KR20110020105A - Composition for surface treatment, preparation method thereof and surface-treated steel plate using the same - Google Patents

Abstract

PURPOSE: A composition for surface treatment is provided to improve corrosion resistance and abrasion resistance by comprising mica with excellent anti-penetration effect of foreign materials. CONSTITUTION: A composition for surface treatment comprises a base coating agent and mica included within the base coating agent. The base coating agent is a photocurable coating agent including a photocurable acrylic oligomer, reactive diluent and photopolymerization initiator. The mica includes one or more selected from the group consisting of muscovite, paragonite, biotite, phlogopite, lepidolite and zinnwaldite.

Description

Composition for surface treatment, preparation method thereof and surface-treated steel plate using the same}

The present invention relates to a resin composition for surface treatment, a preparation method thereof and a surface treated steel sheet using the same.

In general, the purpose of performing a surface treatment on the steel sheet is to protect the surface of the steel sheet from external factors or impact.

Examples of the composition used in the coating layer for surface treatment applied to conventional coated steel sheet, etc. may include a coating composition using a polymer.

The coating composition using the polymer is acrylic, epoxy, polyester, polyurethane, urea, urethane-acryl, epoxy-urethane a variety of materials have been used.

The permeability of the material in the polymer coating layer is determined by the diffusion coefficient of the material and solubility in the coating layer, as shown in Equation 1 below. If it is composed of a uniform phase, the diffusion and solubility may be controlled according to the composition and crystallinity of the polymer.

Permeability (P) = Diffusion (D) × Solubility (S)

However, when the surface treatment using the polymer coating material as described above is performed alone, there is a problem that it is difficult to effectively block various materials such as external moisture, oxygen, acid, base, organic solvent.

Therefore, as a method of more effectively blocking the external material, a method of effectively lowering the permeation rate of the external material has been developed by introducing an inorganic material into the surface treatment coating layer.

Conventionally, isotropic particles such as silica nanoparticles are mainly introduced into the surface treatment coating layer to reduce the permeation rate of the external material. However, the effect of reducing the permeation rate of the external material is not sufficient, resulting in a slight improvement in corrosion resistance. there was.

Therefore, a method of introducing a smectic inorganic material into the surface treatment coating layer has been developed to more effectively lower the penetration rate of external materials. Examples of such inorganic materials include serpentine (Mg ₃ Si ₂ O). Hydrated magnesium-iron silicates called ₅ (OH) ₄ ), and specifically, antigorite, chrysotile, and lizardite have been used.

In addition, a method of controlling the penetration rate by using clay minerals has been proposed. As a representative example, clay of a relatively thin multilayer thin film structure (2: 1, tetrahedral / central octahedral sheet) such as montmorillonite (MMT) is used. It was.

In addition to the montmorillonite ((Na, Ca) 0.33 (Al, Mg) ₂ (Si ₄ O ₁₀ ) (OH) ₂ · nH ₂ O) kaolinite (kaolinite; Al ₂ Si ₂ O ₅ (OH) ₄ ) or Vermiculite ((MgFe, Al) ₃ (Al, Si) ₄ O ₁₀ (OH) ₂ .4H ₂ O), etc., which is easily expanded by heat may be mentioned.

In the case of the conventional organic-inorganic composite material, the inorganic materials as described above were mixed with the polymer matrix, but there was still a need for improvement in dispersion stability and corrosion resistance, so as to improve the corrosion resistance of steel sheets, The development of surface treatment technology is required.

The present invention has been created to meet the needs of the above-described technology development, by including mica having an effect of preventing the penetration of foreign substances remarkably superior to the inorganic materials that have been used to improve the corrosion resistance remarkably corrosion resistance and wear resistance It is an object of the present invention to provide an improved surface treatment composition and method for producing the same.

Another object of the present invention is to provide a surface-treated steel sheet having remarkably excellent corrosion resistance by forming a resin coating layer on a substrate using the surface treatment composition.

The present invention as a means for solving the above problems, a base coating agent; And it provides a surface treatment composition comprising mica contained in the base coating agent.

In another aspect, the present invention provides a method for producing a composition for surface treatment according to the present invention comprising the step of mixing mica to the base coating agent.

In addition, the present invention as another means for solving the above problems, the substrate; And a resin coated layer formed on the substrate using the composition according to the present invention.

According to the present invention, superior corrosion resistance is achieved by significantly lowering the permeation rate of external materials than inorganic materials such as silica nanoparticles or montmorillonite, which have been added to compositions used for surface treatment such as steel sheets to improve physical properties such as corrosion resistance. It can provide a composition for surface treatment and a method for producing the same containing mica that can provide.

In addition, according to the method for preparing a composition for surface treatment according to the present invention, by performing hydrothermal treatment and / or hydrophobization treatment to mica added as an inorganic material, not only excellent diffusion and hydration ability, but also compatibility and dispersion stability with the base coating agent It can be improved, thereby providing a surface-treated steel sheet comprising a resin coating layer with improved adhesion to the substrate.

The present invention is a base coating agent; And a mica contained in the base coating agent.

Hereinafter, the composition for surface treatment of this invention is demonstrated in detail.

Surface treatment composition according to the present invention, as described above, the base coating agent; And mica contained in the base coating.

In the present invention, the base coating agent corresponds to the base material of the composition used for the surface treatment, and the type thereof is not particularly limited, and includes all coating agents that may be used as the surface treatment composition for improving corrosion resistance by containing the mica. can do.

For example, a polymer matrix or a photocurable coating agent may be used without particular limitation, and specifically, photocuring may further improve dispersion stability and compatibility when mixed with mica as it contains monomers or oligomers which are not polymers. Coating agents can be used.

Herein, the photocurable coating agent refers to a coating agent that is cured in response to UV light irradiation, and the like, and may include a UV photocurable coating agent commonly used in this field, and the like is not particularly limited. For example, it may be one containing a photocurable acrylic oligomer, a reactive diluent and a photopolymerization initiator.

Here, the type of photocurable acrylic oligomer is not particularly limited, and may be selected from the group consisting of polyester acrylic oligomers, urethane acrylic oligomers, epoxy acrylic oligomers, and silicone acrylic oligomers commonly used in the art. It may be a urethane acrylic oligomer, and more specifically, may be a urethane acrylate oligomer.

