CN108486902B - Graphene film-coated rubber glove and preparation method thereof - Google Patents
Graphene film-coated rubber glove and preparation method thereof Download PDFInfo
- Publication number
- CN108486902B CN108486902B CN201810205090.6A CN201810205090A CN108486902B CN 108486902 B CN108486902 B CN 108486902B CN 201810205090 A CN201810205090 A CN 201810205090A CN 108486902 B CN108486902 B CN 108486902B
- Authority
- CN
- China
- Prior art keywords
- graphene
- latex
- glove
- rubber
- vulcanized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- D06N3/0043—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
-
- 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
-
- 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
-
- 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
- D06N3/04—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
-
- 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
- D06N2209/10—Properties of the materials having mechanical properties
- D06N2209/103—Resistant to mechanical forces, e.g. shock, impact, puncture, flexion, shear, compression, tear
-
- 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
- D06N2209/10—Properties of the materials having mechanical properties
- D06N2209/105—Resistant to abrasion, scratch
-
- 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
-
- 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
- D06N2211/10—Clothing
- D06N2211/103—Gloves
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Gloves (AREA)
Abstract
The invention relates to a graphene film-covered rubber glove, which comprises: the glove comprises a glove blank, a rubber layer attached to the outer surface of the glove blank, and a graphene film layer covering the outer surface of the rubber layer; the rubber layer is foamed rubber or non-foamed rubber without graphene. The preparation method of the glove comprises the following steps: preparing mucilage without graphene, and impregnating the knitted glove blank with the mucilage; preparing a graphene-latex dispersion liquid, and dipping the rubberized glove blank dipped with the rubber cement into the graphene-latex dispersion liquid; and vulcanizing and drying to obtain the graphene coated rubber glove. The rubber body structure part of the glove is formed after the rubber cement which is dipped for the second time and is dipped for the first time is solidified, so that the quality of the body structure is ensured to meet the relevant standard (EN388), and the basic labor protection effect of the glove is ensured; the graphene coating is formed by secondary impregnation, so that the rubber surface formed by primary impregnation can be protected, and all performances of the whole glove product are improved.
Description
Technical Field
The invention relates to a preparation method of gloves, in particular to graphene coated rubber gloves and a preparation method thereof.
Background
Graphene is the thinnest two-dimensional material found at present as a monoatomic layer material, the theoretical thickness of the graphene is only 0.35nm, and the graphene has a large specific surface area 2600m2The modulus of elasticity is 1000Gpa, and the material is often applied to the fields of physics, materials, electronic information, computers and the like. The elastic modulus is an index for measuring the difficulty of the material in elastic deformation, and the larger the value is, the larger the rigidity of the material is. The graphene is added into the rubber, so that the rubber product has various effects of increasing the abrasion resistance, high strength and antibacterial activity, improving the mechanical strength of the rubber and the like. However, the prior art for applying the rubber gloves to rubber gloves is not much and the technology is immature.
For example, chinese patent application CN107118410A discloses a method for preparing graphene-butyronitrile foamed gloves, in which graphene is directly mixed with a prepared butyronitrile foamed slurry to obtain a graphene-containing composite slurry, and a knitted glove blank is impregnated with the composite slurry. The graphene is a nano material, has very high viscosity, and even if the addition amount of the graphene is only 0.1-0.2% when the graphene is mixed with the adhesive cement, the viscosity of the composite adhesive cement reaches 3000mpa.s or more. The mucilage with high viscosity is not only difficult to add various compounding agents (even if the mucilage is added, the dispersion uniformity is poor), but also causes a series of quality problems due to excessively high viscosity, for example, the glove has the quality problems of glue opening and glue penetration, web formation between fingers and the like after being dried because the mucilage has extremely poor wetting capacity and the glove blank is difficult to soak and glue even. If the graphene and the viscosity are required to be added, the addition amount of the graphene is controlled to be less than 0.1%, so that the overall performance of the glove is not obviously improved; or the surface tension of the latex is reduced by adding a synergist (such as Span, Tween and the like) so that more graphene is dissolved into the slurry, and the problems of glue penetration, glue cracking and the like are easily caused by adding the synergist.
The reason is mainly that (1) the specific surface area of graphene is large, and graphene only has solubility in a nonpolar solvent, so even if the graphene is added into latex in a low content, the graphene brings high viscosity, and the amount of graphene which can be added is small, so that the overall performance of the glove is difficult to improve. (2) When the viscosity of the mucilage is too high, the wettability of the mucilage to a knitted glove blank (the impregnation resistance of the knitted glove blank is large due to the fact that the holes contain air, the fibers are many, the surface is rough and the like) is extremely poor, the gum dipping and glue leveling difficulty is large, the gum material on the surface of the glove blank after gum dipping is in a shape of slag, blocks, bulges under the gum surface, the gum material on different parts is broken or uneven in thickness and the like, the gum surface after drying is broken and cracked, even the gum penetrates through (local through holes), even fingers of the glove blank are connected into webs, and the glove product is seriously unqualified. In summary, the processing technology of directly mixing graphene and latex for dipping knitted glove blanks cannot produce qualified glove products.
