KR102450376B1 - Non-woven fabric including fibrous graphene composite molded body - Google Patents

Abstract

It relates to a nonwoven fabric containing a graphene composite molded body in the form of a fiber, and more specifically, the graphene composite molded body includes graphene dispersed in a polymer resin, and the graphene composite molded body is a filtering process for discharging foreign substances to the outside It is characterized in that the nonwoven fabric containing the same has excellent antibacterial, antibacterial, deodorizing rate for harmful gas, antistatic, far-infrared emission, ultraviolet blocking rate, tensile strength and elongation characteristics.

Description

Non-woven fabric containing graphene composite molded body in fiber form {NON-WOVEN FABRIC INCLUDING FIBROUS GRAPHENE COMPOSITE MOLDED BODY}

The present invention relates to a nonwoven fabric containing a graphene composite molded body in the form of a fiber, and more particularly, the graphene composite molded body includes graphene dispersed in a polymer resin, and the graphene composite molded body discharges foreign substances to the outside Because it is manufactured through a filtering process, the nonwoven fabric containing it is characterized by having excellent antibacterial, bactericidal, deodorizing rate against harmful gas, antistatic, far-infrared emission, UV blocking rate, tensile strength and elongation characteristics.

A nonwoven fabric is a felt-form made by arranging fibers in a parallel or normal direction without going through a weaving process and bonding them with a synthetic resin adhesive. Synthetic fibers such as nylon were also used.

There are wet (濕 formula) and dry (乾 formula) processing methods for non-woven fabrics. Wet type is also called immersion type or papermaking type, and it is similar to paper, which is obtained by soaking fibers in a synthetic resin adhesive container and then drying and heat-treating them. Drying is a process in which a synthetic resin is sprayed on a fiber made into a thin cotton-like material, and heat is applied to dry it.

The production technology of non-woven fabric has developed rapidly in the United States since around 1950, and since the fibers are entangled, there is no longitudinal and horizontal direction, and there is no grain, so the cut edges do not come loose, so they are widely used for various industrial purposes. In particular, the cut surface does not come loose, and although the price is low, the strength can be maintained even when immersed in water or solvent, and the fibrous tissue does not dissociate. has been However, as the nonwoven fabric used in the past is a fibrous tissue bonded using synthetic fibers and resin-based adhesives, it is pointed out that the disadvantages are that the fibers themselves do not have excellent absorbency or moisture retention ability, and the absorption ability for various harmful substances accumulated in the skin is insufficient. .

Meanwhile, as environmental pollution worsens, efforts have been made to impart antibacterial and deodorizing properties to textile products for comfort, and efforts to impart antibacterial and deodorizing properties to nonwoven fabrics are continuing.

In this regard, in the early days of antibacterial processing, antibacterial agents were largely divided into aromatic halogen compounds, organosilicon quaternary ammonium salts, and other compounds. Among them, the most commonly used are metal or metal-containing inorganic particles, quaternary ammonium salts and organosilicon quaternary ammonium salts. This means that the cell wall is destroyed and removed to kill microorganisms and inhibit proliferation.

However, some aromatic halogen compounds are not currently used due to safety problems. In the past, antibacterial processing methods using metal ions or metals are processed after manufacturing the fabric. In particular, in the case of nonwoven fabrics used as sanitary agents, inorganic materials such as silver are easily removed and thus difficult to apply, and the use of nano-sized inorganic materials is gradually decreasing for safety reasons.

In addition, in the prior art, deodorizing properties were generally applied by a method of supporting a deodorant, which corresponds to a physical post-processing method, and the deodorant is lost due to reasons such as premature dropout, and there has been a disadvantage that the deodorization rate is significantly reduced.

Therefore, while the present inventors were studying to solve the above problems, when a graphene composite molded body containing graphene and a polymer resin is used as a fiber of the nonwoven fabric, the nonwoven fabric containing the same is excellent in antibacterial, bactericidal, and harmful gas. The present invention was completed by discovering that it had deodorization rate, antistatic, far-infrared ray emission, ultraviolet blocking rate, tensile strength and elongation characteristics.

In this regard, Korean Patent Registration No. 10-0643515 discloses a polypropylene spunbond nonwoven fabric having excellent antibacterial and deodorizing properties and a method for manufacturing the same.

The present invention has been devised to solve the problems of the prior art, and an object of the present invention is to provide a nonwoven fabric containing a graphene composite molded body in the form of a fiber.

Another object of the present invention is to provide a method for manufacturing the graphene composite molded body.

As a technical means for achieving the above-described technical problem, one aspect of the present invention is,

Provided is a nonwoven fabric containing a graphene composite molded article in the form of a fiber including graphene and a polymer resin.

The graphene may include a material selected from the group consisting of multilayer nanographene, nanographene plate-shaped powder, nanographene ribbon, functional graphene, graphene oxide, or combinations thereof.

The polymer resin is polyethylene (polyethylene, PE), polyvinyl chloride (PVC), polyethylene terephthalate (PET), polyolefin elastomer (POE), polypropylene (polypropylene, PP), Polyamide (PA), polycarbonate (PC), polybutylene terephthalate (PBT), ABS resin (acrylonitrile butadiene styrene copolymer), polyacetal (polyacetal), polyoxymethylene (POM) ), polyetherimide, polyurethane (PU), or a combination thereof may include a polymer resin selected from the group consisting of.

The content of the mixed graphene may be 0.001 parts by weight to 5 parts by weight based on 100 parts by weight of the polymer resin.

The nonwoven fabric may further contain at least one of natural fibers and synthetic fibers.