Examples of the kind of the photocurable acrylic oligomers include alkyl (meth) acrylate oligomers, (meth) acrylic acid oligomers, (meth) acrylonitrile oligomers, (meth) acrylamide oligomers, and N-substituted (meth) acrylamides. Oligomer, N-methylol (meth) acrylamide oligomer, hydroxyethyl (meth) acrylate oligomer, carboxyethyl (meth) acrylate oligomer, (meth) acryloyl morpholine oligomer, ethylene glycol mono (meth) acrylate oligomer , Diethylene glycol mono (meth) acrylate oligomer, polyethylene glycol mono (meth) acrylate oligomer, dimethylaminopropyl (meth) acrylamide oligomer, tetrahydrofurfuryl (meth) acrylate oligomer, ethylene glycol di (meth) acrylic Late oligomer, diethylene glycol di (meth) acrylate oligomer, polyethylene Recall di (meth) acrylate oligomer, 1,6-hexane glycol di (meth) acrylate oligomer, pentaerythritol tetra (meth) acrylate oligomer, pentaerythritol (meth) acrylate oligomer, trimethylolpropane tri A (meth) acrylate oligomer, a trimethylolpropane di (meth) acrylate oligomer, a urethane acrylate oligomer, etc. can be used, It can also be used in combination of 2 or more types.

In addition, the reactive diluent is a material that becomes a part of the curing structure by lowering the photocurable acrylic oligomer to improve the workability or crosslinking or addition polymerization at the time of curing, monomers capable of performing such a function All of them may be included therein. For example, a photopolymerizable acrylic monomer, an organic solvent, or a mixture thereof may be used.

Further, the reactive diluent may use an organic solvent such as methyl isobutyl ketone (MIBK) or methyl ethyl ketone (methyl ethyl ketone), but specifically methyl (meth) acrylate, Ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, oxyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, methylcyclohexyl (meth) acrylate, iso Bonyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, chlorophenyl (meth) acrylate, methoxyphenyl (meth) acrylate, bromophenyl (meth) acrylate, ethylene glycol di (Meth) acrylate, 1,2-propylene glycol (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,3-propylene glycol (meth) acrylate, 1,4-butanedi Di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, neopentylglycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxy Ethoxyethyl acrylate, glycidyl methacrylate epoxyacrylate, 1,6-hexanediol di (meth) acrylate, glycerin tri (meth) acrylate, methylpropanediol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, glycerol propoxylate tri (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate From the group consisting of N- vinyl pyrrolidone, and the like agent may be one comprising at least one selected.

The reactive diluent may be composed of one or a combination of two or more of the materials exemplified above, but is not limited thereto.

On the other hand, the photopolymerization initiator may also include all materials that can be used to initiate the photopolymerization reaction, and the kinds thereof are not particularly limited, for example, benzoin ether compounds, acetophenone compounds, anthraqui It may include one or more selected from the group consisting of a non-based compound, a thioxanthone-based compound, a ketal-based compound and a benzophenone-based compound.

More specific examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether and benzoin phenyl ether. Acetophenone compounds include acetophenone, 2,2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroaceto Phenone, 1-hydroxy cyclohexyl phenyl ketone, and the like.

Examples of the anthraquinone compounds include 2-methyl anthraquinone and 2-amyl anthraquinone, and the thioxanthone compounds include 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone and 2- Chlorothioxanthone, 2,4-diisopropyl thioxanthone, and 1-chloro-4-propoxy thioxanthone, and the like, and ketal compounds include acetophenone dimethyl ketal and benzyl dimethyl ketal; Phenolic compounds include benzophenone, diethylamino benzophenone, 4,4'-bis-diethyl aminobenzophenone, 3,3-dimethyl-4-methoxy benzophenone and 3,3 ', 4,4'- Tetra- (t-butyl peroxyl carbonyl) benzophenone and the like can be used.

Furthermore, 4-benzoyl-4'-methyl diphenyl sulfido, xanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one 2,4,6-trimethyl benzoyldiphenyl phosphine oxide and the like can be used.

In addition, the photopolymerization initiator may be used with known photopolymerization accelerators or sensitizers such as p-dimethyl aminobenzoic acid isoamyl ester, 2-dimethyl aminoethyl benzoate and the like.

In addition, the content of the photocurable acrylic oligomer, the reactive diluent and the photopolymerization initiator in the photocurable coating agent is not particularly limited, but, for example, 60 to 240 parts by weight of the reactive diluent and photopolymerization based on 100 parts by weight of the photocurable acrylic oligomer. It may include 5 to 70 parts by weight of the initiator.

Here, when the reactive diluent is contained in less than 60 parts by weight based on 100 parts by weight of the photocurable acrylic oligomer, there is a fear that the dilution effect is lowered, causing a problem of high viscosity, if contained in excess of 240 parts by weight, There exists a possibility that the adhesive force to may fall.

In addition, when the photopolymerization initiator is contained in less than 5 parts by weight with respect to 100 parts by weight of the photocurable acrylic oligomer, there is a fear that the curing is difficult to occur due to the lowering of the curing reaction rate, when exceeding 70 parts by weight, workability There is a possibility that the surface hardness is lowered.

On the other hand, the mica contained in the surface treatment composition according to the present invention is a generic term for specific silicate minerals having plate-like cleavage, and is generally monoclinic and has a hexagonal plate-like crystal form. The mica has a relatively wide plate length and low water permeability compared to other inorganic materials, has a low coefficient of thermal expansion (3 × 10 ^-5 ℃ ^-1 or less at 100 ℃) and high elastic modulus (2.5 to 3.5 GPa, at 50 to 350 ° C.).

The mica is mixed with the base coating to form a plate-like film layer in the base coating to bring about the effect of preventing the penetration of foreign materials, thereby improving the corrosion resistance.

As such, the surface treatment composition according to the present invention contains a mica and a photocurable coating agent having a high elastic force, a low coefficient of thermal expansion, a high barrier property (barrier property), etc. as an inorganic filler to improve the surface treatment for corrosion resistance of steel sheets, etc. It can be usefully used.

Referring to FIG. 1, the composition for surface treatment containing mica according to the present invention is compared with a polymer film containing no inorganic material or a polymer film containing a spherical isotropic inorganic material (a, b). (c) is an anisotropic substance in the form of a plate crystal, and the penetration time of an external substance can be reduced more efficiently, and the corrosion resistance of the polymer film can be further improved.

In the present invention, the mica may include a component represented by the following Chemical Formula 1, but is not limited thereto.

X _m1 Y _m2 Z _m3 O _m4 (T) ₄

Where

X is K, Na, Ca, Ba, Rb or Cs, m1 is 1 to 2;

Y is Al, Mg, Fe, Mn, Cr, Ti or Li, m2 is 2-4;

Z is Si, Al or SiAl, m3 is 4 to 8;

m 4 is 10 to 20;

T is OH, F or OHF and m5 may be 2-4.

More specifically, the mica used in the present invention may include KAl ₂ (AlSi ₃ O ₁₀ ) (OH) ₂ or K ₂ Al ₄ (Si ₆ Al ₂ ) O ₂₀ (OH) ₄ .

