CN108385403B - A kind of antistatic antibiotic microfiber leather and preparation method thereof - Google Patents
A kind of antistatic antibiotic microfiber leather and preparation method thereof Download PDFInfo
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- CN108385403B CN108385403B CN201810117939.4A CN201810117939A CN108385403B CN 108385403 B CN108385403 B CN 108385403B CN 201810117939 A CN201810117939 A CN 201810117939A CN 108385403 B CN108385403 B CN 108385403B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/04—Properties of the materials having electrical or magnetic properties
- D06N2209/046—Anti-static
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1671—Resistance to bacteria, mildew, mould, fungi
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Abstract
The invention discloses a kind of antistatic antibiotic microfiber leathers and preparation method thereof.Activation of the preparation method of the leather including 1) woven fabric staple fiber, 2) configuration of silver nitrate-graphene oxide water solution；3) silver nitrate-graphene oxide impregnation, 4) Ag2S- sulphur-graphene/woven fabric staple fiber preparation, 5) non-woven fabrics the impregnation of alkalescent strong reductant, 6) desulfurization and reduction reaction, 7) washing, 8) is prepared, 9) prepare microfiber leather.Graphene is combined by chemical bond force with woven fabric staple fiber in the present invention, securely, is uniformly coated on around woven fabric staple fiber, has intentional antistatic property and anti-microbial property.
Description
Technical field
The invention belongs to superfine fiber chemical leather technical field more particularly to a kind of antistatic antibiotic microfiber leather and its systems
Preparation Method.
Background technique
Superfine fiber chemical leather is the direction of synthetic leather future development.Since it does base with the non-woven fabrics of three-dimensional net structure
Body, and polyurethane mesh and nylon fascicular texture with open-celled structure, really simulate the form of natural leather, have natural skin
Remove from office most like performance.
With the improvement of living standards, requirement of the people to fabric is also more and more.Such as high-speed train chair fabric,
To anti-flammability, can dripping and smoke density etc. there is high requirement；Conductive glove fabric, to wearability and electric conductivity
It has higher requirements；And be used for the fabric of health product, then to radiation protection, antistatic, magnetic good etc. have particular/special requirement.In order to meet
The multifunctionality of these products, existing technique are usually all the material particles addition poly- ammonia of wet process that will be provided with corresponding function special efficacy
It in ester, then is impregnated into base fabric, to obtain the microfiber leather for having various functions.Such as the conductive materials such as carbon black are added to
In wet polyurethane, the fillers such as carbon black be easy to happen precipitating, agglomeration phenomena such as, keep final product electric conductivity unstable, base
Phenomena such as cloth surface is easy to appear blackspot.
Chinese patent CN106675006A discloses a kind of antistatic antibiotic microfiber synthetic leather and its production method, by charcoal
Black, carbon nanotube, graphene, dispersing agent, heat stabilizer, antioxidant and nylon mixing granulation obtain antistatic antibiotic color masterbatch
Grain；The antistatic antibiotic Masterbatch is mixed with nylon 6, carries out melt spinning, the synthesis of antistatic antibiotic woven fabric is then made
Leather.Antistatic antibiotic material in this method is evenly dispersed in fiber, and it is non-uniform effectively to solve antistatic antibiotic performance
Problem.However carbon black, carbon nanotube and graphene and nylon are only simple physical blending, bonding force is weak, and the strength of materials needs
It further increases.
Summary of the invention
The object of the present invention is to provide a kind of antistatic antibiotic microfiber leathers and preparation method thereof, to overcome the prior art to deposit
Technological deficiency.
