has soybean protein/viscose weight ratio of 10-40 to 60-90, viscosity of 30-60 S and maturing degree of 10-17 %. It is produced through a wet spinning process in a common apparatus by means of excellent alkali solubility of soybean protein and cellulose sulfonate. The blend fiber may be used in producing various kinds of filament and staple yarn fabric with novel and exquisite style, excellent performance, wool-like hand feeling silky brightness and outstanding wear comfort.
Description
Technical field
The present invention relates to a kind of novel regenerated protein and cellulose blending fibre, manufacture method and purposes, belong to the high polymer material chemical fiber art.
Technical background
In the existing chemical fibre, utilize the kind of protein blending technology production mainly to comprise polyvinyl base soybean fiber (China) and acrylic fibers base milk protein fiber (Japan), all belong to the synthetic fiber class, soybean protein/viscose glue blending fiber involved in the present invention is to utilize the aqueous slkali of soybean protein and viscose glue to mix, fiber by wet spinning is produced belongs to the regenerated fiber class.Its production procedure is: soybean protein aqueous slkali and viscose glue aqueous slkali mixing → filtration → deaeration → metering → wet spinning → coagulating bath shaping → plasticizing drawing-off → desulfurization → washing → dehydration → acetal is handled → is washed → oil → dry → (typing of curling) → (cut-out) → finished product.
Wherein the preparation of soybean protein and viscose solution is respectively known technology, the present invention relates to contain the mixing of soybean viscose glue, comprises mixing ratio, mixes technological parameters such as viscosity, degree of ripeness; Coagulation bath composition comprises every technological parameter of sulfuric acid, sodium sulphate, zinc sulfate and coagulating bath; In order to strengthen the active force between soybean protein and the cellulose macromolecule, improve the mechanical performance of fiber, need reason row crosslinking Treatment, employing acetal of the present invention is handled, and uses formaldehyde, glyoxal or defends dialdehyde etc.; In addition, also comprise the operation that oils, comprise finish and technological parameter thereof.
Soybean protein is a contained Main Ingredients and Appearance in the residual substance behind the soybean extract oil (soya-bean cake), contains crude protein, carbohydrate material, isopropyl acetone and crude fibre etc. after the soybean degreasing, can extract soybean protein through pulverizing with separating.The chemical composition of soybean protein and wool angle protein, fibroin are basic identical, are the complicated macromolecule of multiple a-amino acid condensation, and they are the polypeptide that are connected with peptide bond or claim many propylhomoserins that general chemical structural formula is:
The molecular mass of soybean protein is a uneven distribution, and between about 8000～600000, the big molecule of soybean protein is α-Luo Xuanjiegou in the ordinary course of things, forms approximate spherical labyrinth.But under spinning condition, the soybean protein that separates need be reconciled into the spinning solution component with diluted alkaline, content is about 10～30%, and the pH value is about about 13.5, under this condition, and soybean protein generation sex change, big molecule is the beta chain conformation.
The viscosity of soybean protein component in the spinning solution is decided by content, pH value, ageing time and the temperature of soybean protein.Generally, the soy bean proteinous soln viscosity of just having dissolved is higher, elasticity is bigger than normal, is gel, does not have spinnability, have only aging a period of time after, viscosity is reduced to and spinnability to a certain degree just occurs.
Because the pH value of spinning solution is up to more than 10, soybean protein is easy to take place hydrolysis, causes that viscosity reduces, and influences stability of spinning process, can add an amount of disulfide bond blocking agent in spinning solution for this reason, stops soybean protein hydrolysis.Disulfide bond blocking agent commonly used has cysteine, sodium sulfite, potassium sulfite, mercaptoethanol etc.The addition of disulfide bond blocking agent is different because of kind, and for example, the aminothiopropionic acid addition is 0.3～3.0mg/100g soybean protein, and sulfurous acid is 5.0～50mg/100g soybean protein, and mercaptoethanol is 0.4～40mg/100g soybean protein.Add after the two sulphur blocking agents, the viscosity of spinning solution not only can not reduce, and also can raise on the contrary, but this variation is not obvious in a period of time of stoste preparation beginning.
