CN103114351B - Preparation method and dry-wet spinning method of regenerated protein chitosan blended solution - Google Patents
Preparation method and dry-wet spinning method of regenerated protein chitosan blended solution Download PDFInfo
- Publication number
- CN103114351B CN103114351B CN201310072694.5A CN201310072694A CN103114351B CN 103114351 B CN103114351 B CN 103114351B CN 201310072694 A CN201310072694 A CN 201310072694A CN 103114351 B CN103114351 B CN 103114351B
- Authority
- CN
- China
- Prior art keywords
- solution
- regenerated protein
- concentration
- preparation
- chitosan
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention relates to a preparation method and a dry-wet spinning method of a regenerated protein chitosan blended solution. The preparation method comprises the steps of: carrying out ultrafine grinding on raw materials of leftovers of reeling silks and leftovers of animal coarse hairs such as goat hairs, pig hairs, camel hairs and wools, dissolving the crushed raw materials in an ionic liquid to obtain a regenerated protein solution with high molecular weight, and blending the regenerated protein solution with a chitosan liquid to obtain a spinning solution. The spinning solution is molded by using a dry-wet spinning technology, the structure uniformity and the orientation degree of fibers are enhanced through solidification and drafting, and the elongation and the elasticity of the fibers are improved through oxidation crosslinking. The regenerated protein chitosan blended fiber has high protein content, and has functions of bacteria resistance, moisture prevention and promotion of blood coagulation and wound healing; and all compositions in the fiber are in biomass states, have good biodegradability and biocompatibility and can be applied to textile fibers and biomedical materials.
Description
Technical field
The invention belongs to biomass resource regeneration field, relate to a kind of preparation method of the regenerated protein that contains shitosan, be specifically related to a kind of raw egg again that adopts dry-wet spinning technique
The white preparation of chitosan blend solution and the method for dry-wet spinning.
Background technology
Protein fibre has good moisture pick-up properties and antistatic property, has good compatibility with human body skin, in recent years, utilizes the marketization of soybean protein, milk protein and pupa albumen fiber of Protein processing, and demonstrates certain premium properties.But, the preparation of these azelons is all as the copolymerization such as polyvinyl alcohol, polyacrylonitrile or blend by protein and synthetic high polymer, obtain through wet spinning, in fiber, the content of albumen is very low, generally be no more than 15%, main body composition remains synthetic macromolecule, so described azelon is not the azelon in complete meaning, does not also just possess the good characteristic of natural protein fiber.
Summary of the invention
The object of the invention is, in order to overcome the existing defect of utilizing synthetic high polymer to prepare protein fibre, to invent a kind of preparation of the regenerated protein chitosan blend solution that utilizes chitosan to replace synthetic high polymer and the method for dry-wet spinning.Shitosan claims again chitin, chitin or chitin, at occurring in nature, shitosan is extensively present in the cell of rudimentary plant mushroom algae and the shell of arthropod shrimp crab insect, use chitosan to replace synthetic high polymer, can make blended fiber possess the good characteristic of natural protein fiber, greatly improve comfortableness, health and the health of fiber.
The object of the invention is to realize as follows:
Described regenerated protein chitosan blend solution is made take silk, animal hair and shitosan as raw material, and its preparation is to realize by following step:
(1) under the condition of boiling, to put concentration into be 0.5% Na to silk
2cO
3in solution, come unstuck, the 1%-4% that the weight of silk is solution weight, comes unstuck 3 times altogether, and each 10-90 minute uses hot water injection 3 times after coming unstuck, then at 50-90 ℃, dry, shred;
(2) silk fiber of drying, shredding is mixed according to the ratio of quality 1:0.1-20 with animal hair, be then ground into the albumen fine powder of diameter 0.01-30 micron by air-flow micronizer;
(3) albumen fine powder is joined in ionic liquid solution, at 60-150 ℃, strong agitation is dissolved 20-240 minute, filters and obtains the regenerated protein solution that concentration is 5-35%;
(4) shitosan is joined in ionic liquid solution, under 50-135 ℃ of condition, dissolve 30-180 minute, filter and obtain the chitosan solution that concentration is 1.5-35%;
(5) by regenerated protein solution and chitosan solution blend, obtaining concentration is the regenerated protein chitosan blend solution of 5-35%, and wherein the mass ratio of regenerated protein and shitosan is 1-10:1.
