CN1245543C - Preparing method for collagen stroma composite medical fibre spinning stoste - Google Patents
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- CN1245543C CN1245543C CN 200410022640 CN200410022640A CN1245543C CN 1245543 C CN1245543 C CN 1245543C CN 200410022640 CN200410022640 CN 200410022640 CN 200410022640 A CN200410022640 A CN 200410022640A CN 1245543 C CN1245543 C CN 1245543C
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Abstract
The present invention discloses a preparation method of a collagen based composite medical fiber spinning stock solution. Healthy animals are selected, butchered and skinned; pretreatment of cleaning, degreasing, etc. are carried out to raw hide; then the raw hide is treated by hydrolyzation and purification by utilizing a composite enzyme hide collagen treating agent and chemical substances, and animal hide collagen with favorable biocompatibility and bioactivity is obtained; the hydrolytic animal hide collagen is treated by further purification; then the hide collagen and chitosan are together blended, and a collagen based composite medical fiber spinning stock solution is obtained. The stock solution can be used for preparing biologic medical films, iatrical stitches for operations, and stock solutions of collagen based composite medical fiber materials.
Description
One, technical field
The present invention relates to a kind of preparation method of collagen base composite medical fiber spinning dope, belong to biomedical materials field.
Two, background technology
Collagen is present in the animal body widely, is the main component of mammalian body inner structure tissue, constitutes the protein of human body about 30%.Collagen has unique physical and chemical properties and good biocompatibility, biologically active and degradability, characteristic such as hypoimmunity and hemostatic function, and be absorbed easily in vivo, hydrophily is strong, have no side effect, security is good, thereby, be considered to be one of the most rising natural biological medical material.
For a long time, people utilize the performance characteristics of animal dermal collagen, research and develop out a series of collagen base biological medical materials, as biological dressing, artificial skin, biological medicinal membrane, styptic sponge etc., but the report of relevant collagen base composite medical fiber is not seen as yet.
Utilize protein to be raw material, make the existing many reports of azelon, as milk protein being joined spinning fibre in the viscose glue abroad, the final use that makes fiber have good flexibility, feel and dyeability, product is blanket, sheet, towel, baby's clothing, gloves and non-weaving cloth etc., this fiber also resists the staphylococcus aureus of methicillinum in hygiene care and medical field propagation has protective action (seeing TTM for details, The International textileMagazine 2000:24-25).Content of cellulose 8.5% in viscose glue, and milk protein 30.% and fat 3.6% are spun into together and contain H
2SO
4Coagulating bath in, stretch 50%, through cutting off, fiber 1.95CN/dtex (dry state), extension at break 15.7% (dry state) are made in washing, have soft hand feeling and resilience and (see Daina Spining JB-192928 for details, 2001:7-17).
Make the fibrous raw material spinning fibre with chitin both at home and abroad and make fiber have some function, be used for that the research of medical science and field of new is more deep (to see Ka (Pinskip for details Kichin, Kifosan Kenkyu, 1999,5 (2) P182-183); Lee Young Moo; KR-9615656 (1996.11.20) Korea Spro; The big volume of Jiang Ting, " chitin ", China Environmental Science Press, Beijing, 1995).Domestic research to protein fibre has many reports, but mainly is silk-fibroin, pupa albumen, soybean protein and milk protein etc.During " eight or five ", Chengdu Univ. of Science ﹠ Technology adopts silk offcut, dissolving back and PVA co-blended spinning, and excellences such as its fibrous mechanical property and dyeability, the back has stopped research because of raw material sources and spinning solution and less stable.
Chemical fibre factory, Yibin, Sichuan adopts pupa albumen and viscose glue viscose glue blending spinning altogether, spin protein modified artificial silk, fiber is except that turning to be yellow than ordinary artificial silk's color, mechanical property is all approaching with the ordinary artificial silk, Shanghai weaving group cooperates with the Donghua University technique center, and acrylonitrile grafting to pupa albumen, is developed JC pupa albumen fiber, passed through technical appraisement, laid the foundation for further studying.
Puyang, Henan Province China health chemical-biological engineering associating group company separation and Extraction soybean protein from dregs of beans, and with the PVA co-blended spinning, make soybean fiber through post processings such as acetalations.This fiber has good leads moist and hygroscopicity, available ACID DYES and reactive dyeing, and color is the high-grade clothing raw material near tussah silk.
