KR101714847B1 - Graphene coating composition, graphene coated steel sheet and manufacturing method thereof - Google Patents

Abstract

Graphene coating compositions, graphene coated steel sheets and methods for their preparation are disclosed. In one aspect of the present invention, there is provided a method for producing a polymer electrolyte membrane, which comprises, on a solid basis, 1 to 50% by weight of polymer grafted graphene, 1 to 30% by weight of acrylate modified graphene, 5 to 30% 5 to 30% by weight of an acrylic monomer, and 0.1 to 10% by weight of a photoinitiator.

Description

TECHNICAL FIELD [0001] The present invention relates to a graphene coating composition, a graphene coated steel sheet, and a method of manufacturing the same. BACKGROUND ART < RTI ID = 0.0 &

The present invention relates to a graphene coating composition, a graphene coated steel sheet, and a method for producing the same.

A UV curing technology (hereinafter, referred to as 'photocuring technology') is a technique capable of imparting high-gloss and scratch resistance characteristics that can not be realized in conventional PCM, and various compositions for UV coating have been developed depending on necessary physical properties.

On the other hand, graphene has a two-dimensional carbon atomic plane structure in which the carbon atom layer is filled with a hexagonal lattice point plane. These graphene have tensile strength 311 times stronger than steel, electron mobility 1000 times faster than silicon, thermal conductivity 10 times better than copper, transparent enough to pass 98% of light, The characteristics are retained.

Accordingly, attempts have been made to produce coating compositions capable of realizing high gloss and scratch resistance, which are characteristics of the photocuring technique, and simultaneously exhibiting the properties of graphene, such as conductivity, heat radiation, transparency, and super water repellency.

However, in general, the coating film formed by the photo-curing technique has a high crosslinking density due to the network structure between the compositions, and thus the scratch resistance is very strong. However, there is a problem in that the workability is improved, There is a problem in that it is difficult to use the steel sheet as a coating film in order to open the adhesion of the steel sheet.

One aspect of the present invention is to provide a graphene coating composition capable of simultaneously realizing properties of a photocurable coating and graphene, and to provide a graphene coating composition having excellent processability and adhesion to a steel sheet, and a process for producing the same.

Another aspect of the present invention is to provide a graphene-coated steel sheet coated with the graphene coating composition and a method for producing the same.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.

In one aspect of the present invention, there is provided a method for producing a polymer electrolyte membrane, which comprises, on a solid basis, 1 to 50% by weight of polymer grafted graphene, 1 to 30% by weight of acrylate modified graphene, 5 to 30% 5 to 30% by weight of an acrylic monomer, and 0.1 to 10% by weight of a photoinitiator.

According to another aspect of the present invention, there is provided a method for fabricating a semiconductor device, comprising: preparing a grafted graphene of a polymer; Preparing an oxidized graphene modified with acrylate; And mixing the acrylic oligomer, the acrylic monomer and the photoinitiator to the grafted oxide graphene modified with the grafted oxidized graphene and the acrylate to obtain the graphene coating composition, , 1 to 50% by weight of polymer grafted graphene oxide, 1 to 30% by weight of acrylate modified graphene, 5 to 30% by weight of acrylic oligomer, 5 to 30% by weight of acrylic monomer, 0.1 to 10% by weight of a photoinitiator.

According to another aspect of the present invention, A thermosetting graphene coating layer formed on the base steel sheet and comprising polymer grafted graphene; And a photocurable graphene coating layer formed on the thermosetting graphene coating layer and containing oxidized graphene modified with acrylate.

According to another aspect of the present invention, there is provided a method of manufacturing a graphene coating composition, Heating the base steel sheet coated with the graphene coating composition to 80 to 340 캜 to form a thermosetting graphene coating layer; And irradiating ultraviolet (UV) light onto the base steel sheet on which the thermosetting graphene coating layer is formed to form a photocurable graphene coating layer.

According to one aspect of the present invention, there can be provided a graphene coating composition and a graphene-coated steel sheet which can realize not only the characteristics of the photocurable coating and the characteristics of graphene but also the workability and adhesion to the steel sheet.

1 is an SEM image of a section of a graphene-coated steel sheet according to Inventive Example 1 of the present invention.
2 is an SEM image of a section of a graphene-coated steel sheet according to Comparative Example 1 of the present invention.
3 is an SEM image of a cross section of a graphene-coated steel sheet according to Comparative Example 3 of the present invention.

The present inventors have disclosed a graphene coating composition capable of simultaneously realizing characteristics of photocurable coating and graphene in Korean Patent Laid-Open Publication No. 10-2014-0080929. The gist of the patent is to modify the graphene oxide to acrylate to directly participate in the photocuring reaction.

However, the coating film produced by the technique disclosed in the above patent publication still has a problem in that the coating film formed by the photo-curing technique is poor, that is, the workability is poor, and the adhesion with the steel material is poor.

The inventors of the present invention have been intensively investigating to solve this problem. The inventors of the present invention found that (i) a part of the graphene graphene contained in the graphene coating composition is modified with acrylate and the remaining part is grafted with a polymer, And a photocurable graphene coating layer are successively formed on the surface of the steel sheet and a thermosetting graphene coating layer is formed between the steel sheet and the photocurable graphene coating layer It was found that not only the properties of the photocurable coating and the characteristics of the graphene are simultaneously displayed but also the workability and the adhesion with the steel sheet are remarkably improved, and thus the present invention has been accomplished.