The nonwoven fabric may have a tensile strength of 57 Mpa to 100 Mpa.

The nonwoven fabric may have an elongation of 165% to 190%.

The nonwoven fabric may have a bacteriostatic reduction rate of 80% or more for Staphylococcus aureus or Klebsiella pneumoniae after 18 hours, respectively.

The nonwoven fabric may have a deodorization rate of 20% or more of ammonia, acetic acid, trimethylamine and formaldehyde for 2 hours, respectively.

In addition, another aspect of the present invention,

A method of manufacturing the graphene composite molded body, comprising: mixing graphene and a polymer resin; extruding the mixture; and filtering the foreign substances contained in the extruded mixture by discharging to the outside.

As described above, in the graphene composite molded article according to the present invention, foreign substances such as gas, water vapor, and low molecular chemical substances contained in graphene and molten polymer resin are removed, so that graphene and polymer resin are interfacing without adding a compatibilizer or coupling agent. Since they are not separated from each other, they have excellent mechanical properties.

In addition, since the graphene composite molded article as described above has excellent antibacterial, antibacterial, deodorizing rate for harmful gas, antistatic, far-infrared emission, tensile strength and elongation characteristics, when used as a fiber of the nonwoven fabric, the nonwoven fabric has very excellent efficacy. it could be

1 is a flowchart illustrating a method of manufacturing a graphene composite molded body according to an embodiment of the present invention.
2 is a schematic view showing an apparatus for manufacturing a graphene composite molded body according to an embodiment of the present invention.
3 is a schematic view showing a cross section of a hole plate according to an embodiment of the present invention.
4 is a schematic diagram illustrating a cross-section of a cutting part according to an embodiment of the present invention.
5a and 5b are graphs showing the emissivity and radiant energy according to the wavelength of the graphene composite molded body according to an experimental example of the present invention, respectively.
6 and 7 are photographs showing the antibacterial performance of the graphene composite molded body according to an experimental example of the present invention, respectively.
8 is a graph showing the deodorization rate of the graphene composite molded body according to an experimental example of the present invention.
9 is a photograph showing the antifungal performance of the graphene composite molded body according to an experimental example of the present invention.

Hereinafter, the present invention will be described in more detail. However, the present invention may be embodied in various different forms, and the present invention is not limited by the embodiments described herein, and the present invention is only defined by the claims to be described later.

In addition, the terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the entire specification of the present invention, 'including' any component means that other components may be further included, rather than excluding other components, unless otherwise stated.

The first aspect of the present application is

Provided is a nonwoven fabric containing a graphene composite molded article in the form of a fiber including graphene and a polymer resin.

Hereinafter, the nonwoven fabric according to the first aspect of the present application will be described in detail.

In one embodiment of the present application, the nonwoven fabric may be classified into a wet nonwoven fabric and a dry nonwoven fabric according to a web forming method. That is, the nonwoven fabric according to the present invention may be applicable to both the wet nonwoven fabric and the dry nonwoven fabric.

In one embodiment of the present application, the wet nonwoven fabric may refer to a nonwoven fabric mainly bonded with an adhesive using a web in which fibers are laminated in water using the principle of a conventional papermaking technique. In this case, as the type of the wet-laid nonwoven fabric, a spun-bonded non-woven fabric, a spunlacenon-woven fabric, a melt-blown non-woven fabric, a heat-sealed non-woven fabric ( thermally bonded non-woven fabric). To briefly describe each of the above nonwoven fabrics, first of all, the spunbond nonwoven fabric is also called a long fiber nonwoven fabric because it uses filaments. It is a kind of non-woven fabric made by blowing the fibers out onto a moving conveyor to form a layer of long fibers on the conveyor. It is efficient in terms of manufacturing process and has economic advantages.

In addition, the spunlace nonwoven fabric is a method of bonding fibers by spraying a jet water stream onto the web, and various designs can be obtained according to the pattern of the plate installed under the web receiving the jet water flow, and since no adhesive is used, the manufactured product Because of its excellent drape, absorbency, and bulkiness, it is widely used in medical sponges, surgical gowns, wicks, coated fabric bubbles, diaper covers, sanitary packs, and disposable industrial clothing.

In addition, the melt blown nonwoven fabric generally undergoes a manufacturing process of input of raw materials, extrusion/spinning, web formation, web cooling, and well bonding. That is, the nonwoven fabric manufactured by the above process is referred to as a melt blown nonwoven fabric, and since the web used is an ultrafine fiber, it has advantages that cannot be obtained from general nonwovens such as softness, heat retention and high filtration performance. However, the disadvantage is that the web strength is very weak, and there are many restrictions on use alone, so it is used in combination with a web or pulp or short fibers by the spunbond method.

Finally, the heat-sealed non-woven fabric refers to a non-woven fabric in which a low-melting-point thermoplastic fiber is melted and bonded to each other, and as a manufacturing device, a calender, a conventional conveyor oven, a through-air system, an ultrasonic bonding, an infrared heater, etc. are mainly used. It is mainly used in the production of thin, soft and soft nonwoven fabrics such as coverstock, cushioning material, thermal insulation material, filter, civil engineering material, conductive sheet, medical wick, etc.

Therefore, the nonwoven fabric containing the graphene composite molded article in the form of a fiber including the graphene and the polymer resin according to the present invention may be used for all of the above types of nonwoven fabric when used as a wet nonwoven fabric.

