Nanohybrid material of functionalized graphene and flake-like inorganic material, and polymer composite comprising same

Abstract

The present invention relates to nanohybrid material comprising flake-like inorganic material, and functionalized graphene having a zeta potential of +25 MV or more and bonded spontaneously to the flake-like inorganic material.

Description

Nanohybrid materials of functionalized graphene and plate-shaped inorganic materials and polymer composites containing the same

[0001] The present invention relates to a nano hybrid material of functionalized graphene and a plate-shaped inorganic material, which can be applied to a housing part of an automobile headlamp or digital side mirror to solve a fogging problem, or can be applied to a solid electrolyte of a secondary battery, and a polymer composite including the same.

[0002] Automotive headlights have evolved from halogen lamps to LEDs and lasers. Recently, adaptive headlights, which use sensors and cameras to adjust the direction and intensity of headlights based on vehicle speed, steering, and external conditions, have been developed and are available to consumers. Furthermore, recently released digital side mirrors replace traditional mirrors, capturing the rear view with a camera and providing the driver with the resulting image.

[0003] However, in winter, the heat generated by headlights and digital side mirror cameras causes moisture inside the housing to condense, resulting in fogging. This fogging obstructs the driver's view.

[0004] To prevent fogging, the headlamp housing and the digital side mirror camera housing are sealed. However, moisture entering the sealed housing can cause fogging over time.

[0005] Moisture doesn't just enter through the gaps between the housing components. Even if each component is completely sealed, the hygroscopic nature of the polymer material (or polymer composite) that makes up the housing allows moisture to enter the housing. Moisture is adsorbed on the surface of the polymer material (or polymer composite) that makes up the housing, then absorbed into the voids within the polymer (or polymer composite), and then permeates through these voids to enter the interior.

[0006] In order to ensure the safety of vehicle users based on headlamps, the area of ​​moisture generation in headlamps must be reduced from the existing 20% ​​to 13% or less.

[0007]

[0008] One object of the present invention is to provide a new material capable of reducing hygroscopicity when included in a polymer composite by spontaneously combining functionalized graphene and a plate-like inorganic material.

[0009] Meanwhile, other unspecified purposes of the present invention will be additionally considered within a range that can be easily inferred from the detailed description and effects thereof below.

[0010]

[0011] To achieve the purpose proposed above, the following solutions are proposed.

[0012] A nano hybrid material according to one embodiment of the present invention comprises a plate-like inorganic material; and functionalized graphene having a zeta potential of +25 mV or higher and spontaneously bonded to the plate-like inorganic material.

[0013] In one embodiment, the plate-shaped inorganic material is nano clay, Ca 2+ -Montmorillonite, Na + -Montmorillonite, Li + - It may be characterized by at least one selected from the group consisting of montmorillonite, molybdenum disulfide, and boron nitride.

[0014] In one embodiment, the mass ratio of the plate-shaped inorganic material and the functionalized graphene may be 1000:1 to 20:1.

[0015] In one embodiment, the plate-like inorganic material may be an organic montmorillonite, wherein the organic montmorillonite has a negative zeta potential and is characterized by spontaneous electrostatic bonding with the functionalized graphene.

[0016] In one embodiment, the mass ratio of the plate-shaped inorganic material and the functionalized graphene may be 1000:1 to 10:1.

[0017] In one embodiment, the contact angle of the nano hybrid material with water is 92 o It can be characterized by the following:

[0018] A polymer composite according to another embodiment of the present invention may include a polymer material and a nano hybrid material, and the nano hybrid material may be characterized as being a polymer composite according to one embodiment.

[0019] In another embodiment, the content of the nano hybrid material may be characterized as being 0.1 to 2.0 wt%.

[0020] In another embodiment, the polymer material may include a matrix polymer and an additive, wherein the matrix polymer is at least one selected from the group consisting of polyethylene, polypropylene, polyamide, polycarbonate, acrylonitrile styrene acrylate, acrylonitrile butadiene styrene, polybutylene terephthalate, and polyethylene terephthalate, and the additive may be at least one selected from the group consisting of talc, glass fiber, carbon fiber, nanoclay, and silica.

[0021] In another embodiment, the polymer composite may be characterized as being used as a material for a headlamp housing.

