KR101726095B1 - Chromium-free coating composition, producing method of chromium-free coating steel sheet using the same and chromium-free coating steel sheet produced thereby - Google Patents
Chromium-free coating composition, producing method of chromium-free coating steel sheet using the same and chromium-free coating steel sheet produced thereby Download PDFInfo
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
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Abstract
The present invention provides a chromium-free coating composition for forming a coating layer excellent in corrosion resistance, scratch resistance and stain resistance, a method for producing a chrome-free coating steel sheet using the chromium-free coating composition, and a chromium-free coating steel sheet produced thereby. 0.0001 part by weight to 5 parts by weight of a surfactant selected from the group consisting of a cationic surfactant, an anionic surfactant and a nonionic surfactant per 100 parts by weight of the hydrophobic silica airgel particles, a pH adjusting agent and water of 200 parts by weight to 50000 parts by weight Wherein when the anionic surfactant is compounded, the pH adjusting agent is added so that the pH of the chrome pre-coating composition is from 8 to 11, when the anionic surfactant is blended, Wherein the pH adjusting agent is added so that the pH of the composition is 2 to 6 and the pH adjusting agent is added so that the pH of the chrome precoating composition is 2 to 11 when the nonionic surfactant is compounded Chromium-free coating composition; Applying a chromium-free coating composition to the steel sheet; And curing the coated layer to form a coating layer; There is also provided a chromium-free coated steel sheet having a coating layer formed of a chromium-free coating composition on a steel sheet and a steel sheet.
Description
The present invention relates to a chromium-free coating composition, a chromium-free coated steel sheet using the same, and a chromium-free coated steel sheet produced thereby. More particularly, the present invention relates to a chromium-free coating composition having excellent corrosion resistance, scratch resistance and stain resistance, a chromium-free coating steel sheet using the same, and a chrome-free coating steel sheet produced thereby.
Metal plates widely used for automobiles, home appliances, and building materials have many advantages, but suffer from many problems due to their weak corrosion resistance. Commonly used metal steel sheets include cold rolled steel sheets, hot rolled steel sheets, galvanized steel sheets, zinc plated alloy coated steel sheets, aluminum coated steel sheets, and aluminum alloy coated steel sheets. Therefore, the surface treatment is applied to such a metal sheet to secure the corrosion resistance to the metal surface. In general, a surface treatment technique widely used as a conventional technique includes a chromate film coating method using chromium as a main component. As the main chromate treatment, there are an electrolytic chromate and a coating type chromate. Among them, the electrolytic chromate treatment uses a treatment liquid in which hexavalent chromium is used as a neutral component and various anions such as sulfuric acid, phosphoric acid, boric acid and halogen are added A method of electrolyzing a metal plate to a negative electrode is generally carried out. On the other hand, the coating type chromate treatment is generally carried out by immersing a metal plate in a treatment solution in which inorganic colloid and inorganic ions are added to a solution in which a part of hexavalent chromium is reduced in advance, or spraying such treatment solution onto a metal plate have. However, this method has been environmentally restricted due to the toxicity of hexavalent chromium contained in the chromate treatment liquid. In the future, surface treatment methods using hexavalent chromium in all industrial fields will no longer be used due to human hazards and environmental pollution problems.
In order to overcome such a problem, a chrome-free coated steel sheet which does not contain hexavalent chromium based on a water-soluble coating solution and satisfies the properties required for various steel sheets including corrosion resistance has been developed. However, efforts have been made to provide more high performance and new functionality to chrome-coated steel sheets due to technological advancement.
In general, the chrome-free coated steel sheet is vulnerable to corrosion because it is made of a water-soluble thin film coating, and when the steel sheet is transferred or used, scratches easily occur on the surface of the steel sheet and the surface of the steel sheet is easily contaminated. The present invention solves the problem of water-soluble thin film coating of such conventional chrome precoated steel sheets.
It is an object of the present invention to provide a chromium-free coating composition which forms a coating layer excellent in corrosion resistance, scratch resistance and stain resistance.