In one embodiment of the present application, the dry nonwoven fabric refers to a web formed by dry lamination by carding technique, air lay method, and electrostatic method, and refers to a nonwoven fabric manufactured irrespective of thermal, physical and chemical bonding methods. can In this case, as the manufacturing method of the dry nonwoven fabric, it can be classified into dry laying, needle punching, stitch bonding, chemical bonding, and the like. Briefly explaining each of the above manufacturing methods, first, dry lamination means laminating a fiber web in a completely dry state without using moisture in manufacturing a web used for a nonwoven fabric. ), an air-lay method using an air stream, and one using static electricity.

In addition, the needle punching method is one of the methods for mechanically bonding the web, which has been used in the production of felt before the nonwoven fabric was formed. However, the current needle punching technology is used to have a higher density than the equipment used for the conventional felt manufacturing. Needle punching non-woven fabric is a three-dimensional random structure of a part of a two-dimensional random fiber arrangement by moving a needle plate with a needle up and down when passing a web formed by a card machine or an airlay method through a needle loom. is to combine

In addition, the stitch bonding method is a method of bonding the formed web in a manner of sewing using a knitting needle. It mainly applies the warp knitting principle of the tricot to form a web similar to that for a general wicking, and quilts it as a thread without using an adhesive.

Finally, although various adhesives are used in the chemical bonding method, emulsion-type adhesives are commonly used, and among them, acrylic and SBR are the most used. The chemical bonding method mainly uses four methods: the impregnation method, the spray method, the foam method, and the print method. It greatly affects the properties of the nonwoven fabric, such as elongation.

Therefore, the nonwoven fabric containing the graphene composite molded body in the form of fibers including the graphene and the polymer resin according to the present invention may be manufactured by employing all of the above manufacturing methods when used as a dry nonwoven fabric.

In one embodiment of the present application, the nonwoven fabric may be used in various fields, for example, clothing, protection, medical care, architecture, civil engineering, vehicle, hygiene, furniture/interior, wiper, filter, bedding, agriculture/horticulture, leather , and other living and industrial materials. That is, the nonwoven fabric according to the present invention has excellent antibacterial, antibacterial, deodorizing rate against harmful gas, antistatic, far-infrared emission, tensile strength and elongation characteristics, etc. by containing the graphene composite molded body, so that it can be used in various fields as described above. can

In one embodiment of the present application, the fibrous graphene composite molded article may include graphene and a polymer resin, and more specifically, may include graphene in a dispersed form in the polymer resin. In this case, the graphene may include a material selected from the group consisting of multilayer nanographene, nanographene plate-like powder, nanographene ribbon, functional graphene, graphene oxide, or combinations thereof. In addition, the polymer resin is polyethylene (poly ethylene, PE), polyvinyl chloride (PVC), polyethylene terephthalate (polyethylene terephthalate, PET), polyolefin elastomer (polyolefin elastomer, POE), polypropylene (polypropylene, PP) ), polyamide (PA), polycarbonate (PC), polybutylene terephthalate (PBT), ABS resin (acrylonitrile butadiene styrene copolymer), polyacetal (polyacetal), polyoxymethylene , POM), polyetherimide, polyurethane (polyurethane, PU), or a polymer resin selected from the group consisting of combinations thereof.

In one embodiment of the present application, the content of the graphene may be 0.001 parts by weight to 5 parts by weight based on 100 parts by weight of the polymer resin, preferably 0.001 parts by weight to 1 parts by weight, more preferably 0.005 parts by weight to 0.1 parts by weight. At this time, when the content of the graphene is less than 0.001 parts by weight relative to 100 parts by weight of the polymer resin, the graphene content is too small, and the graphene composite molded body or nonwoven fabric including the same may not have excellent characteristics inherent in graphene, 5 When the content is more than 1 part by weight, the content of the polymer resin may be relatively small, and the dispersion stability of graphene dispersed in the polymer resin may be reduced. According to an embodiment of the present application, the weight mixing ratio of the mixed graphene and the polymer resin may be about 0.05: 99.95 or about 0.005: 99.995.

In one embodiment of the present application, the graphene composite molded body may have a triboelectric electrification of 250 V or less for the scrim measured by KS K 0555 (2015, method B), and KS K 0555 (2015, method B). The tribological electrification for the blanket measured by may be 100 V or less. In addition, according to an embodiment of the present application, the graphene composite molded body may have a triboelectric electrification of about 200 V for the scrim measured by KS K 0555 (2015, method B), and KS K 0555 (2015, method B). ) may have a triboelectricity of about 76 V for the blanket measured by . That is, the nonwoven fabric containing the graphene composite molded body having the above properties may exhibit low triboelectricity, and thus may exhibit an excellent antistatic effect.

In one embodiment of the present application, the nonwoven fabric may have a bacteriostatic reduction rate of 99% or more for Staphylococcus aureus or klebsiella pneumoniae after 18 hours, respectively, and preferably about 99.9%. can This may be because the nonwoven fabric contains the graphene composite molded body, thereby exhibiting an excellent antibacterial effect, thereby preventing the propagation of bacteria harmful to the human body, thereby enabling the user to provide a cleaner nonwoven fabric. In addition, the nonwoven fabric may have a bacterial reduction rate of 99% or more after 24 hours for Escherichia coli or Staphylococcus aureus, preferably about 99.9%. This may also indicate an excellent bacterial reduction rate because the nonwoven fabric includes the graphene composite molded body, and may indicate a difference in the antibacterial effect depending on the weight content range of the graphene and the polymer resin. According to an experimental example of the present invention, as the weight content range of the graphene decreases, the antibacterial effect of the nonwoven fabric including the graphene may be excellent.

