CN103820992B - A kind of preparation method of silver golden regenerated celulose fibre/regenerated celulose fibre fabric - Google Patents
A kind of preparation method of silver golden regenerated celulose fibre/regenerated celulose fibre fabric Download PDFInfo
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- CN103820992B CN103820992B CN201410081956.9A CN201410081956A CN103820992B CN 103820992 B CN103820992 B CN 103820992B CN 201410081956 A CN201410081956 A CN 201410081956A CN 103820992 B CN103820992 B CN 103820992B
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- regenerated celulose
- celulose fibre
- silver
- regenerated
- golden
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- 239000000835 fiber Substances 0.000 title claims abstract description 149
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 67
- 239000004332 silver Substances 0.000 title claims abstract description 67
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004744 fabric Substances 0.000 title abstract description 56
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract description 5
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 4
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 4
- 241001330002 Bambuseae Species 0.000 claims abstract description 4
- 229920000742 Cotton Polymers 0.000 claims abstract description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 4
- 229920001131 Pulp (paper) Polymers 0.000 claims abstract description 4
- 239000011425 bamboo Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000661 sodium alginate Substances 0.000 claims abstract description 3
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 3
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 12
- 230000005670 electromagnetic radiation Effects 0.000 claims description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims description 10
- 159000000000 sodium salts Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 238000007730 finishing process Methods 0.000 claims description 8
- 238000002161 passivation Methods 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 238000005238 degreasing Methods 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940071536 silver acetate Drugs 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- 239000006210 lotion Substances 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 14
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000007772 electroless plating Methods 0.000 abstract description 2
- 230000036541 health Effects 0.000 abstract description 2
- 229920003043 Cellulose fiber Polymers 0.000 abstract 1
- 230000001877 deodorizing effect Effects 0.000 abstract 1
- 230000005855 radiation Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 8
- 229920000297 Rayon Polymers 0.000 description 7
- 239000004753 textile Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000003093 cationic surfactant Substances 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000003378 silver Chemical class 0.000 description 6
- 239000010931 gold Substances 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 210000004243 sweat Anatomy 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000010946 fine silver Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 3
- 229920004933 Terylene® Polymers 0.000 description 3
- 229940072056 alginate Drugs 0.000 description 3
- 235000010443 alginic acid Nutrition 0.000 description 3
- 229920000615 alginic acid Polymers 0.000 description 3
- 239000000648 calcium alginate Substances 0.000 description 3
- 235000010410 calcium alginate Nutrition 0.000 description 3
- 229960002681 calcium alginate Drugs 0.000 description 3
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 239000010930 yellow gold Substances 0.000 description 3
- 229910001097 yellow gold Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000433 Lyocell Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 description 2
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 244000052769 pathogen Species 0.000 description 2
- 230000001717 pathogenic effect Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000003754 fetus Anatomy 0.000 description 1
- 229940085805 fiberall Drugs 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011536 re-plating Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000027272 reproductive process Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 238000009941 weaving Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a kind of preparation method of silver golden regenerated celulose fibre/regenerated celulose fibre fabric, with regenerated celulose fibre fiber and/or regenerated celulose fibre fabric for raw material, adopt soluble silver salt, under lewis acid catalyst effect, the golden yellow regenerated celulose fibre/regenerated celulose fibre fabric obtained by catalytic nanometer electroless plating technology.This fiber/fabric has antibacterial, deodorizing, antistatic, anti-electromagnetic radiation function, can be applicable to the fields such as military affairs, health care, household and dress ornament; The raw materials used regenerated fiber cellulose fibre of the present invention and/or regenerated celulose fibre fabric are Cotton Pulp regenerated celulose fibre, wood pulps regenerated celulose fibre, bamboo pulp regenerated celulose fibre or sodium alginate regenerated celulose fibre, and they pure is spun, blending or with other chemical fibre blended fabrics.
Description
Technical field
The present invention relates to the dyeing and finishing method of a kind of regenerated celulose fibre/regenerated celulose fibre fabric, particularly relate to a kind of preparation method of silver golden regenerated celulose fibre/regenerated celulose fibre fabric.