Therefore, how to better utilize the performance of the graphene to manufacture the rubber gloves without influencing the normal manufacture and production of the rubber gloves is a technical problem to be solved by the invention.
Disclosure of Invention
The invention aims to provide a technical scheme which can not only make full use of excellent physical and chemical properties of graphene, but also effectively ensure the quality of rubber glove products
In order to solve the problems in the prior art, the invention provides a graphene film-coated rubber glove and a preparation method thereof, wherein graphene and latex are mixed to prepare a graphene film, the graphene film is covered on the outer surface of the rubber surface of the glove, the graphene film is tightly adhered to the surface of the rubber surface by taking the latex as an adhesive, the rubber surface of the inner layer of the glove is protected, and the overall strength, the friction resistance, the bacteriostasis, the cutting resistance, the tearing resistance and other comprehensive performances of the glove are improved; the rubber glove body formed by the inner rubber surface is used for protecting hands from labor.
In order to achieve the purpose, the invention adopts the main technical scheme that:
a graphene-coated rubber glove comprising: the glove comprises a glove blank, a rubber layer attached to the outer surface of the glove blank, and a graphene film layer covering the outer surface of the rubber layer; the rubber layer is foamed rubber or non-foamed rubber without graphene.
A preparation method of graphene coated rubber gloves comprises the following steps:
preparing mucilage without graphene, and impregnating the knitted glove blank with the mucilage;
preparing a graphene-latex dispersion liquid, and dipping the rubberized glove blank dipped with the rubber cement into the graphene-latex dispersion liquid;
and vulcanizing and drying to obtain the graphene coated rubber glove.
According to one embodiment of the invention, the cement is prepared by the following method: mixing and blending 90-120 parts by weight of first latex, 0-3 parts by weight of antifrost agent, 0-4 parts by weight of anti-sticking agent and 0-3 parts by weight of foaming agent, and thickening with a thickening agent to obtain the mucilage; the first latex is one or a combination of more of pre-vulcanized butyronitrile latex, pre-vulcanized natural latex, pre-vulcanized chloroprene latex, pre-vulcanized butyl latex, pre-vulcanized styrene-butadiene latex or water-based PU resin.
According to one embodiment of the present invention, the graphene-latex dispersion is prepared by the following method: mixing 90-120 parts by weight of graphene, 100-500 parts by weight of second latex and 800-5000 parts by weight of water to prepare a graphene-latex dispersion liquid; the second latex is the same as or different from the first latex, and is one or a combination of more of pre-vulcanized butyronitrile latex, pre-vulcanized natural latex, pre-vulcanized neoprene latex, pre-vulcanized butyl latex, pre-vulcanized styrene-butadiene latex or water-based PU resin.
In the graphene-latex dispersion liquid, latex and water are used for dispersing graphene, wherein the latex is mainly used as an adhesive, the graphene is tightly adhered to the rubber surface of the rubber glove blank, and a graphene coating is formed on the rubber surface.
Preferably, the first latex used in the latex and the second latex in the graphene-latex dispersion are the same kind of latex, so that the adhesive force of the graphene coating adhering to the inner layer rubber surface can be improved, and the graphene coating can be adhered to the surface of the glove for a longer time after being dried.
According to an embodiment of the present invention, the graphene is selected from one or more of graphene prepared by a chemical vapor deposition method, carbon dioxide supercritical expansion exfoliated graphene, chemical oxidation exfoliated graphene, coupling agent modified graphene oxide, amino polymer modified graphene oxide, cationic surfactant modified graphene oxide, bromododecane modified graphene oxide, bromohexadecane modified graphene oxide, bromooctadecane modified graphene oxide, high temperature thermal expansion reduced graphene oxide, low temperature thermal expansion reduced graphene oxide, electrochemical exfoliated graphene, modified electrochemical exfoliated graphene, mechanical ball milling exfoliated graphene, and three-roll mill mechanical exfoliated graphene.