In order to achieve the above object, present invention employs following technical solutions:
A kind of preparation method of antistatic antibiotic microfiber leather, includes the following steps:
Step 1: woven fabric staple fiber being put into alkaline solution and is activated, is then neutralized with acid solution, then squeezes and goes woven fabric
Solution in staple fiber；
Step 2, silver nitrate is dispersed in graphene oxide water solution, it is water-soluble constitutes silver nitrate-graphene oxide mixing
Liquid；
Step 3: the woven fabric staple fiber shredding that step 1 is handled is immersed in silver nitrate-graphene oxide mixed aqueous solution,
So that woven fabric staple fiber is fully absorbed silver nitrate-graphene oxide mixed aqueous solution, then removes unabsorbed silver nitrate-oxidation
Graphene mixed aqueous solution；
Step 4: by H2S gas makes H from the woven fabric staple fiber that bottom is passed through that step 3 is handled2S and graphene oxide and nitre
Sour silver reacts, and Ag is made2S- sulphur-graphene/woven fabric staple fiber compound squeezes go in woven fabric staple fiber after the reaction was completed
Solution；
Step 5: the woven fabric staple fiber shredding that step 4 is handled immerses in alkalescent strong reductant solution, makes the short fibre of woven fabric
Dimension fully absorbs alkalescent strong reductant solution, removes unabsorbed alkalescent strong reductant solution；
Step 6: the woven fabric staple fiber that step 5 is handled further restores Ag+ and oxidation in 70~85 DEG C of 1~5h of constant temperature
Graphene dissolves sulphur simple substance, and Ag- graphene/woven fabric staple fiber compound is made, and squeezes go in woven fabric staple fiber after the reaction was completed
Solution；
Step 7: washing Ag- graphene/woven fabric staple fiber compound, until scrub raffinate pH is less than or equal to 8, drying；
Step 8: by step 7, treated that Ag- graphene/woven fabric staple fiber compound weighs, comb, mixes old miscellaneous, paving
Net, pre-needling, positive and negative needling shape at three-dimensional structure network non-woven fabrics；
Step 9: non-woven fabrics made from step step 8 being passed through into wet processing, PU resin impregnated, Alkali reduction grinds skin dyeing and finishing
Technique is finally made antistatic antibiotic microfiber leather.
As the improved technical solution of the present invention, in step 1, the alkaline solution is the sodium hydroxide of 0.01~1mol/L
Or potassium hydroxide, activation time are 0.5~1h, the acid solution is dilute hydrochloric acid, the dust technology of 0.01~1mol/L.
As the improved technical solution of the present invention, the concentration of graphene oxide water solution described in step 2 is 0.01~
1mg/mL, the silver nitrate are 5~20%wt of graphene oxide dosage.
As the improved technical solution of the present invention, in step 4, the H2The reaction temperature of S and graphene oxide be 45~
70℃。H2The intake of S and reaction time are adjusted according to the quality of woven fabric staple fiber and graphene oxide, specifically, 1mg
Graphene oxide is passed through H2S1~2mg, 1~5h of reaction time.
As the improved technical solution of the present invention, in step 5, the pH value of the alkalescent strong reductant solution is 8~10,
The pH value is adjusted using ammonium hydroxide, and the alkalescent strong reductant is hydrazine hydrate or sodium borohydride.Hydrazine hydrate or sodium borohydride
Concentration and dosage are adjusted according to the quality of woven fabric staple fiber and graphene oxide, and specifically, hydrazine hydrate or sodium borohydride are molten
The concentration of liquid is 0.008~0.8mg/mL, and the volume of hydrazine hydrate or sodium borohydride solution is more than or equal to silver nitrate-oxygen in step 3
The absorbed volume of graphite alkene mixed aqueous solution.
As the improved technical solution of the present invention, in step 8, the needling density of the pre-needling is 90~92 thorns/cm2,
Depth of needling is 8.2~8.5mm；Just piercing the needling density of plate in the positive purl thorn is 270~280 thorns/cm2, depth of needling
For 5.5~6mm, the anti-needling density for piercing plate is 420~450 thorns/cm2, depth of needling is 8.2~8.5mm.
Further, the resistivity of the non-woven fabrics is 1.28 × 103~2 × 104Ω/cm2。
The present invention also provides using antistatic antibiotic microfiber leather made from above-mentioned preparation method.
In addition, it includes the short fibre of woven fabric the present invention also provides the preparation facilities for preparing above-mentioned antistatic antibiotic microfiber leather
Dimension prepares microfiber leather assembly line, further includes woven fabric staple fiber opener and woven fabric staple fiber processing pond, the short fibre of woven fabric
Tieing up processing pond has funnel tubbiness wall, and the bottom of funnel tubbiness wall is provided with porous filter plate, is arranged in the lower section of porous filter plate
Waste liquid effuser road and switch are provided with gas flow channel and switch between porous filter plate and waste liquid effuser road, are leaking
Pie extruder is additionally provided with above bucket shape wall.