In addition, the specific types of the mica is not particularly limited, and may include all mica that can exhibit the characteristics described above according to the object of the present invention, for example, muscovite, so down mica, biotite, gold mica. It may include one or more selected from the group consisting of red mica and eukaryote, more specifically may be used mucovite mica.

Referring to FIG. 2, the dolomite is sandwiched between a portion in which oxygen (oxygen) and Al ions are octahedral and a portion in which hydroxyl (OH) ions are (Si, Al) O ₄ tetrahedral, and the hardness is 2 To 2.5, specific gravity of 2.7 to 3, and may be a colorless or white mineral.

The mica may be contained in an appropriate amount to improve the corrosion resistance of the surface treatment composition according to the invention at the same time to improve the efficiency of the process, the range of the content is not particularly limited, for example, It may be contained in an amount of 0.1 to 10 parts by weight, and more specifically 0.1 to 5 parts by weight based on 100 parts by weight of the paint coating agent.

In the composition for surface treatment according to the present invention, when the mica is contained in less than 0.1 part by weight based on 100 parts by weight of the photocurable coating agent, there is a fear that the effect of improving the corrosion resistance is lowered, and when it is contained in excess of 10 parts by weight, the composition Due to the increase in the viscosity of the coating, there is a risk of uneven coating thickness and storage stability of mica, and furthermore, in the case of the coating layer formed by using the same, the light transmittance is lowered so that the photocuring reaction is not terminated or the surface roughness of the coating is reduced. There is a risk of rising.

On the other hand, the size and use of the mica is not particularly limited, for example, by forming a small platelet by delamination or exfoliation of mica particles having a particle size of about 300 mesh. Although the size of the mica is not particularly limited, for example, the mica may have an average plate length of 5 µm to 50 µm and an average thickness of 1 nm to 200 nm through a peeling process or the like. .

Here, the "average plate length" means an average value for the longest length of the plate in order to specify the size of the mica peeled into a small plate shape, and the "average thickness" means an average value for the thickness of the plate. .

The average plate length of the mica is 5 If less than 1 μm or the average thickness is less than 1 nm, it may be difficult to develop a sufficient corrosion resistance improving effect, and if the average laminar length of the mica exceeds 50 μm or the average thickness exceeds 200 nm, the coating thickness becomes uneven. As a result, the storage stability of the mica is reduced, or the light curing reaction is not terminated or the coating surface roughness may be increased due to the decrease in the light transmittance.

Here, the peeling process may be carried out through a high temperature, high pressure hydrothermal process, through which the size control and dispersion stability of the particles can be established.

On the other hand, in the present invention, the mica may be a hydrophobic agent is introduced to the surface. That is, by introducing a hydrophobizing agent into the surface of the mica, the surface of the mica can be hydrophobized, thereby improving miscibility with the base coating agent mixed therewith and improving adhesion to the substrate.

Here, the type of hydrophobization agent is not particularly limited, but may include, for example, one or more selected from the group consisting of cationic materials, nonionic materials, and mixtures thereof.

In addition, the kind of the cationic material is not particularly limited, but for example, cetyltrimethylammonium bromide (CTAB), dodecyltrimethylammonium bromide (DTAB), cetylpyridinium chloride; CPC), polyethoxylated tallow amine (POEA), bezalkonium chloride (BAC) and bezethonium chloride (BZT) For example, cetyltrimethylammonium bromide or dodecyltrimethylammonium bromide may include at least one selected. More specifically, the length of the hydrocarbon may be shorter to more effectively hydrophobize the surface of the mica and greatly improve the degree of cation exchange. In that sense, Dodecyltrimethylammonium bromide can be used.

Although the type of the nonionic material is not particularly limited, for example, the nonionic material is a group consisting of polyalkyleneimine, polyalkyleneoxide, polyvinyl alcohol and polyvinylpyrrolidone. It may include one or more selected from, and more specifically, may include one or more selected from polyethyleneimine (PEI) or polyethylene oxide (PEO).

The content of such a hydrophobic agent is not particularly limited, but may be, for example, 10 parts by weight to 140 parts by weight with respect to 100 parts by weight of mica, and specifically, may be contained in an amount of 60 parts by weight to 100 parts by weight. have.

When the hydrophobization agent is contained in less than 10 parts by weight with respect to 100 parts by weight of mica, the peak of the d-spacing appears at a relatively high angle, thereby reducing the dispersion stability of mica, unterminated polymerization during photopolymerization, light transmittance of the coating film There is a fear that the lowering, the corrosion resistance of the coating layer and the increase in the roughness of the coating surface, and the like, when contained in excess of 140 parts by weight, the difference in the effect compared to the content of the added hydrophobic agent is not so large that the efficiency may be reduced. have.

On the other hand, the composition for surface treatment according to the present invention may further include a silane coupling agent represented by the following formula (2).

R-Si (A) ₃

Where

R is a C ₁ to C ₁₂ alkylamine, vinyl group, acrylic group, epoxy group or urethane group, and A is C ₁ to C ₁₂ alkoxy or halogen element.

Specifically, R may be C ₁ to C ₈ alkylamine, vinyl group, acryl group, epoxy group or urethane group, and more specifically, epoxy group or vinyl group may be used to improve corrosion resistance and strength.

In addition, more specifically, A may be OCH ₃ , OCH ₂ CH ₃ or Cl.

The silane coupling agent serves to increase the compatibility between the base coating agent and mica in the surface treatment composition according to the present invention.

On the other hand, the present invention relates to a method for producing a composition for surface treatment according to the invention comprising the step of mixing the base coating and mica.

That is, according to the manufacturing method of the surface treatment composition according to the present invention, by mixing the mica and the base coating as described above, to disperse the mica in the base coating, using the mica corrosion resistance and wear resistance improving effect and excellent corrosion resistance and The composition for surface treatment which has abrasion resistance can be provided.

Here, the manufacturing method of the surface treatment composition according to the present invention may include a step of hydrothermal treatment of mica. Through such hydrothermal treatment, ions having a small hydration number and a low cation exchange capacity value can be easily diffused into the interlaminar structure due to their high hydration ability and small size, and are easily exchanged with ions that can increase the interlayer spacing. can do.

Specifically, the hydrothermal treatment may include a first step of thermally treating mica; And a second step of reacting the mica obtained in the first step in a solution containing a lithium compound.

In the first step, the heat treatment conditions of the mica are not particularly limited, but, for example, in an argon or nitrogen gas atmosphere, 700 It may be heat treated for 1 to 10 hours at a temperature of to 1000 ℃.

In addition, the second step contains a compound for ion exchange such as a lithium compound in order to exchange ions having low hydration water (ex. K ⁺ ions) from mica obtained through the heat treatment to ions having excellent hydration water such as Li + ions. The ion exchange reaction can be carried out in a solution.