Hereinafter, the graphene coating composition which is one aspect of the present invention will be described in detail.

The polymer Grafted Oxidized graphene

The thermosetting graphene coating layer is positioned between the base steel sheet and the photocurable graphene coating layer to improve the adhesion to the steel sheet, Thereby improving workability.

The grafted graphene grafted with the polymer may be contained in an amount of 10 to 50% by weight, preferably 20 to 50% by weight, based on 100% by weight of the graphene coating composition. If the content of grafted graphene in the polymer is less than 10% by weight, the graphene grafted polymer chain may be too small to have sufficient adhesion with the steel sheet, The content of the grafted graft polymer chains is too large to form a coating layer due to photocuring on the surface.

The type of the polymer is not particularly limited as long as it has a functional group such as COOH or OH at the terminal and serves as a binder favorable to adhere to the steel sheet. Examples of such a polymer include polyester, water-dispersible urethane, epoxy Epoxy-phosphates, epoxy-phosphates modified with acrylic or vinyl monomers, vinyl-based and acryl-urethanes modified with acrylic or vinyl monomers, and the like. Therefore, although a separate binder is not required, other binders may be added according to the curing method.

In addition to the binding function, it is possible to secure specific properties by introducing a polymer chain. In the case of polyurethane and polyester, the processability is improved. In the case of epoxy, the hardness is. Polyvinylidene fluoride has a function of improving mechanical / do.

As factors affecting physical properties of the coated steel sheet, not only the kinds of polymers but also molecular weight, glass transition temperature, degree of polymerization of polymer chains, structure of polymer chains, content of polymer chains and the like can be mentioned.

For example, a high molecular weight polyester resin can be used to exhibit excellent stretchability and processability. The polyester resin has a molecular structure composed of aliphatic groups, and therefore exhibits low viscosity and high elongation. The polyester resin preferably has a number average molecular weight of 5,000 to 20,000, preferably 5,500 to 15,000, and more preferably 6,000 to 12,000. When the number average molecular weight is less than 5,000, there is a problem that workability is lowered. When the number average molecular weight is more than 20,000, there is a problem of chemical resistance and gloss drop.

The epoxy resin preferably has a number average molecular weight of 900 to 7,000. When the number average molecular weight is less than 900, there is a problem in that the steel sheet has a slow curing rate upon coating and poor water resistance. When the number average molecular weight is more than 7,000, the water resistance due to the denaturation reaction is difficult.

However, in general, the larger the number average molecular weight of the resin is, the more flexible the molecules are, and the resin is easy to elongate during deep drawing, which is advantageous in terms of crack resistance.

When the glass transition temperature is 5 DEG C or higher, excellent hardness can be secured when the graphene coating is carried out, and it is preferable that the glass transition temperature be 5 DEG C to 30 DEG C because the lowering of the workability can be prevented.

If the degree of polymerization of the polymer chain is too low, the unreacted monomer remains, so that the polymer chain can not be grafted sufficiently and the length of the polymer chain is too short to sufficiently lift the graphene to the upper portion of the coating layer, . If it is too high, the length of the polymer chain is too long to widen the gap between the steel sheet and the graphene layer, so that the electrical / thermal properties such as conductivity and heat dissipation are lowered and the polymer chain is partially present on the graphene layer, It can not exist and can not exhibit graphene characteristics efficiently.

Therefore, it is preferable to control the acid value of the polyester resin to 5 to 20 mgKOH / g, the NCO / OH equivalent ratio of the polyurethane to 1 to 3, and the epoxy equivalence to 450 to 3,500.

The structure of the polymer chain is superior to that of the branch structure in the linear structure.

Acrylate Reformed Oxidized graphene

The acrylate-modified oxide graphene directly participates in the photo-curing reaction to form a photocurable graphene coating layer and serves to develop the characteristics of graphene such as conductivity, heat dissipation, transparency, and super water repellency.

In general, graphene is a material having no functional group capable of participating in the photocuring reaction. When the photocurable coating composition contains a substance which does not participate in the photocuring reaction such as graphene, the photocuring efficiency is remarkably lowered there is a problem. However, in the present invention, by replacing the functional group of the graphene oxide with an acrylate, it is possible to directly participate in the photo-curing reaction. As a result, side reactions do not occur and the curing efficiency can be improved without delaying the photo-curing reaction.

The acrylate-modified oxide graphene may be contained in an amount of 1 to 30% by weight, preferably 5 to 30% by weight based on 100% by weight of the graphene coating composition. When the content of the graft oxide modified with acrylate is less than 1% by weight, the content thereof is too small and the graphene is difficult to be present on the surface of the coating layer. On the other hand, when the content is more than 30% by weight, There is a problem that it is difficult to take advantage of the advantage of UV coating such as high gloss / high definition.

According to an embodiment of the present invention, the acrylate may be at least one selected from the group consisting of a monofunctional acrylic monomer, a bifunctional acrylic monomer, and a polyfunctional acrylic monomer.