[0022]

[0023] A nano hybrid material according to one embodiment of the present invention is formed by self-bonding functionalized graphene to a hydrophilic plate-shaped inorganic material, thereby making it plate-shaped and hydrophobic.

[0024] Therefore, when a nano hybrid material according to one embodiment of the present invention is mixed with a polymer to produce a polymer composite, the movement path of moisture absorbed into the polymer in the form of a plate-like structure can be increased, and further, the nano hybrid material has hydrophobicity, thereby hindering the movement of moisture and lowering the hygroscopicity of the polymer composite.

[0025] Therefore, when a polymer composite according to another embodiment of the present invention is used as a housing material for a headlamp, the moisture generation area of ​​the headlamp can be reduced from the existing 20% ​​level to 13% or less.

[0026] Meanwhile, even if the effect is not explicitly mentioned herein, it is added that the effect and its provisional effect described in the following specification expected by the technical features of the present invention are treated as described in the specification of the present invention.

[0027]

[0028] Figure 1 is a schematic diagram of a nano hybrid material according to one embodiment of the present invention.

[0029] Figure 2 is a schematic flow chart of a method for manufacturing a nano hybrid material according to another embodiment of the present invention.

[0030] Figure 3 is a schematic diagram of a polymer composite according to another embodiment of the present invention.

[0031] Fig. 4 is Ca 2+ -The results of hybridization of montmorillonite and functionalized graphene were photographed.

[0032] Figure 5 is pure Ca 2+ -Ca hybridized with montmorillonite and functionalized graphene 2+ -Comparison of the appearance of montmorillonite.

[0033] Figure 6 shows Ca hybridized with functionalized graphene. 2+ -This is the result of FT-IR spectrum analysis of montmorillonite.

[0034] Figure 7 shows the results of hybridization of organic montmorillonite and functionalized graphene.

[0035] Figure 8 shows the results of measuring the zeta potential of organic montmorillonite and functionalized graphene.

[0036] Figure 9 shows a process of fabricating a nano hybrid material using organic montmorillonite.

[0037] Figure 10 shows the results of FT-IR spectrum analysis of organic montmorillonite hybridized with functionalized graphene.

[0038] Figure 11 is pure Ca 2+ -Montmorillonite (MMT-Ca 2+ ) and the microstructure of pure organic montmorillonite (Organo-MMT) and nano hybrid (MMT-G) using organic montmorillonite were compared.

[0039] Figure 12 is pure Ca 2+ -These are the results of measuring the contact angle of water for montmorillonite, pure organic montmorillonite, and nano hybrid (MMT-G) using organic montmorillonite.

[0040] Figure 13 shows the results of resistivity measurement by pressurized powder resistance measurement of nano hybrid (MMT-G) using organic montmorillonite.

[0041] Figure 14 is a reference diagram for explaining the process of manufacturing a headlamp housing using a polymer composite including a nano hybrid (MMT-G) using organic montmorillonite.

[0042] Figure 15 shows the results of measuring the moisture generation area of ​​a conventional headlamp and a headlamp of the present invention.

[0043] It is to be understood that the attached drawings are provided for reference only to help understand the technical concept of the present invention, and the scope of the present invention is not limited thereby.

[0044]

[0045] Hereinafter, with reference to the drawings, the configuration of the present invention, guided by various embodiments thereof, and the effects resulting from such configurations will be examined. In describing the present invention, detailed descriptions of related, well-known functions that are obvious to those skilled in the art and that may unnecessarily obscure the gist of the present invention will be omitted.

[0046] Figure 1 is a schematic diagram of a nano hybrid material according to one embodiment of the present invention.

[0047] In one embodiment of the present invention, a nano hybrid material (10) is formed by spontaneously bonding functionalized graphene (2) to a plate-shaped inorganic material (1).

[0048] Plate-shaped inorganic material (1) refers to an inorganic material having a plate-shaped structure that is large in length and width but very thin. It may be formed of a single layer as in Fig. 1(a), or may be formed of multiple layers stacked as in Fig. 1(b). Examples of plate-shaped inorganic material (1) include nano clay, Ca 2+ -Montmorillonite, Na + -Montmorillonite, Li + - At least one selected from the group consisting of montmorillonite can be used. Such plate-shaped inorganic material (1) generally has hydrophilicity and no electrical conductivity.