An object of the present invention is to provide a method for producing a chrome-free coated steel sheet excellent in corrosion resistance, scratch resistance and stain resistance by applying a chromium-free coating composition to a steel sheet.
An object of the present invention is to provide a chromium-free coated steel sheet having a coating layer excellent in corrosion resistance, scratch resistance and stain resistance.
The present invention relates to a composition comprising 0.0001 part by weight to 5 parts by weight of a surfactant selected from the group consisting of a cationic surfactant, an anionic surfactant and a nonionic surfactant per 100 parts by weight of hydrophobic silica airgel particles, To 50,000 parts by weight,
In the case where the cationic surfactant is compounded, the pH adjusting agent is added so that the pH of the chrome precoating composition is 8 to 11, when the anionic surfactant is blended, 2 to 6 and the non-ionic surfactant is blended, the pH adjusting agent is added so that the pH of the chrome pre-coating composition is from 2 to 11, the chromium free coating comprising an aqueous dispersion of hydrophobic silica airgel particles Lt; / RTI >
The pH adjusting agent may be selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, sodium hydroxide, ammonia, and amine.
The chromium-free coating composition preferably comprises an aqueous dispersion of the hydrophobic silica aerogel particles so that the content of the hydrophobic silica aerogel particles is 0.01 wt% to 5 wt% based on the solid content of the chromium-free coating composition.
The present invention relates to a method for preparing a chromium-free coating composition, And curing the applied chromium-free coating composition to form a coating layer.
The present invention relates to a steel plate; And a chromium-free coating steel sheet having a coating layer formed of a chromium-free coating composition according to the present invention on a steel sheet.
Since the hydrophobic silica airgel is stably dispersed and impregnated by the surfactant and pH control, the chromium-free coating composition of the present invention is excellent in solution stability and can be easily coated in the same manner as the conventional chrome precoating method, It is applicable to the mass production of metal plate materials. Further, the present invention can ensure the corrosion resistance, scratch resistance and stain resistance of a steel sheet by coating a steel sheet with a chrome precoat composition containing hydrophobic silica airgel particles.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of a hydrophobic silica aerogel particle included in the chrome-free coating composition of the present invention. FIG.
2 is a schematic view showing a process for producing a chromium-free coated steel sheet using the chromium-free coating composition of the present invention.
3 is a schematic view showing a coating layer formed of a chromium-free coating composition according to the present invention on a steel sheet.
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below.
According to an embodiment of the present invention, there is provided a hydrophobic silica aerogel particle comprising, per 100 parts by weight of the hydrophobic silica airgel particles, 0.0001 to 5 parts by weight of a surfactant selected from the group consisting of a cationic surfactant, an anionic surfactant and a nonionic surfactant, 200 < / RTI > parts by weight to 50,000 parts by weight of water,
In the case where the cationic surfactant is compounded, the pH adjusting agent is added so that the pH of the chrome precoating composition is 8 to 11, when the anionic surfactant is blended, 2 to 6 and wherein the pH adjusting agent is formulated such that the pH of the chrome precoat composition is between 2 and 11 so as to provide a chrome precoat composition comprising an aqueous dispersion of silica airgel particles / RTI > Hereinafter, the composition of the chrome-free coating composition of the present invention will be described.
Fig. 1 shows a schematic diagram of the hydrophobic silica airgel particles incorporated in the chrome-free coating composition of the present invention. As shown in FIG. 1, the hydrophobic silica airgel particles to be incorporated in the chrome pre-coating composition of the present invention are in the form of a cluster (10), and
As described above, innumerable nanopores are formed inside the airgel particle clusters, and the average size of the nanopores is 0.01 nm to 300 nm. When the average size of the nano pores is less than 0.01 nm, it is difficult to obtain effects on the corrosion resistance, scratch resistance and stain resistance due to the minute pores, and if the average size of the nano pores exceeds 300 nm, The effect of raising the roughness is lost and it is difficult to realize the characteristics to be achieved.
