CN104594025B - Method for preparing zinc-oxide-modified ultraviolet-resistant silk - Google Patents
Method for preparing zinc-oxide-modified ultraviolet-resistant silk Download PDFInfo
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- CN104594025B CN104594025B CN201510055927.XA CN201510055927A CN104594025B CN 104594025 B CN104594025 B CN 104594025B CN 201510055927 A CN201510055927 A CN 201510055927A CN 104594025 B CN104594025 B CN 104594025B
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- silkworm silk
- zinc oxide
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Abstract
The invention discloses a method for preparing zinc-oxide-modified ultraviolet-resistant silk. According to the method, a zinc oxide film layer covers the surface of the silk by adopting an in situ synthesis method. The method specifically comprises the following steps: degumming the silk and performing surface activation; respectively dipping the silk in a zinc precursor solution and a reaction solvent; and finally, adding the silk into a heated and humidified steam, standing, taking out the silk, washing, and drying, thereby obtaining the zinc-oxide-modified ultraviolet-resistant silk. The preparation method is simple, convenient, high in efficiency and low in cost, solves the problem that zinc oxide is difficult to disperse and is suitable for large-scale production. The zinc oxide film layer covers the surface of the silk modified by the method, and the silk has high ultraviolet resistance, and improved mechanical property.
Description
Technical field：
The invention belongs to silk product technical field, particularly to a kind of anti-purple of modified zinc oxide
The preparation method of outer silkworm silk.
Background technology：
Silkworm silk is thread azelon, and containing 18 kinds of aminoacid, these aminoacid can be with
Ultraviolet produces photochemical reaction, but very strong photochemical reaction can make silk protein molecular backbone
Peptide bond ruptures, and leads to the mechanical strength of silkworm silk to decline and yellowing, the usability of impact silkworm silk,
Thus while silkworm silk itself has certain protective action to ultraviolet, but the protection of itself
Effect is very faint, needs to carry out anti-ultraviolet finishing.
The uvioresistant material of conventional textile mainly divides organic uv absorbers and inorganic UV
Screener, organic uv absorbers are that the mode that the energy of ultraviolet is converted into light and heat discharges
Go out, inorganic UV screener is by ultraviolet reflection or scattering.Organic uv absorbers are main
For salicylate system, benzophenone series, enumerate BTA system and triazine system etc., the light of such material
Less stable, service life is short, can make fabric variable color, and being irritating to the skin property etc. is inorganic
Ultraviolet light screener is mainly the microgranule such as zinc oxide, titanium dioxide, the full wave shielding to UVB
Good, and good light stability, arrange in colourless, fabric color is no affected, and environmentally friendly
Deng.
The anti-ultraviolet finishing of silkworm silk typically adopts organic uv absorbers, but sends out with economic
Exhibition, the raising that environment and quality of the life are required, inorganic UV screener increasingly receives publicity,
The developing direction of the high-performance ultraviolet light screener wherein with nanotechnology for supporting is particularly wide.
Chinese patent CN 101187164B (publication date 2008.07.23) discloses a kind of crease-resistant
Antibacterial uvioresistant composite function silk fabric, is that silk fabric is padded in nano titanium oxide is molten
Obtain in the multifunction finishing agent that glue is mixed with Fibroin Hydrolysis liquid.Chinese patent CN
Functionalized nano shitosan and nanometer disclosed in 102677465B (publication date 2012.11.14)
Titania modified tussah silk textiles, tussah silk woven fabric or non-woven fabrics are immersed shitosan
In titania solution, obtain the tussah silk textiles of modification.Chinese patent CN 103572585A
(publication date 2014.02.12) discloses a kind of titania modified silkworm silk, is to be with titanate esters
Reactant and petroleum ether are that solvent generates fine and close titanium dioxide in silkworm silk surface in situ.Receive at present
The application on silk fabric is relatively broad as anti ultraviolet agent for rice titanium dioxide, but nanometer
The application of zinc oxide is less.