The dry-wet spinning method of described regenerated protein chitosan blend solution, its technological process comprises: solidify-preliminary draft-drawing-off-compacting by drying-HEAT SETTING, the process conditions of each step are as follows:
solidify
Coagulation bath composition: the ionic liquid aqueous solution that concentration is 5-70%
Coagulation bath temperature: 10-35 ℃
Air layer height: 1-20 centimetre (be spinning head surface with coagulating bath liquid level apart from)
Spinning speed: 2-25 m/min
preliminary draft
Preliminary draft is bathed composition: the ionic liquid aqueous solution that concentration is 1-50%
Preliminary draft bath temperature: 30-65 ℃
Pre-draft multiple: 1.2-4.5
drawing-off
Composition is bathed in drawing-off: the aqueous oxidizing agent solution that concentration is 0.5-5.0%
Drawing-off bath temperature: 50-98 ℃
Drafting multiple: 2.5-8 doubly
compacting by drying
Compacting by drying temperature: 100-145 ℃
The compacting by drying time: 5-25 minute
Tension force condition: length is fixed, nervous state (maintenance fiber tension)
hEAT SETTING
HEAT SETTING medium: steam
Steam pressure: 2-10 kg/cm
2
Shaping time: 1-25 minute.
The molecular weight of described shitosan is 10,000-200,000, and deacetylation is more than or equal to 90%.
Described animal hair is pig hair, goats hair, the rabbit hair, camel hair, consumption ox hair, and the sheep's wool of on-woven value.
Described ionic liquid is 1-butyl-3-methylimidazole villaumite, 1-butyl-3-methyl imidazolium tetrafluoroborate or 1-ethyl-3-methylimidazole diethyl phosphate.
Described oxidant is Peracetic acid or hydrogen peroxide.
Good effect of the present invention is as follows: the present invention adopts dry jet wet spinning technology to realize the fibration of regenerated protein chitosan blend solution, by solidifying and drawing-off, improve the uniformity and the degree of orientation of fibre structure, by oxidation cross-linked, improved elongation and the elasticity of fiber.Regenerated protein chitosan blend fiber of the present invention, there is higher protein content, and there is the function of antibacterial, moisturizing, promotion blood coagulation and wound healing, in fiber, all the components is living beings, there is good biological degradability and biocompatibility, not only can apply to textile fabric, also can be used as bio-medical material.
The specific embodiment
case study on implementation 1
The present embodiment adopts dry-wet spinning technique to produce composite fibre take regenerated protein chitosan blend solution as raw material;
Regenerated protein chitosan blend solution, makes take silk, animal hair and shitosan as raw material, and its preparation process is as follows:
(1) under the condition of boiling, to put concentration into be 0.5% Na to silk
2cO
3in solution, come unstuck, the consumption of silk is solution weight 1.5%, comes unstuck altogether 3 times, each 15 minutes, after coming unstuck, with hot water injection 3 times, then at 90 ℃, dries, shreds;
(2) by drying, the silk fiber that shreds and pig hair be ground into the albumen fine powder of 25 microns of left and right of diameter by air-flow micronizer after according to mass ratio 1:0.2 blend.
(3) albumen fine powder is joined in 1-butyl-3-methylimidazole chloride aqueous solution, at 80 ℃, strong agitation is dissolved 140 minutes, and filtering and obtaining concentration is 25% regenerated protein solution.
(4) by molecular weight be 12,000, deacetylation is more than or equal to 90% shitosan and joins in 1-butyl-3-methylimidazole chloride aqueous solution, under 75 ℃ of conditions, dissolves 150 minutes, filtering and obtaining concentration is 5% chitosan solution.
(5) by regenerated protein solution and chitosan solution blend, obtain concentration and be 23% regenerated protein chitosan blend solution, the mass ratio of regenerated protein and shitosan is 9:1.
The technological process that utilizes above-mentioned regenerated protein chitosan blend solution to carry out dry-wet spinning comprises: solidify-preliminary draft-drawing-off-compacting by drying-HEAT SETTING, the process conditions of each step are as follows:
solidify
Coagulation bath composition: 1-butyl-3-methylimidazole chloride aqueous solution that concentration is 70%
Coagulation bath temperature: 15 ℃
Air layer height: 7 centimetres
Spinning speed: 10 ms/min
preliminary draft
Preliminary draft is bathed composition: 1-butyl-3-methylimidazole chloride aqueous solution that concentration is 30%
Preliminary draft bath temperature: 65 ℃
Pre-draft multiple: 1.5
drawing-off
Composition is bathed in drawing-off: the aqueous hydrogen peroxide solution that concentration is 5.0%
Drawing-off bath temperature: 98 ℃
Drafting multiple: 8 times
compacting by drying
Compacting by drying temperature: 135 ℃
The compacting by drying time: 5 minutes
Tension force condition: length is fixed, nervous state
hEAT SETTING
HEAT SETTING medium: steam
Steam pressure: 5.0 kg/cm
2
Shaping time: 5.0 minutes.
