WO2014021520A1

WO2014021520A1 - Organic-inorganic hybrid coating solution composition and organic-inorganic hybrid coated steel sheet

Info

Publication number: WO2014021520A1
Application number: PCT/KR2012/011541
Authority: WO
Inventors: Kyoung-Pil KO; Rho-Bum Park; Jong-Sang Kim; Jung-Hwan Lee
Original assignee: Posco
Priority date: 2012-08-03
Filing date: 2012-12-27
Publication date: 2014-02-06
Also published as: US20150299472A1; EP2880108A1; JP5927347B2; KR101449109B1; CN104520393A; CN104520393B; JP2015531818A; EP2880108A4; EP2880108B1; KR20140018736A

Abstract

Provided are an organic-inorganic hybrid coating solution composition including 12 wt% to 36 wt% of a urethane-acryl hybrid resin, 8 wt% to 24 wt% of a nanosilicate-phenoxy hybrid resin, and 40 wt% to 80 wt% of an inorganic-based anti-corrosion agent based on a solid content, and an organic-inorganic hybrid coated steel sheet having a coating layer formed with the coating solution composition. According to the present invention, a coating solution composition having excellent solution stability and a coated steel sheet having improved corrosion resistance, solvent resistance, and conductivity may be provided.

Description

[DESCRIPTION]

[invention Title]

ORGANIC-INORGANIC HYBRID COATING SOLUTION COMPOSITION AND ORGANIC-INORGANIC HYBRID COATED STEEL SHEET

[Technical Field]

[0001] The. present invention relates to an organic-inorganic hybrid coating solution composition and an organic-inorganic hybrid coated steel sheet using the same.

[Background Art]

[0002] Surface treatment methods, in which zinc-plated steel sheets and zinc-based alloy-plated steel sheets, aluminum- plated steel sheets, aluminum-based alloy-plated steel sheets, cold-rolled steel sheets, and hot-rolled steel sheets used for automotive materials, household appliances, or building materials are coated with a chromate coating layer having chromium as a main component in order to provide corrosion resistance and plating adhesion, have been generally performed in the related art. Major chromate treatments may be classified as an electrolytic type chromate treatment and a coating type chromate treatment. With respect to the electrolytic type chromate treatment, a method of cathodic electrolysis of a metal plate has been generally used by employing a treatment solution having hexavalent . chromium as a main component and other various negative ions, from sources such as sulfuric acid, phosphoric acid and boric acid, as well as halogens, added thereto. Meanwhile, with respect to the coating type chromate treatment, a method of dipping a metal plate in a treatment solution or spraying . the treatment solution onto the metal plate has generally been used by employing a treatment solution having inorganic colloids and inorganic ions added to . a solution having a portion of hexavalent chromium reduced into trivalent chromium.

[0003] In the case that these methods are used, various safety measures may be required in working environments as well as waste water treatment processes, due to the toxicity of hexavalent chromium (Cr) contained in a chromate treatment solution, and the recycling and waste disposal of automobiles, household appliances, or building materials having the foregoing surface treated metal used therein may also cause hazards to the human body and environmental contamination issues.

[0004] Therefore, steel mills have focused o developing Cr- free surface-treated steel sheets . satisfying various properties required in addition to corrosion resistance, while as not having hexavalent chromium contained therein.

[0005] In addition, since the price of zinc, a main material of a plating layer in a plated steel sheet, has been rapidly increasing, research into replacing zinc with other elements, decreasing a content of zinc or reducing, a coating weight thereof has been continuously conducted by various steel mills [0006] A technique of using zinc aluminum-magnesium (ZAM) has been proposed as a representative technique. This technique uses a smaller amount of zinc in comparison to the related art and aims at using common aluminum . or magnesium as a main component of the plating layer. With respect to such alloy- plated steel sheets, a predetermined level of corrosion resistance or greater may be secured, but operability, surface appearance, high-temperature and high-humidity resistance, and weldability may be deteriorated.

[0007] Also, a technique of reducing a coating weight of a plated steel sheet has been suggested as another method. However, coating weight is a factor greatly affecting corrosion inhibition and long-term rust resistance of metal. Accordingly, in a hot-dip galvanized steel sheet, the time required for red rust to be generated, i.e., corrosion resistance, may increase as zinc coating weight increases. Thus, higher manufacturing costs may be incurred by steel mills because zinc coating weight may not be able to be reduced due to the decrease in corrosion resistance in which red rust is facilitated.

[0008] Therefore, there is a need for research into a technique able to compensate for a decrease in corrosion resistance as well as reducing zinc coating weight and not using a Cr-containing solution.

[Disclosure]

[Technical Problem]

[0009] An aspect of the present invention provides a coating solution composition able to compensate for a decrease in corrosion resistance (SST) despite a reduction in a zinc coating weight and a coated steel sheet using the same.

[Technical Solution]

[0010] According. to an aspect of the present invention, there is provided an organic-inorganic hybrid coating solution composition including: 12 wt% to 36 wt% of a urethane-acryl hybrid resin; 8 wt% to 24 wt% of a nanosilicate-phenoxy hybrid resin; and 40 wt% to 80 wt% of an inorganic-based anti- corrosion agent based on a solid content.