The foaming agent is added in an amount larger than 0, and has the function of enabling the prepared mucilage to be foaming type mucilage, wherein the foaming times of the foaming type mucilage are 1.1-1.6 times, and the foaming type mucilage is thickened by a thickening agent until the viscosity is 1200-2500 mpa.s; the thickener is used in an amount of about 0.5 to 4 parts. The glove product prepared from the foaming type adhesive cement has air holes on the adhesive surface, has air permeability, is softer and more flexible in texture, and is more comfortable for a wearer. The non-foamed butyronitrile polar latex gloves are relatively hard, and the comfort in use can be obviously improved after foaming.
The foaming agent is one or any combination of anionic surfactants such as potassium oleate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium ricinoleate and potassium laurate. These anionic surfactants provide more stability to the resulting foamed cement than cationic surfactants.
According to an embodiment of the invention, the addition amount of the anti-sticking agent is greater than 0, and the anti-sticking agent can be selected from one or a combination of several of paraffin emulsion, zinc stearate emulsion, calcium stearate emulsion, silicone oil emulsion or fluorine-containing high molecular compound. Antiblocking agents, also called antiblocking agents (antiadhesion agents), reduce the tackiness of the glue or adhesive, reduce surface adhesion and have the effect of producing a slightly rough surface. Usually, it is a ground infusible powder, and a lubricant such as paraffin may be used.
According to one embodiment of the invention, the amount of said antifrost is greater than 0, and it is possible to choose from the group of paraffin and beeswax-like emulsions. The antifrost agent can increase the dissolving capacity of rubber to a vulcanizing agent (the vulcanizing agent is contained in pre-vulcanized rubber), and prevent the surface of a glove product from generating sulfur precipitation and blooming phenomena which can prevent the graphene-latex dispersion liquid from firmly adhering to the rubber surface. The main component of the antifrost agent is alkaline substance, and the antifrost purpose is achieved through acid-base neutralization reaction. In addition, the solubility of the rubber compound to the compounding agents can be increased by pine tar oil and the like so as to reduce the blooming phenomenon.
Wherein the thickening agent is one or any combination of carboxymethylcellulose sodium CMC, hydroxymethyl ethyl cellulose, hydroxyethyl propyl cellulose, sodium polyacrylate, polyacrylic acid, casein and polyvinyl alcohol PVA. And (3) blending the foaming type mucilage with a thickening agent to obtain the viscosity of 1200-2500 mpa.s. The viscosity determines the thickness of the glue layer retained on the surface of the glove blank and the thickness of the rubber product after the glove blank is dipped, so that in the actual production, the addition amount of the thickening agent can be adjusted according to the required thickness to control the viscosity to a required value.
According to one embodiment of the invention, after the glove blank is impregnated with the rubber cement, taking out the rubberized glove blank, placing for 15-30 s by dripping the rubber, dripping the redundant rubber, and homogenizing for 30-120 s to make the rubber cement on the surface of the glove blank uniform; dipping the graphene-latex dispersion liquid, taking out the glove intermediate product hung with the graphene-latex dispersion liquid, dripping glue for 15-45 s, dripping redundant glue, and homogenizing the glue for 30-120 s, so that the graphene-latex dispersion liquid is more uniformly attached/covered.
According to one embodiment of the invention, the glove blank is a chemical fiber knitted glove blank or a cotton wool glove blank, the chemical fiber knitted glove blank further comprises pretreatment of dipping a coagulant before dipping, and the coagulant is an alcoholic solution of calcium chloride, calcium nitrate or zinc chloride; the temperature of the glove blank is 45-55 ℃ when the coagulant is impregnated.
Because the holes of the chemical fiber knitted glove blank (the inner container of the rubber glove) are large, if the pre-dipping coagulant treatment is not carried out, the rubber material can permeate into the inner side (the side contacted with the skin of the hand) of the glove blank during gum dipping, so that a user feels uncomfortable and the product is not satisfactory. The holes of the cotton interlock gloves are very small, and the cotton interlock gloves can not permeate the inner side after being dipped with glue. When the coagulant is soaked, the glove blank needs to be heated to a certain temperature, so that alcohol (liquid alcohol such as methanol or ethanol at normal temperature) in the coagulant can be volatilized quickly, otherwise, if the temperature of the glove when the glove is soaked in the coagulant is too low, the alcohol liquid is difficult to volatilize in time, a series of problems such as dripping, glue permeation or peeling can occur during subsequent gum dipping processing, and therefore the glove blank needs to have a certain temperature, preferably 45-55 ℃ when the coagulant is soaked.
According to one embodiment of the invention, the vulcanization drying comprises two stages of low-temperature vulcanization drying and high-temperature vulcanization drying, wherein the low-temperature vulcanization drying temperature is 70-90 ℃ and the time is 10-40 min; the high-temperature vulcanization drying temperature is 100-130 ℃ for 90-130 min.