Background technology
Silver is the metal that in all metals, resistivity is minimum; so have high conductivity; 5000 volts of electrostatic can be resisted; there is electro-magnetic screen function; as long as a small amount of silver-colored fiber exists on clothing; to eliminate rapidly because of the electrostatic produced that rubs; product is made to have comfort without electrostatic; therefore silver-colored fiber can very fast and expeditiously electrostatic is conducted, can protect human body especially protect foetus from electromagnetic wave influence to pregnant woman from electromagnetic wave infringement and ensure that the health of staff has important health-care function near the electromagnet sources such as computer for a long time.The mechanism of argent sterilization is exactly the physiology course blocking bacterium.Under wet conditions, silver ion can make the protein coagulating inside and outside bacterial cell membrane, thus blocks breathing and the reproductive process of bacterial cell.The antibacterial ability of silver ion is very surprising, and the silver of parts per billion milligram just can purify 1 kg water.Common antibiotic can eliminate six kinds of different pathogen, and the antibiotic of argentiferous then can eliminate the pathogen of more than 650 kinds.This characteristic of silver material, before more than 2,000 years, is just widely used in medical aspect.Just because of the excellent antibacterial function of silver, silver-colored fiber has mildew-resistant odour repellent function.
Adopt American Society for Testing Materials ASTMD4935-99 standard testing, silver-colored fiber electromagnetic radiation attenuation rate >=99.9%, shielding broadband 500KHZ-6GHZ, and high-efficiency antimicrobial, antistatic.In fields such as clothes (pregnant woman fetus ELECTROMAGNETIC RADIATION SHIELDING clothes, antistatic clothes, military uniform etc.), decorative fabrics (performance clothes, curtain, automotive trim, naval vessel interior trim, curtain), its functional fibre and textiles thereof have important market value.
Silver fibre manufacture has fine silver fiber elongation method and textile fabric deposition of silver method.Fine silver fiber is not only expensive, and itself does not have absorbing sweat, the textile fiber character such as ventilative, soft, and application is restricted.Textile fabric deposition of silver method is generally obtain silvering fiber at chemical fibre (as nylon, terylene etc.) substrate surface by chemical plating or vacuum sublimation deposition, this fiber is moderate, powerful high, but chemical fibre does not have absorbing sweat, ventilating performance, and wearability is poor.Especially, no matter be fine silver fiber elongation method or textile fabric deposition of silver method, the silver-colored fiber obtained be all silver gray or silver gray to the intermediate color of black, can not get the golden fiber as gold.
Such as, silver plated fiber brand is the earliest the X-Static of U.S. Nobel Fiber Tech-nologies (Nobel's fiber scientific & technical corporation) in the world.Its original adoption be electroless plating technology, namely at nylon fiber plated surface one deck fine silver.Japan TOYOSHIMA & Co., Ltd (Feng Dao weave Co., Ltd.) developed in 1999 the silver-plated polyester fiber (silver-plated terylene) that trade mark is called μ-func.Calendar year 2001, Mitsubishi Material Company also developed silver-plated polyester fiber-AGposs fiber.
Chinese patent application 200410024079.8 discloses a kind of preparation method of silver-plated fiber fabric; it makes matrix with chemical & blended fabric or terylene non-woven fabric; under the protection of nitrogen or argon gas; adopt the silver-plated or stainless steel of ion plating method; again by traditional electroplating plastic technique at the continuous nickel plating of matrix surface, copper or silver; last re-plating one deck silver, produces the non-silver-plated fiber fabric with shielding properties taken.
The paper " preparation of Conductive Silver-Coated PET Fibers and performance " that Jiao Hongjuan etc. deliver describes the method for chemical silvering polyester staple fiber.
In above-mentioned prior art, its silver plated fiber all with the synthetic fiber such as polyester or nylon for base material, and final products are silver gray, can not get silver golden fiber, and regenerated celulose fibre/regenerated celulose fibre fabric more can not be adopted to prepare silver plated fiber.