As the improved technical solution of the present invention, blender is also equipped in funnel tubbiness wall, the blender has
Round tubbiness wall is provided with stirring protrusion far from funnel tubbiness wall in round barreled wall, at the top of round tubbiness wall on one side
It is provided with flange, flange periphery is provided with a circle tooth, the tooth and external drive gear mesh.
Compared with prior art, the present invention has as follows a little:
(1) surface of graphene oxide contains the functional groups such as more OH, COOH, has good water solubility.Pass through highly basic
Woven fabric staple fiber is activated, woven fabric staple fiber and graphene oxide is enabled to pass through H-OH chemical bond progress bridging, oxygen
Graphite alkene by chemical bond force equably, be firmly adsorbed on each woven fabric staple fiber surface.So that subsequent Ag- obtained
More evenly, and graphene is very secured in conjunction with woven fabric staple fiber for graphene/woven fabric staple fiber antistatic antibiotic performance.
(2)H2Redox reaction occurs for S and graphene oxide, and reacts with silver nitrate, generates Ag2S- sulphur-graphite
Alkene/woven fabric staple fiber compound, Ag2S- sulphur-graphene is coated on woven fabric staple fiber surface in solid-state.H2The reducing power of S is inadequate
By force, therefore the chemical bond power between graphene and woven fabric staple fiber will not be destroyed.
(3) further make Ag using strong reducing property hydrazine hydrate or sodium borohydride2S- sulphur-graphene/woven fabric staple fiber is compound
Object reduction, is remarkably improved Ag- graphene/woven fabric staple fiber compound electric conductivity, improves its antistatic effect.Hot alkaline solution
It can remove the sulphur simple substance in conjunction with graphene, to form porous Ag- graphene/woven fabric staple fiber compound, enhance Ag-
Graphene/woven fabric staple fiber compound adsorption capacity is subsequent Ag- graphene/coloring of woven fabric staple fiber compound, PU tree
The offers such as rouge impregnation are convenient.The Ag of attachment on the surface of graphene2S solid particle is in ammonium hydroxide and alkalescent strong reductant collective effect
Under, it is reduced into Ag, continues attachment on the surface of graphene, to improve Ag- graphene/woven fabric staple fiber compound antibacterial
Property.
(4) since graphene oxide is by H2S softly pre-reduction treatment, thus when alkalescent strong reductant act on by
When the graphene oxide restored, reaction just becomes mildly, thus not destroying between graphene and woven fabric staple fiber
Chemical bond power while, significantly improve graphene/woven fabric staple fiber antistatic antibiotic ability.
(5) present invention can also utilize industrial waste gas H2S carrys out redox graphene, solve industrial waste gas removing and
Effectively recycle problem.
(6) the device of the invention is designed exclusively for method of the invention.Its structure is simple, easy to use.Work people
Member only needs to add various solution into woven fabric staple fiber processing pond, is then squeezed out by pie extruder molten in woven fabric staple fiber
Liquid, so that it may realize that easily material shifts.Woven fabric staple fiber of the transfer containing tank solution is avoided, it is time saving and energy saving.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of woven fabric staple fiber processing pond of the present invention.
Fig. 2 schemes for the SEM of Ag- graphene/woven fabric staple fiber compound obtained in embodiment 3.
Specific embodiment
In order to make it will be apparent to those skilled in that legibly understand the present invention, it is right now in conjunction with the drawings and specific embodiments
The present invention is described in detail.
As shown in Figure 1, device of the present invention prepares microfiber leather assembly line in conventional woven fabric staple fiber
On the basis of, also add woven fabric staple fiber opener and woven fabric staple fiber processing pond.The woven fabric staple fiber processing pond has leakage
Bucket shape wall 1 is provided with porous filter plate 2 in the bottom of funnel tubbiness wall 1, and waste liquid effuser is arranged in the lower section of porous filter plate 2
Road 3 and switch 4, are provided with gas flow channel 5 and switch 6 between porous filter plate 2 and waste liquid effuser road 3, in funnel barrel
Pie extruder 7 is additionally provided with above shape wall 1.