The vulcanizing and drying are divided into two stages: because the latex film forming process is slow, a compact accumulation process is required, if high-temperature vulcanization is used at the beginning, the surface of a product is easily formed into a film rapidly and compactly, and the interior of the product cannot discharge water vapor due to more water, and only bubbles can be formed on the surface of the product, so that serious product defects are caused, especially latex dipped thick products, and therefore low-temperature vulcanization (less than or equal to 90 ℃) needs to be carried out for about 10-40 minutes, so that the product is easier to process, and the defects are avoided; then high-temperature vulcanization (not less than 100 ℃) is carried out for more than 90 minutes, and the use performance and the production standard of the product are achieved.
Pre-vulcanized latex: it is a light vulcanization treatment process in which a vulcanizing agent is added to a latex dispersion and treated under heating for a predetermined time.
The invention has the beneficial effects that:
(1) according to the invention, graphene is prepared into graphene-latex dispersion liquid, wherein the graphene is covered outside the rubber surface of the glove as a coating film to protect the rubber surface of the glove on the inner layer, so that the overall performances of friction resistance, puncture resistance, cutting resistance, tear resistance and the like of the glove product are improved, and the glove has antibacterial property.
(2) The method changes the glove preparation process from the primary dipping process in the prior art into the secondary dipping process, namely, the primary dipping is carried out on the adhesive cement without graphene, so that the surface of a glove blank is coated with adhesive; and then dipping the graphene-latex dispersion liquid for the second time to enable a layer of graphene-latex dispersion liquid to be attached to the surface of the rubber surface dipped for the first time. And then drying, so that the graphene-latex dispersion liquid forms a layer of covering film containing graphene, and the covering film covers the rubber surface formed by primary gum dipping.
(3) Because the preparation of the rubber cement for one-time dipping does not contain graphene components, the problem of overlarge viscosity of the rubber cement caused by adding graphene can be solved, the rubber cement can obtain ideal wetting capacity, the rubber material on the surface of the glove blank after dipping is uniform, continuous and smooth, the quality problems of rubber breakage, rubber cracking, rubber penetration, web formation between fingers and the like can be avoided, and the quality of the body part of the rubber glove is ensured.
And the second dipping graphene-latex dispersion liquid is prepared by mixing graphene, latex and water, wherein the latex plays a role of a binder here, and the graphene is adhered to the glue surface formed by the first dipping. Although the graphene-latex dispersion liquid also has the problem of overlarge viscosity and difficulty in preparation, the graphene-latex dispersion liquid used in the secondary dipping does not form the body structure of the glove, so that any other compounding agents (vulcanizing agent, accelerator, active agent, antifrost agent, dispersing agent, anti-sticking agent and the like) do not need to be added into the dispersion liquid, and the adding proportion of the graphene can be increased. Meanwhile, the serious quality problems of the basic use functions of the glove, such as glue cracking, glue penetration, web formation between fingers and the like caused by the overlarge viscosity of the graphene dispersion liquid, can be avoided. The reason is that after the rubber cement is dipped for the first time, the glove blank has a smoother base surface (the knitted glove blank is covered by the rubber cement) after being rubberized, the infiltration resistance is reduced, the graphene-latex dispersion liquid is convenient to dip for the second time, and the graphene dispersion liquid with high viscosity can still be rubberized and homogenized well even if the graphene dispersion liquid is dipped. During secondary dipping, the whole or part (such as only palm parts and finger parts) of the rubberized glove blank dipped at one time is quickly dipped into the graphene-latex dispersion liquid, and then the whole or part is taken out and dried. The positions dipped by the graphene-latex dispersion liquid after drying are covered with a graphene film, so that the inner glove rubber surface can be well protected, the overall performances of friction resistance, puncture resistance, cutting resistance, tear resistance and the like of the glove product are improved, and the glove has antibacterial property.
(4) After secondary dipping and curing of the primary dipped mucilage, a rubber body structure part of the glove is formed, so that the quality of the body structure is ensured to meet the relevant standard (EN388), and the basic labor protection effect of the glove is ensured; the graphene coating is formed by secondary impregnation, so that the rubber surface formed by primary impregnation can be protected, and all performances of the whole glove product are improved.
In conclusion, the protective layer is formed on the surface of the rubber glove by using the graphene, so that a good expected effect is achieved, particularly, the abrasion resistance is obviously improved, and the tensile strength and the tear resistance of the glove are obviously improved. The 13-needle (the type of the needle used by the pointer glove knitting machine) polyester butyronitrile foaming gloves manufactured according to the method are 3142 (numbers respectively correspond to abrasion resistance, cutting, tearing and puncturing) according to an EN388 test grade, while the common 13-needle polyester butyronitrile gloves are only 2131 according to the EN388 test grade, so that the overall performance of the gloves manufactured according to the method is obviously improved, and the wearing resistance can reach more than 6 days.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
Step S1: preparing a graphene-free adhesive cement: 100 parts by weight of the prevulcanised nitrile latex and 2 parts of CMC (2% mass fraction) were mixed to obtain a cement having a viscosity of 1800 mpa.s.