Therefore, mainly be to be raw material both at home and abroad with native proteins such as soybean, milk, silkworm chrysalises, make azelon with applicability by special treatment, compare with these albumen, soybean, milk, pupa albumen molecule are spherical in shape, and it is yellow that color shows, and raw materials used, resource-constrained, the poor stability of spinning solution; The mechanical property and the DIMENSIONAL STABILITY that are spun into fiber are relatively poor.
Utilize collagen to make medical fibre, the domestic and foreign literature report is very few.Do not see that having with Animal Skin collagen is the bibliographical information that raw material is made medical fibre.
Three, summary of the invention
The purpose of this invention is the preparation method that a kind of collagen base composite medical fiber spinning dope is provided at the deficiency of prior art, be characterized in utilizing collagen to be raw material, prepare collagen base composite medical fiber spinning dope with shitosan, acetic acid blending and modifying.
The objective of the invention is to realize that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise:
The preparation method of collagen base composite medical fiber spinning dope may further comprise the steps:
(1) raw material is prepared: choose the healthy animal of 30-120Kg, butcher, peeling behind the frizing, refrigerates standby.
(2) clean: get 100 parts of refrigeration Animal Skin, put into rotary drum and add peregal 3.0-30.0 part, normal-temperature water 200-800 part, NaCl 5-30 part, build the rotary drum door, rotate 120-240min, control dried waste liquid, add normal-temperature water 200-800 part, rotate 120-240min, control dried waste liquid.
(3) cropping: utilize shearing machine or the manual hair that cuts off on the Animal Skin.
(4) degreasing: get 100 parts of the Animal Skin of cutting hair, put into CO
2In the treatment with supercritical fluid device, add Na
2CO
31.0-15.0 part, penetrating agent JFC 0.5-2.0 part are rotated 30-240min, add peregal 0.5-10.0 part, degreasing agent PT-101 1.0-15.0 part, and washing powder 0.5-10.0 part is rotated 30-240min, controls dried waste liquid.
(5) clean: the defatted animal skin is put into rotary drum, the adding temperature is hot water 200-800 part of 32-40 ℃, rotate 120-240min, control dried waste liquid, add temperature again and be hot water 200-800 part of 32-40 ℃, rotate 120-240min, control dried waste liquid, so repeatable operation is 2-6 time, uses centrifuge dewatering.
(6) shear: earlier Animal Skin is divided into fritter, then, is cut into the skin grain of 1 * 1 * 1cm size with cutter, after rinsing well with deionized water, draining, low temperature dries.
(7) extraction of Animal Skin collagen: 100 parts of the skin grains that the low temperature of learning from else's experience dries, put into reactor, add sodium acetate-hydrochloride buffer 2000-8000 part, after soaking 10-20h, supernatant is removed in control, adds sodium acetate-hydrochloride buffer 2000-8000 part again, adjust pH is to 1.0-4.0, add complex enzyme collagen finishing agent 0.3-0.5 part, stir 10-30h, centrifugation then, get supernatant, to 7.5-8.0, add NaCl 80-150 part with the NaOH adjust pH, behind the stirring 0.5-2.0h, leave standstill 8-20h, supernatant is got in centrifugation, obtains slightly to carry Animal Skin collagen.
(8) purifying of hydrolysis collagen: get and slightly carry 100 parts of Animal Skin collagens, put into reactor, use normal temperature, distilled water washing 10-60min through sterilization, add acetic acid 25-150 part, make its dissolving, carry out centrifugation then, remove insoluble matter, regulate the pH value to 7.5-8.0 with NaOH again, add NaCl 50-450 part, placing temperature is 5-15 ℃ of freezer, stirs 30-180min, leave standstill 6-20h, treat that its post precipitation carries out centrifugation, supernatant is removed in control, at last collagen is dissolved in the acetic acid of the citric acid of 0.05M or 0.5M, making extracellular fluid dialysis with the acetic acid of 0.05M citric acid or 0.5M again, is the 48-72h that dialyses under 5-20 ℃ the condition in temperature.With the NaCl solution dialysis 24-36h of 130mmol/L, obtain purifying Animal Skin collagen then.
(9) preparation of spinning solution: get 100 parts of Animal Skin collagens, put into reactor, add 0.5M acetic acid 1500-3500 part, make its concentration reach 2.5-6.4%, dissolving fully, add 10-20wt% chitosan solution 6000-14000 part again, stir 8-16h, obtain collagen base composite medical fiber spinning dope.