[0049] In one embodiment of the present invention, the nano hybrid material (10) spontaneously bonds functionalized graphene (2) to the plate-shaped inorganic material (1) to hybridize the functionalized graphene, thereby converting the hydrophilic plate-shaped inorganic material (1) into a hydrophobic nano hybrid material (10) and converting the insulating plate-shaped inorganic material (1) into a conductive nano hybrid material (10). At this time, the flexural strength or impact strength of the plate-shaped inorganic material (1) increases further as it becomes the nano hybrid material (10), or at least remains at an equivalent level.

[0050] However, combining graphene with a plate-shaped inorganic material (1) is not an easy task. Due to graphene's low dispersibility, it is difficult to evenly react the plate-shaped inorganic material with graphene, and graphene and the plate-shaped inorganic material do not spontaneously react with each other. In the present invention, this problem was solved by utilizing our functionalized graphene.

[0051] The functionalized graphene used in the present invention may have a zeta potential of +25 mV or more, preferably 30 mV or more, and more preferably +60 mV or more.

[0052] Functionalized graphene refers to graphene in which a functional group is introduced into the graphene during the manufacturing process, thereby controlling the elemental content of carbon, oxygen, and nitrogen in the graphene. The functionalized graphene may be formed with at least one selected from the group consisting of a silane group, an amide group, an azide group, an anhydride group, a urea group, a urethane group, an amine group, an alkylene group, an epoxide group, and a mercapto group. In addition, the functionalized graphene of the present invention may have a carbon (C) element content of 76 to 83 atom %, an oxygen element content of 5 to 10 atom %, and a nitrogen (N) element content of 9 to 18 atom %. In particular, O / N may be satisfied to be 0.7 or less, preferably O / N may be 0.5 or less, and more preferably O / N may be 0.3 or less. The functionalized graphene of the present invention can satisfy the required zeta potential by satisfying the above elemental composition. Since the absolute value of the zeta potential of the functionalized graphene of the present invention is 25 mV or higher, it exhibits high dispersion. In other words, the low dispersion problem of conventional graphene is resolved.

[0053] Also, Ca 2+ -Montmorillonite, Na + -Montmorillonite and Li +Montmorillonite is a layered silicate mineral that possesses a negative surface charge due to ion substitution that occurs naturally within its structure. In particular, the negative surface charge of organically modified montmorillonite increases further during the organic modification process. As described above, the functionalized graphene of the present invention possesses a positive zeta potential. Therefore, the plate-like inorganic material (1) and the functionalized graphene (2) spontaneously bind to each other electrostatically.

[0054] Functionalized graphene (2) can be formed on one side or both sides of the plate-shaped inorganic material (1).

[0055] Meanwhile, the nano hybrid material (10) of the present invention may have a content ratio of the plate-shaped inorganic material (1) and the functionalized graphene (2) of 1000:1 to 20:1, 1000:1 to 10:1, 200:1 to 20:1, or 200:1 to 10:1.

[0056] Figure 2 is a schematic flow chart of a method for manufacturing a nano hybrid material according to another embodiment of the present invention.

[0057] Referring to FIG. 2, a method for manufacturing a nano hybrid material according to another embodiment of the present invention includes a step of manufacturing a functionalized graphene colloid, a step of manufacturing a dispersion in which a plate-like inorganic material is dispersed in a solvent, a step of introducing the functionalized graphene colloid into the dispersion and homogenizing it, a step of spontaneously hybridizing the functionalized graphene and the plate-like inorganic material, and a step of separating, washing, and drying the nano hybrid material.

[0058] The fabrication of functionalized graphene is performed as follows.

[0059] Prepare a graphene oxide solution. The graphene oxide solution can be prepared by producing graphite oxide using the Hummers and Improved Methods, or by performing an exfoliation process using commercially available graphite oxide.

[0060] Next, functional groups are imparted to the graphene oxide. An additive for forming functional groups is added to the graphene oxide aqueous solution, stirred, and then dispersed ultrasonically to impart functional groups to the graphene oxide, forming functionalized graphene. Specifically, 50 to 150 parts by weight of the additive is added to 100 parts by weight of the graphene oxide aqueous solution, and stirred at 90 to 120°C for 12 to 36 hours to form functionalized graphene.

[0061] The functional groups to be imparted to graphene can be determined by additives.