In addition, the silica airgel particles are hydrophobized on the surface of the particles, and any hydrophobic silica airgel known in the art can be used. The hydrophobic silica aerogels can be, for example, hydrophobic chemical substances such as silane having a hydrophobic functional group such as a C1 to C12 alkyl group, a fluorine group, etc., although the airgel surface is coated with a hydrophobic chemical substance. The silica airgel particles preferably have an average particle size of 100 nm to 1 mm. When the average particle size is less than 100 nm, it is difficult to obtain effects on corrosion resistance, scratch resistance and stain resistance. When the average particle size is 1 mm or more, the physical properties of the chrome precoat layer, such as workability, adhesiveness, corrosion resistance, .
Such a hydrophobic silica airgel particle has hydrophobic properties and strong hardness. By using the hydrophobic silica airgel particles in a chrome precoat composition, it is expected that the coating layer formed of the chrome precoat composition has improved corrosion resistance, scratch resistance and stain resistance. However, the hydrophobic silica airgel particles have a hydrophobic surface and are difficult to disperse in an aqueous solution as a very fine fine powder.
Accordingly, the present invention is characterized in that the hydrophobic silica airgel particles are stably dispersed or impregnated in water and used in a chromium-free coating composition.
Such hydrophobic silica aerogels are stably dispersed and impregnated in water by using a surfactant and a pH adjusting agent. It is possible to prepare an aqueous dispersion of hydrophobic silica airgel particles in which the hydrophobic silica aerogels are stably dispersed and impregnated by adjusting the pH to an optimal pH range and dispersing the hydrophobic silica aerogels in an aqueous solution depending on the surfactant to be used.
For example, first hydrophobic silica airgel particles are dispersed in water. Thereafter, the hydrophobic silica aerogel particles are stably impregnated with the surfactant in water by adding a surfactant and adjusting the pH with a pH regulator. Water is used in an amount of 200 to 50,000 parts by weight based on 100 parts by weight of the silica airgel particles. If the content of water is less than 100 parts by weight, the amount of the solvent in which the silica airgel particles are dispersed or impregnated is insufficient, and if it exceeds 50000, the amount of water is increased and the effect of the silica airgel particles may not be realized sufficiently.
That is, the hydrophobic silica aerogel particles are physically mixed with the aqueous solution while stirring. However, with this physical agitation, the hydrophobic silica aerogels are only dispersed in water, and most of the particles float on the water. However, as the surfactant is added and the pH is adjusted, the nano pores of the airgel are impregnated with water by the action of the surfactant, and the airgel is uniformly dispersed in the water. When the aerogels float on the water, they appear white, but become uniformly dispersed in the water and become transparent.
As the surfactant, a cationic surfactant, an anionic surfactant or a nonionic surfactant may be used. Depending on the type of surfactant used, the pH range to be controlled varies. This is because, depending on the kind of the surfactant, the hydrophobic aerogel silica is effectively impregnated in an aqueous solution at a specific pH range.
When a cationic surfactant is combined, the pH is adjusted to between 8 and 11. When an anionic surfactant is formulated, the pH is adjusted to 2 to 6. And when the non-ionic surfactant is blended, the pH is adjusted to 2 to 11.
Examples of the cationic surfactant include dodecyltrimethylammonium bromide, cetyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, 5-bromo 5-nitro-1,3-dioxane, dimethyl dioctadecylammonium chloride, Cetrimonium bromide, and dioctadecyldimethylammonium bromide, but are not limited thereto. Examples of anionic surfactants include sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, ammonium lauryl sulfate, sodium lauryl ether sulfate, sodium mymesulfate, dioctyl sodium sulfosuccinate, perfluorooctane But are not limited to, sulfonate, perfluorobutane sulfonate, linear alkylbenzene sulfonate, sodium stearate, perfluorononanoate, perfluorooctanoate, and the like. Examples of the nonionic surfactant include polyoxyethylene sorbitan laurate, octaethylene glycol monododecyl ether, pentaethylene glycol monododecyl ether, polyoxypropylene glycol, decyl glucoside, lauryl glucoside, octyl glucoside, polyoxy Ethylene glycol octylphenol ether, polyoxyethylene glycol alkyl phenol ether, dodecyldimethylamine oxide, and the like, but are not limited thereto. Among these surfactants, dodecyltrimethylammonium bromide, cetyltrimethylammonium bromide and the like can be preferably used.