Used Animal Skin is healthy pig ox, the skin of sheep domestic animal among the preparation method of collagen base composite medical fiber spinning dope of the present invention.
Used rotary drum is suspension type wood rotary drum or stainless steel rotary drum among the preparation method of collagen base composite medical fiber spinning dope of the present invention.
Collagen is linear rodlike molecule, draw ratio about 200, in the spin-drawing process, big molecule is orientated in fiber easily, forms orientation, crystalline texture, and the mechanical property of fiber and DIMENSIONAL STABILITY are good than the former, characteristics are that pure collagen is white, the fiber background color is good, has an aptitude to more bright-coloured shades of colour, and the consumer is more acceptant; Collagen itself is present in the animal, makes really " leatheret " clothes, bedding, commodity by chemistry and physical method, and the easier psychology that satisfies the consumer requires and result of use; What is particularly worth mentioning is that collagen base functional fibre is a kind of biodegradable fiber, after it makes goods, enter consumption and finish whole life cycles discarded after, can not work the mischief to environment, be the ecological property functional fibre.Compared with prior art, the present invention has the following advantages:
(1) raw material sources are abundant, and are good and cheap;
(2) use CO
2The treatment with supercritical fluid device carries out purifying to Animal Skin, and the purity that can guarantee to extract Animal Skin collagen meets the requirement of medical application;
(3) select for use natural polymer shitosan and Animal Skin collagen compound, and prescription and process conditions are optimized, the performance of spinning solution is improved greatly;
(4) process conditions are content with very little, and are workable.
The collagen base composite medical fiber spinning solution that this method is prepared, its performance can satisfy following application requirements:
A) stoste of preparation biological medicinal membrane;
B) stoste of making surgical medical suture;
C) spinning solution of making collagen base composite medical fibrous material.
Four, the specific embodiment
Below by implementing that the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; and can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
Embodiment 1
(1) raw material is prepared: choose the health pig of 30-120Kg, butcher, peeling behind the frizing, refrigerates standby.
(2) clean: get refrigeration pigskin 100Kg, put into rotary drum and add peregal 3.0Kg, normal-temperature water 200Kg, NaCl 5.0Kg build the rotary drum door, rotate 120min, control dried waste liquid, add normal-temperature water 200Kg, rotate 120min, control dried waste liquid.
(3) cropping: utilize shearing machine or the manual hair that cuts off on the pigskin.
(4) degreasing: get the pigskin 100Kg that cut hair, put into CO
2In the treatment with supercritical fluid device, add Na
2CO
33.0Kg, penetrating agent JFC 0.5Kg, rotate 90min, add peregal 2.0Kg, degreasing agent PT-101 2.0Kg, washing powder 2.0Kg rotates 90min, controls dried waste liquid.
(5) clean: the degreasing pigskin is put into rotary drum, add temperature and be 32 ℃ hot water 200Kg, rotate 120min, control dried waste liquid, add temperature again and be 32 ℃ hot water 200Kg, rotate 120min, control dried waste liquid, so repeatable operation is 2 times, uses centrifuge dewatering.
(6) shear: earlier pigskin is divided into fritter, then, is cut into the skin grain of 1 * 1 * 1cm size with cutter, after rinsing well with deionized water, draining, low temperature dries.
(7) extraction of pigskin collagen: the skin grain 100Kg that the low temperature of learning from else's experience dries, put into reactor, add sodium acetate-hydrochloride buffer 2000Kg, after soaking 10h, supernatant is removed in control, adds sodium acetate-hydrochloride buffer 2000Kg again, adjust pH to 1.5 adds 0.3 part of complex enzyme collagen finishing agent, stirs 10h, supernatant is got in centrifugation then, uses the NaOH adjust pH to 7.5-8.0, add NaCl 80Kg, behind the stirring 0.5h, leave standstill 8h, supernatant is got in centrifugation, obtains slightly to carry Animal Skin collagen.
(8) purifying of hydrolysis pigskin collagen: get and slightly carry pigskin collagen 100Kg, put into reactor, use normal temperature, distilled water washing 20min through sterilization, add acetic acid 25Kg, make its dissolving, carry out centrifugation then, remove insoluble matter, regulate the pH value to 7.5-8.0 with NaOH again, add NaCl 100Kg, placing temperature is 5 ℃ freezer, stirs 60min, leave standstill 6h, treat that its post precipitation carries out centrifugation, supernatant is removed in control, at last collagen is dissolved in the acetic acid of the citric acid of 0.05M or 0.5M, making extracellular fluid dialysis with the acetic acid of 0.05M citric acid or 0.5M again, is the 48h that dialyses under 5 ℃ the condition in temperature.Use 130mmol/L then, NaCl solution dialysis 24h, obtain purified pigskin collagen.
