CN108486902A - A kind of graphene overlay film rubber gloves and preparation method thereof - Google Patents
A kind of graphene overlay film rubber gloves and preparation method thereof Download PDFInfo
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- CN108486902A CN108486902A CN201810205090.6A CN201810205090A CN108486902A CN 108486902 A CN108486902 A CN 108486902A CN 201810205090 A CN201810205090 A CN 201810205090A CN 108486902 A CN108486902 A CN 108486902A
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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
- D06N3/0009—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 knitted fabrics
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/0055—Plastic or rubber gloves
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
- C09D109/02—Copolymers with acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- 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
- D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
- D06N3/005—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by blowing or swelling agent
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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
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
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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
- D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
- D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
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- 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
- D06N3/04—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 by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/10—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 by reactions only involving carbon-to-carbon unsaturated bonds with styrene-butadiene copolymerisation products or other synthetic rubbers or elastomers except polyurethanes
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- D06N2209/00—Properties of the materials
- D06N2209/10—Properties of the materials having mechanical properties
- D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
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- D06N2209/00—Properties of the materials
- D06N2209/10—Properties of the materials having mechanical properties
- D06N2209/105—Resistant to abrasion, scratch
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- 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
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- D06N2209/1671—Resistance to bacteria, mildew, mould, fungi
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- D06N2211/00—Specially adapted uses
- D06N2211/10—Clothing
- D06N2211/103—Gloves
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- Chemical & Material Sciences (AREA)
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- Gloves (AREA)
Abstract
The present invention relates to a kind of graphene overlay film rubber gloves, it includes：Gloves embryo, the rubber layer for being attached to the gloves embryo outer surface and the graphene film layer for being covered in the rubber layer outer surface；The rubber layer is not the expansion type rubber of graphene-containing or non-foamed type rubber.The preparation method of the gloves includes：Knitted gloves embryo is impregnated with the rubber cement by the rubber cement for preparing not graphene-containing；Graphene latex dispersions are prepared, the kiss-coating gloves embryo for being impregnated with the rubber cement is impregnated into the graphene latex dispersions again；Vulcanization drying, is made the graphene overlay film rubber gloves.The present invention passes through double-steeping, and the rubber body structure division of gloves is formed after the rubber cement solidification of single-steeping, ensures the basic labor protection effect that the quality of body construction meets relevant criterion (EN388), ensures gloves；Double-steeping forms graphene overlay film, the rubber glue surface that soaking can be protected to be formed, and promotes glove product entirety properties.
Description
Technical field
The present invention relates to the preparation method of gloves, especially a kind of graphene overlay film rubber gloves and preparation method thereof.
Background technology
Graphene is to find that most thin two-dimensional material, theoretic throat are only at present as a kind of monoatomic layer material
0.35nm, graphene have larger specific surface area 2600m2/ g and elasticity modulus 1000Gpa, be often applied to physics, material,
The fields such as electronic information, computer.Elasticity modulus is the index weighed material and generate flexible deformation complexity, and value is bigger,
Material stiffness is bigger.Graphene is added in rubber, plays the wear resistance for increasing rubber product, high intensity, biocidal property, improves rubber
All multiactions such as mechanical strength.But the prior art applied it at present in rubber gloves is few, and technology is immature.
For example, Chinese patent application CN107118410A discloses a kind of preparation method of graphene-butyronitrile foam glove,
This method directly graphene is mixed with previously prepared butyronitrile foamed slurry graphene-containing composite mortar, knitted gloves
Embryo impregnates the composite mortar and is made.Graphene is nano material, and viscosity is very big, even if its addition is only when being mixed with rubber cement
0.1~0.2%, the viscosity of compound rubber cement reaches 3000mpa.s or more.Such highly viscous rubber cement, not only various cooperations
Agent is difficult to add (very poor adding dispersed homogeneous degree), while too high viscosity also results in a series of quality and asks again
Topic, such as since rubber cement wetting capacity is very poor, gloves embryo difficulty impregnation and spin coating, between gloves there is also the seep through that comes unglued, refer to after drying
Occur at web and other issues.And graphene should be added and control viscosity again, or then the addition control of graphene is arrived
0.1% hereinafter, cause gloves overall performance not to be obviously improved；It is reduced by the way that synergist (such as Span, Tween) is added
Surface tension of latex makes more graphenes dissolve into slurry, and the addition of synergist equally easily leads to seep through, splits the problems such as glue and send out
It is raw.
