A resin composition containing graphene quantum dots, a masterbatch, fibers, and a method for producing the resin composition.

Abstract

The present invention provides a resin composition, masterbatch, fiber, and method for producing the same, which contain two components: graphene and graphene quantum dots, which have anti-mite, anti-mold, and deodorizing functions, excellent antibacterial properties, and also possess antistatic, heat retention, heat re-radiation properties, and promote blood microcirculation. [Solution] The resin composition of the present invention comprises graphene quantum dots with a particle size of 10 nm or less, graphene, and a polymer matrix.

Description

Technical Field

[0001] The present invention relates to a resin composition containing graphene quantum dots, a masterbatch, a resin composition, and a method for producing the resin composition.

Background Art

[0002] Graphene has excellent performance and is applied in various fields. In recent years, research on the utilization of graphene in composite materials and spinning has also been advanced. For example, Patent Document 1 discloses a graphene-nano silver composite material. Patent Document 2 discloses a method for preparing a polymer-based silver-containing graphene nano antibacterial material. Patent Document 3 discloses a graphene quantum dot-modified polymer masterbatch for functional fibers and a method for producing the same.

[0003] However, in the materials disclosed in Patent Documents 1 and 2, the particle size of graphene is large, the antibacterial ability is low, and since a metallic silver material is used, it imposes a burden on the environment and is also harmful to health. The functional masterbatch obtained according to the production method disclosed in Patent Document 3, when used in spinning, is not uniformly dispersed when mixed with each raw material, cannot fully exhibit the nano knife effect of graphene quantum dots, and has low antibacterial properties. Further, due to the aggregation of graphene, excessive pressure is applied to the spinning assembly, and graphene is not uniformly dispersed in the fiber matrix, resulting in a reduction in the heat re-radiation blocking effect of graphene. Furthermore, the conductive mesh of graphene in the fiber matrix is not formed, resulting in a reduction in the antistatic performance. In recent years, there has been a demand for graphene quantum dots having new functions and a resin composition containing the graphene quantum dots.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

[0005] The problem that the present invention aims to solve is to provide graphene quantum dots that have anti-mite, anti-mold, and deodorizing functions, excellent antibacterial properties, and also have antistatic, heat-retaining, and heat-re-radiating properties that promote blood microcirculation; a resin composition containing graphene and the graphene quantum dots as two components; a masterbatch; a fiber; and a method for producing the same. [Means for solving the problem]

[0006] In view of the above-mentioned problems, the inventors conducted extensive research and found that graphene quantum dots with flavonoids chemically bonded to their surface, or graphene quantum dots with a particle size of 10 nm or less, possess not only antibacterial properties but also new functionalities. The present invention was completed based on these findings. To achieve the above objective, the present invention provides the following means.

[0007] The present invention provides a resin composition comprising graphene quantum dots with a particle size of 10 nm or less, graphene, and a polymer matrix. The graphene quantum dots with a particle size of 10 nm or less are preferably flavonoid-modified graphene quantum dots in which flavonoids are chemically bonded to the surface. The particle size of the graphene is in the range of 300 to 800 nm. The polymer matrix preferably comprises at least one of polyester, polyamide 6, polypropylene, and polyethylene.

[0008] The present invention provides a masterbatch comprising two components: graphene quantum dots containing the resin composition and graphene.

[0009] The present invention provides a fiber comprising two components: graphene quantum dots composed of the masterbatch and graphene.

[0010] The present invention provides a fabric using the aforementioned fibers.

[0011] The present invention relates to a method for producing a resin composition containing graphene quantum dots with a particle size of 10 nm or less, A two-component graphene powder preparation step involves mixing graphene quantum dots with a particle size of 10 nm or less with graphene until uniform, A matrix powder preparation step involves grinding the matrix material in a high-speed liquid nitrogen cooling atmosphere, The present invention provides a method for producing a resin composition containing two components: graphene quantum dots and graphene, comprising a functional powder preparation step of mixing the two-component graphene powder, the matrix powder, and a dispersant in a mixer to prepare a functional powder.

[0012] The method for producing the resin composition preferably further includes a masterbatch preparation step of producing a masterbatch containing two components: graphene quantum dots with a particle size of 10 nm or less and graphene, the masterbatch preparation step of feeding the resin composition into an ultra-high torque co-directional high-performance twin-screw granulator and granulating it at a temperature of 155 to 285°C.