The surfactant is formulated in an amount of 0.0001 to 5 parts by weight of a surfactant per 100 parts by weight of the hydrophobic silica airgel particles. If the content of the surfactant is less than 0.0001 part by weight, it is difficult to impregnate the hydrophobic silica airgel particles into the aqueous solution. If the content of the surfactant is more than 5 parts by weight, the solution stability may be impaired when mixed with the chrome precoating solution.
The pH can be adjusted by adding a small amount of strong acid or strong alkali. Examples of the pH adjuster include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, sodium hydroxide, ammonia, and amine. If necessary, these may be used alone or in combination of two or more.
Further, the hydrophobic silica aerogel particles are stirred so as to be stably dispersed and impregnated into the water by the surface activity. The stirring speed is preferably about 50 rpm to about 50000 rpm. If the stirring speed is less than 50 rpm, a significant dispersing effect can not be obtained. If the stirring speed is more than 50000 rpm, the dispersion performance value of almost the same level converges, so that the increase in the effect is insignificant.
The stirring method is not particularly limited, and any conventionally known physical stirring method capable of uniformly dispersing and impregnating hydrophobic silica airgel particles in an aqueous solution can be used. The agitation time is also not specified and is performed until the airgel is sufficiently impregnated with water. This makes it easy to judge visually the color of the airgel becomes transparent.
An aqueous dispersion of hydrophobic silica aerogel particles may be prepared as described above, but is not limited thereto.
The aqueous dispersion of the hydrophobic silica airgel particles thus prepared is blended with the chrome precoating solution and used as the chrome precoat composition. The chromium-free coating solution is not particularly limited, and may be any coating solution conventionally used in chromium-free coatings in the art.
The aqueous dispersion of the hydrophobic silica airgel particles can be used as a chrome precoating composition by mixing the chrome precoat composition with a chrome precoating solution such that the content of the hydrophobic silica airgel particles is 0.01 wt% to 5 wt% based on the solid content have.
The content of the hydrophobic silica airgel particles is less than 0.01% by weight and the corrosion resistance, scratch resistance and stain resistance caused by the hydrophobic silica airgel particles are hard to be exhibited. When the content is more than 5% by weight, Physical properties, such as processability, coating adhesion, and the like, may be compromised. The chromium-free coating composition of the present invention may be a water-soluble chromium-free coating composition.
The water-soluble chromium pre-coating solution may generally include a main resin, a negative resin, a hardener, a metal complex compound, a corrosion inhibitor, a lubricant additive and the like. For example, 0 to 50 parts by weight of an asymmetric resin per 100 parts by weight of the main resin; 0.1 to 20 parts by weight of a curing agent; 0.5 to 20 parts by weight of an organic metal complex compound; 1 to 10 parts by weight of a corrosion inhibitor; 0.01 to 5 parts by weight of a lubricant.
Although the type of the main resin is not limited, the main resin may include an aqueous dispersion acrylic resin, an aqueous dispersion urethane resin, an aqueous dispersion acryl-urethane resin, an aqueous dispersion silicone modified polyolefin resin, an aqueous dispersion polyolefin resin, A water-dispersed acrylic-urethane resin can be used. The above-mentioned base resins may be used singly or in combination of two or more thereof, if necessary. By using the water-dispersed acrylic resin, more excellent coating layer characteristics such as corrosion resistance, alkali resistance, gloss, and hardness can be realized.
The main resin preferably has a weight average molecular weight (Mw) of 1,000 to 100,000. If the Mw is less than 1,000, the chemical resistance and scratch resistance of the coating are disadvantageous. If the Mw exceeds 100,000, the viscosity is so high that securing the workability of the coating is difficult and it is difficult to obtain a beautiful surface appearance.
Although the kind of the subbing resin is not limited, examples of the subbing resin include water-dispersible urethane resin, water-dispersed acrylic resin, water-dispersed acrylic-urethane resin, water-dispersible silicone-modified polyolefin resin, A water-dispersed acrylic-urethane resin can be used. These sub-resin may be used singly or in combination of two or more thereof, if necessary. By using the water-dispersible urethane resin in the present invention, more excellent coating layer characteristics could be realized.