In order to accelerate being blended for solution and woven fabric staple fiber, also mountable blender, the stirring in funnel tubbiness wall 1
Device has round tubbiness wall 8, stirring protrusion 9 is provided on one side far from funnel tubbiness wall 1 in round barreled wall 8, in circle
It is provided with flange 10 at the top of tubbiness wall 8,10 periphery of flange is provided with a circle tooth 11, the tooth 11 and 12 tooth of external drive gear
It closes.
Using above-mentioned apparatus, the technique for preparing conductive microfiber leather is as follows:
Step 1: turning off the switch 4, woven fabric staple fiber is put into funnel tubbiness wall 1, alkaline solution is added, makes the short fibre of woven fabric
Dimension fully absorbs alkaline solution, activates 0.5~1h, acid solution is then added, and is allowed to that neutralization reaction occurs with alkaline solution, makes
The pH value for obtaining mixing liquid in woven fabric staple fiber is about 7.Then 4 are turned on the switch, squeezes out woven fabric staple fiber using pie extruder 7
In liquid.In the process, external drive gear 12 can be rotated, drives round tubbiness wall 8 to rotate, so that it is short to accelerate woven fabric
The CONTACT WITH FRICTION of fiber and solution accelerates the mass transfer rate of solution.In other steps, it also can according to need starting stirring
Device.Wherein, the alkaline solution be 0.01~1mol/L sodium hydroxide or potassium hydroxide, the acid solution be 0.01~
Dilute hydrochloric acid, the dust technology of 1mol/L.
Step 2, silver nitrate crystal is added in graphene oxide water solution, configures silver nitrate-graphene oxide mixing water
Solution.Wherein, the concentration of the graphene oxide water solution is 0.01~1mg/mL, and the silver nitrate is graphene oxide dosage
5~20%wt.
Step 3: taking out the woven fabric staple fiber that step 1 is handled and be put into shredding in opener.4 are turned off the switch, after shredding
Woven fabric staple fiber is put into funnel tubbiness wall 1, and silver nitrate-graphene oxide mixed aqueous solution is then added, makes woven fabric staple fiber
Fully absorb silver nitrate-graphene oxide mixed aqueous solution.4 are turned on the switch, unabsorbed nitric acid in funnel tubbiness wall 1 is bled off
Silver-graphene oxide mixed aqueous solution, turns off switch 4.
Step 4: opening switch 6, make H2S gas enters porous filter plate 2 and waste liquid effuser road by gas flow channel 5
Between 3.At this point, porous filter plate 2 plays the role of air distribution plate, H2S gas is passed through that be full of silver nitrate-graphene oxide mixed from bottom
In the woven fabric staple fiber of Heshui solution.H2Redox reaction occurs for S and graphene oxide, generates elemental sulfur and is attached to graphene
Surface, while H2S reacts with silver nitrate, generates Ag2S precipitating and is also attached to graphene surface, so that Ag be made2S- sulphur-stone
Black alkene/woven fabric staple fiber compound.Those skilled in the art can according to need, and be laid with one layer of aperture more on porous filter plate
Small filter plate, more uniformly spreads gas.In addition, can also a sealing cover in 1 top cover of funnel tubbiness wall as needed,
Prevent H2S loss.After the reaction was completed, 6 are turned off the switch, then squeezes out Ag using pie extruder 72S- sulphur-graphene/woven fabric is short
Liquid in fibre composites.At this point, the important substance A g, graphene coated in solution be on woven fabric staple fiber surface, admittedly it stays in
Ag2In S- sulphur-graphene/woven fabric staple fiber compound.Wherein, the H2The reaction temperature of S and graphene oxide is 45~70
℃。H2The intake of S and reaction time are adjusted according to the quality of woven fabric staple fiber and graphene oxide, specifically, 1mg oxygen
Graphite alkene is passed through H2S1~2mg, 1~5h of reaction time.In order to make H2S is reacted with graphene oxide in defined temperature model
Interior progress is enclosed, woven fabric staple fiber processing pond can be moved into drying chamber.