Step S2: and (3) soaking the knitted glove blank at the temperature of 50 ℃ into a 2.5% calcium nitrate methanol solution coagulant for coagulating agent soaking treatment, then soaking into the glue paste prepared in the step S1, dripping glue for 18 seconds, and homogenizing for 50 seconds.
Step S3: preparing a graphene-latex dispersion liquid: 100 parts by weight of chemical oxidation stripping graphene (10-100 nm), 150 parts of pre-vulcanized butyronitrile latex and 2000 parts of water are mixed to obtain graphene-latex dispersion liquid.
Step S4: dipping the rubberized glove blank processed in the step S2 into the graphene-latex dispersion liquid prepared in the step S3, dripping glue for 20 seconds, and homogenizing glue for 50 seconds.
Step S5: vulcanizing and drying, and then carrying out low-temperature vulcanization at the temperature of 80 ℃ for 30 minutes; then carrying out high-temperature vulcanization at 105-110 ℃ for 120 minutes; and preparing the graphene film-coated rubber glove.
The glove of this example was compared with the existing glove and the results were as follows:
example 2
Step S1: preparing a graphene-free adhesive cement: 120 parts by weight of pre-vulcanized butyronitrile latex is mixed with 1 part of potassium oleate, and the mixture is added and mixed with 4 parts of CMC (2 percent of mass fraction) to obtain the foaming type adhesive cement with the viscosity of 2100 mpa.s.
Step S2: and (3) soaking the knitted glove blank at the temperature of 45 ℃ into a 3% calcium chloride methanol solution coagulant for coagulant treatment, then soaking into the foaming type adhesive cement prepared in the step S1, dripping the adhesive for 20 seconds, and homogenizing for 60 seconds.
Step S3: preparing a graphene-latex dispersion liquid: 120 parts by weight of chemical oxidation stripping graphene (10 nm-100 nm), 300 parts of pre-vulcanized butyronitrile latex and 3000 parts of water are mixed to obtain graphene-latex dispersion liquid.
Step S4: dipping the rubberized glove blank processed in the step S2 into the graphene-latex dispersion liquid prepared in the step S3, dripping the glue for 40 seconds, and homogenizing for 100 seconds.
Step S5: and (3) vulcanization and drying: then, low-temperature vulcanization is carried out for 20 minutes at the temperature of 70 ℃; then carrying out high-temperature vulcanization at the temperature of 110-120 ℃ for 90 minutes; and preparing the graphene film-coated rubber glove.
The glove of this example was compared with the existing glove and the results were as follows:
example 3
Step S1: preparing a graphene-free adhesive cement: 90 parts by weight of pre-vulcanized neoprene latex, 0.5 part of sodium ricinoleate and 1 part of silicone oil emulsion anti-sticking agent are mixed, and then the mixture is added and mixed with 0.5 part of PVA to obtain the foaming type adhesive cement with the viscosity of 1600 mpa.s.
Step S2: and (3) soaking the knitted glove blank at the temperature of 55 ℃ into a 3% zinc chloride methanol solution coagulant for coagulant treatment, then soaking into the foaming type adhesive cement prepared in the step S1, dripping the adhesive for 20 seconds, and homogenizing for 80 seconds.
Step S3: preparing a graphene-latex dispersion liquid: 90 parts by weight of chemical oxidation exfoliated graphene (10 nm-100 nm), 160 parts by weight of pre-vulcanized neoprene latex and 2500 parts by weight of water are mixed to obtain the graphene-latex dispersion liquid.
Step S4: dipping the rubberized glove blank processed in the step S2 into the graphene-latex dispersion liquid prepared in the step S3, dripping glue for 30 seconds, and homogenizing glue for 90 seconds.
Step S5: and (3) vulcanization and drying: then, low-temperature vulcanization is carried out for 20 minutes at the temperature of 70 ℃; then carrying out high-temperature vulcanization at the temperature of 110-120 ℃ for 90 minutes; and preparing the graphene film-coated rubber glove.
Example 4
Step S1: preparing a graphene-free adhesive cement: 100 parts by weight of pre-vulcanized styrene-butadiene latex is mixed with 1.5 parts of potassium laurate, 4 parts of zinc stearate emulsion anti-sticking agent and 1 part of beeswax emulsion, and then the mixture is added and mixed with 4 parts of casein, so as to obtain the foaming type adhesive cement with the viscosity of 2200 mpa.s.
