CN106283241A - Prepare the method that nanometer silver blends native cellulose fibre - Google Patents
Prepare the method that nanometer silver blends native cellulose fibre Download PDFInfo
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Abstract
The present invention relates to a kind of method preparing nanometer silver blending native cellulose fibre, be to add pure water with polyvinyl alcohol (PVA) powder body to make the protective agent of gel state, add silver nitrate (AgNO3) and sodium borohydride (NaBH4); this polyvinyl alcohol protective agent is made to form nano silver colloidal sol with silver nitrate reduction; then; by this nano silver colloidal sol add wood pulp with in the cellulose serosity of methyl morpholine oxide phase mixed dissolution; the mucus (dope) of nanometer silver native cellulose is formed after removing moisture removal; with dry spray-wet-spinning (Dry-Jet Wet Spinning), this mucus is squeezed out into tow from spinning mouth again; after finally via programs such as washing, be dried and oil, can be prepared by the nanometer silver native cellulose fibre with antistatic and antibacterial functions.
Description
Technical field
The present invention relates to a kind of method preparing nanometer silver blending native cellulose fibre, be belonging to environmental protection processing procedure and manufacture natural fiber adhesive-bonded fabric
Technical field, it is to add pure water with polyvinyl alcohol (PVA) powder body to make the poly-vinyl alcohol solution of gel state, and adds silver nitrate (AgNO3)
Solution is slaine precursor body, adds sodium borohydride (NaBH4), make the reduction of this poly-vinyl alcohol solution form nano silver colloidal sol, then, this is received
Rice silver sol addition wood pulp, with in the cellulose serosity of oxidation methyl beautiful jade phase mixed dissolution, forms nanometer silver native cellulose after removing moisture removal
Mucus (dope), then this mucus is squeezed out into tow from spinning mouth with dry spray-wet-spinning (Dry-Jet Wet Spinning), after warp
After programs such as washing, be dried and oil, i.e. prepare the nanometer silver native cellulose fibre with antistatic and antibacterial functions.
Background technology
At present nano silver colloidal sol is mixed made chemical fibre technology mutually with high polymer fibre, disclosed such as Chinese Patent Application No.
200410062799.3,200510070895.7,201010230063.8,201010285121.7 and 201310523647.8 etc., due to this change
Learn fiber to there is antibacterial effect and the cloth with antibacterial functions can be made, but, when aforementioned high polymer fibre becomes garbage after a procedure,
Because not decomposed by natural environment, environment is produced huge impact and burden, in processing procedure, also can discharge harmful material simultaneously, additionally, front
The antibiotic effect degree stating nanometer silver chemical fibre obtained by each processing procedure differs, it is impossible to reach to use the exact requirements of end.
Therefore, such as the native cellulose fibre of the most not present environmental risks, and under the process conditions being accurately controlled, reach preparation have anti-
The nanometer silver native cellulose fibre of electrostatic and antibacterial functions, just seems anxious for urgent and needs.
