CN101654862A - Preparation method of waterborne nano slurry - Google Patents
Preparation method of waterborne nano slurry Download PDFInfo
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- CN101654862A CN101654862A CN200910034332A CN200910034332A CN101654862A CN 101654862 A CN101654862 A CN 101654862A CN 200910034332 A CN200910034332 A CN 200910034332A CN 200910034332 A CN200910034332 A CN 200910034332A CN 101654862 A CN101654862 A CN 101654862A
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- 239000002002 slurry Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 22
- 238000000498 ball milling Methods 0.000 claims abstract description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000077 silane Inorganic materials 0.000 claims abstract description 10
- 229920005862 polyol Polymers 0.000 claims abstract description 6
- 150000003077 polyols Chemical class 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 230000003750 conditioning effect Effects 0.000 claims description 4
- KXZLHMICGMACLR-UHFFFAOYSA-N 2-(hydroxymethyl)-2-pentylpropane-1,3-diol Chemical compound CCCCCC(CO)(CO)CO KXZLHMICGMACLR-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 239000004744 fabric Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 239000004753 textile Substances 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 238000010790 dilution Methods 0.000 abstract description 3
- 239000012895 dilution Substances 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 238000007730 finishing process Methods 0.000 abstract 1
- 239000011858 nanopowder Substances 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 239000007822 coupling agent Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 238000003921 particle size analysis Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a preparation method of waterborne nano slurry. The method takes polyol as bridge group to firstly modify the surface of the nano particle, increases hydroxyl groups on the surface of the nano particle, improves the dispersity of the nano particle in water medium, and then adopts ball milling technology in the water medium to implement modification of silane coupling agentto directly prepare dispersed and stable waterborne nano concentrated slurry with the concentration of 80-100g/L. The slurry after dilution can be directly used for after finishing process of textiles, thereby endowing the textiles with firm nano function. The preparation method solves the dispersion problem and the binding problem with fabric of nano powder in textile field application at present, thereby expanding the application of nano materials in textile field.
Description
Technical field
The present invention relates to the preparation method that a kind of water nano concentrates slurry, belong to the function nano field of material preparation.
Background technology
Nano-oxide is one of more nano inorganic functional material of research at present, and it has very strong photocatalysis, antibiotic property and ultraviolet screener performance, is widely used in fields such as sun care preparations, fabric, coating, plastics, rubber, wastewater treatment.But the nanoparticle specific area is big, and the surface energy height is in thermodynamic (al) non-steady state, very easily reunited by the effect of Van der Waals force, with having a strong impact on the application and the performance of nano material, promotes the use of thereby limited it.As everyone knows, the dispersion of nano material usually be unable to do without chemical modification, promptly by coming the decorated nanometer particle surface with the reactive organic matter of particle surface group generation chemical action, strengthen the dispersion of nano particle in medium, usual way has three kinds: coupling agent method, esterification reaction method and polymer overmold method.Wherein, the coupling agent method is the most effective for the inorganic nanoparticles that hydroxyl is contained on the surface, and silane coupler be study the earliest, one of most widely used coupling agent, obtaining significant effect aspect nano zine oxide, silica, the titanium oxide modification.At present, many researchers adopt silane coupler that inorganic material is carried out organic surface modifying in organic solvent.As in document [WileyInterscience, 2008,102], a kind of method that adopts silane coupler silica to be carried out surface modification is disclosed; Document [Applied Surface Science, 2003,217] adopts silane coupler that titanium oxide is carried out surface modification.Carrying out surface modification in organic solvent mainly has the following disadvantages: the firstth, and in organic solvent such as toluene, acetone or alcohol, adopt silane coupler that inorganic material is carried out organic surface modifying, its cost height, pollute big, be not easy to suitability for industrialized production, and because inorganic material surface is polarity, in organic solvent, be difficult to disperse, in fact the organic surface modifying agent mostly react or the aggregate attached to nano particle on, have a strong impact on modified effect; The secondth, because the adsorbed hydroxyl instability of inorganic particulate so modified effect is not very good, is unfavorable for long-time storage; The 3rd is that nanoparticle surface after the modification is a hydrophobicity, is not suitable for disperseing in water, and field of textiles is very limited on using using especially.Therefore it is significant to explore simpler, more effective nano material dispersion technology.