[0062] As an additive for forming a silane group, an organic silane compound capable of forming a silane group can be used, for example, triethoxysilane, tetraethoxysilane, aminopropyltriethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, octadecyltrimethoxysilane, (3-methacryloxy)propyltrimethoxysilane, 3-Glycidoxypropyl Methyldimethoxysilane, 3-Glycidoxypropyl Trimethoxysilane, 3-Glycidoxypropyl methyldiethoxysilane, 3-Glycidoxypropyl triethoxysilane, Any one selected from the group consisting of 3-Isocyanatepropyltriethoxysilane, 3-(Trimethoxysilyl)propylsuccinic anhydride can be used."As the additive, an organic monomer or polymer capable of forming an amine group or an amide group can be used, for example, ethylenediamine, triethylamine, paraphenylenediamine, o-phenylenediamine, mesophenylenediamine, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminoterphenyl, benzidine, 1,5-diaminonaphthalene, (E)-4,4'-(diazene-1,2-diyl)dianiline, ethylenediamine, Any one selected from the group consisting of 1,6-diaminohexane, 1,8-diaminooctane, and 4,4-oxidianiline can be used.

[0063] As an additive for forming an amine group or an amide group, an organic monomer or polymer capable of forming an amine group or an amide group can be used, for example, ethylenediamine, triethylamine, paraphenylenediamine, o-phenylenediamine, mesophenylenediamine, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminoterphenyl, benzidine, 1,5-diaminonaphthalene, (E)-4,4'-(diazene-1,2-diyl)dianiline, Any one selected from the group consisting of ethylenediamine, 1,6-diaminohexane, 1,8-diaminooctane, and 4,4-oxidianiline can be used.

[0064] As an additive for forming an anhydride functional group, an organic monomer or polymer capable of forming an anhydride functional group can be used, and for example, any one selected from the group consisting of maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, naphthalic anhydride, and trimellitic anhydride can be used.

[0065] An organic monomer or polymer can be used as an additive capable of forming an azide group, and for example, any one selected from the group consisting of sodium azide, methyl azidoacetate, phenyl azide, 2-azidoethanol, azidoacetic acid, and 2-azidoethylamine can be used.

[0066] As an additive capable of forming a urea group or urethane group, an organic monomer or polymer may be used, and for example, any one selected from the group consisting of isocyanate, polyol, ethoxysilane, polyethylene glycol, toluene diisocyanate, methylene diphenyl diisocyanate, polytetramethylene ether glycol, and polycaprolactone may be used.

[0067] Any one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, and 1,8-octanediol can be used.

[0068] As an additive capable of forming an epoxide group, an epoxidized organic monomer or polymer may be used, and for example, any one selected from the group consisting of epoxidized alkylene oxide, glycidyl methacrylate, styrenized epoxide, glycidyl amine, bisphenol A epoxy, epoxidized novolac, and epoxidized polyethylene oxide may be used.

[0069] As an additive capable of forming a mercapto group, an organic monomer or polymer may be used, and for example, any one selected from the group consisting of 2-mercaptoethanol, 1-thioglycerol, 3-mercaptopropanesulfonic acid, D-pentaerythritol tetra(3-mercaptopropionate), 4-mercaptophenol, methyl 3-mercaptopropionate, 6-thioguanine, 1-hexanethiol, ethanethiol, and benzylmercaptan may be used.

[0070] For reference, the amount of functional group introduced can be determined by adjusting the amount of additive, stirring temperature, and stirring time. More specifically, the ratio of additive to graphene oxide, the timing and rate of additive addition at the beginning of the reaction, and the stirring speed and time are important.

[0071] Once stirring is complete, a functionalized graphene colloid is produced at a rate of 1 ton per hour through a large-capacity circulating ultrasonic dispersion system. The functionalized graphene colloid can be produced by mixing 1 to 5 wt% of functionalized graphene, 70 to 90 wt% of deionized water, and 10 to 30 wt% of ethanol, and then ultrasonically dispersing and homogenizing the mixture for 30 minutes or more.

[0072] Table 1 below shows the results of measuring the atomic composition of carbon, oxygen, and nitrogen and the zeta potential of the functionalized graphene contained in the manufactured functionalized graphene colloid.