Step 5: taking out Ag made from step 42S- sulphur-graphene/woven fabric staple fiber compound, is put into opener and opens
Pine.4 are turned off the switch, by the Ag after shredding2S- sulphur-graphene/woven fabric staple fiber compound is put into funnel tubbiness wall 1, is added
Alkalescent strong reductant solution, the Ag after then making shredding2S- sulphur-graphene/woven fabric staple fiber compound fully absorbs weak base
Property strong reductant solution until saturation, turn on the switch 4, exclude unabsorbed alkalescent strong reductant solution, be then shut off out
Close 4.The pH value of the alkalescent strong reductant solution is 8~10, and the pH value is adjusted using ammonium hydroxide, and the alkalescent restores by force
Agent is hydrazine hydrate or sodium borohydride.The concentration and dosage of hydrazine hydrate or sodium borohydride are according to woven fabric staple fiber and graphene oxide
Quality is adjusted, and specifically, the concentration of hydrazine hydrate or sodium borohydride solution is 0.008~0.8mg/mL, hydrazine hydrate or boron hydrogen
The volume for changing sodium solution is more than or equal to silver nitrate-absorbed volume of graphene oxide mixed aqueous solution in step 3.
Step 6: woven fabric staple fiber processing pond is moved into 70~85 DEG C of 1~5h of drying chamber constant temperature.At this temperature, not by
H2The graphene oxide that S is sufficiently restored further is reduced into graphene, and sulphur simple substance and hot alkaline solution react and generate Asia
Sulfate liquor and sulfide solution, from Ag2It is removed in S- sulphur-graphene/woven fabric staple fiber compound；Ag2S is in ammonium hydroxide and weak
Under the collective effect of alkaline strong reductant, it is reduced into Ag attachment on the surface of graphene, it is short finally obtains Ag- graphene/woven fabric
Fibre composites.After the reaction was completed, 4 are turned on the switch, is squeezed using pie extruder 7 and removes Ag- graphene/woven fabric staple fiber compound
In solution.
Step 7: 4 are turned off the switch, water is added, stirring, rinsing Ag- graphene/woven fabric staple fiber compound turn on the switch 4,
It is squeezed using pie extruder 7 and excludes scrub raffinate.Repeatedly, until scrub raffinate pH is less than or equal to 8, drying.
Step 8: by step 7, treated that Ag- graphene/woven fabric staple fiber compound weighs, comb, mixes old miscellaneous, paving
Net, pre-needling, positive and negative needling shape at three-dimensional structure network non-woven fabrics.The needling density of the pre-needling be 90~92 thorn/
cm2, depth of needling is 8.2~8.5mm；Just piercing the needling density of plate in the positive purl thorn is 270~280 thorns/cm2, needle thorn is deeply
Degree is 5.5~6mm, and the anti-needling density for piercing plate is 420~450 thorns/cm2, depth of needling is 8.2~8.5mm, the non-woven fabrics
Resistivity be 1.28 × 103~2 × 103Ω/cm2。
Step 9: non-woven fabrics made from step step 8 being passed through into wet processing, PU resin impregnated, Alkali reduction grinds skin dyeing and finishing
Technique is finally made antistatic antibiotic microfiber leather.
Wherein, equipment used in step 8 and step 9 is conventional woven fabric staple fiber microfiber leather assembly line.
Technological parameter in the present invention is as follows:
Embodiment 1
In step 1, the alkaline solution is the sodium hydroxide of 0.01mol/L, activation time 0.5h, the acid solution
For the dust technology of 0.01mol/L.
In step 2, the concentration of the graphene oxide water solution is 0.01mg/mL, and the silver nitrate is graphene oxide
The 5%wt of dosage.
In step 4, the H2The reaction temperature of S and graphene oxide is 45 DEG C.H2The intake of S and reaction time according to
Woven fabric staple fiber and the quality of graphene oxide are adjusted, and specifically, 1mg graphene oxide is passed through H2S1mg, reaction time
1h。
In step 5, the pH value of the alkalescent strong reductant solution is 8, and the pH value is adjusted using ammonium hydroxide.The weak base
Property strong reductant be hydrazine hydrate.The concentration and dosage of hydrazine hydrate are adjusted according to the quality of woven fabric staple fiber and graphene oxide
Section, specifically, the concentration of hydrazine hydrate solution are 0.008mg/mL, and the volume of hydrazine hydrate solution is more than or equal to silver nitrate-in step 3
The absorbed volume of graphene oxide mixed aqueous solution.
In step 6, the reaction temperature is 70 DEG C, constant temperature time 1h.