Summary of the invention
The main object of the present invention prepares the method that nanometer silver blends native cellulose fibre providing a kind of, and its step comprises: a, by polyvinyl alcohol
(Polyvinyl Alcohol is called for short PVA) powder body adds pure water stirring and forms the poly-vinyl alcohol solution of gel state, and adds silver nitrate (AgNO3)
Solution is slaine precursor body；B, addition sodium borohydride (NaBH4) in polyvinyl alcohol gel solution, be stirred titration reduction and form nanometer silver
Colloidal sol；Wherein, this sodium borohydride is to carry out reductometry with mole number than 1:4～1:8, and titration speed is per minute 5～15ml, stirring frequency
At 200rpm, the response time titrated is 10 minutes, and obtained nano silver colloidal sol concentration is 500～20,000ppm, nano-Ag particles grain
Footpath is 10～150nm；C, nano silver colloidal sol is added wood pulp and oxidation methyl agate drench (N-methylmorpholine N-oxide is called for short NMMO)
In the serosity of mixed dissolution；Raw material of wood pulp is first shredded and jointly puts into mix and blend in expansion dissolving tank with oxidation methyl agate beautiful jade, tranquilizer by it,
Groove domestic demand heated at constant temperature is between 60～80 DEG C, and vacuum condensation equipment of arranging in pairs or groups is carried out except water；D, removal nanometer silver native cellulose are blended serosity
Moisture formed spinning mucus (dope)；It is to use Vacuum film evaporation device (Thin Film Evaporator, TFE) to evaporate unnecessary water
Part, the vacuum in this Vacuum film evaporation device is between-9.39*10^4～-9.26*10^4Pa, and with 80 DEG C～130 DEG C heating, in 5 minutes
Cellulose dissolution, to 5%～13%, can be become the mucus of spinning by eliminating moisture；E, with dry spray-wet-spinning (Dry-Jet Wet Spinning)
Carry out spinning, be with dosing pump pressure-increasing unit, enter after continuous filter (CPF) filtration, deaeration in manifold, formed by spinning mouth extrusion
Solution thread, and it is refined into tow through an airspace (air gap) extension；F, the tow after air curing is entered in coagulating bath solidify
Regeneration and washing；And g, by the spinning after solidification regeneration washing after being dried, oil and batching program, i.e. prepare nanometer silver native cellulose fine
Dimension.By size and the concentration that can control this nano silver colloidal sol in processing procedure so that prepare the antibiotic effect of nanometer silver native cellulose fibre,
In addition to can meeting the different consumption end requirement to antibiotic effect degree, its effect more exceeds well over and typically sells on the market with surface process or add anti-
The fiber of bacterium, and its use abandon after by natural decomposition, and the environment-protection fiber of harmless natural environment can be become again.
Another mesh of the present invention is to provide a kind of method preparing nanometer silver blending native cellulose fibre, by controlling this nanometer in its processing procedure
The size of silver sol and concentration so that prepare antistatic effect of nanometer silver native cellulose fibre, can meet different consumption end antagonism
The requirement of electrostatic degree, and its use abandon after by natural decomposition, and the environment-protection fiber of harmless natural environment can be become again.
The technical scheme is that and a kind of prepare the method that nanometer silver blends native cellulose fibre, its step comprises: a, by polyvinyl alcohol powder
Body adds pure water stirring and forms the poly-vinyl alcohol solution of gel state, and to add silver nitrate solution be slaine precursor body；Wherein, this polyvinyl alcohol water
Solution weight percentage rate is 3-12wt%, and the part alkalization type polyvinyl alcohol powder body using basicity to be 86～89mole%, and its molecular weight is
14700～98000, this silver nitrate solution be silver nitrate crystal is dissolved in pure water formulated；B, addition sodium borohydride are molten in polyvinyl alcohol gel
In liquid, it is stirred titration reduction and forms nano silver colloidal sol；Wherein, this sodium borohydride is to carry out reductometry with mole number than 1:4～1:8, drips
Constant speed rate is per minute 5～15ml, and stirring frequency is at 200rpm, and the time of drop reaction is 10 minutes, obtained nano silver colloidal sol concentration be 500～
20,000ppm, nano-Ag particles particle diameter is 10～150nm；C, nano silver colloidal sol is added in the serosity of wood pulp and oxidation methyl agate beautiful jade mixed dissolution；
It first puts into mix and blend in expansion dissolving tank jointly by raw material of wood pulp chopping and with oxidation methyl agate beautiful jade, tranquilizer, groove domestic demand heated at constant temperature in 60～
Between 80 DEG C, and vacuum condensation equipment of arranging in pairs or groups is carried out except water, and the vacuum in this expansion dissolving tank is between-9.33*10^4Pa, wherein, is blended
In serosity, the ratio of nano silver colloidal sol is between 5～35wt%, and the concentration of nano silver particles is between 100～5000ppm；D, removal nanometer silver and sky
So the moisture of cellulose blending oar liquid forms spinning mucus；It is the moisture content using the evaporation of Vacuum film evaporation device unnecessary, this Vacuum film evaporation device
Interior vacuum is between-9.39*10^4～-9.26*10^4Pa, and with 80 DEG C～130 DEG C heating, in 5 minutes, eliminating moisture is to 5%～13%,
Cellulose dissolution can be become the mucus of spinning；Wherein, in mucus, each composition proportion is: water accounts for 9%～18%, and oxidation methyl agate beautiful jade accounts for
75%～87%, cellulose accounts for 6%～11%；E, carry out spinning with dry spray-wet-spinning；It is with dosing pump pressure-increasing unit, through filtering continuously
Enter after machine filtration, deaeration in manifold, formed solution thread by spinning mouth extrusion, and be refined into tow through an airspace extension；F, general
Tow after air curing enters solidification regeneration and washing in coagulating bath；Wherein, solidification liquid concentration is 4.5%～8.0%, the oxygen of residual after washing
Changing methyl agate beautiful jade quantity of solvent and be less than 0.1%, polyvinyl alcohol residual quantity is less than 0.3%；And g, will solidification regeneration washing after spinning through being dried,
After oiling and batching program, i.e. prepare nanometer silver native cellulose fibre.