To find out its cause, essentially consisting in:(1) graphene specific surface area is very big, and only has dissolubility in nonpolar solvent, because
Even if this is added to the very low amount very little that can bring about very high viscosity, therefore can add of content inside latex, lead to the whole of gloves
Body performance is difficult to be promoted.(2) when the viscosity of rubber cement is excessively high, to knitted gloves embryo (it is porous containing air, fiber is more, surface is thick
The reasons such as rough cause the infiltration resistance of knitted gloves embryo big) wetting capacity is very poor, and impregnation and spin coating difficulty are big, gloves embryo after impregnation
The sizing material on surface is in bulge, the sizing material disconnection of different parts or became uneven etc., glue surface after drying under group's scoriform, bulk, glue surface
There is disconnected glue, split glue even seep through (local open-work), or even can also be linked to be web between the finger portion of gloves embryo, keeps glove product serious
It is unqualified.Comprehensive speech, graphene and latex are directly mixed with the processing technology for impregnating knitted gloves embryo, Wu Fasheng
The glove product of output qualification.
For this purpose, how preferably to make rubber gloves using the performance of graphene, and the normal of rubber gloves is not influenced
It makes and produces, be the technical issues of present invention wishes to solve.
Invention content
The object of the present invention is to provide a kind of physicochemical characteristic that graphene can be made full use of excellent but also rubber is effectively ensured
The technical solution of Rubber gloves quality of item
In order to solve the above problem of the prior art, a kind of graphene overlay film rubber gloves of present invention offer and its preparation side
Method is covered in the outer surface of gloves glue surface by the way that graphene and latex are prepared by mixing into graphene overlay film, graphene overlay film with
Latex therein is adhesive, is adhered tightly to glue surface surface, protects the gloves glue surface of internal layer, improve gloves entirety intensity,
Rub resistance, antibacterial, cut resistant and the comprehensive performances such as tear-resistant；The rubber gloves ontology being made of internal layer glue surface is used for hand
Play labor protection.
In order to achieve the above object, the main technical schemes that the present invention uses include：
A kind of graphene overlay film rubber gloves, including：Gloves embryo, the rubber layer for being attached to the gloves embryo outer surface and
It is covered in the graphene film layer of the rubber layer outer surface；The rubber layer is the expansion type rubber or non-foamed of not graphene-containing
Type rubber.
A kind of preparation method of graphene overlay film rubber gloves, including：
Knitted gloves embryo is impregnated with the rubber cement by the rubber cement for preparing not graphene-containing；
Graphene-latex dispersions are prepared, the kiss-coating gloves embryo for being impregnated with the rubber cement is impregnated into the graphene-glue again
Newborn dispersion liquid；
Vulcanization drying, is made the graphene overlay film rubber gloves.
According to an embodiment of the present invention, the rubber cement is prepared by the following method：By the first of 90~120 parts of parts by weight
Latex, 0~3 part of anti-creme, 0~4 part of antitack agent, 0~3 part of foaming agent mixing preparation, then thickened and be made with thickener
The rubber cement；First latex is presulfurization NBR latex, presulfurization natural emulsion, presulfurization polychloroprene latex, presulfurization fourth
The combination of one or more of base latex, presulfurization styrene-butadiene latex or aqueous PU resins.
According to an embodiment of the present invention, the graphene-latex dispersions are prepared by the following method：By parts by weight 90
~120 parts of graphene, 100~500 part of second latex, 800-5000 parts of water mixing preparations obtain graphene-latex dispersions；Institute
It states the second latex and the first latex is identical or different, second latex is presulfurization NBR latex, presulfurization natural emulsion, pre-
Vulcanize the combination of one or more of polychloroprene latex, pre-vulcanized butyl rubber breast, presulfurization styrene-butadiene latex or aqueous PU resins.