Content of the invention：
It is an object of the invention to provide a kind of preparation method of the uvioresistant silkworm silk of modified zinc oxide,
It is precursor solution and the reaction solution of zinc, warp after the surface active of silkworm silk, will to be impregnated in respectively
Reaction in-situ silkworm silk surface formed zinc hydroxide thin film, after obtain oxygen through high temperature steam treatment
Change the silkworm silk of zinc modification.This preparation method is simple, low cost, it is suitably applied large-scale production
In, the silkworm silk of preparation possesses higher ultraviolet-resistent property and mechanical performance.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of the uvioresistant silkworm silk of modified zinc oxide is it is characterised in that the method
Comprise the following steps：
(1) silkworm silk is gone after the removal of impurity, with the sodium bicarbonate solution degumming 60min of 0.05g/L,
It is washed with deionized clean, 40 DEG C of silkworm silks being dried to obtain degumming；
(2) after the surface activation process of the silkworm silk of the degumming obtaining step (1), with bath raio
1:35-50s in 40 precursor solutions that impregnated in zinc, then with bath raio 1:30 be soaked in reaction molten
In agent, react 5-10min at 60-70 DEG C, take out the silkworm silk obtaining zinc hydroxide covering；
(3) silkworm silk covering the zinc hydroxide that step (2) obtains is placed in the steaming of warming and humidifying
Stand in vapour, take out washing and dry, obtain the silkworm silk of modified zinc oxide.
Preferred as technique scheme, the silkworm silk described in step (1) is mulberry silk, toothed oak
Silkworm silk or regenerated fibroin fiber.
Preferred as technique scheme, the surface activation process described in step (1) is etc.
Gas ions process or soak strong oxidizer.
Preferred as technique scheme, described oxidant is potassium permanganate solution.
Preferred as technique scheme, the precursor solution of the zinc described in step (2) is
Mass fraction is the zinc nitrate hexahydrate aqueous solution of 20-30%.
Preferred as technique scheme, the reaction dissolvent described in step (2) divides for quality
The ammonia for 40-50% for the number.
Preferred as technique scheme, the steam of the warming and humidifying described in step (3) is
Ammonia and the mixed vapour of water, ammonia is 2 with the volume ratio of water:1, the temperature of steam is
125-130 DEG C, humidity is 20%.
Preferred as technique scheme, the time of the standing described in step (3) is
15-20min.
Preferred as technique scheme, the number of times of the washing described in step (3) is 2-3
Secondary.
Preferred as technique scheme, the temperature of the drying described in step (3) is 30 DEG C.
Compared with prior art, the present invention has advantages below：
(1) present invention adopts silkworm silk surface active to combine in-situ synthesis and gives birth on the surface of silkworm silk
Become one layer of zinc-oxide film, it is to avoid the difficult scattered problem of zinc oxide, preparation method is simple, cost
Low it is adaptable to large-scale production.
(2) preparation method that the present invention adopts is not using simple dipping maneuver, but adopts
Combine the means of moist steam with of short duration multiple dipping, in the atmosphere of wet-hot steam, promote oxygen
Change the synthesis of zinc, the generation nano granular of zinc oxide that the method can be slowly gentle, the table to silkworm silk
Face almost not damaged.
(3) the modified silkworm silk of this method uniformly covers the thick zinc oxide of one layer of 200nm
Thin film, except giving the preferable uvioresistant performance of silkworm silk, goes back bacteriostasis antibiosis deodorization, and improves silkworm
The mechanical performance of silk.
Specific embodiment：
In order to deepen the understanding of the present invention, with reference to embodiment, the present invention is made detailed further
State, this embodiment is only used for explaining the present invention, does not constitute limiting the scope of the present invention.
Embodiment 1：
(1) mulberry silk is gone after the removal of impurity, with the sodium bicarbonate solution degumming of 0.05g/L
60min, is washed with deionized clean, 40 DEG C of silkworm silks being dried to obtain degumming.