The invention have the benefit that and provide a kind of nanometer silver of preparing to blend the method for native cellulose fibre by its processing procedure can control this nanometer
The size of silver sol and concentration so that prepare the antibiotic effect of nanometer silver native cellulose fibre, except meeting different consumption end antagonism
Outside the requirement of bacterium effect degree, its effect more exceeds well over typically to sell on the market and processes or add antibacterial fiber with surface, and it uses after abandoning
By natural decomposition, and the environment-protection fiber of harmless natural environment can be become again.It addition, it is big by the particle diameter that can control this nano silver colloidal sol in its processing procedure
Little and concentration so that prepare antistatic effect of nanometer silver native cellulose fibre, can meet the different consumption end requirement to antistatic degree,
And it uses after abandoning and by natural decomposition, and can become the environment-protection fiber of harmless natural environment again.
Accompanying drawing explanation
Fig. 1 is the manufacturing process block chart of the present invention.
Fig. 2 is the chemical structural drawing of polyvinyl alcohol used herein (Polyvinyl Alcohol is called for short PVA).
Fig. 3 is the chemical structural drawing of oxidation methyl agate beautiful jade solvent used herein (N-methylmorpholine N-oxide is called for short NMMO).
Fig. 4 is the chemical structural drawing of wood pulp cellulose used herein (Cellulose).
Fig. 5 is the grain size distribution of 1000ppm nano silver colloidal sol in the present invention.
Fig. 6 is ultramicroscope (TEM) figure in the present invention after 1000ppm nano silver colloidal sol dilution 100 times.
In figure, concrete label is as follows:
Nothing
Detailed description of the invention
For further illustrating Making programme and effect of the present invention, Zi Zuo describes in detail as rear with diagram and each test examples:
Referring to shown in Fig. 1 to Fig. 4, the present invention " prepares the method that nanometer silver blends native cellulose fibre ", and its step comprises:
A, polyvinyl alcohol (Polyvinyl Alcohol, be called for short PVA) powder body is added pure water stirring form the poly-vinyl alcohol solution of gel state, and
Add silver nitrate (AgNO3) solution is slaine precursor body；Wherein, the weight percent that this poly-vinyl alcohol solution adds is 3-12wt%, and adopts
With the part alkalization type polyvinyl alcohol powder body that basicity is 86～89mole%, its molecular weight is 14700～98000, chemical structural drawing such as Fig. 2 institute
Showing, it has, and the degree of polymerization is low and cold soluble is in the characteristic of water, and the concentration added can be coated with and protect the generation of silver microgranule really；This silver nitrate
Solution be silver nitrate crystal is dissolved in pure water formulated；
B, addition sodium borohydride (NaBH4) in polyvinyl alcohol gel solution, be stirred titration reduction and form nano silver colloidal sol；Wherein, this boron
Sodium hydride is to carry out reductometry with mole number than 1:4～1:8, and titration speed is per minute 5～15ml, and stirring frequency, at 200rpm, has titrated
The response time become is 10 minutes, and obtained nano silver colloidal sol concentration is 500～20,000ppm, and nano-Ag particles particle diameter is 10～150nm；
C, nano silver colloidal sol is added wood pulp and oxidation methyl agate beautiful jade (N-methylmorpholine N-oxide is called for short NMMO) mixed dissolution