[0011] According to another aspect of the present invention, there is provided an organic-inorganic hybrid coated steel sheet including: a base steel sheet; a zinc-based plating layer formed on the base steel sheet; and a coating layer formed on the plating layer, wherein the coating layer may be formed with the _. organic-inorganic hybrid coating solution composition. [Advantageous Effects]

[0012] According to an aspect of the present invention, solution stability of an organic-inorganic hybrid coating solution may be improved. In the case that an organic- inorganic hybrid coating layer is formed on a surface of a zinc-plated steel sheet with the coating solution, corrosion resistance of the steel sheet may be significantly increased. Also, solvent resistance of the coating layer may be increased and conductivity of the coated steel sheet may be improved.

[Description of Drawings]

[0013] The above and other aspects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:

[0014] FIG. 1 is a schematic view illustrating a method of securing corrosion resistance in an organic-inorganic hybrid coated steel sheet according to an aspect of the present invention;

[0015] FIG. 2 is a photograph illustrating evaluation of corrosion resistance of a coated steel sheet in a Conventional Example; and

[0016] FIG. 3 is a photograph illustrating evaluation of corrosion resistance of an organic-inorganic hybrid coated steel sheet in the Inventive Example, according to an embodiment of the present invention. [Best Mode]

[0017] As a result of a significant amount of research conducted, into securing corrosion resistance of a plated steel sheet, the present inventors deduced an optimum combination, of a binder, resin able to maximize a barrier effect of an organic-based material and a rust inhibition effect of an inorganic-based material as well as accommodation of an inorganic-based anti-corrosion agent, and recognize that corrosion resistance may be secured by forming an organic- inorganic hybrid coating layer on one side or both sides of the steel sheet despite a reduction of the coating weight of a zinc-plating layer, thereby leading to completion of the present invention.

[0018] Hereinafter, an organic-inorganic hybrid coating solution composition according to an aspect of the present, invention will be described in detail. The coating solution composition ' may include 12 wt% to 36 wt% of a urethane-acryl hybrid resin, 8 wt% to 24 wt% of. a nanosilicate-phenoxy hybrid resin, and 40 wt% to 80 wt% of an inorganic-based anti- corrosion agent based on a solid content.

[0019] The urethane-acryl hybrid resin and the nanosilicate- phenoxy hybrid resin as an organic-based resin are included in a total amount ranging from 20 wt% to 60 wt%, and the inorganic-based anti-corrosion agent is included in an amount ranging from 40 wt% to 80 wt%. Herein, the organic-based resin acts as a binder resin and may be set to accommodate a large amount of the inorganic-based anti-corrosion agent for securing corrosion resistance.

[0020] The reason for limiting a content of each component will be described below.

[0021] 1) Urethane-acryl hybrid resin: 12 to 36 wt%

[0022] The urethane-acryl hybrid resin used in the present invention is prepared by simultaneously mixing two resins in the process of synthesizing each resin. That is, the urethane- acryl hybrid resin is a hybrid resin prepared by mixing urethane and acryl emulsion immediately before the completion of the synthesis of each resin at a temperature of 80°C while triethylamine (TEA) is added thereto, and may provide a coating layer having a dense structure. At this time, the urethane-acryl hybrid resin may be included in an amount of 12 wt% or more in order to secure corrosion resistance and solvent resistance. However, since an effect of improving physical properties due to the input of the urethane-acryl hybrid resin is insignificant even in that case that the input content thereof is excessively high, an upper limit thereof may be controlled to be 36 wt%.

[0023] The lower the weight-average molecular weight of the urethane-acryl hybrid resin is, the higher the cross-linking density is. However, since stability of the inorganic anti- corrosion agent may be deteriorated, control of the weight- average molecular weight is important. In the case that the weight-average molecular weight is less than 40,000, the inorganic anti-corrosion agent may be precipitated. In contrast, in , the case that the .. weight-average molecular weight is greater^■ than 90, 000, . corrosion resistance may. be deteriorated. Therefore, the weight-average molecular weight of the urethane-acryl hybrid resin may be controlled to be within a range of 40,000 to 90,000. Also, the weight-average molecular weight may be controlled to be within a range of 65, 000 to 70,000 and for example, may be controlled to be 68,000.

[0024] In addition, resin hardness may be secured by controlling a compositional ratio of isocyanate constituting a hard segment. For this purpose, an equivalence, ratio between a NCO group and an OH group may be controlled to be within a range of 1 to 3 during the polymerization of the urethane- acryl hybrid resin. Herein, in the case that a value of the NCO/OH equivalence ratio is less than 1, blackening resistance after processing may be deteriorated. In contrast, in the case in which the value of the NCO/OH equivalence ratio is greater than 3, solution stability and corrosion resistance may be deteriorated. Further, the value of the NCO/OH equivalence ratio may be controlled to be within a range of 1.3 to 1.9 in order to secure the foregoing effect, and for example, may be controlled . to be 1.6.

[0025] (2) Nanosilicate-phenoxy hybrid resin: 8 to 24 wt%

[0026] The nanosilicate-phenoxy hybrid resin used in the present invention is a hybrid resin prepared by adding a nanosilicate anti-corrosion agent. i the process of synthesizing a phenoxy resin and the nanosilicate-phenoxy hybrid resin may act to improve corrosion resistance, blackening resistance after processing, and chemical resistance of the coated steel sheet. At this time, the nanosilicate-phenoxy hybrid resin may be included in an amount of 8 wt% or more in order to secure corrosion, resistance and blackening resistance after processing. However, since an effect of improving physical properties due to the input of the nanosilicate-phenoxy hybrid resin is insignificant even in the case that the input content thereof is excessively high, an upper limit thereof may be controlled to be 24 wt%.