According to an embodiment of the present invention, the monofunctional acrylic monomer may be selected from the group consisting of acrylic morpholine (ACMO), tetrahydrofurfuryl acrylate (THFA), hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA ) And isobornyl acrylate (IBOA).

According to an embodiment of the present invention, the bifunctional acrylic monomer may be at least one selected from the group consisting of diethylene glycol diacrylate (DEGDA), dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), hexanediol di Acrylate (HDDA), polyethylene glycol 400 diacrylate (PEG 400DA), and ethylene glycol 600 diacrylate (PEG 600DA).

According to an embodiment of the present invention, the polyfunctional acrylic monomer may be at least one selected from the group consisting of trimethyl propane ethoxylate triacrylate and trimethyl propane triacrylate.

Acrylic Oligomer

The acrylic oligomer also participates in the photocuring reaction to form a photocurable graphene coating layer and serves as a binder in the photocurable graphene coating layer. Here, the acrylic oligomer means an oligomer having at least one acrylic group in the molecule.

The acrylic oligomer may be contained in an amount of 5 to 30% by weight, preferably 10 to 30% by weight based on 100% by weight of the graphene coating composition. When the content of the acrylic oligomer is less than 5% by weight, the photopolymerization reaction proceeds rapidly and the cross-linking density is increased to increase the brittleness of the coating film. When the content of the acrylic oligomer is more than 30% by weight, There is a possibility that the UV irradiation amount for hardening the coating film is high or the UV irradiation time is prolonged.

According to one embodiment of the present invention, the acrylic oligomer is at least one selected from the group consisting of epoxy acrylate, urethane-based modified epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, acrylic acrylate, silicone acrylate, melamine acrylate, Acrylate, a polythiol acrylate derivative, and a polythiolacetype acetal-based acrylate.

Acrylic Monomer

The acrylic monomer also participates in the photocuring reaction to form a photocurable graphene coating layer and serves as a binder in the photocurable graphene coating layer.

The acrylic monomer may be contained in an amount of 5 to 30% by weight, preferably 10 to 30% by weight based on 100% by weight of the graphene coating composition. When the content of the acrylic monomer is less than 5% by weight, the photopolymerization reaction rate is lowered, the crosslinking density is difficult to control, the UV irradiation amount for curing the coating film is increased, the UV irradiation time is prolonged, The photopolymerization reaction proceeds rapidly, and as a result, the crosslinking density increases and the brittleness of the coating film may increase.

According to an embodiment of the present invention, the acrylic monomer may be one or more of a monofunctional acrylic monomer, a bifunctional acrylic monomer, and a polyfunctional acrylic monomer.

According to an embodiment of the present invention, the monofunctional acrylic monomer used as the acrylic monomer may be one or more selected from the group consisting of alkyl acrylate, aryl acrylate, alkoxy acrylate, and tetrahydrofurfuryl acrylate, It may be a mixture of two or more.

Also, according to one embodiment of the present invention, the bifunctional acrylic monomer used as the acrylic monomer may be one or a mixture of two or more kinds selected from the group consisting of tripropylene glycol diacrylate and hexanediol diacrylate .

Also, according to one embodiment of the present invention, the polyfunctional acrylic monomer used as the acrylic monomer may be a mixture of one or more kinds selected from the group consisting of trimethyl propane ethoxylate triacrylate and trimethyl propane triacrylate .

ore Initiator

The photoinitiator serves to initiate the photo-curing reaction. In the present invention, the content of the photoinitiator is not particularly limited, but may be 0.1 to 10% by weight based on 100% by weight of the graphene coating composition. If it is less than 0.1% by weight, there is a possibility that the photo-curing reaction may not be sufficiently carried out. If it exceeds 10% by weight, the physical properties of the coating layer may be deteriorated.

According to an embodiment of the present invention, the photoinitiator may be benzophenone, diphenoxibenzophenone, anthraquinone, xanthone, thioxanthone, or benzyl. In addition, initiators such as Micure HP-8, Irgacure 819, Darocur TPO, and Micure CP-4, which are commercially available photoinitiators, can be used, but the present invention is not limited thereto.

additive

The graphene coating composition according to the present invention may be used in combination with the above-mentioned composition in combination with a defoaming agent, a leveling agent, an adhesion promoter, a light stabilizer, an antioxidant, an ultraviolet absorbent, a thermal polymerization inhibitor, a smoothing agent, a dispersant, 0.1 to 15% by weight, preferably 0.3 to 10% by weight, more preferably 0.5 to 6% by weight of at least one additive selected from the group consisting of When the additive is added within the above-mentioned content range, the effect of the additive can be exhibited without changing the physical properties of the coating film.

The antifoaming agent is used to remove air bubbles generated during coating, and specific examples thereof include TEGO Airex 920, TEGO Airex 932, BYK 088, and BYK 1790.

The leveling agent is for improving the surface appearance and scratch resistance. Specific examples thereof include TEGO Glide 410, TEGO Glide 440, TEGO Rad 2250, BYK-UV 3500, and BYK-UV 3510.

The adhesion-promoting agent is for improving the adhesion to the base steel sheet. Specific examples thereof include acrylate-based adhesion promoters such as hydroxyethyl acryloyl phosphate or hydroxyethyl methacrylate phosphate.