The negative-working resin preferably has a weight-average molecular weight (Mw) of 1,000 to 100,000. If the Mw is less than 1,000, the chemical resistance and scratch resistance of the coating are disadvantageous. If the Mw exceeds 100,000, the viscosity is so high that securing the workability of the coating is difficult and it is difficult to obtain a beautiful surface appearance.
The content of the subbing resin is not particularly limited, but may be 0 to 50 parts by weight per 100 parts by weight of the main resin. The unsubstituted resin may be used as needed and may not be used, and if it exceeds 50 parts by weight, the resin may inhibit the surface exposure of the hydrophobic silica aerogel particles. When the negative resin is blended, the physical properties of the main resin can be complemented and controlled by using a negative resin different from the negative resin.
Although the main resin may be used alone, for example, when the acrylic resin is used alone as the main resin, ductility of the surface coating layer may be deteriorated and the coating layer may be peeled off when the steel sheet is processed. When the urethane resin is used alone, the ductility of the surface coating layer is increased, but the corrosion resistance of the coating layer may be lowered. Therefore, it is preferable to mix different kinds of the main resin and the sub resin in consideration of the physical properties of the coating layer. Those skilled in the art can appropriately adjust the types of resin to be used and the blending amount thereof in order to realize the intended physical properties in the coating layer.
Although the kind of the curing agent is not limited, one or more curing agents selected from the group consisting of melamine-based, carbodiimide-based, block isocyanate-based, aziridine-based, oxazoline-based and phosphate based ones can be used, Aziridine group and / or carbodiimide group may be used. More specifically, a carbodiimide group may be used. The carbodiimide system not only provides excellent solution stability but also exhibits better coating layer properties.
The content of the curing agent is not particularly limited and may be 0.1 to 20 parts by weight per 100 parts by weight of the main resin. If the content is less than 0.1 part by weight, the curing reaction of the coating layer does not occur properly and the physical properties of the coating layer are not properly realized. If the content exceeds 20 parts by weight, unreacted curing agent which has not reacted with the resin remains, Can be reduced.
The chromium pre-coating solution may include an organic metal complex compound imparting corrosion resistance and improving the hardenability of the coating layer. Although there is no particular limitation on the kind of the organometallic complex compound, for example, at least one organometallic complex compound selected from the group consisting of a silane coupling agent, a titanium coupling agent and a zirconium coupling agent may be used.
Specific examples of the silane-based coupling agent include vinyltriethoxysilane, 3-glycyloxypropyltrimethoxysilane, 3-glycyloxypropyltriethoxysilane, 3-glycyloxypropylmethyldimethoxysilane, N- 2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and mixtures thereof. As the titanium-based coupling agent, titanium acetylacetonate, iso-butoxy titanium ethylacetoacetate, tetraisopropyl titanate, tetranormal butyl titanate, and mixtures thereof can be used. As the zirconium-based coupling agent, tetranormal-propylzirconate, tetranormal-butylzirconate, triethanolamine zirconate, hexafluorozirconate, and mixtures thereof can be used.
The content of the organic metal complex compound is not particularly limited and may be 0.5 to 20 parts by weight per 100 parts by weight of the main resin. If the content is less than 0.5 part by weight, the adhesion and corrosion resistance between the surface treatment composition and the steel sheet may be deteriorated. If the content exceeds 20 parts by weight, no further increase in the effect is obtained, and the storage stability of the chromium- There is concern about deterioration.
The type of the corrosion inhibitor (rust inhibitor) included in the composition of the present invention is not particularly limited and at least one selected from the group consisting of phosphoric acid type, aluminum salt type, molybdenum type, fluorine type, vanadium type, cerium type and selenium type can be used have.
The content of the corrosion inhibitor is not particularly limited and may be 1 to 10 parts by weight per 100 parts by weight of the main resin. If the content is less than 1 part by weight, it is difficult to secure corrosion resistance, and even if it exceeds 10 parts by weight, further improvement in corrosion resistance can not be expected.