In serosity；It first by raw material of wood pulp chopping and puts into expansion dissolving tank with oxidation methyl agate beautiful jade (chemical structural drawing is as shown in Figure 3), tranquilizer jointly
Middle mix and blend, groove domestic demand heated at constant temperature is between 60～80 DEG C, and vacuum condensation equipment of arranging in pairs or groups is carried out except water, the vacuum in this expansion dissolving tank
Degree is between-9.33*10^4Pa, and wherein, this raw material of wood pulp mixes with short fine wood pulp (hard wood) mutually for long fine wood pulp (soft wood),
The mixed proportion of both celluloses is 0:100～100:0, and the wood pulp degree of polymerization of use is 500～1200, and alpha-cellulose content is 85%
Above, as shown in Figure 4, and in this blended serosity, the ratio of nano silver colloidal sol is between 5～35wt%, the concentration of nano silver particles for its chemical structural drawing
Between 100～5000ppm；
The moisture that d, removal nanometer silver are blended serosity with native cellulose forms spinning mucus (dope)；It is to use Vacuum film evaporation device (Thin
Film Evaporator, TFE) evaporate unnecessary moisture content, the vacuum in this Vacuum film evaporation device between-9.39*10^4～-
9.26*10^4Pa, and with 80 DEG C～130 DEG C heating, in 5 minutes, eliminating moisture is to 5%～13%, and cellulose dissolution can become the mucus of spinning；
Owing to having the good compatibility between native cellulose and polyvinyl alcohol two system, in the Blending Processes of sizing mixing of step c, both can be tight for it
Close combination and running through each other, then the structure of approximate continuous phase can be formed through churned mechanically shear action, biphase homogenization degree is the highest,
The stability of spinning mucus improves the most relatively, and can ensure that dispersed in spinning mucus of nano-Ag particles；Wherein, each composition institute in mucus
Accounting example is: water (H2O) accounting for 9%～18%, oxidation methyl agate beautiful jade (NMMO) accounts for 75%～87%, and cellulose (cellulose) accounts for 6
%～11%；
E, carry out spinning with dry spray-wet-spinning (Dry-Jet Wet Spinning), be with dosing pump pressure-increasing unit, through continuous filter
(CPF) enter after filtration, deaeration in manifold, formed solution thread by spinning mouth extrusion, and extend through an airspace (air gap)
It is refined into tow；
F, the tow after air curing is entered solidification regeneration and washing in coagulating bath；Wherein, solidification liquid concentration is 4.5%～8.0%, after washing
The oxidation methyl agate beautiful jade quantity of solvent of residual is less than 0.1%, and polyvinyl alcohol residual quantity is less than 0.3%；And
G, by solidification regeneration washing after spinning after being dried, oil and batching program, i.e. prepare nanometer silver native cellulose fibre.
Wherein, the polyvinyl alcohol after regenerating in step f and washing, can must be acted upon through the mode dissolution in the lump being combined with water liquid, be
It is conducted in chromatography tank, and sequentially adds Natrii Sulfas 100g/L (Na2SO4), Borax 16.7g/L (Na2B4O7.10H2O) two kinds of quantitative joining
Ratio, adds a small amount of sodium carbonate (Na2CO3) as pH adjusting agent so that polyvinyl alcohol is condensed, gel separates out, via just can be with after filtering
Oxidation methyl agate beautiful jade solvent mutually separates out, can avoid having influence on recovery and the utilization of oxidation methyl agate beautiful jade solvent.
