KR20170024379A - Coating composition for preparing graphene oxide-containing organic-inorganic hybrid coating film, and method for preparing the same - Google Patents

Coating composition for preparing graphene oxide-containing organic-inorganic hybrid coating film, and method for preparing the same Download PDF

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KR20170024379A
KR20170024379A KR1020150119558A KR20150119558A KR20170024379A KR 20170024379 A KR20170024379 A KR 20170024379A KR 1020150119558 A KR1020150119558 A KR 1020150119558A KR 20150119558 A KR20150119558 A KR 20150119558A KR 20170024379 A KR20170024379 A KR 20170024379A
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graphene
coating film
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KR101765587B1 (en
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이규걸
장광일
허승헌
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현대자동차주식회사
한국세라믹기술원
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    • C09D7/1216—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60Q—ARRANGEMENT OF SIGNALLING OR LIGHTING DEVICES, THE MOUNTING OR SUPPORTING THEREOF OR CIRCUITS THEREFOR, FOR VEHICLES IN GENERAL
    • B60Q1/00—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor
    • B60Q1/02—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor the devices being primarily intended to illuminate the way ahead or to illuminate other areas of way or environments
    • B60Q1/04—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor the devices being primarily intended to illuminate the way ahead or to illuminate other areas of way or environments the devices being headlights
    • B60Q1/06—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor the devices being primarily intended to illuminate the way ahead or to illuminate other areas of way or environments the devices being headlights adjustable, e.g. remotely-controlled from inside vehicle
    • B60Q1/08—Arrangement of optical signalling or lighting devices, the mounting or supporting thereof or circuits therefor the devices being primarily intended to illuminate the way ahead or to illuminate other areas of way or environments the devices being headlights adjustable, e.g. remotely-controlled from inside vehicle automatically
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances

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  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Paints Or Removers (AREA)
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Abstract

The present invention is to provide a graphene oxide-containing organic-inorganic hybrid coating film comprising: at least one type of hydrates represented by chemical formula 1; graphene oxide which is located in a discontinuous island form on the surface of the hydrates represented by chemical formula 1; and silica secondary particles respectively located on the surface of the hydrates represented by chemical formula 1 and the surface of the graphene oxide which is located in a discontinuous island form, wherein the silica secondary particles are in a form in which a plurality of silica nanoparticles are condensed. Also, the present invention is to provide a head lamp for vehicles, and a method for preparing the coating film. The chemical formula 1 is represented by X_n-M-(OH)_(4-n). The description of the chemical formula 1 is the same as described herein.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic-inorganic hybrid coating film containing graphene oxide, and a method for producing the same. BACKGROUND ART [0002]

The present invention relates to a graphene oxide-containing organic-inorganic hybrid coating film and a method for producing the same.

Graphene oxide (graphite oxide, graphite oxide, hereinafter referred to as GO) is a plate-shaped carbon material produced by acid treatment of graphite. It contains a large amount of hydrophilic functional group, carboxyl group (-COOH), hydroxyl group Lt; / RTI > GO is prepared in the form of a hydrate form or a water-containing slurry in which the surface oxidation groups generated through an acid treatment process naturally form hydrogen bonds with H 2 O. Generally, the solid content concentration of such a slurry is about 2 to 8% by weight, unless subjected to special treatment.

The GO improves the strength and has appropriate thermal conductivity when contained in a film or a structure, but treatment of the contained GO is a great obstacle to the manifestation of physical properties.

Generally, the GO is manufactured in a graphene form through a chemical reduction process (hydrazine process, etc.) and a heat reduction process, and is used widely. At this time, the reduced graphene is called Reduced Graphene Oxide (RGO).

It has been proven that some of the oxidizing groups on the RGO surface can not be completely removed and the oxygen content by the surface oxidizing group is usually 5 wt% or less with respect to the carbon backbone, so that the graphene (RGO) Means that the oxygen content by the oxidizing agent is 5% by weight or less based on the carbon backbone.

Recently, the properties of GO and RGO have been attracting much attention because of the possibility of improving the physical properties through the synergy effect between the materials beyond the limit of existing materials. Typical examples of the high-strength composite material and the fuel cell include graphene-nanowire (semiconductor) hybrid structures (KR2011-0012479), which generate electron-hole pairs by absorbing light energy on the upper portion of the graphene conductive portion, pin sheet / CNT / method of manufacturing a hybrid composite including a polymeric nanoparticles (KR2010-0114646), yes by the addition of Fe precursor and PO 4 precursor to the pin method of producing a cathode material for a lithium secondary battery, the hybrid material (KR2010- (US Pat. No. 8,257,867), a method of producing a graphene composite sintered body having excellent charging / discharging rates by sintering graphene and metal oxide particles in air (US Pat. No. 8,257,867), graphene-TiO 2 2 hybrid material manufacturing method (US2011-986379), and a graphene ceramic composite manufacturing method (10-2012-0039799, 10-2013-0014327).

In addition, JP-A-2001-0039799 discloses a technique of chemically bonding a ceramic precursor directly to a carboxyl group (-COOH) at the edge of the GO to improve dispersibility, thereby improving the coating property of the graphene itself. Although the graphene itself is coated with a chemical bond at the edge of the GO, a high electrical conductivity can be induced, but there is no binder between the GO and the graphene layer to be coated. Open patent application KR10-2013-0014327 discloses a method of making a graphene complex by mixing a ceramic precursor in the form of a salt (SALT such as chloride) with graphene or graphene oxide and calcining at high temperature. However, when a direct chemical bond is formed between the ceramic and the graphene, the plate-like structure of the graphene itself is broken and the inherent physical properties of the graphene are lost.

This problem is particularly serious when the ceramic is an oxide because the carbon component of graphene bonds with the oxygen component of the ceramic and is released as a gas in the form of CO 2 and CO 2 , and the residues are fragmented like carbon waste. Similar problems arise when the oxide ceramic precursor, or oxide ceramic sol, is calcined with graphene.

Further, when the graphene is reacted at a low temperature at which the graphene does not react with oxygen in order to reduce the above problems, there is a problem that the interface between the oxide ceramics and the graphene is extremely poor and peeling occurs. That is, the hydrophobicity of graphene and the hydrophilicity of ceramic.

In general, when a ceramic film is prepared by coating a ceramic sol with gelation, there is a problem that the membrane is collapsed due to evaporation of the solvent and osmotic pressure during the drying process. In addition, when the graphene is introduced into the ceramic film, And the prevention of drying (the problem that the graphene layer is located on the surface, the movement of the solvent is prevented and diffusion is prevented and the drying becomes non-uniform), it is actually a difficult technique to produce a hybrid film containing graphene at an appropriate concentration.

From the practical commercialization point of view, graphene is uniformly dispersed in one layer so as not to bend in the solid phase matrix, and the problem of manifesting the physical properties of the graphene-containing composite is overlooked, and no concrete process examples are presented.

As a technique for solving the above problems, there have been proposed methods for producing a composite powder or a composite membrane by applying a method of reducing a metal precursor at room temperature to powder, a plating method, and a sputtering method to graphene. The use of the entire amount of polymer resin is the most common.

However, the dispersibility of the graphene composite materials is very poor, and the resin has a disadvantage of drastically lowering thermal conductivity and film durability of graphene.

The present invention relates to a process for producing an organic-inorganic hybrid ceramic coating film, which comprises forming graphene grains containing oxidized graphene which exhibits the function of graphene without damaging the graphene oxide during the heat treatment and calcination and from which thermal conductivity and surface function are improved, A coating composition for forming an organic-inorganic hybrid ceramic sol, and a process for producing the same.

One embodiment of the present invention is a method for preparing a hydrate of a hydrate of the formula (1), which comprises at least one hydrate represented by the following formula (1), an oxide graphene discontinuously located on the surface of the hydrate represented by the formula And a second secondary particle of silica located on the surface of the discontinuous island-shaped oxide graphene, wherein the secondary particle of the silica is an oxide graphene-containing oil grains in which a plurality of silica nanoparticles are agglomerated, Inorganic hybrid coating film.

[Chemical Formula 1]

X n -M- (OH) 4-n

In Formula 1,

M is selected from Si, Ti, Ag, Sn, In, Zn, and combinations thereof,

X represents an epoxy group, a glycidoxy group, a vinyl group, an acryl group, a methacryl group, a carboxyl group, an amino group, a thiol group, a phosphoric group, a fluoro group, a chloro group, a bromo group, A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted C1 to C10 ketone group, A C1 to C30 alkyl group substituted or unsubstituted with at least one functional group selected from unsubstituted C1 to C10 silyl groups;

An epoxy group, a glycidoxy group, a vinyl group, an acryl group, a methacryl group, a carboxyl group, an amino group, a thiol group, a phosphoric group, a fluoro group, a chloro group, a bromo group, an iodo group, a hydroxy group, a substituted or unsubstituted C1 to C10 alkoxy group , A substituted or unsubstituted C1 to C10 ketone group, a substituted or unsubstituted C1 to C10 amine group, a substituted or unsubstituted C1 to C10 sulfur group, a substituted or unsubstituted C1 to C10 ester group, A C1 to C30 alkenyl group which is substituted or unsubstituted with at least one functional group selected from a C1 to C10 silyl group; or

An epoxy group, a glycidoxy group, a vinyl group, an acryl group, a methacryl group, a carboxyl group, an amino group, a thiol group, a phosphoric group, a fluoro group, a chloro group, a bromo group, an iodo group, a hydroxy group, a substituted or unsubstituted C1 to C10 alkoxy group , A substituted or unsubstituted C1 to C10 ketone group, a substituted or unsubstituted C1 to C10 amine group, a substituted or unsubstituted C1 to C10 sulfur group, a substituted or unsubstituted C1 to C10 ester group, And a C1 to C10 silyl group which is substituted or unsubstituted with at least one functional group selected from a substituted or unsubstituted C1 to C10 silyl group,

n is an integer of 1 to 3;

The oxide-graphene-containing organic-inorganic hybrid coating film may include a first region where the hydrate represented by Formula 1 and the silica secondary particles are bonded; And a second region in which the hydrate of Formula 1, the oxide graphene, and the silica secondary particles are bonded.

The average diameter of the silica secondary particles in the first region may be 5 nm to 50 nm and the average diameter of the silica secondary particles in the second region may be 5 nm to 25 nm.

The average diameter of the silica nanoparticles may be between 5 nm and 30 nm.

The thickness of the graphene oxide may be 0.4 nm to 2 nm.

The major axis length of the graphene grains may be 100 nm to 10 탆, and the minor axis length may be 100 nm to 5 탆.

The content of the graphene oxide may be 0.002 wt% to 50 wt% based on the total weight of the hydrate, the oxidized graphene, and the silica nanoparticle represented by Formula 1.

When the transmittance is 70% or more, the content of the graphene oxide may be 0.002 wt% to 4.2 wt% based on the total weight of the hydrate, the graphene, and the silica nanoparticles represented by Formula 1.

The graphene oxide-containing organic-inorganic hybrid coating film may have a thickness of 100 nm to 2 占 퐉.

When the transmittance is 70% or more, the graphene oxide-containing organic-inorganic hybrid coating film may have a thickness of 200 nm to 500 nm.

The formula 1 may be represented by any one of the following formulas 1-1 to 1-3.

