CN103789857B - A kind of preparation method of collagen regenerated celulose fibre - Google Patents
A kind of preparation method of collagen regenerated celulose fibre Download PDFInfo
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Abstract
The invention provides a kind of preparation method of collagen regenerated celulose fibre, comprise the following steps: produce rayon spinning stoste; Collagen solution is added in rayon spinning stoste, collagen addition accounts for 4% ~ 15% of the fine quality of rayon spinning liquid first, albumen viscose glue blending liquid is obtained after mixing, add initator again, initator addition accounts for 2.3% ~ 5% of collagen quality, then stirs at 19 DEG C ~ 25 DEG C after 2 ~ 8 hours and obtains spinning solution; Wet spinning is carried out after gained spinning solution is filtered deaeration.Collagen successfully grafts on regenerated celulose fibre by the present invention, spins out collagen regenerated celulose fibre, grafting efficiency and percent grafting higher, gained collagen fabric has the gloss as silk, and the fluffy softness of feel.
Description
Technical field
The invention belongs to textile fabric processing technique field, be specifically related to a kind of preparation method of collagen regenerated celulose fibre.
Background technology
Collagen is a kind of natural fibrin, and being mainly present in the tissues such as the skin of animal, bone, tendon, is structural proteins important in connective tissue, plays the function supporting organ, protection body.Collagen is also known as collagen, and its molecular weight is 300,000 dalton, and it is formed by 2 I chains, 1 II chain combination, and then forms triple helix structure.These 3 peptide chains are mutually wound around with distinctive left-handed α chain and are formed right hand composite screw collagen, it is characterized in that amino acid presents chain Gly-x-y periodic structure.
There is the active forces such as the hydrophobic bond of ionic bond, hydrogen bond, Van der Waals force and non-polar group generation in collagen peptide interchain.Meanwhile, also there are 3 kinds of crosslinked actions with intermolecular in tropocollagen molecule, 3 of collagen peptide chains are coupled together securely, makes collagen have very high tensile strength.Assemble by " 1/4th stagger arrangement " mode supermolecule between tropocollagen molecule and form the fibrillation very stable, toughness is very strong, formation collagenous fibres assembled further by fibrillation.In addition, in molecule and intermolecular covalent cross-linking give physical and chemical stability and the biological nature of collagen height, as high-tensile strength, biodegradability, biocompatibility, low antigenicity, low irritant and low cytotoxicity, and the performance such as Promote cell's growth.
The diversity of this 26S Proteasome Structure and Function feature of collagen and complexity, determine it in the good application prospect of field of textiles.The modification of collagen to silk fiber has been seen in current field of textiles, to the modification of cotton fiber, with the blending and modifying of synthetic fiber, the wearability of the excellence of current cellulose fibre has obtained the accreditation of textile industry and has had large-scale commercial application, therefore itself and collagen be combined with important Research Significance.But collagen combines with regenerated cellulose and to spin out collagen regenerated celulose fibre actually rare, the influence factor of the percent grafting that is collagen and cellulose macromolecule chain and grafting efficiency of tracing it to its cause is more, and more difficult control, the content of the concentration on fiber protein of initator also has considerable influence.
Publication number is 102286803A, name is called " a kind of collagen/cellulose composite fiber and preparation method thereof " patent document discloses a kind of collagen/cellulose composite fiber and preparation method thereof, first collagen solution is joined in cellulose viscose solution, mix with viscose solution; Collagen/cellulose composite fiber is obtained through spinning.This invention is just by collagen solution and cellulose viscose solution co-blended spinning, and collagen cannot form bonding with cellulose fibre with covalent bond, spinning, weaves to add with dyeing and finishing and is easily subject to external influence man-hour and the loss that causes collagen.It is more that collagen and acrylonitrile carry out the conduct oneself patent in fraud originating party face of graft modification, but the collagen graft modification patent based on regenerated celulose fibre also rarely has report.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art and the preparation method that a kind of collagen regenerated celulose fibre is provided.