In step 8, the needling density of the pre-needling is 91 thorns/cm2, depth of needling 8.4mm；In the positive purl thorn
The needling density of positive thorn plate is 275 thorns/cm2, depth of needling 5.8mm, the anti-needling density for piercing plate is 435 thorns/cm2, needle thorn is deeply
Degree is 8.4mm.
The resistivity for measuring non-woven fabrics is 2 × 104Ω/cm2。
Embodiment 2
In step 1, the alkaline solution is the sodium hydroxide of 0.05mol/L, and activation time 1h, the acid solution is
The dust technology of 0.05mol/L.
In step 2, the concentration of the graphene oxide water solution is 0.05mg/mL, and the silver nitrate is graphene oxide
The 8%wt of dosage.
In step 4, the H2The reaction temperature of S and graphene oxide is 50 DEG C.H2The intake of S and reaction time according to
Woven fabric staple fiber and the quality of graphene oxide are adjusted, and specifically, 1mg graphene oxide is passed through H2S1.3mg, when reaction
Between 2h.
In step 5, reaction temperature is 75 DEG C, and the pH value of the alkalescent strong reductant solution is 9, and the pH value utilizes ammonia
Water is adjusted.The alkalescent strong reductant is hydrazine hydrate.The concentration and dosage of hydrazine hydrate are according to woven fabric staple fiber and graphite oxide
The quality of alkene is adjusted, and specifically, the concentration of hydrazine hydrate solution is 0.04mg/mL, and the volume of hydrazine hydrate solution is more than or equal to
Silver nitrate-absorbed volume of graphene oxide mixed aqueous solution in step 3.
In step 6, the reaction temperature is 75 DEG C, constant temperature time 2h.
In step 8, the needling density of the pre-needling is 91 thorns/cm2, depth of needling 8.4mm；In the positive purl thorn
The needling density of positive thorn plate is 275 thorns/cm2, depth of needling 5.8mm, the anti-needling density for piercing plate is 435 thorns/cm2, needle thorn is deeply
Degree is 8.4mm.
The resistivity for measuring non-woven fabrics is 1.15 × 104Ω/cm2。
Embodiment 3
In step 1, the alkaline solution is the sodium hydroxide of 0.1mol/L, and activation time 1h, the acid solution is
The dust technology of 0.1mol/L.
In step 2, the concentration of the graphene oxide water solution is 0.1mg/mL, and the silver nitrate is graphene oxide use
The 12%wt of amount.
In step 4, the H2The reaction temperature of S and graphene oxide is 60 DEG C.H2The intake of S and reaction time according to
Woven fabric staple fiber and the quality of graphene oxide are adjusted, and specifically, 1mg graphene oxide is passed through H2S1.5mg, when reaction
Between 3h.
In step 5, reaction temperature is 80 DEG C, and the pH value of the alkalescent strong reductant solution is 9, and the pH value utilizes ammonia
Water is adjusted.The alkalescent strong reductant is hydrazine hydrate.The concentration and dosage of hydrazine hydrate are according to woven fabric staple fiber and graphite oxide
The quality of alkene is adjusted, and specifically, the concentration of hydrazine hydrate solution is 0.08mg/mL, and the volume of hydrazine hydrate solution is more than or equal to
Silver nitrate-absorbed volume of graphene oxide mixed aqueous solution in step 3.
In step 6, the reaction temperature is 80 DEG C, constant temperature time 3h.
In step 8, the needling density of the pre-needling is 91 thorns/cm2, depth of needling 8.4mm；In the positive purl thorn
The needling density of positive thorn plate is 275 thorns/cm2, depth of needling 5.8mm, the anti-needling density for piercing plate is 435 thorns/cm2, needle thorn is deeply
Degree is 8.4mm.
The resistivity for measuring non-woven fabrics is 5.21 × 103Ω/cm2。
Fig. 2 schemes for the SEM of Ag- graphene/woven fabric staple fiber compound obtained in the present embodiment.By that can be seen in figure
It arrives, is coated on to graphene uniform woven fabric staple fiber surface, also adheres to have Ag particle on the surface of graphene.
Embodiment 4
In step 1, the alkaline solution is the sodium hydroxide of 0.5mol/L, and activation time 1h, the acid solution is
The dust technology of 0.5mol/L.
In step 2, the concentration of the graphene oxide water solution is 0.5mg/mL, and the silver nitrate is graphene oxide use
The 16%wt of amount.