[Formula 1-1]

X 1 -M- (OH) 3

[Formula 1-2]

X 1 X 2 -M- (OH) 2

[Formula 1-3]

X 1 X 2 X 3 -M- (OH)

In Formulas 1-1 through 1-3,

M is selected from Si, Ti, Ag, Sn, In, Zn, and combinations thereof,

X 1 to X 3 each independently represent an epoxy group, a glycidoxy group, a vinyl group, an acryl group, a methacryl group, a carboxyl group, an amino group, a thiol group, a phosphoric group, a fluoro group, a chloro group, a bromo group, A substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted C1 to C10 ketone group, a substituted or unsubstituted C1 to C10 amine group, a substituted or unsubstituted C1 to C10 substituent, a substituted or unsubstituted C1 A C1 to C30 alkyl group substituted or unsubstituted with at least one functional group selected from substituted or unsubstituted C1 to C10 silyl groups;

An epoxy group, a glycidoxy group, a vinyl group, an acryl group, a methacryl group, a carboxyl group, an amino group, a thiol group, a phosphoric group, a fluoro group, a chloro group, a bromo group, an iodo group, a hydroxy group, a substituted or unsubstituted C1 to C10 alkoxy group , A substituted or unsubstituted C1 to C10 ketone group, a substituted or unsubstituted C1 to C10 amine group, a substituted or unsubstituted C1 to C10 sulfur group, a substituted or unsubstituted C1 to C10 ester group, A C1 to C30 alkenyl group which is substituted or unsubstituted with at least one functional group selected from a C1 to C10 silyl group; or

An epoxy group, a glycidoxy group, a vinyl group, an acryl group, a methacryl group, a carboxyl group, an amino group, a thiol group, a phosphoric group, a fluoro group, a chloro group, a bromo group, an iodo group, a hydroxy group, a substituted or unsubstituted C1 to C10 alkoxy group , A substituted or unsubstituted C1 to C10 ketone group, a substituted or unsubstituted C1 to C10 amine group, a substituted or unsubstituted C1 to C10 sulfur group, a substituted or unsubstituted C1 to C10 ester group, And a C1 to C10 silyl group which is substituted or unsubstituted with at least one functional group selected from a substituted or unsubstituted C1 to C10 silyl group.

The M may be Si or Ti.

The oxide-graphene-containing organic-inorganic hybrid coating film may further include additives selected from inorganic powder, organic additives, or combinations thereof.

The average diameter of the inorganic powder may be from 5 nm to 50 nm.

Another embodiment of the present invention is a method for fabricating a semiconductor device, comprising: preparing a highly dispersed oxide graphene; Mixing and dispersing the silica nanoparticles and the precursor of the hydrate represented by Formula 1 in a hydrophilic solvent and mixing with the highly dispersed oxide graphene; Hydrolyzing and polycondensation reaction of the mixed dispersion solution to prepare a graft-containing organic-inorganic hybrid ceramic sol solution; Applying the hybrid sol solution to a substrate and then drying at a temperature of from 25 캜 to 100 캜; And heat treating the dried film at a temperature of 50 ° C to 900 ° C. The present invention also provides a method for producing a graft oxide-coated organic-inorganic hybrid coating film.

The silica nanoparticles are added in an amount of 5 to 20% by weight based on the total amount of the mixed dispersion solution; The precursor of the hydrate represented by the formula (1) is 10 to 40% by weight based on the total amount of the mixed dispersion solution; The highly dispersed graphene oxide is present in an amount of 0.002 to 15% by weight based on the total amount of the mixed dispersion solution; And the hydrophilic solvent balance.

The step of preparing the highly dispersed oxide grains may be carried out by a mechanical dispersion treatment or a solvent substitution method.

The solvent substitution method comprises the steps of: preparing a grafted oxide graft slurry solution substituted with a first nonaqueous solvent; Adding the slurry solution to a second non-aqueous solvent and a precursor of the hydrate to prepare a mixture; And mixing the mixture with a dispersant and water to prepare a coating composition for forming an organic graphene-containing oil-inorganic ceramic hybrid sol.

In the step of mixing and dispersing the silica nanoparticles and the hydrate precursor represented by the formula 1 in a hydrophilic solvent and mixing with the highly dispersed oxidized graphene, additives selected from an inorganic powder, an organic additive, or a combination thereof And a step of mixing the water and the water.

The inorganic powder may be mixed in an amount of 5 to 30 parts by weight based on 100 parts by weight of the mixed dispersion solution.

The organic additive may be mixed in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the mixed dispersion solution.

The precursor of the hydrate represented by the above formula (1) may be at least one selected from the group consisting of trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, , Propyltriethoxysilane, isobutyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane allyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, (N, N- Dimethylaminopropyl) trimethoxysilane, (N, N-dimethylaminopropyl) triethoxysilane, N, N - {(2-aminoethyl) (3-aminopropyl)} trimethoxysilane, Lt; / RTI >

Another embodiment of the present invention provides an automotive headlamp including the oxide-graphene-containing organic-inorganic hybrid coating film described above.

The present invention provides a coating composition for forming an organic-inorganic ceramic hybrid sol containing oxide graphene with improved stability and dispersibility, and is capable of improving the dispersibility, interfacial bonding property, graphene stability, and surface function of graphene in ceramics Inorganic hybrid ceramic coating film containing graphene oxide and a manufacturing method thereof and can realize an automobile head lamp including the graphene oxide-containing ceramic-organic hybrid coating film.

1 is an FE-SEM photograph of a graphene-containing oil-inorganic hybrid coating film according to an embodiment of the present invention.
FIG. 2 is a schematic view showing various forms of hydrates included in a coating composition for forming an organic-inorganic hybrid sol according to an embodiment of the present invention. FIG.
FIG. 3 is a schematic view showing a form in which a hydrate precursor is condensed in an oxide-graphene-containing organic-inorganic hybrid coating film according to an embodiment of the present invention.
4 is a graph showing the content of graphene oxide in a graphene-containing oil-inorganic hybrid coating film in which sol stability is maintained in various embodiments of the present invention.
5 is a photograph showing the dispersion stability and the storage stability of the coating composition for forming an oxide-graphene-containing organic-inorganic hybrid sol according to an embodiment of the present invention.
6 is a photograph showing the uniformity and transparency of the oxide-graphene-containing organic-inorganic hybrid coating film according to an embodiment of the present invention.
7 is a graph showing the transmittance of a bare PC substrate without a coating film.
8 is a graph showing transmittance of a graft oxide-coated organic-inorganic hybrid ceramic coating film according to an embodiment of the present invention.
9 is a graph showing the thermal conductivity effect of the graphene oxide-containing organic-inorganic hybrid coating film according to an embodiment of the present invention.
10 is a schematic view showing a water droplet contact angle of a coating film containing no graphene oxide.
11 is a schematic view showing a water droplet contact angle of a hydrate-containing coating film not containing an organic functional group.
FIG. 12 is a schematic view illustrating a water droplet contact angle of a graphene-containing organic-inorganic hybrid ceramic coating film according to an embodiment of the present invention. FIG.
13 is a scanning electron microscope (FE-SEM) photograph of a graft oxide-coated organic-inorganic hybrid coating film according to an embodiment of the present invention.
14 is an FE-SEM photograph of a heat-treated oxide-graphene-containing oil-inorganic hybrid coating film according to Comparative Examples and various embodiments of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

The graphene oxide-containing organic-inorganic hybrid coating film according to an embodiment includes at least one hydrate represented by the following formula (1), an oxide graphene discontinuously located on the surface of the hydrate represented by the formula (1) And a silica secondary particle located on the surface of the hydrate represented by the general formula (1) and on the surface of the graphene oxide positioned in the discontinuous island shape, respectively, and the silica secondary particle is formed by aggregating a plurality of silica nanoparticles to be.

[Chemical Formula 1]

X n -M- (OH) 4-n

In Formula 1,

M is selected from Si, Ti, Ag, Sn, In, Zn, and combinations thereof,

X represents an epoxy group, a glycidoxy group, a vinyl group, an acryl group, a methacryl group, a carboxyl group, an amino group, a thiol group, a phosphoric group, a fluoro group, a chloro group, a bromo group, A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted C1 to C10 ketone group, A C1 to C30 alkyl group substituted or unsubstituted with at least one functional group selected from unsubstituted C1 to C10 silyl groups;

An epoxy group, a glycidoxy group, a vinyl group, an acryl group, a methacryl group, A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted C1 to C10 alkyl group, Substituted or unsubstituted C1 to C10 amine groups, substituted or unsubstituted C1 to C10 substituted groups, substituted or unsubstituted C1 to C10 ester groups, and substituted or unsubstituted C1 to C10 silyl groups Or an unsubstituted C1 to C30 alkenyl group; or

An epoxy group, a glycidoxy group, a vinyl group, an acryl group, a methacryl group, A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted C1 to C10 alkyl group, Substituted or unsubstituted C1 to C10 amine groups, substituted or unsubstituted C1 to C10 substituted groups, substituted or unsubstituted C1 to C10 ester groups, and substituted or unsubstituted C1 to C10 silyl groups Or an unsubstituted C1 to C30 alkynyl group,

n is an integer of 1 to 3;

Since the hydrate represented by Formula 1 contains at least one organic functional group represented by "X ", the functional group of the hydrate and the hydrophilic group in the hydrophilic sol solution are fused, so that the hydrate and the silica nanoparticles in the hydrophilic sol solution, The interface of the pin can be stably bonded. This form is stable even in the drying and heat treatment processes, and has a buffering effect even in the case of excessive introduction of inorganic additives and organic additives, so that a stable film can be formed.

The organic functional group of the hydrate exhibits a hydrophilic property, and examples thereof include an epoxy group, a ketone group, a carboxyl group, a hydroxyl group, an amino group, an amine group (which may be primary, secondary or tertiary amine), a thiol group, S, P, N, Si, and the like in the backbone of the alkyl group, the alkenyl group, and the alkynyl group, and may be in the form of a group (for example, F, Cl, Br or I) , And some of them may exist in organic or inorganic salt form.

In addition, X is not particularly limited to the molecular weight. However, when the oligomer, the macromolecule, or the polymer is in the form of X, the functional group in the hydrated form capable of inducing the second and third sol- That is, -Si-OH, -Si (OH) 2 , and -Si (OH) 3 are included, and the sol-gel reaction can be diffused by binding with surrounding molecules.

Since the graphene oxide-containing organic-inorganic hybrid coating film contains graphene oxide, it has a "two-dimensional-reinforced ceramic hybrid" effect to improve the strength of the coating film and enhance the superhydrophilic property and thermal conductivity. Improve.

Representative examples of the organic functional groups of X include epoxy groups, glycidoxy groups, vinyl groups, acryl groups, methacryl groups, carboxyl groups, amino groups, thiol groups, phosphoric groups, fluoro groups, A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted C1 to C10 ketone group, a substituted or unsubstituted C1 to C10 amine group, a substituted or unsubstituted C1 to C10 sulfur group, A C1 to C30 alkyl group which is substituted or unsubstituted with at least one functional group selected from a substituted or unsubstituted C1 to C10 silyl group; A C1 to C30 alkenyl group; Or a C1 to C30 alkynyl group.

The formula (1) may be represented by any one of the following formulas (1-1) to (1-3).

[Formula 1-1]

X 1 -M- (OH) 3

[Formula 1-2]

X 1 X 2 -M- (OH) 2

[Formula 1-3]

X 1 X 2 X 3 -M- (OH)

In the above formulas 1-1 to 1-3, the definitions of X 1 to X 3 are the same as those of X described above.

M may be selected from Si, Ti, Ag, Sn, In, Zn, and combinations thereof. Specifically, M may be Si or Ti.

As a most specific example according to one embodiment of the present invention, M may be Si.