And golden yellow fiber of the prior art generally adopts true yellow gold wire drawing or obtain by adding Gold production pigment in chemical fibre.All there is obvious defect in this two eka-golds yellow fibers, on the one hand, the former is expensive, and such as Nylstar company of the U.S. in 2011 develops a kind of 24KNylgold gold fiber, it is said skin care, beauty treatment, anti-aging effects, but every gram of price is more than 90 U.S. dollars; The latter does not shield, antibacterial effect, and owing to introducing containing the chrome yellow of toxic element Cr, the chemical pigment of medium chrome yellow, the fastness of the combination between fiber with pigment compared with " coating ", cannot be difficult to the pollution invariably existed to a certain degree, and is not suitable for home textile product use.On the other hand, adopt the golden yellow fiber prepared of true yellow gold drawing process do not have yet natural cotton fiber absorbing sweat, ventilative, comfortable wear performance, be difficult to take; By adding the golden yellow fiber that Gold production pigment obtains in chemical fibre, owing to adopting chemical fibre as base material, the discarded object after its use is difficult to degraded at nature, is unfavorable for environmental protection.
Summary of the invention
The object of the invention is, there is provided one with regenerated celulose fibre/regenerated celulose fibre fabric for base material, utilize soluble silver salt or silver complex, under the effect of catalyst, prepared by catalytic nanometer chemical plating process that added value of product is high, the regenerated celulose fibre of the silver gold of good decorating effect/regenerated celulose fibre fabric.
The technical scheme that the present invention is adopted for achieving the above object is: a kind of preparation method of silver golden regenerated celulose fibre/regenerated celulose fibre fabric, is characterized in that, comprise the following steps successively:
(1) the degreasing regenerated celulose fibre that also washing is clean and/or regenerated celulose fibre fabric are placed in Final finishing process equipment by bath raio 1: 4-100, body lotion ensures under the condition of Efficient Cycle, add soluble silver salt or silver complex, adding proportion is 1:0.01-0.10 by the weight ratio of regenerated cellulose and/or regenerated celulose fibre fabric and silver, isothermal reaction 20-100min at 10-75 DEG C;
(2) add the compound stabilizer containing ethylenediamine, tetraacethyl sodium salt, BTA, thiosemicarbazide, ammoniacal liquor five kinds of components, at 10-90 DEG C, react 30-90min; Wherein,
In above-mentioned compound stabilizer, the ratio of weight and number of ethylenediamine, tetraacethyl sodium salt, BTA, thiosemicarbazide, ammoniacal liquor five kinds of components is 1: 0.2: 0.1:0.3: 1-5;
The weight ratio of regenerated celulose fibre and/or regenerated celulose fibre fabric and above-mentioned compound stabilizer is 1: 0.01-0.10;
(3) be first 1: 0.0001-0.05 by the weight ratio of regenerated celulose fibre and/or regenerated celulose fibre fabric and lewis acid catalyst, add their solution and the 15-40min that circulates;
Be 1:0.02-0.20 by the weight ratio of regenerated celulose fibre and/or regenerated celulose fibre fabric and glucose or inferior sodium phosphate again, be added dropwise to their solution, isothermal reaction 20-70min at 35-65 DEG C;
(4) by the regenerated celulose fibre after process and/or regenerated celulose fibre fabric successively through surfactant wash, passivation, then through clear water rinsing, dehydration, oven dry and get final product.
As preferably, above-mentioned soluble silver salt is silver nitrate, silver acetate, and described silver soluble complex compound is imino-diacetic sulfonic acid complex silver.
Further preferably, above-mentioned regenerated celulose fibre is Cotton Pulp regenerated celulose fibre, wood pulps regenerated celulose fibre, bamboo pulp regenerated celulose fibre or sodium alginate regenerated celulose fibre.
Further preferably, above-mentioned lewis acid catalyst is palladium chloride, ammonium chloroplatinate, Nickel Chloride.
Further preferably, above-mentioned regenerated celulose fibre fabric is the BLENDED FABRIC of regenerated celulose fibre PURE YARN FABRIC or regenerated celulose fibre and chemical fibre.
