CN108385403A - 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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- CN108385403A CN108385403A CN201810117939.4A CN201810117939A CN108385403A CN 108385403 A CN108385403 A CN 108385403A CN 201810117939 A CN201810117939 A CN 201810117939A CN 108385403 A CN108385403 A CN 108385403A
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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.The preparation method of the leather includes the activation of 1) woven fabric staple fiber, 2) configuration of silver nitrate graphene oxide water solution；3) impregnation of silver nitrate graphene oxide, 4) Ag2The preparation of S sulfur graphites alkene/woven fabric staple fiber, 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 technology
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 that will be provided with the material particles addition poly- ammonia of wet method of 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 precipitation, caking phenomena such as, keep final product electric conductivity unstable, base
Phenomena such as cloth surface is susceptible to blackspot.
Chinese patent CN106675006A discloses a kind of antistatic antibiotic microfiber synthetic leather and its production method, by charcoal
Black, carbon nanotube, graphene, dispersant, 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, antistatic antibiotic woven fabric synthesis 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.
Invention content
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 is 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 superbhort fiber is fully absorbed silver nitrate-graphene oxide mixed aqueous solution, then removes unabsorbed silver nitrate-oxidation stone
Black alkene mixed aqueous solution；
Step 4：By H2S gases make 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, reaction after the completion of squeeze go it is molten in superbhort fiber
Liquid；
Step 5：The woven fabric staple fiber shredding that step 4 is handled immerses in alkalescent strong reductant solution, makes superbhort fiber
Alkalescent strong reductant solution is fully absorbed, unabsorbed alkalescent strong reductant solution is removed；
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- graphenes/woven fabric staple fiber compound is made, squeezed after the completion of reaction go it is molten in superbhort fiber
Liquid；
Step 7：Ag- graphenes/woven fabric staple fiber compound is washed, until scrub raffinate pH is less than or equal to 8, drying；
Step 8：By step 7, treated that Ag- graphenes/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 is passed through into wet processing, PU resin impregnateds, 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, soak 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, graphene oxide water solution described in step 2 a concentration of 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 weak base strong reductant solution is 8~10, institute
It states pH value to adjust using ammonium hydroxide, the strong reductant is hydrazine hydrate or sodium borohydride.The concentration and use of hydrazine hydrate or sodium borohydride
Amount is adjusted according to the quality of woven fabric staple fiber and graphene oxide, specifically, the concentration of hydrazine hydrate or sodium borohydride solution
For 0.008~0.8mg/mL, the volume of hydrazine hydrate or sodium borohydride solution is more than or equal to graphene oxide water solution quilt in step 2
The volume of absorption.
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；It is 270~280 thorns/cm just to pierce the needling density of plate in the positive purl thorn2, 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, the present invention also provides the preparation facilities for preparing above-mentioned antistatic antibiotic microfiber leather, it includes the short fibre of woven fabric
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
It is additionally provided with pie extruder 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, at the top of round tubbiness wall on one side in round barreled wall far from funnel tubbiness wall
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 so that woven fabric staple fiber and graphene oxide can carry out bridging, oxygen by H-OH chemical bonds
Graphite alkene by chemical bond force equably, be firmly adsorbed on each woven fabric staple fiber surface.So that follow-up Ag- obtained
The antistatic antibiotic performance of graphene/woven fabric staple fiber evenly, and graphene combined with woven fabric staple fiber it is very secured.
(2)H2With graphene oxide redox reaction occurs for S, 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 sulphur-graphene/woven fabric staple fiber compound also using strong reducing property hydrazine hydrate or sodium borohydride
Original is remarkably improved the electric conductivity of Ag- graphenes/woven fabric staple fiber compound, improves its antistatic effect.Hot alkaline solution can be with
The sulphur simple substance combined with graphene is removed, to form porous Ag- graphenes/woven fabric staple fiber compound, enhances Ag- graphite
The adsorption capacity of alkene/woven fabric staple fiber compound contains for follow-up Ag- graphenes/coloring of woven fabric staple fiber compound, PU resins
The offers facilities such as leaching.The Ag of attachment on the surface of graphene2S solid particles are reduced under ammonium hydroxide and strong reductant collective effect
At Ag, continue attachment on the surface of graphene, to improve the antibiotic property of Ag- graphenes/woven fabric staple fiber compound.
(4) since graphene oxide is by H2S softly pre-reduction treatments, therefore be reduced when strong reductant acts on
Graphene oxide when, reaction just becomes mildly, to not destroying the chemistry between graphene and woven fabric staple fiber
While key active force, the antistatic antibiotic ability of graphene/woven fabric staple fiber is significantly improved.