[0027] Also, the nanosilicate-phenoxy hybrid resin may include 1.0 wt% to 3.0 wt% of nanosilicate. The nanosilicate may be included in an amount of- 1.0 wt% or more in order to exhibit an effect of an anti-corrosion agent. However, since a degree of improving the foregoing effect with respect to the addition amount is insignificant even in that case that the input content thereof is high and solution stability of the hybrid resin is deteriorated, an upper limit thereof may be controlled to be 3.0 wt%.

[0028] The lower the weight-average molecular weight of the nanosilicate-phenoxy . hybrid resin is, the higher the cross- linking density is. However, since stability of the inorganic anti-corrosion agent nanosilicate may be deteriorated, control of the weight-average molecular weight is important. . In the case that the weight-average, molecular weight is less than 40,000, the inorganic anti-corrosion agent may be precipitated. In contrast, . in the case that the weight-average . molecular weight is greater than 90,000,. corrosion, resistance may be deteriorated. Therefore, the weight-average molecular weight of the nanosilicate-phenoxy hybrid resin may be controlled to be within a range of 40,000 to 90,000. Also, the weight- average molecular weight may be controlled to be within a range of 74, 000 to 82, 000 and for example, may be controlled to be 78,000.

[0029] 3) Inorganic-based anti-corrosion agent: 40 to 80 wt%

[0030] The inorganic-based anti-corrosion agent may include one or more of 8 wt% to 33 wt% of silane A., 28 wt% to 57 wt% of silane B, .3 wt% to 11 wt% of vanadium phosphate, 0.5 wt% to 7 wt% of thio-urea, 0.1 wt% to 1.4 wt% of magnesium (Mg) oxide, 2 wt% to 10 wt% of zinc phosphate, 0.5 wt% to 3.4 wt% of titanium carbonate, 0.5 wt% to 4 wt% of a zirconium (Zr) compound and 0.4 wt% to 3 wt% of silica. Herein, the silane A and the silane B are categorized according to the type of silane and are described to indicate that two different types of silane are included in the present invention.

[0031] Silane A: 8 to 33 wt%

[0032] In general, silane compounds may include epoxy-based, chloro-based, amino-based, or acryl-based silane, and, in the present invention, epoxy-based silane may^■ be used in view of solution stability. Herein, the epoxy-based silane may include at least one of gamma glycidoxypropyl triethoxysilane and gamma aminopropyl triethoxysilane. A content of the silane A introduced may be controlled to be 8 wt% or more in order to effectively block corrosive factors by considering solvent resistance and water repellency of the coating layer and securing a sufficient hydrophobic group. However, in the. case that the content of the silane A is excessively high, solution stability may decrease and an effect of improving corrosion resistance according to the increase in the content thereof may be insignificant, _.and thus, an upper limit of the content thereof may be controlled to .be 33 wt%. However, the content thereof, for example, may be within a range of 12 wt% to 33 wt%.

[0033] Silane B: 28 to 57 wt%

[0034] The silane B, different from the foregoing silane A, may maximize corrosion ^■ resistance. The silane B may be included in an amount of 28 wt% or more in order to improve corrosion resistance. An upper limit thereof may be controlled to be^' 57 wt% in consideration of solution stability and an effect of improving corrosion resistance with respect to the addition amount. The silane B may include one or more of a vinyl-based silane, an epoxy-based silane, and an alkoxy-based silane.

[0035] . Vanadium phosphate: 3 to 11 wt%

[ 0036] The coating solution may include 3 wt% or more of vanadium phosphate in order to improve corrosion resistance. Since a blackening phenomenon, in which appearance of the steel sheet changes to black in a high-temperature and high- humidity atmosphere, may. occur, an upper limit thereof may be controlled to be 11 wt%.

[0037] Thio-urea: 0.5 to 7 wt%

[0038] Thio-urea is an organic compound used for preparing resins and medicines, and is used as a hardening accelerator in the present invention and thus, almost no effect may be obtained in the case that a content thereof is 0.5 wt% or less In the case in which the content thereof is 0.5 wt% or more, an effect of decreasing time required for hardening the coating layer may be obtained, but solution stability may decrease in the case that the content thereof is excessively high. Therefore, an upper limit thereof may be limited to 7 wt%. . ^'

[0039] Mg oxide: 0.1 to 1.4 wt%

[0040 ] Mg may be used by dissolving magnesium oxide (MgO) in a vanadium phosphate aqueous solution. Also, Mg oxide may be included in an amount of 0.1 wt% or more in order to secure the effect of corrosion resistance. Since solution stability may decrease in the case that a content thereof is excessively high, an upper limit thereof may be controlled to be 1.4 t%.

[0041] Zinc phosphate: 2 to 10 wt%

[0042] Zinc, phosphate, is added as an auxiliary additive for improving corrosion resistance. Herein, a content of the zinc phosphate may be controlled to be 2 wt% in order to secure corrosion resistance. However, since solution stability is decreased and an effect of improving physical properties is insignificant with respect to the addition amount in the case that the content thereof is excessively high, an upper limit thereof may be controlled to be 10 wt%.