When M is Si, typical precursors of the silicon compound forming the hydrate include trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane , Propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, glycidoxypropyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, A compound selected from the group consisting of a silane coupling agent, a silane coupling agent, a silane coupling agent, a silane coupling agent, a silane coupling agent, a silane coupling agent, a silane coupling agent, a silane coupling agent, But is not limited thereto.

In addition, precursors having M-OR bonds (alkoxy bonds) with other metals M, or M-OOR bonds (ester bonds) are also possible.

The hydrate represented by the formula (1) is a form in which the ceramic precursor is a HYDROLYSIS type, for example, as shown in FIG. 2, X 1 -Si- (OH) 3 , X 1 X 2 -Si- (OH) 2 , X 1 X 2 X 3 -Si- (OH). ≪ / RTI > At this time, when the precursor reagent containing the organic components X 1 , X 2 , and X 3 is hydrolysis, the modified form (chemical change, complex, salt formation, etc.) of X 1 , X 2 , and X 3 is contained The interfacial properties with the fins are improved and the organic materials react before the carbon of the graphene during firing to protect the graphene.

X 1 , X 2 , and X 3 may be the same or different.

In addition, when forming the oxide-graphene-containing organic-inorganic-ceramic hybrid coating film, polymerization (network formation is performed) as shown in Fig. 3 can be achieved. This results in the formation of a -Si-O-Si- bond as a condensed form and, in some cases, addition of -Si- and -O-Si- bonds to the substituent portions of X 1 , X 2 and X 3 . Particularly, when the X moiety contains an organic functional group such as an epoxy group, it can be cured by using a curing agent.

The curing agent is used for curing the curable resin, and the curing may be performed by reacting using a catalyst, or may be formed by crosslinking with a curing agent.

The curing agent is not particularly limited, and any compound that is commonly used as a curing agent for an ordinary epoxy resin can be used. Examples thereof include amine compounds, amide compounds, acid anhydride compounds, phenol compounds and the like. Specific examples of the amine compound include diaminodiphenylmethane, ethylenediamine, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complexes and guanidine derivatives. Examples of the amide compound include dicyandiamide, a polyamide resin synthesized from dimer of linolenic acid and ethylenediamine, and examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, Examples of the phenol compound include phenol novolak resin, cresol novolak resin, cresol novolak resin, and the like. Examples of the phenol compound include phenol novolak resin, cresol novolak resin , Aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition-type resin, phenol aralkyl resin Naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol novolak resin, naphthol novolak resin, naphthol novolak resin, naphthol novolak resin, Phenol-co-axial novolak resin, naphthol-cresol co-novolak resin, biphenyl-modified phenol resin (polyhydric phenol compound having a phenylene core linked to a bismethylene group), biphenyl-modified naphthol resin (bifunctional naphthol- Aminotriazine-modified phenol resins (polyhydric phenol compounds in which phenol nuclei are linked via melamine, benzoguanamine, etc.) or alkoxy group-containing aromatic ring-modified novolak resins (formaldehyde having phenolic core and alkoxy group- A polyhydric phenol compound). These curing agents may be used singly or in combination of two or more kinds.

The amount of the epoxy resin and the curing agent to be blended in the epoxy resin composition of the present invention is not particularly limited, but it is preferable that the active group in the curing agent is 0.7 to 1.5 equivalents relative to one equivalent of the total epoxy groups of the epoxy resin.

For example, in the case of glycidoxypropyltriethoxysilane, curing can be performed using a curing agent such as ethylenediamine for an epoxy group which is an organic functional group contained in the X portion.

The oxidized graphene is placed in a discontinuous island shape on the surface of the hydrate of Formula 1, and silica secondary particles are formed on the surface of the oxidized graphene, in which a large number of silica nanoparticles are aggregated.

By containing the graphene oxide, a "two-dimensional-reinforced ceramic hybrid" effect can be obtained. As the graphene oxide is located on the surface of the hydrate represented by the above formula (1) in a discontinuous island shape, The interface between the hydrate represented by the formula (1) and the oxide graphene, and the stability at the interface between the oxide graphene and the silica nanoparticle can be increased.

Particularly, the silica secondary particles located on the surface of the graphene oxide are relatively densely aggregated as compared with the silica secondary particles located on the surface of the hydrate represented by the formula (1), and the secondary grain- It is possible to obtain a structure which is advantageous for realizing physical properties close to the superhydrophilic characteristics, and the thermal conductivity characteristics can also be increased.

The thickness of the graphene oxide may be 0.4 nm to 2 nm.

Specifically, it can be from 0.4 nm to 3 nm, and more specifically from 0.4 nm to 2.8 nm.

Regarding the thickness of the graphene oxide, the thickness when the number of graphene grains is about 10 layers is about 4 nm, and the thickness when the number of graphene grains is about 7 layers is about 2.8 nm.

The major axis length of the graphene grains may be 100 nm to 10 탆, and the minor axis length may be 100 nm to 5 탆.

Specifically, the major axis length may be 100 nm to 2 占 퐉, and the minor axis length may be 100 nm to 500 nm.

When the thickness and size of the graphene oxide are as described above, the hydrophilic property and thermal conductivity property of the oxide-graphene-containing organic-inorganic hybrid coating film can be improved, and even the superhydrophilic property can be realized.

The oxidized graphene is defined as including all possible forms of graphene oxide, reduced graphene, and partially reduced graphene depending on the heat treatment conditions.

In the case of oxidized graphene, it contains essentially oxidative groups such as -OH, -COOH, epoxy groups, and sulfur-containing functional groups. These functional groups are replaced or further modified by chemical reaction A substituent is modified, a derivative, a form in which it is combined with a third substance, etc.), or a doped form. In the present invention, all of the above-mentioned forms are hereinafter referred to as unified graphene grains.

In the present invention, a highly dispersed oxide graphene is used, and a method of highly dispersing the oxidized graphene will be described later.

On the other hand, the oxide-graphene-containing organic-inorganic hybrid coating film comprises a first region where the hydrate represented by Formula 1 and the silica secondary particles are bonded; And a second region in which the hydrate of Formula 1, the oxide graphene, and the silica secondary particles are bonded.

The specific structure of the oxide-graphene-containing organic-inorganic hybrid coating film according to one embodiment of the present invention can be illustrated in FIG.

1 is an FE-SEM photograph of a graphene-containing oil-inorganic hybrid coating film according to an embodiment of the present invention.

Referring to FIG. 1, the A region corresponds to the second region, and the B region corresponds to the first region.

The first region and the second region may be classified according to the shape of the silica secondary particles located in the outermost layer.

The average particle size of the silica nanoparticles may be from 5 nm to 30 nm, more specifically from 7 nm to 25 nm, and the average particle size of the silica nanoparticles used in the present invention may be, for example, 7 nm, 15 nm, have.

When the average particle diameter of the silica nanoparticles is more than 30 nm, the silica nanoparticles do not adhere well to the coating film formed from the hybrid sol solution. As a result, the film surface becomes rough and the contact angle of the water droplet increases, There may be adverse effects of reduced properties.

Specifically, the first region is a region where no graphene oxide protruding from the surface is present, and means a region directly bonded with silica secondary particles on the surface of the hydrate represented by Formula 1.

The average diameter of the silica secondary particles located in the first region may be 5 nm to 50 nm, and may be specifically 10 nm to 50 nm. For example, from 10 nm to 30 nm.

The silica secondary particles located in the first region maintain a large and rounded shape while a large number of grain boundaries are distributed relatively widely between the silica secondary particles.

On the other hand, the second region is, specifically, a region in which graphene oxide protruding from the surface is present, in which oxide graphene binds on the surface of the hydrate represented by Formula 1, and silica secondary particles Quot; region "

The average diameter of the silica nanoparticles located in the second region may be from 5 nm to 25 nm, and more specifically from 5 nm to 20 nm. For example, from 5 nm to 15 nm.

The silica secondary particles located in the second region are densely aggregated in the silica nanoparticles so that the grain boundary between the silica secondary particles is relatively less distributed.

The presence of the second region in which the silica secondary particles, in which the silica nanoparticles are densely agglomerated, is present in the graphene oxide-containing organic-inorganic hybrid coating film enables formation of a contact angle of water favorable to hydrophilicity, The thermal conductivity can be improved by graphene.

In addition, since the oxide graphene contained in the second region is formed in a wide and thin plate shape, it can contribute to the improvement of interfacial bonding stability and the stability of the oxide-inorganic hybrid coating film containing graphene.

The content of the graphene oxide contained in the graphene oxide-containing organic-inorganic hybrid coating film is 0.002 to 50% by weight based on the total weight of the hydrate, the oxidized graphene, and the silica nanoparticle represented by Formula 1, Specifically, it may be 0.002 wt% to 30 wt%, more specifically 0.002 wt% to 17 wt%.

When an additive such as a polymer is included, the content of the graphene oxide may increase from 0.002 wt% to 50 wt%.

The graphene grains contained in the graphene oxide-containing organic-inorganic hybrid coating film can improve the strength and thermal conductivity of the coating film. However, when the graphene grains are contained at a certain level or more, It is recognized that it is a very difficult problem to produce a smooth and uniform type of coating film because it causes nonuniformity of the graphene-ceramic mixture and thus problems in interface bonding.

Accordingly, in the present invention, a coating film having enhanced strength and thermal conductivity by incorporating graphene oxide at a level that does not deteriorate bonding properties with ceramics is prepared.

The coating composition for forming an organic-inorganic hybrid ceramic sol containing graphene oxide for producing a coating film according to an embodiment of the present invention includes a hydrate represented by formula (1) containing at least one organic functional group, It is possible to increase the content of graphene oxide.

In the case of a coating film formed from a coating composition for forming an organic-inorganic hybrid ceramic sol containing oxide graphene containing a ceramic in the form of hydrate, which does not contain an organic functional group at all, a coating film The content of the graphene can be 0.002 to 1.8% by weight based on the total weight of the coating film. At this time, if the hydrate contains at least one functional group, the interface between the oxide graphene and the ceramic is improved and the dispersibility is improved. Therefore, the content of graphene in the coating film, Can be improved to 0.002 wt% to 17 wt% based on the total weight of the coating film.

Further, when the additive is further included, the dispersibility is further improved, so that the content of graphene oxide in the coating film, which can be contained in a uniformly dispersed form in the sol, is from 0.002 wt% to 50 wt% % ≪ / RTI >

The additive may be selected from inorganic powders, organic additives, or combinations thereof.

By further including the inorganic powder, the stability of the coating film (composite effect) and the film functionality such as super hydrophilicity can be imparted.

There may be mentioned ceramic particles as the preferred embodiment of the inorganic powder, as a specific example of the ceramic particles, SiO 2, Al 2 O 3, Li 4 Ti 5 O 12, TiO 2, SnO 2, CeO 2, ZrO 2, V 2 O 5, B 2 O 3, BaTiO 3, Y 2 O 3, WO 3, MgO, CuO, ZnO, AlPO 4, AlF, Si 3 N 4, AlN, TiN, WC, SiC, TiC, MoSi 2, Fe 2 O 3 , GeO 2 , Li 2 O, MnO, NiO, zeolite, hollow ceramic, and the like, but the present invention is not limited thereto.

Examples of the method for obtaining the oxide graphene-ceramic composite powder by applying the ceramic grains to the oxidized graphene include a graphene-metal precursor reduction method, an oxidized graphene-ceramic precursor heat treatment method, a plating method, a substitution method, and a sputtering method .

The diameter of the inorganic powder may be 5 nm to 50 nm.

Specifically, it may be from 5 nm to 30 nm, more specifically from 7 nm to 25 nm, for example from 10 nm to 20 nm.