(2) by after plasma-treated for the silkworm silk of degumming surface active, with bath raio 1:40 leachings
Stain 50s in 20% zinc nitrate hexahydrate aqueous solution, then with bath raio 1:30 are soaked in 40%
In ammonia, react 10min at 60 DEG C, take out the silkworm silk obtaining zinc hydroxide covering.
(3) silkworm silk that zinc hydroxide covers is placed in, volume ratio is 2:1 ammonia is mixed with water
Close in steam, be under 20% in humidity, 125 DEG C of standing 20min, taking-up washing 2 times, 30 DEG C
Dry the silkworm silk obtaining modified zinc oxide.
Embodiment 2：
(1) tussah silk is gone after the removal of impurity, with the sodium bicarbonate solution degumming of 0.05g/L
60min, is washed with deionized clean, 40 DEG C of silkworm silks being dried to obtain degumming.
(2) the Silk Soaking potassium permanganate solution of degumming is processed after surface active, with bath raio
1:40 impregnated in 50s in 20% zinc nitrate hexahydrate aqueous solution, then with bath raio 1:30 immersions
In 40% ammonia, react 5min at 70 DEG C, take out the silkworm silk obtaining zinc hydroxide covering.
(3) silkworm silk that zinc hydroxide covers being placed in volume ratio is 2:1 ammonia is mixed with water
In steam, it is under 20% in humidity, 130 DEG C of standing 15min, take out washing 3 times, 30 DEG C of bakings
The dry silkworm silk obtaining modified zinc oxide.
Embodiment 3：
(1) regenerated fibroin fiber is gone after the removal of impurity, with the sodium bicarbonate of 0.05g/L
Solution degumming 60min, is washed with deionized clean, 40 DEG C of silkworm silks being dried to obtain degumming.
(2) by after plasma-treated for the silkworm silk of degumming surface active, with bath raio 1:40 leachings
Stain 40s in 25% zinc nitrate hexahydrate aqueous solution, then with bath raio 1:30 are soaked in 45%
In ammonia, react 7min at 65 DEG C, take out the silkworm silk obtaining zinc hydroxide covering.
(3) silkworm silk that zinc hydroxide covers is placed in, volume ratio is 2:1 ammonia is mixed with water
Close in steam, be under 20% in humidity, 127 DEG C of standing 17min, taking-up washing 3 times, 30 DEG C
Dry the silkworm silk obtaining modified zinc oxide.
Embodiment 4：
(1) mulberry silk is gone after the removal of impurity, with the sodium bicarbonate solution degumming of 0.05g/L
60min, is washed with deionized clean, 40 DEG C of silkworm silks being dried to obtain degumming.
(2) the Silk Soaking potassium permanganate solution of degumming is processed after surface active, with bath raio
1:40 impregnated in 48s in 29% zinc nitrate hexahydrate aqueous solution, then with bath raio 1:30 immersions
In 42% ammonia, react 10min at 67 DEG C, take out the silkworm silk obtaining zinc hydroxide covering.
(3) silkworm silk that zinc hydroxide covers is placed in, volume ratio is 2:1 ammonia is mixed with water
Close in steam, be under 20% in humidity, 126 DEG C of standing 16min, taking-up washing 3 times, 30 DEG C
Dry the silkworm silk obtaining modified zinc oxide.
Embodiment 5：
(1) regenerated fibroin fiber is gone after the removal of impurity, with the sodium bicarbonate of 0.05g/L
Solution degumming 60min, is washed with deionized clean, 40 DEG C of silkworm silks being dried to obtain degumming.
(2) by after plasma-treated for the silkworm silk of degumming surface active, with bath raio 1:40 leachings
Stain 50s in 30% zinc nitrate hexahydrate aqueous solution, then with bath raio 1:30 are soaked in 50%
In ammonia, react 10min at 70 DEG C, take out the silkworm silk obtaining zinc hydroxide covering.