A preparation method for collagen regenerated celulose fibre, comprises the steps:
Step 1, produces rayon spinning stoste;
Step 2, collagen solution is added in the rayon spinning stoste of step 1, collagen addition accounts for 4% ~ 15% of the fine quality of rayon spinning liquid first, albumen viscose glue blending liquid is obtained after mixing, add initator again, initator addition accounts for 2.3% ~ 5% of collagen quality, then stirs at 19 DEG C ~ 25 DEG C after 2 ~ 8 hours and obtains spinning solution;
Step 3, carries out wet spinning after step 2 gained spinning solution is filtered deaeration.
The mass ratio of collagen solution and rayon spinning liquid directly affects percent grafting and grafting efficiency.The angle chemically balanced is considered, increases the concentration of reactant, and balance always moves right.The increase of collagenic protein solution proportion, the free radical of generation increases, and the probability with cellulosic molecule making contact increases, and facilitate protein and cellulosic grafting, therefore percent grafting and grafting efficiency increase all to some extent.But, when the consumption of protein is excessive, cause that mixture system viscosity is less is unfavorable for spinning, thus can not fibroblast.
The impact of temperature on percent grafting and grafting efficiency is comparatively complicated, and percent grafting and grafting efficiency are all first along with the rising of temperature is risen, and then decline again.This is because the rising of temperature, the collision frequency between Small molecular is increased, facilitates graft reaction, percent grafting and grafting efficiency are all raised, but when temperature is too high, then depolymerization reaction is accelerated thereupon, percent grafting and grafting efficiency decline on the contrary.When temperature is more than 48 DEG C, there is gelatin phenomenon, do not possess spinning condition.
Free radical grafting reaction is along with the increase of time, and grafting efficiency improves very fast, but after reaction certain hour, increases not obvious, and this is because reaction tends to balance gradually.And rayon spinning liquid at a certain temperature, after placing certain hour, the performance of rayon spinning liquid can change, so after adding initator, take into account the change of viscose ripening degree, ensure the synchronism of degree of ripeness and reaction speed, make spinning solution have good spinnability, otherwise be easy to occur spinning solution too " always ", and be unfavorable for spinning.
Under lower initiator ions concentration, most of initiator ions is adsorbed in initial reaction stage, and the free radical that cellulose molecular chain produces is less, add that part initiator free radical generation coupling stops, therefore percent grafting and grafting efficiency is all lower; Along with the increase of initiator ions concentration, leaving the free radical that the cellulose initiated strand of initiator ions of q.s produces after being reacted by cellulose absorption increases, and percent grafting and grafting efficiency also increase thereupon; After initiator ions concentration exceedes finite concentration, because grafted chain increases, the diffusion velocity of protein declines, and add that the stopped reaction of free radical on initiator ions and cellulose molecular chain increases, percent grafting and grafting efficiency decline gradually.If it is very large just to have started initator addition, cause initial concentration higher, now spinning solution there will be gelation, be unfavorable for spinning, if addition is lower, cause insufficient, the reduction of percent grafting and grafting efficiency can be caused, the prolongation in reaction time and the increasing of protein loss rate.
As foregoing invention further preferably, described collagenic protein concentration of polymer solution is 5% ~ 25%.
As foregoing invention further preferably, described initator is persulfate-slaine or non-peroxide.
Redox initiation system mainly divides five classes: the redox system of hydrogen peroxide system, persulfate system-slaine system, organic peroxide systems, multielectron transfer and non-peroxide systems.Organic peroxide evocating agent is water-soluble poor, and rayon spinning liquid is water solution system, and compatibility is between the two poor; The redox system initiation temperature of multielectron transfer is higher, and reach about 50 DEG C, and the temperature of rayon spinning liquid is generally at about 20 DEG C, the too high meeting of temperature causes the gelation of spinning solution, cannot spinning; Efficiency of initiation and the result reappearance of peroxisome series initiators are poor, therefore also inadvisable.