[0043] Titanium carbonate: 0.5 to 3.4 wt%

[0044] Titanium carbonate is included for. the stability of the coating solution and the reactivity of the base steel sheet and the coating solution, and may act as a coupling agent for the resin and the inorganic material. The titanium carbonate may be included in an amount of 0.5 wt% or more in order to secure corrosion resistance. However, since an effect of improving corrosion resistance may be insignificant with respect to the addition amount even in the case that the content thereof is high, an upper limit thereof may be controlled to be 3.4 wt%. [0045] Zr compound: 0.5 to 4 wt%

[0046] The Zr compound is included in. order to improve corrosion resistance. The Zr compound may be included in an amount of 0.5 wt% or more in order to secure corrosion resistance. However, since an effect of improving corrosion resistance, may be insignificant with respect to the addition amount even in the case that the content thereof is. high, an upper limit thereof may be limited to 4 wt%. .

[0047] Silica: 0.4 to 3 wt.% .

[0048] Silica is included for improving corrosion resistance and colloidal silica is mainly used. The silica may be included in . an amount of 0.4 t% or more in order to secure corrosion resistance. However_/ since solution stability may be decreased in the case that the content thereof is high, an upper limit thereof may be limited to 3 wt% .

[0049] Corrosion resistance of the steel sheet may be maximized by forming a coating layer on one side or both sides of the steel sheet to be later described with a . coating solution having the foregoing composition.

[0050] Hereinafter, an organic-inorganic hybrid coated steel sheet according to another aspect of the present invention will be described in detail. The organic-inorganic hybrid coated steel sheet of the present invention may include a base steel sheet, a zinc-based plating layer formed on the base steel sheet, an organic-inorganic hybrid coating layer formed on the zinc-based plating layer, and may include 12 wt% to 36 wt%. of a urethane-acryl hybrid resin, 8 wt% to 24 wt% of a nanosilicate-phenoxy hybrid resin, and 40 wt% to 80 wt% of an inorganic-based anti-corrosion agent based on a solid content.

[0051] The base steel sheet is not particularly, limited, and any steel sheet may be used so long as the .base steel sheet is suitable for the purpose of the present invention.

[0052] A method of forming the zinc-based plating layer may be performed with a hot-dip galvanizing method. However, any method may be additionally used so long as the method may form a zinc-based plating layer. Also, a component system of the zinc-based plating layer, is not particularly limited, a component system of a plating layer of a typical hot-dip galvanized steel sheet or electrogalvanized steel sheet may be used.

[0053] Also, the organic-inorganic, hybrid coated steel sheet may include a coating layer formed on one side or both sides of the steel sheet having the zinc-based plating layer formed thereon. One side or both sides of the steel sheet may be coated with the coating solution. At this time, a coating weight of the coating layer may be controlled to.be within a range of 0.5 g/m² to 2 g/m². A lower limit of the coating weight may be controlled to be 0.5 g/m² in order to secure corrosion resistance intended in the present invention. However, in the case that the coating weight is greater than 2 g/m², conductivity of the coating layer may decrease.

[ 0054 ] Hereinafter, a component system of . the coating layer will be described in detail. The coating layer may be formed with the foregoing coating solution and the component system may also . be deduced from a component system of the coating solution.

[0055] The urethane-acryl hybrid resin and the nanosilicate- phenoxy- hybrid resin may be included in an amount of 20 wt% or. more in order to secure corrosion resistance, solvent resistance, and blackening resistance after processing. However, since these components act as a binder and an effect of improving physical properties due to the input thereof is insignificant even in the case that the input content thereof is excessively . high, an upper limit thereof may be controlled to be 60 wt%. Herein, characteristics of the resin may exhibit the characteristics of the hybrid resin described in the foregoing coating solution.

[ 0056] Also, as schematically illustrated in FIGS. 1(a) and 1 (b) , silane A, silane B, and vanadium phosphate included in the coating, layer act as a barrier, and silica, titanium carbonate, a Zr compound, Mg oxide, and zinc phosphate act to provide rust resistance (corrosion delay) as an anti-corrosion agent.

[ 0057 ] The silane A and the silane B included in the coating layer are overall distributed in the coating layer and act to protect corrosion factors. The silane A and the silane B may have good hydrophobic and. barrier effects, but may have limitations in solution stability when excessive amounts thereof are added. Therefore, the silane A and the silane B are included in an amount ranging from 1 wt% to 2 wt% . A maximum amount of 33 wt% of the silane A and the silane B is included in . the present invention and thus, even an intermediate layer as well as an uppermost portion of the coating layer may maintain, the barrier effect as well as the hydrophobicity of the coating layer.

[0058] Further, the corrosion factors may. penetrate the foregoing barrier to reach vanadium phosphate . (V-P0₄), a last layer. In particular, the vanadium phosphate layer reacts with a zinc layer thereunder to form a phosphate layer, and thus, may act as a final corrosion inhibition barrier in the coating layer. However, since the corrosion factors may attack the coating layer when some time has elapsed, white rust may occur in the zinc layer.