Step S2: and (3) soaking the knitted glove blank at the temperature of 45 ℃ into a 5% zinc chloride ethanol solution coagulant for coagulant treatment, then soaking into the foaming type adhesive cement prepared in the step S1, dripping the adhesive for 30 seconds, and homogenizing for 100 seconds.
Step S3: preparing a graphene-latex dispersion liquid: 100 parts by weight of chemical oxidation stripping graphene (10-100 nm), 450 parts of pre-vulcanized styrene-butadiene latex and 4000 parts of water are mixed to obtain the graphene-latex dispersion liquid.
Step S4: dipping the rubberized glove blank processed in the step S2 into the graphene-latex dispersion liquid prepared in the step S3, and dripping glue for 40 seconds and homogenizing glue for 80 seconds.
Step S5: and (3) vulcanization and drying: then, low-temperature vulcanization is carried out for 20 minutes at the temperature of 80 ℃; then carrying out high-temperature vulcanization at the temperature of 110-118 ℃ for 120 minutes; and preparing the graphene film-coated rubber glove.
Example 5
Step S1: preparing a graphene-free adhesive cement: 100 parts by weight of pre-vulcanized butyl latex is mixed with 3 parts of sodium dodecyl benzene sulfonate, 0.5 part of zinc stearate emulsion anti-sticking agent, 0.5 part of beeswax emulsion and 4 parts of hydroxymethyl ethyl cellulose, and then the mixture is mixed to obtain the foaming type adhesive cement with the viscosity of 2000 mpa.s.
Step S2: and (3) soaking the knitted glove blank at the temperature of 50 ℃ into a 5% calcium chloride ethanol solution coagulant for coagulant treatment, then soaking into the foaming type adhesive cement prepared in the step S1, dripping the adhesive for 20 seconds, and homogenizing for 70 seconds.
Step S3: preparing a graphene-latex dispersion liquid: 100 parts by weight of carbon dioxide supercritical expansion exfoliated graphene (10 nm-100 nm), 350 parts of pre-vulcanized butyl latex and 3500 parts of water are mixed to obtain the graphene-latex dispersion liquid.
Step S4: dipping the rubberized glove blank processed in the step S2 into the graphene-latex dispersion liquid prepared in the step S3, dripping the glue for 15 seconds, and homogenizing the glue for 90 seconds.
Step S5: and (3) vulcanization and drying: then, low-temperature vulcanization is carried out for 20 minutes at the temperature of 80 ℃; then carrying out high-temperature vulcanization at the temperature of 110-118 ℃ for 120 minutes; and preparing the graphene film-coated rubber glove.
Example 6
Step S1: preparing a graphene-free adhesive cement: 100 parts by weight of pre-vulcanized natural latex is mixed with 2 parts of sodium dodecyl benzene sulfonate, 2 parts of silicone oil emulsion anti-sticking agent and 3 parts of beeswax emulsion, and then the mixture is added and mixed with 3 parts of polyacrylic acid to obtain the foaming type adhesive cement with the viscosity of 19000 mpa.s.
Step S2: and (3) soaking the knitted glove blank at the temperature of 50 ℃ into a 5% calcium chloride ethanol solution coagulant for coagulant treatment, then soaking into the foaming type adhesive cement prepared in the step S1, dripping the adhesive for 30 seconds, and homogenizing for 60 seconds.
Step S3: preparing a graphene-latex dispersion liquid: 100 parts by weight of electrochemically exfoliated graphene (10nm to 100nm), 400 parts of pre-vulcanized natural latex and 2000 parts of water are mixed to obtain the graphene-latex dispersion.
Step S4: dipping the rubberized glove blank processed in the step S2 into the graphene-latex dispersion liquid prepared in the step S3, dripping glue for 30 seconds, and homogenizing glue for 100 seconds.
Step S5: and (3) vulcanization and drying: then, low-temperature vulcanization is carried out for 20 minutes at the temperature of 80 ℃; then carrying out high-temperature vulcanization at the temperature of 110-118 ℃ for 120 minutes; and preparing the graphene film-coated rubber glove.
The graphene film-coated gloves prepared according to the methods of examples 3 to 6 have no serious quality problems of glue cracking and glue penetration, web formation between fingers, solid or gas bulge and the like on the surfaces, which affect the use, through appearance inspection, the wear resistance, cutting, tearing and puncture resistance of the glove products are obviously improved through testing, the wear resistance can reach more than 5 days (usually only about 3 days), and the gloves have certain antibacterial performance due to the graphene film coating.