As foregoing invention further preferably, the persulfate in described persulfate-slaine is ammonium persulfate or potassium peroxydisulfate, and slaine is the one in sulfurous acid iron, sodium hydrogensulfite or sodium sulfite; Described non-peroxide is ammonium ceric nitrate.
Compared with prior art, its remarkable advantage is: the first in the present invention, successfully grafts on regenerated celulose fibre by collagen, spins out collagen regenerated celulose fibre, grafting efficiency and percent grafting higher; The second, collagen fabric prepared by the method has the gloss as silk, and the fluffy softness of feel; 3rd, retain the build-in attribute of collagen, skin-friendly is excellent, and has maintenance effect to human body skin.In a preferred embodiment of the invention, percent grafting can reach 23.1%, and grafting efficiency can reach 50.8%.
Detailed description of the invention
Embodiment 1
A preparation method for collagen regenerated celulose fibre, comprises the steps:
The preparation of viscose solution: the Cotton Pulp adopting the fine mass content 93.5% of the degree of polymerization 520, first, successively through dipping, squeezing, pulverize, experienced, yellow, the operation such as dissolving prepare spinning viscose solution.The fine mass content 8.9% of obtained viscose solution first, NaOH mass content 5.5%, viscosity (falling ball method) 50s, degree of ripeness (10%NH
4cl) 8.5mL.
Falling ball method: the time that 2mm steel ball falls needed for 20cm from described viscose solution.
The preparation of the graft copolymerization liquid of collagen liquid and rayon spinning liquid:
(1) preparation of the blended liquid of collagen liquid and rayon spinning liquid: prepare the collagenic protein solution that mass concentration is 20% with distilled water, this solution is added in above-mentioned rayon spinning liquid, wherein collagenic protein addition accounts for 8% of the fine quality of rayon spinning liquid first, mix, obtain albumen viscose glue blending liquid.
(2) blended liquid graft copolymerization: be 0.017mol/L ceric ammonium nitrate solution with distilled water compound concentration; This ceric ammonium nitrate solution is joined in the blended liquid obtained by step (1), abundant stirring, in ceric ammonium nitrate solution, ammonium ceric nitrate quality accounts for 3.5% of collagen quality, at 19 DEG C, fully stir graft copolymerization 8 hours, the spinning solution after grafting is filtered deaeration and sends into spinning.
Wet spinning: the mixed solution of precrosslink protein and viscose glue is sent into wet spinning operation and carries out spinning.Spinning head specification is 21000 holes × 0.06mm, and spinning speed is 55m/min, and coagulation bath temperature is 52 DEG C, and plasticizing-bath temperature is 95 DEG C.Coagulation bath composition is: sulfuric acid 90g/L, sodium sulphate 300g/L, zinc sulfate 15g/L.Post processing desulfurization adopts the sodium sulfite doctor solution of 70 DEG C of 30g/L to carry out desulfurization.
The leading indicator of the fiber prepared through above-mentioned steps is as follows: fiber number 1.69dtex; Dry strong 2.24cN/dtex; Wet strong 1.32cN/dtex; Dryly stretch 17.6%.
Embodiment 2
The preparation of viscose solution: the Cotton Pulp adopting the fine mass content 93.5% of the degree of polymerization 520, first, successively through dipping, squeezing, pulverize, experienced, yellow, the operation such as dissolving prepare spinning viscose solution.Fine mass content 8.9%, the NaOH mass content 5.4%, viscosity (falling ball method) 48s of obtained first, degree of ripeness (10%NH4Cl) 8.3ml, is stand-by viscose solution.
Falling ball method: the time that 2mm steel ball falls needed for 20cm from described viscose solution.
The preparation of the graft copolymerization liquid of collagen liquid and rayon spinning liquid:
(1) preparation of the blended liquid of collagen liquid and rayon spinning liquid: be the collagenic protein solution of 25% by 5%NaOH solution preparation mass concentration, this solution is added in above-mentioned rayon spinning liquid, wherein collagenic protein addition accounts for 15% of the fine quality of rayon spinning liquid first, mix, obtain albumen viscose glue blending liquid.