[0073]

[0074] Sample C(at%)O(at%)N(at%)O / NZeta potential(mV)1831071.4- 11.1282991.0+ 5.63819100.9+ 13.74808120.7+28.35797140.5+31.06777160.4+40.37766180.3+60.28775180.27+ 65.7

[0075] As can be seen in Table 1, the functionalized graphene of the present invention may have a carbon (C) element content of 76 to 83 atom %, an oxygen element content of 5 to 10 atom %, and a nitrogen (N) element content of 9 to 18 atom %. In particular, O / N may satisfy 0.7 or less, preferably O / N may be 0.5 or less, and more preferably O / N may be 0.3 or less. Accordingly, the functionalized graphene used in the present invention may have a zeta potential of +25 mV or more, preferably 30 mV or more, and more preferably +60 mV or more.

[0076] Once the production of the functionalized graphene colloid is complete, a step of producing a dispersion liquid in which the plate-shaped inorganic material is dispersed in a solvent is performed.

[0077] 5 to 15 wt% of a plate-shaped inorganic material, 70 to 90 wt% of deionized water, and 10 to 30 wt% of ethanol can be mixed and dispersed and homogenized for 30 minutes or more using a high-speed homogenizer.

[0078] Next, a step of adding a functionalized graphene colloid to the dispersion and homogenizing the dispersion is performed. At this time, the functionalized graphene colloid may be added so that the content ratio of the plate-like inorganic material to the functionalized graphene is 1000:1 to 20:1, 1000:1 to 10:1, 200:1 to 20:1, or 200:1 to 10:1. Homogenization may be performed at room temperature at 3000 rpm for 30 minutes using a high-speed homogenizer.

[0079] Next, a step is performed in which the functionalized graphene and the plate-like inorganic material spontaneously hybridize. After homogenization, the rotation speed is reduced to 1,000 rpm, and the functionalized graphene and the plate-like inorganic material are allowed to spontaneously hybridize for 4 hours.

[0080] Finally, the resulting nanohybrid material is separated, washed, and dried. Once the nanohybrid material is formed, a coprecipitate is formed. This is centrifuged, washed, and filtered using a vacuum filter. The nanohybrid material is then dried under vacuum at 50 to 70°C for 7 to 12 hours to complete the process.

[0081] Figure 3 is a schematic diagram of a polymer composite according to another embodiment of the present invention.

[0082] Referring to FIG. 3, a polymer composite (100) according to another embodiment of the present invention includes a polymer material (20) and a nano hybrid material (10) included in a high-molecular-weight material.

[0083] The polymer composite (100) can be used as a housing for vehicle parts such as headlamps or digital side mirrors, used where anti-static performance is required, or used as a solid electrolyte for a secondary battery.

[0084] When the polymer composite (100) of the present invention is used as a housing for a vehicle component such as a headlamp or a digital side mirror, as shown in FIG. 3, the movement path of moisture absorbed into the polymer can be increased, and further, the nano hybrid material has hydrophobic properties, thereby hindering the movement of moisture, thereby reducing the hygroscopicity of the polymer composite. At the same time, the nano hybrid material improves the flexural strength and impact strength of the polymer composite.

[0085] When the polymer composite (100) of the present invention is used as a solid electrolyte for an antistatic unit or a secondary battery, it has conductivity due to the introduced functionalized graphene.

[0086] The polymer material may include a matrix polymer and an additive. The matrix polymer may be at least one selected from the group consisting of polyethylene, polypropylene, polyamide, polycarbonate, acrylonitrile styrene acrylate, acrylonitrile butadiene styrene, polybutylene terephthalate, and polyethylene terephthalate, and the additive may be at least one selected from the group consisting of talc, glass fiber, carbon fiber, nanoclay, and silica. However, the present invention is not limited thereto.

[0087]

[0088] Example

[0089] Functionalized graphene colloids with a zeta potential of approximately +40 mV were prepared. The prepared functionalized graphene colloids were dispersed and homogenized using ultrasonic waves for more than 30 minutes using a solvent containing 1 wt% functionalized graphene, 80% deionized water, and 20% ethanol.

[0090] Ca 2+-Montmorillonite, Na + -Montmorillonite, Li + -Montmorillonite, an organic montmorillonite dispersion was prepared. The dispersion was prepared using a solvent of 10 wt% plate-shaped inorganic material, 80% deionized water, and 20% ethanol, and was dispersed and homogenized for more than 30 minutes using a high-speed homogenizer.