In graphene-latex dispersions, latex and water are used for dispersed graphite alkene, and wherein latex is mainly used as adhesive,
Graphene is tightly adhered in the glue surface of kiss-coating gloves embryo, a layer graphene overlay film is formed in glue surface.
Preferably, the first latex used and the second latex in graphene-latex dispersions are identical type in rubber cement
Latex can be improved graphene overlay film and adhere to adhesion strength in internal layer glue surface, and after drying, graphene overlay film can be attached to more long
Glove surface.
According to an embodiment of the present invention, the type of the graphene be selected from chemical vapor infiltration prepare graphene,
CO 2 supercritical expansion stripping graphene, chemical oxidation stripping graphene, coupling agent modified graphene oxide, amino high score
Sub- modified graphene oxide, cationic surfactant modified graphene oxide, bromododecane modified graphene oxide, bromo
Hexadecane modified graphene oxide, bromo-octadecane modified graphene oxide, high-temperature heat expansion redox graphene, Low Temperature Thermal
It expands redox graphene, electrochemical stripping graphene, the electrochemical stripping graphene of modification, mechanical ball mill and removes graphite
One or more of alkene, three-roll grinder mechanical stripping graphene.
Wherein, the additive amount of the foaming agent is more than 0, and effect is that the rubber cement for making to be prepared is expansion type rubber cement, institute
The coefficient of foaming for stating expansion type rubber cement is 1.1~1.6 times, be used in combination thickener be thickened to viscosity be 1200mpa.s~
2500mpa.s；The usage amount of thickener is about 0.5~4 part.Glove product glue surface prepared by expansion type rubber cement has stomata,
There is gas permeability and quality more soft conformable, wearer's experience is more comfortable.Non-foamed type butyronitrile class polarity latex glove is harder,
And it can be significantly improved using comfort after foaming.
Wherein, the foaming agent is potassium oleate, neopelex, lauryl sodium sulfate, sodium ricinoleate, the moon
The arbitrary combination of one kind or aforementioned items in the anion surfactants such as cinnamic acid potassium.These anion surfactants, phase
For cationic surfactant, the expansion type rubber cement being prepared can be made more stable.
According to an embodiment of the present invention, the additive amount of the antitack agent is more than 0, may be selected to be paraffin wax emulsions, stearic acid
One or more of zinc lotion, calcium stearate lotion, silicone oil emulsion or fluorine-containing polymer compound combine.Antitack agent is called
Anti-blocking agent (antiadhesion agent) can reduce sizing material or sizing tack, reduce the adhesion on surface and have generation slightly
The substance of micro- rough surface effect.The infusibility powder usually ground, it is also possible to the lubricants such as paraffin.
According to an embodiment of the present invention, the additive amount of the anti-creme is more than 0, may be selected to be the breast of paraffin and beeswax class
Liquid.The anti-creme can increase rubber to the solvability of vulcanizing agent (sulfur-bearing agent in prevulcanized rubber), prevent gloves system
There is analysis sulphur bloom phenomenon in product surface, and analyses the secure adhesion that sulphur bloom can interfere graphene-latex dispersions in glue surface.Frost prevention
Agent main component is alkaline matter, achievees the purpose that frost prevention by acid-base neutralization reaction.In addition, can also be increased with pine tar etc.
Sizing material is to the solubility of above-mentioned compounding agent, to reduce bloom phenomenon.
Wherein, the thickener be sodium carboxymethylcellulose CMC, hydroxymethyl ethylcellulose, hydroxyethylpropyl cellulose,
The arbitrary combination of one kind or aforementioned items in Sodium Polyacrylate, polyacrylic acid, casein, PVAC polyvinylalcohol.Pass through thickener
By the expansion type rubber cement formulated viscosity to 1200mpa.s~2500mpa.s.After viscosity determines gloves embryo impregnation, it is stranded in
The thickness and product rubber thickness of gloves embryo surface glue-line, thus in actual production, can be allocated according to the thickness of needs
The additive amount of thickener controls viscosity to desirable value.