Because the difference of kind and region, the a-amino acid content of soybean protein also is not quite similar, but and natural protein fibres such as wool, silk by comparison, the composition of a-amino acid is basic identical, more be close to wool, but the component number is less slightly, the difference of every kind of component content is then bigger,, slightly higher as the cystine of soybean protein than the corresponding content of fibroin than wool angle protein much less.The amino acid contained polar group quantity of soybean protein more approaches wool angle protein apparently higher than fibroin.
In protein macromolecule, various a-amino acids are arranged in certain sequence, have constituted the different classes of of protein macromolecule according to the difference that puts in order.The big molecule of soybean protein has four classes at least: 15S globulin, 11S globulin, 7S globulin, 2S globulin, wherein 11S globulin and 7S globulin account for 70～80%.
Summary of the invention
The purpose of this invention is to provide a kind of novel soybean protein and viscose glue blending fiber.
Another object of the present invention provides a kind of above-mentioned soybean protein and the machining manufacture of viscose glue blending fiber.
Purpose of the present invention also provides a kind of above-mentioned soybean protein and the purposes of viscose glue blending fiber.
Soybean protein and viscose glue blending fiber belong to two component regenerated fibers, and wherein viscose glue is the spinning solution of regenerated celulose fibre, and becoming fine big molecule is cellulose.Cellulose is the linear macromolecule with certain regularity, has the hydroxyl than horn of plenty, can form more hydrogen bond between the big molecule behind the cellulose regenerated one-tenth fibre, and has the degree of crystallinity about 30～35%.The big molecule of soybean protein is β-linear structure in alkaline spinning solution, though amino acid profiles carries the various polarity group, may form hydrogen bond, salt type bond and a spot of disulfide bond between the big molecule of soybean protein, but because soybean protein macromolecular structure complexity, amino acid is arranged the kind difference in big molecule, side chain is big, regularity is lower, does not generally have crystallizing power, and the big molecule of soybean protein becomes fine ability very weak separately.If soybean protein is sneaked into viscose, will exert an influence to becoming fine macromolecular regularity, molecular separating force weakens, and crystallizing power descends, thereby the mechanical performance of fiber-forming polymer is produced adverse influence, and mixed volume the more influences bigger.Because the intensity of viscose itself is not very high just, so soybean protein and viscose glue blending fiber are carried out crosslinking Treatment is necessary.The reaction that with formaldehyde is crosslinking agent is as follows:
Soybean protein after the crosslinking Treatment/viscose glue blending fiber aggregated structure is the linear macromolecular network structure, it has guaranteed the serviceability of this fiber, and improved the big shortcoming of viscose fiber wet strength loss significantly, also improved the initial modulus of fiber simultaneously.
Soybean protein of the present invention and viscose glue blending fiber are that soybean protein and viscose glue weight ratio are (10～40): the soybean protein of (90～60) and viscose glue blending fiber.Recommending soybean protein and viscose glue weight ratio is (20～30): the soybean protein of (80～70) and viscose glue blending fiber.Its viscosity 30～60S, degree of ripeness 10～17%.Recommendation viscosity is 35～55S, degree of ripeness 12～15.
The present invention is a kind of brand-new chemical fibre, and main manufacturing technology is to utilize soybean protein and the good alkali solubility principle of cellulose sulfonate, and the mixed solution of design soybean protein viscose glue mainly contains mixing ratio, mixes technological parameters such as viscosity, degree of ripeness; The coagulating bath prescription and the technological parameter of the mixed solution of design soybean protein viscose glue; Prescription and technological parameter that the acetalation of design soybean protein/viscose semi-finished product silk is handled; Oil the operation prescription and the technological parameter of design soybean protein/viscose semi-finished product silk.