In the second step, the reaction conditions are not particularly limited, and suitable conditions that can be employed in this field for exchanging ions having low hydrated water and cation exchange capacity with ions having high hydrated water and good cation exchange capacity. It may include all, for example, may be performed for 40 hours or more at a temperature of 150 to 200 ℃, specifically may be performed for more than 48 hours.

In the second step, if the reaction is performed for less than 40 hours outside the reaction conditions, there is a fear that the hydrothermal reaction of mica does not occur, and the longer the reaction time, the better the hydrothermal reaction occurs. The upper limit is not particularly limited.

In addition, in view of the reaction efficiency compared to the reaction time, under the same temperature conditions, the reaction may be performed for 70 hours to 100 hours, more specifically, the reaction may be performed for 72 hours to 96 hours.

On the other hand, the lithium compound serves to exchange the potassium ions contained in the mica to lithium ions containing lithium, although the type is not particularly limited, for example, lithium nitrate, lithium perchlorate It may include one or more selected from the group consisting of (lithium perchlorate) and lithium sulfate (lithium sulfate).

Further, in the second step, the content of mica mixed in the solution containing the lithium compound is not particularly limited, but for example, the amount of mica is 0.1 to 5 parts by weight based on 100 parts by weight of the solution containing the lithium compound. It may be mixed with, more specifically in the amount of 0.5 to 3 parts by weight.

When the content of the mica is less than 0.1 parts by weight based on 100 parts by weight of the solution containing the lithium compound, the content of potassium ions to be ion exchanged is greatly reduced, despite the relatively high concentration of the lithium compound. The degree of cation exchange may be rather low, and if it is contained in an amount of more than 0.5 parts by weight, the concentration of the lithium compound is relatively low, so that a lower level of cation exchange may occur during a certain reaction time, thereby reducing the efficiency of the process. .

The solvent containing the lithium compound is not particularly limited as long as it contains the lithium compound as described above. For example, ultrapure water or the like can be used. In this case, the solution containing the lithium compound is ultrapure water. 100 parts by weight to 200 parts by weight of the lithium compound may be contained.

On the other hand, the method for producing a surface treatment composition according to the present invention may include the step of surface treatment of mica using a hydrophobization agent.

Wherein the surface treatment comprises the steps of 1) mixing mica with a hydrophobic agent and cooling circulation; And reacting the mixture obtained in step 1) with the base coating using an ultrasonic processor.

The cooling circulation performed in step 1) is not particularly limited in its manner, and may be circulated in a cooling manner using a method known in the art, and the type of cooling water used is not particularly limited, but for example Cooling circulation may be performed using a double jacket for sonication, and specifically, a cone type double jacketed flask for ultrasound may be used.

The ultrasonic double jacket is a forced circulation form, and when the cooling cycle is performed using the ultrasonic wave, the mica peeling efficiency is increased, and the average thickness of the mica can be reduced.

Further, in step 2), the type of ultrasonic processor used is not particularly limited, but for example, a probe type ultrasonic processor may be used. The reaction condition using the ultrasonic processor is not particularly limited, but may be performed by, for example, loading 40% to 70% of power for 20 minutes to 1 hour.

On the other hand, the present invention is also a substrate; And a resin coated layer formed on the substrate using the composition for surface treatment according to the present invention.

Here, the substrate may include a substrate of all metal materials on which the surface treatment can be performed, but the type is not limited, but may be, for example, a metal steel sheet or the like.

The metal steel sheet includes all metals used for the purpose of automobile materials, home appliances, building materials, and the like, specifically metals such as iron plates, and any steel sheet commonly used in the art for the above purposes may be used. However, for example, cold rolled steel sheet; Zinc-based electroplating steel sheets such as galvanized steel sheet, zinc nickel plated steel sheet, galvanized steel sheet, zinc titanium plated steel sheet, zinc magnesium plated steel sheet, zinc manganese plated steel sheet and zinc aluminum plated steel sheet; Hot-dip galvanized steel sheet; Aluminum plated steel sheet; Magnesium plated steel sheet; Further, plated steel sheets containing, as the dissimilar metals or impurities in these plating layers, for example, cobalt, molybdenum, tungsten, nickel, titanium, aluminum, manganese, iron, magnesium, tin, copper, and the like; Further, plated steel sheet in which inorganic materials such as silica and alumina are dispersed in these plating layers; Or an aluminum alloy plate containing silicon, copper, magnesium, iron, manganese, titanium, zinc or the like; Magnesium alloy plate; Phosphate coated galvanized steel sheet; Alternatively, a hot rolled steel sheet or the like may be used, and a multilayer plated sheet obtained by sequentially treating two or more kinds during the plating may be used as necessary.

On the other hand, the method of forming the resin coating layer is also not particularly limited, and may be appropriately employed by selecting a coating method known in the art depending on the type and use of the base coating agent to be used.

For example, when the photocuring coating agent is used as the base coating agent, a surface treatment composition including the photocuring coating agent and mica is applied onto the substrate, and a method of curing through UV light irradiation may be used. It is not limited to this.

In addition, the thickness of the resin coating layer is not particularly limited, and may be appropriately employed and selected within the thickness range of the coating layer that is usually applied for surface treatment of steel sheets or the like in the art.

3 is a schematic cross-sectional view of the surface-treated steel sheet 10 according to an embodiment of the present invention.

As shown in FIG. 3, the resin coating layer 200 formed using the surface treatment composition according to the present invention may be formed on the substrate 100, and the substrate 100 may form the resin coating layer 200. It may be a galvanized steel sheet in which the galvanized layer 300 is formed.

On the other hand, the resin coating layer 200 has a mica 210 in the interlayer structure in the base coating agent 230, it can significantly reduce the penetration rate of the external material, and can exhibit a corrosion resistance effect.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by the following examples.

[Production Example 1]

300 mesh (plate average Pristine muscovite of approximately 46 μm in length mica) was prepared. The dolomite particles were placed in an IR furnace and subjected to heat treatment at an temperature of 700 ° C. under an argon gas atmosphere for 1 hour.

Subsequently, 100 g (ml) of ultrapure water and 170 g of lithium nitrate (LiNO ₃ ) were added to a hydrothermal reactor, and 1 part by weight of heat treated white mica was added based on 100 parts by weight of the mixed solution of ultrapure water and lithium nitrate. Stirred at rpm.

At this time, the temperature of the hydrothermal reactor was maintained at 170 ℃, the reaction time was carried out for 72 hours. The mica that was separated through the reaction was rinsed with excess ultrapure water using a vacuum filter, and dried to prepare a powder of mica that was separated by hydrothermal treatment.

Production Example 2 and 3

In the hydrothermal treatment, except that the reaction time was set to 48 hours and 96 hours, respectively, the method of preparing the mica powder according to Preparation Example 1 and other conditions were the same to prepare the mica powder.