According to an embodiment of the present invention, gloves embryo takes out kiss-coating gloves embryo after being impregnated with the rubber cement, is placed through dripping glue
15~30s, extra glue drip, and 30~120s of spin coating keeps the rubber cement of gloves embryo surface uniform；Graphene-the glue is impregnated again
Newborn dispersion liquid then takes out product among the gloves for hanging with graphene-latex dispersions, drips 15~45s of glue, and extra glue drips,
30~120s of spin coating makes graphene-latex dispersions attachment/cover more uniform.
According to an embodiment of the present invention, the gloves embryo is chemical fibre knitted gloves embryo or cotton wool gloves embryo, the chemical fibre
Knitted gloves embryo further includes the pretreatment for impregnating coagulator before impregnation, and the coagulator is calcium chloride, calcium nitrate or chlorination
The alcoholic solution of zinc；Gloves embryo temperature is 45~55 DEG C when impregnating coagulator.
Due to, chemical fibre knitted gloves embryo (rubber gloves liner) hole is larger, is such as handled without pre-soaked coagulator,
When can lead to impregnation, sizing material penetrates on the inside of gloves embryos (side contacted with skin of hand), and user is uncomfortable, product does not conform to and wants
It asks.And the hole very little of cotton interlock gloves, it generally will not there is a situation where penetrate into inside after impregnation.When impregnating coagulator, hand
Set embryo requires heat to certain temperature, can so help the alcohol (alcohol of liquid under the room temperature such as methanol or ethyl alcohol) in coagulator can
Quickly volatilize away, if otherwise gloves temperature when immersing in coagulator is too low, alcohol liquid is difficult to wave to send out in time, after
Will appear when continuous impregnation processing drop wear, seep through, or a series of problems, such as decortication, so will there is centainly gloves embryo when dipping coagulator
Temperature, preferably 45 DEG C~55 DEG C.
According to an embodiment of the present invention, the vulcanization drying includes cryogenic vulcanization drying and two ranks of high temperature vulcanized drying
Section, wherein it is 10~40min that the cryogenic vulcanization drying temperature, which is 70~90 DEG C of times,；The high temperature vulcanized drying temperature is
100~130 DEG C of 90~130min of time.
Vulcanization drying, which is divided into the benefit in two stages, is：Since latex film forming process is slower, to pass through tightly packed
Process, if start just using high temperature vulcanized, it is easy to so that the surface quick film-forming of product is fine and close, and inside due to moisture compared with
It is more, it causes steam that can not be discharged, can only be formed and be bubbled in product surface, cause serious product defects, especially latex dipping
Class thick product, it is therefore desirable to first pass through cryogenic vulcanization (≤90 DEG C) 10~40 minutes or so, make product processing be easier, avoid lacking
It falls into and generates；Then high temperature vulcanized (>=100 DEG C) 90 minutes or more are carried out, product performance and production standard are reached.
Prevulcanized latex：Refer to it is a kind of be added vulcanizing agent into latex dispersions, and processing one is predetermined in a heated condition
The slight vulcanizing treatment technique of time.
The beneficial effects of the invention are as follows：
(1) graphene is configured to graphene-latex dispersions by the present invention, and wherein graphene is covered in as a kind of overlay film
Outside gloves glue surface, internal layer gloves glue surface is formed and is protected, anti-friction, being folded without breaking, the cut resistant for improving glove product entirety are anti-tear
It the performances such as splits, while making gloves that there is biocidal property.
(2) gloves preparation section is changed to double-steeping process, i.e., one by the present invention by the single-steeping process of the prior art
The secondary rubber cement for impregnating not graphene-containing, makes gloves embryo surface kiss-coating；Then double-steeping graphene-latex dispersions make primary
One layer graphene-latex dispersions are adhered on the glue surface surface of dipping.Then drying is handled, the graphene-latex dispersions shape
At one layer of overlay film containing graphene, it is covered in soaking and is formed in rubber face.