Further preferably, the silver golden regenerated celulose fibre/regenerated celulose fibre fabric prepared by above-mentioned preparation method, is characterized in that, bacteriostasis rate >=90%, electromagnetic radiation attenuation rate >=91%.
Further preferably, the silver golden regenerated celulose fibre prepared by above-mentioned preparation method, it both may be used for pure spinning, and also may be used for other fibers with arbitrary proportion blending.
The technique effect that technique scheme is directly brought is, with regenerated celulose fibre/regenerated celulose fibre fabric for raw material, adopt soluble silver salt or silver complex, under the effect of catalyst, prepared by catalytic nanometer chemical plating process that added value of product is high, the regenerated celulose fibre of the silver gold of good decorating effect/regenerated celulose fibre fabric, there is following characteristic and advantage:
1, utilize relatively inexpensive soluble silver salt or silver complex to be raw material, obtain the product of the identical gold color of product directly adopting true yellow gold drawing process to prepare with prior art, its added value is high, good decorating effect.
2, remain the excellent easing characteristic such as absorbing sweat that regenerated celulose fibre has, ventilative, softness, anti-sensitivity, easily cleaning, not easily fluffing, balling-up preferably, and the discarded object after use can natural degradation.
3, owing to adopting catalytic nanometer chemical plating process to carry out " silver-plated ", it has the function such as antibacterial, self-cleaning, conduction, antistatic, electromagnetic radiation shielding preferably, and the excellent in durability of color.
4, the silver golden regenerated celulose fibre prepared by method of the present invention both can purely spin, also can with other fibers with arbitrary proportion blending.There is good moisture-absorbing moisture-keeping, absorbing sweat gas permeability, the features such as snugness of fit is good through the silver golden natural regeneration fiber textile made of weaving again.
Accompanying drawing explanation
Fig. 1 is silver golden regenerated celulose fibre/regenerated celulose fibre fabric X-ray diffraction spectrogram; Wherein: the common regenerated celulose fibre x-ray diffraction pattern of (a) not argentiferous; (b) golden silver-plated regenerated celulose fibre/regenerated celulose fibre fabric x-ray diffraction pattern;
Fig. 2-1 to Fig. 2-6 is the electromicroscopic photograph of silver golden regenerated celulose fibre.
Detailed description of the invention
Embodiment 1
(1) by the degreasing viscose 100Kg that also washing is clean, be placed in injecting type Final finishing process equipment by bath raio 1: 4, in batching kettle, add 1.6Kg silver nitrate, after being prepared into solution, enter the circulatory system, at 35 DEG C, react 100min.
(2) step that continues (1), be be mixed into compound stabilizer at 1: 0.2: 0.1:0.3: 1 by ratio of weight and the number of copies by ethylenediamine, tetraacethyl sodium salt, BTA, thiosemicarbazide, ammoniacal liquor five component, take after 1Kg is prepared into solution and enter the circulatory system, at 40 DEG C, react 30min.
(3) step that continues (2), takes after palladium chloride 0.01Kg is prepared into solution and enters circulatory system circulation 30min;
Take again after glucose 2Kg is prepared into solution and be added dropwise to the circulatory system, isothermal reaction 70min at 45 DEG C.
(4) step that continues (3), regenerated fiber after process or its fabric are first washed, again through cationic surfactant passivation through non-ionic surface active agent, finally by clear water rinsing, dehydration, oven dry, obtain silver golden viscose or its fabric.
The color of this silver golden viscose or its fabric is golden yellow, and bacteriostasis rate is greater than 90%, electromagnetic radiation attenuation rate >=91%.
Embodiment 2
(1) by degreasing wood pulps regenerated fiber fabric (Modal fibre) 100Kg that also washing is clean, injecting type Final finishing process equipment is placed in by bath raio 1: 4,0.065Kg silver acetate is added in batching kettle, enter the circulatory system after being prepared into solution, at 75 DEG C, react 60min.