If the diameter is out of the above range, physical properties of the film may be deteriorated.

By further including the organic additive, dispersibility, coating property, stability, adhesiveness, leveling property, viscosity property, coating film property, dry property and the like can be improved.

The organic additive may be selected from the group consisting of a curing agent, a resin binder, a monomer, a dispersant, a dispersion stabilizer, a surfactant, a polyimide precursor, an organic solvent, an amphoteric solvent, a hydrophilic solvent, A silane coupling agent, a thermoplastic resin, a conductive polymer, or a combination thereof, but is not limited thereto.

Specific examples of the resin binder include thermosetting resin (urethane resin, epoxy resin, melamine resin, polyimide, and mixtures thereof), photocurable resin (epoxy resin, polyethylene oxide, urethane resin and mixture thereof, Acrylate, a polyester acrylate, a urethane acrylate, a polyether acrylate, a thiolate, an organosilicon polymer, an organosilicon copolymer and a mixture thereof, a reactive monomer is a monofunctional monomer such as 2-ethylhexyl acrylate Acrylate, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, methacrylic acid, maleic anhydride, Ethyl acrylate, hydroxyethyl methacrylate, Butyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate, and the like. Examples of the reactive monomers include 1,3-butanediol diacrylate, 1,4-butanediol diacrylate , 1,6-hexanediol diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, neopentyl glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol methacrylate, polyethylene glycol di Methacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, and mixtures thereof, a reactive monomer is a trifunctional monomer such as trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, penta Erythritol triacrylate, glycidyl penta triacrylate, glycidyl There may be mentioned other triacrylate and mixtures thereof, a photoinitiator, benzophenone, benzyl dimethyl Kane talgye, acetophenone, anthraquinone, and the polymer, and so on) a mixture thereof,

Specific examples of the monomers include thermosetting monomers, UV-curable monomers, and chemically curable monomers.

Specific examples of the dispersant and the dispersion stabilizer include Triton X-100, polyethylene oxide, polyethylene oxide-polypropylene oxide copolymer, polyvinylpyrrole, polyvinyl alcohol, Ganax, starch, polysaccharide, dodecyl benzene sulfate, sodium dodecyl benzene sulfonate (NaDDBS), sodium dodecylsulfonate (SDS), 4-vinylbenzoic acid Such as cetyltrimethylammounium 4-vinylbenzoate, pyrene derivatives, Gum Arabic, GA, nafion and mixtures thereof, and other surfactants such as LDS (Lithium Dodecyl Sulfate), CTAC (Cetyltrimethyl Ammonium Chloride), DTAB (Dodecyl-trimethyl Ammonium Bromide), nonionic C12E5 (Pentaoxoethylenedocyl ether), polysaccharide (Dextrin), PEO (Poly Ethylene Oxide), Gum Arabic ene cellulose, commercial BYK, block copolymer, BTK-Chemie, Germany), leveling agent,

The silane coupling agent is a compound capable of forming Si (OH) 4 by hydrolysis and condensation reaction, and examples thereof include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, Tetraalkoxysilanes composed of tetraisopropoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane and mixtures thereof; Methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i- Propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n- Vinyltrimethoxysilane, trimethoxysilane, trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane , 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- (Meth) acryloxypropyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) Methacryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and mixtures thereof; Dimethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di- N-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di- n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and dialkoxysilanes composed of a mixture thereof, and mixtures thereof . They can also act as dispersion stabilizers.

The thermoplastic resin may be selected from the group consisting of polystyrene and its derivatives, polystyrene butadiene copolymer, polycarbonate, polyvinyl chloride, polysulfone, polyethersulfone, polyetherimide, polyacrylate, polyester, polyimide, polyamic acid, cellulose acetate, , Polyolefin, polymethyl methacrylate, polyether ketone, polyoxyethylene, and mixtures thereof,

The conductive polymer may be selected from a polythiophene-based homopolymer, a polythiophene-based copolymer, polyacetylene, polyaniline, polypyrrole, poly (3,4-ethylenedioxythiophene), pentacene-based compounds, and mixtures thereof.

In addition to the above-mentioned inorganic powder and organic additives, if necessary, antioxidants, carbon nanotubes, metal nanowires (such as silver nanowires), metal flakes, nanoparticles, metal nanoparticles, fullerenes, semiconductor nanoparticles , Semiconductor nanowires, semiconductor nanowires, and quantum dots.

On the other hand, when the transmittance is increased to 50% or more for the purpose of improving the transparency of the oxide-graphene-containing organic-inorganic hybrid coating film, the content of the graphene oxide is determined by the hydrate, About 0.002 wt.% To about 6.5 wt.%, Based on the total weight of the silica nanoparticles.

When the transmittance is increased to 70% or more, the content of the graphene oxide is about 0.002 wt% to about 4.2 wt% based on the total weight of the hydrate, the oxidized graphene, and the silica nanoparticle represented by Formula 1 %. ≪ / RTI >

In order to increase the transparency, the content of the graphene oxide should be reduced. The content of the graphene oxide in the coating film, which may be included in the form of uniformly dispersed oxide graphenes in the sol, may be 4 wt% to 7 wt% %, The graphene oxide-containing organic-inorganic hybrid coating film according to the present invention is useful for the production of a transparent film having excellent thermal conductivity.

The graphene oxide-containing organic-inorganic hybrid coating film may have a thickness of about 100 nm to about 2 탆, specifically about 200 nm to 900 nm.

When the thickness of the coating film is the same as above, uniformity and stability of the film surface can be secured.

On the other hand, when the transmittance is increased to 70% or more for the purpose of improving transparency, the thickness of the oxide-graphene-containing organic-inorganic hybrid coating film may be about 200 nm to about 500 nm.

The substrate as the support member for forming the coating film may be a substrate made of inorganic material such as glass or quartz or silicon substrate; (PET), polyethylene naphthalate (PEN), polycarbonate (PC), cycloolefin polymer (COP), polymethylmethacrylate (PMMA), polystyrene (PS), polyimide (PI), polyarylate Or the like can be used.

Further, the substrate in the present invention can be used regardless of the type and shape of the substrate such as a large-area substrate, a curved substrate, and the like.

According to another embodiment, there is provided a method of manufacturing an organic-inorganic hybrid coating film containing graphene, comprising: preparing a highly dispersed oxide graphene; Mixing and dispersing the silica nanoparticles and the precursor of the hydrate represented by Formula 1 in a hydrophilic solvent, and mixing the precursor with the highly dispersed oxide graphene; Hydrolyzing and polycondensation reaction of the mixed dispersion solution to prepare a graft-containing organic-inorganic hybrid ceramic sol solution; Applying the hybrid sol solution to a substrate and then drying at a temperature of from 25 캜 to 100 캜; And heat treating the dried film at a temperature of 50 ° C to 900 ° C.

The silica nanoparticles are added in an amount of 5 to 20% by weight based on the total amount of the mixed dispersion solution; The precursor of the hydrate represented by the formula (1) is 10% by weight to 40% by weight based on the total amount of the mixed dispersion solution; The highly dispersed graphene oxide is present in an amount of 0.002 to 15% by weight based on the total amount of the mixed dispersion solution; And the hydrophilic solvent balance.

And a precursor mixture solution of the graft oxide and the silica nanoparticle and the hydrate represented by the formula (1) are separately dispersed, and then they are mixed to prepare a sol solution. Thus, the silica nanoparticles or the silica nanoparticles The ceramic precursor molecule species corresponding to the hydrate can be dispersed and adsorbed to the maximum, and thereby a uniform coating composition can be produced.

The hydrophilic solvent is the most important mediator for stability and reactivity of the sol. In order to easily fuse the hydrophilic ceramic sol and the oxidized graphene, a precondition for dispersing the oxidized graphene in the hydrophilic solvent should be established.

The reason why hydrophilicity is required is that in the case of the main reaction of the present invention, water is necessarily required in the sol-gel reaction, and it has to be well fused with H 2 O as the reaction product, and silanol (-Si -OH) must be fused well with the surrounding solvent, a hydrophilic solvent having a single or biphasic system is required.

If the preconditions for dispersing the graphene oxide in the hydrophilic solvent are not satisfied, it is difficult to expect a uniform fusion of the hydrophilic sol and the oxidized graphene.

Herein, "precondition for dispersing the graphene oxide in a hydrophilic solvent" is, for example, three cases.

First, a dispersion of water-based graphene oxide dispersed in water can be mentioned.

The aqueous graphene graphene dispersion can be produced by chemically oxidizing graphite by oxidation and further by applying electricity to the graphite in a liquid phase, and the graphene grains thus formed are characterized by the presence of water-based substituents (-OH, -COOH), whereby water-based dispersion occurs. By uniformly mixing the aqueous-based oxide graphene dispersion with an aqueous-based ceramic sol, a uniform oxidized graphene-ceramic hybrid sol solution can be formed. That is, the aqueous graphene dispersion can be directly applied to the mixing process without the addition of a dispersant or an additional process.

Second, a small amount of graphene oxide containing a large number of hydrophilic groups on its surface is used.

According to an embodiment of the present invention, since the content of graphene oxide mixed in the ceramic sol solution is as small as about 0.01 wt% to 0.1 wt%, it is preferable that graphene containing a large amount of surface hydrophilic groups is dispersed in a hydrophilic solvent such as water or alcohol It is possible to prepare a uniform hybrid sol solution even when it is used in the production of a ceramic sol solution.

At this time, a binder, an inorganic powder, an organic additive, etc., which are added together, may serve as an auxiliary agent to prevent aggregation of graphene.

Third, a method in which graphene oxide is dispersed in a non-aqueous solvent so as to be highly dispersed, and then the solvent is replaced with an aqueous solvent is used. In the present invention, this is referred to as a solvent substitution method, and the solvent substitution method can be carried out, for example, by a step shown in the following.

Figure pat00001

That is, the solvent substitution method comprises the steps of: preparing a grafted oxide graft slurry solution substituted with a first nonaqueous solvent; Adding the slurry solution to a second non-aqueous solvent and a precursor of the hydrate to prepare a mixture; And mixing the mixture with a dispersant and water to prepare a coating composition for forming an organic graphene-containing oil-inorganic hybrid sol.

The "step of producing a grafted oxide graft slurry solution substituted with the first nonaqueous solvent", which is the first step of the method for producing a coating composition for forming an organic graphene oxide-containing hybrid sol, Replacing with an environment,

Mixing the aqueous graphene graphene slurry and the first non-aqueous solvent, and then performing mechanical dispersion treatment and centrifugation.

The mechanical dispersion treatment and the centrifugation may be performed at least twice, and the step of separating the supernatant formed in the centrifugation may be further included.

The coating composition for forming an oxide-graphene-containing organic-inorganic ceramic hybrid sol according to the number of times of the mechanical dispersion treatment and the centrifugal separation is not significantly different at the time of manufacturing, but the mechanical dispersion treatment and the centrifugal separation are performed twice or more , The storage stability of the graphene oxide-containing organic-inorganic ceramic hybrid sol can be improved. This is because as the number of times of substitution into the non-aqueous environment in the aqueous environment increases, the non-aqueous atmosphere increases relatively, and moisture that interferes with the affinity with the ceramic sol can be removed more effectively.

Hydrophilic functional groups such as carboxyl group (-COOH), hydroxyl group (-OH), and the like can be removed from the surface of the oxidized graphene by replacing the graphene oxide grains with a non-aqueous environment in the aqueous environment.

That is, in the mixing step with the ceramic sol solution which is performed in the next step, the graphene slurry solution and the ceramic sol solution can be easily fused, thereby ensuring the uniformity of the mixed solution.