(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 the method for the present invention.Its is simple in structure, 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 which easily material shifts to realize.Woven fabric staple fiber of the transfer containing tank solution is avoided, it is time saving and energy saving.
Description of the drawings
Fig. 1 is the structural schematic diagram of woven fabric staple fiber processing pond of the present invention.
Fig. 2 is the SEM figures of Ag- graphenes obtained/woven fabric staple fiber compound in embodiment 3.
Specific implementation mode
In order to make it will be apparent to those skilled in that legibly understand the present invention, it is right 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, in funnel barrel between porous filter plate 2 and waste liquid effuser road 3
1 top of shape wall is additionally provided with pie extruder 7.
In order to accelerate being blended for solution and woven fabric staple fiber, blender, the stirring can be also installed in funnel tubbiness wall 1
Utensil 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
8 top of tubbiness wall is provided with flange 10, and 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 1：4 are turned off the switch, 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, woven fabric staple fiber is squeezed out using pie extruder 7
In liquid.In the process, external drive gear 12 can be rotated, round tubbiness wall 8 is driven to rotate, 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, stirring can also be started as needed
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, a concentration of 0.01~1mg/mL of the graphene oxide water solution, the silver nitrate are graphene oxide dosage
5~20%wt.
Step 3：It takes out the woven fabric staple fiber that step 1 is handled and is 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：Switch 6 is opened, H is made2S gases enter 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 gases are passed through that be full of silver nitrate-graphene oxide mixed from bottom
In the woven fabric staple fiber of Heshui solution.H2With graphene oxide redox reaction occurs for S, generates elemental sulfur and is attached to graphene
Surface, while H2S reacts with silver nitrate, generates Ag2S precipitations and is also attached to graphene surface, to which Ag be made2S- sulphur-stone
Black alkene/woven fabric staple fiber compound.Those skilled in the art can be as needed, and one layer of aperture is laid with more on porous filter plate
Small filter plate, makes gas more uniformly spread.In addition, can also a sealing cover in 1 top cover of funnel tubbiness wall as needed,
Prevent H2S loss.After the completion of reaction, 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 Ag, 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 H21~2mg of S, 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：Take 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
Then alkalescent strong reductant solution makes the Ag after shredding2S- sulphur-graphene/woven fabric staple fiber compound fully absorbs strong also
Former agent solution turns on the switch 4, excludes unabsorbed strong reductant solution, be then shut off switch 4 until saturation.The weak base
The pH value of strong reductant solution is 8~10, and the pH value is adjusted using ammonium hydroxide, and the strong reductant is hydrazine hydrate or hydroboration
Sodium.The concentration and dosage of hydrazine hydrate or sodium borohydride are adjusted according to the quality of woven fabric staple fiber and graphene oxide, specifically
The volume of a concentration of 0.008~0.8mg/mL of ground, hydrazine hydrate or sodium borohydride solution, hydrazine hydrate or sodium borohydride solution is more than
Equal to the absorbed volume of graphene oxide water solution in step 2.
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 fully restored further is reduced into graphene, and sulphur simple substance reacts with hot alkaline solution and generates 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 by force
Under the collective effect of reducing agent, it is reduced into Ag attachments on the surface of graphene, it is multiple finally obtains Ag- graphenes/woven fabric staple fiber
Close object.After the completion of reaction, turn on the switch 4, using pie extruder 7 squeeze go it is molten in Ag- graphenes/woven fabric staple fiber compound
Liquid.
Step 7：4 are turned off the switch, water is added, stirring, rinsing Ag- graphenes/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- graphenes/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；It is 270~280 thorns/cm just to pierce the needling density of plate in the positive purl thorn2, 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 is passed through into wet processing, PU resin impregnateds, Alkali reduction grinds skin dyeing and finishing
Technique is finally made antistatic antibiotic microfiber leather.
Wherein, the 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, soak time 0.5h, the acid solution
For the dust technology of 0.01mol/L.
In step 2, a concentration of 0.01mg/mL of the graphene oxide water solution, 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 oxides are passed through H2S 1mg, reaction time
1h。
In step 5, the pH value of the weak base strong reductant solution is 8, and the pH value is adjusted using ammonium hydroxide.The strong reduction
Agent is hydrazine hydrate.The concentration and dosage of hydrazine hydrate are adjusted according to the quality of woven fabric staple fiber and graphene oxide, specifically,
The volume of a concentration of 0.008mg/mL of hydrazine hydrate solution, hydrazine hydrate solution are more than or equal to graphene oxide water solution in step 2
Absorbed volume.