Main production of the present invention is produced with wet spinning, and has increased the acetal operation in the fiber post processing.Its flow process is: soybean protein aqueous slkali and the mixing of viscose glue aqueous slkali, filtration, deaeration, spinning technique, desulfurization, washing, dehydration, acetal are handled, wash, oil, dry, are curled and finalize the design, cut into finished product.Wherein, mixing, filtration, deaeration, spinning technique, desulfurization, washing, dehydration, acetal handle, wash, oil, dry, curl typing, to cut off all be common textile technology.Difference is as follows:
(1) spinning solution is formed:
To contain the weight soybean protein 7～11% and contain the aqueous slkali of soybean protein of alkali 3.5～5.5% and two kinds of solution that contain weight prezenta 7～11% and contain the viscose glue stoste of alkali 3.5～5.5% mix, wherein, the weight mixing ratio of soybean protein and viscose glue is (10～40): (90～60), viscosity 30～60S, degree of ripeness 10～17%;
(2) coagulation bath composition: sulfuric acid 100～140g/l, sodium sulphate 250～400g/l, zinc sulfate 9～14g/l, 40～55 ℃ of temperature;
(3) acetal is handled: adopt formaldehyde, glyoxal or defend dialdehyde, normal temperature is handled, acetalizing degree 20～30%, and the concentration of aldehyde solution is 15～30%, handles 5～10 minutes; The weight ratio of spinning and aldehyde is 1: (10～20).
(4) 40～55 ℃ of the oil bath temperatures that oils, oil formula are ammonia soap 0.5～2.5g/l, and rate 1～4% oils.
The aqueous slkali of the soybean protein described in the invention is to contain soybean protein 8.5～9.0% and alkali 4.3% and described viscose glue stoste to contain cellulose 8.5～9.0% and alkali 4.3% for well.
Described coagulating bath prescription is with sulfuric acid 118 ± 2g/l, sodium sulphate 320 ± 10g/l, and zinc sulfate 11-12g/l, 47～50 ℃ of temperature are for well.Described oil formula is with ammonia soap 1.0～1.2g/l, 50 ℃ of temperature, and the rate that oils 2% is for well.
Described spinning solution is formed more preferably as follows:
● contain the aqueous slkali of the soybean protein of weight soybean protein 8.5～9.0% and alkali 4.3%;
● contain the viscose glue stoste of weight prezenta 8.5～9.0% and alkali 4.3%;
● above-mentioned two kinds of solution are mixed, and wherein, the weight mixing ratio of soybean protein and viscose glue is (20～30): (80～70).Its viscosity is 35～55S, and degree of ripeness is 12～15%.
Described coagulation bath composition can be sulfuric acid 118 ± 2g/l, sodium sulphate 320 ± 10g/l, zinc sulfate 11～12g/l, 47～50 ℃ of temperature.
Described oil bath suggestion is: ammonia soap 1.0～1.2g/l, and 50 ℃ of temperature, rate 2% oils.
Equipment used in the present invention is the common apparatus that general chemical fibre factory has, no special installation.
With soybean protein of the present invention and viscose glue blending fiber be raw material make Fabric Style novel graceful, function admirable, the physical and chemical performance index of fiber:
| Performance indications | Fibre and soya/viscose glue blending fiber | Viscose | Wool fibre |
| Dry state fracture strength (cN/dtex) hygrometric state fracture strength (cN/dtex) hygrometric state extension at break degree (%) density (g/cm 3) regain (%) | 2.0～2.2 1.6～1.8 18～20 1.45～1.50 13.50 | 2.3～2.7 1.2～1.8 16～18 1.50～1.52 13.20 | 0.9～1.5 0.67～1.43 24～26 1.32 15.0 |
Soybean protein/viscose glue blending fiber is cellulosic protein modified fiber, so fiber outward appearance, feel all improve.This fibre strength is higher than wool, a little less than viscose; But its wet strength loss is little, obviously is better than viscose.The initial modulus of this fiber has raising, and the soft partially disadvantage of viscose fiber fabric body bone is improved, and this is the result of crosslinking Treatment.Soybean protein/viscose glue blending fiber has good hygroscopicity, gas permeability and heat insulating ability, and antistatic effect is good, handling ease.This fiber also has good dyeability, both can also can carry out the dyeing of multiple dyestuff under acid condition in alkalescence, but will avoid the use of strong acid and strong basicity dyestuff.
The rebound performance of soybean protein/viscose glue blending fiber, heat resistance are better than soybean protein/polyvinyl alcohol blending fiber, but still remain to be improved.
Have wool touch, silk gloss has been given prominence to the comfort property of taking.Be suitable for various long filaments, also be suitable for the preparation of various staple fibre products.
The specific embodiment
To help to understand the present invention by following examples, but not limit content of the present invention.