The mechanical dispersion treatment can be carried out specifically by ultrasonication, stirring, shear stress and shearing force, homogenizer, or a combination thereof,

The centrifugation can be performed at a rotation speed of 1200 to 3500 rpm, specifically 2000 to 3300 rpm.

Since the non-aqueous-based graphene slurry solution is directly added to the ceramic sol solution process by adding and mixing the graphene oxide slurry solution substituted with the first non-aqueous solvent to the second non-aqueous solvent and hydrate precursor, The problem of wrinkling that occurs when the oxidized graphene sheets are mixed in the ceramic sol solution having high and high viscosity is alleviated,

Since the ceramic and the oxidized graphene are well dispersed in the non-aqueous solvent, the mobility of ions and chemical species derived from the ceramic precursor can be improved upon network formation of the ceramic precursor within the ceramic sol solution (sol reaction) .

The graphene oxide grains contained in the graphene oxide slurry substituted with the first nonaqueous solvent may be included in an amount of 2 to 7 wt% based on the total weight of the graphene oxide grains substituted with the first nonaqueous solvent.

When the solid content of the graphene oxide is in the above range, the molecular species of the ceramic precursor can be maximally adsorbed to the graphene oxide, which is a plate-shaped nanostructure, and a uniform oxidized graphene-ceramic sol solution can be formed.

The dispersing agent used in the solvent substitution method may be polyethylene glycol (PEG), glycerol, hydrochloric acid (HCl), acetic acid, formic acid, citric acid, a binder, or a combination thereof.

The first non-aqueous solvent and the second non-aqueous solvent may each independently be an amphoteric solvent, a water-soluble solvent other than water, a non-aqueous solvent, a polar solvent, a non-polar solvent, or a combination thereof.

Specifically, the first non-aqueous solvent and the second non-aqueous solvent are each independently selected from the group consisting of iso-propyl alcohol, ethanol, acetone, methyl ethyl ketone, methyl alcohol, ethyl alcohol, isopropyl alcohol, , Butyl alcohol, ethylene glycol, polyethylene glycol, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, hexane, cyclohexanone, toluene, chloroform, dichlorobenzene, dimethyl Benzene, trimethylbenzene, pyridine, methylnaphthalene, nitromethane, acrylonitrile, octadecylamine, aniline, dimethylsulfoxide, or combinations thereof.

Specific examples of the hydrophilic solvent include water; But are not limited to, alcohols such as methanol, ethanol, propanol, butanol, and isopropyl alcohol (IPA), glycols, or combinations thereof. For example, a mixed solvent of water and alcohol.

The hydrophilic solvent may be mixed in an amount of 10 to 500 parts by weight based on 100 parts by weight of water, and specifically, the mixing ratio by weight of water to alcohols is 100: 50, 100: : 100, 100: 150, 100: 200, 100: 300, 100: 400. 100: 500, and may be mixed at a weight ratio of usually 100: 100, or 100: 200.

Examples of the precursor of the hydrate represented by Formula 1 include a silicon compound, titanium isopropoxide (TTIP), and tetramethylorthosilicate (TMOS).

The most specific examples of the silicon compound include trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltrimethoxysilane, But are not limited to, triethoxysilane, isobutyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltri (N, N-dimethylamino) silane, diphenylmethoxysilane, diphenyldiethoxysilane, diphenyldiethoxysilane, diphenylmethoxysilane, diphenylmethoxysilane, Propyl) trimethoxysilane, (N, N-dimethylaminopropyl) triethoxysilane, N, N - {(2- aminoethyl) (3-aminopropyl)} trimethoxysilane, have.

The formula 1 may be represented by any one of the following formulas 1-1 to 1-3.

[Formula 1-1]

X 1 -M- (OH) 3

[Formula 1-2]

X 1 X 2 -M- (OH) 2

[Formula 1-3]

X 1 X 2 X 3 -M- (OH)

In the above Formulas 1-1 to 1-3, the definitions of M and X 1 to X 3 are as described above.

On the other hand, M may be Si as a most specific example.

For example, the precursor of the hydrate may be glycidoxypropyltrimethoxysilane and may be used in admixture with a silane coupling agent selected from tetramethoxysilane, tetraethoxysilane, diphenylethoxysilane, and combinations thereof .

The coating step may be performed by a conventional coating method, and specifically, a coating method such as dip coating, spin coating, spray coating, paint coating, bar coating Or may be carried out by a combination of these methods. More specifically, the coating may be performed by dip coating, spin coating, or spray coating ). ≪ / RTI >

The coating process according to one embodiment can be performed by spray coating without any restriction on the type and shape of the substrate such as a large area and a curved substrate. However, the present invention is not limited thereto.

According to an embodiment of the present invention, in the step of mixing and dispersing the silica nanoparticles and the hydrate precursor represented by the formula (1) in a hydrophilic solvent and mixing with the highly dispersed graphene, the inorganic powder, An organic additive, or a combination thereof.

For example, the inorganic powder may be mixed in an amount of 5 to 30 parts by weight based on 100 parts by weight of the mixed dispersion solution.

Specifically, it may be 5 parts by weight to 25 parts by weight, more specifically 7 parts by weight to 20 parts by weight, for example, 7 parts by weight to 10 parts by weight.

If the content of the inorganic powder is out of the above range, physical properties of the coating may be deteriorated.

For example, the organic additive may be mixed in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the mixed dispersion solution.

Specifically, it may be 0.01 to 5 parts by weight, more specifically 0.1 to 3 parts by weight, for example, 0.01 to 2 parts by weight.

If the content of the organic additive is out of the above range, the physical properties of the coating film may be deteriorated.

The diameter of the inorganic powder may be 5 nm to 50 nm.

Specifically, it may be from 5 nm to 30 nm, more specifically from 7 nm to 25 nm, for example from 10 nm to 20 nm.

If the diameter is out of the above range, physical properties of the film may be deteriorated.

May be included in an amount of 5 to 30 parts by weight based on 100 parts by weight of the coating composition for forming a graft oxide-containing organic-inorganic ceramic hybrid sol.

Specifically, it may be 5 parts by weight to 25 parts by weight, more specifically 7 parts by weight to 20 parts by weight, for example, 7 parts by weight to 10 parts by weight.

If the content of the inorganic powder is out of the above range, physical properties of the coating may be deteriorated.

By further including the organic additive, dispersibility, coating property, stability, adhesiveness, leveling property, viscosity property, coating film property, dry property and the like can be improved.

Another embodiment of the present invention provides an automotive headlamp including the oxide-graphene-containing organic-inorganic hybrid coating film described above.

In particular, due to the effect of the present invention as described above, for example, excellent thermal conductivity, it is expected that the anti-fogging function due to heat conduction by the lamp heat can be exerted.

As an application example of a specific industry, it can be applied to a lens (PC curved substrate) of an automobile headlamp in which the problem of fogging is improved.

Hereinafter, specific examples of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

In addition, contents not described here can be inferred sufficiently technically if they are skilled in the art, and a description thereof will be omitted.

Production Example 1

(Production of graphene oxide (graphite)) [

10 g of natural graphite and 7.5 g of sodium nitrate were added to the reactor, and 621 g of 96% sulfuric acid was added slowly while stirring. When the three substances are sufficiently mixed, 45 g of manganese peroxide is added. Manganese peroxide is explosive when it reacts with concentrated sulfuric acid and generates heat and gas. After adding manganese dioxide, the mixture is stirred at room temperature and allowed to react for about 4 to 6 days. Then, 1L of 5% sulfuric acid is added, so heat and gas are generated. Cool the reactor appropriately and slowly add over 1 hour, and stir at room temperature for one day. After one day, 30 g of 30% hydrogen peroxide is slowly added and reacted for 2 hours. Several washing and centrifugation steps were performed to remove excess sulfuric acid and hydrogen peroxide in the final product. In this final step, centrifuge first, discard the supernatant, add a mixture of 3% sulfuric acid and 0.5% hydrogen peroxide in a 1: 1 mixture to the remaining supernatant, shake thoroughly, and centrifuge to discard the supernatant. Add the mixed solution to the remaining precipitate and mix. After repeating this process 15 times, replacing the mixed solution with water and repeating it 5-6 times, finally a water-based graphene oxide slurry is obtained.

The GO slurry is usually obtained by acid treatment of graphite or may be obtained naturally during purification. Therefore, the GO slurry in the present invention is not limited to this and may be a plate-like graphene oxide or graphite oxide which is generally known. Typically, the water-based GO slurry has a solids content of 2 to 8% by weight based on the centrifuged slurry.

Production Example 2

(Preparation of oxidized graphene powder)

The aqueous GO slurry of Preparation Example 1 was used after being washed 10 times with secondary distilled water. This aqueous GO slurry was vacuum dried at 80 DEG C for 24 hours, pulverized, and then heat-treated at 160 DEG C for 48 hours to prepare graphene oxide powder.

Production Example 3

(Preparation of GO slurry containing IPA)

100 g of the aqueous GO slurry of Production Example 1 (solid content: 2.5% as a result of thermal analysis) was placed in a 500 mL plastic bottle and 300 mL of IPA was added, followed by ultrasonic dispersion for 5 minutes. The GO solution dispersed in H 2 O / IPA was centrifuged at 3,000 rpm and the supernatant was discarded. The IPA was added 10 times from the IPA addition to the supernatant disposal. Thus, an IPA-containing GO slurry can be obtained. It was found that the effect of the present invention was satisfactory when the IPA addition-dispersion-centrifugal-upper layer liquid removal process was performed three times or more with the removal efficiency of H 2 O.

Production Example 4

(Preparation of GO slurry containing DMF)

100 g of the aqueous GO slurry of Preparation Example 1 (solid content: 2.5%) was added to a 500 ml plastic bottle and 300 ml of DMF was added. The mixture was homogenized at 15,000 rpm for 15 minutes using a homogenizer, centrifuged at 3,000 rpm and discarded , And the DMF addition was performed 10 times from the process of adding DMF to the process of discarding the supernatant. Thus, a DMF-containing GO slurry can be obtained.

Production Example 5

(Preparation of GO slurry containing ethanol)

100 g of the aqueous GO slurry of Preparation Example 1 (solid content: 2.5%) was added to a 500 ml plastic bottle, and 300 ml of ethanol was added. The mixture was homogenized at 15,000 rpm for 15 minutes using a homogenizer, centrifuged at 3,000 rpm, Ethanol was added 10 times from the process of adding ethanol to the process of discarding the supernatant. Thus, an ethanol-containing GO slurry can be obtained.

Comparative Example 1

(Si (OH) 4 of the type SiO 2 Preparation of Sol Solution)

50 mg of the oxidized graphene powder of Preparation Example 2 was placed in a 500 mL plastic bottle, 150 mL of IPA was added, 10 g of PEG was added, and ultrasonic dispersion was performed for 10 minutes. Add 100 ml of ethanol, add 10 ml of TMOS (tetramethyl orthosilicate), and stir well for at least 24 hours. At this time, pH was maintained at about 3.3 using hydrochloric acid. The HYDROLYSIS form of TMOS is Si (OH) 4 without organic functional groups.

(Preparation of oxide graphene-SiO 2 hybrid coating film I)

The oxidized graphene-ceramic hybrid sol solution was spin-coated on a plasma-treated glass substrate (rpm 800). The spin-coated film was vacuum-dried at room temperature and then heat-treated at 180 ° C for 1 hour to prepare a GO-SiO 2 hybrid coating film.