Summary of the invention
In order to overcome the existing deficiency of background technology, the object of the present invention is to provide a kind ofly to have high dispersion stability and have the preparation method of waterborne nano slurry of good binding with fabric.
The technical scheme that realizes the foregoing invention purpose provides a kind of preparation method of waterborne nano slurry, and its step comprises:
(1) nanoparticle is washed in organic solvent under the ultrasonic wave effect, after filtration, oven dry back removes its surface impurity; Described organic solvent is ethanol, acetone or chloroform;
(2) nanoparticle was mixed by mass ratio with polyol in 1: 1～10: 1, ball-milling treatment is 0.5～2 hour in ball mill, obtains the nanometer slurry that nano-particle surface fully activates;
(3) silane coupler is dissolved in the ethanol, is prepared into mass concentration and is 0.5～5% solution, join in the above-mentioned nanometer slurry, with weak acid or weak base is pH value conditioning agent, regulating the pH value is 3～10, and ball-milling treatment is 0.5～3 hour again, obtains a kind of waterborne nano slurry.
Described nanoparticle is the solid-oxide of metal or nonmetalloid, and granularity is 10～100nm.
Described polyol is glycerol, Trimethylolhexane, trimethylolpropane, pentaerythrite, diethanol amine or triethanolamine; Described weak acid or weak base pH value conditioning agent are a kind of in acetate, sodium acetate, sodium carbonate, the sodium bicarbonate, or their mixture.
The present invention is directed to the available technology adopting silane coupler to the existing deficiency of nanometer particle-modified processing, with the polyol is abutment, nano grain surface is modified in advance, increase the oh group of nanoparticle surface, improve its dispersiveness in aqueous medium, it is silane coupler modified to adopt ball-milling technology to implement in aqueous medium again, and the water nano that can directly prepare stably dispersing concentrates slurry.With the titanium oxide is example, and its reaction mechanism is shown below:
Compared with prior art, outstanding advantage of the present invention is:
1. the decentralized medium of the concentrated slurry of nanometer is water, and is pollution-free, is particularly suitable for the application in the field of textiles.
The nanometer thickened pulp have high dispersion stability and with the high associativity of fabric, need not to use other binder can firm attachment on fabric, after dilution, can directly use.
3. the concentrated slurry of nanometer and other auxiliary agents have compatibility preferably, can be used.
Description of drawings
Fig. 1 is the transmission electron microscope picture of the prepared waterborne nano slurry of the embodiment of the invention 1;
Fig. 2 is the laser particle size analysis figure of the prepared waterborne nano slurry of the embodiment of the invention 1;
Fig. 3 is the sem photograph that adopts after diluted waterborne nano slurry is handled fabric.
The specific embodiment
Below in conjunction with drawings and Examples the present invention is further described.
Present embodiment technical scheme concrete steps are as follows:
With the 15g nano-TiO
2Particulate washs in alcohol solvent under the ultrasonic wave effect, filters, and oven dry is to remove nano-particle surface impurity; Then with the nano-TiO after the 10g washing
2Being dispersed in 100mL contains in the water of 2g triethanolamine, ball milling 0.5h in XQM-2L type planetary ball mill, under high-speed stirred, add the ethanolic solution that contains 2% coupling agent KH-560 then, regulate the pH value 9～10 with sodium bicarbonate, continue ball milling 0.5h and promptly get the water nano thickened pulp that the nanometer titanium dioxide Ti content is 100g/L.