The lubricant contained in the composition of the present invention can be used for improving processability and imparting self-lubricating properties. The type of the lubricant is not particularly limited and may be selected from the group consisting of paraffin wax, olefin wax, carnauba wax, polyester wax, polyethylen wax, polypropylene wax, polyethylene-Teflon modified wax and polytetrap wax ≪ / RTI > may be used. Specifically, polyethylene wax, polyethylene-Teflon wax and polytetron wax can be used, and more specifically, polyethylenethephon wax can be used.
The content of the lubricant is not particularly limited and may be 0.01 to 5 parts by weight per 100 parts by weight of the main resin. If the content is less than 0.01 part by weight, it is difficult to expect a lubricating effect. If the content is more than 5 parts by weight, corrosion resistance, alkali resistance and heat resistance of the coating layer may be lowered due to excessive lubricant particle distribution on the surface of the coating layer.
The chrome free solution may have a solid content of 5 wt% to 30 wt%. When the solid content is less than 5% by weight, the physical properties such as workability and adhesion of the coating layer and the material are not ensured. When the solid content is more than 30% by weight, the viscosity is high and, in view of workability by a conventional coating method such as roll coating It becomes disadvantageous.
The chrome free solution preferably has a viscosity of 0.8 cP to 3 cP. The lower the viscosity, the better the coating operation. However, it is difficult to prepare an aqueous solution based coating solution with a viscosity of 0.8 cP or less, and if the rheological property improving solution is excessively added, the stability of the solution is problematic. When the viscosity exceeds 3 cP, it is difficult to ensure workability by a conventional coating method such as roll coating and there is a problem that the uniformity of the coating is lowered.
The solids and / or viscosity of the chrome free solution can be controlled with water.
According to another embodiment of the present invention, there is provided a method of manufacturing a steel plate, And curing the applied chrome pre-coating composition to form a coating layer. FIG. 2 is a schematic view showing a process for producing a chromium-free coating steel sheet using the chromium-free coating composition of the present invention. In the method for producing a chrome-free coating steel sheet of the present invention, the matters described in the above-mentioned chromium-free coating composition are applied equally.
The steel sheet is not particularly limited and includes, for example, a cold rolled steel sheet, a hot rolled steel sheet, a galvanized steel sheet, a zinc alloy coated steel sheet, a galvanized electroplated steel sheet, a hot dip galvanized steel sheet, an aluminum coated steel sheet, cobalt, molybdenum, tungsten, A coated steel sheet having a plated layer containing an impurity or a dissimilar metal which is an impurity such as titanium, aluminum, manganese, iron magnesium, tin, copper or a mixture thereof, or an aluminum alloy containing silicon, copper magnesium, iron, manganese, titanium, zinc, Chromium-treated steel sheets, fingerprint steel sheets, rare earth surface treated steel sheets, cold-rolled steel sheets, or hot-rolled steel sheets may be used.
The method of applying the chromium-free coating composition of the present invention to the steel sheet is not particularly limited and may be applied by any method conventionally used in this technical field. For example, it can be applied to a steel sheet by a conventional method such as a roll-rotor method, a shower-squeeze method, a deposition method, and a spray method.
The chromium-free coating composition may be coated such that the thickness of the dried coating layer is 0.1 to 500 μm. If the dry coating layer is less than 0.1 탆, the hydrophobic silica aerogel particles are hardly fixed on the surface of the steel sheet. If the dry coating layer is more than 500 탆, the hydrophobic silica aerogel particles are embedded in the coating layer.
After coating, the chrome precoat composition is cured. The curing can be performed at a steel sheet surface temperature of 30 to 300 캜. If the surface temperature of the steel sheet is less than 30 캜, the resin is not sufficiently cured, and it is difficult to expect a sufficient effect due to the formation of the coating layer. If the surface temperature exceeds 300 캜, The overall performance may be degraded.