(3) not graphene-containing ingredient in being prepared due to the rubber cement of single-steeping, will not caused by graphene is added glue
The excessive problem of slurry viscosity, the rubber cement can get ideal wetting capacity, and the sizing material uniformly continuous of gloves embryo surface is flat after impregnation
It is sliding, be not in disconnected glue, split glue, seep through and refer between portion into web and other issues, ensures the quality of rubber gloves body part.
And double-steeping graphene-latex dispersions, the dispersion liquid are formed by graphene, latex and water mixed preparing,
Middle latex serves as the effect of adhesive herein, graphene is adhered in the glue surface of single-steeping formation.Although graphene-
Latex dispersions also have viscosity excessive the problem of being difficult to allocate, but graphene-latex dispersions that double-steeping uses are not constituted
The body construction of gloves, therefore without adding any other compounding agent (vulcanizing agent, accelerating agent, activating agent, frost prevention in dispersion liquid
Agent, dispersant, antitack agent etc.), therefore, the adding proportion of graphene can be enhanced.It simultaneously will not be viscous because of graphene dispersing solution
Between spending big and causing to split glue, seep through, refer to the serious quality problems that gloves use function substantially are influenced at web etc..This is because,
After single-steeping rubber cement, have there are one relatively smooth base surface that (knitted gloves indusium rubber cement covers after gloves embryo kiss-coating
Lid), infiltration resistance reduces, and is convenient for double-steeping graphene-latex dispersion, even if being impregnated into the prodigious graphene dispersion of viscosity
Liquid remains to preferably kiss-coating and spin coating.It, only need to be by the kiss-coating gloves embryo overall local of single-steeping (as only in double-steeping
Palmar hand and finger portion) quickly immerse in graphene-latex dispersions, take out drying.By graphene-latex dispersion after drying
The impregnated position of liquid all covers a layer graphene overlay film, and good protection can be formed to internal layer gloves glue surface, improves gloves system
The performances such as anti-friction, being folded without breaking, the cut resistant tear-proof of product entirety, while making gloves that there is biocidal property.
(4) pass through double-steeping, form the rubber body structure division of gloves after the rubber cement solidification of single-steeping, ensure this
The basic labor protection effect that the quality of body structure meets relevant criterion (EN388), ensures gloves；Double-steeping forms graphene
Overlay film, the rubber glue surface that soaking can be protected to be formed, and promote glove product entirety properties.
In conclusion the present invention forms protective layer using graphene in rubber glove surface, good expected effect is reached
Fruit, especially abrasion resistance are obviously improved, and gloves tensile strength and tear-resistant intensity are all significantly improved.According to the present invention
What method made, 13 needles (model of needle used in pointer glove knitter) terylene butyronitrile foam glove is by EN388 tests grade
3142 is (digital to correspond to respectively：It is wear-resisting, cut, tear, pierce through), and common 13 needle terylene butyronitrile gloves test grade by EN388
Only 2131, therefore, gloves overall performance prepared by the method for the present invention is obviously improved, and resistance to wearing property was up to 6 days or more.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1
Step S1：Prepare the rubber cement of not graphene-containing：By the presulfurization NBR latex of 100 parts by weight and 2 parts of CMC (2% matter
Measure score) after mixing, the viscosity that obtains is the rubber cement of 1800mpa.s.
Step S2：50 DEG C of knitted gloves embryos are immersed in 2.5% calcium nitrate methanol soln coagulator, carries out dipping solidification
Agent is handled, then is immersed in rubber cement prepared by step S1, drop glue 18 seconds, spin coating 50 seconds.
Step S3：Prepare graphene-latex dispersions：By the chemical oxidations of 100 parts by weight stripping graphene (10nm~
100nm), 150 parts of presulfurization NBR latexes and 2000 parts of water mix to obtain graphene-latex dispersions.
Step S4：The kiss-coating gloves embryo that will be handled through step S2, then impregnate the graphene-latex dispersions of S3 preparations
In, drop glue 20 seconds, spin coating 50 seconds.
Step S5：Vulcanization drying, after first carry out cryogenic vulcanization temperature be 80 DEG C, the time be 30 minutes；High temperature sulphur is carried out again
It is 105~110 DEG C to change temperature, and the time is 120 minutes；The graphene overlay film rubber gloves is made.