[0059] Next, silica, titanium carbonate, and the. Zr compound as rust inhibitors react with the corrosion factors penetrating into the coating layer .to form a more stable compound, and thus, may prevent white rust in the zinc layer by blocking the additional attack of the corrosion factors.

[0060] Hereinafter, the present invention will be described in detail, according to specific examples. However, the following examples are merely provided to allow for a clearer understanding of the present invention, rather than to limit the scope thereof. The scope of the present invention is defined by the appended claims and items reasonably inferable therefrom.

[0061] [Example 1]

[0062] A hot-dip galvanized steel sheet having a coating weight of 70 g/m². based . on one . side : thereof was coated with a chromium (Cr)-free solution (Patent Application No.: KR2005- 0128523)- with a bar coating method, and the hot-dip galvanized steel sheet was then heated to a peak metal temperature (PMT) of 140°C with an induction heater for baking and drying to prepare Conventional Example 1. At this time, measurement of a wet coating weight in Conventional Example 1 resulted in 680 mg/m². A photograph for identifying corrosion resistance with respect to the occurrence of white rust and red rust in Conventional Example 1 is shown in FIG. 2.

[0063] A hot-dip galvanized steel sheet having a coating weight of 40 g/m² based on one side thereof was. coated with a coating solution described in the present invention with a bar coating method, and the hot-dip galvanized steel sheet was. then heated to 140°C with an induction heater for baking and drying to prepare Inventive. Example 1. Measurement of a wet coating weight in Inventive Example 1 resulted, in 680 mg/m². A photograph for identifying corrosion resistance with respect to the occurrence of white rust and red rust in Inventive Example 1 is shown in FIG. 3.

[0064 ] Corrosion resistance, plating adhesion, solvent resistance, and blackening resistance were measured and the results thereof are presented in the following Table 1.

[ 0065] Corrosion resistances were; evaluated by performing salt spray tests on coated samples, under conditions of a ..salt concentration of 5%, a temperature of 35 °C, and a spray pressure of 1 kg/cm², and. times, required for generating 5% of red rust were measured. Also, the coated samples were rubbed ten times with a gauze soaked with a methyl ethyl ketone (MEK) reagent and solvent resistances were then evaluated by measuring color differences (delta E) after being compared with the original steel sheets. In addition, blackening resistances were evaluated by measuring color differences (delta E) before and after maintaining the samples in a constant temperature, and humidity chamber having a temperature of 50°C and a relative humidity of 95% for 120 hours. .

[0066] [Table 1]

Inventive

500 1.0 1.0

Example 1

[0067] In Conventional Example 1, 5% of red rust was generated in 300 hours. Also, a value of solvent resistance measured was 1.0, and a value of blackening, resistance resulted in 2.0. [0068]. In contrast, in Inventive Example 1, 5% of red rust was generated in 500 hours. According to the results of evaluating solvent resistance and blackening resistance, values of color difference for both solvent resistance and blackening resistance resulted in 1.0.

[0069] Therefore, despite the fact that the hot-dip galvanized steel sheet using the coating . solution described in the present invention had a zinc coating weight of 40 g/m² based on one side thereof, lower than that of 70 g/m² in Conventional Example 1, the time required for generating red rust was markedly increased, and thus, excellent corrosion resistance was obtained. [0070] [Example 2]

[0071] Surfaces of hot-dip galvanized steel sheets (zinc coating weight of 40 g/m²) were coated with coating solutions satisfying component systems described in the following Tables 2 and 3 with a roll coater method to control a coating weight to be 680 mg/m² and the hot-dip galvanized steel sheets were then heated to 140°C for baking and drying to prepare coated samples.

[0072] Solution stability of each coating solution prepared according to compositions in the following Tables 2 and 3 was evaluated, and corrosion resistance, solvent resistance, and blackening resistance of the coated steel sheets having the coating . solutions coated thereon were evaluated and the results thereof are presented. in the following Tables 2 and 3.

[0073] The solution stability was evaluated as poor (X) in the case that . viscosity of the coating solution . was increased in. an amount of 20% or more . with respect to that of an initial period, or, as a result of visual observation, precipitation, decomposition, and gellation of the solution were performed.

[0074] Corrosion resistances were evaluated by measuring times required for generating 5% of red rust on flat sheets under conditions of a salt concentration of 5%, a temperature of 35°C, and a spray pressure of 1 kg/cm². Also, evaluation criteria of corrosion resistance were described below based on 300 hours, a level greater than or equal to that of Conventional Example 1.

[0075] 0: 300 hours or more .

[0076] X: less than 300 hours

[0077] Also, the coated steel sheets were rubbed ten times with a gauze soaked with a methyl ethyl ketone (MEK) reagent and solvent resistances were then evaluated by measuring color differences (delta E) after being compared with the original steel sheets, and were then evaluated as below based on 2.0, a level required for a typical Cr-free coated steel sheet.

[0078] 0: 2.0 or less

[0079] X: greater than 2.0

[0080] In addition, blackening resistances were evaluated by measuring color differences (delta . E) before and after maintaining the coated steel sheets in a constant temperature and humidity chamber having a temperature of 50°C and a relative humidity of 95%, for 120 hours and were then evaluated as below based on 2.0, a level required for a typical Cr-free .coated steel sheet.