In one embodiment of the present application, the nonwoven fabric may have a UV blocking rate in a wavelength band of 200 nm to 400 nm of 90% or more, preferably 94% or more, and more preferably 98% or more. More specifically, the nonwoven fabric may have a UV blocking rate in a wavelength band of 290 nm to 315 nm of about 96.5% or more, preferably about 99.6%, and a UV blocking rate in a wavelength band of 315 nm to 400 nm is preferably about 94.2% or more may be about 98.8%. That is, the nonwoven fabric may have an excellent UV blocking rate as described above by including the graphene composite molded body, and may effectively block UV rays exposed to the human body by using the nonwoven fabric having the above characteristics for clothes, etc.

In one embodiment of the present application, the nonwoven fabric may have a two-hour deodorization rate of ammonia, acetic acid, trimethylamine and formaldehyde of 60% or more, respectively, and according to an embodiment, a two-hour deodorization rate of ammonia is about 60%, and acetic acid The two-hour deodorization rate may be about 63%. On the other hand, the deodorization rate may be calculated by the following formula (1).

[Equation 1]

Deodorization rate (%) = [(blank concentration)-(sample concentration)/(blank concentration)] × 100

In this case, in Equation 1, the blank concentration may be a concentration measured in the absence of a sample, and the sample concentration may mean a concentration measured in the presence of the graphene composite molded body included in the nonwoven fabric.

In one embodiment of the present application, the nonwoven fabric may have very excellent mechanical properties having a tensile strength of 57 Mpa to 100 Mpa and an elongation of 165% to 190%. That is, the graphene composite molded body contained in the nonwoven fabric can exhibit excellent properties inherent in the raw material because foreign substances such as gas, water vapor, and low-molecular chemicals are removed, and the graphene and polymer resin are not separated from each other at the interface, making it very stable. it could be

In one embodiment of the present application, the nonwoven fabric may further contain at least one of natural fibers and synthetic fibers. In this case, as the natural fiber, fibers such as cotton, hemp, wood pulp, wool, and silk fiber may be used. In addition, the synthetic fibers may include acrylic, polyamide (eg, nylon 6, nylon 6/6, nylon 12, polyaspartic acid, polyglutamic acid, etc.), polyamine, polyimide, polyamide, polyacrylic (eg, poly acrylamide, polyacrylonitrile, esters of methacrylic acid and acrylic acid, etc.), polycarbonate (e.g. polybisphenol A carbonate, polypropylene carbonate, etc.), polydiene (e.g. polybutadiene, polyisoprene, poly norbomen, etc.), polyepoxides, polyesters (eg, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polycaprolactone, polyglycolide, polylactide, polyhydroxybutyrate, poly Hydroxyvalerate, polyethylene adipate, polybutylene adipate, polypropylene succinate, etc.), polyester (e.g., polyethylene glycol (polyethylene oxide), polybutylene glycol, polypropylene oxide, polyoxymethylene (para formaldehyde), polytetramethylene ether (polytetrahydrofuran), polyepichlorohydrin, etc.), polyfluorocarbons, formaldehyde polymers (e.g. urea-formaldehyde, melamine-formaldehyde, phenol formaldehyde, etc.) ), natural polymers (e.g., cellulose, chitosan, lignin, waxy, etc.), polyolefins (e.g., polyethylene, polypropylene, polybutylene, polybutene, polyoctene, etc.), polyphenylene (e.g., polyphenylene oxide, polyphenylene sulfide, polyphenylene ether sulfone, etc.), silicone-containing polymers (e.g. polydimethyl siloxane, polycarbomethyl silane, etc.), polyurethane, polyvinyl (e.g. polyvinyl butyrate) ral, polyvinyl alcohol, esters and ethers of polyvinyl alcohol, polyvinyl acetate, polystyrene, polymethylstyrene, polyvinyl chloride, polyvinyl pyrrolidone, polymethyl vinyl ether, polyethyl vinyl ether, polyvinyl methyl ketone, etc.) , polyacetals, polyarylates, and copolymers (eg, polyethylene-co-vinyl acetate, polyethylene-co-acrylic acid, polybutylene terephthale yt-co-polyethylene terephthalate, polylauryllactam-block-polytetrahydrofuran, etc.) may also be used.

In one embodiment of the present application, the nonwoven fabric may use an adhesive to adhere each fiber, for example, a natural material composed of a water-soluble polymer may be used to induce the properties of an environmentally friendly material, and , corn, potato starch, etc. may be used. In addition, polyvinyl acetate, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetate, isobutene, maleic anhydride copolymer, polyacrylamide, acrylic copolymer Coales and the like can also be used as the adhesive.

The second aspect of the present application is

As a method for manufacturing a graphene composite molded body according to the first aspect of the present application, the method comprising: mixing graphene and a polymer resin; extruding the mixture; and filtering the foreign substances contained in the extruded mixture by discharging to the outside.

The third aspect of the present application is

a hopper 10 for accommodating a mixture of graphene and polymer resin; an extruder connected to the hopper 10 and using a screw 30 for extruding a mixture of graphene and polymer resin accommodated in the hopper 10; and a filter 50 installed at the distal end of the extruder, wherein the filter 50 is installed on the outer circumferential surface of the screw 30, and a fine passage through which foreign substances pass is formed. manufacturing equipment is provided.