The coating film forming process may be spray coating, bar coating, knife coating, screen printing, dip coating,

The heat treatment process can be performed by a vacuum heat treatment, an atmosphere heat treatment, an IR heat treatment, a convection heat treatment, a heat treatment by a heater, a laser, or the like, a heat wave by an electromagnetic wave or a microwave heat treatment.

On the other hand, when the coating was heat-treated at 300 ° C, a hybrid coating film containing graphene reduced to about 50% (functional group identification using FT-IR)

It was confirmed that when annealed at 600 ℃ in an inert gas atmosphere, a hybrid coating film containing reduced graphene was obtained.

(Preparation of oxide graphene-SiO 2 hybrid coating film II)

The oxidized graphene-ceramic hybrid sol solution was spray coated onto a plasma-treated PC (Polycarbonate) substrate. The spray coating film was subjected to a surface heat treatment by repeatedly applying an instantaneous thermal impact with an IR lamp after vacuum drying at 50 ° C. The heat treatment temperature was 300 占 폚, and the film exposure time was 3 seconds. The heat treatment and film exposure process were repeated. Repeatedly, the temperature of the substrate was sufficiently dropped to room temperature and then repeated. To keep the temperature of the backside of the substrate at about 100 ° C, the substrate was cooled with water (air-cooling is also possible).

Referring to FIG. 4, the oxidized graphene-ceramic hybrid coating film formed from the oxidized graphene-ceramic hybrid sol solution has an oxidized graphene (carbon) content of about 1.8 wt%.

Example 1

(Preparation of Si (OH) 3 X 1 type oxidized graphene-ceramic hybrid sol solution)

According to the mixing method, the following three methods were used.

1) Simple mixing method using mechanical dispersion treatment method

The graphene oxide powder of Production Example 2 50 mg was added to 100 ml of IPA and ultrasonic dispersion was performed for 10 minutes. 1 ml of the top layer solution which did not settle after one hour was collected, 100 ml of ethanol was added thereto, and 10% by weight to 40% by weight of glycidoxypropyl trimethoxysilane (hereinafter referred to as GT) was dissolved in water: ethanol = And 20% by weight of rudox (20 nm silica sol) and nitric acid were added to adjust the pH to 2 to 4, and the mixture was stirred for 24 hours. After the reaction, an ethylenediamine curing agent was added as much as the number of GT molar times, and the mixture was sintered for 30 minutes to prepare a graft-ceramic hybrid sol solution of Si (OH) 3 X 1 type. The final film had a graphene content of 0.02 wt% to 11.5 wt%.

2) a method of mixing and mixing aqueous graphene graphene solution from the beginning

100 ml of ethanol was added to 1 ml of a commonly used aqueous dispersion of graphene oxide (1% by weight solution), 10% by weight to 40% by weight of glycidoxypropyl trimethoxysilane (GT) Ethanol = 1: 1 by weight, and 20 wt% of rudox (20 nm silica sol) and nitric acid were added to adjust the pH to 2 to 4, and the mixture was stirred for 24 hours. After the reaction, an ethylenediamine curing agent was added as much as the number of GT molar times, and the mixture was sintered for 30 minutes to prepare a graft-ceramic hybrid sol solution of Si (OH) 3 X 1 type. The final film had a graphene content of 0.02 wt% to 17 wt%.

Depending on the type of graphene, if it is possible to disperse easily in water or alcohol, the process can be shortened. For example, in the case of graphene produced by an electric stripping method, graphene local oxidation or the like, or a graphene containing a large number of hydrophilic groups on its surface, a small amount of graphene of about 0.01 wt% to 0.1 wt% Can be used. In this case, by using a binder, an inorganic powder, an organic additive, etc. as an additive, graphene aggregation can be prevented.

3) Mixing by solvent substitution method

100 ml of the solvent IPA and 50 ml of Acetylacetone were added to 1200 mg of the GO slurry (obtained by thermal analysis, solid content 3.0%, IPA 97%) solvent-substituted with IPA of Preparation Example 3, and 10 to 40% by weight of glycidoxypropyltrimethoxy (Glycidoxypropyl Trimethoxysilane, hereinafter referred to as GT) was dissolved in a mixed solvent of water and ethanol at a weight ratio of 1: 1, and 20 wt% of rudox (20 nm silica sol) and nitric acid were added to adjust the pH to 2 to 4 Followed by stirring for 24 hours (reaction product A). 150 ml of water, 20 g of PEG (polyethylene glycol) and 1 ml of HCl were added to the previously prepared reaction product A, followed by uniform reaction (stirring) for 90 minutes. Subsequently, an ethylenediamine curing agent was added by GT number of times, and the resultant mixture was subjected to a stirrer for 30 minutes to prepare an oxidized graphene-ceramic hybrid sol solution of Si (OH) 3 X 1 type.

(Preparation of coating film)

A coating film was prepared in the same manner as the graphene-SiO 2 hybrid coating film of Comparative Example 1, except that the above-mentioned Si (OH) 3 X 1 type oxide graphene-ceramic hybrid sol solution was used.

Referring to FIG. 4, the graphene (carbon) content of the coating film in which sol stability is maintained as an oxidized graphene-ceramic hybrid coating film formed from the oxidized graphene-ceramic hybrid sol solution according to Example 1 is about 0.002 wt% to about 11.5 wt% Weight%.

It can be confirmed that the maximum content of graphene in the coating film in which the sol stability is maintained by five times or more is improved from 1.8 wt% to 10 wt% by including one organic functional group (X 1 ) as compared with Comparative Example 1.

When the highly dispersed oxide graphene solution and the ceramic sol solution are simply mixed, the maximum can be improved to about 7.5% by weight,

When the dispersed graphene graphene solution is added from the beginning to prepare the ceramic sol solution, the maximum can be improved to about 8.5 wt%

When the highly dispersed oxidized graphene obtained from the solvent substitution method and the ceramic sol solution were mixed, the maximum was increased to about 11.5% by weight.

Example 2

(Si (OH) 3 X One  + Si (OH) 2 X One X 2  Type hybrid graphene-ceramic hybrid sol solution)

1) Simple mixing method using mechanical dispersion treatment method

The graphene oxide powder of Production Example 2 50 mg was added to 100 ml of IPA and ultrasonic dispersion was performed for 10 minutes. After 1 hour, 1 ml of the uppermost layer liquid which did not settle was collected. 100 ml of ethanol was added thereto, and then glycidoxypropyl trimethoxysilane (GT) and diphenyldiethoxysilane (weight ratio of 1: 1) , 20% by weight of rudox (20 nm silica sol), and nitric acid were added to adjust the pH to 2 to 4 Followed by stirring for 24 hours. After the reaction, an ethylenediamine curing agent was added as much as the number of GT molar times, and the mixture was sintered for 30 minutes to prepare an oxidized graphene-ceramic hybrid sol solution of Si (OH) 3 X 1 + Si (OH) 2 X 1 X 2 type. The final film had a graphene content of about 0.02 wt% to 16.7 wt%.

2) a method of mixing and mixing aqueous graphene graphene solution from the beginning

100 ml of ethanol was added to 1 ml of a commercially available aqueous dispersion of graphene oxide (1% by weight solution), 10% by weight to 40% by weight of glycidoxypropyl trimethoxysilane (hereinafter referred to as GT) 10 to 40% by weight of a mixture of diethoxysilane (1: 1 by weight) was dissolved in a mixed solvent of water and ethanol at a weight ratio of 1: 1, followed by addition of 20% by weight of rudox (15 nm silica sol) Nitric acid was added to adjust the pH to 2 to 4, and the mixture was stirred for 24 hours. After the reaction, an ethylenediamine curing agent was added as much as GT mole and the mixture was stood for 30 minutes to prepare a graft-ceramic hybrid sol solution of Si (OH) 3 X 1 + Si (OH) 2 X 1 X 2 type. The final film had a graphene content of about 0.02 wt% to 14.7 wt%.

3) Mixing by solvent substitution method

100 ml of the solvent IPA and 50 ml of Acetylacetone were added to 1,200 mg of the GO slurry (obtained by thermal analysis, solid content 3.0%, IPA 97%) solvent-substituted with IPA of Preparation Example 3, and glycidoxypropyl trimethoxysilane 10 to 40% by weight of a mixture of a mixture of water and ethanol (1: 1 by weight) and diphenyldiethoxysilane (1: 1 by weight) was dissolved in a mixed solvent of water and ethanol at a weight ratio of 1: 1, ), And nitric acid were added to adjust the pH to 2 to 4, and the mixture was stirred for 24 hours (reactant A). 150 ml of water, 20 g of PEG (polyethylene glycol) and 1 ml of HCl were added to the previously prepared reaction product A, followed by uniform reaction (stirring) for 90 minutes. Subsequently, an ethylene diamine curing agent was added by GT mole ratio and stuttering was conducted for 30 minutes to prepare an oxidized graphene-ceramic hybrid sol solution of Si (OH) 3 X 1 + Si (OH) 2 X 1 X 2 type.

(Preparation of coating film)

The graphene oxide-SiO 2 hybrid coating film of Comparative Example 1 and the graphene-SiO 2 hybrid coating film of Comparative Example 1 were produced in the same manner as in Comparative Example 1, except that the graphene-ceramic hybrid sol solution of the Si (OH) 3 X 1 + Si (OH) 2 X 1 X 2 type was used. A coating film was prepared in the same manner.

Referring to FIG. 4, the graphene (carbon) content of the coating film in which the sol stability is maintained as the oxidized graphene-ceramic hybrid coating film formed from the oxidized graphene-ceramic hybrid sol solution according to Example 2 is about 0.002 wt% to 16.7 Weight%.

As a result, it was confirmed that the maximum content of graphene was improved from 1.8 wt% to 16.7 wt% in a coating film in which the sol stability was maintained by containing two organic functional groups (X 1 X 2 ) as compared with Comparative Example 1.

When the highly dispersed oxide graphene solution and the ceramic sol solution are simply mixed, the maximum can be improved to about 13.5% by weight,

When the dispersed graphene graphene solution is added from the beginning to prepare the ceramic sol solution, it can be improved to about 14.7 wt%

When the highly dispersed oxide graphene obtained from the solvent substitution method and the ceramic sol solution were mixed, the maximum of about 16.7 wt% could be obtained.

At this time, when the content of the graphene oxide is reduced to be transparent, the graphene content can be up to about 6.5 wt% at a transmittance of 50%, and the graphene can reach about 4.2 wt% at a transmittance of 70%.

Example 3

(Si (OH) 3 X 1 + Si (OH) 4 type and curing agent type organic / inorganic hybrid sols)

1) Simple mixing method using mechanical dispersion treatment method

Manufacturing example 3 oxide graphene powder 50 mg was added to 100 ml of IPA and ultrasonic dispersion was performed for 10 minutes. 1 ml of the top layer solution which did not settle after one hour was collected, 100 ml of ethanol was added thereto, and 10 to 10 ml of a mixture of glycidoxypropyl trimethoxysilane (hereinafter referred to as GT) and TMOS (weight ratio of 1: 40% by weight was dissolved in a mixed solvent of water: ethanol = 1: 2 by weight and 20% by weight of rudox (15 nm silica sol) and nitric acid were added to adjust pH to 2 to 4, . After the reaction, an ethylenediamine curing agent was added as much as GT mole and the mixture was stood for 30 minutes to prepare an oxide graphene-ceramic hybrid sol solution of Si (OH) 3 X 1 + Si (OH) 4 type. The final film had a graphene content of 0.02 wt% to 4.5 wt%.