[0013] The method for producing the resin composition preferably further includes a spinning step to produce fibers containing two components: graphene quantum dots with a particle size of 10 nm or less and graphene, the spinning step including a mixed molten preparation step of mixing and melting the masterbatch, polymer matrix slices and a lubricant; a filament fiber spinning step of feeding the mixed molten material to a spinning machine and spinning it, and cooling it through a spinning sleeve to obtain continuous filament fibers having a fineness of 0.5 Dex or less; and a short fiber spinning step of cutting the filament fibers into short fibers using a cutting device to obtain short fibers. [Effects of the Invention]

[0014] The resin composition, masterbatch and fiber containing the two components of graphene quantum dots with a particle size of 10 nm or less and graphene according to the present invention have excellent antibacterial properties with acaricidal, antifungal and deodorizing functions, and also have antistatic properties, heat storage and heat preservation properties, and heat re-radiation properties, and can promote blood microcirculation. Since they do not use silver, they can prevent contamination of the human body by heavy metals and are environmentally friendly.

Brief Description of the Drawings

[0015] [[ID=⑦]] [[ID=⑧]] [Figure 1] [[ID=⑨]]It is a TEM measurement photograph showing the particle size and its distribution of graphene quantum dots as an embodiment of the present invention. [[ID=⑩]] [[ID=⑪]] [[ID=⑫]]

Embodiments for Carrying Out the Invention

[0016] [[ID=⑯]] [[ID=⑰]]The present invention will be described in more detail. [[ID=⑱]] [[ID=⑲]]Note that "~" in the numerical range represents "from... to..." and includes both end values unless otherwise specified. Also, when a numerical range is indicated, the upper limit value and the lower limit value can be appropriately combined, and the numerical range thus obtained is also disclosed. [[ID=⑳]] [[ID=㉑]]

[0017] [[ID=㉒]] [[ID=㉓]]<Graphene Quantum Dots>[[ID=㉔]] [[ID=㉕]]The graphene quantum dots of the present invention are graphene quantum dots with a particle size of 10 nm or less. These graphene quantum dots have excellent bactericidal and deodorizing performance. When they come into contact with bacteria, pressure is applied to the cell membrane, and an oxidation reaction occurs between the functional groups of the graphene quantum dots and the cell membrane, breaking through the cell wall, causing the RNA or DNA inside the bacterial cell to flow out and be inactivated. In addition, the specific surface area of the graphene quantum dots with a particle size of 10 nm or less according to the present invention is extremely large, reaching 500 - 1000 m[[ID=㉖]]

[0018] , , 2 , , , , ,

[0017] , [[ID=㉗]] / g, and its adsorption capacity is particularly strong, having an excellent adsorption and removal effect on odors, and being excellent in biocompatibility, toxicity and safety, and also environmentally friendly. [[ID=㉘]] [[ID=㉙]]

[0018] [[ID=㉚]] The graphene quantum dots of the present invention have flavonoids chemically bonded to their surfaces. By grafting flavonoids onto the graphene quantum dots, the graphene quantum dots can be modified, which is useful for killing mites and can endow the function of repelling mites. As the raw material of flavonoids, it is preferable to use mugwort extract.

[0019] The graphene quantum dots of the present invention preferably have flavonoids chemically bonded to their surfaces and a particle size of 10 nm or less. By grafting flavonoids onto the surfaces of the graphene quantum dots, a mite repellent effect is imparted. Moreover, since the particle size is 10 nm and the specific surface area is extremely large, the deodorizing and antibacterial effects can be improved. Furthermore, the graphene quantum dots with a particle size of 10 nm or less can form a prism-shaped diffuse reflection effect on ultraviolet rays in the long wavelength range, effectively dissipate the ultraviolet rays, and reduce the damage to the skin.

[0020] <Resin composition> The resin composition of the present invention contains graphene quantum dots with a particle size of 10 nm or less, graphene, and a polymer matrix.

[0021] The graphene quantum dots with a particle size of 10 nm or less are preferably flavonoid-modified graphene quantum dots having flavonoids chemically bonded to their surfaces.