case study on implementation 2
The present embodiment adopts dry-wet spinning technique to produce composite fibre take regenerated protein chitosan blend solution as raw material;
Regenerated protein chitosan blend solution, makes take silk, animal hair and shitosan as raw material, and its preparation process is as follows:
(1) under the condition of boiling, to put concentration into be 0.5 Na to silk
2cO
3in solution, come unstuck, the consumption of silk is solution weight 2.0%, comes unstuck altogether 3 times, each 50 minutes, after coming unstuck, with hot water injection 3 times, then at 60 ℃, dries, shreds.
(2) by drying, the silk fiber that shreds and goats hair be ground into the albumen fine powder of 5.0 microns of left and right of diameter by air-flow micronizer after according to mass ratio 1:5 blend.
(3) albumen fine powder is joined in 1-butyl-3-methyl imidazolium tetrafluoroborate aqueous solution, at 100 ℃, strong agitation is dissolved 80 minutes, and filtering and obtaining concentration expressed in percentage by weight is 20% regenerated protein solution.
(4) by molecular weight be 15,000, deacetylation is more than or equal to 90% shitosan and joins in 1-butyl-3-methyl imidazolium tetrafluoroborate aqueous solution, under 105 ℃ of conditions, dissolves 30 minutes, filtering and obtaining concentration expressed in percentage by weight is 3.5% chitosan solution.
(5) by regenerated protein solution and chitosan solution blend, obtain concentration and be 16.7% regenerated protein chitosan blend solution, the mass ratio of regenerated protein and shitosan is 4:1;
The technological process that utilizes above-mentioned regenerated protein chitosan blend solution to carry out dry-wet spinning comprises: solidify-preliminary draft-drawing-off-compacting by drying-HEAT SETTING, the process conditions of each step are as follows:
solidify
Coagulation bath composition: 1-butyl-3-methyl imidazolium tetrafluoroborate aqueous solution that concentration is 40%
Coagulation bath temperature: 10 ℃
Air layer height: 3 centimetres
Spinning speed: 3.5 ms/min
preliminary draft
Preliminary draft is bathed composition: 1-butyl-3-methyl imidazolium tetrafluoroborate aqueous solution that concentration is 10%
Preliminary draft bath temperature: 45 ℃
Pre-draft multiple: 2.5
drawing-off
Composition is bathed in drawing-off: the peroxide acetate aqueous solution that concentration is 0.5%
Drawing-off bath temperature: 88 ℃
Drafting multiple: 6.0 times
compacting by drying
Compacting by drying temperature: 115 ℃
The compacting by drying time: 15 minutes
Tension force condition: length is fixed, nervous state
hEAT SETTING
HEAT SETTING medium: steam
Steam pressure: 8 kg/cm
2
Shaping time: 5.5 minutes.
case study on implementation 3
The present embodiment adopts dry-wet spinning technique to produce composite fibre take regenerated protein chitosan blend solution as raw material;
Regenerated protein chitosan blend solution, makes take silk, animal hair and shitosan as raw material, and its preparation process is as follows:
(1) under the condition of boiling, to put concentration into be 0.5% Na to silk
2cO
3in solution, come unstuck, the consumption of silk is solution weight 3.5%, comes unstuck altogether 3 times, each 40 minutes, after coming unstuck, with hot water injection 3 times, then at 70 ℃, dries, shreds.
(2) by drying, the silk fiber that shreds and camel hair be ground into the albumen fine powder of 2.0 microns of left and right of diameter by air-flow micronizer after according to mass ratio 1:10 blend.
(3) albumen fine powder is joined in 1-ethyl-3-methylimidazole p diethylaminobenzoic acid aqueous solution of ester, at 115 ℃, strong agitation is dissolved 100 minutes, and filtering and obtaining concentration is 30% regenerated protein solution.
(4) by molecular weight be 18,000, deacetylation is more than or equal to 90% shitosan and joins in 1-ethyl-3-methylimidazole p diethylaminobenzoic acid aqueous solution of ester, under 85 ℃ of conditions, dissolves 90 minutes, filtering and obtaining concentration expressed in percentage by weight is 7.5% chitosan solution.