(2) step that continues (1), be be mixed into compound stabilizer at 1: 0.2: 0.1:0.3: 3 by ratio of weight and the number of copies by ethylenediamine, tetraacethyl sodium salt, BTA, thiosemicarbazide, ammoniacal liquor five component, take after 1.3Kg is prepared into solution and enter the circulatory system, at 75 DEG C, react 40min.
(3) step that continues (2), takes after ammonium chloroplatinate 0.05Kg is prepared into solution and enters circulatory system circulation 40min;
Take again after inferior sodium phosphate 20Kg is prepared into solution and be added dropwise to the circulatory system, isothermal reaction 45min at 65 DEG C.
(4) step that continues (3), first washs the regenerated fiber after process or its fabric, again through cationic surfactant passivation, finally by clear water rinsing, dehydration, oven dry, obtains silver golden modal fabric through non-ionic surface active agent.
The color of this silver golden viscose of silver golden modal fabric or its fabric is golden yellow, and bacteriostasis rate is greater than 99%, electromagnetic radiation attenuation rate >=98%.
Embodiment 3
(1) by degreasing bamboo pulp regenerated fiber (sky silk) 100Kg that also washing is clean, overflow-type Final finishing process equipment is placed in by bath raio 1: 100,0.11Kg imino-diacetic sulfonic acid complex silver concentrate (silver content 27%) is added in batching kettle, enter the circulatory system after being prepared into solution, at 45 DEG C, react 60min.
(2) step that continues (1), be be mixed into compound stabilizer at 1: 0.2: 0.1:0.3: 4 by ratio of weight and the number of copies by ethylenediamine, tetraacethyl sodium salt, BTA, thiosemicarbazide, ammoniacal liquor five component, take after 5Kg is prepared into solution and enter the circulatory system, at 45 DEG C, react 50min.
(3) step that continues (2), takes after Nickel Chloride 2Kg is prepared into solution and enters circulatory system circulation 40min;
Take again after glucose 20Kg is prepared into solution and be added dropwise to the circulatory system, isothermal reaction 20min at 50 DEG C.
(4) step that continues (3), first washs the regenerated fiber after process or its fabric, again through cationic surfactant passivation, finally by clear water rinsing, dehydration, oven dry, obtains silver golden tencel fiber through non-ionic surface active agent.
The color of this silver golden tencel fiber is golden yellow, and bacteriostasis rate is greater than 97%, electromagnetic radiation attenuation rate >=96%.
Embodiment 4
(1) by the degreasing calcium alginate regenerated celulose fibre 100Kg that also washing is clean, overflow-type Final finishing process equipment is placed in by bath raio 1: 50, in batching kettle, add 15.75Kg silver nitrate, after being prepared into solution, enter the circulatory system, at 10 DEG C, react 85min.
(2) step that continues (1), be be mixed into compound stabilizer at 1: 0.2: 0.1:0.3: 5 by ratio of weight and the number of copies by ethylenediamine, tetraacethyl sodium salt, BTA, thiosemicarbazide, ammoniacal liquor five component, take after 10Kg is prepared into solution and enter the circulatory system, at 20 DEG C, react 90min.
(3) step that continues (2), takes after palladium bichloride 0.03Kg is prepared into solution and enters circulatory system circulation 25min;
Take again after inferior sodium phosphate 13.8Kg is prepared into solution and be added dropwise to the circulatory system, isothermal reaction 65min at 35 DEG C.
(4) step that continues (3), first washs the regenerated fiber after process or its fabric, again through cationic surfactant passivation, finally by clear water rinsing, dehydration, oven dry, obtains silver golden calcium alginate fibre through non-ionic surface active agent.
The color of this silver golden calcium alginate fibre is golden yellow, and bacteriostasis rate is greater than 99.9%, electromagnetic radiation attenuation rate >=99.9%.
Embodiment 5
(1) by 30/70% clean for washing polyester-viscose blended cloth 100Kg, be placed in injecting type Final finishing process equipment by bath raio 1: 20, in batching kettle, add 3.15Kg silver nitrate, after being prepared into solution, enter the circulatory system, at 25 DEG C, react 75min.