Another step f regenerates with washing after the oxidation methyl agate beautiful jade solvent that disengages, also must all be reclaimed fully to circulate because of high number and made
With, its step reclaimed comprises:
A. first carry out filtering for the first time with the PP filter element of 1～20 μ；
B. the solvent after filtering for the first time injects in flocculation tank, and the dosage of the additive of flocculant and cooperation thereof is 1.5mg/L, preliminary treatment
1 hour time, the colloidal impurity in solvent is produced poly-attached by the effect of flocculant, and in solution, non-solubility impurity can form the flocculation of high state of aggregation
Thing, measures big flocculate and can start sedimentation, intercept through filter screen and discharge；
C. the solvent after at flocks is passed directly in ion-exchange purification system, through absorption, the conjugation of charging property anions and canons,
Foreign pigment in solution can be separated, and add the purification of strong solvent, the pH scope during this process is maintained at 8～9；
With ultrafilter (UF) and reverse osmosis (RO) filter, solvent after purification is carried out second time the most again to filter；And
E. low-concentration oxidizing methyl agate beautiful jade solvent (4.5%～8.0%) after finally second time being filtered carries out concentration, and it adopts multi-stage evaporation groove
System is circulated, circulation during oxidation methyl agate beautiful jade solvent will gradually purify until 50.0%～78.0% output and reach recovery, again may be used
It puts into recurrence production line again use, the response rate of oxidation methyl agate beautiful jade can be made by aforementioned recovery process to reach more than 99.5%.
For proving the feature of the present invention further and implementing effect, it is to have carried out every test examples and illustrated as rear:
Embodiment one:
5.0g part alkalization type polyvinyl alcohol is added in 95.0g pure water, the continuously stirred poly-vinyl alcohol solution i.e. obtaining 5wt% for 2 hours, with
Appropriate silver nitrate crystal is dissolved in pure water and is configured to 0.1N silver nitrate solution 0.5ml, and adds in polyvinyl alcohol gel solution and stir,
Carry out reductometry with the sodium borohydride of 0.2N with the speed of 5ml per minute again, obtain the nano silver colloidal sol of 1000ppm, in reduction process
Polyvinyl alcohol gel can become yellowish-brown again with translucent gradually flavescence, should be brown even dark brown when reaching titration end-point.
Nano silver colloidal sol sample obtained as above is carried out particle diameter distribution, as shown in Figure 5.And carry out ultramicroscope after diluted sample 100 times
(TEM) image authentication, as shown in Figure 6.
Can be learnt the nano silver colloidal sol of 1000ppm by the result of granularmetric analysis in Fig. 5, its size is distributed mainly between 15～25nm.And Fig. 6
TEM micrograph picture display that, its most reducible go out nanoscale less than the silver particles of 100nm.
Embodiment two:
Wood pulp that the degree of polymerization is 650 and oxidation methyl agate beautiful jade solvent are mixed into cellulose serosity, then add the nano silver colloidal sol of 5～35wt% and enter
Row blends；Wherein the concentration of nano silver particles is 100～5000ppm, with the moisture content that the evaporation of Vacuum film evaporation device is unnecessary, with 80 DEG C～130 DEG C
Heating, in 5 minutes, eliminating moisture is to 5%～13%, and cellulose dissolution can become spinning mucus (dope), spinning mucus composition table such as [table one]
Shown in, then this spinning mucus is carried out spinning, through continuous filter (CPF) with dry spray-wet-spinning (Dry-Jet Wet Spinning)
Enter after filtration, deaeration in manifold, formed solution thread by spinning mouth extrusion, and extend refinement filamentation through an airspace (air gap)
Bundle, and via coagulating bath regeneration, washing molten removing after, drying, oil and batch the natural fibre of nanometer silver that can be prepared by having antibacterial functions
Cellulose fiber, fiber sample obtained as above is as shown in sample number into spectrum 1～11 in [table one].
Embodiment three:
The wood pulp that the degree of polymerization is 1050 is mixed into cellulose serosity with oxidation methyl agate beautiful jade solvent, then adds the nano silver colloidal sol of 5～35wt% afterwards
Blend；Wherein the concentration of nano silver particles is 100～5000ppm, with the moisture content that the evaporation of Vacuum film evaporation device is unnecessary, with 80 DEG C～130
DEG C heating, gets rid of moisture to 5%～13%, cellulose dissolution can become spinning mucus (dope), spinning mucus composition table such as [table in 5 minutes
One] shown in, then this spinning mucus is carried out spinning, through continuous filter (CPF) with dry spray-wet-spinning (Dry-Jet Wet Spinning)
Enter after filtration, deaeration in manifold, formed solution thread by spinning mouth extrusion, and extend refinement filamentation through an airspace (air gap)
Bundle, and via coagulating bath regeneration, washing molten removing after, drying, oil and batch the natural fibre of nanometer silver that can be prepared by having antibacterial functions
Cellulose fiber, fiber sample obtained as above is as shown in sample number into spectrum 12～22 in [table one].