Experimental example 1: the processing of soybean protein/viscose glue blending fiber 56dtex/24f long filament
Spinning solution mixes: soybean protein-containing 8.5% and the aqueous slkali and the cellulose 8.5% that contain the soybean protein of alkali 4.3%, and contain alkali 4.3% conventional viscose glue stoste and mix, mixing ratio is soybean protein aqueous slkali/viscose glue stoste=20/80, viscosity 38S, degree of ripeness 12%.
Filter: adopt frame filter press, three roads filter, and the first road filter material adds two layers of flannelette for one deck fine cloth, and pressure is 7.5Kg/cm
2The second road filter material adds two layers of flannelette again for one deck fine cloth adds one deck poplin cloth, and pressure is 7.5Kg/cm
2The 3rd road filter material adds one deck flannelette again for one deck fine cloth adds one deck poplin cloth, and pressure is 7.5Kg/cm
2
Deaeration: adopt standing and defoaming, deaeration time 18h.
Spinning moulding: wet spinning, adopt R531 type centrifugal pot spinning machine, coagulating bath prescription sulfuric acid 118g/L, sodium sulphate 320g/L, zinc sulfate 11g/L, 47 ℃ of temperature; Length of immersion 300mm; Spinning speed 80m/min; Extensibility 20%.
Desulfurization: adopt the sodium sulfite doctor treatment, sodium sulfite solution concentration 22g/L.
Washing: 50 ℃ of temperature.
Dehydration: adopt centrifugal dehydrator.
Acetal is handled: defend dialdehyde normal temperature and handle.The concentration of aldehyde solution is 15%, handles 10 minutes; The weight ratio of spinning and aldehyde is 1/10.
Washing: 47 ℃ of temperature.
Oil bath: ammonia soap 1.0g/L, 50 ℃ of temperature, rate 2% oils.
Oven dry: adopt hf drying, 20min.
Experimental example 2: soybean protein/viscose glue blending fiber 1.38dtex, the processing of 38mm staple fibre
Spinning solution mixes: the aqueous slkali of the legumin of soybean protein-containing 9% and alkali 4.3% mixes with the conventional viscose glue stoste of cellulose 9.0% and alkali 4.3%, and mixing ratio is soybean protein aqueous slkali/viscose glue stoste=35/65, viscosity 48S, degree of ripeness 14%.
Filter: adopt frame filter press, three roads filter, and the first road filter material is that two layers of flannelette add one deck poplin cloth and add one deck fine cloth again, and pressure is 6.5Kg/cm
2The second road filter material is that two layers of flannelette add two layers of poplin cloth and add one deck fine cloth again, and pressure is 8Kg/cm
2The 3rd road filter material adds one deck fine cloth again for one deck flannelette adds one deck poplin cloth, and pressure is 7Kg/cm
2
Deaeration: adopt standing and defoaming, deaeration time 18h.
Spinning moulding: wet spinning, adopt the two-sided single shallow bath spinning machine of R372 type, coagulating bath prescription sulfuric acid 118g/L, sodium sulphate 330g/L, zinc sulfate 12g/L, 47 ℃ of temperature; Length of immersion 300mm; Spinning speed 80m/min; Extensibility 20%.
Desulfurization: adopt the sodium sulfite doctor treatment, sodium sulfite solution concentration 22g/L.
Washing: 50 ℃ of temperature.
Dehydration: adopt centrifugal dehydrator.
Acetal is handled: defend dialdehyde normal temperature and handle.The concentration of defending dialdehyde solution is 30%, handles 5 minutes; The weight ratio of spinning and aldehyde is 1/20.
Washing: 47 ℃ of temperature.
Oil bath: ammonia soap 1.2g/l, 50 ℃ of temperature, rate 2% oils.
Cut off: carousel-type cutting machine, shearing length 38mm.
Oven dry: adopt belt drying machine.
Claims (8)
1, a kind of soybean protein and viscose glue blending fiber is characterized in that soybean protein and viscose glue weight ratio are (10～40): the soybean protein of (90～60) and viscose glue blending fiber.
2, soybean protein as claimed in claim 1 and viscose glue blending fiber is characterized in that soybean protein and viscose glue weight ratio are (20～30): the soybean protein of (80～70) and viscose glue blending fiber, its viscosity 30～60S, degree of ripeness 10-17%.