Production Example 4 and 5

In the hydrothermal reactor, except that 0.5 parts by weight and 3 parts by weight of heat treated mica were added based on 100 parts by weight of the mixed solution of ultrapure water and lithium nitrate, respectively. All other conditions were the same to prepare the mica powder.

Production Example 6

In addition, except that the heat treatment was not performed on the pristine muscovite mica used in Preparation Example 1, the powder was prepared by hydrothermal treatment using lithium nitrate in the same manner as Preparation Example 1.

Preparation Example 7 Preparation of Hydrophobized Mica

33.3 parts by weight of dodecyltrimethylammonium bromide (DTAB) was added to 100 parts by weight of the mica powder prepared according to Preparation Example 1, and the cooling water (tap water) was circulated using a double jacketed flask for ultrasonic circulation. Using a probe-type ultrasonic processor (VibraCell 750VCX, 750W) was reacted at 70% load for 30 minutes (1 second on / 1 second off cycle).

Thereby, hydrothermal treatment and hydrophobized surface were treated.

 Production Examples 8 to 11

The surface of the dodecyltrimethylammonium bromide was added in the same manner as in Preparation Example 7, except that 16.7 parts by weight, 66.7 parts by weight, 100 parts by weight and 133.3 parts by weight were respectively added to 100 parts by weight of the mica powder. Hydrophobized white mica powders of Preparation Examples 8 to 11 were prepared.

Production Examples 12 and 13

Instead of dodecyltrimethylammonium bromide, except that a 1: 1 mixture of cetyltrimethylammonium bromide (CTAB), polyethyleneimine (PEI) and polyethylene oxide (PEO), respectively, was used. The preparation method and other conditions of the mica powder were all the same to prepare the mica powder of Preparation Examples 12 and 13, respectively.

[Production Example 14]

The same conditions as those of Preparation Example 1 were all the same, and only after the heat treatment, the only difference was that no hydrothermal treatment was performed, and the mica powder was prepared.

Production Examples 15 to 17

The inorganic materials of Preparations 15 to 17 were prepared in the same manner as in Preparation Examples 7, 12 and 13, except that Na ⁺ -montmorillonite (MMT) was used instead of dolomite and no hydrothermal treatment was used. .

Preparation Example 18 Preparation of UV Curable Coating Liquid

30% by weight of acrylate oligomer Ebecryl 870 (Cytec) and 15% by weight Ebecryl 284 (Cytec), 25% by weight of hydroxy ethyl acrylate (HEA) and 20% by weight of trimethylolpropane triacrylate (TMPTA) A UV curing coating solution was prepared by adding 8 wt% of Micure bp (Miwon Corporation) as a photoinitiator and 1 wt% of Airex 920 and Acryl phosphate, respectively, as other additives.

[Examples 1 to 9]

After mixing the mica powders according to Preparation Examples 1, 7 to 14 in an amount of 1 part by weight based on 100 parts by weight of the UV curable coating solution according to Preparation Example 18, a homogeneous solution was prepared under ultrasonic conditions, and the homogeneous solution prepared above. Was prepared as a composition for surface treatment according to Examples 1 to 9, respectively.

Example 10

Except for mixing the mica powder according to Preparation Example 1 in an amount of 3 parts by weight based on 100 parts by weight of the UV curable coating liquid according to Preparation Example 18, under the same conditions as the composition for surface treatment according to Example 1 A surface treatment composition according to 10 was prepared.

 Comparative Example 1

A surface treatment composition according to Comparative Example 1 was prepared under the same conditions as in Example 1, except that pure Na ⁺ -montmorrylonitrile (MMT) was used in place of the mica powder according to Preparation Example 1.

Comparative Example 2

According to Comparative Example 2 under the same conditions as in Comparative Example 1 except that the content of Na ⁺ -montmorylonitrile (MMT) was mixed in an amount of 3 parts by weight based on 100 parts by weight of the UV curable coating solution according to Preparation Example 18. The surface treatment composition was prepared.

Comparative Example 3

Pure UV curable coating solution according to Preparation Example 18 was prepared as a surface treatment composition according to Comparative Example 3.

Table 1 shows the compositions of the compositions for surface treatment according to Examples 1 to 10 and Comparative Examples 1 to 3.

A (inorganic substance) B (UV photocuring coating) Kinds Content (parts by weight) Content (parts by weight) Example 1 Dolomite of Preparation Example 1 One 100 Example 2 Dolomite of Preparation Example 7 One 100 Example 3 Dolomite of Preparation Example 8 One 100 Example 4 Dolomite of Preparation Example 9 One 100 Example 5 Dolomite of Preparation Example 10 One 100 Example 6 Dolomite of Preparation Example 11 One 100 Example 7 Dolomite of Preparation Example 12 One 100 Example 8 Dolomite of Preparation Example 13 One 100 Example 9 Dolomite of Preparation Example 14 One 100 Example 10 Dolomite of Preparation Example 1 3 100 Comparative Example 1 Na ⁺ -MMT One 100 Comparative Example 2 Na ⁺ -MMT 3 100 Comparative Example 3 - - 100

Test Example 1 Characterization of Mica

1. Characterization of mica after hydrothermal reaction

4 shows the results of the scanning electron microscope (SEM-EDX) analysis of the dorsal mica particles (pristine muscovite mica) and the mica powder prepared according to Preparation Example 1 before performing the hydrothermal reaction process according to Preparation Example 1.

Referring to FIG. 4, in the mica powder according to Preparation Example 1, K ⁺ ion content (atomic%) present in mica was reduced from 3.06% to 0.40% through a hydrothermal reaction process using lithium nitrate (LiNO ₃ ). This qualitatively confirmed that the hydrothermal reaction process was effective for K ⁺ ion exchange.

In addition, referring to the digital image and the X-ray diffraction (XRD) pattern of the mica powder according to Preparation Example 1 obtained after the hydrothermal reaction with reference to Figure 5, before (c) and after the heat treatment (IR) furnace (furnace) There was no change in the XRD pattern of a), but after the hydrothermal reaction process using LiNO ₃ (b), the layer spacing increased from 9.98 kPa to 11.04 kPa. In addition, a new d-spacing value of 22.07 ms was observed. This qualitatively confirmed that the hydrothermal reaction process was effective for K ⁺ ion exchange.

2. Effect analysis by hydrothermal reaction time

As hydrothermal treatment conditions of the mica powder according to Preparation Examples 1 to 3, the reaction temperature, the ratio of LiNO ₃ / H ₂ O, the concentration of the mica powder and the reaction time are as shown in Table 2 below.