[table one]: each sample spinning mucus composition table
Embodiment four (assessment of antibacterial functions):
The assessment of antibacterial functions uses staphylococcus aureus (ATCC 6538P) and pneumobacillus (ATCC 4352) for test strain.Nanorize
Silver particles positively charged, when nano silver particles is in free state, can contact with electronegative bacterial cell membrane, both are i.e. formed after be combineding with each other
The structure of one dehydrogenase-SAg.Enter endobacillary nanometer silver to destroy its cytoactive, damage DNA of bacteria and interrupt cellular signal transduction,
Bacteria growing inhibiting further；Somatic cells film after nanometer silver effect simultaneously can the weakest even occur perforation, cause substantial amounts of reducing sugar,
Protein and K+It is consumed totally from thalline internal leakage, transmembrane potential and ATP, makes antibacterial to breathe, metabolism and breeding, until dead.
By the native cellulose fibre containing nano silver particles prepared by the present invention being carried out the test of antibiotic property, test whether it possesses antibiotic property.
[table two], [table three] are the result of the test containing nano silver particles native cellulose fibre antibacterial functions.This test method is JIS L1902
-1998 quantitative methods, test strain is staphylococcus aureus (ATCC 6538P) and pneumobacillus (ATCC 4352).Wherein, bacteria concentration is planted
Representing experiment effectively in 1.0 ± 0.3 E+5 (bacterium number/milliliter), Ma=is undressed, and sample washes away rear bacterium number for 0 hour immediately, Mb=is undressed sample
Bacterium number after bacterium number after product 18～cultivation in 24 hours, Mc=processed sample 18～cultivation in 24 hours；Antibacterial growth activity value=logMb-logMa, carefully
Bacterium growth activity value > 1.5 represent experiment effectively, antibacterial value=logMb-logMc, sterilizing value=logMa-logMc；According to Japan's fibre
New function evaluates the antibacterial standard of consultation (JAFET), and antibacterial value has fungistatic effect more than 2.2 expression test samples, and sterilizing value is more than 0 expression
Test sample has bactericidal effect；1.3 E+4 represent 13000, and the rest may be inferred.
From [table two] and [table three], via prepared by the present invention containing nano silver particles native cellulose fibre, itself is for golden yellow
Color staphylococcus and pneumobacillus have possessed the best fungistatic effect and bactericidal effect.
The antibacterial tests result of each sample is as shown in [table two], [table three]
[table two]: the antibacterial functions test containing nano silver particles native cellulose fibre
This test method is JIS L1902-1998 quantitative method, and test strain is staphylococcus aureus (ATCC 6538P).
[table three]: the antibacterial functions test containing nano silver particles native cellulose fibre
This test method is JIS L1902-1998 quantitative method, and test strain is pneumobacillus (ATCC 4352).
Embodiment five (washing the assessment of the antibacterial functions after 10 times):
Each sample, with the laundry paks of 5g/L, is cleaned 45 minutes 10 times in the hot water of 70 DEG C, gained each sample is carried out antibacterial tests, gained
Result as shown in [table four].
[table four]: containing the antibacterial functions test after washing 10 times of nano silver particles native cellulose fibre
This test method is JIS L1902-1998 quantitative method, and test strain is pneumobacillus (ATCC 4352).
Shown by [table two], [table three] native cellulose fibre antibacterial functions result of the test Han nano silver particles, the present invention containing nano silver particles
Native cellulose fibre i.e. has effect of sterilization when the concentration that nano silver particles adds reaches more than 100ppm, if adding concentration more than 1500ppm i.e.