(9) preparation of spinning solution: get pigskin collagen 100Kg, put into reactor, add 0.5M acetic acid 1500Kg, make its concentration reach 2.5-6.4%, dissolving adds 10wt% chitosan solution 6000Kg more fully, stir 8h, obtain collagen base composite medical fiber spinning dope.
Embodiment 2
(1) raw material is prepared: choose the healthy goat of 30-60Kg, butcher, peeling behind the frizing, refrigerates standby.
(2) clean: get refrigeration goat skin 100Kg, put into rotary drum and add peregal 16.0Kg, normal-temperature water 500Kg, NaCl 17.0Kg build the rotary drum door, rotate 180min, control dried waste liquid, add normal-temperature water 500Kg, rotate 180min, control dried waste liquid.
(3) cropping: utilize shearing machine or the manual hair that cuts off on the goat skin.
(4) degreasing: get the goat skin 100Kg that cut hair, put into CO
2In the treatment with supercritical fluid device, add Na
2O
38.0Kg, penetrating agent JFC 1.5Kg, rotate 120min, add peregal 6.0Kg, degreasing agent PT-101 8.0Kg, washing powder 5.5Kg rotates 120min, controls dried waste liquid.
(5) clean: the degreasing goat skin is put into rotary drum, add temperature and be 36 ℃ hot water 500Kg, rotate 180min, control dried waste liquid, add temperature again and be 36 ℃ hot water 500Kg, rotate 180min, control dried waste liquid, so repeatable operation is 4 times, uses centrifuge dewatering.
(6) shear: earlier goat skin is divided into fritter, then, is cut into the skin grain of 1 * 1 * 1cm size with cutter, after rinsing well with deionized water, draining, low temperature dries.
(7) extraction of goat skin collagen: the skin grain 100Kg that the low temperature of learning from else's experience dries, put into reactor, add sodium acetate-hydrochloride buffer 5000Kg, after soaking 15h, supernatant is removed in control, adds sodium acetate-hydrochloride buffer 5000Kg again, adjust pH is to 1.0-4.0, add complex enzyme collagen finishing agent 0.4Kg, stir 20h, centrifugation then, get supernatant, to 7.5-8.0, add NaCl 120Kg with the NaOH adjust pH, behind the stirring 1.5h, leave standstill 14h, supernatant is got in centrifugation, obtains slightly to carry goat skin collagen.
(8) purifying of hydrolysis goat skin collagen: get and slightly carry goat skin collagen 100Kg, put into reactor, use normal temperature, distilled water washing 40min through sterilization, add acetic acid 90Kg, make its dissolving, carry out centrifugation then, remove insoluble matter, regulate the pH value to 7.5-8.0 with NaOH again, add NaCl 250Kg, placing temperature is 10 ℃ of freezers, stirs 120min, leave standstill 12h, treat that its post precipitation carries out centrifugation, supernatant is removed in control, at last with collagenolysis in the acetic acid of the citric acid of 0.05M or 0.5M, making extracellular fluid dialysis with the acetic acid of 0.05M citric acid or 0.5M again, is the 60h that dialyses under 12 ℃ the condition in temperature.With the NaCl solution dialysis 30h of 130mmol/L, obtain purifying goat skin collagen then.
(9) preparation of spinning solution: get goat skin collagen 100Kg, put into reactor, add 0.5M acetic acid 2500Kg, make its concentration reach 2.5-6.4%, dissolving adds 15wt% chitosan solution 10000Kg more fully, stir 12h, obtain collagen base composite medical fiber spinning dope.
Embodiment 3
(1) raw material is prepared: choose the healthy ox of 30-120Kg, butcher, peeling behind the frizing, refrigerates standby.
(2) clean: get refrigeration cattle hide 100Kg, put into rotary drum and add peregal 30.0Kg, normal-temperature water 800Kg, NaCl 30Kg build the rotary drum door, rotate 240min, control dried waste liquid, add normal-temperature water 800Kg, rotate 240min, control dried waste liquid.