3, soybean protein as claimed in claim 1 and viscose glue blending fiber is characterized in that its viscosity is 35～55S, degree of ripeness 12～15.
4, the manufacture method of a kind of soybean protein as claimed in claim 1 and viscose glue blending fiber, it is characterized in that adopting common wet spinning to produce, and in the fiber post processing, increased the acetal operation, its flow process is: handle, wash, oil, dry, the curl typing and cut into finished product of soybean protein aqueous slkali and the mixing of viscose glue aqueous slkali, filtration, deaeration, spinning technique, desulfurization, washing, dehydration, acetal, wherein:
(1) spinning solution is formed:
To contain the weight soybean protein 7～11% and contain the aqueous slkali of soybean protein of alkali 3.5～5.5% and two kinds of solution that contain weight prezenta 7～11% and contain the viscose glue stoste of alkali 3.5～5.5% mix, wherein, the weight mixing ratio of soybean protein and viscose glue is (10～40): (90～60), viscosity 30～60S, degree of ripeness 10～17%;
(2) coagulation bath composition: sulfuric acid 100～140g/l, sodium sulphate 250～400g/l, zinc sulfate 9～14g/l, 40～55 ℃ of temperature;
(3) acetal is handled: adopt formaldehyde, glyoxal or defend dialdehyde, normal temperature is handled, acetalizing degree 20-30%, and the concentration of aldehyde solution is the solution of 15～30% weight, handles 5～10 hours; The weight ratio of spinning and aldehyde is 1: (10～20).
(4) 40～55 ℃ of the oil bath temperatures that oils, oil formula are ammonia soap 0.5～2.5g/l, and rate 1～4% oils.
5, the manufacture method of soybean protein as claimed in claim 4 and viscose glue blending fiber is characterized in that the aqueous slkali of described soybean protein contains soybean protein 8.5～9.0% and alkali 4.3%; Described viscose glue stoste contains cellulose 8.5～9.0% and alkali 4.3%.
6, the manufacture method of soybean protein as claimed in claim 4 and viscose glue blending fiber is characterized in that described coagulating bath prescription: sulfuric acid 118 ± 2g/l, sodium sulphate 320 ± 10g/l, zinc sulfate 11～12g/l, 47～50 ℃ of temperature.
7, the manufacture method of soybean protein as claimed in claim 4 and viscose glue blending fiber is characterized in that described oil formula is ammonia soap 1.0-1.2g/l, 50 ℃ of temperature, and rate 2% oils.
8, a kind of soybean protein as claimed in claim 1 and viscose glue blending fiber is characterized in that described fiber is used for the preparation of long filament and staple fibre goods.
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| CNB2005101117102A CN100395382C (en) | 2005-12-20 | 2005-12-20 | Mixed soybean protein-viscose fiber |
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| CNB2005101117102A CN100395382C (en) | 2005-12-20 | 2005-12-20 | Mixed soybean protein-viscose fiber |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101298708B (en) * | 2008-06-25 | 2010-06-02 | 宜宾丝丽雅集团有限公司 | Protein cellulose viscose and preparing method thereof |
| CN102220650A (en) * | 2011-04-29 | 2011-10-19 | 西南科技大学 | Soy protein fibers and preparation method thereof |
| CN101457411B (en) * | 2008-12-19 | 2011-11-30 | 苏州恒光化纤有限公司 | Method for manufacturing protein cellulose fiber |
| CN102493020A (en) * | 2011-12-06 | 2012-06-13 | 山东海龙股份有限公司 | Regenerated animal micro powder protein cellulose fiber and preparation method thereof |
| CN102677221A (en) * | 2012-06-04 | 2012-09-19 | 武汉纺织大学 | Method for preparing cellulose protein fibers |