The gloves of the present embodiment are compared with existing gloves, it is as a result as follows：
Embodiment 2
Step S1：Prepare the rubber cement of not graphene-containing：By the presulfurization NBR latex of 120 parts by weight, it is mixed into 1 part of oleic acid
Potassium, after addition is mixed with 4 parts of CMC (2% mass fraction), the viscosity obtained is the expansion type rubber cement of 2100mpa.s.
Step S2：45 DEG C of knitted gloves embryos are immersed in 3% calcium chloride methanol solution coagulator, carries out dipping coagulator
Processing, then immerse in expansion type rubber cement prepared by step S1, drop glue 20 seconds, spin coating 60 seconds.
Step S3：Prepare graphene-latex dispersions：By the chemical oxidations of 120 parts by weight stripping graphene (10nm~
100nm), 300 parts of presulfurization NBR latexes and 3000 parts of water mix to obtain graphene-latex dispersions.
Step S4：The kiss-coating gloves embryo that will be handled through step S2, then impregnate the graphene-latex dispersions of S3 preparations
In, drop glue 40 seconds, spin coating 100 seconds.
Step S5：Vulcanization drying：It is 70 DEG C first to carry out cryogenic vulcanization temperature afterwards, and the time is 20 minutes；High temperature sulphur is carried out again
It is 110~120 DEG C to change temperature, and the time is 90 minutes；The graphene overlay film rubber gloves is made.
The gloves of the present embodiment are compared with existing gloves, it is as a result as follows：
Embodiment 3
Step S1：Prepare the rubber cement of not graphene-containing：By the presulfurization polychloroprene latex of 90 parts by weight, it is mixed into 0.5 portion of castor-oil plant
Enuatrol, after 1 part of silicone oil emulsion antitack agent, addition are mixed with 0.5 part of PVA, the viscosity obtained is the expansion type glue of 1600mpa.s
Slurry.
Step S2：55 DEG C of knitted gloves embryos are immersed in 3% zinc chloride methanol solution coagulator, carries out dipping coagulator
Processing, then immerse in expansion type rubber cement prepared by step S1, drop glue 20 seconds, spin coating 80 seconds.
Step S3：Prepare graphene-latex dispersions：By the chemical oxidations of 90 parts by weight stripping graphene (10nm~
100nm), 160 parts of presulfurization polychloroprene latexs and 2500 parts of water mix to obtain graphene-latex dispersions.
Step S4：The kiss-coating gloves embryo that will be handled through step S2, then impregnate the graphene-latex dispersions of S3 preparations
In, drop glue 30 seconds, spin coating 90 seconds.
Step S5：Vulcanization drying：It is 70 DEG C first to carry out cryogenic vulcanization temperature afterwards, and the time is 20 minutes；High temperature sulphur is carried out again
It is 110~120 DEG C to change temperature, and the time is 90 minutes；The graphene overlay film rubber gloves is made.
Embodiment 4
Step S1：Prepare the rubber cement of not graphene-containing：By the presulfurization styrene-butadiene latex of 100 parts by weight, it is mixed into 1.5 portions of bays
Sour potassium, after 4 parts of zinc stearate lotion antitack agents, 1 part of beeswax lotion, addition are mixed with 4 parts of casein, the viscosity obtained is
The expansion type rubber cement of 2200mpa.s.
Step S2：45 DEG C of knitted gloves embryos are immersed in 5% zinc chloride ethanol solution coagulator, carries out dipping coagulator
Processing, then immerse in expansion type rubber cement prepared by step S1, drop glue 30 seconds, spin coating 100 seconds.
Step S3：Prepare graphene-latex dispersions：By the chemical oxidations of 100 parts by weight stripping graphene (10nm~
100nm), 450 parts of presulfurization styrene-butadiene latexes and 4000 parts of water mix to obtain graphene-latex dispersions.
Step S4：The kiss-coating gloves embryo that will be handled through step S2, then impregnate the graphene-latex dispersions of S3 preparations
In, drop glue 40 seconds, spin coating 80 seconds.