(3) silkworm silk that zinc hydroxide covers is placed in, volume ratio is 2:1 ammonia is mixed with water
Close in steam, be under 20% in humidity, 130 DEG C of standing 20min, taking-up washing 3 times, 30 DEG C
Dry the silkworm silk obtaining modified zinc oxide.
Embodiment 6：
(1) tussah silk is gone after the removal of impurity, with the sodium bicarbonate solution degumming of 0.05g/L
60min, is washed with deionized clean, 40 DEG C of silkworm silks being dried to obtain degumming.
(2) the Silk Soaking potassium permanganate solution of degumming is processed after surface active, with bath raio
1:40 impregnated in 35s in 20% zinc nitrate hexahydrate aqueous solution, then with bath raio 1:30 immersions
In the ammonia of 40-50%, react 5min at 60 DEG C, take out the silkworm obtaining zinc hydroxide covering
Silk.
(3) silkworm silk that zinc hydroxide covers is placed in, volume ratio is 2:1 ammonia is mixed with water
Close in steam, be under 20% in humidity, 125 DEG C of standing 15min, taking-up washing 3 times, 30 DEG C
Dry the silkworm silk obtaining modified zinc oxide.
By embodiment 1-6 preparation modified zinc oxide uvioresistant silk fabric with untreated
Silk fabric is compared, the grammes per square metre of silk fabric, ultraviolet-resistent property, antibiotic property and mechanical properties results
As shown in the table：
From above-mentioned data, the uvioresistant silk fabric of modified zinc oxide of this method preparation
Anti-ultraviolet property is excellent, and the antibiotic property of fabric and mechanical strength have lifting.
Claims (9)
1. a kind of preparation method of the uvioresistant silkworm silk of modified zinc oxide is it is characterised in that be somebody's turn to do
Method comprises the following steps：
(1) silkworm silk is gone after the removal of impurity, with the sodium bicarbonate solution degumming 60min of 0.05g/L,
It is washed with deionized clean, 40 DEG C of silkworm silks being dried to obtain degumming；
(2) after the surface activation process of the silkworm silk of the degumming obtaining step (1), with bath raio
1:35-50s in 40 precursor solutions that impregnated in zinc, then with bath raio 1:30 be soaked in reaction molten
In agent, react 5-10min at 60-70 DEG C, take out the silkworm silk obtaining zinc hydroxide covering；
(3) silkworm silk covering the zinc hydroxide that step (2) obtains is placed in the steaming of warming and humidifying
Stand in vapour, take out washing and dry, obtain the silkworm silk of modified zinc oxide；
The steam of the warming and humidifying described in step (3) is the mixed vapour of ammonia and water, ammonia
Volume ratio with water is 2:1, the temperature of steam is 125-130 DEG C, and humidity is 20%.
2. the preparation side of the uvioresistant silkworm silk of a kind of modified zinc oxide as claimed in claim 1
Method is it is characterised in that the silkworm silk described in step (1) is mulberry silk, tussah silk or regeneration
Fibroin fiber.
3. the preparation side of the uvioresistant silkworm silk of a kind of modified zinc oxide as claimed in claim 1
Method it is characterised in that surface activation process described in step (1) be corona treatment or
Person soaks strong oxidizer.
4. the preparation side of the uvioresistant silkworm silk of a kind of modified zinc oxide as claimed in claim 3
Method is it is characterised in that described strong oxidizer is potassium permanganate solution.
5. the preparation side of the uvioresistant silkworm silk of a kind of modified zinc oxide as claimed in claim 1
Method is it is characterised in that the precursor solution of zinc described in step (2) is 20-30% for mass fraction
Zinc nitrate hexahydrate aqueous solution.
6. the preparation side of the uvioresistant silkworm silk of a kind of modified zinc oxide as claimed in claim 1
Method is it is characterised in that the reaction dissolvent described in step (2) is 40-50%'s for mass fraction
Ammonia.
7. the preparation side of the uvioresistant silkworm silk of a kind of modified zinc oxide as claimed in claim 1
Method is it is characterised in that the time of standing described in step (3) is 15-20min.