According to still another embodiment of the present invention, there is provided a steel plate comprising: a steel plate; And a chromium-free-coated steel sheet having a coating layer formed of the chromium-free coating composition of the present invention on a steel sheet. FIG. 3 is a schematic view showing a coating layer formed of a chromium-free coating composition according to the present invention on a steel sheet. 3, the coating layer formed of the chromium-free coating composition according to the present invention includes a
In the chrome-free coating steel sheet of the present invention, the same items as described above for the chromium free-coating composition and the method for manufacturing a printed steel sheet are applied. As described above, the coating layer formed of the chromium-free coating composition of the present invention imparts excellent corrosion resistance, scratch resistance and stain resistance to the steel sheet.
Hereinafter, the present invention will be described more specifically by way of specific examples. The following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited thereto.
1. Manufacture of chrome-free coated steel sheet
(Example 1)
5 g of hydrophobic silica aerogel particles were mixed with 100 ml of water. The hydrophobic silica airgel particles had an average particle size of 5 μm, an average pore size of 5 nm, and a surface coated with methyl silane. Thereafter, cetyltrimethylammonium bromide surfactant was added in an amount of 0.5 g based on the weight of the hydrophobic silica aerogel particles, and stirring was continued at 300 rpm. After stirring for 5 minutes, the pH was adjusted to 8.5 by the addition of NaOH. The aqueous dispersion of hydrophobic silica airgel particles thus prepared was stirred for 30 minutes at 300 rpm, mixed with a chrome precoating solution, and further stirred for 30 minutes to prepare a chrome precoat composition. The content of aerogels with respect to the total solid content of the chrome-free coating composition was adjusted to 0.01 wt%.
10 parts by weight of water-dispersed acrylic resin (Mw 10,000), 3 parts by weight of water-dispersed urethane resin (Mw 10,000), 1.5 parts by weight of carbodiimide curing agent, 2 parts by weight of glycyloxypropyltrimethoxysilane, 1 part by weight of a phosphoric acid corrosion inhibitor, 0.5 part by weight of a lubricant and water in a remaining amount. The chrome-free coating solution had a solid content of 20% by weight and a viscosity of 1.2 cP.
The chrome precoat composition was applied to a galvanized steel sheet and cured. The chrome-free coating composition was applied so that the amount of the dried coating layer was 8 占 퐉 to 10 占 퐉, and drying of the applied composition was performed within 5 seconds at a peak metal temperature (PMT) of 120 占 폚.
(2) Examples 2 to 7 and Comparative Examples 1 to 6
In Examples 2 to 7 and Comparative Examples 2 to 6, the chrome precoating composition was prepared in the same manner as in Example 1, except that the content of the airgel content with respect to the total solid content was changed as shown in the following Table 1, A composition was prepared.
In Comparative Example 1, a chrome precoat composition was prepared in the same manner as in Example 1, except that nano silica particles were used instead of the hydrophobic silica aerogel particles.
2. Property evaluation
The corrosion resistance, scratch resistance and stain resistance of the chrome-free coated steel sheets of the above-described Examples and Comparative Examples were evaluated as follows and are shown in Table 1 below.
(1) Evaluation of corrosion resistance
5% by weight of salt water was sprayed in a Salt Spray Tester at 35 ° C for 196 hours, and the area where the white rust was generated was observed and evaluated as follows.
Excellent (○): Less than 5% of white rust
Good (△): White rust less than 5% and less than 10% of area
Defective (x): more than 10% of area
(2) Evaluation of scratch resistance
The pencil hardness test was carried out to evaluate the scratch resistance of the coating layer. A pencil having various hardness grades was scratched on a coated steel sheet with a constant force, and the scratch resistance of the coating was evaluated by displaying a pencil value having a hardness at which the pencil marks start to appear. 6B-5B-4B-3B-2B-B-HB-F-H-2H-3H-4H-5H-6H.
Excellent (∘): Pencil hardness value of 3H to 6H
Good (?): Pencil hardness value of B to 2H
Poor (x): Pencil hardness value of 6B to 2B
(3) Evaluation of stain resistance
The stain resistance is a value indicating the degree of adhesion of foreign matter to the coating layer, and the lower the surface energy of the coating, the more the stain resistance increases. The stain resistance was evaluated by measuring the contact angle of the coating layer formed on the steel sheet with respect to water.