Show the inhibitory effect of its excellence.Being proved by the example of [table two], [table three], the native cellulose fibre containing nano silver particles of the present invention is true
Antibacterial effect can be reached in fact.
Separately shown by [table four] antibacterial functions result of the test after washing 10 times containing nano silver particles native cellulose fibre, the present invention containing nanometer
Silver particles native cellulose fibre is after the hot water of 10 times and detergent treatment, and the antibacterial functions effect of fiber still maintains before originally not washing
More than 90%, thus the result display present invention's is an anti-bacterial fibre cellulose fiber with long-acting type containing nano silver particles native cellulose fibre, its effect
Fruit exceeds well over and typically sells the fiber processing or adding antibacterial with surface on the market.
Embodiment six (anti-static function assessment):
Anti-static function detection is according to antistatic textile standard FTTS-FA-009, and the specification of reference AATCC76 is with concentric electrode sheet resistance
Carry out, test the sheet resistance value of each sample, use the antistatic effect evaluated containing nano silver particles native cellulose fibre.
[table five]: the cellulose fibre anti-static function test containing nano silver particles
Shown by the result of [table five], containing nano silver particles native cellulose fibre in addition to adding the content sample less than 100ppm, be grade
The specification grade of 2；I.e. represent that its antistatic effect is " good " evaluation, and the sheet resistance value (resistance) of fiber, as well as being added
The increase of plus nano silver particles concentration and promote.Additionally, the present invention prepare containing nano silver particles native cellulose fibre, its antistatic property
Also fine far above the wood pulp length typically sold on the market.
In sum, prepared by the present invention containing nano silver particles native cellulose fibre, it has an effect of obvious antibacterial functions, therefore is conducive to
Improve value and the application of textile, and the consumption end requirement to antimicrobial levels can be met, fine containing nano silver particles native cellulose by this
Textile made by dimension can effectively suppress breeding and the growth of microorganism (comprising antibacterial, mycete or fungus), even kills pathogenic bacteria, simultaneously can
Reach and avoid the cross infection of antibacterial, control transmission of disease, and be conducive to promoting health, cleaning, comfortable life.Additionally, it is more because of tool
The antistatic effect having had, therefore with this containing the textile made by nano silver particles native cellulose fibre, also can effectively avoid wear off clothing winter
The electrocution conditions occurred during thing, thus reach and reduce the negative effect that blood circulation of human body, immunity and nervous system are caused by accumulation of static electricity.Its
Being really a quite practical innovation, should meet patent application condition, files an application in whence in accordance with the law.
Claims (6)
1. prepare the method that nanometer silver blends native cellulose fibre for one kind, it is characterised in that step comprises:
A, polyvinyl alcohol powder body is added pure water stirring form the poly-vinyl alcohol solution of gel state, and to add silver nitrate solution be slaine precursor body；Wherein, this polyvinyl alcohol water solution weight percent is 3-12wt%, and the part alkalization type polyvinyl alcohol powder body using basicity to be 86～89mole%, its molecular weight is 14700～98000, this silver nitrate solution be silver nitrate crystal is dissolved in pure water formulated；
B, addition sodium borohydride, in polyvinyl alcohol gel solution, are stirred titration reduction and form nano silver colloidal sol；Wherein, this sodium borohydride is to carry out reductometry with mole number than 1:4～1:8, and titration speed is per minute 5～15ml, stirring frequency is at 200rpm, and the time of drop reaction is 10 minutes, and obtained nano silver colloidal sol concentration is 500～20,000ppm, nano-Ag particles particle diameter is 10～150nm；
C, nano silver colloidal sol is added in the serosity of wood pulp and oxidation methyl agate beautiful jade mixed dissolution；Raw material of wood pulp is first shredded and jointly puts into mix and blend in expansion dissolving tank with oxidation methyl agate beautiful jade, tranquilizer by it, groove domestic demand heated at constant temperature is between 60～80 DEG C, and vacuum condensation equipment of arranging in pairs or groups is carried out except water, the vacuum in this expansion dissolving tank is between-9.33*10^4