(2) blended liquid graft copolymerization: be 0.025mol/L ammonium persulfate and solution of sodium bisulfite with distilled water compound concentration; Joined by this solution in the blended liquid obtained by step (1), fully stir, in ammonium persulfate solution, ammonium persulfate quality accounts for 5% of collagen quality, at 25 DEG C, fully stir graft copolymerization 2 hours, the spinning solution after grafting is filtered deaeration and sends into spinning.
Wet spinning: the mixed solution of precrosslink protein and viscose glue is sent into wet spinning operation and carries out spinning.Spinning head specification is 21000 holes × 0.06mm, and spinning speed is 55m/min, and coagulation bath temperature is 52 DEG C, and plasticizing-bath temperature is 95 DEG C.Coagulation bath composition is: sulfuric acid 92g/L, sodium sulphate 305g/L, zinc sulfate 14g/L.Post processing desulfurization adopts the sodium sulfite doctor solution of 70 DEG C of 25g/L to carry out desulfurization.
The leading indicator of the fiber prepared through above-mentioned steps is as follows: fiber number 1.58dtex; Dry strong 2.07cN/dtex; Wet strong 1.26cN/dtex; Dryly stretch 18.5%.
Embodiment 3
The preparation of viscose solution: the Cotton Pulp adopting the fine mass content 93.5% of the degree of polymerization 520, first, successively through dipping, squeezing, pulverize, experienced, yellow, the operation such as dissolving prepare spinning viscose solution.Fine mass content 8.9%, the NaOH mass content 5.4%, viscosity (falling ball method) 48s of obtained first, degree of ripeness (10%NH4Cl) 8.3ml, is stand-by viscose solution.
Falling ball method: the time that 2mm steel ball falls needed for 20cm from described viscose solution.
The preparation of the graft copolymerization liquid of collagen liquid and rayon spinning liquid:
(1) preparation of the blended liquid of collagen liquid and rayon spinning liquid: be the collagenic protein solution of 5% by 1%NaOH solution preparation mass concentration, this solution is added in above-mentioned rayon spinning liquid, wherein collagenic protein addition accounts for 4% of the fine quality of rayon spinning liquid first, mix, obtain albumen viscose glue blending liquid.
(2) blended liquid graft copolymerization: be 0.012mol/L ceric ammonium nitrate solution with distilled water compound concentration; This ceric ammonium nitrate solution is joined in the blended liquid obtained by step (1), abundant stirring, in ceric ammonium nitrate solution, ammonium ceric nitrate quality accounts for 2.3% of collagen quality, at 20 DEG C, fully stir graft copolymerization 6 hours, the spinning solution after grafting is filtered deaeration and sends into spinning.
Wet spinning: the mixed solution of precrosslink protein and viscose glue is sent into wet spinning operation and carries out spinning.Spinning head specification is 21000 holes × 0.06mm, and spinning speed is 55m/min, and coagulation bath temperature is 55 DEG C, and plasticizing-bath temperature is 95 DEG C.Coagulation bath composition is: sulfuric acid 88g/L, sodium sulphate 295g/L, zinc sulfate 12g/L.Post processing desulfurization adopts the sodium sulfite doctor solution of 70 DEG C of 25g/L to carry out desulfurization.
The leading indicator of the fiber prepared through above-mentioned steps is as follows: fiber number 1.52dtex; Dry strong 2.32cN/dtex; Wet strong 1.28cN/dtex; Dryly stretch 16.8%.
Embodiment 4
The preparation of viscose solution: the Cotton Pulp adopting the fine mass content 93.5% of the degree of polymerization 520, first, successively through dipping, squeezing, pulverize, experienced, yellow, the operation such as dissolving prepare spinning viscose solution.Fine mass content 8.9%, the NaOH mass content 5.4%, viscosity (falling ball method) 48s of obtained first, degree of ripeness (10%NH4Cl) 8.3ml, is stand-by viscose solution.