The light stabilizer is for the purpose of facilitating shelf life. Specific examples thereof include a phenolic antioxidant, an alkylated monophenol, an alkylthiomethyl phenol, a hydroquinone, an alkylated hydroquinone, a tocopherol, a hydroxylated thiodiphenyl ether, Alkylidene bisphenol, O-, N- and S-benzyl compounds, hydroxybenzylated malonates, aromatic hydroxybenzyl compounds, triazine compounds, amine antioxidants, arylamines, diarylamines, polyarylamines, acyl Aminophenol, oxamide, metal deactivator, phosphite, phosphonite, benzylphosphonate, ascorbic acid, hydroxylamine, nitrone, thiosynergist, benzofuranone, or indolinone. In addition, products of BASF such as Tinuvin 292, Tinuvin 144 or Tinuvin 622LD, which are commercially available light stabilizers; And SANKYO products such as Sanol LS-770 (sanol LS-770), Sanol LS-765 (sanol LS-765), Sanol LS-292 (sanol LS-292) or Sanol LS-744 Can be used.

The antioxidant is used for preventing the oxidation reaction and thus facilitating storage. Specific examples thereof include Irganox 1010, Irganox 1035, Irganox 1076 and Irganox 1222 (Irganox 1222) available from BASF.

The ultraviolet absorber is used for enhancing UV curing reaction efficiency during the photo-curing reaction. Specific examples thereof include Tinuvin P, Tinuvin 234, Tinuvin 320, 328 (Tinuvin 328); And Sumisorb 110, Sumisorb 130, Sumisorb 140, Sumisorb 220, Sumisorb 250, Sumoisorb 320, (Sumisorb 320) or Sumisorb 400 (Sumisorb 400).

In addition, the thermal undercoating agent is used for enhancing the photo-curing reaction efficiency by preventing the reaction from being terminated due to heat, and specific examples thereof include HQ, THQ and HQMME.

The smoothing agent and the dispersant are used to smoothly disperse in a solvent, and products of additives such as BYK, TEGO and EFKA can be selected and used.

The antistatic agent is added for the purpose of preventing electrification in the photo-curing reaction. Specific examples thereof include nonionic systems such as polyoxyethylene alkyl ethers, polyoxyethylene amines, glycerin or sorbitol fatty ester, and alkyl sulfonates, Alkylbenzene sulfonates, alkyl sulfates, and alkyl phosphates, quaternary ammonium salts, and mixtures thereof.

The silane coupling agent is used for improving the adhesive strength of the coating composition of the present invention. Specific examples thereof include methacryloxypropyltrimethoxysilane, gamma-methacryloxypropylethoxysilane, gamma-chloropropylmethoxysilane , Vinyltriethoxysilane, vinyltris (beta-methoxyethoxy) silane, vinyltriacetoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, beta- ( Aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyl (meth) acrylate, vinyltrimethoxysilane, vinyltrimethoxysilane, Trimethoxysilane, or mixtures thereof.

Hereinafter, a method for producing a graphene coating composition, which is another aspect of the present invention, will be described in detail.

The graphene coating composition may be prepared by preparing an oxidized graphene in which the polymer is modified with grafted oxidized graphene and an acrylate and then polymerizing the grafted oxidized graphene and acrylate modified graphene with the oligomer, By mixing the photoinitiator at the above-mentioned ratio.

At this time, the step of preparing the grafted graft oxide of the polymer is not particularly limited, but it may be prepared by the following method.

First, the graphene oxide is dissolved in an organic solvent to prepare a graphene oxide solution. Examples of the organic solvent include acetone, methanol, ethanol, 1-propanol, ethylene glycol, dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), N-methylpyrrolidone , NMP), tetrahydrofuran (THF), and the like.

Thereafter, at least one of the monomer and the polymer is mixed with the oxidized graphene solution. The polymer may be selected from the group consisting of polyester, water-dispersible urethane, epoxy, epoxy-phosphate, epoxy-phosphate modified with an acrylic or vinyl monomer, vinyl-based or acryl-urethane modified with an acrylic or vinyl monomer But it is not limited thereto. On the other hand, the monomer may be a monomer of the above-mentioned polymer, but is not limited thereto.

Thereafter, the solution is heated to 100 to 300 DEG C to obtain a grafted oxide graphene. If the heating temperature is lower than 100 ° C, the coating layer may be pushed or peeled off, that is, sticky and the coating layer may peel off or be pushed. On the other hand, when the heating temperature is higher than 300 ° C, Or there is a fear that peeling may be caused to open the adhesion.

The step of preparing the grafted oxide grafted with acrylate is not particularly limited, but it may be prepared by the following method.

Oxidized graphene has a functional group such as a hydroxyl group, a carbonyl group, a carboxyl group and an amine group, and the functional group of the oxidized graphene is substituted with an acrylate to prepare an oxidized graphene modified with an acrylate. The method of modifying the graphene oxide with an acrylate may differ depending on the type of acrylate.

For example, when a hydroxyalkyl acrylate is attached to graphene, the acrylate polymerization proceeds by a hydrogen transfer reaction between a diisocyanate and a polyol having an active hydrogen. First, the hydroxyl group of the GO functional group is reacted with an isocyanate group To which a hydroxyalkyl acrylate can be attached.