[0022] The particle size of the graphene is preferably in the range of 300 to 800 nm, and more preferably in the range of 300 to 500 nm. As a natural carbon material, graphene generates far-infrared waves, and when its frequency matches the vibration frequency of molecules, resonance occurs, the energy of the far-infrared waves is absorbed by the molecules, and the resonance absorption phenomenon appears. Graphene with a particle size in the range of 300 to 800 nm generates far-infrared waves of 8 to 14 μm, which is close to the wavelength of the human body, and its vibration frequency matches the vibration frequency of water molecules. Therefore, the energy of the graphene is completely absorbed by water molecules, activating the activity of biomacromolecules, promoting vasodilation, and improving metabolism, thus having a physiotherapy effect. With continuous use, it can relieve fatigue and alleviate problems such as body pain.

[0023] In the present invention, by combining the graphene quantum dots and the graphene, it is possible to achieve excellent heat retention while maintaining mite-repellent, deodorizing, and antibacterial properties.

[0024] Preferably, the polymer matrix contains at least one of polyester, polyamide 6, polypropylene, and polyethylene.

[0025] The aforementioned polyesters include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene-2,6-naphthalate (PEN), polymethylene terephthalate (PMT), polypropylene terephthalate (PPT), polyethylene-p-oxybenzoate (PEOB), poly-1,4-cyclohexylenedimethylene terephthalate (PCT), and copolymer components such as diethylene glycol, neopentyl glycol, polyalkylene glycol, diol components, adipic acid, and seba. It contains at least one selected from the group consisting of polyesters copolymerized with dicarboxylic acid components such as tinic acid, phthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid (excluding biodegradable polyesters), liquid crystal polyester, polylactic acid, polyhydroxyalkanoate, polybutylene succinate, cellulose acetate, polyvinyl alcohol, polyglycolic acid, polybutylene succinate-co-adipate, polybutylene adipate terephthalate, and polyethylene terephthalate succinate.

[0026] The polyethylene includes at least one selected from the group consisting of low-density polyethylene, medium-density polyethylene, high-density polyethylene, and ultra-high-density polyethylene.

[0027] In the resin composition comprising graphene quantum dots and graphene of the present invention, it is preferable to include a dispersant. The dispersant preferably comprises at least one selected from the group consisting of dopamine and polyvinylpyrrolidone, and more preferably dopamine and polyvinylpyrrolidone. In particular, using dopamine and polyvinylpyrrolidone in combination produces a synergistic effect, improving the dispersibility and compatibility of graphene and graphene quantum dots in the matrix.

[0028] <Masterbatch> The masterbatch of the present invention comprises the resin composition described above.

[0029] In the masterbatch of the present invention, the content of graphene quantum dots is preferably 1 to 5% by mass. The content of graphene is preferably 1 to 10% by mass, more preferably 4 to 10% by mass. The content of the polymer matrix is ​​preferably, more preferably 80 to 93% by mass. The content of the dispersant is preferably, more preferably 2 to 5% by mass.

[0030] In the resin composition of the present invention, the content of graphene quantum dots is preferably 1 to 5% by mass. The content of graphene is preferably 5 to 10% by mass.

[0031] <Textiles> The present invention relates to a fiber comprising the masterbatch described above and containing two components: graphene quantum dots and graphene. In this fiber containing two components, graphene quantum dots are preferably 0.1 to 0.5% by mass, and graphene is more preferably 0.1 to 0.5% by mass. The graphene is uniformly dispersed within the fiber, efficiently absorbing ultraviolet blue light and ultraviolet red light, effectively reducing the penetration of ultraviolet rays, and protecting human skin.

[0032] The fiber containing graphene quantum dots and graphene, as described in the present invention, can be used in bedding, household goods, clothing, and the like.

[0033] <Fabric> The present invention relates to a fabric composed of the aforementioned fibers and containing two components: graphene quantum dots and graphene. The graphene can effectively increase electron movement and conduction, reduce the accumulation of static electricity on the fabric surface, and enhance the antistatic properties of the fabric.