Falling ball method: the time that 2mm steel ball falls needed for 20cm from described viscose solution.
The preparation of the graft copolymerization liquid of collagen liquid and rayon spinning liquid:
(1) preparation of the blended liquid of collagen liquid and rayon spinning liquid: be the collagenic protein solution of 5% by 1%NaOH solution preparation mass concentration, this solution is added in above-mentioned rayon spinning liquid, wherein collagenic protein addition accounts for 4% of the fine quality of rayon spinning liquid first, mix, obtain albumen viscose glue blending liquid.
(2) blended liquid graft copolymerization: be 0.012mol/L potassium peroxydisulfate and solution of sodium bisulfite with distilled water compound concentration; Joined by this solution in the blended liquid obtained by step (1), fully stir, in potassium persulfate solution, potassium peroxydisulfate quality accounts for 5% of collagen quality, at 25 DEG C, fully stir graft copolymerization 2 hours, the spinning solution after grafting is filtered deaeration and sends into spinning.
Wet spinning: the mixed solution of precrosslink protein and viscose glue is sent into wet spinning operation and carries out spinning.Spinning head specification is 21000 holes × 0.06mm, and spinning speed is 55m/min, and coagulation bath temperature is 55 DEG C, and plasticizing-bath temperature is 95 DEG C.Coagulation bath composition is: sulfuric acid 88g/L, sodium sulphate 302g/L, zinc sulfate 15g/L.Post processing desulfurization adopts the sodium sulfite doctor solution of 70 DEG C of 28g/L to carry out desulfurization.
The leading indicator of the fiber prepared through above-mentioned steps is as follows: fiber number 1.63dtex; Dry strong 2.18cN/dtex; Wet strong 1.22cN/dtex; Dryly stretch 17.6%.
The method of testing of percent grafting and grafting efficiency:
The graft copolymerization liquid of about 1-1.5g collagen liquid and rayon spinning liquid is taken in measuring cup or small beaker, be placed in 10 × 10 centimetres of clean glass sheet, the sheet glass measure-alike with another block weighs wounded, makes viscose glue be pressed into a film, and even low distribution on the glass sheet.Then make two blocks of sheet glass pull open in the opposite direction, be immersed in 45-47 DEG C of solidification liquid and (as muddiness, use after clarification), make viscose glue be frozen into a film.Fully washed by this film hot water, desulfurization 5-10min in the sodium sulfite doctor solution (25-30g/L) being placed on 70 DEG C, makes thin-film transparent.Finally use distilled water washes clean, dry at 105 DEG C, and cool in drier, weigh.Reach constant weight to check whether, then dry half an hour in an oven, as front cooling, weigh, weigh for twice and be more or less the same in 0.5 ㎎.
The percent grafting of protein is the mass percent that the protein be grafted on cellulose accounts for cellulose matrix, is calculated as follows:
Percent grafting %=(m
1-m
c)/m
c× 100%
M
1for the quality of cellulose sample after grafting, m
cfor the quality of cellulose sample before grafting.
The grafting efficiency of protein is the mass percent that the protein participating in graft reaction consumption accounts for the protein before grafting in system, is calculated as follows: grafting efficiency %=(m
1-m
c)/m
p× 100%, m
pfor the amount of protein added.
The percent grafting of collagenic protein and grafting efficiency under table 1 different condition
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Percent grafting % | 23.1 | 19.8 | 25.3 | 16.1 |
| Grafting efficiency % | 50.8 | 25.5 | 46.2 | 29.2 |
Claims (3)
1. a preparation method for collagen regenerated celulose fibre, is characterized in that, comprises the steps:
Step 1, produces rayon spinning stoste;
Step 2, collagen solution is added in the rayon spinning stoste of step 1, collagen addition accounts for 4% ~ 15% of the fine quality of rayon spinning liquid first, albumen viscose glue blending liquid is obtained after mixing, add initator again, initator addition accounts for 2.3% ~ 5% of collagen quality, then stirs at 19 DEG C ~ 25 DEG C after 2 ~ 8 hours and obtains spinning solution;
Step 3, carries out wet spinning after step 2 gained spinning solution is filtered deaeration;
Described initator is persulfate-slaine or non-peroxide.