(2) step that continues (1), be be mixed into compound stabilizer at 1: 0.2: 0.1:0.3: 2 by ratio of weight and the number of copies by ethylenediamine, tetraacethyl sodium salt, BTA, thiosemicarbazide, ammoniacal liquor five component, take after 2.1Kg is prepared into solution and enter the circulatory system, at 35 DEG C, react 90min.
(3) step that continues (2), takes after palladium chloride 0.02Kg is prepared into solution and enters circulatory system circulation 35min;
Take again after glucose 5.2Kg is prepared into solution and be added dropwise to the circulatory system, isothermal reaction 60min at 45 DEG C.
(4) step that continues (3), regenerated fiber after process or its fabric are first washed, again through cationic surfactant passivation through non-ionic surface active agent, finally by clear water rinsing, dehydration, oven dry, obtain silver golden viscose or its fabric.
This silver golden 30/70 polyester-viscose blended cloth bacteriostasis rate is greater than 95%, electromagnetic radiation attenuation rate >=99%.
Embodiment 6
(1) by alginate fibre cloth 100Kg clean for washing, be placed in overflow-type Final finishing process equipment by bath raio 1: 50, in batching kettle, add 4.7Kg silver nitrate, after being prepared into solution, enter the circulatory system, at 55 DEG C, react 65min.
(2) step that continues (1), be be mixed into compound stabilizer at 1: 0.2: 0.1:0.3: 3.5 by ratio of weight and the number of copies by ethylenediamine, tetraacethyl sodium salt, BTA, thiosemicarbazide, ammoniacal liquor five component, take after 4.25Kg is prepared into solution and enter the circulatory system, at 55 DEG C, react 30min.
(3) step that continues (2), takes after palladium chloride 0.055Kg is prepared into solution and enters circulatory system circulation 15min;
Take again after glucose 7.6Kg is prepared into solution and be added dropwise to the circulatory system, isothermal reaction 20min at 55 DEG C.
(4) step that continues (3), first washs the regenerated fiber after process or its fabric, again through cationic surfactant passivation, finally by clear water rinsing, dehydration, oven dry, obtains silver golden alginate fibre cloth through non-ionic surface active agent.
The color of this silver golden alginate fibre cloth is golden yellow, and bacteriostasis rate is greater than 99%, electromagnetic radiation attenuation rate >=99%.
Fig. 1 is silver golden regenerated celulose fibre/regenerated celulose fibre fabric X-ray diffraction spectrogram; Wherein: the common regenerated celulose fibre x-ray diffraction pattern of (a) not argentiferous; (b) golden silver-plated regenerated celulose fibre/regenerated celulose fibre fabric x-ray diffraction pattern;
As shown in Figure 1, at 38.2 °, 44.4 °, the diffraction maximum of 64.7 ° and 77.3 ° is the diffraction maximum corresponding to centroid cubic crystal system (fcc) elemental silver (111), (200), (220) and (311) four crystal faces.Prove that the silver on silver golden regenerated celulose fibre/regenerated celulose fibre fabric is Nano Silver.
Fig. 2-1 to Fig. 2-6 is the electromicroscopic photograph of silver golden regenerated celulose fibre.Wherein, Fig. 2-1 to Fig. 2-6 is respectively the electromicroscopic photograph of the silver golden regenerated celulose fibre obtained by embodiment 1-6, and the multiplication factor of Fig. 2-2 is 100,000 times, and other are 50,000 times.
As shown in Fig. 2-1 to Fig. 2-6, the product that above-described embodiment 1-6 obtains, under Electronic Speculum, all visible silver exists with nano particle state in the fibre, and particle diameter is 10-20nm.