Specifically, the compound containing a functional group capable of reacting with the hydroxyl group of the graphene oxide is a compound having an isocyanate group, an alkoxy group, or a carboxyl group in its structure; A compound containing a halogen atom; Or a cyclic anhydride.

More specifically, the compound containing a functional group capable of reacting with the hydroxyl group of the graphene oxide may be represented by the formula -N═C═O, RO═CX, R-COOH, R 4-x-Si- (R ') x, R '. ≪ / RTI > Wherein R represents C1-30 alkyl, C2-30 alkyl, C2-30 alkynyl, C5-12 aryl, or C6-24 aralkyl. The R may be substituted or unsubstituted, respectively, by one or more substituents selected from the group consisting of C1-12 alkyl, C2-12 alkyl, C2-12 alkynyl and C5-12 aryl. R 'represents C1-12 alkoxy, x represents an integer of 1 to 3, and y represents an integer of 1 to 4.

More specifically, the compound containing a functional group capable of reacting with the hydroxyl group of the graphene oxide is benzyl isocyanate, hexyl isocyanate, 3-isopropenyl-a, a-dimethylbenzyl isocyanate, methacryloyl chloride, Fatty acid succinic anhydrides, and fatty acid succinic anhydrides.

After the graphene oxide is dissolved in an organic solvent, a compound containing a functional group capable of reacting with a hydroxyl group is mixed. Examples of usable organic solvents include acetone, methanol, ethanol, 1-propanol, ethylene glycol, DMSO, DMF, NMP, THF and the like.

At this time, (graphene oxide): (a compound containing a functional group capable of reacting with a hydroxyl group) is preferably mixed in a molar ratio of 1: 2 to 2.1. When the molar ratio is less than 1: 2, unreacted hydroxyl groups may be present, which may cause problems such as low curing degree and low polymerization rate during polymerization. When the molar ratio is larger than 1: 2.1, unreacted functional groups Etc.) are present in the reaction product, a purification process is required to remove them, or they may remain in the final product, which may lead to toxicity problems and deteriorate film appearance.

A compound containing a functional group capable of reacting with a carbonyl group, a carboxyl group, an amine group or the like in addition to the hydroxyl group can be mixed at the same molar ratio.

The reforming temperature of the graphene oxide is preferably 30 to 80 캜. If the temperature is lower than 30 ° C, the reaction time becomes too long. If the temperature is higher than 80 ° C, it may be difficult to control the reaction heat due to a high reaction rate. As a side reaction of functional groups (isocyanate etc.), biuret and allophanate ) Formation reaction may occur.

Next, the graphene oxide modified with isocyanate or the like is blocked with an alkyl acrylate such as hydroxyethyl acrylate (HEA) or hydroxyethylmethyl acrylate (HEMA).

Through the above process, the hydroxyl group in the functional group of the graphene oxide is reacted with the isocyanate group, and the hydroxyalkyl acrylate is attached to the hydroxyl group, thereby obtaining the oxidized graphene modified with the acrylate.

Hereinafter, a graphene-coated steel sheet according to another aspect of the present invention will be described in detail.

The graphene-coated steel sheet according to still another aspect of the present invention comprises a base steel sheet; A thermosetting graphene coating layer formed on the base steel sheet; And a photocurable graphene coating layer formed on the thermosetting graphene coating layer.

The kind of the base steel sheet is not particularly limited, and for example, a cold-rolled steel sheet; Hot - rolled steel; galvanized steel; Aluminum-plated steel sheet; Copper, magnesium, iron, manganese, titanium, zinc, or a mixture thereof, or a mixture of two or more of these metals, It may be an aluminum alloy plate added.

The thermosetting graphene coating layer includes graphene graphene grafted with a polymer and is positioned between the base steel sheet and the photocurable graphene coating layer to provide adhesion.

The thickness of the thermosetting graphene coating layer is preferably 1 to 20 mu m. If the thickness is less than 1 탆, the thickness of the steel sheet is too thin, resulting in deterioration of the workability due to a decrease in adhesion with the steel sheet, resulting in deterioration in corrosion resistance. On the other hand, .

The photocurable graphene coating layer includes graphene grains modified with acrylate and is located at the top of the graphene coated steel sheet to provide a high gloss and scratch resistance characteristic of the photocurable coating layer and a conductive, Transparency, super water repellency, and the like can be expressed together.

The thickness of the photocurable graphene coating layer is preferably 0.5 to 20 mu m. If it is less than 0.5 mu m, the cured product of the UV curing type coating composition is insufficient, and scratch resistance and glossiness may be deteriorated. On the other hand, when the thickness is more than 20 mu m, the coating thickness is too thick, There is a concern.

Hereinafter, a method of manufacturing a graphene-coated steel sheet according to another aspect of the present invention will be described in detail.

The method of manufacturing a graphene-coated steel sheet according to still another aspect of the present invention includes the steps of: applying the graphene coating composition to a surface of a steel sheet; Heating the coated steel sheet coated with the coating composition to 80 to 340 캜 to form a thermosetting graphene coating layer; And irradiating ultraviolet (UV) light to the base steel sheet on which the thermosetting graphene coating layer is formed to form a photocurable graphene coating layer.