Hereinafter, a method for manufacturing a graphene composite molded body according to the second aspect of the present application and an apparatus for manufacturing a graphene composite molded body according to the third aspect of the present application will be described in detail with reference to FIGS. 1 to 4 . At this time, FIG. 1 is a flowchart showing a method of manufacturing the graphene composite molded body, and FIGS. 2 to 4 are schematic views showing an apparatus for manufacturing the graphene composite molded body. The method of manufacturing a graphene composite molded body according to the second aspect of the present application is It may be manufactured using the apparatus for manufacturing a graphene composite molded body according to the third aspect of the present application. On the other hand, since the manufacturing apparatus of the graphene composite molded body shown in FIGS. 2 to 4 is only one embodiment, it is understood that some forms of deformation or substitution of components are included within the scope that does not impair the scope of the present invention. should be In addition, in the present specification, "graphene composite molded body" may mean a mixture of graphene and polymer resin after filtering to be described later, and may mean a mixture molded in the form of pellets, which is a subsequent step. Meanwhile, the “fibre-form graphene composite molded body” according to the first aspect of the present application may refer to a molded body formed in a fiber form by melting the “graphene composite molded body”.

First, in one embodiment of the present application, the method of manufacturing the graphene composite molded body may include a step of mixing graphene and a polymer resin.

In one embodiment of the present application, the form of the graphene may be liquid graphene or graphene in powder form, and the types include multilayer nanographene, nanographene plate-like powder, nanographene ribbon, and functional graphene. It may include a material selected from the group consisting of fin, graphene oxide, or combinations thereof. In addition, the graphene may be nano graphene formed in a nano size, and thus the size of the graphene may be less than 1 μm. In this case, the graphene may preferably be a liquid graphene using multi-layered nano graphene or graphene oxide, and the multi-layered nano graphene may have the form of 1 to 5 layers as a two-dimensional structure. On the other hand, when the graphene is liquid graphene, a liquid additive may be mixed with the graphene raw material, and the liquid additive may use a conventional additive without limitation as long as it can dissolve graphene smoothly.

In one embodiment of the present application, the polymer resin is polyethylene (polyethylene, PE), polyvinyl chloride (PVC), polyethylene terephthalate (PET), polyolefin elastomer (POE), Polypropylene (PP), polyamide (PA), polycarbonate (PC), polybutylene terephthalate (PBT), ABS resin (acrylonitrile butadiene styrene copolymer), polyacetal , may include a polymer resin selected from the group consisting of , polyoxymethylene (POM), polyetherimide, polyurethane (PU), or combinations thereof, preferably the polymer resin is It may be polyvinyl chloride (PVC), polyethylene terephthalate (PET), or polypropylene (PP). On the other hand, the mixing of the graphene and the polymer resin may be performed by impregnating or coating the graphene in the polymer resin, and the content of the mixed graphene is 0.001 parts by weight to 5 parts by weight based on 100 parts by weight of the polymer resin. It may be one, preferably 0.005 parts by weight to 1 parts by weight, more preferably 0.01 parts by weight to 0.1 parts by weight. At this time, when the content of the mixed graphene is less than 0.001 parts by weight relative to 100 parts by weight of the polymer resin, the graphene composite molded article prepared because the content of graphene is too small may not have excellent characteristics inherent in graphene, When the amount is exceeded, the content of the polymer resin is relatively small, so that there may be a problem that the graphene is not smoothly dispersed in the polymer resin.

In one embodiment of the present application, the mixing of the graphene and the polymer resin comprises the steps of preparing a liquid graphene oxide by mixing the graphene oxide with a liquid additive; mixing the polymer resin into the liquid graphene oxide; and drying the mixture. In this case, the drying may be performed at a temperature of about 80 °C to 120 °C. That is, the mixture of graphene and polymer resin mixed as described above may have a moisture content of about 15 wt% or less because the drying step is performed. Extrusion may not be performed smoothly.

In one embodiment of the present application, the mixture of graphene and polymer resin mixed as described above may be accommodated in the hopper 10 as shown in FIG. 2 , and the mixture accommodated in the hopper 10 is then transferred to an extruder It may be conveyed to perform extrusion.

Next, in one embodiment of the present application, the method for producing the graphene composite molded body comprises the steps of extruding the mixture; and filtering the foreign substances contained in the extruded mixture by discharging to the outside.

In one embodiment of the present application, referring to FIG. 2 , the extrusion may be preferably performed using an extruder using a screw 30 . At this time, the upper part of one side of the extruder may be connected to the lower surface of the hopper 10 for accommodating the mixture, and the mixture supplied from the hopper 10 is transferred into one side of the extruder and extruded in the other direction of the extruder. it may be On the other hand, in addition to the mixture of the graphene and the polymer resin, the extruder may be additionally supplied with a base polymer, auxiliary materials, additives, and the like to be extruded together. To this end, the base polymer accommodating hopper 12, the auxiliary material accommodating hopper 14 and the additive accommodating hopper 16 may be additionally installed so that each raw material can be supplied along the extrusion direction of the extruder. In this regard, the base polymer accommodating hopper 12 is connected to the graphene and polymer resin accommodating hopper 10, and accordingly, the mixture of graphene and polymer resin and the base polymer are mixed together into the extruder. it could be

In one embodiment of the present application, the base polymer and the auxiliary material may be selected and supplied with an appropriate material to satisfy the physical properties of the product to be manufactured. In addition, the additive may include a reinforcing agent, a filler, and the like, and may include, for example, glass fiber (GF) or carbon fiber (CF). That is, the base polymer, auxiliary materials and additives may be added in a small amount to satisfy the physical properties of the graphene composite molded body to be manufactured, and the type or content of the added material is appropriately selected and added for the physical properties to be achieved. it could be

In one embodiment of the present application, the extruder includes a body 20 having a passage through which a mixture of graphene and polymer resin moves therein; a screw 30 accommodated in the internal mixture moving passage of the body 20 and extruding the mixture into the hole plate 80 and the cutting part 90 while mixing and melting the mixture supplied from the hopper 10; a heater 40 installed on the outer circumferential surface of the body 20 to heat and melt the mixture; a filter 50 for discharging foreign substances generated from the mixture melted by the heater 40 to the outside; and a head 70 positioned at an end of the body 20 . On the other hand, the foreign material may include a material selected from the group consisting of gas, water vapor, low molecular weight chemicals, and combinations thereof, and the physical properties or properties of the graphene composite molded body manufactured by removing such foreign materials are remarkably excellent. it could be In this case, the low molecular weight chemical substance may be, for example, stearic acid, an oligomer, a trigomer, etc., and such substances are harmful to the human body, and the graphene composite manufactured by removing it The molded body may be harmless to the human body.