[0034] <Method for manufacturing graphene quantum dots> The present invention provides a method for producing graphene quantum dots with a particle size of 10 nm or less. A first aqueous dispersion preparation step involves reacting graphene oxide, hydrogen peroxide, and aqueous ammonia to prepare a first graphene quantum dot aqueous dispersion, A second aqueous dispersion preparation step involves adding a reducing agent and a phosphate to the first aqueous dispersion of graphene quantum dots, irradiating it with microwaves in the range of 100-200°C, and preparing a second aqueous dispersion of graphene quantum dots in which graphene quantum dots with a particle size of 10 nm or less are dispersed; The method includes a freeze-drying step in which the second graphene quantum dot aqueous dispersion is freeze-dried to obtain graphene quantum dots with a particle size of 10 nm or less.

[0035] The present invention's method for producing graphene quantum dots with a particle size of 10 nm or less preferably further includes a flavonoid reaction step, in which the second graphene quantum dot aqueous dispersion is mixed with a flavonoid, and ultrasonic treatment is performed at 185-200°C for 2-5 hours to react the graphene quantum dots with the flavonoid.

[0036] Examples of the flavonoids include flavonoid-containing substances such as mugwort extract. In the flavonoid reaction step, the mass ratio of the second graphene quantum dot aqueous dispersion to the mugwort extract is preferably in the range of 50-70:50-30.

[0037] The graphene quantum dots produced by the manufacturing method of the present invention have a particle size of 10 nm or less and a uniform particle size, and their specific surface area is extremely large, thus improving deodorizing and antibacterial effects. Furthermore, the grafting of flavonoids onto the surface provides excellent mite-repellent effects.

[0038] <Method for producing a resin composition containing graphene quantum dots> The present invention provides a method for producing a resin composition containing graphene quantum dots with a particle size of 10 nm or less. A two-component graphene powder preparation step involves mixing graphene quantum dots with a particle size of 10 nm or less with graphene until uniform, A matrix powder preparation step involves grinding the matrix material in a high-speed liquid nitrogen cooling atmosphere, The process includes a functional powder preparation step of mixing the two-component graphene powder, the matrix powder, and a dispersant in a mixer to prepare a functional powder.

[0039] The particle size of the graphene is preferably in the range of 300 to 800 nm, and more preferably in the range of 300 to 500 nm. The polymer matrix preferably contains at least one of polyester, polyamide 6, polypropylene, and polyethylene. [Examples]

[0040] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0041] [Example 1] <Preparation of graphene quantum dots> Graphene oxide, hydrogen peroxide, and aqueous ammonia were reacted in a 1 L glass reaction vessel, and the temperature was gradually increased from 70°C to 90°C for 4 hours to obtain the first graphene quantum dot aqueous dispersion. 50 mL of sodium hypophosphite solution was placed in a 100 mL glass reaction vessel, 9 g of the above graphene quantum dot aqueous dispersion was added, and after stirring until homogeneous, sonication was performed for 40 minutes. The glass reaction vessel was placed in a microwave reactor, the temperature was set to 150°C and the microwave output to 600 W, and microwave treatment was performed for 30 minutes. After the obtained liquid was cooled to room temperature, it was centrifuged for 10 minutes in a high-speed centrifuge at 9000 r / min, the supernatant was removed, and a second graphene quantum dot aqueous dispersion was obtained. The above-mentioned second graphene quantum dot aqueous dispersion and mugwort extract were mixed in a glass container in a mass ratio of 70:30, and ultrasonic treatment was performed for 2 to 5 hours at 185 to 200°C using an ultrasonic rod of 200 watts or more to obtain a graphene quantum dot aqueous dispersion in which flavonoids were chemically bonded to the surface. A water dispersion of graphene quantum dots, on which flavonoids are chemically bonded to the surface, was mixed with 3.5 times its mass of deionized water and filtered three times to obtain a purified dispersion. The dispersion was freeze-dried at -70°C for 7 hours using a freeze-dryer to obtain graphene quantum dot powder with a particle size of 10 nm or less and possessing mite-repellent properties.