2) A method in which a water-based dispersed graphene solution is added from the beginning and mixed

100 ml of ethanol was added to 1 ml of a commercially available aqueous dispersion of graphene oxide (1% by weight solution), mixed with a mixture of glycidoxypropyl trimethoxysilane (GT) and TMOS (1: 1 weight ratio) 10 to 40% by weight was dissolved in a mixed solvent of water: ethanol = 1: 2 by weight, 20% by weight of rudox (15 nm silica sol) and nitric acid were added to adjust the pH to 2 to 4, The reaction was allowed to proceed. After the reaction, an ethylenediamine curing agent was added as much as the number of GT molar times, and the mixture was sintered for 30 minutes to prepare a graft-ceramic hybrid sol solution of Si (OH) 3 X 1 + Si (OH) 4 type. The final film had a graphene content of 0.02 wt% to 5 wt%.

3) Mixing by solvent substitution method

100 ml of the solvent IPA and 50 ml of Acetylacetone were added to 1200 mg of the GO slurry (obtained by thermal analysis, solid content 3.0%, IPA 97%) solvent-substituted with IPA of Preparation Example 3, and 10 to 40% by weight of glycidoxypropyltrimethoxy 10 to 40% by weight of a mixture of silane (Glycidoxypropyl Trimethoxysilane, hereinafter referred to as GT) and TMOS (weight ratio of 1: 1) was dissolved in a mixed solvent of water: ethanol = 1: 2, 20% by weight), and nitric acid were added to adjust the pH to 2 to 4, and the mixture was stirred for 24 hours (reaction product A). 150 ml of water, 20 g of PEG (polyethylene glycol) and 1 ml of HCl were added to the previously prepared reaction product A, followed by uniform reaction (stirring) for 90 minutes. Subsequently, an ethylene diamine curing agent was added as much as the number of GT moles and the mixture was stitched for 30 minutes to prepare an oxidized graphene-ceramic hybrid sol solution of Si (OH) 3 X 1 + Si (OH) 4 type.

(Preparation of coating film)

SiO 2 hybrid coating film of Comparative Example 1, except that the above-mentioned graphene-ceramic hybrid sol solution of Si (OH) 3 X 1 + Si (OH) 4 type was used, .

The oxide graphene-ceramic hybrid coating film formed from the graphene-ceramic hybrid sol solution according to Example 3 has a graphene (carbon) content of about 0.02 wt% to 7 wt%.

This result shows that the maximum content of graphene in the coating film in which the sol stability is maintained compared with Comparative Example 1 is improved by about 2 to 3 times.

(Polymer added)

Example 4

Except that 10 parts by weight of PVA was further added to 100 parts by weight of the precursor of the oxidized graphene-solvent-hydrate before addition of the curing agent in the preparation of the oxidized graphene-ceramic hybrid sol solution, oxidation was carried out in the same manner as in Example 1 A graphene-ceramic hybrid sol solution and a coating film formed therefrom were prepared.

The maximum content of graphene in a coating film in which sol stability is maintained can be improved to about 17% by weight.

This is the result of confirming that the dispersion stability of graphene increases with the increase of organic component at the interface of ceramic-graphene.

Example 5

Except that 10 parts by weight of PVA (polyvinyl alcohol) was further added to 100 parts by weight of the precursor solution of the graphene-solvent-hydrate before addition of the curing agent in the preparation of the oxidized graphene-ceramic hybrid sol solution. An oxide graphene-ceramic hybrid sol solution and a coating film formed therefrom were prepared in the same manner as in Example 2.

Referring to FIG. 4, the maximum content of graphene in a coating film in which sol stability is maintained can be improved to about 50% by weight.

Example 6

Except that 10 parts by weight of PVA (polyvinyl alcohol) was further added to 100 parts by weight of the precursor of the oxidized graphene-solvent-hydrate before addition of the curing agent in the preparation of the oxidized graphene-ceramic hybrid sol solution. Oxide graphene-ceramic hybrid sol solution and a coating film formed therefrom were prepared in the same manner as in Example 3.

The maximum content of graphene in a coating film in which sol stability is maintained can be improved to about 38% by weight.

(Silica particles added)

Comparative Example 2

Insert the IPA 50ml, Si (OH) 3 X 1 50ml to put after gave was stirred for more than 30 minutes, water 10ml, PEG (Polyethylene glycol) 10g, Ludox (sol of 20 nm silica), followed by the addition of the HCl 1ml 90 (Stirring) for a minute to prepare a sol solution of Si (OH) 3 X 1 type, and a coating film formed therefrom.

Example 7

(Polyvinyl alcohol), 0.1 part by weight of silver nanowires and 0.1 part by weight of silver nanoparticles were added to 100 parts by weight of a precursor solution of a graphene-solvent-hydrate, to prepare a graphene-ceramic hybrid sol solution and a coating film Was prepared in the same manner as in Example 4 above.

Evaluation 1: Evaluation of uniformity (stability) of graphene oxide-containing ceramic hybrid sol solution

FIG. 5 is a graph showing the relationship between the concentration of graphene grains dispersed in the coating film formed from the graphene oxide-containing organic-inorganic ceramic hybrid sol solution and the resultant graphene grains by 11.5 weight% using Example 1 and Comparative Example 1 It is the result of adding graphene. Example 1 of Fig. 5 shows that the dispersion stability is excellent as a result of using Si (OH) 3 X 1 , and Comparative Example 1 of Fig. 5 shows that most of the precipitation occurred as a result of using only Si (OH) 4 Able to know. In Comparative Example 1 of Fig. 5, the transparent brown portion of the supernatant means that the amount of graphene was saturated, and the graphene content of the coating film obtained from the supernatant was 0.002 to 2.5 wt%.

In Examples 2 to 4, the same phenomenon as in Example 1 of Fig. 5 can be observed. The dispersion prepared according to the principle of the present invention exhibited a stability of about 1 month or more at a very high concentration (stability was maintained for at least 1 month even in a refrigerator and a 60 ° C thermal shock test) and exhibited an improved stability not found in conventional graphene graphene dispersions. The presently reported graphene graphene content in the dispersion is less than about 0.5% by weight.

Evaluation 2: Evaluation of stability of graft oxide-coated ceramic hybrid coating film

FIG. 6 shows the result of coating the coating solution obtained in Comparative Example 1 and Example 1 on a PC substrate, followed by drying.

It can be seen that the film obtained in Comparative Example 1 was easily peeled off as it was wrinkled, and that the coating film of the present invention obtained in Example 1 exhibited a smooth and transparent surface, showing good coating properties.

Evaluation 3: Evaluation of transmittance of a graphene-containing hybrid coating film

The results of the evaluation of the transmittance of the hybrid coating film containing oxidized graphene obtained in Example 2 using an ultraviolet-visible spectrophotometer (JASCO, V-530) are shown in Fig.

8 is a graph showing the transmittance of the oxide-graphene-containing organic-inorganic hybrid coating film according to an embodiment of the present invention.

7 and 8, the transmittance of the oxide-graphene-containing organic-inorganic hybrid coating film according to an embodiment of the present invention is 75 to 82% as compared with the transmittance of the bare PC substrate having no coating film of 88.7% , And approximately 76.7%.

From this, it can be confirmed that the oxide-graphene-containing organic-inorganic hybrid coating film according to an embodiment of the present invention has a relatively low transmittance reduction ratio and thus shows excellent transmittance. At this time, the graphene oxide content was 3 wt%, and the film thickness was about 1100 nm.

Evaluation 4: Evaluation of thermal conductivity of graphene-containing hybrid coating film

The thermal conductivity of the graphene-containing ceramic hybrid coating film manufactured using the principle of the present invention was compared and evaluated using a home made thermal conductivity meter.

The apparatus for evaluating the thermal conductivity of the graphene oxide-containing ceramic hybrid coating was a heating source (heating shape and diameter: circular and 5 cm) using a halogen lamp on a PC (poly carbonate) substrate (size 10 cm x 10 cm, thickness 2 mm) And the thermocouple (TC2), which is the central part of the PC substrate, was heated up to about 120 ° C. and the substrate edge temperature (TC1) was measured simultaneously.

The results of measuring the thermal conductivity using this apparatus are shown in Fig.

9 is a graph showing the thermal conductivity effect of the graphene oxide-containing organic-inorganic hybrid coating film according to an embodiment of the present invention.

In the case of Comparative Example 2 produced by using pure GT alone (ceramic sol) on a general PC substrate, the thermal conductivity had only a temperature increase effect of about 2.8 ° C. per hour, whereas in the case of the coating film according to Example 1, The result is a temperature rise effect of 9.3 ° C per hour, showing a large thermal conduction effect. This shows that the graphenes are uniformly and well dispersed in the coating film according to the present invention, so that the physical properties of graphene are well expressed. If the graphene dispersion is unstable and interface delamination occurs, the thermal conductivity value can not be achieved, for example, when the ceramic sol contains only the ceramic sol at around 2.8 DEG C and below.

In the present invention, it can be seen that the improvement in thermal conductivity at a minimum graphene content of 0.001 wt% is about twice that before graphene addition.

In the case of the coating film according to Example 2, the thermal conductivity showed the highest at about 12.5 ° C.

Evaluation 5: Oxidation by additives Grapina  contain hybrid Of the coating film  Surface Functional Evaluation

9 is a graph illustrating a measurement result of the contact angle of water droplets of the graphene-containing ink-inorganic hybrid coating film according to an embodiment of the present invention.

Specifically, FIGS. 10 to 12 show the result of measuring the contact angle of water on the coating film.

10 is a schematic view showing a case where a coating film is formed using a coating solution according to Comparative Example 2 in which graphene oxide is not contained, and FIG. 11 is a schematic view showing a case where a coating film is formed using a coating solution containing a hydrate containing no organic functional group FIG. 12 is a measurement result of the contact angle of water droplets when a coating film is formed using the coating solution according to Example 1. FIG.

Referring to FIGS. 10 to 12, it can be seen that the contact angle decreases with the addition of graphene, and that the contact angle further decreases with further addition of the silica nanoparticles.

In addition, it is also understood that the contact angle is also decreased when a hydrate containing an organic functional group is contained.

When the contact angle is decreased, the surface hydrophilic property can be increased.

13 is a TEM (Transmission Electron Microscope) image of a graft oxide-coated organic-inorganic hybrid ceramic coating film according to an embodiment of the present invention.

13, it can be confirmed that graphene (two-dimensional plate-like material), silver nanowire (one-dimensional linear material), and silver nanoparticles (zero-dimensional particle material) are well fused between the sol matrices. In this case, since various types of solid materials are contained, it is preferable to add a small amount of polymer binder to adhere them well.

In Evaluation 4 and Evaluation 5, this example shows sufficiently the thermal conductivity effect and the surface contact angle effect (surface functionality) of the graphene oxide.

Evaluation 6: Evaluation of heat treatment of graphene oxide-containing organic-inorganic hybrid coating film

The coating film obtained in Example 2 was subjected to a heat treatment at 200 캜 in the air, a heat treatment at 500 캜 in an oxygen atmosphere, and a heat treatment at 900 캜 in a nitrogen atmosphere.

Referring to FIG. 14, it can be confirmed that grafting in the form of a two-dimensional carpet is vividly maintained by the addition of a polymer-added coating solution, silver nanowires, and silver nanoparticles.

These embodiments, as described above, require an organic component for bonding them to form a good bond between the oxidized graphene and the ceramic, and it is very important to design the ceramic precursor to contain organic functional groups from the starting ceramic And it is necessary that the graphene is oxidized prior to graphene in order to prevent the oxidation of graphene during the physical properties of graphene and sintering. On the basis of this, additives such as HYDROLYSIS in the form of M (OH) 4 Other new properties are revealed by possible reagents, polymer additives, dispersants, organic additives, one-dimensional nanomaterials, and zero-dimensional nanomaterials.