2. the preparation method of collagen regenerated celulose fibre according to claim 1, is characterized in that: described collagenic protein concentration of polymer solution is 5% ~ 25%.
3. the preparation method of collagen regenerated celulose fibre according to claim 1, it is characterized in that: the persulfate in described persulfate-slaine is ammonium persulfate or potassium peroxydisulfate, slaine is the one in sulfurous acid iron, sodium hydrogensulfite or sodium sulfite; Described non-peroxide is ammonium ceric nitrate.
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| CN106139232A (en) * | 2016-07-29 | 2016-11-23 | 江苏蓝湾生物科技有限公司 | A kind of preparation method of collagen protein regenerated cellulose combine dressing |
| TWI683043B (en) * | 2018-11-16 | 2020-01-21 | 達紡企業股份有限公司 | Silk collagen fiber, fabric and producing method thereof |
| CN111485420A (en) * | 2020-04-23 | 2020-08-04 | 罗莱生活科技股份有限公司 | Skin care fiber with semi-interpenetrating network structure and preparation method and application thereof |
| CN112877880A (en) * | 2021-01-11 | 2021-06-01 | 浙江大能纺织印染有限公司 | Preparation method of fragrant antibacterial collagen fiber cotton blended dyed knitted fabric |
| CN116005361B (en) * | 2022-12-29 | 2023-07-21 | 东莞盛翔新材料技术有限公司 | Preparation method of cellulose-collagen composite nanofiber membrane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5358679A (en) * | 1993-04-21 | 1994-10-25 | Parekh Indubhai H | Manufacture of regenerated cellulosic fiber by zinc free viscose process |
| CN1468986A (en) * | 2003-07-01 | 2004-01-21 | 张建华 | Animal protein and acrylonitrile grafting copolymerizing fiber and its production process |
| CN102286803A (en) * | 2011-06-23 | 2011-12-21 | 阜宁澳洋科技有限责任公司 | Collagen/cellulose composite fiber and preparation method thereof |
| CN103333356A (en) * | 2013-06-27 | 2013-10-02 | 无锡贝迪生物工程有限公司 | Method for preparing collagen modified regenerated cellulose composite material |
-
2014
- 2014-01-13 CN CN201410013961.6A patent/CN103789857B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5358679A (en) * | 1993-04-21 | 1994-10-25 | Parekh Indubhai H | Manufacture of regenerated cellulosic fiber by zinc free viscose process |
| CN1468986A (en) * | 2003-07-01 | 2004-01-21 | 张建华 | Animal protein and acrylonitrile grafting copolymerizing fiber and its production process |
| CN102286803A (en) * | 2011-06-23 | 2011-12-21 | 阜宁澳洋科技有限责任公司 | Collagen/cellulose composite fiber and preparation method thereof |
| CN103333356A (en) * | 2013-06-27 | 2013-10-02 | 无锡贝迪生物工程有限公司 | Method for preparing collagen modified regenerated cellulose composite material |
Non-Patent Citations (1)
| Title |
|---|
| 大豆蛋白/粘胶共混溶液的可纺性;张瑞文等;《纺织学报》;20060630;第27卷(第6期);第58-61页 * |
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Address after: 226314 Jiangsu city of Nantong province Tongzhou District Industrial Park building sun Zhihao Patentee after: JIANGSU GOLDSUN TEXTILE TECHNOLOGY CO., LTD. Address before: 226314 Jiangsu city of Nantong province Tongzhou District Industrial Park building sun Zhihao Patentee before: Goldsun Holding Group Co., Ltd. |