Sample name Hydrothermal reaction time
(hr) Hydrothermal reaction temperature
( ^o C) LiNO ₃ / H ₂ O
Weight ratio Mica content based on 100 parts by weight of lithium nitrate aqueous solution
(Parts by weight) Production Example 1
(LiMC-1) 72 170 1.7 One Preparation Example 2
(LiMC-2) 48 170 1.7 One Preparation Example 3
(LiMC-3) 96 170 1.7 One

Atomic Absorption Spectrum (AAS) analysis was carried out on the mica powders according to Preparation Examples 1 to 3, in which the hydrothermal reaction time was changed and Preparation Example 14, which were not subjected to hydrothermal treatment, to quantitatively analyze the degree of K ⁺ ion exchange according to hydrothermal reaction time. The results were summarized in Table 3 below.

Sample name K (%) Li (%) Preparation Example 1 (LiMC-1) 4.70 0.66 Preparation Example 2 (LiMC-2) 4.75 0.67 Preparation Example 3 (LiMC-3) 4.78 0.67 Preparation Example 14 7.61 0.02

Referring to Table 3, compared to Preparation Example 14, which was not subjected to hydrothermal treatment, the dolomite powder was increased from 48 hours (Preparation Example 2) to 72 hours (Preparation Example 1) and 96 hours (Preparation Example 3), respectively. In the case of Li ⁺ ions increased dramatically.

In addition, referring to Figure 6 showing the XRD analysis for the mica after the hydrothermal reaction, when the reaction for more than 48 hours (Preparation Example 2, LiMC-2), the intensity change for the [002] peak appeared, In the case of dolomite according to Example 14, there was no change in d-spacing.

In addition, Figure 7 shows the results of analyzing the SEM photograph and EDX component analysis graph of mica according to hydrothermal reaction time for the mica powder according to Preparation Examples 1 to 3.

As a result of EDX measurement of FIG. 7, K element was significantly reduced to 0.57% in the mica powder (a) according to Preparation Example 2, which was subjected to hydrothermal treatment for 48 hours compared to before hydrothermal treatment, and Preparation Example 1, which was subjected to reaction for 72 hours or more. In the case of the mica powder (b) and the mica powder (c) according to Preparation Example 3, no peak was observed for the K element.

3. Effect analysis of mica content in hydrothermal reaction

As shown in Table 4, 0.5 parts by weight of the mica content based on 100 parts by weight of lithium nitrate aqueous solution in a fixed state, so that the cation exchange characteristics according to the change in the content of mica compared to the LiNO ₃ / H ₂ O solution can be confirmed. The analysis was performed using the mica powders of Preparation Examples 1, 4, and 5 changed to 1 part by weight and 3 parts by weight.

Sample name Hydrothermal reaction time
(hr) Hydrothermal reaction temperature
( ^o C) LiNO ₃ / H ₂ O
Weight ratio Mica content based on 100 parts by weight of lithium nitrate aqueous solution
(Parts by weight) Production Example 1
(LiMC-1) 72 170 1.7 One Preparation Example 4
(LiMC-4) 72 170 1.7 0.5 Preparation Example 5
(LiMC-5) 72 170 1.7 3

AAS analysis was performed to quantitatively analyze the degree of K ⁺ ion exchange according to the change in the content of mica, and the results are shown in Table 5 below.

Sample name K (%) Li (%) Preparation Example 1 (LiMC-1) 4.70 0.66 Preparation Example 4 (LiMC-4) 3.78 0.94 Preparation Example 5 (LiMC-5) 6.60 0.38 Preparation Example 14 7.61 0.02

Referring to Table 5, the content of mica is 0.5 parts by weight, 1 part by weight and 3 parts by weight based on 100 parts by weight of lithium nitrate aqueous solution (LiNO ₃ / H ₂ O), as in Preparation Examples 4, 1 and 5, respectively. As increased, the Li ⁺ ion content was found to be 0.94 parts by weight, 0.66 parts by weight, and 0.38 parts by weight based on 100 parts by weight of mica.

Here, the dolomite powder of Preparation Example 4 had the highest degree of cation exchange, and the XRD patterns for these are shown in FIG. 8.

Referring to FIG. 8, as the content of mica compared to the LiNO ₃ / H ₂ O solution was decreased, the intensity of the peak corresponding to the d-spacing of the [002] plane gradually decreased, and the new d-spacing due to cation exchange was decreased. The intensity of the corresponding peak gradually increased, and in Preparation Example 14 without performing hydrothermal treatment, no peak corresponding to new d-spacing was observed.

4. Comparative Analysis of MMT and MMT Surface-treated with Hydrophobization Agent

In preparation examples 7, 12 and 13, a 1: 1 mixture of dodecyltrimethylammonium bromide (DTAB), cetyltrimethylammonium bromide (CTAB) and polyethyleneimine / polyethylene oxide was added at 33.3 parts by weight based on 100 parts by weight of mica, respectively. Peeling and hydrophobicity characteristics were measured for the mica powder according to Preparation Example 14 which performed only the mica powder and heat treatment and Preparation Example 6 which performed only the hydrothermal treatment without heat treatment.

Referring to FIG. 9, (a) shows the XRD pattern for the dolomite powder according to Preparation Example 14, which performed only heat treatment, and a peak on a typical plane appeared at about 9.9 kPa, and (b) XRD patterns for hydrothermally treated muscovite powders according to Preparation Example 6 showed new d-spacing values at about 21 kPa and 11 kPa, showing the d-spacing values of the heat treated and untreated. There was little difference.

In addition, (c) is an XRD pattern of dolomite powder prepared according to Preparation Example 12 surface-treated with CTAB, indicating that the intensity of the peak is increased at 2 ^o or less as the peak from about 8 ^o is broadened. (D) is a mica powder according to Preparation 7 surface treated with DTAB, the peak coming out at 8 ^o shifted to a lower angle and the intensity of the peak at 2 ^o or less was stronger, (e ) Is the XRD pattern of the mica powder according to Preparation Example 13 surface treated with a mixed cation exchanger of PEO / PEI 1: 1 in the polymer form, and the exfoliation and dispersion stability were lower than those of Preparation Examples 7 and 12.

Through this, it was shown that the 1: 1 mixture of PEO / PEI and DTAB having a shorter hydrocarbon length than the CTAB hydrophobized the surface of the mica more effectively and increased the degree of cation exchange.

10 is prepared by hydrophobization treatment under the same treatment conditions as those of Preparation Examples 7, 12 and 13, except that Na ⁺ -MMT was used instead of Na ⁺ -MMT and dolomite without treatment with a hydrophobization agent. XRD patterns of Na ⁺ -MMT according to Examples 15-17 are shown.