8. the preparation side of the uvioresistant silkworm silk of a kind of modified zinc oxide as claimed in claim 1
Method is it is characterised in that the number of times of washing described in step (3) is 2-3 time.
9. the preparation side of the uvioresistant silkworm silk of a kind of modified zinc oxide as claimed in claim 1
Method is it is characterised in that the temperature of drying described in step (3) is 30 DEG C.
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| CN201510055927.XA CN104594025B (en) | 2015-02-03 | 2015-02-03 | Method for preparing zinc-oxide-modified ultraviolet-resistant silk |
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| CN201510055927.XA CN104594025B (en) | 2015-02-03 | 2015-02-03 | Method for preparing zinc-oxide-modified ultraviolet-resistant silk |
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| CN104594025B true CN104594025B (en) | 2017-02-15 |
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| CN105803805A (en) * | 2016-04-21 | 2016-07-27 | 安徽皖翎羽绒制品有限公司 | Treatment method of anti-bacterial and anti-UV (Ultraviolet) down feather |
| CN106149352B (en) * | 2016-08-09 | 2018-05-18 | 东华大学 | A kind of preparation method of nano zinc oxide modified cotton fabric |
| CN106835673A (en) * | 2017-03-27 | 2017-06-13 | 广西科技大学 | A kind of UV resistance zinc oxide silk composite fiber and preparation method thereof |
| CN107287877A (en) * | 2017-06-28 | 2017-10-24 | 合肥市聚丰制丝有限责任公司 | It is a kind of to improve the method for silk performance |
| CN107419519A (en) * | 2017-07-16 | 2017-12-01 | 长沙善道新材料科技有限公司 | A kind of preparation method of the affine uvioresistant anti bacteria natural silk fiber of zinc oxide |
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| CN107630351A (en) * | 2017-09-29 | 2018-01-26 | 安徽省创安体育用品有限公司 | A kind of preparation method of Anti-static cap cloth |
| CN109680480A (en) * | 2018-11-28 | 2019-04-26 | 湖州品创孵化器有限公司 | A kind of preparation method of health uvioresistant silk fabric |
| CN109695150A (en) * | 2018-11-28 | 2019-04-30 | 湖州品创孵化器有限公司 | A kind of preparation method of pro-skin type uvioresistant silk fabric |
| CN111136968B (en) * | 2019-08-27 | 2022-05-27 | 江苏大毛牛新材料有限公司 | Waterproof anti ultraviolet textile fabric |
| CN113832729B (en) * | 2021-09-15 | 2023-06-16 | 苏州同构科技有限公司 | Washable ultraviolet absorbent and preparation method thereof |
| CN114673006B (en) * | 2022-03-08 | 2023-09-29 | 浙江理工大学 | Antibacterial medical textile coating material based on ZnO-silk fibroin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101012621A (en) * | 2007-01-30 | 2007-08-08 | 东华大学 | Preparation method of zinc oxide nano-rod film on fibre product |
| US8277518B1 (en) * | 2011-10-11 | 2012-10-02 | The Sweet Living Group, LLC | Ecological fabric having ultraviolet radiation protection |
| CN103194885A (en) * | 2013-04-19 | 2013-07-10 | 中国民航大学 | Method for microwave synthesis of nano-ZnO assembled cotton fibers |
| CN103898735B (en) * | 2014-04-11 | 2015-09-02 | 西南大学 | Zinc oxide nano rod matrix modifies preparation method of silk and products thereof |
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Inventor after: Wang Junhong Inventor before: Chen Yonglin |
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Effective date of registration: 20161114 Address after: 518000, Guangdong, Longhua province Shenzhen New District Guanlan street, Tong Hang Kong community, A8 Industrial Zone, the first floor of the southern tip of the first floor, two, three Applicant after: Shenzhen warm home textile Co., Ltd. Address before: 313026 Zhejiang Province, Huzhou city Nanxun District Hefu town re trillion Industrial Park Applicant before: Huzhou Xinchuang Silk Co., Ltd. |
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