(5) by regenerated protein solution and chitosan solution blend, obtain concentration and be 24.4% regenerated protein chitosan blend solution, the mass ratio of regenerated protein and shitosan is 3:1.
The technological process that utilizes above-mentioned regenerated protein chitosan blend solution to carry out dry-wet spinning comprises: solidify-preliminary draft-drawing-off-compacting by drying-HEAT SETTING, the process conditions of each step are as follows:
solidify
Coagulation bath composition: concentration is 55% from 1-ethyl-3-methylimidazole p diethylaminobenzoic acid aqueous solution of ester
Coagulation bath temperature: 25 ℃
Air layer height: 4 centimetres
Spinning speed: 8 ms/min
preliminary draft
Preliminary draft is bathed composition: the 1-ethyl-3-methylimidazole p diethylaminobenzoic acid aqueous solution of ester that concentration is 18%
Preliminary draft bath temperature: 55 ℃
Pre-draft multiple: 2.1 times
drawing-off
Composition is bathed in drawing-off: the aqueous hydrogen peroxide solution that concentration is 1.5%
Drawing-off bath temperature: 90 ℃
Drafting multiple: 6.5 times
compacting by drying:
Compacting by drying temperature: 125 ℃
The compacting by drying time: 12 minutes
Tension force condition: length is fixed, nervous state
hEAT SETTING
HEAT SETTING medium: steam
Steam pressure: 3.0 kg/cm
2
Shaping time: 10 minutes.
Claims (7)
1. a preparation for regenerated protein chitosan blend solution, is characterized in that: this solution is made take silk, animal hair and shitosan as raw material, and its preparation is to realize by following step:
(1) under the condition of boiling, to put concentration into be 0.5% Na to silk
2cO
3in solution, come unstuck, the 1%-4% that the weight of silk is solution weight, comes unstuck 3 times altogether, and each 10-90 minute uses hot water injection 3 times after coming unstuck, then at 50-90 ℃, dry, shred;
(2) silk fiber of drying, shredding is mixed according to the ratio of quality 1:0.1-20 with animal hair, be then ground into the albumen fine powder of diameter 0.01-30 micron by air-flow micronizer;
(3) albumen fine powder is joined in ionic liquid solution, at 60-150 ℃, strong agitation is dissolved 20-240 minute, filters and obtains the regenerated protein solution that concentration is 5-35%;
(4) shitosan is joined in ionic liquid solution, under 50-135 ℃ of condition, dissolve 30-180 minute, filter and obtain the chitosan solution that concentration is 1.5-35%;
(5) by regenerated protein solution and chitosan solution blend, obtaining concentration is the regenerated protein chitosan blend solution of 5-35%, and wherein the mass ratio of regenerated protein and shitosan is 1-10:1.
2. the preparation of regenerated protein chitosan blend solution according to claim 1, is characterized in that: the molecular weight of described shitosan is 10,000-200,000, and deacetylation is more than or equal to 90%.
3. the preparation of regenerated protein chitosan blend solution according to claim 1, is characterized in that: described animal hair is pig hair, goats hair, the rabbit hair, camel hair, yak hair, and the sheep's wool of on-woven value.
4. the preparation of regenerated protein chitosan blend solution according to claim 1, is characterized in that: described ionic liquid is 1-butyl-3-methylimidazole villaumite, 1-butyl-3-methyl imidazolium tetrafluoroborate or 1-ethyl-3-methylimidazole diethyl phosphate.
5. a method of carrying out dry-wet spinning with regenerated protein chitosan blend solution claimed in claim 1, is characterized in that:
The dry-wet spinning method of described regenerated protein chitosan blend solution, its technological process comprises: solidify-preliminary draft-drawing-off-compacting by drying-HEAT SETTING, the process conditions of each step are as follows:
solidify
Coagulation bath composition: the ionic liquid aqueous solution that concentration is 5-70%
Coagulation bath temperature: 10-35 ℃
Air layer height: 1-20 centimetre, the i.e. distance of spinning head surface and coagulating bath liquid level
Spinning speed: 2-25 m/min
preliminary draft
Preliminary draft is bathed composition: the ionic liquid aqueous solution that concentration is 1-50%
Preliminary draft bath temperature: 30-65 ℃
Pre-draft multiple: 1.2-4.5
drawing-off
Composition is bathed in drawing-off: the aqueous oxidizing agent solution that concentration is 0.5-5.0%
Drawing-off bath temperature: 50-98 ℃
Drafting multiple: 2.5-8 doubly
compacting by drying
Compacting by drying temperature: 100-145 ℃
The compacting by drying time: 5-25 minute
Tension force condition: length is fixed, nervous state
hEAT SETTING
HEAT SETTING medium: steam
Steam pressure: 2-10 kg/cm
2
Shaping time: 1-25 minute.