Referring to FIG. 10, in the case of Na ⁺ -MMT not treated with a hydrophobization agent, a peak for basal spacing was found at 11.93 Hz, and in Example 16 treated with CTAB, the interlayer spacing was increased to 13.97 Hz. The peak intensity was very high, and in the case of Preparation 15 treated with DTAB, the interlayer spacing was increased to 15.095 Å and the peak was relatively broad. In the case of Na ⁺ -MMT, unlike mica, the surface treatment by a separate hydrophobic agent did not significantly affect the interlayer spacing change of MMT.

5. Characterization of Hydrophobized and Hydrophobized Mica by Varying DTAB Content

Based on 100 parts by weight of the lithium nitrate aqueous solution, the content conditions of the dolomite powder of Preparation Examples 7 to 11 according to the change of the content of DTAB are shown in Table 6 below.

Sample name DTAB content
(Parts by weight) Mica content in hydrothermal treatment
(Parts by weight) Preparation Example 8
(DTAB 16.7%) 0.167 One Preparation Example 7
(DTAB 33.3%) 0.333 One Preparation Example 9
(DTAB 66.7%) 0.667 One Preparation Example 10
(DTAB 100.0%) One One Preparation Example 11
(DTAB 133.3%) 1.333 One

As shown in Table 6, while increasing the content of DTAB from 16.7 parts by weight to 133.3 parts by weight based on 100 parts by weight of mica, the characteristics of the mica powder according to Preparation Examples 7 to 11 hydrophobized with DTAB was not treated with DTAB. Comparative analysis with dolomite powder according to Preparation Example 1 did not.

Referring to the results of the XRD pattern of FIG. 11, in the case of mica not treated with DTAB (Preparation Example 1), a peak of d-spacing was typically observed around 4 ^o and 8 ^o , but the DTAB content was increased. as according to the peak at 4 ^{o o} was reduced to 2.5, the peak intensity was decreased peak at 8 ^o as is reduced to 7 ^o.

This indicates that the separation process is further progressed and the interlayer spacing is increased by mica interlayer hydration, and the layers of mica are separated from each other through a hydrophobic process.

When the content of DTAB was 33.3 parts by weight or more (Preparation Examples 7, 9 to 11), there was no significant change. The DTAB content was 16.7 parts by weight (Preparation Example 8). Showed a completely different aspect from the other Preparation Examples 7, 9-11.

[Test Example 2] Characterization of the surface treatment composition containing mica and base coating agent

1. Dispersion Stability Analysis of Inorganic Substances in Compositions for Surface Treatment

Using an online turbidimeter (Turbiscan, Formulations, France) to observe the aggregation phenomenon and dispersion stability of the peeled inorganic material in the surface treatment composition according to Examples 1, 2, 7 to 9 and Comparative Example 1, Aggregation behavior was observed for 24 hours.

12 is a mica powder (a) according to Preparation Example 14, a mica powder according to Preparation Example 1 hydrothermally treated with LiNO ₃ (b), pure Na ⁺ -MMT (c), prepared by treatment with three kinds of hydrophobization agents Example 1 (b), Example 2 (e), Example 7 (d), and Example 8 (through the online turbidity data of the mica powder according to Examples 7 (e), 12 (d) and 13 (f)) f) The transmittance of the surface treatment composition according to Example 9 (a) and Comparative Example 1 (c) is measured.

The on-line turbidity was measured for 24 hours, and the precipitation behavior appeared in most samples over time, and compared to the composition for surface treatment according to Example 9, the inorganic material in the composition for surface treatment according to Example 1 Dispersion stability was shown to be better.

In addition, the dispersion stability of the inorganic substance was not good in the composition according to Comparative Example 1, the surface treatment composition according to Examples 2, 7 and 8 containing a mica powder according to Preparation Example 7 treated with DTAB The dispersion stability of the inorganic substance was the best in the composition for surface treatment of Example 2.

2. Analysis of Dispersion Stability of Mica Powder with Changes in DTAB Content

After 3 days in the surface treatment composition of Examples 2 to 6, the degree of precipitation of the mica powder was confirmed.

As a result, in the composition for surface treatment according to Examples 4, 5 and 6, no precipitation of the inorganic substance occurred for 3 days.

Figure 13 shows the online turbidity data of the inorganic material contained in the surface treatment composition of Examples 2 to 6 according to the change in the content of DTAB. As a result of measuring for 24 hours, the dispersion stability of the inorganic material in the surface treatment composition according to Example 2 was superior to the surface treatment composition according to Example 3, the composition for the surface treatment according to Examples 4 to 6 Showed little change in transparency.

3. Corrosion resistance analysis (salt spray test: SST)

In order to perform the steel sheet coating on the surface treatment compositions according to Examples 1 and 10 and Comparative Examples 1 to 3 with a bar coater, and to analyze the corrosion resistance of the coated steel sheet, a salt spray test was performed. It was carried out for hours.

In the coating of the steel sheet, no separate rust inhibitor was used. In order to perform a salt spray test on the resin layer, 10 wt% NaCl aqueous solution was sprayed for 30 hours, washed with water, and dried for 1 hour.

Here, the thickness of the resin layer formed on the UV coated steel sheet was uniform to 5 to 6 ㎛.

When comparing the before and after the SST test using the coated steel sheet, compared to the case of forming a resin layer using a pure UV coating solution according to Comparative Example 3, Examples 1, 10 and Comparative Example 1 and mica or MMT introduced The coated steel sheet coated with the resin layer using the surface treatment composition according to 2 showed more excellent corrosion resistance, and the coated steel sheet coated with the composition for surface treatment according to Example 10 showed the most excellent corrosion resistance.

The results are shown in Table 7 below.

UV coating condition Quality characteristic Amount of adhesion (㎛) Inorganic material Corrosion resistance (SST 72 hours) Example 1 5 ~ 6 Mica 1wt% of Preparation Example 1 Good (front white blue, red blue 1%) Example 10 5 ~ 6 3 wt% of mica in preparation example 1 Good (partly white blue, red blue 0%)) Comparative Example 1 5 ~ 6 Na ⁺ -MMT 1wt% Poor (8% of red blue) Comparative Example 2 5 ~ 6 Na ⁺ -MMT 3wt% Poor (37% of red blue) Comparative Example 3 5 ~ 6 - Poor (28% of red blue)

4. Structure Analysis of Resin Coating Layer

A solution obtained by mixing Na ⁺ -MMT powder of Preparation Example 15 surface treated with DTAB and a UV curable coating solution according to Preparation Example 18 was prepared as a surface treatment composition according to Comparative Example 4, and used for surface treatment according to Comparative Example 4. The dispersion state of the silica nanoparticles in the coating cross section of the coated steel sheet coated with the composition and the surface treatment composition according to Example 2 was measured by electron micrographs of the fracture surface.