In one embodiment of the present application, to describe the filter 50 in more detail, the filter 50 is a plurality of donut-shaped vent rings 52 stacked in the axial direction of the screw 30 . As a structure, between the adjacent vent ring 52 and the vent ring 52 may be one in which a foreign material passes and a fine passage through which the molten mixture does not pass is formed radially. Therefore, the molten mixture moves in the direction of the head 70 along the movement passage by the rotation of the screw 30, and the foreign material passes through the micro passage and is collected in the gas collection space 51, and then the first and second discharge pipes It may be discharged to the outside by the vacuum pump 62 via (60, 61). In this case, it may be preferable to connect a pipe through which external air is introduced in the middle of the first and second discharge pipes 60 and 61 so that foreign substances discharged from the filter 50 are discharged more rapidly. To this end, one end of the air suction pipe 63 through which external air is introduced is connected in the middle of the first and second discharge pipes 60 and 61, and an air filter 64 is installed at the other end of the air suction pipe 63 to install external air. It blocks the inhalation of foreign substances, and the second discharge pipe 61 and the air suction pipe 63 may be arranged in the same straight line and the first discharge pipe 60 may be connected in a right angle direction.

The foreign material discharge system configured as described above forms a negative pressure in the first discharge pipe 60 based on Bernoulli's theorem while external air passes through the air intake pipe 63 and the second discharge pipe 61 at a high speed, so gas The foreign substances collected in the collecting space 51 can be quickly discharged to the outside. In FIG. 2, a vacuum pump 62 is installed at the downstream end of the second discharge pipe 61 to discharge gas and water vapor, but instead of installing the vacuum pump 62, the air suction pipe 63 is located at the upstream end. It is also possible to install a blower at the (upstream end), and the negative pressure is formed in the first discharge pipe 60 in the same principle as above by the blowing of the blower, so that foreign substances in the gas collection space 51 can be quickly discharged to the outside, , in this case, the blower does not come in direct contact with the foreign material, so there is an advantage in that the blower can be prevented from being corroded by the foreign material. In addition, as another method of rapidly discharging foreign substances, an air inlet 53 may be installed on the outer wall of the filter 50 so that the gas collection space 51 of the filter 50 communicates with external air. The air introduced into the gas collection space 51 through the air inlet 53 passes between the outer peripheral surface of the vent ring 52 constituting the gas collection space 51 and the outer wall of the filter 50 at a high speed to pass the first and second The first discharge pipe 60 ), a negative pressure is formed in the micro passage of the vent ring 52 on the same principle as the negative pressure is formed in the vent ring 52, so that foreign substances generated from the molten mixture can quickly pass through the micro passage and be discharged to the outside. At this time, the first discharge pipe 60 and the air inlet 53 are installed at the farthest position from each other, that is, opposite to each other based on the axial direction and the circumferential direction of the filter 50, so that the entire micro passage of the vent ring 52 is located. It is desirable to create a negative pressure.

2 shows a single screw extrusion device having one screw 30, but it is also possible to use a twin screw extrusion device having two screws 30, and although not shown in FIG. A device for removing organic compounds in foreign substances in accordance with environmental standards may be separately provided.

Next, in one embodiment of the present application, the method for producing the graphene composite compact includes the steps of filtering; Thereafter, the step of molding the mixture in the form of pellets; may further include.

In one embodiment of the present application, the molding may be performed by the hole plate 80 and the cutting unit 90 shown in FIGS. 2 to 4 . In this case, one surface of the hole plate 80 may be attached to the end of the head 70 , and the cutting part 90 may be attached to the other surface of the hole plate 80 . Specifically, the mixture of graphene and polymer resin ejected through the outlet 75 of the head 70 may be in a molten state. Accordingly, the mixture in the molten state as described above may be ejected to the cutting unit 90 through the plurality of holes 85 formed in the hole plate 80 as shown in FIG. 3 . In this case, the cutting unit 90 may include a cutter 92 rotating along a central axis therein, and a cooling water transfer pipe 95 for supplying and discharging cooling water therein is installed on the outer surface. can That is, the mixture ejected through the hole plate 80 may be cut and molded in the form of pellets by the cutter 92, and since the temperature is lowered by cooling water at the same time as cutting, the mixture in a molten state rapidly It may be hardening.

In one embodiment of the present application, the mixture molded in the form of pellets as described above may be stored in a product (graphene composite molded body) storage hopper (not shown), and may be shipped after molding into a mattress. This will be described in more detail below.

In one embodiment of the present application, the graphene composite molded article prepared as described above can exhibit excellent properties inherent in the raw material because foreign substances such as gas, water vapor, and low molecular weight chemicals are removed, and graphene and polymer resin are interfacing with each other. They are not separated from each other and may be very stable.

