CN104928916A - Method for preparing silver-texture golden regenerated cellulose fabric - Google Patents

Method for preparing silver-texture golden regenerated cellulose fabric Download PDF

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CN104928916A
CN104928916A CN201510382591.8A CN201510382591A CN104928916A CN 104928916 A CN104928916 A CN 104928916A CN 201510382591 A CN201510382591 A CN 201510382591A CN 104928916 A CN104928916 A CN 104928916A
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silver
regenerated celulose
celulose fibre
fabric
golden
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CN104928916B (en
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李群
赵昔慧
夏延致
王艳玮
***
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Qingdao University
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Qingdao University
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Abstract

The invention discloses a method for preparing a silver-texture golden regenerated cellulose fabric. Regenerated cellulose fabric as a raw material and a soluble silver salt in the presence of a Lewis acid catalyst are prepared into golden cotton regenerated cellulose fabric by a nano catalytic chemical plating technology. The fabric has antibacterial, deodorant, anti-static and anti-electromagnetic radiation functions, can be used in the fields of military, medical health, household and clothing. The regenerated cellulose fiber fabric used in the present invention comprises the raw materials of cotton pulp regenerated cellulose fiber, wood pulp regenerated cellulose fiber, bamboo pulp regenerated cellulose fiber or sodium alginate regenerated cellulose fiber, as well as the pure spinning, blending thereof or blended fabric with other chemical fiber fabrics.

Description

A kind of preparation method of silver golden regenerated celulose fibre fabric
The application is the divisional application of " applying date be: March 7, application number were in 2014: 201410081956.9, denomination of invention is: a kind of preparation method of silver golden regenerated celulose fibre/regenerated celulose fibre fabric " this application for a patent for invention.
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 the preparation method of a kind of silver golden regenerated celulose fibre and/or 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: the preparation method of a kind of silver golden regenerated celulose fibre and/or 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 chloride 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 fabric, is characterized in that, comprise the following steps successively:
(1) the degreasing regenerated celulose fibre fabric 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 fabric 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 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 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 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 fabric 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 fabric according to claim 1, it 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 fabric according to claim 1, it is characterized in that, described regenerated celulose fibre fabric is the BLENDED FABRIC of regenerated celulose fibre PURE YARN FABRIC or regenerated celulose fibre and chemical fibre.
4. the preparation method of silver golden regenerated celulose fibre fabric according to claim 1, it is characterized in that, described lewis acid catalyst is palladium chloride, ammonium chloroplatinate, Nickel Chloride.
5. according to the preparation method of the arbitrary described silver golden regenerated celulose fibre fabric of claim 1-4, it is characterized in that, the raw materials of described regenerated celulose fibre fabric is Cotton Pulp regenerated celulose fibre, wood pulps regenerated celulose fibre, bamboo pulp regenerated celulose fibre or sodium alginate regenerated celulose fibre.
6., by the silver golden regenerated celulose fibre fabric that preparation method described in claim 1 prepares, it is characterized in that, bacteriostasis rate >=90%, electromagnetic radiation attenuation rate >=91%.
CN201510382591.8A 2014-03-07 2014-03-07 A kind of preparation method of silver golden regenerated celulose fibre fabric Expired - Fee Related CN104928916B (en)

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