| CN103510179A (en) * | 2013-09-12 | 2014-01-15 | 江苏金太阳纺织科技有限公司 | Preparation method for gluten protein regenerated cellulose fiber |
| CN103668545A (en) * | 2012-09-21 | 2014-03-26 | 江苏蓝品纤维科技发展有限公司 | Soft fiber and functional fiber prepared therefrom |
| CN103668546A (en) * | 2012-09-21 | 2014-03-26 | 江苏蓝品纤维科技发展有限公司 | Yonic fiber and functional fiber prepared therefrom |
| CN105105922A (en) * | 2015-07-29 | 2015-12-02 | 李文新 | Method of preparing medical acarus killing and anti-microbial bandage |
| CN114775088A (en) * | 2022-05-10 | 2022-07-22 | 江苏康溢臣生命科技有限公司 | Soybean protein plant traditional Chinese medicine multifunctional viscose fiber and preparation method thereof |
| CN115787120A (en) * | 2022-09-23 | 2023-03-14 | 当阳市鸿阳新材料科技有限公司 | Protein modified lyocell fiber and production method thereof |
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| FR2953132B1 (en) * | 2009-11-30 | 2012-09-21 | Oreal | COSMETIC PRODUCT APPLICATION DEVICE COMPRISING SOYA FIBERS AND METHOD OF MANUFACTURING THE SAME. |
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| GB1025798A (en) * | 1963-01-16 | 1966-04-14 | Kanegafuchi Spinning Co Ltd | Method for producing composite protein-cellulose fibres |
| CN1195109C (en) * | 2002-07-22 | 2005-03-30 | 新乡化纤股份有限公司 | Method for manufacturing soybean protein glued fiber |
| CN1244726C (en) * | 2004-06-04 | 2006-03-08 | 新乡化纤股份有限公司 | Preparing method for soybean protein cellulose |
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- 2005-12-20 CN CNB2005101117102A patent/CN100395382C/en not_active Expired - Fee Related
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| CN101298708B (en) * | 2008-06-25 | 2010-06-02 | 宜宾丝丽雅集团有限公司 | Protein cellulose viscose and preparing method thereof |
| CN101457411B (en) * | 2008-12-19 | 2011-11-30 | 苏州恒光化纤有限公司 | Method for manufacturing protein cellulose fiber |
| CN102220650A (en) * | 2011-04-29 | 2011-10-19 | 西南科技大学 | Soy protein fibers and preparation method thereof |
| CN102493020A (en) * | 2011-12-06 | 2012-06-13 | 山东海龙股份有限公司 | Regenerated animal micro powder protein cellulose fiber and preparation method thereof |
| CN102493020B (en) * | 2011-12-06 | 2013-12-18 | 恒天海龙股份有限公司 | Regenerated animal micro powder protein cellulose fiber and preparation method thereof |
| CN102677221B (en) * | 2012-06-04 | 2014-03-26 | 武汉纺织大学 | Method for preparing cellulose protein fibers |
| CN102677221A (en) * | 2012-06-04 | 2012-09-19 | 武汉纺织大学 | Method for preparing cellulose protein fibers |
| CN103668546A (en) * | 2012-09-21 | 2014-03-26 | 江苏蓝品纤维科技发展有限公司 | Yonic fiber and functional fiber prepared therefrom |
| CN103668545A (en) * | 2012-09-21 | 2014-03-26 | 江苏蓝品纤维科技发展有限公司 | Soft fiber and functional fiber prepared therefrom |
| CN103510179A (en) * | 2013-09-12 | 2014-01-15 | 江苏金太阳纺织科技有限公司 | Preparation method for gluten protein regenerated cellulose fiber |
| CN103510179B (en) * | 2013-09-12 | 2016-08-24 | 江苏金太阳纺织科技股份有限公司 | A kind of preparation method of gluten protein regenerated celulose fibre |
| CN105105922A (en) * | 2015-07-29 | 2015-12-02 | 李文新 | Method of preparing medical acarus killing and anti-microbial bandage |
| CN105105922B (en) * | 2015-07-29 | 2018-03-09 | 张作玮 | A kind of preparation method of except mite antibacterial medical bandage |
| CN114775088A (en) * | 2022-05-10 | 2022-07-22 | 江苏康溢臣生命科技有限公司 | Soybean protein plant traditional Chinese medicine multifunctional viscose fiber and preparation method thereof |
| CN115787120A (en) * | 2022-09-23 | 2023-03-14 | 当阳市鸿阳新材料科技有限公司 | Protein modified lyocell fiber and production method thereof |
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