Step S5：Vulcanization drying：It is 80 DEG C first to carry out cryogenic vulcanization temperature afterwards, and the time is 20 minutes；High temperature sulphur is carried out again
It is 110~118 DEG C to change temperature, and the time is 120 minutes；The graphene overlay film rubber gloves is made.
Embodiment 5
Step S1：Prepare the rubber cement of not graphene-containing：By the pre-vulcanized butyl rubber breast of 100 parts by weight, it is mixed into 3 parts of dodecanes
Base benzene sulfonic acid sodium salt, 0.5 part of zinc stearate lotion antitack agent, 0.5 part of beeswax lotion are added and are mixed with 4 parts of hydroxymethyl ethylcelluloses
After conjunction, the viscosity obtained is the expansion type rubber cement of 2000mpa.s.
Step S2：50 DEG C of knitted gloves embryos are immersed in 5% calcium chloride ethanol solution coagulator, carries out dipping coagulator
Processing, then immerse in expansion type rubber cement prepared by step S1, drop glue 20 seconds, spin coating 70 seconds.
Step S3：Prepare graphene-latex dispersions：By the CO 2 supercritical expansion stripping graphite of 100 parts by weight
Alkene (10nm~100nm), 350 parts of pre-vulcanized butyl rubber breasts and 3500 parts of water mix to obtain graphene-latex dispersions.
Step S4：The kiss-coating gloves embryo that will be handled through step S2, then impregnate the graphene-latex dispersions of S3 preparations
In, drop glue 15 seconds, spin coating 90 seconds.
Step S5：Vulcanization drying：It is 80 DEG C first to carry out cryogenic vulcanization temperature afterwards, and the time is 20 minutes；High temperature sulphur is carried out again
It is 110~118 DEG C to change temperature, and the time is 120 minutes；The graphene overlay film rubber gloves is made.
Embodiment 6
Step S1：Prepare the rubber cement of not graphene-containing：By the presulfurization natural emulsion of 100 parts by weight, it is mixed into 2 parts of dodecanes
Base benzene sulfonic acid sodium salt, after 2 parts of silicone oil emulsion antitack agents, 3 parts of beeswax lotions, addition are mixed with 3 parts of polyacrylic acid, the viscosity obtained is
19000mpa.s expansion type rubber cement.
Step S2：50 DEG C of knitted gloves embryos are immersed in 5% calcium chloride ethanol solution coagulator, carries out dipping coagulator
Processing, then immerse in expansion type rubber cement prepared by step S1, drop glue 30 seconds, spin coating 60 seconds.
Step S3：Prepare graphene-latex dispersions：By the electrochemical stripping graphenes of 100 parts by weight (10nm~
100nm), 400 parts of presulfurization natural emulsions and 2000 parts of water mix to obtain graphene-latex dispersions.
Step S4：The kiss-coating gloves embryo that will be handled through step S2, then impregnate the graphene-latex dispersions of S3 preparations
In, drop glue 30 seconds, spin coating 100 seconds.
Step S5：Vulcanization drying：It is 80 DEG C first to carry out cryogenic vulcanization temperature afterwards, and the time is 20 minutes；High temperature sulphur is carried out again
It is 110~118 DEG C to change temperature, and the time is 120 minutes；The graphene overlay film rubber gloves is made.
According to graphene overlay film gloves prepared by the method for embodiment 3-6, through visual examination, surface do not occur splitting glue and
Seep through, the serious quality problems used at influences such as web, solid or gas bulges between referring to, after tested glove product cut wear-resisting
It cuts, tears, penetration performance is all significantly improved, and resistance to wearing is reachable 5 days or more (usually only 3 days or so), and due to graphene
Overlay film makes gloves also have certain bacteriostasis property.
Claims (10)
1. a kind of graphene overlay film rubber gloves, which is characterized in that include：Gloves embryo, the rubber for being attached to the gloves embryo outer surface
Glue-line and the graphene film layer for being covered in the rubber layer outer surface；The rubber layer is the expansion type rubber of not graphene-containing
Glue or non-foamed type rubber.