Claims (23)

At least one of the hydrates represented by the following formula (1)
Graphene grains discontinuously island-shaped on the surface of the hydrate of Formula 1, and
A silica secondary particle positioned on the surface of the hydrate of Formula 1 and on the surface of the discontinuous island-shaped oxide grains,
The silica secondary particle is a graphene-containing organic-inorganic hybrid coating film in which a plurality of silica nanoparticles are aggregated:
[Chemical Formula 1]
X n -M- (OH) 4-n
In Formula 1,
M is selected from Si, Ti, Ag, Sn, In, Zn, and combinations thereof,
X represents an epoxy group, a glycidoxy group, a vinyl group, an acryl group, a methacryl group, a carboxyl group, an amino group, a thiol group, a phosphoric group, a fluoro group, a chloro group, a bromo group, A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted C1 to C10 ketone group, A C1 to C30 alkyl group substituted or unsubstituted with at least one functional group selected from unsubstituted C1 to C10 silyl groups;
An epoxy group, a glycidoxy group, a vinyl group, an acryl group, a methacryl group, a carboxyl group, an amino group, a thiol group, a phosphoric group, a fluoro group, a chloro group, a bromo group, an iodo group, a hydroxy group, a substituted or unsubstituted C1 to C10 alkoxy group , A substituted or unsubstituted C1 to C10 ketone group, a substituted or unsubstituted C1 to C10 amine group, a substituted or unsubstituted C1 to C10 sulfur group, a substituted or unsubstituted C1 to C10 ester group, A C1 to C30 alkenyl group which is substituted or unsubstituted with at least one functional group selected from a C1 to C10 silyl group; or
An epoxy group, a glycidoxy group, a vinyl group, an acryl group, a methacryl group, a carboxyl group, an amino group, a thiol group, a phosphoric group, a fluoro group, a chloro group, a bromo group, an iodo group, a hydroxy group, a substituted or unsubstituted C1 to C10 alkoxy group , A substituted or unsubstituted C1 to C10 ketone group, a substituted or unsubstituted C1 to C10 amine group, a substituted or unsubstituted C1 to C10 sulfur group, a substituted or unsubstituted C1 to C10 ester group, And a C1 to C10 silyl group which is substituted or unsubstituted with at least one functional group selected from a substituted or unsubstituted C1 to C10 silyl group,
n is an integer of 1 to 3; The method of claim 1,
A first region in which the hydrate represented by Formula 1 and the silica secondary particles are bonded; And
Inorganic hybrid coating film comprising a graphene oxide graphene represented by the general formula (1), a graphene oxide, and a second region in which silica secondary particles are bonded. 3. The method of claim 2,
The average diameter of the silica secondary particles in the first region is 5 nm to 50 nm,
Inorganic hybrid coating film having graphene oxide having an average diameter of silica secondary particles of the second region of 5 nm to 25 nm. The method of claim 1,
Wherein the silica nanoparticles have an average diameter of 5 nm to 30 nm. The method of claim 1,
Wherein the graphene oxide has a thickness of 0.4 nm to 2 nm. The method of claim 1,
The major axis length of the graphene oxide is 100 nm to 10 탆,
Inorganic hybrid coating film containing graphene oxide having a short axis length of 100 nm to 5 탆. The method of claim 1,
Wherein the content of the graphene oxide is 0.002 wt% to 50 wt% based on the total weight of the hydrate, the oxidized graphene, and the silica nanoparticle represented by Formula (1). The method of claim 1,
When the transmittance is 70% or more, the content of the graphene oxide is 0.002 wt% to 4.2 wt% based on the total weight of the hydrate, the graphene, and the silica nanoparticles represented by Formula 1, Inorganic hybrid coating. The method of claim 1,
An organic-inorganic hybrid coating film containing graphene oxide having a thickness of 100 nm to 2 占 퐉. The method of claim 1,
Inorganic hybrid coating film having graphene oxide having a thickness of 200 nm to 500 nm when the transmittance is 70% or more. The method of claim 1,
Wherein the chemical formula 1 is a graphene-containing oil-inorganic hybrid coating film represented by any one of Chemical Formulas 1-1 to 1-3:
[Formula 1-1]
X 1 -M- (OH) 3
[Formula 1-2]
X 1 X 2 -M- (OH) 2
[Formula 1-3]
X 1 X 2 X 3 -M- (OH)
In Formulas 1-1 through 1-3,
M is selected from Si, Ti, Ag, Sn, In, Zn, and combinations thereof,
X 1 to X 3 each independently represent an epoxy group, a glycidoxy group, a vinyl group, an acryl group, a methacryl group, a carboxyl group, an amino group, a thiol group, a phosphoric group, a fluoro group, a chloro group, a bromo group, A substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted C1 to C10 ketone group, a substituted or unsubstituted C1 to C10 amine group, a substituted or unsubstituted C1 to C10 substituent, a substituted or unsubstituted C1 A C1 to C30 alkyl group substituted or unsubstituted with at least one functional group selected from substituted or unsubstituted C1 to C10 silyl groups;
An epoxy group, a glycidoxy group, a vinyl group, an acryl group, a methacryl group, a carboxyl group, an amino group, a thiol group, a phosphoric group, a fluoro group, a chloro group, a bromo group, an iodo group, a hydroxy group, a substituted or unsubstituted C1 to C10 alkoxy group , A substituted or unsubstituted C1 to C10 ketone group, a substituted or unsubstituted C1 to C10 amine group, a substituted or unsubstituted C1 to C10 sulfur group, a substituted or unsubstituted C1 to C10 ester group, A C1 to C30 alkenyl group which is substituted or unsubstituted with at least one functional group selected from a C1 to C10 silyl group; or
An epoxy group, a glycidoxy group, a vinyl group, an acryl group, a methacryl group, a carboxyl group, an amino group, a thiol group, a phosphoric group, a fluoro group, a chloro group, a bromo group, an iodo group, a hydroxy group, a substituted or unsubstituted C1 to C10 alkoxy group , A substituted or unsubstituted C1 to C10 ketone group, a substituted or unsubstituted C1 to C10 amine group, a substituted or unsubstituted C1 to C10 sulfur group, a substituted or unsubstituted C1 to C10 ester group, And a C1 to C10 silyl group which is substituted or unsubstituted with at least one functional group selected from a substituted or unsubstituted C1 to C10 silyl group. The method of claim 1,
Wherein the M is Si or Ti. The method of claim 1,
Inorganic hybrid coating film further comprising an additive selected from inorganic powder, organic additive, or a combination thereof. The method of claim 13,
Inorganic hybrid coating film containing graphene oxide having an average diameter of the inorganic powder of 5 nm to 50 nm. Preparing a highly dispersed oxide graphene;
Mixing and dispersing the silica nanoparticles and the precursor of the hydrate represented by Formula 1 in a hydrophilic solvent and mixing with the highly dispersed oxide graphene;
Hydrolyzing and polycondensation reaction of the mixed dispersion solution to prepare a graft-containing organic-inorganic hybrid ceramic sol solution;
Applying the hybrid sol solution to a substrate and then drying at a temperature of from 25 캜 to 100 캜; And
Treating the dried film at a temperature of from 50 캜 to 900 캜
METHOD FOR MANUFACTURING OXYLENE HYBRID COATING MEMBRANE COMPRISING GRAPHION OXIDE
[Chemical Formula 1]
X n -M- (OH) 4-n
In Formula 1,
M is selected from Si, Ti, Ag, Sn, In, Zn, and combinations thereof,
X represents an epoxy group, a glycidoxy group, a vinyl group, an acryl group, a methacryl group, a carboxyl group, an amino group, a thiol group, a phosphoric group, a fluoro group, a chloro group, a bromo group, A substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted C1 to C10 ketone group, A C1 to C30 alkyl group substituted or unsubstituted with at least one functional group selected from unsubstituted C1 to C10 silyl groups;
An epoxy group, a glycidoxy group, a vinyl group, an acryl group, a methacryl group, a carboxyl group, an amino group, a thiol group, a phosphoric group, a fluoro group, a chloro group, a bromo group, an iodo group, a hydroxy group, a substituted or unsubstituted C1 to C10 alkoxy group , A substituted or unsubstituted C1 to C10 ketone group, a substituted or unsubstituted C1 to C10 amine group, a substituted or unsubstituted C1 to C10 sulfur group, a substituted or unsubstituted C1 to C10 ester group, A C1 to C30 alkenyl group which is substituted or unsubstituted with at least one functional group selected from a C1 to C10 silyl group; or
An epoxy group, a glycidoxy group, a vinyl group, an acryl group, a methacryl group, a carboxyl group, an amino group, a thiol group, a phosphoric group, a fluoro group, a chloro group, a bromo group, an iodo group, a hydroxy group, a substituted or unsubstituted C1 to C10 alkoxy group , A substituted or unsubstituted C1 to C10 ketone group, a substituted or unsubstituted C1 to C10 amine group, a substituted or unsubstituted C1 to C10 sulfur group, a substituted or unsubstituted C1 to C10 ester group, And a C1 to C10 silyl group which is substituted or unsubstituted with at least one functional group selected from a substituted or unsubstituted C1 to C10 silyl group,
n is an integer of 1 to 3; 16. The method of claim 15,
The silica nanoparticles are added in an amount of 5 to 20% by weight based on the total amount of the mixed dispersion solution;
The precursor of the hydrate represented by the formula (1) is 10% by weight to 40% by weight based on the total amount of the mixed dispersion solution;
The highly dispersed graphene oxide is present in an amount of 0.002 to 15% by weight based on the total amount of the mixed dispersion solution; And
The hydrophilic solvent balance
Inorganic hybrid coating film containing graphene oxide. 16. The method of claim 15,
Wherein the step of preparing the highly dispersed oxide graphene is carried out by a mechanical dispersion treatment or a solvent substitution method. The method of claim 17,
In the solvent substitution method,
Preparing a grafted oxide graft slurry solution substituted with a first non-aqueous solvent;
Adding the slurry solution to a second non-aqueous solvent and a precursor of the hydrate to prepare a mixture; And
Mixing the mixture with a dispersant and water to prepare a coating composition for forming an organic graphene-containing oil-inorganic hybrid sol
Inorganic hybrid coating film containing graphene oxide. 16. The method of claim 15,
In the step of mixing and dispersing the silica nanoparticles and the hydrate precursor represented by Formula 1 in a hydrophilic solvent and mixing the silica nanoparticles with the highly dispersed oxide graphene,
Inorganic hybrid powder coating film further comprising mixing an additive selected from inorganic powder, organic additive, or a combination thereof. 20. The method of claim 19,
Wherein the inorganic powder is mixed in an amount of 5 parts by weight to 30 parts by weight with respect to 100 parts by weight of the mixed dispersion solution. 20. The method of claim 19,
Wherein the organic additive is mixed in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the mixed dispersion solution. 16. The method of claim 15,
The precursor of the hydrate represented by the above formula (1) may be at least one selected from the group consisting of trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, , Propyltriethoxysilane, isobutyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane allyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, (N, N- Dimethylaminopropyl) trimethoxysilane, (N, N-dimethylaminopropyl) triethoxysilane, N, N - {(2-aminoethyl) (3-aminopropyl)} trimethoxysilane, Phosphorus oxide graphene-containing organic-inorganic hybrid Gt; An automotive headlamp comprising the oxide-graphene-containing organic-inorganic hybrid coating film according to any one of claims 1 to 14.
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