[0081] 0: 2.0 or less

[0082] X: greater than 2.0

[0083] [Table 2]

Inventive

5 0.7 12 30 3 0.7 1.5 0.8 41 0 0 0 Example 6

Comparative

5 0.7 12 30 3 0.7 1.5 0.8 41 X 0 0 Example 4

Comparative

5 0.7 5 30 3 0.7 1.5 0.8 41 0 X 0 Example 5

Inventive

5 0.7 8 30 3 0.7 1.5 0.8 41 0 0 0 Example 7

Inventive

5 0.7 33 30 3 0.7 1.5 0.8 41 0 0 0 Example 8

Comparative

5 0.7 35 30 3 0.7 1.5 0.8 41 X 0 0 Example 6

Comparative

5 0.7 12 15 3 0.7 1.5 0.8 41 0 0 X Example 7

Inventive

5 0.7 12 20 3 0.7 1.5 0.8 41 0 0 0 Example 9

Inventive

5 0.7 12 60 3 0.7 1.5 0.8 41 0 0 0 Example 10

Comparative

5 0.7 12 65 3 0.7 1.5 0.8 41 0 X 0 Example 8

(Where, the hybrid resin A+B is a urethane-acryl hybrid resin and a nanosilicate-phenoxy hybrid resin) [0084] [Table 3]

Comparative

5 0.7 12 30 3 4.0 1.5 0.8 41 X 0 0 Example 12

Comparative

5 0.7 12 30 3 0.7 0.3 0.8 41 0 X 0 Example 13

Inventive

5 0.7 12 30 3 0.7 0.5 0.8 41 0 0 0 Example 15

Inventive

5 0.7 12 30 3 0.7 4.0 0.8 41 0 0 0 Example 16

Comparative

5 0.7 12 30 3 0.7 4.5 0.8 . 41 X 0 0 Example 14

Comparative

5 0.7 12 30 3 0.7 1.5 0.2 41 0 X 0 Example 15

Inventive

5 0.7 12 30 3 0.7 1.5 0.4 41 0 ^■ 0 0 Example 17

Inventive

5 0.7 12 30 3 0.7 1.5 3.0 41 0 0 0 Example 18

Comparative

5 0.7 12 30 3 0.7 1.5 3.5 41 X 0 0 Example 16

Comparative

5 0.7 12 30 3 0.7 1.5 0.8 20 0 X 0 Example 17

Inventive

5 0.7 12 30 3 0.7 1.5 0.8 28 0 0 0 Example 19

Inventive

5 0.7 12 30 3 0.7 1.5 0.8 57 0 . 0 0 Example 20

Comparative

5 0.7 12 30 ^• 3 0.7 ^' 1.5 0.8 60 X 0 0 Example 18

(Where, the hybrid resin A+B is a urethane-acryl hybrid resin and a nanosilicate-phenoxy hybrid resin)

[0085] Since a content of vanadium phosphate in Comparative Example 1 was lower than the range limited in the present invention, a zinc phosphate layer blocking . the penetration of corrosion factors was insufficient, and thus, corrosion resistance was decreased.

[0086] Since the content of vanadium phosphate in Comparative Example 2 was higher than the range limited in the present invention, etching occurred excessively, and thus, blackening resistance was decreased. [0087] Since a content of Mg oxide in Comparative Example 3 was lower than the range limited in the present invention, a function of inhibiting corrosion through the formation of Mg hydrate was insufficient, and thus, corrosion resistance was decreased.

[0088] . Since the content of Mg oxide in Comparative Example 4 was higher than the range limited in the present invention, Mg oxide in the solution was included in . an amount more than required, and thus, solution stability was decreased due to the reaction with other anti-corrosion additives.

[0089] - Since a content of silane A in Comparative Example 5 was lower than the range limited in the present invention, a cross-linking role between a silane resin and an inorganic material was insufficient, and thus, corrosion resistance was decreased.

[0090] Since the content of silane A in Comparative Example 6 was higher than the range limited in the present invention, solution stability was decreased due to an excessive content of silane stably dispersed in the solution.

[0091] Since a content of the hybrid resin in Comparative Example 7 was lower than the range limited in the present invention, a function of a binder resin was insufficient, and thus, moisture penetration in a high-temperature and high- humidity environment was facilitated to decrease blackening resistance. [0092] Since the content of the hybrid resin in Comparative Example 8 was higher than the range limited in the present invention, a content of the inorganic anti-corrosion agent was relatively decreased, and thus, corrosion resistance was decreased.

[0093] Since . a content of zinc phosphate in Comparative Example 9 was lower than the range limited in the present invention, a role of assisting corrosion resistance was insufficient, and thus, corrosion resistance of the steel sheet was decreased.

[00.94] Since the content of zinc phosphate in Comparative Example 10 was higher than the range limited in the present invention, appropriate mixing and dispersion with other anti- corrosion agents in the solution were not obtained, and thus, solution stability was decreased.

[0095] Since a content of titanium carbonate ( iC0₃) in Comparative Example 11 was lower than the range limited in the present invention, a cross-linking role with respect to the resin was insufficient, and thus, corrosion resistance was decreased.

[0096] Since the content of titanium carbonate in Comparative Example 12 was higher than the range limited in the present invention, appropriate mixing and dispersion with other anti- corrosion agents in the solution were not obtained, and thus, solution stability was decreased. [0097] Since a content of the Zr compound in Comparative Example 13 was lower than the range limited in the present invention, a role of assisting corrosion resistance was insufficient, and thus, corrosion resistance of the steel sheet was decreased.