Excellent (∘): The contact angle is 100 ° or more
Good (?): The contact angle is 80 ° or more and less than 100 °
Poor (x): contact angle less than 80 °
(4) Evaluation of solution stability
For solution stability, the solution was left in a thermostat at 50 ° C. for 48 hours, and the extent of precipitation in the solution was checked and evaluated.
Excellent (∘): Maintain viscosity within 2 cP (initial 1.2 cP)
Poor (x): viscosity increased above 2 cP (initial 1.2 cP)
10, 12 ... hydrophobic silica aerogel particles, 11 ... nano pore
13 ...
31 ...
Claims (6)
Wherein the surfactant is a cationic surfactant and the pH adjuster is added so that the pH of the chrome precoat composition is from 8 to 11. The chrome precoat composition of claim 1,
Wherein the surfactant is an anionic surfactant and the pH adjuster is added so that the pH of the chrome precoat composition is 2 to 6. The chrome precoat composition of claim 1,
And then curing the coated layer to form a coating layer.
A chromium-free coated steel sheet having a coating layer formed of the chromium-free coating composition of claim 1 or 2 on a steel sheet.
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Cited By (4)
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| KR20190081423A (en) * | 2017-12-29 | 2019-07-09 | 주식회사 동진쎄미켐 | Coating composition with reduced fingerprint visibility and method of making coating layer using same |
| EP3783076A4 (en) * | 2018-04-16 | 2021-03-31 | Showa Denko Materials Co., Ltd. | Method for suppressing corrosion under heat-insulating material, and paste for suppressing corrosion under heat-insulating material |
| US20220010147A1 (en) * | 2018-11-12 | 2022-01-13 | Posco | Organic-inorganic composite coating composition, and zinc-plated steel sheet surface-treated using same |
| KR20220086356A (en) * | 2020-12-16 | 2022-06-23 | 주식회사 포스코 | Coating composition containing silicate and galvanized steel sheet coated using the same |
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| US20070027232A1 (en) * | 2005-07-27 | 2007-02-01 | Chemcoat, Inc. | Coating compositions incorporating nanotechnology and methods for making same |
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| KR20040006464A (en) * | 2002-07-12 | 2004-01-24 | 주식회사 하이닉스반도체 | Method for forming inductor of semiconductor device |
| US20070027232A1 (en) * | 2005-07-27 | 2007-02-01 | Chemcoat, Inc. | Coating compositions incorporating nanotechnology and methods for making same |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190081423A (en) * | 2017-12-29 | 2019-07-09 | 주식회사 동진쎄미켐 | Coating composition with reduced fingerprint visibility and method of making coating layer using same |
| KR102571619B1 (en) | 2017-12-29 | 2023-08-28 | 주식회사 동진쎄미켐 | Coating composition with reduced fingerprint visibility and method of making coating layer using same |
| EP3783076A4 (en) * | 2018-04-16 | 2021-03-31 | Showa Denko Materials Co., Ltd. | Method for suppressing corrosion under heat-insulating material, and paste for suppressing corrosion under heat-insulating material |
| JPWO2019202635A1 (en) * | 2018-04-16 | 2021-04-22 | 昭和電工マテリアルズ株式会社 | Method for suppressing corrosion under heat insulating material and paste for suppressing corrosion under heat insulating material |
| JP7196907B2 (en) | 2018-04-16 | 2022-12-27 | 昭和電工マテリアルズ株式会社 | Method for suppressing corrosion under insulation and paste for suppressing corrosion under insulation |
| US20220010147A1 (en) * | 2018-11-12 | 2022-01-13 | Posco | Organic-inorganic composite coating composition, and zinc-plated steel sheet surface-treated using same |
| KR20220086356A (en) * | 2020-12-16 | 2022-06-23 | 주식회사 포스코 | Coating composition containing silicate and galvanized steel sheet coated using the same |
| KR102590094B1 (en) * | 2020-12-16 | 2023-10-18 | 주식회사 포스코 | Coating composition containing silicate and galvanized steel sheet coated using the same |
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