[0091] Meanwhile, organic montmorillonite (see structure in Fig. 1(b)) was prepared as follows: 10 wt of Ca 2+ - 2HT (Dihydrogenated tallow dimethyl ammonium chloride) was added to the montmorillonite aqueous solution in a 1:1 ratio, stirred at room temperature for 2 hours, and then ion exchange reaction was performed at 60℃ for 12 hours. Afterwards, centrifugation was performed 3 times, washed, and filtered under reduced pressure, and then dried under vacuum at 60℃ for 10 hours to complete the final organic montmorillonite.

[0092] Next, functionalized graphene colloids were added to the dispersion. To examine the effect of functionalized graphene content, various samples were prepared with varying amounts of functionalized graphene. After adding functionalized graphene colloids to the dispersion, homogenization was performed at room temperature for 30 minutes at 3,000 rpm, followed by spontaneous hybridization via graphene adsorption at 1,000 rpm for 4 hours.

[0093] Finally, the precipitate formed from the nanohybrid material was centrifuged three times, washed, and then filtered under reduced pressure. The final nanohybrid material was then completed by vacuum drying at 60°C for 10 hours.

[0094] Fig. 4 is Ca 2+ -The results of hybridization of montmorillonite and functionalized graphene were photographed.

[0095] Referring to Fig. 4, Ca 2+- It can be seen that coprecipitation occurs as nanohybrid materials are spontaneously formed in samples with a content ratio of montmorillonite and functionalized graphene of 1000:1 to 20:1.

[0096] Figure 5 is pure Ca 2+ -Ca hybridized with montmorillonite and functionalized graphene 2+ -Comparison of the appearance of montmorillonite.

[0097] As shown in Fig. 5, functionalized graphene is Ca 2+ -It can be seen that the appearance of the particles changes as they spontaneously bond to montmorillonite.

[0098] Figure 6 shows Ca hybridized with functionalized graphene. 2+ -This is the result of FT-IR spectrum analysis of montmorillonite.

[0099] Referring to Figure 6, Ca hybridized with functionalized graphene 2+ - FT-IR spectrum of nano hybrid material of montmorillonite (MMT-CMG) All analysis results showed characteristic peaks of functionalized graphene with positive charge. That is, functionalized graphene and Ca 2+ - It was confirmed that montmorillonite was fully bonded.

[0100] Figure 7 shows the results of hybridization of organic montmorillonite and functionalized graphene.

[0101] Referring to FIG. 7, it can be seen that coprecipitation occurs as nanohybrid materials are spontaneously formed in samples having a content ratio of organic montmorillonite and functionalized graphene of 1000:1 to 10:1.

[0102] Organic montmorillonite has a zeta potential of -35 mV (see Fig. 8), and therefore, it is spontaneously adsorbed by electrostatic attraction with the functionalized graphene of the present invention, which has a positive zeta potential. Therefore, Ca 2+ -Montmorillonite, Na +-Montmorillonite, Li + - Compared to the upper limit of the combination ratio of montmorillonite and functionalized graphene, which was 20:1, the upper limit of the combination ratio of organic montmorillonite and functionalized graphene increases to 10:1. As the content of functionalized graphene increases, the hydrophobic properties further increase and the conductivity also improves.

[0103] Figure 9 is a photograph of the process of fabricating a nanohybrid material using organic montmorillonite. The label shown in the photograph in Figure 9 indicates the weight ratio of functionalized graphene to organic montmorillonite.

[0104] Figure 10 shows the results of FT-IR spectrum analysis of organic montmorillonite hybridized with functionalized graphene.

[0105] Referring to Fig. 10, the FT-IR spectrum of the nanohybrid material of functionalized graphene and organo-MMT-CMG showed that the characteristic peak of the functionalized graphene with a positive charge was observed in all analysis results. In other words, it was confirmed that the functionalized graphene and organo-MMT-CMG were completely combined.

[0106] Figure 11 is pure Ca 2+ -Montmorillonite (MMT-Ca 2+ ) and the microstructure of pure organic montmorillonite (Organo-MMT) and nano hybrid (MMT-G) using organic montmorillonite were compared.