[0098] Since the content of the Zr compound in Comparative Example 14 was higher than the . range limited in the present invention, appropriate mixing and dispersion _. with other anti- corrosion agents were not obtained, and thus, solution stability was decreased.

[0099] Since . a^■ content of silica in Comparative Example 15 was lower than the range limited in the present invention, bonding force with a resin layer was decreased, and thus, corrosion resistance was decreased.

[00100] Since the content of silica in Comparative Example

16 was higher than the range limited in the present invention, appropriate mixing and dispersion with other anti-corrosion agents were not obtained, and thus, solution stability was decreased.

[00101] Since a content of silane B in Comparative Example

17 was lower than the range limited in the present invention, functions of combining with an organic material and an inorganic additive and increasing corrosion resistance were decreased, and thus, corrosion resistance was decreased.

[00102] Since the content of silane B in Comparative Example 18 was higher than the range limited in the present invention,. solution stability, was decreased, and thus, corrosion resistance was decreased.

[00103] In contrast, it may be confirmed that with respect to Inventive Examples 2 to 20 satisfying the composition of the coating solution controlled in the present invention, solution .. stabilities, corrosion resistances, and. blackening resistances were evaluated as excellent.

[00104] [Example 3]

[00105] Surfaces of hot-dip galvanized steel sheets (zinc coating weight of 40 g/m²) were coated with coating solutions, in which the compositions of the hybrid . resin A+B were changed according to the conditions listed in Table 4 while the coating solution described in the composition of Inventive Example 2 is used as a base composition, with a roll coater method to form organic-inorganic hybrid coating layers and the hot-dip galvanized steel sheets were then heated to a PMT of 140°C for baking and drying to prepare coated samples.

[00106] Thereafter, solution stabilities and corrosion resistances of the coated steel sheets were evaluated by the same conditions and criteria as those of Example 2 and the results thereof are presented in Table 4. Herein, the hybrid resin A denotes a urethane-acryl hybrid resin and the hybrid resin B denotes a nanosilicate-phenoxy hybrid resin.

[00107] [Table 4] Hybrid resin A Hybrid resin B

Solution Corrosion Othe¬

Addition Molecular NCO/ Addition Molecular

silicate stability resistance rs amount weight OH amount weight

Comparative

10 68,000 1.6 12 78,000 1.5 0 X 0 Example 18-1

Inventive

12 68,000 1.6 12 78,000 1.5 0 0 0 Example 21

Inventive

18 68,000 1.6 12 78,000 1.5 0 0 0 Example 22

Inventive

36 68, 000 1.6 12 78,000 1.5 0 0 0 Example 23

Comparative

40 68,000 1.6 12 78,000 1.5 0 X 0 Example 19

Comparative

5 35,000 1.6 12 78, 000 1.5 ,0 X 0 Example 20

Inventive

5 40,000 1.6· 12 78, 000 1.5 0 0 0 Example 24

Inventive

5 ^'90, 000 1.6 12 78, 000 1.5 0 0 0 Example 25

Comparative

5 95,000 1.6 12 78, 000 1.5 X 0 0 Example 21

Comparative

^■ 5 68,000 0.5 12 78, 000 1.5 0 0 X Example 22

Inventive

5 68,000 1 12 78,000 1.5^■ 0 0 0 Example 26

Inventive

5 68,000 3 12 78, 000 1.5 0 0 0 Example 27

Comparative

5 68,000 3.5 12 78,000 1.5 X X 0 Example 23

Comparative

5 68, 000 1.6 6 78,000 1.5 0 X 0 _. Example 24

Inventive

5 68, 000 1.6 8 78,000 1.5 0 0 0 Example 28

Inventive

5 68,000 1.6 24 78,000 1.5 0 0 0 Example 29

Comparative

5 68,000 1.6 30 ^• 78,000 1.5 0 X 0 Example 25

Comparative

5 68,000 1.6 12 35,000 ^■ 1.5 0 X 0 Example 26

Inventive

5 68,000 1.6 12 40,000 1.5 0 0 0 Example 30

Inventive

5 68,000 1.6 12 90,000 1.5 0 0 0 Example 31

Comparative

5 68,000 1.6 12 95,000 1.5 X 0 0 Example 27 Comparative

5 68,000 1.6 12 78,000 0.5 0 X 0 Example 28

Inventive

5 68, 000 1.6 12 78,000 1 0 0 0 Example 3.2

Inventive

5 68,000 1.6 12 78,000 3 0 0 0 Example 33

Comparative

5 68,000 1.6 12 78,000 3.5 X 0 0 Example 29

[00108] . In the case that contents of the hybrid resin A in Comparative Examples 18-1 and 24 were low at less than 12 wt%, a content of a resin constituting a coating layer having a dense structure by mixing with an inorganic material may be insufficient, and thus, corrosion resistances may deteriorate. However, even in the case that the input content of the hybrid resin was excessively high, an effect of improving physical properties due to the input thereof may not only be insignificant ■ as in Comparative Examples 19 and 25, but corrosion resistances may also tend to be decreased again.