6. method of carrying out dry-wet spinning with regenerated protein chitosan blend solution according to claim 2, is characterized in that: described ionic liquid is 1-butyl-3-methylimidazole villaumite, 1-butyl-3-methyl imidazolium tetrafluoroborate or 1-ethyl-3-methylimidazole diethyl phosphate.
7. method of carrying out dry-wet spinning with regenerated protein chitosan blend solution according to claim 2, is characterized in that: described oxidant is Peracetic acid or hydrogen peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310072694.5A CN103114351B (en) | 2013-03-07 | 2013-03-07 | Preparation method and dry-wet spinning method of regenerated protein chitosan blended solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310072694.5A CN103114351B (en) | 2013-03-07 | 2013-03-07 | Preparation method and dry-wet spinning method of regenerated protein chitosan blended solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103114351A CN103114351A (en) | 2013-05-22 |
| CN103114351B true CN103114351B (en) | 2014-05-14 |
Family
ID=48412770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310072694.5A Expired - Fee Related CN103114351B (en) | 2013-03-07 | 2013-03-07 | Preparation method and dry-wet spinning method of regenerated protein chitosan blended solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103114351B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10011931B2 (en) | 2014-10-06 | 2018-07-03 | Natural Fiber Welding, Inc. | Methods, processes, and apparatuses for producing dyed and welded substrates |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103451770B (en) * | 2013-09-04 | 2015-08-12 | 东华大学 | A kind of preparation method of green low-carbon flame retardant wig fiber |
| US10982381B2 (en) | 2014-10-06 | 2021-04-20 | Natural Fiber Welding, Inc. | Methods, processes, and apparatuses for producing welded substrates |
| KR102591968B1 (en) | 2016-03-25 | 2023-10-20 | 네추럴 파이버 웰딩 인코포레이티드 | Methods, processes, and apparatuses for producing welded substrates |
| CN109196149B (en) | 2016-05-03 | 2021-10-15 | 天然纤维焊接股份有限公司 | Method, process and apparatus for producing dyed weld matrix |
| CN107299447A (en) * | 2017-07-16 | 2017-10-27 | 长沙秋点兵信息科技有限公司 | The technique that a kind of use silk prepares moisture absorption stretch-proof fabric |
| CN108950721A (en) * | 2018-07-10 | 2018-12-07 | 安徽省宇鸿纺织工艺制品有限公司 | A kind of production technology of fibroin albumen composite fibre |
| CN110512304B (en) * | 2019-08-23 | 2021-11-30 | 大连工业大学 | Preparation method of chitosan/euphausia superba protein composite fiber |
| CN113005532B (en) * | 2019-12-19 | 2022-07-19 | 武汉大学 | Method for continuously preparing silk nanofiber and chitin or chitosan composite fiber |
| CN111962174A (en) * | 2020-08-30 | 2020-11-20 | 上海视物科技有限公司 | Goat milk shred and preparation method and application thereof |
| CN114622304B (en) * | 2022-02-07 | 2023-03-28 | 江南大学 | Preparation method of functional keratin composite fiber based on ionic liquid |
| CN115852506B (en) * | 2022-12-01 | 2023-07-07 | 温州佳远生物科技有限公司 | Drying method for wet spinning of chitosan fibers |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1370856A (en) * | 2002-02-28 | 2002-09-25 | 陈福库 | Regenerated protein fiber and its production process |
| CN1435516A (en) * | 2002-12-12 | 2003-08-13 | 内蒙古鄂尔多斯羊绒集团有限责任公司 | Technique for processing regenerated keratin functional fibre |
| CN101109115A (en) * | 2007-08-17 | 2008-01-23 | 东华大学 | Method of preparing protein modified polyacrylonitrile fibre |
| US8202379B1 (en) * | 2009-12-03 | 2012-06-19 | The United States Of America As Represented By The Secretary Of The Air Force | Natural fiber welding |
-
2013
- 2013-03-07 CN CN201310072694.5A patent/CN103114351B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1370856A (en) * | 2002-02-28 | 2002-09-25 | 陈福库 | Regenerated protein fiber and its production process |