In step 4, the H2The reaction temperature of S and graphene oxide is 65 DEG C.H2The intake of S and reaction time according to
Woven fabric staple fiber and the quality of graphene oxide are adjusted, and specifically, 1mg graphene oxide is passed through H2S1.8mg, when reaction
Between 4h.
In step 5, the pH value of the alkalescent strong reductant solution is 10, and the pH value is adjusted using ammonium hydroxide.It is described weak
Alkaline strong reductant is hydrazine hydrate.The concentration and dosage of hydrazine hydrate are adjusted according to the quality of woven fabric staple fiber and graphene oxide
Section, specifically, the concentration of hydrazine hydrate solution are 0.4mg/mL, and the volume of hydrazine hydrate solution is more than or equal to silver nitrate-oxygen in step 3
The absorbed volume of graphite alkene mixed aqueous solution.
In step 6, the reaction temperature is 80 DEG C, constant temperature time 4h.
In step 8, the needling density of the pre-needling is 91 thorns/cm2, depth of needling 8.4mm；In the positive purl thorn
The needling density of positive thorn plate is 275 thorns/cm2, depth of needling 5.8mm, the anti-needling density for piercing plate is 435 thorns/cm2, needle thorn is deeply
Degree is 8.4mm.
The resistivity for measuring non-woven fabrics is 3.59 × 103Ω/cm2。
Embodiment 5
In step 1, the alkaline solution is the sodium hydroxide of 1mol/L, and activation time 1h, the acid solution is
The dust technology of 1mol/L.
In step 2, the concentration of the graphene oxide water solution is 1mg/mL, and the silver nitrate is graphene oxide dosage
20%wt.
In step 4, the H2The reaction temperature of S and graphene oxide is 70 DEG C.H2The intake of S and reaction time according to
Woven fabric staple fiber and the quality of graphene oxide are adjusted, and specifically, 1mg graphene oxide is passed through H2S 2mg, reaction time
5h。
In step 5, the pH value of the alkalescent strong reductant solution is 10, and the pH value is adjusted using ammonium hydroxide.It is described weak
Alkaline strong reductant is hydrazine hydrate.The concentration and dosage of hydrazine hydrate are adjusted according to the quality of woven fabric staple fiber and graphene oxide
Section, specifically, the concentration of hydrazine hydrate solution are 0.8mg/mL, and the volume of hydrazine hydrate solution is more than or equal to silver nitrate-oxygen in step 3
The absorbed volume of graphite alkene mixed aqueous solution.
In step 6, the reaction temperature is 85 DEG C, constant temperature time 5h.
In step 8, the needling density of the pre-needling is 91 thorns/cm2, depth of needling 8.4mm；In the positive purl thorn
The needling density of positive thorn plate is 275 thorns/cm2, depth of needling 5.8mm, the anti-needling density for piercing plate is 435 thorns/cm2, needle thorn is deeply
Degree is 8.4mm.
The resistivity for measuring non-woven fabrics is 1.28 × 103Ω/cm2。
Embodiment 1-5 anti-microbial property test
The detection of antistatic antibiotic cloth bacterium, mould bacteriostasis rate respectively refers to the Quinn test method of improvement, JIS Z
2911 antifungi test method(s)s, testing result are shown in Table 1.
1 embodiment 1-5 anti-microbial property test result of table
Obviously, above-described embodiment is just for the sake of clearly demonstrating example, rather than the limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.As long as being made on the basis of the embodiment of the present invention
The change scheme of common-sense, among protection scope of the present invention.