[00109] Comparative Examples 20 and 26 had limitations in that a portion of the inorganic anti-corrosion agent was precipitated due to the low weight-average molecular weight (Mw) of the hybrid resin. In contrast, in Comparative Examples 21 and 27, cross-linking densities were not secured because the weight-average molecular weights were relatively high, and thus, corrosion resistances were deteriorated.

[00110] Since hardness of the resin coating layer may not be secured _in Comparative Example 22, the resin may be blackened during processing. In contrast, solution stability and corrosion resistance may be deteriorated in Comparative Example 23.

[00111] With respect to Comparative Example 28, corrosion resistance was deteriorated due to an insufficient content of silicate, an anti-corrosion agent. In contrast, with respect to Comparative Example 29, solution stability was deteriorated

[00112] Alternatively, with respect to Inventive Examples 21 to 33 satisfying the composition of the coating solution controlled in the present invention, it may be confirmed that qualities, such as solution stability, corrosion resistance, and other blackening resistance after processing were evaluated as excellent.

[00113] [Example 4]

[00114] Surfaces of hot-dip galvanized steel sheets (zinc coating weight of 40 g/m²) were coated with the coating solution of Inventive Example 3 listed in Table 2 with a roll coater method to form organic-inorganic hybrid coating layers having .coating weights listed in the following Table 5 and the hot-dip galvanized steel sheets were then heated to a PMT of 140°C for baking and drying to prepare coated samples.

[00115] Thereafter, conductivities of the coated steel sheets were evaluated and the results thereof are presented in Table 5. At this time, conductivity was measured with a Loresta GP meter and was evaluated as below based on a level required for a typical Cr-free coated steel sheet of 0.1 rnO. Corrosion resistance was evaluated by the same conditions and criteria as those of Example 2.

[00116] 0: 0.1 mQ or less

[00117] X: greater than 0.1 mQ ^'

[00118] [Table 5]

[00119] With respect to Comparative Example 30, since the coating weight was lower than the range limited in the present invention, a coating layer inhibiting corrosion was not formed in a sufficient thickness, and thus, corrosion resistance was decreased.

[00120] With respect to Comparative Example 31, since the coating weight was higher than the range limited in the present invention, electron flow was inhibited as non- conductive components were increased in the coating layer, and thus, a decrease in electrical conductivity resulted.

[00121] . In contrast, with respect to Inventive Examples 34 to 36 satisfying the composition of the coating solution controlled in the present invention, it may be confirmed that both . corrosion resistance and conductivity . were evaluated as being excellent.

[00122] While the present invention has been shown and described in connection with the exemplary embodiments, it will be apparent to those skilled in the art that modifications and variations can be made without departing from the spirit and scope of the invention as defined by the appended claims .

Claims

[CLAIMS]

[Claim l]

An. organic-inorganic hybrid coating solution composition comprising:

12 wt% to 36 wt% of a urethane-acryl hybrid resin;

8 wt% to 24 wt% of a nanosilicate-phenoxy hybrid resin; and

40 wt% to 80 wt% of an inorganic-based anti-corrosion agent, based on a solid content.

[Claim 2]

The organic-inorganic hybrid coating solution composition of claim 1, wherein the nanosilicate-phenoxy hybrid resin comprises 1.0 wt% to 3.0 wt% of nanosilicate .

[Claim 3]

The organic-inorganic hybrid coating solution composition of claim 1, wherein a weight-average molecular weight (Mw) of each of the urethane-acryl hybrid resin and the nanosilicate- phenoxy hybrid resin is in a range of 40,000 to 90,000.

[Claim 4]

The organic-inorganic hybrid coating solution composition of claim 1, wherein an NCO/OH equivalence ratio of the urethane-acryl hybrid resin is in a range of 1 to^' 3. [Claim 5]

The organic-inorganic hybrid coating solution composition of claim 1, where the inorganic-based anti-corrosion agent comprises one or. more of 8 wt% to 33 wt% of silane A, 28 wt% to 57. wt% of silane B, 3 wt% to 11 wt% of vanadium phosphate, 0.5 wt% to 7 wt% of thio-urea, 0.1 wt% to 1.4 wt% of magnesium (Mg) oxide, 2 wt% to 10 wt% of_. zinc phosphate, 0.5 wt% to 3.4 wt% of titanium carbonate, 0.

5 wt% to 4 wt% of a zirconium (Zr) compound and 0.4 wt% to 3 wt% of silica.

[Claim 6]

The organic-inorganic hybrid coating solution composition of claim 5, wherein the silane A is a mixture of at least one of gamma glycidoxypropyl triethoxysilane and gamma aminopropyl triethoxysilane .

[Claim 7]

The organic-inorganic hybrid coating solution composition of claim 5, wherein the silane B is a mixture of one or more of a vinyl-based silane, an epoxy-based silane, and an alkoxy- based silane.

[Claim 8]

. An organic-inorganic hybrid coated steel sheet comprising:

a base steel sheet;

a zinc-based plating layer formed on the base steel sheet; and

a coating layer formed on the plating layer,

wherein the coating layer is formed with any one of the coating solution compositions of claims 2 to 7.

[Claim 9]

The organic-inorganic hybrid coated steel sheet of claim 8, wherein a coating weight of the coating layer is in a range of 0.3 g/m² to 2 g/m² based on one side of the steel sheet.