[0107] Referring to Fig. 11, Ca 2+ -Montmorillonite (MMT-Ca 2+ ) has a shape of spherical flakes aggregated together, and the organic montmorillonite (Organo-MMT) has a distinct plate-like morphology. Furthermore, the nano hybrid material (MMT-G) has a more distinct plate-like morphology, and graphene-specific morphology (wrinkle, folding, edge, etc.) appears on the surface.

[0108] Next, the thermal stability of the nano hybrid material was measured and shown in Table 2. The thermal stability was measured using TGA at 10 min in an air environment. o It was evaluated under the conditions of a heating rate of C.

[0109]

[0110] Sample name Decomposition start temperature (℃) 5% weight loss temperature (℃) 10% weight loss temperature (℃) Comparative example 1 Organo-MMT 295.8 278.9 304.4 Example 1 MMT-0.1G 312.2 289.5 317.7 Example 2 MMT-0.5G 314.1 291.4 317.8 Example 3 MMT-1.0G 315.3 291.5 318.1 Example 4 MMT-3.0G 316.0 291.4 317.9 Example 5 MMT-5.0G 316.8 291.3 319.3 Example 6 MMT-10G 316.2 290.8 319.6

[0111] As shown in Table 2, the nano hybrid material of the present invention showed improved thermal stability in all examples due to the improved molecular bonding between the functionalized graphene and the plate-shaped inorganic material.

[0112] Figure 12 is pure Ca 2+ -These are the results of measuring the contact angle of water for montmorillonite, pure organic montmorillonite, and nano hybrid (MMT-G) using organic montmorillonite.

[0113] Referring to Figure 12, pure Ca 2+ -Montmorillonite exhibited hydrophilicity, and pure organic montmorillonite had a contact angle of 85.6 for water. o It had weak hydrophobicity. However, it was confirmed that the nano hybrid material of the present invention had increased hydrophobicity by increasing the contact angle with water, and in particular, when the content ratio of the plate-like inorganic material and functionalized graphene was 200:1 or more, that is, as the content of functionalized graphene increased, the contact angle with water increased to 92. o As can be seen above, it has strong hydrophobicity.

[0114] Figure 13 shows the results of resistivity measurement by pressurized powder resistance measurement of nano hybrid (MMT-G) using organic montmorillonite.

[0115] After measuring the powder volume resistivity according to pressure and converting it into resistivity, it was found that although organic montmorillonite is an insulator, the nano hybrid material using it showed a tendency for the resistivity to decrease with increasing functionalized graphene content. In other words, the nano hybrid material of the present invention has antistatic properties and can be used as a solid electrolyte for secondary batteries.

[0116] Next, a polymer composite for use in the headlamp housing was manufactured and its properties were tested.

[0117] The polymer composite contained polypropylene (PP) as a polymer matrix used in headlamps, 30 wt% talc as an additive, and a content ratio of 10:1 of organic montmorillonite and functionalized graphene as nano hybrid materials. Polymer composite samples were manufactured using a twin-screw extruder at 205°C and 300 rpm.

[0118] First, the mechanical properties of the polymer composite samples were evaluated.

[0119]

[0120] MMT-G content (wt%) Tensile strength (MPa) Flexural strength (MPa) Impact strength (J / m) Comparative example 20 29.5 5 7.6 37.1 Example 7 0.1 29.8 5 7.9 37.5 Example 8 0.2 3 0.3 5 8.0 38.1 Example 9 0.3 3 0.6 5 8.3 38.7 Example 10 0.5 3 0.8 5 8.5 4 0.1 Example 11 1.0 29.4 5 7.6 38.1 Comparative example 32.0 29.3 5 7.5 38.0

[0121] Referring to Table 3, it was confirmed that mechanical properties improved with the inclusion of nanohybrid materials. However, when the nanohybrid material content was excessive, such as 2.0 wt%, mechanical properties actually decreased. Therefore, to improve mechanical properties, the content of nanohybrid materials in the polymer composite may be 0.1 to 1.0 wt%.

[0122] Next, the thermal stability of the polymer composite samples was evaluated. Thermal stability was evaluated using the same method as in Table 2.

[0123]

[0124] MMT-G content (wt%) 1% weight loss temperature (℃) 10% weight loss temperature (℃) Comparative example 40 39 3.0 43 1 Example 1 20.1 412.8 43 8.1 Example 1 30.2 413.1 43 8.4 Example 1 40.3 415.3 43 9.2 Example 1 50.5 417.2 43 9.7 Example 1 61.0 418.5 440.1 Example 1 72.0 419.7 440.2

[0125] As shown in Table 5, thermal stability was improved in all examples.