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 soak time 1h, the acid solution is
The dust technology of 0.05mol/L.
In step 2, a concentration of 0.05mg/mL of the graphene oxide water solution, 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 oxides are passed through H2S 1.3mg, when reaction
Between 2h.
In step 5, reaction temperature is 75 DEG C, and the pH value of the weak base strong reductant solution is 9, and the pH value utilizes ammonium hydroxide
It adjusts.The strong reductant is hydrazine hydrate.The concentration and dosage of hydrazine hydrate are according to the quality of woven fabric staple fiber and graphene oxide
It is adjusted, specifically, the volume of a concentration of 0.04mg/mL of hydrazine hydrate solution, hydrazine hydrate solution are more than or equal to oxygen in step 2
The absorbed volume of graphite aqueous solution.
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 soak time 1h, the acid solution is
The dust technology of 0.1mol/L.
In step 2, a concentration of 0.1mg/mL of the graphene oxide water solution, the silver nitrate is used for graphene oxide
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 oxides are passed through H2S 1.5mg, when reaction
Between 3h.
In step 5, reaction temperature is 80 DEG C, and the pH value of the weak base strong reductant solution is 9, and the pH value utilizes ammonium hydroxide
It adjusts.The strong reductant is hydrazine hydrate.The concentration and dosage of hydrazine hydrate are according to the quality of woven fabric staple fiber and graphene oxide
It is adjusted, specifically, the volume of a concentration of 0.08mg/mL of hydrazine hydrate solution, hydrazine hydrate solution are more than or equal to oxygen in step 2
The absorbed volume of graphite aqueous solution.
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 is the SEM figures of Ag- graphenes obtained/woven fabric staple fiber compound 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 particles on the surface of graphene.
Embodiment 4
In step 1, the alkaline solution is the sodium hydroxide of 0.5mol/L, and soak time 1h, the acid solution is
The dust technology of 0.5mol/L.
In step 2, a concentration of 0.5mg/mL of the graphene oxide water solution, the silver nitrate is used for graphene oxide
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 oxides are passed through H2S 1.8mg, when reaction
Between 4h.
In step 5, the pH value of the weak base strong reductant solution is 10, and the pH value is adjusted using ammonium hydroxide.It is described strong also
Former agent is hydrazine hydrate.The concentration and dosage of hydrazine hydrate are adjusted according to the quality of woven fabric staple fiber and graphene oxide, specifically
The volume on ground, a concentration of 0.4mg/mL of hydrazine hydrate solution, hydrazine hydrate solution is more than or equal to graphene oxide water solution in step 2
Absorbed volume.
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 soak time 1h, the acid solution is
The dust technology of 1mol/L.
In step 2, a concentration of 1mg/mL of the graphene oxide water solution, 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 oxides are passed through H2S 2mg, reaction time
5h。
In step 5, the pH value of the weak base strong reductant solution is 10, and the pH value is adjusted using ammonium hydroxide.It is described strong also
Former agent is hydrazine hydrate.The concentration and dosage of hydrazine hydrate are adjusted according to the quality of woven fabric staple fiber and graphene oxide, specifically
The volume on ground, a concentration of 0.8mg/mL of hydrazine hydrate solution, hydrazine hydrate solution is more than or equal to graphene oxide water solution in step 2
Absorbed volume.
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 tests
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 results of table
-------------------------------------------------------
Obviously, above-described embodiment is used for the purpose 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 is 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
Staple fiber fully absorbs silver nitrate-graphene oxide mixed aqueous solution, then removes unabsorbed silver nitrate-graphene oxide
Mixed aqueous solution；
Step 4：By H2S gases make 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 squeezes the solution gone in superbhort fiber after the completion of reaction；
Step 5：The woven fabric staple fiber shredding that step 4 is handled immerses in alkalescent strong reductant solution, keeps superbhort fiber abundant
Alkalescent strong reductant solution is absorbed, unabsorbed alkalescent strong reductant solution is removed；
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 dissolves sulphur simple substance, and Ag- graphenes/woven fabric staple fiber compound is made, the solution gone in superbhort fiber is squeezed after the completion of reaction；
Step 7：Ag- graphenes/woven fabric staple fiber compound is washed, until scrub raffinate pH is less than or equal to 8, drying；
Step 8：By step 7, treated that Ag- graphenes/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 is passed through into wet processing, PU resin impregnateds, 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, soak 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 specifically, 1mg graphene oxides are passed through H21~2mg of S, reaction
Time is 1~5h.