The 5g COTTON FABRIC is washed in alkaline soap lye before processing in advance to remove surface impurity, get a certain amount of above-mentioned titanium dioxide water nanometer thickened pulp, softener, water etc. then and be mixed with the fabric finishing liquor that contains titanium dioxide 10g/L, adopt the textile finishing common process promptly roll-dry by the fire-bake the PROCESS FOR TREATMENT fabric, promptly through padding processing, the control liquid carrying rate is 90%, and the fabric that pads after the processing passes through 2min again, 90 ℃ of preliminary dryings and 2min, 140 ℃ bake processing, promptly get the nano functional fabric after soaping.
Referring to accompanying drawing 1, the transmission electron microscope picture of the nanometer thickened pulp that makes by the described processing method of present embodiment.By the transmission electron microscope image as can be known, be the high degree of dispersion state in the nanometer thickened pulp, particulate is evenly to exist with the single particle form basically, and a spot of aggregate structure is more open, and local particle alignment becomes the strand shape.
Referring to accompanying drawing 2, the laser particle size analysis figure of the nanometer thickened pulp that makes by the described processing method of present embodiment.By grain size analysis as can be known, the nano particle diameter narrowly distributing in the nanometer thickened pulp has only a peak, and average grain diameter is 61.25nm.
Above-mentioned nanometer is concentrated slurry dilution back fabric is handled, referring to accompanying drawing 3, it is the sem photograph of this fabric.Can see that by Fig. 3 fabric face presents even and tiny nano particle, the size with transmission electron microscope picture in consistent.
Embodiment 2
10g nano-ZnO particulate is washed in acetone solvent under the ultrasonic wave effect, filter, oven dry is to remove nano-particle surface impurity; Then the nano-ZnO after the 7g washing being dispersed in 100mL contains in the water of 1g Trimethylolhexane, ball milling 0.5h in XQM-2L type planetary ball mill, under high-speed stirred, add the ethanolic solution that contains 2% coupling agent KH-550 then, regulate the pH value 8～9 with sodium carbonate and sodium bicarbonate, continue ball milling 0.5h and promptly get the water nano thickened pulp that nano-ZnO content is 70g/L.
Embodiment 3
With 10g nanometer SiO
2Particulate washs in alcohol solvent under the ultrasonic wave effect, filters, and oven dry is to remove nano-particle surface impurity; Then with the nanometer SiO after the 8g washing
2Being dispersed in 100mL contains in the water of 2.5g glycerol, ball milling 0.5h in XQM-2L type planetary ball mill, under high-speed stirred, add the ethanolic solution that contains 2.5% coupling agent KH-602 then, regulate the pH value 4～5, continue ball milling 0.5h and promptly get nanometer SiO with acetate and sodium acetate
2Content is the water nano thickened pulp of 80g/L.
Claims (4)
1. preparation method of waterborne nano slurry is characterized in that step comprises:
(1) nanoparticle is washed in organic solvent under the ultrasonic wave effect, after filtration, oven dry back removes its surface impurity; Described organic solvent is ethanol, acetone or chloroform;
(2) nanoparticle was mixed by mass ratio with polyol in 1: 1～10: 1, ball-milling treatment is 0.5～2 hour in ball mill, obtains the nanometer slurry that nano-particle surface fully activates;
(3) silane coupler is dissolved in the ethanol, is prepared into mass concentration and is 0.5～5% solution, join in the above-mentioned nanometer slurry, with weak acid or weak base is pH value conditioning agent, regulating the pH value is 3～10, and ball-milling treatment is 0.5～3 hour again, obtains a kind of waterborne nano slurry.
2. a kind of preparation method of waterborne nano slurry according to claim 1 is characterized in that: described nanoparticle is the solid-oxide of metal or nonmetalloid, and granularity is 10～100nm.
3. a kind of preparation method of waterborne nano slurry according to claim 1 is characterized in that: described polyol is glycerol, Trimethylolhexane, trimethylolpropane, pentaerythrite, diethanol amine or triethanolamine.