Claims (4)
1. A preparation method of graphene coated rubber gloves is characterized by comprising the following steps:
preparing mucilage without graphene, and impregnating the knitted glove blank with the mucilage; the mucilage is prepared by the following method: mixing and blending 90-120 parts by weight of first latex, 0.5-3 parts by weight of antifrost agent, 0.5-4 parts by weight of anti-sticking agent and 0-3 parts by weight of foaming agent, and thickening with a thickening agent to prepare the mucilage; the first latex is one or a combination of more of pre-vulcanized butyronitrile latex, pre-vulcanized natural latex, pre-vulcanized chloroprene latex, pre-vulcanized butyl latex, pre-vulcanized styrene-butadiene latex or water-based PU resin; the antifrost agent is emulsion of paraffin and beeswax;
the anti-sticking agent is one or a combination of a plurality of paraffin wax emulsion, zinc stearate emulsion, calcium stearate emulsion, silicone oil emulsion or fluorine-containing high molecular compounds;
preparing a graphene-latex dispersion liquid, and dipping the rubberized glove blank dipped with the rubber cement into the graphene-latex dispersion liquid;
the graphene-latex dispersion is prepared by the following method: mixing 90-120 parts by weight of graphene, 100-500 parts by weight of second latex and 800-5000 parts by weight of water to prepare a graphene-latex dispersion liquid; the graphene-latex dispersion is free of compounding components other than graphene, a second latex, and water;
the second latex is the same latex as the first latex, and the second latex is one or a combination of more of pre-vulcanized butyronitrile latex, pre-vulcanized natural latex, pre-vulcanized neoprene latex, pre-vulcanized butyl latex, pre-vulcanized styrene-butadiene latex or water-based PU resin;
the type of the graphene is selected from one or more of graphene prepared by a chemical vapor deposition method, carbon dioxide supercritical expansion stripping graphene, chemical oxidation stripping graphene, coupling agent modified graphene oxide, amino polymer modified graphene oxide, cationic surfactant modified graphene oxide, bromododecane modified graphene oxide, bromohexadecane modified graphene oxide, bromooctadecane modified graphene oxide, high-temperature thermal expansion reduced graphene oxide, low-temperature thermal expansion reduced graphene oxide, electrochemical stripping graphene, modified electrochemical stripping graphene, mechanical ball milling stripping graphene and mechanical stripping graphene by a three-roll grinder;
and vulcanizing and drying to obtain the graphene coated rubber glove.
2. The method for preparing the graphene coated rubber glove according to claim 1, wherein the amount of the foaming agent is greater than 0, and the foaming agent is one of potassium oleate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium ricinoleate and potassium laurate or any combination of the above.
3. The method for preparing the graphene coated rubber glove according to claim 1, wherein the glove blank is taken out of the rubberized glove blank after being impregnated with the rubber cement, placed for 15-30 s by dropping rubber, homogenized for 30-120 s, and then impregnated with the graphene-latex dispersion, and taken out of the rubberized glove blank, dropped for 15-45 s, and homogenized for 30-120 s.
4. The preparation method of the graphene coated rubber glove according to claim 1, wherein the vulcanization drying includes two stages of low-temperature vulcanization drying and high-temperature vulcanization drying, wherein the low-temperature vulcanization drying temperature is 70-90 ℃ for 10-40 min; the high-temperature vulcanization drying temperature is 100-130 ℃ for 90-130 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810205090.6A CN108486902B (en) | 2018-03-13 | 2018-03-13 | Graphene film-coated rubber glove and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810205090.6A CN108486902B (en) | 2018-03-13 | 2018-03-13 | Graphene film-coated rubber glove and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108486902A CN108486902A (en) | 2018-09-04 |
| CN108486902B true CN108486902B (en) | 2021-06-08 |
Family
ID=63338822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810205090.6A Active CN108486902B (en) | 2018-03-13 | 2018-03-13 | Graphene film-coated rubber glove and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108486902B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110625967B (en) * | 2019-08-13 | 2021-06-08 | 山东星宇手套有限公司 | Surface treatment method for preventing frosting of rubber product |
| CN110804873A (en) * | 2019-10-22 | 2020-02-18 | 芜湖华烨新材料有限公司 | Production method of graphene modified polyester impregnated canvas |