(3) cropping: utilize shearing machine or the manual hair that cuts off on the cattle hide.
(4) degreasing: get the cattle hide 100Kg that cut hair, put into CO
2In the treatment with supercritical fluid device, add Na
2CO
315.0Kg, penetrating agent JFC 2.0Kg, rotate 240min, add peregal 10.0Kg, degreasing agent PT-101 15.0Kg, washing powder 10.0Kg rotates 240min, controls dried waste liquid.
(5) clean: the defatted animal skin is put into rotary drum, add temperature and be 40 ℃ hot water 800Kg, rotate 240min, control dried waste liquid, add temperature again and be 40 ℃ hot water 800Kg, rotate 240min, control dried waste liquid, so repeatable operation is 6 times, uses centrifuge dewatering.
(6) shear: earlier cattle hide is divided into fritter, then, is cut into the skin grain of 1 * 1 * 1cm size with cutter, after rinsing well with deionized water, draining, low temperature dries.
(7) extraction of cattle hide collagen: the skin grain 100Kg that the low temperature of learning from else's experience dries, put into reactor, add sodium acetate-hydrochloride buffer 8000Kg, after soaking 20h, supernatant is removed in control, adds sodium acetate-hydrochloride buffer 8000Kg again, adjust pH is to 1.0-4.0, add complex enzyme collagen finishing agent 0.5kg, stir 30h, centrifugation then, get supernatant, to 7.5-8.0, add NaCl 150Kg with the NaOH adjust pH, behind the stirring 2h, leave standstill 20h, supernatant is got in centrifugation, obtains slightly to carry cattle hide collagen.
(8) purifying of hydrolysis cattle hide collagen: get and slightly carry cattle hide collagen 100Kg, put into reactor, use normal temperature, distilled water washing 60min through sterilization, add acetic acid 150Kg, make its dissolving, carry out centrifugation then, remove insoluble matter, regulate the pH value to 7.5-8.0 with NaOH again, add NaCl 450Kg, placing temperature is 15 ℃ of freezers, stirs 180min, leave standstill 20h, treat that its post precipitation carries out centrifugation, supernatant is removed in control, at last collagen is dissolved in the acetic acid of the citric acid of 0.05M or 0.5M, making extracellular fluid dialysis with the acetic acid of 0.05M citric acid or 0.5M again, is the 72h that dialyses under 20 ℃ the condition in temperature.With the NaCl solution dialysis 36h of 130mmol/L, obtain purifying cattle hide collagen then.
(9) preparation of spinning solution: get cattle hide collagen 100Kg, put into reactor, add 0.5M acetic acid 3500Kg, make its concentration reach 2.5-6.4%, dissolving adds 20wt% chitosan solution 14000Kg more fully, stir 16h, obtain collagen base composite medical fiber spinning dope.
Used complex enzyme collagen finishing agent is that Chengdu enlightening Australia collagen Hitek Ltd produces, enzyme-added auxiliary liming agent EA produces for the auxiliary reagent factory, Shanghai for the chemical plant production of Guangdong PERICARPIUM CITRI RETICULATAE leather, peregal, washing powder and penetrating agent JFC among the present invention, degreasing agent PT-101 produces for the detergent factory, Guilin, and shitosan is the Long Huagongzhujichang of Chengdu section production.All the other chemical reagent are commercially available analysis pure preparation.