The graphene coating composition may be applied to the surface of the base steel sheet by a method commonly used in the art, for example, dip coating, spray coating, roll coating, or bar coating.

If the heating temperature for forming the thermosetting graphene coating layer is less than 80 ° C, there is a risk of uncured. On the other hand, if the heating temperature exceeds 340 ° C, peeling or cracking of the coating layer may occur due to overcuring. In the case of hot air heating, heating is carried out at a temperature of 80 to 340 ° C. for 3 to 50 seconds. In the case of induction heating, a frequency range of 5 to 50 MHz, electric power 3 to 15 kW and 100 to 300 캜 for 2 to 30 seconds.

The wavelength of ultraviolet rays for forming the photocurable graphene coating layer is preferably 400 nm or less. As a light source for irradiating the ultraviolet ray, a metal halide, a medium pressure mercury lamp, a high pressure mercury lamp, an H bulb without electrode, a D bulb, a V bulb (fusion, USA) can be selected and used as needed. The amount of ultraviolet light is preferably in the range of 0.1 to 10 J / cm ² , but can be appropriately adjusted depending on the composition of the graphene coating composition and the user's choice.

Meanwhile, the heating and ultraviolet (UV) irradiation may proceed sequentially, but the same effect can be obtained even if they proceed simultaneously. When heating and ultraviolet (UV) irradiation are simultaneously performed, productivity can be greatly improved have.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are provided to aid understanding of the present invention and should not be construed as limiting the present invention.

( Example )

1. Preparation of oxidized graphene

The oxidized graphene used for the practice of the present invention was prepared using the generally well-known Hummer's method.

2. Preparation of polymer grafted graphene oxide

Monomers were prepared by combining neopentyl glycol (NPG): ethylene glycol (EG): phthalic anhydride (PhAn): adipic acid (AA) = 1.5: 0.5% by weight based on the monomer, butyl chlorotine dihydroxide as an esterification catalyst, 0.05% by weight based on the monomer, and butyl acetate as a solvent were mixed and grafted at 280 DEG C to prepare grafted oxide graphene.

3. Preparation of oxidized graphene modified with acrylate

The reaction solution in which the graphene oxide was dissolved in THF and the benzyl isocyanate were mixed at a molar ratio of 1: 2 and reacted at 45 ° C to modify the functional group (for example, hydroxyl group) of the oxidized graphene to an isocyanate. Then, hydroxyethyl acrylate (HEA) was slowly added to the isocyanate-modified oxide graphene and the reaction was carried out at about 40 ° C to prepare an acrylate-modified oxide graphene. Through the FT-IR analysis in real time, the intensity of the NCO peak detected at 2270-3 cm-1 was observed, and the completion time of the reaction and the amount of consumed isocyanate were determined.

4. Preparation of graphene coating composition

Polymer grafted graphene, oxidized graphene modified with acrylate, bifunctional oligomer [urethane acrylate, SUPER RESIN 1327, Samhwa Paint, Korea], polyfunctional oligomer [urethane acrylate, SUPER RESIN 1315, , Monofunctional monomer 1 [tetrahydroperfuryl acrylate (THFA), SR285, Sartomer, USA], monofunctional monomer 2 [isobornyl acrylate (IBOA), SK-UCB, [Trifluoropropylene glycol diacrylate (TPGDA), Mi Won Sang, Korea], photoinitiator 1 [Darocur 1173, Ciba Chemicals, Switzerland], diisocyanate diisocyanate , TEGO Airex 920, Evonik, Germany) and leveling agent (TEGO Rad 2250, Evonik, Germany) as adhesion promoters, photoinitiator 2 [IRGACURE 184, CIBA, Switzerland], defoamer [TEGO Airex 920, Evonik, Germany], and hydroxyethyl acryloylphosphate It was combined to prepare a coating composition. The component contents of the coating composition were varied as shown in Table 1 for Examples and Comparative Examples. The units represent the respective weight percentages relative to 100 wt% (based on solids) of the total coating composition.

Inventory 1 Inventory 2 Inventory 3 Honorable 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 When the polymer is grafted with oxidized graphene 25 30 35 45 5 55 50 15 Acrylate modified graphene oxide 25 20 15 10 30 5 0.5 35 Bifunctional oligomer 5 5 5 5 10 5 4.5 5 Polyfunctional oligomer 10 10 10 10 15 10 10 10 Monofunctional monomer 1 5 5 5 5 5 5 5 5 Monomeric Monomer 2 10 10 10 5 10 - 5 10 Bifunctional Monomer 1 5 5 5 5 5 5 5 5 Bifunctional Monomer 2 5 5 5 5 10 5 5 5 Photoinitiator 1 3 3 3 3 3 3 3 3 Photo initiator 2 2 2 2 2 2 2 2 2 Defoamer and leveling agent 4 4 4 4 4 4 4 4 Adhesion promoter One One One One One One One One system 100 100 100 100 100 100 100 100

5. Manufacture of graphene coated steel sheet

The prepared graphene coating composition was coated on the surface of a galvanized (GI) steel plate with a # 3 bar coater and dried at 250 ° C for 40 seconds with PMT. Thereafter, nitrogen was injected, and ultraviolet light was irradiated at a light amount of 100 to 2000 mJ / cm 2 using an ultraviolet ray irradiator (Fusion 600vps, Fusion, USA) to prepare a graphene coated steel sheet.