4. a kind of preparation method of waterborne nano slurry according to claim 1 is characterized in that: described weak acid or weak base pH value conditioning agent are acetate, sodium acetate, sodium carbonate, sodium bicarbonate or their mixture.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100343320A CN101654862B (en) | 2009-08-24 | 2009-08-24 | Preparation method of waterborne nano slurry |
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| CN2009100343320A CN101654862B (en) | 2009-08-24 | 2009-08-24 | Preparation method of waterborne nano slurry |
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| CN101654862B CN101654862B (en) | 2012-04-04 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219534A (en) * | 2011-04-27 | 2011-10-19 | 中国地质大学（武汉） | Method for preparing nano oxide slurry |
| CN102628213A (en) * | 2012-04-09 | 2012-08-08 | 徐雨来 | Method for dispersing anatase nano titanium dioxide on surface of textile fabric |
| CN102675921A (en) * | 2012-05-11 | 2012-09-19 | 上虞市精亮工贸有限公司 | Water-phase thinning modification method of halogen-free flame retardant |
| CN102733174A (en) * | 2011-03-31 | 2012-10-17 | 香港理工大学 | Method for finishing fabrics |
| CN102925119A (en) * | 2012-11-01 | 2013-02-13 | 上海第二工业大学 | Cooling fluid for cooling power cell and preparation method of cooling fluid |
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| CN100369818C (en) * | 2005-06-09 | 2008-02-20 | 江苏大学 | Process for preparing rutile-type nano TiO2 by meta titanic acid |
| US8106229B2 (en) * | 2006-05-30 | 2012-01-31 | Nalco Company | Organically modifid silica and use thereof |
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| CN102733174B (en) * | 2011-03-31 | 2015-02-25 | 香港理工大学 | Method for finishing fabrics |
| CN102733174A (en) * | 2011-03-31 | 2012-10-17 | 香港理工大学 | Method for finishing fabrics |
| CN102219534A (en) * | 2011-04-27 | 2011-10-19 | 中国地质大学（武汉） | Method for preparing nano oxide slurry |
| CN102628213B (en) * | 2012-04-09 | 2013-12-25 | 瑞阜景丰(北京)科技有限公司 | Method for dispersing anatase nano titanium dioxide on surface of textile fabric |
| CN102628213A (en) * | 2012-04-09 | 2012-08-08 | 徐雨来 | Method for dispersing anatase nano titanium dioxide on surface of textile fabric |
| CN102675921A (en) * | 2012-05-11 | 2012-09-19 | 上虞市精亮工贸有限公司 | Water-phase thinning modification method of halogen-free flame retardant |
| CN102925119A (en) * | 2012-11-01 | 2013-02-13 | 上海第二工业大学 | Cooling fluid for cooling power cell and preparation method of cooling fluid |
| CN102925119B (en) * | 2012-11-01 | 2015-10-28 | 上海二工大资产经营有限公司 | A kind of cooling fluid for power cell cooling and preparation method thereof |
| CN106186716A (en) * | 2016-07-15 | 2016-12-07 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of hydrophobic antimicrobial coating |
| CN106186716B (en) * | 2016-07-15 | 2019-01-01 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of hydrophobic antimicrobial coating |
| CN109468690A (en) * | 2018-10-17 | 2019-03-15 | 李涛 | A kind of antibacterial aloe fabric lining and preparation method thereof |
| CN109608890A (en) * | 2018-12-13 | 2019-04-12 | 西南科技大学 | A kind of preparation method of silicon rubber radiation protection nanocomposite |
| CN110356059A (en) * | 2019-08-20 | 2019-10-22 | 浙江仁派服饰有限公司 | A kind of antibacterial ultraviolet-resistannanofiber line fabric |
| CN110438795A (en) * | 2019-08-20 | 2019-11-12 | 浙江新派服饰有限公司 | A kind of radiation protection antibacterial fabric |
| CN110356059B (en) * | 2019-08-20 | 2021-06-08 | 浙江仁派服饰有限公司 | Antibacterial ultraviolet-proof fabric |
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| CN101654862B (en) | 2012-04-04 |
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