| CN1435516A (en) * | 2002-12-12 | 2003-08-13 | 内蒙古鄂尔多斯羊绒集团有限责任公司 | Technique for processing regenerated keratin functional fibre |
| CN101109115A (en) * | 2007-08-17 | 2008-01-23 | 东华大学 | Method of preparing protein modified polyacrylonitrile fibre |
| US8202379B1 (en) * | 2009-12-03 | 2012-06-19 | The United States Of America As Represented By The Secretary Of The Air Force | Natural fiber welding |
Non-Patent Citations (8)
| Title |
|---|
| 丝素在离子液体中的溶解及再生丝素纤维的结构;张慧慧 等;《高分子材料科学与工程》;20110715;第27卷(第7期);66-68，72 * |
| 从丝素水溶液中再生的丝纤维的结构与性能;解芳 等;《合成纤维工业》;20060410;第29卷(第2期);8-11 * |
| 天然蛋白质材料在离子液体中的溶解与再生;谢桂军 等;《丝绸》;20080515(第05期);49-52 * |
| 张慧慧 等.丝素在离子液体中的溶解及再生丝素纤维的结构.《高分子材料科学与工程》.2011,第27卷(第7期),66-68，72. |
| 离子液体在纺织中的应用;袁久刚 等;《印染》;20080401(第7期);44-47 * |
| 袁久刚 等.离子液体在纺织中的应用.《印染》.2008,(第7期),44-47. |
| 解芳 等.从丝素水溶液中再生的丝纤维的结构与性能.《合成纤维工业》.2006,第29卷(第2期),8-11. |
| 谢桂军 等.天然蛋白质材料在离子液体中的溶解与再生.《丝绸》.2008,(第05期),49-52. |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10011931B2 (en) | 2014-10-06 | 2018-07-03 | Natural Fiber Welding, Inc. | Methods, processes, and apparatuses for producing dyed and welded substrates |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103114351A (en) | 2013-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103114351B (en) | Preparation method and dry-wet spinning method of regenerated protein chitosan blended solution | |
| CN102851777B (en) | Preparation method of fibroin blending regenerated cellulose fiber | |
| CN104997206B (en) | A kind of bamboo fiber garment fabric with bacteriostasis | |
| KR102302656B1 (en) | Liquid-impregnated nonwoven fabric which contains zinc oxide-containing cellulose fibers | |
| CN107385678A (en) | A kind of alginate fibre non-woven cloth and its preparation and application | |
| CN105821518B (en) | A kind of preparation method of pupa albumen/lotus cellulose composite fiber | |
| CN104005114B (en) | A kind of preparation method of wool keratin regenerated celulose fibre | |
| CN103102694A (en) | Method for preparation and wet spinning of regenerative keratin and silk-fibroin blended solution | |
| CN108411402A (en) | A kind of garment material based on one-D nano zinc oxide polyester antibacterial plastic concentrate | |
| CN109267163A (en) | A kind of lavender cellulose fibre and preparation method thereof | |
| CN102260933B (en) | Milk protein blending regenerating cellulose fiber, and preparation process and application thereof | |
| CN103669014A (en) | Bangni fiber and functional fiber prepared therefrom | |
| CN112553709A (en) | ES macrobio fiber containing wormwood active ingredient | |
| CN105457095A (en) | Keratin/silk fibroin composite dense membrane and preparing method thereof | |
| CN106702572A (en) | Anion containing bamboo carbon fiber quilt with antibacterial and deodorizing functions and preparation method of bamboo carbon fiber quilt | |
| CN102505170B (en) | Method for preparing silk protein composite cellulose fibers | |
| CN109056093A (en) | A kind of rosemary cellulose fibre and preparation method thereof | |
| KR102356631B1 (en) | The mask pack sheet | |
| TWI632261B (en) | Method for preparing bamboo cellulose fiber with natural antibacterial, deodorizing and negative ion functions | |
| CN105369389B (en) | Collagen fiber and its production process | |
| CN101503834B (en) | Collagen - Na-MMT complex fiber, and spinning technological process thereof | |
| CN105887236A (en) | Artificial wig fibers containing peacock feather and having heat accumulation effect | |
| CN109235038A (en) | A kind of preparation method of antibacterial facial mask fabric | |
| CN106012072A (en) | Functional cellulosic fiber with silk and linen characteristics and preparation method thereof | |
| CN105442075A (en) | Procyanidine cellulosic fiber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140514 Termination date: 20170307 |