6. Morphology analysis of graphene coated steel sheet

The graphene-coated steel sheets thus prepared were observed by SEM analysis to see whether a coating layer having a double structure was formed, and the thicknesses of the respective coating layers were measured. The results are shown in Table 2 below.

Remarks Whether a dual structure coating layer is formed Graphene coating layer thickness (탆) Thermosetting type Light-curing type Inventory 1 Formation of dual structure coating layer 4.24 8.25 Inventory 2 Formation of dual structure coating layer 6.73 7.03 Inventory 3 Formation of dual structure coating layer 8.95 5.14 Honorable 4 Formation of dual structure coating layer 10 2.72 Comparative Example 1 Formation of a dual structure coating layer
(Formation of thermosetting type coating layer) - 10.79 Comparative Example 2 Formation of dual structure coating layer 10.16 1.07 Comparative Example 3 Formation of a dual structure coating layer
(No photocurable coating layer was formed) 10 - Comparative Example 4 Formation of dual structure coating layer 3.29 13.01

Referring to Table 2, it can be confirmed that a coating layer of a double structure satisfying all of the conditions proposed by the present invention is appropriately formed. On the other hand, in the case of Comparative Example 1, the content of grafted oxide graphene was too small to form an integral coating layer of a double structure. In Comparative Example 3, the content of grafted oxide graphene modified with acrylate was too high It was not possible to form an integral coating layer having a double structure.

FIG. 1 is an SEM image of a section of a graphene-coated steel sheet according to Inventive Example 1 of the present invention, FIG. 2 is an SEM image of a section of a graphene-coated steel sheet according to Comparative Example 1 of the present invention, Is an SEM image of a section of the graphene-coated steel sheet according to Comparative Example 3 of the present invention.

7. Analysis of physical properties of graphene coated steel sheet

The appearance, gloss, scratch resistance, corrosion resistance, bending property, lubricity, adhesiveness and conductivity of each of the produced graphene-coated steel sheets were measured and shown in Table 3 below.

Measurement methods and evaluation criteria are as follows.

(1) Appearance

The appearance of the coated film was evaluated to be good without any foreign matter and uncoated areas. The evaluation results were evaluated in the following manner.

◎: No abnormality.

○: There is little tea.

C: Partial crater ring.

X: Multiple cratering and yellowing.

(2) Glossiness

Using the gloss meter, the angle selector was fixed at 60 ° and the black gloss plate was placed on the sample table. After turning on the switch, it was left for 1 ~ 2 minutes. After adjusting the standardizing control knob until the gloss of the standard plate became 96.4%, the sample to be tested was replaced with the standard plate and the scale of micro amperes was read And then give an average value.)

⊚: 85 or more

?: 70 to 80

?: 60 to 70

×: 60 or less

(3) scratch resistance

The pencil hardness was measured in order to evaluate the scratch resistance, and the pencil hardness was measured according to JIS K5600-5-4KS. Here, the pencil hardness is measured sequentially from 9B to 9H, and the closer to 9B the hardness is, the closer to 9H the harder the hardness.

F ↑: Excellent scratch resistance

B ↓: scratch resistance

◎: HB or more

○: B or more to F or less

DELTA: 4B or more to 2B or less

×: 5 B or less

(4) Corrosion resistance

The initial wetness of the coated specimens was evaluated by continuous spraying of 5% saline at 35 ° C and 95% humidity. The evaluation results were evaluated in the following manner.

◎: No more than 480 hours.

◯: Initial screening after 240 hours.

△: Initial call after 120 hours.

×: Initial call before 72 hours.

(5) Bending property

The surface of the coated specimen was bent by 180 °, then inserted into a vise and tightened to a flat surface. (0, 1, 2, 3T-Bending). A scotch tape was attached to the curved coating film, and when the coating film was peeled off, the state of peeling off the tape was evaluated.

◎: 0T, 1T, 2T, 3T No peeling.

◯: Initial screening after 240 hours.

△: Initial call after 120 hours.

×: Initial call before 72 hours.

(6) Lubrication

The lubricity was measured using a drag bead friction tester (load 1,000 kgf, speed 1,000 mm / min, distance 100 mm).

?: Friction coefficient less than 0.15

?: Friction coefficient 0.15 or more and less than 0.30

X: Friction coefficient 0.30 or more

(7) Adhesiveness

The coated specimens were cut with a cutter so as to have a width of 1 mm and a length of 1 mm to prepare 100 pieces, and 3M tape was attached and then peeled off to evaluate the adhesion of the coating. The evaluation results were evaluated in the following manner.

◎: No abnormality.

○: 10 or less eliminated.

△: Within 50 pieces.

×: Completely eliminated.