In one embodiment of the present application, the graphene composite molded body may have a tensile strength of 57 Mpa to 100 Mpa and an elongation of 165% to 190%, thereby having very excellent mechanical properties. In addition, in addition to the above mechanical properties, it may have excellent antibacterial, bactericidal, antistatic or far-infrared emission characteristics.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

Example One. graphene complex molded body Produce ( graphene 0.05 wt% / PET 99.95 wt% )

In order to prepare a graphene composite matrix using the manufacturing method of FIG. 1 and the manufacturing apparatus of FIG. 2, first, multilayered nanographene was mixed with a liquid additive to obtain liquid multilayered nanographene. Thereafter, by mixing polyethylene terephthalate (PET) with the obtained liquid multilayer nanographene, impregnation and coating processes were performed. At this time, the weight mixing ratio of the graphene and PET was 0.05 wt%: 99.95 wt%. Then, after drying the mixture of graphene and PET, it was put into the manufacturing apparatus of FIG. 2 to perform an extrusion process, and the extruded mixture was molded to obtain a graphene composite molded body in the form of pellets.

Example 2. graphene complex molded body Produce ( graphene oxide 0.05 wt% / PET 99.95 wt% )

A graphene composite molded body in the form of pellets was obtained in the same manner as in Example 1, except that nano graphene oxide was used instead of multilayer nano graphene.

Example 3. graphene complex molded body Produce ( graphene 0.05 wt% / PP 99.95 wt% )

In Example 1, a graphene composite molded body in the form of pellets was obtained using the same method except that a polypropylene (PP) melt-blown nonwoven fabric (60 g/m ² ) was used instead of PET.

Example 4. graphene complex molded body Produce ( graphene 0.1 wt% / pp 99.9 wt% )

A graphene composite molded body in the form of pellets was obtained in the same manner as in Example 3, except that the weight mixing ratio of graphene and PP was changed to 0.1 wt%: 99.9 wt%.

Example 5. graphene complex molded body Produce ( graphene 0.005 wt% / PP 99.995 wt% )

A graphene composite molded body in the form of pellets was obtained in the same manner as in Example 3, except that the weight mixing ratio of graphene and PP was changed to 0.005 wt%: 99.995 wt%.

Experimental example One. triboelectricity evaluation

In order to evaluate the triboelectricity of the graphene composite molded body prepared in Example 1, triboelectricity was measured for scrim and blanket according to KS K 0555 (2015, method B) and shown in Table 1 below, At this time, the test conditions were 20±2℃, 40±2%R.H., 400 r/min.

[Table 1]

As shown in Table 1, it was confirmed that the graphene composite molded article prepared according to an embodiment of the present invention exhibited low triboelectricity, and from this, it was confirmed that it had an excellent antistatic effect.

Experimental example 2. radiant energy evaluation

In order to evaluate the far-infrared emissivity and radiant energy of the graphene composite molded body prepared in Examples 1 and 5, an experiment was conducted by requesting it to the Korea Far Infrared Association, and the results are shown in Tables 2 and 3, respectively. indicated. The measurement method was measured based on KFIA-FI-1005, the wavelength was 5 to 20 μm, and the temperature was measured based on 37°C. In addition, by measuring the far-infrared emissivity and radiant energy according to the wavelength of the graphene composite molded body prepared in Example 5, graphs thereof are shown in FIGS. 5A and 5B, respectively.

[Table 2] - Example One

[Table 3] - Example 5

As shown in Tables 2 and 3 and FIGS. 5A and 5B, the graphene composite molded article prepared according to an embodiment of the present invention has emissivity of 0.894 and 0.893 and 3.45 x 10 ² W/ m ² ·μm, 3.44 x 10 ² W/m ² ·μm was confirmed to have a radiation energy emission. Therefore, it was confirmed that the graphene composite molded article had excellent far-infrared emissivity and radiant energy emission.

Experimental example 3. Evaluation of UV protection performance

In order to evaluate the UV blocking performance of the graphene composite molded body prepared in Examples 1 and 5, UV-A (315 to 400 nm) and UV-B (290 to 315 nm) according to KS K 0850:2014 ) was measured and the UV protection factor (UPF) was measured, and the results are shown in Table 4 below. In this case, a UV Transmittance Analyzer was used as a test device, and a Xenon Arc was used as a light source.

[Table 4]

As shown in Table 4, it was confirmed that the graphene composite molded article prepared according to an embodiment of the present invention exhibited an excellent UV blocking rate and UV blocking index, and from this, it was confirmed that it had excellent UV blocking performance.

Experimental example 4. Antibacterial performance evaluation

In order to evaluate the antibacterial performance of the graphene composite molded body prepared in Examples 1 and 2, an experiment was conducted based on KS K 0693:2016 by requesting the FITI Test Research Institute, and the results are shown in Tables 5 and 6 (execution). Examples 1) and 7 (Example 2) are respectively shown. The strains used at this time were Staphylococcus aureus (Staphylococcus aureus) and Klebsiella pneumoniae (Pneumococcus pneumoniae). An attached white cloth for fastness was used.

[Table 5]

As shown in Table 5 and FIGS. 6 (Example 1) and 7 (Example 2), the graphene composite molded articles prepared in Examples 1 and 2 all showed a high bacteriostatic reduction rate, especially in Example 1 The prepared graphene composite molded article exhibited a bacteriostatic reduction rate of 99.9%, confirming that the antibacterial performance was very good.

In addition, in order to evaluate the antibacterial performance of the graphene composite molded body prepared in Example 5, an experiment was conducted based on JIS Z 2801:2013 (film adhesion method) by requesting the Korea Institute of Microbiology and Technology, and the results are shown in the table below. 6 is shown. The strains used at this time were Escherichia coli (E. coli) and Staphylococcus aureus (Staphylococcus aureus), and 0.05% nonionic surfactant (snogen) was used for the inoculum as a nonionic surfactant, and a general plastic sheet was used for the control group.