Pa, wherein, in blended serosity, the ratio of nano silver colloidal sol is between 5～35 wt%, and the concentration of nano silver particles is between 100～5000 ppm；
The moisture that d, removal nanometer silver are blended oar liquid with native cellulose forms spinning mucus；It is the moisture content using the evaporation of Vacuum film evaporation device unnecessary, vacuum in this Vacuum film evaporation device is between-9.39*10^4～-9.26*10^4Pa, and with 80 DEG C～130 DEG C heating, in 5 minutes, eliminating moisture is to 5%～13%, and cellulose dissolution can become the mucus of spinning；Wherein, in mucus, each composition proportion is: water accounts for 9%～18%, and oxidation methyl agate beautiful jade accounts for 75%～87%, and cellulose accounts for 6%～11%；
E, carry out spinning with dry spray-wet-spinning；It is with dosing pump pressure-increasing unit, enters after continuous filter filtration, deaeration in manifold, formed solution thread by spinning mouth extrusion, and be refined into tow through an airspace extension；
F, the tow after air curing is entered solidification regeneration and washing in coagulating bath；Wherein, solidification liquid concentration is 4.5%～8.0%, and after washing, the oxidation methyl agate beautiful jade quantity of solvent of residual is less than 0.1%, and polyvinyl alcohol residual quantity is less than 0.3%；And
G, by solidification regeneration washing after spinning after being dried, oil and batching program, i.e. prepare nanometer silver native cellulose fibre.
The method preparing nanometer silver blending native cellulose fibre the most according to claim 1, it is characterized in that: in step c, this raw material of wood pulp mixes with short fine wood pulp mutually for long fine wood pulp, the mixed proportion of both celluloses is 0:100～100:0, the wood pulp degree of polymerization used is 500～1200, and alpha-cellulose content is more than 85%.
The method preparing nanometer silver blending native cellulose fibre the most according to claim 1, it is characterised in that: in step c, this raw material of wood pulp is long fine wood pulp, and the wood pulp degree of polymerization of use is 500～1200, and alpha-cellulose content is more than 85%.
The method preparing nanometer silver blending native cellulose fibre the most according to claim 1, it is characterised in that: in step c, this raw material of wood pulp is short fine wood pulp, and the wood pulp degree of polymerization of use is 500～1200, and alpha-cellulose content is more than 85%.
The method preparing nanometer silver blending native cellulose fibre the most according to claim 1, it is characterised in that: the polyvinyl alcohol after regenerating in step f and washing, is to be conducted in chromatography tank, and sequentially adds Natrii Sulfas 100
G/L, two kinds of quantitative proportionings of Borax 16.7 g/L, add a small amount of sodium carbonate as pH adjusting agent so that polyvinyl alcohol is condensed, gel separates out.
The most according to claim 1 prepare the method that nanometer silver blends native cellulose fibre, it is characterised in that: step f regenerates with wash after the recycling step of oxidation methyl agate beautiful jade solvent that disengages comprise:
A. first carry out filtering for the first time with the PP filter element of 1～20 μ；
B. the solvent after filtering for the first time injects in flocculation tank, the dosage of the additive of flocculant and cooperation thereof is 1.5 mg/L, 1 hour preliminary treatment time, colloidal impurity in solvent is produced poly-attached by the effect of flocculant, in solution, non-solubility impurity can form the flocculate of high state of aggregation, measure big flocculate and can start sedimentation, intercept through filter screen the most again and discharge；
C. the solvent after at flocks is passed directly in ion-exchange purification system, through absorption, the conjugation of charging property anions and canons, the foreign pigment in solution can be separated, and add the purification of strong solvent, and the pH scope during this process is maintained at 8～9；
With ultrafilter and reverse osmosis filter, solvent after purification is carried out second time the most again to filter；And
E. low-concentration oxidizing methyl agate beautiful jade solvent (4.5%～8.0%) after finally second time being filtered carries out concentration, it is adopted multi-stage evaporation tank systems and is circulated, and during circulation, oxidation methyl agate beautiful jade solvent will gradually purify until 50.0% ~ 78.0% output can reach recovery.
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