Claims (3)
1. the preparation method of collagen base composite medical fiber spinning dope is characterized in that:
(1) raw material is prepared: choose the healthy animal of 30-120Kg, butcher, peeling, behind the frizing, refrigerate standby,
(2) clean: get refrigeration Animal Skin 100 weight portions and put into rotary drum, add peregal 3.0-30.0 weight portion, normal-temperature water 200-800 weight portion, NaCl5-30 weight portion, build the rotary drum door, rotate 120-240min, control dried waste liquid, add normal-temperature water 200-800 weight portion, rotate 120-240min, control dried waste liquid
(3) cropping: utilize shearing machine or the manual hair that cuts off on the Animal Skin,
(4) degreasing: get Animal Skin 100 weight portions of cutting hair, put into CO
2In the treatment with supercritical fluid device, add Na
2CO
31.0-15.0 weight portion, penetrating agent JFC 0.5-2.0 weight portion rotate 30-240min, add peregal 0.5-10.0 weight portion, degreasing agent PT-1011.0-15.0 weight portion, and washing powder 0.5-10.0 weight portion rotates 30-240min, controls dried waste liquid,
(5) clean: the defatted animal skin is put into rotary drum, the adding temperature is 32-40 ℃ a hot water 200-800 weight portion, rotate 120-240min, control dried waste liquid, add temperature again and be 32-40 ℃ hot water 200-800 weight portion, rotate 120-240min, control dried waste liquid, so repeatable operation is 2-6 time, uses centrifuge dewatering
(6) shear: earlier Animal Skin is divided into fritter, then, is cut into the skin grain of 1 * 1 * 1cm size with cutter, after rinsing well with deionized water, draining, low temperature dries,
(7) extraction of Animal Skin collagen: skin grain 100 weight portions that the low temperature of learning from else's experience dries, put into reactor, add sodium acetate-hydrochloride buffer 2000-8000 weight portion, behind the immersion 10-20h, supernatant is removed in control, add sodium acetate-hydrochloride buffer 2000-8000 weight portion again, adjust pH adds complex enzyme collagen finishing agent 0.3-0.5 weight portion to 1.0-4.0, stirs 10-30h, centrifugation then, get supernatant, to 7.5-8.0, add the NaCl80-150 weight portion with the NaOH adjust pH, after stirring 0.5-2.0h, leave standstill 8-20h, supernatant is got in centrifugation, obtain slightly to carry Animal Skin collagen
(8) purifying of hydrolysis collagen: get and slightly carry Animal Skin collagen 100 weight portions, put into reactor, use normal temperature, distilled water washing 10-60min through sterilization, add acetic acid 25-150 weight portion, make its dissolving, carry out centrifugation then, remove insoluble matter, regulate the pH value to 7.5-8.0 with NaOH again, add NaCl 50450 weight portions, placing temperature is 5-15 ℃ of freezer, stirs 30-180min, leave standstill 6-20h, treat that its post precipitation carries out centrifugation, supernatant is removed in control, at last with collagenolysis in the acetic acid of the citric acid of 0.05M or 0.5M, making extracellular fluid dialysis with the acetic acid of 0.05M citric acid or 0.5M again, is the 48-72h that dialyses under 5-20 ℃ the condition in temperature.With the NaCl solution dialysis 24-36h of 130mmol/L, obtain purifying Animal Skin collagen then,
(9) preparation of spinning solution: get Animal Skin collagen 100 weight portions, put into reactor, add 0.5M acetic acid 1500-3500 weight portion, make its concentration reach 2.5-6.4%, dissolving fully, be incorporated as 10-20wt% chitosan solution 6000-14000 weight portion again, stir 8-16h, promptly obtain collagen base composite medical fiber spinning dope.
2. according to the preparation method of the described collagen base of claim 1 composite medical fiber spinning dope, it is characterized in that healthy animal is pig, ox, sheep domestic animal.
3. according to the preparation method of claim 1 or 2 described collagen base composite medical fiber spinning dopes, it is characterized in that rotary drum is suspension type wood rotary drum or stainless steel rotary drum.
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| CN101569759B (en) * | 2009-04-10 | 2012-09-26 | 天津市贝亿生物制品有限公司 | Isotonic collagen sponge and preparation method thereof |
| CN102877147A (en) * | 2012-09-24 | 2013-01-16 | 四川大学 | Method for preparing nanofiber by electrostatic spinning of collagen aqueous solution |
| CN103263694B (en) * | 2013-05-14 | 2014-12-03 | 北京华信佳音医疗科技发展有限责任公司 | Collagen-based dura and preparation method thereof |
| CN104711702B (en) * | 2015-03-24 | 2016-08-17 | 四川大学 | There is the collagen aggregation composite type medical fiber of antibacterial/bacteria resistance function |
| CN106496608B (en) * | 2016-11-02 | 2018-12-07 | 四川大学 | Collagen-based compounds the preparation method of non-ionic polysaccharide building composite hydrogel |
| CN106983680A (en) * | 2017-01-13 | 2017-07-28 | 浙江百寿堂药业有限公司 | A kind of frosted mildy wash |
| CN108396403A (en) * | 2018-03-07 | 2018-08-14 | 兴业皮革科技股份有限公司 | A method of preparing the compound biodegradable fiber of collagen-based using shavings containing metallic |
| CN109137116B (en) * | 2018-07-09 | 2020-03-10 | 天津工业大学 | Preparation method of collagen fiber containing carbon nano tube |
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