6. preparation method according to claim 1, it is characterised in that：In step 5, the pH of the weak base strong reductant solution
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 strong reductant is hydrazine hydrate or boron
The concentration and dosage of sodium hydride, hydrazine hydrate or sodium borohydride are adjusted according to the quality of woven fabric staple fiber and graphene oxide,
Specifically, the volume of a concentration of 0.008~0.8mg/mL of hydrazine hydrate or sodium borohydride solution, hydrazine hydrate or sodium borohydride solution
More than or equal to the absorbed volume of graphene oxide water solution in step 2.
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；The needling density that plate is just being pierced in the positive purl thorn 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 claim 1-9 any one of them preparation methods.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111764158A (en) * | 2020-07-28 | 2020-10-13 | 唐山烯彤科技有限公司 | Preparation method of conductive short fiber |
| CN115029924A (en) * | 2022-06-07 | 2022-09-09 | 华侨大学 | Preparation method of antistatic non-woven fabric |
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| US20230002961A1 (en) * | 2021-06-30 | 2023-01-05 | Microsoft Technology Licensing, Llc | Graphene-impregnated microfiber fabric |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012169804A2 (en) * | 2011-06-07 | 2012-12-13 | 단국대학교 산학협력단 | Method for manufacturing a graphene-treated fiber |
| CN103390745A (en) * | 2013-07-05 | 2013-11-13 | 清华大学深圳研究生院 | Preparation method for graphene-based composite material |
| CN105386154A (en) * | 2015-11-27 | 2016-03-09 | 宁波三邦超细纤维有限公司 | Antistatic imitation cotton polyester-chinlon composite ultra-fine fiber and production method |
| CN105463598A (en) * | 2015-11-16 | 2016-04-06 | 四川大学 | Graphite-enhanced ultrafine synthetic leather fiber |
| CN107570209A (en) * | 2017-08-08 | 2018-01-12 | 东南大学 | A kind of method for preparing Nano silver grain graphene luffa composite |
| CN107585758A (en) * | 2017-09-07 | 2018-01-16 | 长沙理工大学 | A kind of graphene aerogel and its preparation method and application |
-
2018
- 2018-02-06 CN CN201810117939.4A patent/CN108385403B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012169804A2 (en) * | 2011-06-07 | 2012-12-13 | 단국대학교 산학협력단 | Method for manufacturing a graphene-treated fiber |
| CN103390745A (en) * | 2013-07-05 | 2013-11-13 | 清华大学深圳研究生院 | Preparation method for graphene-based composite material |
| CN105463598A (en) * | 2015-11-16 | 2016-04-06 | 四川大学 | Graphite-enhanced ultrafine synthetic leather fiber |
| CN105386154A (en) * | 2015-11-27 | 2016-03-09 | 宁波三邦超细纤维有限公司 | Antistatic imitation cotton polyester-chinlon composite ultra-fine fiber and production method |
| CN107570209A (en) * | 2017-08-08 | 2018-01-12 | 东南大学 | A kind of method for preparing Nano silver grain graphene luffa composite |
| CN107585758A (en) * | 2017-09-07 | 2018-01-16 | 长沙理工大学 | A kind of graphene aerogel and its preparation method and application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111764158A (en) * | 2020-07-28 | 2020-10-13 | 唐山烯彤科技有限公司 | Preparation method of conductive short fiber |
| CN111764158B (en) * | 2020-07-28 | 2023-01-24 | 唐山烯彤科技有限公司 | Preparation method of conductive short fiber |
| CN115029924A (en) * | 2022-06-07 | 2022-09-09 | 华侨大学 | Preparation method of antistatic non-woven fabric |
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Effective date of registration: 20190614 Address after: 325000 Dingqiao Road, Fengmen Street, Lucheng District, Wenzhou City, Zhejiang Province, 166 Applicant after: WENZHOU XINRAN FOOTWEAR INDUSTRY Co.,Ltd. Address before: 523000 Damaoling, Dongping, Qishi Town, Dongguan City, Guangdong Province Applicant before: DONGGUAN BENPAOBA MICROFIBER LEATHER CO.,LTD. |
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Address after: 325000 Dingqiao Road, Fengmen Street, Lucheng District, Wenzhou City, Zhejiang Province, 166 Patentee after: Zhejiang Xinran Shoes Group Co.,Ltd. Address before: 325000 Dingqiao Road, Fengmen Street, Lucheng District, Wenzhou City, Zhejiang Province, 166 Patentee before: WENZHOU XINRAN FOOTWEAR INDUSTRY Co.,Ltd. |