[Table 6]

As shown in Table 6, the graphene composite molded body prepared in Example 5 always exhibited a high bacterial reduction rate, which exhibited higher antibacterial performance than the graphene composite molded body prepared in Examples 1 and 2.

Experimental example 5. Deodorization rate evaluation

In order to evaluate the deodorization rate for ammonia and acetic acid of the graphene composite molded body prepared in Example 1 at all times, an experiment was conducted based on FTM-5-2: 2004, the gas detection tube method, and the results are shown in Table 7 below. . At this time, the measurement time was set to after the lapse of 2 hours, and the deodorization rate was calculated using Equation 1 below.

[Equation 1]

Deodorization rate (%) = [(blank concentration)-(sample concentration)/(blank concentration)] × 100

In this case, in Equation 1, the blank concentration is a concentration measured in the absence of a sample, and the sample concentration means a concentration measured in the presence of a graphene composite molded body.

[Table 7]

As shown in Table 7, it was confirmed that the graphene composite molded article prepared in Example 1 had excellent deodorization rates of about 20% and 60% for ammonia and acetic acid for 2 hours, respectively.

On the other hand, in order to evaluate the deodorization rate for ammonia of the graphene composite molded body prepared in Example 2, an experiment was conducted based on KFIA-FI-1004 by requesting the KIFA Korea Far Infrared Application Evaluation Institute, and the results are shown in Table 8 and Each is shown in Figure 8.

[Table 8]

As shown in Table 8 and FIG. 8, it was confirmed that the graphene composite molded body prepared in Example 2 had a very good deodorization rate for ammonia.

Experimental example 6. anti-fungal performance evaluation

In order to analyze the antifungal performance of the graphene composite molded body prepared in Examples 3 and 4 at all times, the mold resistance performance analysis (ASTM G-21) was performed at the request of KIFA Korea Far Infrared Application Evaluation Institute, respectively, at the same time as the mold for 4 weeks. The culture was analyzed for the propagation of the fungus. The results are shown in Table 9 and Figure 9, respectively.

[Table 9]

As shown in Table 9, it was confirmed that there was no growth of mold even when the mold was cultured in the graphene composite molded body prepared in Examples 3 and 4, and thus it was confirmed that it had excellent antifungal performance.

Above, the present invention has been described in detail with preferred embodiments with reference to the drawings, but the scope of the technical idea of the present invention is not limited to these drawings and examples. Accordingly, various modifications or equivalent ranges of embodiments may exist within the scope of the technical spirit of the present invention. Therefore, the scope of the technical idea according to the present invention should be interpreted by the claims, and the technical idea within the equivalent or equivalent scope should be interpreted as belonging to the scope of the present invention.

10: hopper for receiving graphene and polymer resin
12: base polymer accommodating hopper 14: sub material accommodating hopper
16: additive receiving hopper 20: body
30: screw 40: heater
50: filter 51: gas collection space
52: vent ring 53: air intake
60: first discharge pipe 61: second discharge pipe
62: vacuum pump 63: air intake pipe
64: air filter 70: head
75: outlet 80: hole plate
85: hole 90: cutting part
92: cutter 95: coolant transfer pipe

Claims (10)

A nonwoven fabric containing a graphene composite molded article in the form of a fiber comprising graphene and a polymer resin,
The content of the mixed graphene is 0.001 parts by weight to 0.5 parts by weight based on 100 parts by weight of the polymer resin,
The nonwoven fabric will have a tensile strength of 57 Mpa to 100 Mpa,
The nonwoven fabric will have an elongation of 165% to 190%,
The graphene composite molded body has a moisture content of 15 wt% or less,
The nonwoven fabric, wherein the graphene and the polymer resin are not separated from each other at the interface.
According to claim 1,
The graphene is a nonwoven fabric comprising a material selected from the group consisting of multilayer nanographene, nanographene plate-like powder, nanographene ribbon, functional graphene, graphene oxide, or combinations thereof.
According to claim 1,
The polymer resin is polyethylene (polyethylene, PE), polyvinyl chloride (PVC), polyethylene terephthalate (PET), polyolefin elastomer (POE), polypropylene (polypropylene, PP), Polyamide (PA), polycarbonate (PC), polybutylene terephthalate (PBT), ABS resin (acrylonitrile butadiene styrene copolymer), polyacetal (polyacetal), polyoxymethylene (POM) ), polyetherimide (polyetherimide), polyurethane (polyurethane, PU), or a nonwoven fabric comprising a polymer resin selected from the group consisting of combinations thereof.
delete According to claim 1,
The nonwoven fabric will further contain at least one of natural fibers or synthetic fibers.
delete delete According to claim 1,
The nonwoven fabric has a bacteriostatic reduction rate of 80% or more, respectively, after 18 hours for Staphylococcus aureus or klebsiella pneumoniae.
According to claim 1,
In the nonwoven fabric, ammonia, acetic acid, trimethylamine, and formaldehyde for 2 hours each have a deodorization rate of 20% or more.
As a method for producing the graphene composite molded body according to claim 1,
mixing graphene and a polymer resin;
extruding the graphene and polymer resin mixture; and
filtering by discharging foreign substances contained in the extruded mixture to the outside;
including,
The content of the mixed graphene is 0.001 parts by weight to 0.5 parts by weight based on 100 parts by weight of the polymer resin,
After the drying step of the mixture of the graphene and the polymer resin, the method for producing a graphene composite molded body, characterized in that the moisture content is 15 wt% or less.

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