Remarks Exterior Polish My Scratchy Castle Corrosion resistance Bending property Lubricity Attachment Inventory 1 ◎ ◎ ○ ○ ◎ ○ ◎ Inventory 2 ◎ ◎ ○ ◎ ◎ ○ ◎ Inventory 3 ◎ ◎ ◎ ◎ ◎ ○ ◎ Honorable 4 ◎ ◎ ◎ ○ ◎ ○ ◎ Comparative Example 1 ◎ ◎ × × △ × × Comparative Example 2 × ○ △ △ × △ × Comparative Example 3 ○ × × △ △ × △ Comparative Example 4 △ × ○ × × △ ×

Examples 3 to 4 which satisfy all of the conditions proposed by the present invention exhibit excellent properties in terms of appearance, gloss, scratch resistance, corrosion resistance, bending property, lubricity, adhesion and conductivity Can be confirmed.

On the contrary, in the case of Comparative Example 1, the graphene graphene graphene graphene graphene content was below the range proposed by the present invention, resulting in poor bendability, lubricity and adhesion. In Comparative Example 2, The grafted graphene graphene content exceeded the range proposed by the present invention and the bendability and adhesion were found to be extremely poor. In the case of Comparative Example 3, the content of graphene oxide modified with acrylate was less than the range suggested by the present invention, and the gloss, scratch resistance and lubricity were extremely poor. In Comparative Example 4, , The graphene oxide content of the modified graphene exceeded the range proposed by the present invention, and the gloss, the corrosion resistance, the bending property and the adhesion property were extremely poor.

Claims (16)

Wherein the solid content is 20 to 50% by weight of grafted graft polymer, 5 to 30% by weight of graft modified with acrylate, 5 to 30% by weight of acrylic oligomer, 5 to 30% by weight of acrylic A monomer, and 0.1 to 10% by weight of a photoinitiator.
The method according to claim 1,
The polymer may be at least one selected from the group consisting of polyester, water-dispersible urethane, epoxy, epoxy-phosphate, epoxy-phosphate modified with an acrylic or vinyl monomer, vinyl-based or acryl- urethane modified with an acrylic or vinyl monomer Lt; / RTI >
The method according to claim 1,
Wherein the acrylate is at least one selected from the group consisting of monofunctional acrylic monomers, bifunctional acrylic monomers and polyfunctional acrylic monomers.
The method according to claim 1,
Wherein the acrylic oligomer is selected from the group consisting of epoxy acrylate, urethane-based modified epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, acrylic acrylate, silicone acrylate, melamine acrylate, acrylic acrylate, polythiol acrylate derivatives, Wherein the polyglycolic acid is a mixture of at least one selected from the group consisting of acetal acrylates.
The method according to claim 1,
Wherein the acrylic monomer is a mixture of one or more of a monofunctional acrylic monomer, a bifunctional acrylic monomer and a polyfunctional acrylic monomer.
The method according to claim 1,
Wherein the photoinitiator is a benzophenone, diphenoxycibenzophenone, anthraquinone, xanthone, thioxanthone, or benzyl group.
The method according to claim 1,
Wherein the composition further comprises at least one additive selected from the group consisting of a defoaming agent, a leveling agent, an adhesion promoter, a stabilizer, an antioxidant, an antistatic agent, an ultraviolet absorber, a thermosetting agent and a silane coupling agent.
Preparing polymer grafted graphene grains;
Preparing an oxidized graphene modified with acrylate;
And mixing the acrylic oligomer, the acrylic monomer and the photoinitiator with the grafted oxide graphene, wherein the polymer is modified with grafted oxidized graphene and acrylate to obtain a graphene coating composition,
Wherein the graphene coating composition comprises, on a solid basis, 20 to 50% by weight of polymer grafted graphene, 5 to 30% by weight of acrylate modified graphene, 5 to 30% by weight of acrylic oligomer, 5 to 30% by weight of an acrylic monomer, and 0.1 to 10% by weight of a photoinitiator.
9. The method of claim 8,
The step of preparing the polymer grafted graphene grains comprises:
Dissolving the graphene oxide in an organic solvent to prepare a graphene oxide solution;
Mixing at least one of a monomer and a polymer in the solution; And
And heating the solution to 100 to 300 DEG C after the mixing to obtain grafted oxide graphene.
9. The method of claim 8,
The step of preparing the grafted oxide grafted with acrylate comprises:
Dissolving the graphene oxide in an organic solvent to prepare a graphene oxide solution;
Mixing the graft oxide solution with a compound containing a functional group capable of reacting with a functional group of the graphene oxide and reacting the mixture; And
After said mixing, blocking with alkyl acrylate,
Wherein the compound containing a functional group capable of reacting with the functional group of the graphene oxide is at least one compound selected from a compound having an isocyanate group, an alkoxy group or a carboxyl group, a compound containing a halogen atom and a cyclic anhydride.
11. The method of claim 10,
Wherein the graphene oxide and the compound containing a functional group capable of reacting with the functional group of the graphene oxide are mixed at a molar ratio of 1: 2 to 2.1.
delete delete delete Applying the graphene coating composition of any one of claims 1 to 7 to the surface of the substrate steel;
Heating the base steel sheet coated with the graphene coating composition to 80 to 340 캜 to form a thermosetting graphene coating layer; And
And irradiating ultraviolet (UV) light to the base steel sheet on which the thermosetting graphene coating layer is formed to form a photocurable graphene coating layer.
16. The method of claim 15,
Wherein the heating and ultraviolet (UV) irradiation are simultaneously carried out.

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