[0042] <Preparing the Masterbatch> 2.5 parts by mass of graphene quantum dot powder with a particle size of 10 nm or less having the above-mentioned anti-mite function and 2 parts by mass of graphene with a particle size of 500 nm or less were mixed in a negative-pressure supercritical mixing apparatus. Pre-mixing was carried out for 2.5 hours under conditions of a temperature of 55°C and a rotation speed of 16000 R / min to obtain a uniformly dispersed two-component graphene powder. A matrix powder was obtained by grinding polyester slices with a viscosity of 1.0 or higher in a liquid nitrogen pulverizer at -169°C for 45 minutes. The above two-component graphene powder, 93 parts by mass of the above matrix powder, and 2.5 parts by mass of dopamine were placed in a mixing device (developed in-house) and mixed until homogeneous to obtain a functional powder. The stirring speed was 35-65 r / min, the stirring time was 1.5-2 hours, and the heating temperature was 45-85°C. The above functional powder was fed into a high-performance twin-screw granulator (CX-HO26, manufactured by Ruiya Co., Ltd.) with ultra-high torque and co-directional properties, and granulated at a temperature of 155-285°C for 15 minutes to obtain a semi-finished masterbatch. A crystal-drying treatment was performed in a dryer at a temperature of 105°C for 3 hours to obtain a masterbatch with a moisture content of less than 1% and a uniform distribution.

[0043] <Fiber preparation> The masterbatch described above was placed in a drum drying circulator and dried at a temperature of 85°C for 8 hours until the moisture content of the masterbatch was 1% by mass or less. The above masterbatch and polyester slices with a viscosity of 1.0 or higher were mixed in a negative pressure pump circulating mixer to obtain a mixed molten material. The mixing time was 2 to 2.5 hours, the mixing temperature was 85°C, the pump pressure was 2.5 standard atmospheres, and the circulation mixing rate was 45 r / min. The above mixed molten material was sent to a spinning machine via a negative pressure extraction device and a metering pump, spun at a temperature of 150-285°C and a pressure of 20-28 standard atmospheres, and cooled through a spinning sleeve to obtain continuous filament fibers with a fineness of 0.5 Dex or less.

[0044] [Example 2] A masterbatch and fibers containing graphene quantum dots and graphene were obtained in the same manner as in Example 1, except that the material composition of 2.5 parts by mass of graphene quantum dot powder with mite-repellent properties and a particle size of 10 nm or less, 2 parts by mass of graphene with a particle size of 500 nm or less, 93 parts by mass of matrix powder, and 2.5 parts by mass of dopamine was replaced with a material composition of 3 parts by mass of graphene quantum dot powder with mite-repellent properties and a particle size of 10 nm or less, 3 parts by mass of graphene with a particle size of 500 nm or less, 91 parts by mass of matrix powder, and 3 parts by mass of dopamine.

[0045] [Example 3] A masterbatch and fibers containing graphene quantum dots and graphene were obtained in the same manner as in Example 1, except that the material composition of 2.5 parts by mass of graphene quantum dot powder with mite-repellent properties and a particle size of 10 nm or less, 2 parts by mass of graphene with a particle size of 500 nm or less, 93 parts by mass of matrix powder, and 2.5 parts by mass of dopamine was replaced with a material composition of 5 parts by mass of graphene quantum dot powder with mite-repellent properties and a particle size of 10 nm or less, 4 parts by mass of graphene with a particle size of 500 nm or less, 86 parts by mass of matrix powder, and 5 parts by mass of dopamine.

[0046] In the examples, various physical properties were measured or calculated as follows.

[0047] The particle size of the graphene quantum dots fabricated in Example 1 was detected using a transmission electron microscope (Talos STEM, Thermo Fisher Scientific). The results are shown in Figure 1.

[0048] The heat storage and insulation performance of the graphene quantum dots and graphene-containing fibers manufactured in Examples 1-3 was detected according to JIS L1096 Method A (constant temperature method). The results are shown in Table 1.

[0049] The thermal re-emission properties of graphene quantum dots and graphene-containing fibers manufactured in Examples 1-3 were detected according to the 45-degree parallel re-emission method, a test method certified by the Far Infrared Association for evaluating thermal re-emission characteristics. The results are shown in Table 1.

[0050] The antibacterial activity of the graphene quantum dots and graphene-containing fibers produced in Examples 1-3 was detected according to the bacterial solution absorption method of JIS L 1902. The results are shown in Table 1.

[0051] The mite-repellent properties of the graphene quantum dots and graphene-containing fibers produced in Examples 1-3 were detected according to the glass tube method A of JIS L 1920. The results are shown in Table 1.