[0126] Next, the moisture absorption reduction effect of the polymer nanocomposite was confirmed. The moisture absorption reduction effect was evaluated by measuring the absorption reduction rate (measured as the weight increase of the specimen after 192 hours of storage under conditions of 23°C and 50% RH) according to the ISO62 standard.

[0127]

[0128] Moisture absorption rate = (Weight after moisture absorption - Initial weight) / Initial weight * 100 (%)

[0129]

[0130] MMT-G content (wt%)Moisture absorption rate (%)Moisture absorption reduction rate (%)Comparative example 500.1210Example 180.10.1127.44Example 190.20.105013.22Example 200.30.08827.27Example 210.50.08430.58Example 221.00.1099.92Example 232.00.1154.96

[0131] As shown in Table 5, a decrease in moisture absorption is observed with the inclusion of nano hybrid materials.

[0132] For reducing moisture absorption, the content of the nano hybrid material in the polymer composite may be 0.1 to 2.0 wt%, preferably 0.1 to 1.0 wt%, more preferably 0.2 to 0.5 wt%, and most preferably 0.3 to 0.5 wt%.

[0133] Next, a headlamp housing part was manufactured using the polymer composite of the present invention and the fogging prevention effect was evaluated.

[0134] Figure 14 is a reference diagram for explaining the process of manufacturing a headlamp housing using a polymer composite including a nano hybrid (MMT-G) using organic montmorillonite.

[0135] As shown in Fig. 14, the headlamp housing part was manufactured by injection molding the headlamp housing part using the polymer composite of Example 20 and assembling it to manufacture the headlamp.

[0136] Figure 15 shows the results of measuring the moisture generation area of ​​a conventional headlamp and a headlamp of the present invention.

[0137] The headlamp moisture generation area was evaluated based on the MS210-14 standard, which is the required specification for finished vehicles.

[0138] Referring to Figure 15, in the case of the existing headlamp, the moisture generation area was 22.26%, but in the case of the headlamp of the present invention, the moisture generation area was reduced to 12.20%. In other words, the moisture generation area was reduced by 45% compared to the existing headlamp.

[0139] The scope of protection of the present invention is not limited to the description and expression of the embodiments explicitly described above. Furthermore, it should be noted that the scope of protection of the present invention may not be limited by obvious modifications or substitutions within the technical field to which the present invention pertains.

Claims

1. Plate-shaped inorganic material; and A nano hybrid material having a zeta potential of +25 mV or higher and comprising functionalized graphene spontaneously bonded to the plate-like inorganic material.

2. In paragraph 1, The above plate-shaped inorganic material is nano clay, Ca 2+ -Montmorillonite, Na + -Montmorillonite, Li + - A nano hybrid material comprising at least one selected from the group consisting of montmorillonite, molybdenum disulfide and boron nitride.

3. In paragraph 2, A nano hybrid material having a mass ratio of the above plate-shaped inorganic material and the above functionalized graphene of 1000:1 to 20:

1.

4. In paragraph 1, The above plate-shaped inorganic material is a nano hybrid material that is an organic montmorillonite.

5. In paragraph 4, A nano hybrid material having a mass ratio of the above plate-shaped inorganic material and the above functionalized graphene of 1000:1 to 10:

1.

6. In paragraph 1, The contact angle of the above nano hybrid material for water is 92 o Ideal nano hybrid materials.

7. A polymer composite comprising a polymer material and a nano hybrid material according to any one of claims 1 to 6 added to the polymer material.

8. In paragraph 7, A polymer composite having a content of the above nano hybrid material of 0.1 to 2.0 wt%.

9. In paragraph 7, The above polymer material comprises a matrix polymer and an additive, The above matrix polymer is at least one selected from the group consisting of polyethylene, polypropylene, polyamide, polycarbonate, acrylonitrile styrene acrylate, acrylonitrile butadiene styrene, polybutylene terephthalate, and polyethylene terephthalate. The above additive is a polymer composite comprising at least one selected from the group consisting of talc, glass fiber, carbon fiber, nanoclay and silica.

10. In paragraph 7, The above polymer composite is a polymer composite used as a material for a headlamp housing.

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