Claims (10)
1. a kind of preparation method of antistatic antibiotic microfiber leather, includes the following steps:
Step 1: woven fabric staple fiber being put into alkaline solution and is activated, is then neutralized with acid solution, then squeezes and removes the short fibre of woven fabric
Solution in dimension；
Step 2, silver nitrate is dispersed in graphene oxide water solution, silver nitrate-graphene oxide mixed aqueous solution is made；
Step 3: the woven fabric staple fiber shredding that step 1 is handled immerses in silver nitrate-graphene oxide mixed aqueous solution, makes to surpass
Fibrillated short fiber fully absorbs silver nitrate-graphene oxide mixed aqueous solution, then removes unabsorbed silver nitrate-graphite oxide
Alkene mixed aqueous solution；
Step 4: by H2S gas makes H from the woven fabric staple fiber that bottom is passed through that step 3 is handled2S and graphene oxide and silver nitrate
It reacts, Ag is made2S- sulphur-graphene/woven fabric staple fiber compound, after the reaction was completed squeeze go it is molten in woven fabric staple fiber
Liquid；
Step 5: the woven fabric staple fiber shredding that step 4 is handled immerses in alkalescent strong reductant solution, fills woven fabric staple fiber
Divide and absorb alkalescent strong reductant solution, removes unabsorbed alkalescent strong reductant solution；
Step 6: the woven fabric staple fiber that step 5 is handled further restores Ag in 70~85 DEG C of 1~5h of constant temperature+And graphite oxide
Alkene, dissolve sulphur simple substance, be made Ag- graphene/woven fabric staple fiber compound, after the reaction was completed squeeze go it is molten in woven fabric staple fiber
Liquid；
Step 7: washing Ag- graphene/woven fabric staple fiber compound, until scrub raffinate pH is less than or equal to 8, drying；
Step 8: by step 7, treated that Ag- graphene/woven fabric staple fiber compound weighs, comb, mixes old miscellaneous, lapping, pre-
Needle thorn, positive and negative needling shape at three-dimensional structure network non-woven fabrics；
Step 9: non-woven fabrics made from step step 8 being passed through into wet processing, PU resin impregnated, Alkali reduction grinds skin dyeing and finishing technology
It is finally made antistatic antibiotic microfiber leather.
2. preparation method according to claim 1, it is characterised in that: in step 1, the alkaline solution be 0.01~
The sodium hydroxide or potassium hydroxide of 1mol/L, activation time are 0.5~1h, and the acid solution is dilute salt of 0.01~1mol/L
Acid, dust technology.
3. preparation method according to claim 1, it is characterised in that: graphene oxide water solution described in step 2 it is dense
Degree is 0.01~1mg/mL, and the silver nitrate is 5~20%wt of graphene oxide dosage.
4. preparation method according to claim 1, it is characterised in that: in step 4, the H2S is reacted with graphene oxide
Temperature is 45~70 DEG C.
5. preparation method according to claim 1, it is characterised in that: in step 4, H2The intake of S and reaction time according to
Woven fabric staple fiber and the quality of graphene oxide are adjusted, and 1mg graphene oxide is passed through H2S1~2mg, the reaction time be 1~
5h。
6. preparation method according to claim 1, it is characterised in that: in step 5, the alkalescent strong reductant solution
PH value is 8~10, and the pH value is adjusted using ammonium hydroxide.
7. preparation method according to claim 1, it is characterised in that: in step 5, the alkalescent strong reductant is hydration
The concentration and dosage of hydrazine or sodium borohydride, hydrazine hydrate or sodium borohydride are carried out according to woven fabric staple fiber and the quality of graphene oxide
It adjusts, the concentration of hydrazine hydrate or sodium borohydride solution is 0.008~0.8mg/mL, and the volume of hydrazine hydrate or sodium borohydride solution is big
In equal to silver nitrate-absorbed volume of graphene oxide mixed aqueous solution in step 3.
8. preparation method according to claim 1, it is characterised in that: in step 8, the needling density of the pre-needling is 90
~92 thorns/cm2, depth of needling is 8.2~8.5mm；Just pierced in the positive purl thorn plate needling density be 270~280 thorns/
cm2, depth of needling is 5.5~6mm, and the anti-needling density for piercing plate is 420~450 thorns/cm2, depth of needling is 8.2~8.5mm.
9. preparation method according to claim 1, it is characterised in that: the resistivity of the non-woven fabrics is 1.28 × 103~2
×104Ω/cm2。
10. a kind of using antistatic antibiotic microfiber leather made from the described in any item preparation methods of claim 1-9.
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| CN115029924B (en) * | 2022-06-07 | 2023-05-09 | 华侨大学 | Preparation method of antistatic non-woven fabric |
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| CN103390745B (en) * | 2013-07-05 | 2016-08-10 | 清华大学深圳研究生院 | The preparation method of graphene-based composite |
| CN105463598B (en) * | 2015-11-16 | 2019-01-29 | 四川大学 | A kind of Super-fine Synthetic Leather fiber of graphene enhancing |
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