2. a kind of preparation method of graphene overlay film rubber gloves, which is characterized in that including：
Knitted gloves embryo is impregnated with the rubber cement by the rubber cement for preparing not graphene-containing；
Graphene-latex dispersions are prepared, the kiss-coating gloves embryo for being impregnated with the rubber cement is impregnated into the graphene-latex point again
Dispersion liquid；
Vulcanization drying, is made the graphene overlay film rubber gloves.
3. the preparation method of graphene overlay film rubber gloves according to claim 2, which is characterized in that the rubber cement passes through
It is prepared by following methods：By the first latex of 90~120 parts of parts by weight, 0~3 part of anti-creme, 0~4 part of antitack agent, 0~3 part
Foaming agent mixing preparation, then with thickener thicken be made the rubber cement；First latex is presulfurization NBR latex, pre- sulphur
Change natural emulsion, presulfurization polychloroprene latex, pre-vulcanized butyl rubber breast, presulfurization styrene-butadiene latex or one kind in aqueous PU resins or
Several combinations.
4. the preparation method of graphene overlay film rubber gloves according to claim 2 or 3, which is characterized in that the graphite
Alkene-latex dispersions are prepared by the following method：By the graphene of 90~120 parts of parts by weight, 100~500 part of second latex,
800-5000 parts of water mixing preparations obtain graphene-latex dispersions；Second latex and the first latex are identical or different, described
Second latex is presulfurization NBR latex, presulfurization natural emulsion, presulfurization polychloroprene latex, pre-vulcanized butyl rubber breast, presulfurization
The combination of one or more of styrene-butadiene latex or aqueous PU resins.
5. the preparation method of graphene overlay film rubber gloves according to claim 4, which is characterized in that the graphene
Type is selected from graphene, CO 2 supercritical expansion stripping graphene, chemical oxidation prepared by chemical vapor infiltration and removes
Graphene, coupling agent modified graphene oxide, the macromolecule modified graphene oxide of amino, cationic surfactant are modified oxidized
Graphene, bromododecane modified graphene oxide, bromohexadecane modified graphene oxide, the modified oxidized stone of bromo-octadecane
Black alkene, high-temperature heat expansion redox graphene, low temperature thermally expand redox graphene, electrochemical stripping graphene, modification
Electrochemical stripping graphene, mechanical ball mill stripping graphene, one or more of three-roll grinder mechanical stripping graphene.
6. the preparation method of graphene overlay film rubber gloves according to claim 3, which is characterized in that the antitack agent
Additive amount is more than 0, and the antitack agent is paraffin wax emulsions, zinc stearate lotion, calcium stearate lotion, silicone oil emulsion or fluorine-containing height
One or more of molecular compound combines.
7. the preparation method of graphene overlay film rubber gloves according to claim 3, which is characterized in that the foaming agent
Additive amount is more than 0, and the foaming agent is potassium oleate, neopelex, lauryl sodium sulfate, sodium ricinoleate, the moon
The arbitrary combination of one kind or aforementioned items in the anion surfactants such as cinnamic acid potassium.
8. the preparation method of graphene overlay film rubber gloves according to claim 3, which is characterized in that the anti-creme
Additive amount is more than 0, and the anti-creme is the lotion of paraffin and beeswax class.
9. the preparation method of graphene overlay film rubber gloves according to claim 2, which is characterized in that the gloves embryo exists
After being impregnated with the rubber cement, kiss-coating gloves embryo is taken out, after dripping glue placement 15~30s, 30~120s of spin coating, then impregnates the graphite
Alkene-latex dispersions after taking-up, drips 15~45s of glue, 30~120s of spin coating.
10. the preparation method of graphene overlay film rubber gloves according to claim 2, which is characterized in that the vulcanization is dried
Dry includes cryogenic vulcanization drying and two stages of high temperature vulcanized drying, wherein when the cryogenic vulcanization drying temperature is 70~90 DEG C
Between be 10~40min；The high temperature vulcanized drying temperature is 100~130 DEG C of 90~130min of time.
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