Claims (6)
1. a preparation method for silver golden regenerated celulose fibre, is characterized in that, comprise the following steps successively:
(1) the degreasing regenerated celulose fibre that also washing is clean is placed in Final finishing process equipment by bath raio 1: 4-100, body lotion ensures under the condition of Efficient Cycle, add soluble silver salt or silver complex, adding proportion is 1:0.01-0.10 by regenerated celulose fibre and the weight ratio of silver, isothermal reaction 20-100min at 10-75 DEG C;
(2) add the compound stabilizer containing ethylenediamine, tetraacethyl sodium salt, BTA, thiosemicarbazide, ammoniacal liquor five kinds of components, at 10-90 DEG C, react 30-90min; Wherein,
In above-mentioned compound stabilizer, the ratio of weight and number of ethylenediamine, tetraacethyl sodium salt, BTA, thiosemicarbazide, ammoniacal liquor five kinds of components is 1: 0.2: 0.1:0.3: 1-5;
The weight ratio of regenerated celulose fibre and above-mentioned compound stabilizer is 1: 0.01-0.10;
(3) be first 1: 0.0001-0.05 by the weight ratio of regenerated celulose fibre and lewis acid catalyst, add their solution and the 15-40min that circulates;
Be 1:0.02-0.20 by the weight ratio of regenerated celulose fibre and glucose or inferior sodium phosphate again, be added dropwise to their solution, isothermal reaction 20-70min at 35-65 DEG C;
(4) by the regenerated celulose fibre after process successively through surfactant wash, passivation, then through clear water rinsing, dehydration, oven dry and get final product.
2. the preparation method of silver golden regenerated celulose fibre according to claim 1, is characterized in that, described soluble silver salt is silver nitrate, silver acetate, and described silver soluble complex compound is imino-diacetic sulfonic acid complex silver.
3. the preparation method of silver golden regenerated celulose fibre according to claim 1, it is characterized in that, described regenerated celulose fibre is Cotton Pulp regenerated celulose fibre, wood pulps regenerated celulose fibre, bamboo pulp regenerated celulose fibre or sodium alginate regenerated celulose fibre.
4. the preparation method of silver golden regenerated celulose fibre according to claim 1, is characterized in that, described lewis acid catalyst is palladium chloride, ammonium chloroplatinate, Nickel Chloride.
5. by the silver golden regenerated celulose fibre that preparation method described in claim 1 prepares, it is characterized in that, bacteriostasis rate >=90%, electromagnetic radiation attenuation rate >=91%.
6. by the silver golden regenerated celulose fibre that preparation method described in claim 1 prepares, it is characterized in that, may be used for pure spinning, also may be used for other fibers with arbitrary proportion blending.
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| CN201510382591.8A CN104928916B (en) | 2014-03-07 | 2014-03-07 | A kind of preparation method of silver golden regenerated celulose fibre fabric |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311369A (en) * | 2000-03-03 | 2001-09-05 | 中国科学院金属研究所 | Chemical silver plating method for organic fibre |
| JP2005105386A (en) * | 2003-10-01 | 2005-04-21 | Nagoya Plating Co Ltd | Electroless silver plating solution for fiber |
| CN102154818A (en) * | 2011-05-16 | 2011-08-17 | 东北林业大学 | Method for preparing nickel coating on surface of cotton fabric or linen fabric |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311369A (en) * | 2000-03-03 | 2001-09-05 | 中国科学院金属研究所 | Chemical silver plating method for organic fibre |
| JP2005105386A (en) * | 2003-10-01 | 2005-04-21 | Nagoya Plating Co Ltd | Electroless silver plating solution for fiber |
| CN102154818A (en) * | 2011-05-16 | 2011-08-17 | 东北林业大学 | Method for preparing nickel coating on surface of cotton fabric or linen fabric |
Non-Patent Citations (4)
| Title |
|---|
| Chemical silver plating and its application to textile fabric design;S.Q.Jiang etal;《Journal of Applied Polymer Science》;20050224;第96卷(第3期);第919-926页 * |
| 化学镀银黏胶纤维的制备及性能分析;刘俊丽等;《产业用纺织品》;20131225(第12期);第34-37页 * |
| 海藻纤维的发展及应用;赵永霞;《纺织导报》;20080708(第7期);第114-116页 * |
| 金属纤维混纺织物防微波辐射性能测试方法的探讨;王瑄等;《棉纺织技术》;20010715;第29卷(第7期);第34-36页 * |
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