Here, the resin layer formed on the coated steel sheet was coated with a thick film of 0.5 mm thickness in order to facilitate the sampling of the cross section of the film, and the resin layer was separated, and the microtoming (to 60 nm thickness) was performed for the internal observation of the cross section. microtoming), and then observed by TEM.

14 is a TEM photograph of a low magnification (a) and a high magnification (b) of the coated steel sheet coated with the composition for treating the surface according to Example 2, and a low magnification of the coated steel sheet coated with the composition for treating the surface according to Comparative Example 4 c) and high magnification (d) photographs.

Referring to FIG. 14, as in (a) and (b), the dorsal mica was present in a thin exfoliated form within 10 layers, and the mica was completely exfoliated into individual sheets. And intercalated between some layers and exfoliated. In addition, compared to the MMT shown in (c) and (d) plate size is maintained significantly larger, the flatness of the plate (flat) was found to be better.

1 is a schematic diagram showing the transmittance of an external material according to the type of material added to the inside of the polymer coating film,

Figure 2 shows a schematic diagram (a) showing the structural shape of pure mica, SEM picture (b) of mica and EDX component analysis table (c) of mica,

3 is a schematic view schematically showing a cross section of the surface-treated steel sheet and the resin coating layer according to an embodiment of the present invention,

Figure 4 shows the SEM photograph and EDX component analysis table of the peeled mica particles before (a) and (b) before the hydrothermal reaction,

Figure 5 shows the XRD pattern of the photographs of the peeled mica obtained after the hydrothermal reaction and the mica powder treated before (c), after (a) and lithium compound (b) heat treatment in the manufacturing process of the mica powder according to Preparation Example 1 Will,

Figure 6 shows the XRD pattern analysis of mica according to Preparation Examples 1 to 3 and 14,

7 shows SEM pictures and EDX analysis data of mica according to Preparation Examples 1 to 3,

8 shows XRD patterns of mica according to Preparation Examples 1, 4 and 5,

9 shows XRD patterns of mica according to Preparation Example 14 (a), Preparation Example 6 (b), Preparation Example 12 (c), Preparation Example 7 (d), and Preparation Example 13 (e).

10 shows the XRD patterns of pure Na ⁺ -MMT and Na ⁺ -MMT samples according to Preparation Examples 15-17,

11 shows changes in XRD patterns of mica according to Preparation Examples 1 and 7 to 11,

12 is Production Example 14 (a) And mica according to Preparation Example 1 (b), pure Na ⁺ -MMT sample (c), Preparation Example 12 (d), Preparation Example 7 (e) and Preparation Example 13 surface-treated with CTAB, DTAB and PEI / PEO, respectively. online turbidity data for mica according to (f),

13 is online turbidity data of inorganic materials contained in the composition for surface treatment according to Examples 2 to 6 divided according to the change in the content of DTAB,

14 is a low magnification (a) and high magnification (b) TEM photograph of the surface treatment composition according to Example 2 and a low magnification (c) and high magnification (d) TEM photograph of the surface treatment composition according to Comparative Example 4.

Claims (23)

Base coatings; And a mica contained in the base coating agent. The method of claim 1, The base coating agent is a photocurable coating agent comprising a photocurable acrylic oligomer, a reactive diluent and a photopolymerization initiator. The method of claim 1, Mica is a surface treatment composition comprising a component represented by the following formula (1): [Formula 1] X _m1 Y _m2 Z _m3 O _m4 (T) _m5 Where X is K, Na, Ca, Ba, Rb or Cs, m1 is 1 to 2; Y is Al, Mg, Fe, Mn, Cr, Ti or Li, m2 is 2-4; Z is Si, Al or SiAl, m3 is 4 to 8; m 4 is 10 to 20; T is OH, F or OHF and m5 is 2-4. The method of claim 1, Mica is a composition for surface treatment, characterized in that it comprises at least one selected from the group consisting of muscovite, cattle down, biotite, gold mica, red mica. The method of claim 1, Mica is a surface treatment composition characterized in that the mica. The method of claim 1, Mica is contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the base coating agent. The method of claim 1, Mica has an average plate length of 5 μm to 50 μm, and an average thickness of 1 nm to 200 nm. The method of claim 1, Mica is a surface treatment composition characterized in that a hydrophobization agent is introduced to the surface. The method of claim 8, The hydrophobic agent is a surface treatment composition, characterized in that it comprises at least one selected from the group consisting of cationic materials, nonionic materials and mixtures thereof. The method of claim 9, The surface is characterized in that the cationic material comprises at least one selected from the group consisting of cetyltrimethylammonium bromide, dodecyltrimethylammonium bromide, cetylpyridinium chloride, polyethoxylatetaloamine, benzalkonium chloride and benzetonium chloride Treatment composition. The method of claim 9, The cationic material is a surface treatment composition comprising at least one selected from the group consisting of cetyltrimethylammonium bromide and dodecyltrimethylammonium bromide. The method of claim 9, The nonionic substance is at least one selected from the group consisting of polyalkyleneimine, polyalkylene oxide, polyvinyl alcohol and polyvinylpyrrolidone. The method of claim 8, The hydrophobization agent is a surface treatment composition, characterized in that contained in 10 parts by weight to 140 parts by weight with respect to 100 parts by weight of mica. The method of claim 1, A composition for surface treatment, further comprising a silane coupling agent represented by Formula 2 below: [Formula 2] R-Si (A) ₃ In Chemical Formula 2, R is C ₁ to C ₁₂ alkylamine, vinyl group, acrylic group, epoxy group or urethane group, A is a C ₁ to C ₁₂ alkoxy or halogen element. A method for preparing a surface treatment composition according to any one of claims 1 to 14, comprising mixing mica with a base coating. The method of claim 15, Method for producing a surface treatment composition comprising the step of hydrothermally treating the mica. The method of claim 16, The hydrothermal treatment includes a first step of thermally treating mica; And a second step of reacting the mica obtained in the first step in a solution containing a lithium compound. The method of claim 17, In the second step, the reaction is a method for producing a composition for surface treatment, characterized in that carried out for at least 40 hours at a temperature of 150 to 200 ℃. The method of claim 17, In the second step, the lithium compound comprises at least one selected from the group consisting of lithium nitrate, lithium perchlorate and lithium sulfate. The method of claim 17, In the second step, 0.1 to 5 parts by weight of mica is mixed with 100 parts by weight of a solution containing a lithium compound to react. The method of claim 15, Method for producing a surface treatment composition comprising the step of surface-treating mica using a hydrophobization agent. The method of claim 21, Surface treatment comprises the steps of 1) mixing and cooling circulation of mica with a hydrophobic agent; And reacting the mixture obtained in step 1) with the base coating agent using an ultrasonic processor. 2. materials; And A surface-treated steel sheet comprising a resin coating layer formed on the substrate using the composition according to any one of claims 1 to 14.

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