[0052] The antistatic properties of the graphene quantum dots and graphene-containing fibers produced in Examples 1-3 were detected according to the electrostatic testing method for woven and knitted fabrics specified in JIS L 1094. The results are shown in Table 1.

[0053] Figure 1 shows the particle size of the graphene quantum dots produced in Example 1. In the transmission electron microscope image (TEM measurement image) in Figure 1, the graphene quantum dots are shown as black dots. The particle size and distribution of the graphene quantum dots were measured using the particle size distribution measurement function of the transmission electron microscope. As shown in Figure 1, the particle size of the graphene quantum dots was 10 nm or less, and graphene quantum dots with a particle size of approximately 3 nm accounted for about 70% of the total.

[0054] [Table 1]

[0055] Table 1 shows the performance parameters of the two-component fibers containing graphene quantum dots and graphene produced in Examples 1 to 3. As shown in Table 1, the two-component fibers containing graphene quantum dots and graphene of the present invention exhibited good heat retention and insulation properties, as well as excellent heat re-radiation characteristics. Antibacterial activity was 2.2 or higher, and mite-resistant properties were also observed. Furthermore, the two-component fibers containing graphene quantum dots and graphene of the present invention were found to have an antistatic effect.

[0056] Although the present invention has been described in detail based on the above-described embodiments, these represent only a portion of the embodiments of the present invention, not all embodiments. Furthermore, other embodiments can be obtained based on these embodiments, and it should be understood that all of these embodiments fall within the scope of protection of the present invention.

Claims

1. A resin composition comprising two components, graphene quantum dots and graphene, characterized by containing graphene quantum dots with a particle size of 10 nm or less, graphene, and a polymer matrix.

2. The resin composition comprising two components, graphene quantum dots and graphene, as described in claim 1, characterized in that the graphene quantum dots with a particle size of 10 nm or less are flavonoid-modified graphene quantum dots in which flavonoids are chemically bonded to the surface.

3. The resin composition comprising two components, graphene quantum dots and graphene, as described in claim 1, characterized in that the particle size of the graphene is in the range of 300 to 800 nm.

4. A resin composition comprising two components, graphene quantum dots and graphene, according to claim 1, wherein the polymer matrix comprises at least one of polyester, polyamide 6, polypropylene, and polyethylene.

5. A masterbatch comprising two components, graphene quantum dots and graphene, characterized by containing the resin composition described in any one of claims 1 to 4.

6. A fiber comprising two components: graphene quantum dots and graphene, which are composed of the masterbatch described in claim 5.

7. A fabric using the fiber described in claim 6.

8. A method for producing a resin composition containing graphene quantum dots with a particle size of 10 nm or less, A two-component graphene powder preparation step involves mixing graphene quantum dots with a particle size of 10 nm or less with graphene until uniform, A matrix powder preparation step involves grinding the matrix material in a high-speed liquid nitrogen cooling atmosphere, A functional powder preparation step involves mixing the two-component graphene powder, the matrix powder, and a dispersant in a mixer to prepare a functional powder. A method for producing a resin composition comprising two components: graphene quantum dots and graphene, characterized by containing the following.

9. The method further includes a masterbatch preparation step for producing a masterbatch containing two components: graphene quantum dots with a particle size of 10 nm or less and graphene. The masterbatch preparation step is: A method for producing a resin composition comprising two components, graphene quantum dots and graphene, according to claim 8, characterized by including a granulation step of feeding the resin composition into an ultra-high torque co-directional high-performance twin-screw granulator and granulating it at a temperature of 155 to 285°C.

10. The process further includes a spinning step to produce a fiber containing two components: graphene quantum dots with a particle size of 10 nm or less and graphene. The spinning step is, A mixed molten preparation step involves mixing and melting the masterbatch, polymer matrix slices, and a lubricant. A filament fiber spinning step involves feeding the mixed molten material to a spinning machine, spinning it, and cooling it through a spinning sleeve to obtain continuous filament fibers with a fineness of 0.5 Dex or less. The short fiber spinning step involves cutting the aforementioned filament fibers into short fibers using a cutting device to obtain short fibers, A method for producing a resin composition comprising two components, graphene quantum dots and graphene, as described in claim 9, characterized by including the following:

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