| CN111805822A (en) * | 2020-07-17 | 2020-10-23 | 世祥（惠州）塑料制品有限公司 | Preparation process of medical gloves |
| CN113071168A (en) * | 2021-03-31 | 2021-07-06 | 牛剑科技有限公司 | Graphene butyronitrile gloves |
| CN113429647A (en) * | 2021-07-07 | 2021-09-24 | 山东星宇手套有限公司 | Conductive rubber gloves and preparation method thereof |
| CN115093511B (en) * | 2022-07-14 | 2022-11-01 | 星宇新材料股份有限公司 | Butyronitrile butadiene styrene composite latex for dipped gloves and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237829A (en) * | 2015-11-23 | 2016-01-13 | 辽宁兰晶科技有限公司 | Preparing method for high-strength high-isolation condom comprising modified graphene/latex interlayer |
| CN105623013A (en) * | 2016-03-22 | 2016-06-01 | 镇江华扬乳胶制品有限公司 | Preparation method of high-strength, high-elongation, antibacterial and soft graphene rubber product |
| CN106065095A (en) * | 2016-06-08 | 2016-11-02 | 上海史墨希新材料科技有限公司 | Functional high-strength protective gloves of Graphene latex and preparation method thereof |
| CN107043477A (en) * | 2017-01-17 | 2017-08-15 | 南通强生安全防护科技股份有限公司 | Graphene NBR latex composite mortar and preparation method thereof, purposes |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532629B (en) * | 2011-12-30 | 2013-06-05 | 北京化工大学 | Preparation method of completely peeled oxidation graphene/ rubber nanometer composite material |
-
2018
- 2018-03-13 CN CN201810205090.6A patent/CN108486902B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105237829A (en) * | 2015-11-23 | 2016-01-13 | 辽宁兰晶科技有限公司 | Preparing method for high-strength high-isolation condom comprising modified graphene/latex interlayer |
| CN105623013A (en) * | 2016-03-22 | 2016-06-01 | 镇江华扬乳胶制品有限公司 | Preparation method of high-strength, high-elongation, antibacterial and soft graphene rubber product |
| CN106065095A (en) * | 2016-06-08 | 2016-11-02 | 上海史墨希新材料科技有限公司 | Functional high-strength protective gloves of Graphene latex and preparation method thereof |
| CN107043477A (en) * | 2017-01-17 | 2017-08-15 | 南通强生安全防护科技股份有限公司 | Graphene NBR latex composite mortar and preparation method thereof, purposes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108486902A (en) | 2018-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108486902B (en) | Graphene film-coated rubber glove and preparation method thereof | |
| CN109320807B (en) | Graphene-latex protective gloves and preparation method thereof | |
| US9781959B2 (en) | Glove having durable ultra-thin polymeric coating | |
| AU2013280209B2 (en) | Abrasion and cut resistant coating and coated glove | |
| EP3023018B1 (en) | Glove | |
| EP2181826B1 (en) | Production of coated gloves | |
| CN101920541B (en) | Production method of rubber gloves dipped in cotton velvet | |
| WO2009101943A1 (en) | Glove and process for producing the same | |
| CN108433220B (en) | Preparation method of butyronitrile particle anti-slip gloves | |
| CN113698679A (en) | Polymer blends of nitrile rubber and polychloroprene | |
| CN107043477A (en) | Graphene NBR latex composite mortar and preparation method thereof, purposes | |
| CN108477714B (en) | Preparation method of chloroprene chemical-resistant gloves | |
| CN106835721A (en) | The preparation method of Graphene NBR latex frosted gloves | |
| CN108456342B (en) | Manufacturing method of imitation frosted gloves | |
| US20200128890A1 (en) | Thin coated supported glove | |
| KR101505265B1 (en) | Synthetic rubber latex resin composition and cotton gloves coated the same | |
| CN108442128B (en) | Water-resistant rubber gloves and preparation method thereof | |
| US20220243367A1 (en) | Thin high cut seamless glove | |
| CN109135257A (en) | A kind of preparation method of aqueous PU frosted gloves | |
| KR100683897B1 (en) | A poly-urethane double gloves and its making method | |
| CN109805475A (en) | A kind of preparation method of wrinkle gloves | |
| JP2018016898A (en) | Glove and method of manufacturing the same | |
| KR20050014337A (en) | Preparation of polyurethane coating glove and polyurethane coating glove thereof | |
| AU2009230758B2 (en) | Production of coated gloves | |
| CN116874898B (en) | Butyronitrile texture superfine foaming glove and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: The invention relates to a graphene coated rubber glove and a preparation method thereof Effective date of registration: 20211112 Granted publication date: 20210608 Pledgee: Shandong Gaomi rural commercial bank Limited by Share Ltd. Pledgor: SHANDONG XINGYU GLOVES Co.,Ltd. Registration number: Y2021980012288 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20230413 Granted publication date: 20210608 Pledgee: Shandong Gaomi rural commercial bank Limited by Share Ltd. Pledgor: SHANDONG XINGYU GLOVES Co.,Ltd. Registration number: Y2021980012288 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |