CHROMATE-FREE PRECOATED METAL SHEET HAVING METALLIC APPEARANCE AND WATER-BASED COATING COMPOSITION USED IN THE SAME

Abstract

A chromate-free coated metal sheet according to the present invention includes: a metal sheet; and a coating film which contains an organic resin A as a film formation component and a flaky aluminum pigment C having a deactivation-treated surface on at least one surface of the metal sheet; wherein the thickness of the coating film is in a range of 1.5 to 10 m.

Claims

1. A chromate-free coated metal sheet including: a metal sheet; and a coating film which contains an organic resin A as a film formation component and 7 to 40% by mass of a flaky aluminum pigment C having a deactivation-treated surface on at least one surface of the metal sheet, wherein a surface of the aluminum pigment C is coated with a film containing at least one selected from the group consisting of a phosphoric acid compound, a molybdic acid compound, and silica, or a two-layer film including a film containing an acrylic resin and a film containing a phosphoric acid compound; a thickness of the coating film is in a range of 1.5 to 10 m; a surface of the metal sheet is coated with the single coating film ; and the amount of the aluminum pigment C in the coating film is in a range of 10 to 20% by mass.

2. The chromate-free coated metal sheet according to claim 1, wherein the coating film further contains silica particles D having an average particle diameter of 5 to 100 nm.

3. The chromate-free coated metal sheet according to claim 1, wherein an average particle diameter of the aluminum pigment C is in a range of 5 to 30 m.

4. The chromate-free coated metal sheet according to claim 1, wherein the surface of the aluminum pigment C is coated with the film containing silica.

5. The chromate-free coated metal sheet according to claim 4, wherein an amount of the film containing silica film in the silica film-coated aluminum pigment C.sub.Si relative to 100% by mass of aluminum is in a range of 10 to 20% by mass in terms of Si.

6. The chromate-free coated metal sheet according to claim 4, wherein a thickness of the film containing silica is in a range of 5 to 100 nm.

7. The chromate-free coated metal sheet according to claim 1, wherein the coating film further contains polyolefin resin particles E having an average particle diameter of 0.5 to 3 m.

8. The chromate-free coated metal sheet according to claim 7, wherein an amount of the polyolefin resin particles E in the coating film is in a range of 0.5 to 5% by mass.

9. The chromate-free coated metal sheet according to claim 1, wherein the organic resin A is a resin cured by a curing agent B.

10. The chromate-free coated metal sheet according to claim 1, wherein the organic resin A contains a polyester resin Ae having a sulfonic acid group in its structure.

11. The chromate-free coated metal sheet according to claim 10, wherein the organic resin A further contains a polyurethane resin having a carboxyl group and an urea group in its structure.

12. The chromate-free coated metal sheet according to claim 1, wherein a surface preparation layer is included between the metal sheet and the coating film .

13. The chromate-free coated metal sheet according to claim 1, wherein the metal sheet is a zinc-base plated steel sheet.

14. The chromate-free coated metal sheet, wherein the coating film in claim 1 is formed by coating and drying by heat a water-based coating composition X containing constituent components of the coating film on at least one surface of the metal sheet.

15. The chromate-free coated metal sheet according to claim 1, wherein the surface of the aluminum pigment C is coated with the film containing the phosphoric acid compound.

16. The chromate-free coated metal sheet according to claim 1, wherein the surface of the aluminum pigment C is coated with the two-layer film including the film containing acrylic resin and the film containing the phosphoric acid compound.

17. The chromate-free coated metal sheet according to claim 1, wherein the surface of the aluminum pigment C is coated with the film containing the phosphoric acid compound or silica.

18. The chromate-free coated metal sheet according to claim 1, wherein the surface of the aluminum pigment C is coated with the film containing the phosphoric acid compound or the two-layer film including the film containing acrylic resin and the film containing the phosphoric acid compound.

19. The chromate-free coated metal sheet according to claim 1, wherein the surface of the aluminum pigment C is coated with the film containing silica or the two-layer film including the film containing acrylic resin and the film containing the phosphoric acid compound.

20. The chromate-free coated metal sheet according to claim 1, wherein the surface of the aluminum pigment C is coated with the film containing the phosphoric acid compound or silica, or the two-layer film including the film containing acrylic resin and the film containing the phosphoric acid compound.

21. The chromate-free coated metal sheet according to claim 1, wherein the surface of the aluminum pigment C is coated with the film containing the molybdic acid compound or the film containing silica.

22. The chromate-free coated metal sheet according to claim 16, wherein the amount of the film containing acrylic resin is in a range of 8 to 20% by mass relative to 100% by mass of aluminum and the amount of the film containing the phosphoric acid compound is in a range of 0.2 to 2.0% by mass relative to 100% by mass of aluminum.

Description

EXAMPLES

[0119] Below, Examples of the present invention will be explained. However, the present invention is not limited to these Examples.

(1) Metal Sheet

[0120] The types of the metal sheets used are shown in Table 1. As a substrate of plated metal sheet, a soft steel sheet having a thickness of 0.5 mm was used. The SUS sheet was a ferritic stainless steel sheet (steel composition: C: 0.008% by mass. Si: 0.07% by mass, Mn: 0.15% by mass, P: 0.011% by mass, S: 0.009% by mass, Al: 0.067% by mass, Cr: 17.3% by mass, Mo: 1.51% by mass, N: 0.0051% by mass, Ti: 0.22% by mass, and a balance of Fe and unavoidable impurities) was used. The metal sheet was used after the surface of the metal sheet was alkali degreased, washed with water and dried.

TABLE-US-00001 TABLE 1 No. Metal sheet (thickness: 0.5 mm, plated both sides) M1 Electrogalvanized steel sheet (plating deposition amount: 20 g/m.sup.2) M2 Hot dip galvanized steel sheet (plating deposition amount: 60 g/m.sup.2) M3 Galvannealed steel sheet (Fe: 10%, plating deposition amount: 45 g/m.sup.2) M4 Electro Zn10% Ni alloy plated steel sheet (plating deposition amount: 20 g/m.sup.2) M5 Hot dip Zn11% Al3% Mg0.2% Si plated steel sheet (plating deposition amount: 60 g/m.sup.2) M6 Hot dip Zn55% Al1.6% Si plated steel sheet (plating deposition amount: 75 g/m.sup.2) M7 Hot dip Al9% Si plated steel sheet (plating deposition amount: 40 g/m.sup.2) M8 SUS sheet (ferritic stainless steel sheet)

(2) Surface Preparation Layer

[0121] A coating material used to form a surface preparation layer was prepared by blending an organic resin (Table 2), a silane coupling agent (Table 3), a polyphenol compound (Table 4), silica particles (Table 5), a phosphoric acid compound (Table 6), a fluoro-containing complex compound (Table 7), a vanadium (IV)-containing compound (Table 8) so as to be a composition ratio (% by mass in terms of a solid component) shown in Table 9, and stirred using a stirrer for a coating material. Then, as necessary, a surface preparation layer was formed by coating the mixture on the surface of the metal sheet prepared in (1) above such that the adhesion amount was 100 mg/m.sup.2, and dried under conditions in which the highest temperature was 70 C.

TABLE-US-00002 TABLE 2 No. Organic resin a1 Polyester resin (Toyobo Co., Ltd.; VYLONAL MD-1200) a2 Epoxy resin (Asahi Denka Kogyo; Adeka Resin EM0436FS-12) a3 Phenol Resin (Sumitomo Bakelite; PR-NPK-261) a4 Polyurethane resin (Dai-ichi KogyoSeiyaku Co., Ltd; SUPERFLEX 620)

TABLE-US-00003 TABLE 3 No. Silane coupling agent b1 3-glycidoxypropyl trimethoxysilane b2 3-aminopropyl triethoxysilane

TABLE-US-00004 TABLE 4 No. Polyphenol compound c1 Tannic acid (Fuji Chemical Industry; Tannic Acid AL)

TABLE-US-00005 TABLE 5 No. Silica particles d1 Colloidal silica (Nissan Chemical Industries, Ltd.; SNOWTEX N; particle diameter: 15 nm) d2 Colloidal silica (Nissan Chemical Industries, Ltd.; SNOWTEX C; particle diameter: 15 nm)

TABLE-US-00006 TABLE 6 No. Phosphoric acid compound e1 Phosphoric acid e2 Magnesium biphosphate

TABLE-US-00007 TABLE 7 No. Fluoro-containing complex compound f1 Hexafluorotitanic acid f2 Hexafluorozirconic acid

TABLE-US-00008 TABLE 8 No. Vanadium (IV)-containing compound g1 Vanadium oxysulfate g2 Vanadium oxyacetyl acetonate

TABLE-US-00009 TABLE 9 Surface preparation layer () Organic resin Silane coupling agent Other components Amount Amount Amount Amount Amount No. Type (%) Type (%) Type (%) Type (%) Type (%) 1 a1 60 b1 40 2 a2 60 b1 40 3 a3 60 b1 40 4 a4 60 b1 40 5 a1 50 b1 30 c1 20 6 a1 40 b1 20 c1 20 d1 20 7 a1 40 b1 20 c1 20 d2 20 8 a1 38 b1 20 c1 20 d2 20 e1 2 9 a4 60 b1 + b2 20 + 20 10 a4 56 b1 + b2 17 + 17 e1 10 11 a4 56 b1 + b2 17 + 17 e2 10 12 a4 53 b1 + b2 16 + 16 e1 10 f1 5 13 a2 53 b1 + b2 16 + 16 e1 10 f2 14 a3 53 b1 + b2 16 + 16 e1 10 f2 5 15 a4 53 b1 + b2 16 + 16 e1 10 f2 16 a4 52 b1 + b2 15 + 15 e1 10 f2 5 g1 3 17 a4 52 b1 + b2 15 + 15 e1 10 f2 5 g2 3

(3) Coating Film Layer

[0122] A coating composition used to form a coating film was prepared by blending an organic resin A (as explained in Production Examples 1 to 3 of Organic Resin in (3-1) below and Table 10), a curing agent B (Table 11), an aluminum pigment C (as explained in Aluminum Pigment Production Examples 1 to 13 in (3-2) below and Table 12), silica particles D (Table 13), and polyolefin resin particles E (Table 14) so as to be a composition ratio (% by mass in terms of a solid component) shown in Table 15, and stirred using a stirrer for a coating material. Then, a coating film was formed by coating the mixture on the surface of the surface preparation layer formed in (2) above (when the surface preparation layer was not formed, on the surface of the metal sheet prepared in (1) Metal sheet above) so as to have a fixed thickness with a roll coater, and heated and dried by heating to a fixed highest temperature.

(3-1) Production Example of Organic Resin A

<Production Example 1 for Organic Resin>

[0123] In a reaction vessel provided with a stirrer, a condenser, and a thermometer, 199 parts of terephthalic acid, 232 parts of isophthalic acid, 199 parts of adipic acid, 33 parts of 5-sodium sulfoisophthalate, 312 parts of ethylene glycol, 125 parts of 2,2-dimethyl-1,3-propanediol, 187 parts of 1,5-pentanediol, and 0.41 parts of tetrabutyl titanate were added, and an esterification reaction was proceeded from 160 C. to 230 C. for 4 hours. Then, the pressure inside the reaction system was gradually reduced to 5 mmHg for 20 minutes, and a polymerization reaction was proceeded in vacuum of 0.3 mmHg or less at 260 C. for 40 minutes. In 100 parts of the obtained copolymerized polyester resin, 20 parts of butyl cellosolve, and 42 parts of methyl ethyl ketone were added, the mixture was dissolved by stirring at 80 C. for 2 hours, 213 g of deionized water was added, and dispersed in water. After that, the solvent was distilled by heating, and filtrated with 200-mesh membrane made of nylon. Thereby, an aqueous polyester resin dispersion A1 having a solid concentration of 30% was obtained.

<Production Example 2 for Organic Resin>

[0124] In a reaction vessel provided with a stirrer, a condenser, and a thermometer, 199 parts of terephthalic acid, 266 parts of isophthalic acid, 199 parts of adipic acid, 312 parts of ethylene glycol, 125 parts of 2,2-dimethyl-1,3-propanediol, 187 parts of 1,5-pentanediol, and 0.41 parts of tetrabutyl titanate were added, and an esterification reaction was proceeded from 160 C. to 230 C. for 4 hours. Then, the pressure inside the reaction system was gradually reduced to 5 mmHg for 20 minutes, and a polymerization reaction was proceeded in vacuum of 0.3 mmHg or less at 260 C. for 40 minutes. The mixture was cooled to 220 C. under nitrogen gaseous stream, 23 parts of trimellitic anhydride and 16 parts of ethylene glycol bisanhydrotrimellitate were added, and reacted for 30 minutes. In 100 parts of the obtained copolymerized polyester resin, 20 parts of butyl cellosolve, and 42 parts of methyl ethyl ketone were added, the mixture was dissolved by stirring at 80 C. for 2 hours, 23 parts of isopropyl alcohol and 3.5 parts of triethylamine were added, then 213 g of deionized water was added, and dispersed in water. After that, the solvent was distilled by heating, and filtrated with a 200-mesh membrane made of nylon. Thereby, an aqueous polyester resin dispersion A2 having a solid concentration of 30% was obtained.

<Production Example 3 for Organic Resin>

[0125] 230 parts of polyester polyol, which was synthesized by adipic acid having a hydroxyl group at the end and 1,4-butylene glycol, and had an average molecular weight of 900, and 15 parts of 2,2-bis(hydroxymethyl) propionic acid were added to 100 parts of N-methyl-2-pyrrolidone, and the mixture was heated to 80 C. to dissolve. After 100 parts of hexamethylene diisocyanate was added, the mixture was heated to 110 C. reacted for 2 hours, and then 11 parts of triethylamine was added to neutralize. The obtained solution was dropped in an aqueous solution containing 5 parts of ethylenediamine and 570 parts of deionized water while stirring strongly. Thereby, an aqueous polyester resin dispersion A3 having a solid concentration of 30% was obtained.

(3-2) Production Example of Aluminum Pigment C

<Production Example 1 of Aluminum Pigment>

[0126] An aluminum paste (Showa Aluminum Powder K.K.; Sap FM4010 (aluminum content: 67% by mass: D.sub.50: 11 m: thickness: 0.2 m)) was weighed such that the aluminum content was 300 g, 4.300 g of propylene glycol monomethyl ether, 1.000 g of deionized water, and 188 g of 25% by mass-ammonia water were added, the mixture was stirred in a 10 L-reaction vessel provided with a stirrer, a cooling pipe, and a dropping funnel. Then, a mixture, which was obtained by diluting a certain amount of tetraethoxysilane with propylene glycol monomethyl ether, was gradually dropped by the dropping funnel. After the completion of the reaction, the reaction solution was filtrated, the obtained filter cake was washed with propylene glycol monomethyl ether, and propylene glycol monomethyl ether was added in the washed filter cake. Thereby, a silica film-coated aluminum pigment paste C1 having a solid content of 50% by mass was obtained. The coated amount of the silica film relative to 100% by mass of aluminum was 1% by mass in terms of Si, and the thickness of the silica film was 5 nm.

<Production Example 2 of Aluminum Pigment>

[0127] A silica film-coated aluminum pigment pastes C2 to C5 having different coated amount and thickness of the silica film from those of the aluminum pigment having a solid content of 50% by mass in Production Example 1 were obtained in a manner identical to that of the Production Example 1 of Aluminum Pigment except that the coated amount and the thickness of the silica film were changed by adjusting the dropping amount of the mixture which was obtained by diluting tetraethoxysilane with propylene glycol monomethyl ether. The coated amount of the silica film relative to 100% by mass of aluminum was, in terms of Si, 3.5% by mass in the paste C2, 7% by mass in the paste C3, 10% by mass in the paste C4, and 20% by mass in the paste C5. The thickness of the silica film was 18 nm in the paste C2, 35 nm in the paste C3, 50 nm in the paste C4, and 100 nm in the paste C5.

<Production Example 3 of Aluminum Pigment>

[0128] An aluminum paste (Showa Aluminum Powder K.K.; Sap 616FP (aluminum content: 70% by mass: D.sub.50: 18 m: thickness: 0.3 m)) was weighed such that the aluminum content was 300 g, 2,000 g of mineral spirit was added, the mixture was stirred in a 5 L-reaction vessel provided with a stirrer, a cooling pipe, and a dropping funnel. Then, 36.9 g of trimethylolpropane acrylate (TMP), 0.34 g of acrylic acid (AA), and 1.34 g of azobisisobutyronitrile were mixed. The obtained mixture was dropped through the dropping funnel in the 5 L-reaction vessel under heated conditions. After that, the mixture was stirred at 90 C. for 2 hours, and the reaction was completed. Then, the reaction solution was filtrated, the obtained filter cake was washed with mineral spirit, and further with propylene glycol, and propylene glycol was added in the washed filter cake. Thereby, an acrylic resin film-coated aluminum pigment paste C6 having a solid content of 50% by mass was obtained. The coated amount of the acrylic resin film relative to 100% by mass of aluminum was 12% by mass.

<Production Example 4 of Aluminum Pigment>

[0129] An aluminum paste (Showa Aluminum Powder K.K.; Sap 561PS (aluminum content: 67% by mass; D.sub.50: 16 m; thickness: 0.2 m)) was weighed such that the aluminum content was 300 g, 1,500 g of propylene glycol monomethyl ether was added, the mixture was stirred in a 5 L-reaction vessel provided with a stirrer, a cooling pipe, and a dropping funnel. Then, an aqueous solution, which was obtained by dissolving a certain amount of ammonium paramolybdate in 300 g of deionized water, was gradually dropped by the dropping funnel, and the reaction was carried out in pH 8 to 9, at room temperature for 1 hour. After the completion of the reaction, the reaction solution was filtrated, the obtained filter cake was washed with deionized water, and further with propylene glycol monomethyl ether. Then, propylene glycol monomethyl ether was added in the washed filter cake. Thereby, a molybdic acid film-coated aluminum pigment paste C7 having a solid content of 50% by mass was obtained. The coated amount of the silica film relative to 100% by mass of aluminum was 2.5% by mass in terms of Mo.

<Production Example 5 of Aluminum Pigment>

[0130] An aluminum paste (Showa Aluminum Powder K.K.; Sap 561PS (aluminum content: 67% by mass: D.sub.50: 16 m; thickness: 0.2 m)) was weighed such that the aluminum content was 300 g, 1.200 g of propylene glycol monomethyl ether was added, the mixture was stirred in a 5 L-reaction vessel provided with a stirrer, a cooling pipe, and a dropping funnel. Then, an aqueous solution, which was obtained by dissolving a certain amount of ammonium dihydrogen phosphate in 300 g of deionized water, was gradually dropped by the dropping funnel, heated to 70 C., and the reaction was carried out for 5 hours. After the completion of the reaction, the reaction solution was filtrated, the obtained filter cake was washed with deionized water, and further with propylene glycol monomethyl ether. Then, propylene glycol monomethyl ether was added in the washed filter cake. Thereby, a phosphoric acid film-coated aluminum pigment paste C8 having a solid content of 50% by mass was obtained. The coated amount of the phosphoric acid film relative to 100%/o by mass of aluminum was 1.0% by mass in terms of P.

<Production Example 6 of Aluminum Pigment>

[0131] An aluminum paste (Showa Aluminum Powder K.K.; Sap FM4010 (aluminum content: 40% by mass; acrylic resin film-coated aluminum particles; the coated amount of the acrylic resin film is 9% by mass relative to 100% by mass of aluminum; D.sub.50: 1 m; thickness: 0.2 m)) was weighed such that the aluminum content was 300 g, mineral spirit contained in the aluminum paste was displaced with propylene glycol, and the mixture was stirred in a 5 L-reaction vessel provided with a stirrer, a cooling pipe, and a dropping funnel. Then, an aqueous solution, which was obtained by dissolving a certain amount of ammonium dihydrogen phosphate in 300 g of deionized water, was gradually dropped by the dropping funnel, heated to 70 C., and the reaction was carried out for 5 hours. After the completion of the reaction, the reaction solution was filtrated, the obtained filter cake was washed with deionized water, and further with propylene glycol monomethyl ether. Then, propylene glycol monomethyl ether was added in the washed filter cake. Thereby, a phosphoric acid film-coated aluminum pigment paste C9 having a solid content of 50% by mass was obtained. The coated amount of the phosphoric acid film relative to 100% by mass of aluminum was 1.0% by mass in terms of P.

<Production Example 7 of Aluminum Pigment>

[0132] A silica film-coated aluminum pigment paste C10 having a solid content of 50% by mass was obtained using an aluminum paste (Showa Aluminum Powder K.K.; Sap 2173SW (aluminum content: 69% by mass; D.sub.50: 6 m; thickness: 0.1 m)) in a manner identical to that of the Production Example 1 of Aluminum Pigment by adjusting the dropping amount of the mixture which was obtained by diluting tetraethoxysilane with propylene glycol monomethyl ether. The coated amount of the silica film in the silica-coated aluminum pigment paste C10 relative to 100% by mass of aluminum was 7% by mass in terms of Si. The thickness of the silica film was 35 nm.

<Production Example 8 of Aluminum Pigment>

[0133] A silica film-coated aluminum pigment paste C11 having a solid content of 50% by mass was obtained using an aluminum paste (Showa Aluminum Powder K.K.; Sap CS430 (aluminum content: 70% by mass: D.sub.50: 9 m: thickness: 0.3 m)) in a manner identical to that of the Production Example 1 of Aluminum Pigment by adjusting the dropping amount of the mixture which was obtained by diluting tetraethoxysilane with propylene glycol monomethyl ether. The coated amount of the silica film in the silica film-coated aluminum pigment paste C11 relative to 100% by mass of aluminum was 7% by mass in terms of Si. The thickness of the silica film was 35 nm.

<Production Example 9 of Aluminum Pigment>

[0134] A silica film-coated aluminum pigment paste C12 having a solid content of 50% by mass was obtained using an aluminum paste (Showa Aluminum Powder K.K.; Sap 561PS (aluminum content: 67% by mass; D.sub.50: 16 m; thickness: 0.2 m)) in a manner identical to that of the Production Example 1 of Aluminum Pigment by adjusting the dropping amount of the mixture which was obtained by diluting tetraethoxysilane with propylene glycol monomethyl ether. The coated amount of the silica film in the silica film-coated aluminum pigment paste C12 relative to 100% by mass of aluminum was 3.5% by mass in terms of Si. The thickness of the silica film was 18 nm.

<Production Example 10 of Aluminum Pigment>

[0135] A silica film-coated aluminum pigment paste C13 having a solid content of 50% by mass was obtained using an aluminum paste (Showa Aluminum Powder K.K.; Sap 576PS (aluminum content: 75% by mass; D.sub.50: 20 m; thickness: 0.4 m)) in a manner identical to that of the Production Example 1 of Aluminum Pigment by adjusting the dropping amount of the mixture which was obtained by diluting tetraethoxysilane with propylene glycol monomethyl ether. The coated amount of the silica film in the silica-coated aluminum pigment paste C13 relative to 100% by mass of aluminum was 3.5% by mass in terms of Si. The thickness of the silica film was 18 nm.

<Production Example 11 of Aluminum Pigment>

[0136] A silica-coated aluminum pigment paste C14 having a solid content of 50% by mass was obtained using an aluminum paste (Showa Aluminum Powder K.K.; Sap LB584 (aluminum content: 76% by mass; D.sub.50: 25 m; thickness: 0.4 m)) in a manner identical to that of the Production Example 1 of Aluminum Pigment by adjusting the dropping amount of the mixture which was obtained by diluting tetraethoxysilane with propylene glycol monomethyl ether. The coated amount of the silica film in the silica film-coated aluminum pigment paste C14 relative to 100% by mass of aluminum was 3.5% by mass in terms of Si. The thickness of the silica film was 18 nm.

[0137] <Production Example 12 of Aluminum Pigment>

[0138] A silica film-coated aluminum pigment paste C15 having a solid content of 50% by mass was obtained using an aluminum paste (Showa Aluminum Powder K.K.; Sap 720N (aluminum content: 78% by mass; D.sub.50: 30 m; thickness: 0.6 m)) in a manner identical to that of the Production Example 1 of Aluminum Pigment by adjusting the dropping amount of the mixture which was obtained by diluting tetraethoxysilane with propylene glycol monomethyl ether. The coated amount of the silica film in the silica film-coated aluminum pigment paste C15 relative to 100% by mass of aluminum was 3.5% by mass in terms of Si. The thickness of the silica film was 18 nm.

<Production Example 13 of Aluminum Pigment>

[0139] A silica film-coated aluminum pigment paste C16 having a solid content of 50% by mass was obtained using an aluminum paste (Showa Aluminum Powder K.K.; Sap LB588 (aluminum content: 77% by mass; D.sub.50: 36 m; thickness: 0.6 m)) in a manner identical to that of the Production Example 1 of Aluminum Pigment by adjusting the dropping amount of the mixture which was obtained by diluting tetraethoxysilane with propylene glycol monomethyl ether. The coated amount of the silica film in the silica film-coated aluminum pigment paste C16 relative to 100% by mass of aluminum was 3.5% by mass in terms of Si. The thickness of the silica film was 18 nm.

TABLE-US-00010 TABLE 10 No. Organic resin (A) A1 Polyester resin having a Na sulfonate group (Production Example 1) A2 Polyester resin having a carboxyl group (Production Example 2) A3 Polyurethane resin having an urea group and a carboxyl group (Production Example 3) A4 Polyurethane resin having a cationic functional group (Dai-ichi KogyoSeiyaku Co., Ltd; SUPERFLEX 620) A5 Acrylic resin (Nippon NSC Ltd. Kanevinol AD121) A6 Polyolefin resin (TOHO Chemical Industry C., Ltd. HYTEC S-3121)

TABLE-US-00011 TABLE 11 No. Curing agent (B) B1 Melamine resin (Nihon Cytec Industries Inc., Cymel 303) B2 Melamine resin (Nihon Cytec Industries Inc., Cymel 325) B3 Isocyanate compound (Mitsui Chemicals, Inc., TAKENATEWD-725)

TABLE-US-00012 TABLE 12 No. Aluminum pigment (C) C1 Silica film-coated aluminum pigment (Preparation Example 1, Particle diameter: 11 m, Coated amount of the silica film: 1% by mass in terms of Si, Thickness of the silica film: 5 nm) C2 Silica film-coated aluminum pigment (Preparation Example 2, Particle diameter: 11 m, Coated amount of the silica film: 3.5% by mass in terms of Si, Thickness of the silica film: 18 nm) C3 Silica film-coated aluminum pigment (Preparation Example 2, Particle diameter: 11 m, Coated amount of the silica film: 7% by mass in terms of Si, Thickness of the silica film: 35 nm) C4 Silica film-coated aluminum pigment (Preparation Example 2, Particle diameter: 11 m, Coated amount of the silica film: 10% by mass in terms of Si, Thickness of the silica film: 50 nm) C5 Silica film-coated aluminum pigment (Preparation Example 2, Particle diameter: 11 m, Coated amount of the silica film: 20% by mass in terms of Si, Thickness of the silica film: 100 nm) C6 Acrylic resin film-coated aluminum pigment (Preparation Example 3, Particle diameter: 18 m, Coated amount of the acrylic resin film: 12% by mass) C7 Molybdic acid film-coated aluminum pigment (Preparation Example 4, Particle diameter: 16 m, Coated amount of the molybdic acid film: 2.5% by mass in terms of Mo) C8 Phosphoric acid film-coated aluminum pigment (Preparation Example 5, Particle diameter: 16 m, Coated amount of the phosphoric acid film: 1.0% by mass in terms of P) C9 Phosphoric acid film and acrylic resin film-coated aluminum pigment (Preparation Example 6, Particle diameter: 11 m, Coated amount of the phosphoric acid film: 1.0% by mass in terms of P, Coated amount of the acrylic resin film: 9% by mass) C10 Silica film-coated aluminum pigment (Preparation Example 7, Particle diameter: 6 m, Coated amount of the silica film: 7% by mass in terms of Si, Thickness of the silica film: 35 nm) C11 Silica film-coated aluminum pigment (Preparation Example 8, Particle diameter: 9 m, Coated amount of the silica film: 7% by mass in terms of Si, Thickness of the silica film: 35 nm) C12 Silica film-coated aluminum pigment (Preparation Example 9, Particle diameter: 16 m, Coated amount of the silica film: 3.5% by mass in terms of Si, Thickness of the silica film: 18 nm) C13 Silica film-coated aluminum pigment (Preparation Example 10, Particle diameter: 20 m, Coated amount of the silica film: 3.5% by mass in terms of Si, Thickness of the silica film: 18 nm) C14 Silica film-coated aluminum pigment (Preparation Example 11, Particle diameter: 25 m, Coated amount of the silica film: 3.5% by mass in terms of Si, Thickness of the silica film: 18 nm) C15 Silica film-coated aluminum pigment (Preparation Example 12, Particle diameter: 30 m, Coated amount of the silica film: 3.5% by mass in terms of Si, Thickness of the silica film: 18 nm) C16 Silica film-coated aluminum pigment (Preparation Example 13, Particle diameter: 36 m, Coated amount of the silica film: 3.5% by mass in terms of Si, Thickness of the silica film: 18 nm) C17 Aluminum pigment (Showa Aluminum Powder K.K., Sap FM4010) C18 Aluminum pigment (Showa Aluminum Powder K.K., Sap 616FP) C19 Aluminum pigment (Showa Aluminum Powder K.K., Sap 561PS)

TABLE-US-00013 TABLE 13 No. Silica particle (D) D1 Colloidal silica (Nissan Chemical Industries, Ltd., SNOWTEX NXS, Particle diameter: 5 nm) D2 Colloidal silica (Nissan Chemical Industries, Ltd., SNOWTEX N, Particle diameter: 15 nm) D3 Colloidal silica (Nissan Chemical Industries, Ltd., SNOWTEX XL, Particle diameter: 50 nm) D4 Colloidal silica (Nissan Chemical Industries, Ltd., SNOWTEX YL, Particle diameter: 65 nm) D5 Colloidal silica (Nissan Chemical Industries, Ltd., MP-1040, Particle diameter: 100 nm) D6 Colloidal silica (Nissan Chemical Industries, Ltd., MP-2040, Particle diameter: 200 nm)

TABLE-US-00014 TABLE 14 No. Polyolefin resin particle (E) E1 Polyethylene (Mitsui Chemicals, Inc. CHEMIPEARL XWF3001, Particle diameter: 0.15 m) E2 Polyethylene (Mitsui Chemicals, Inc. CHEMIPEARL W950, Particle diameter: 0.6 m) E3 Polyethylene (Mitsui Chemicals, Inc. CHEMIPEARL WF640, Particle diameter: 1.0 m) E4 Polyethylene (Mitsui Chemicals, Inc. CHEMIPEARL W500, Particle diameter: 2.5 m) E5 Polyethylene (Mitsui Chemicals, Inc. CHEMIPEARL W400, Particle diameter: 4.0 m) E6 Polypropylene (Mitsui Chemicals, Inc. CHEMIPEARL WP100, Particle diameter: 1.0 m)

(4) Coated Metal Sheet

[0140] As explained in (3) above, the composition, thickness, and highest baking temperature of the coating film of the coated metal sheet on which the coating film was formed are shown in Table 15 below.

TABLE-US-00015 TABLE 15 Coating film () Silica Polyolefin Curing Aluminum particle resin Surface Organic resin (A) agent(B) pigment (C) (D) particle (E) preparation *1 *1 *2 *3 *3 *3 Highest Metal layer Amount Amount Amount Amount Amount Amount Thickness temp. No. sheet () Type (%) Type (% ) Type (%) Type ( % ) Type (%) Type (%) (m) ( C.) Ex. 1 M1 8 A1 70 A3 30 C2 20 5 200 Ex. 2 M1 8 A1 70 A3 30 B1 20 C2 20 5 200 Ex. 3 M1 8 A1 70 A3 30 C2 20 D2 10 5 200 Ex. 4 M1 8 A1 70 A3 30 C2 20 E3 1 3 200 Ex. 5 M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 5 200 Ex. 6 M1 8 A1 70 A3 30 B1 20 C2 20 E3 3 5 200 Ex. 7 M1 8 A1 70 A3 30 C2 20 D2 10 E3 3 5 200 Ex. 8 M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 9 M1 8 A1 100 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 10 M1 8 A1 100 C2 20 D2 10 E3 3 5 200 Ex. 11 M1 8 A2 100 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 12 M1 8 A3 100 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 13 M1 8 A4 100 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 14 M1 8 A5 100 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 15 M1 8 A6 100 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 16 M1 8 A1 50 A3 50 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 17 M1 8 A1 90 A3 10 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 18 M1 8 A1 70 A3 30 B2 20 C2 20 D2 10 E3 3 5 200 Ex. 19 M1 8 A1 70 A3 30 B3 20 C2 20 D2 10 E3 3 5 200 Ex. 20 M1 8 A1 70 A3 30 B1 20 C1 20 D2 10 E3 3 5 200 Ex. 21 M1 8 A1 70 A3 30 B1 20 C3 20 D2 10 E3 3 5 200 Ex. 22 M1 8 A1 70 A3 30 B1 20 C4 20 D2 10 E3 3 5 200 Ex. 23 M1 8 A1 70 A3 30 B1 20 C5 20 D2 10 E3 3 5 200 Ex. 24 M1 8 A1 70 A3 30 B1 20 C6 20 D2 10 E3 3 5 200 Ex. 25 M1 8 A1 70 A3 30 B1 20 C7 20 D2 10 E3 3 5 200 Ex. 26 M1 8 A1 70 A3 30 B1 20 C8 20 D2 10 E3 3 5 200 Ex. 27 M1 8 A1 70 A3 30 B1 20 C9 20 D2 10 E3 3 5 200 Ex. 28 M1 8 A1 70 A3 30 B1 20 C10 20 D2 10 E3 3 5 200 Ex. 29 M1 8 A1 70 A3 30 B1 20 C11 20 D2 10 E3 3 5 200 Ex. 30 M1 8 A1 70 A3 30 B1 20 C12 20 D2 10 E3 3 5 200 Ex. 31 M1 8 A1 70 A3 30 B1 20 C13 20 D2 10 E3 3 5 200 Ex. 32 M1 8 A1 70 A3 30 B1 20 C14 20 D2 10 E3 3 5 200 Ex. 33 M1 8 A1 70 A3 30 B1 20 C15 20 D2 10 E3 3 5 200 Ex. 34 M1 8 A1 70 A3 30 B1 20 C16 20 D2 10 E3 3 5 200 Ex. 35 M1 8 A1 70 A3 30 B1 20 C2 7 D2 10 E3 3 5 200 Ex. 36 M1 8 A1 70 A3 30 B1 20 C2 10 D2 10 E3 3 5 200 Ex. 37 M1 8 A1 70 A3 30 B1 20 C2 15 D2 10 E3 3 5 200 Ex. 38 M1 8 A1 70 A3 30 B1 20 C2 25 D2 10 E3 3 5 200 Ex. 39 M1 8 A1 70 A3 30 B1 20 C2 30 D2 10 E3 3 5 200 Ex. 40 M1 8 A1 70 A3 30 B1 20 C2 35 D2 10 E3 3 5 200 Ex. 41 M1 8 A1 70 A3 30 B1 20 C2 40 D2 10 E3 3 5 200 Ex. 42 M1 8 A1 70 A3 30 B1 20 C9 7 D2 10 E3 3 5 200 Ex. 43 M1 8 A1 70 A3 30 B1 20 C9 10 D2 10 E3 3 5 200 Ex. 44 M1 8 A1 70 A3 30 B1 20 C9 15 D2 10 E3 3 5 200 Ex. 45 M1 8 A1 70 A3 30 B1 20 C9 25 D2 10 E3 3 5 200 Ex. 46 M1 8 A1 70 A3 30 B1 20 C9 30 D2 10 E3 3 5 200 Ex. 47 M1 8 A1 70 A3 30 B1 20 C9 35 D2 10 E3 3 5 200 Ex. 48 M1 8 A1 70 A3 30 B1 20 C9 40 D2 10 E3 3 5 200 Ex. 49 M1 8 A1 70 A3 30 B1 20 C2 20 D1 10 E3 3 5 200 Ex. 50 M1 8 A1 70 A3 30 B1 20 C2 20 D3 10 E3 3 5 200 Ex. 51 M1 8 A1 70 A3 30 B1 20 C2 20 D4 10 E3 3 5 200 Ex. 52 M1 8 A1 70 A3 30 B1 20 C2 20 D5 10 E3 3 5 200 Ex. 53 M1 8 A1 70 A3 30 B1 20 C2 20 D6 10 E3 3 5 200 Ex. 54 M1 8 A1 70 A3 30 B1 20 C2 20 D2 3 E3 3 5 200 Ex. 55 M1 8 A1 70 A3 30 B1 20 C2 20 D2 5 E3 3 5 200 Ex. 56 M1 8 A1 70 A3 30 B1 20 C2 20 D2 20 E3 3 5 200 Ex. 57 M1 8 A1 70 A3 30 B1 20 C2 20 D2 25 E3 3 5 200 Ex. 58 M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 E1 3 5 200 Ex. 59 M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 E2 3 5 200 Ex. 60 M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 E4 3 5 200 Ex. 61 M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 E5 3 5 200 Ex. 62 M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 E6 3 5 200 Ex. 63 M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 0.3 5 200 Ex. 64 M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 0.5 5 200 Ex. 65 M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 1.5 5 200 Ex. 66 M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 5 5 200 Ex. 67 M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 7 5 200 Ex. 68 M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 2 200 Ex. 69 M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 3 200 Ex. 70 M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 7 200 Ex. 71 M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 10 200 Ex. 72 M1 A1 70 A3 30 B1 20 C2 20 D2 10 5 200 Ex. 73 M1 A1 70 A3 30 B1 20 C2 20 E3 3 5 200 Ex. 74 M1 A1 70 A3 30 C2 20 D2 10 E3 3 5 200 Ex. 75 M1 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 76 M1 1 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 77 M1 2 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 78 M1 3 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 79 M1 4 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 80 M1 5 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 81 M1 6 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 82 M1 7 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 83 M1 9 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 84 M1 10 A1 70 A3 30 B1 70 C2 20 D2 10 E3 3 5 200 Ex. 85 M1 11 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 86 M1 12 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 87 M1 13 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 88 M1 14 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 89 M1 15 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 90 M1 16 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 91 M1 17 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 92 M2 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 93 M2 8 A1 100 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 94 M2 8 A1 70 A3 30 B1 20 C9 20 D2 10 E3 3 5 200 Ex. 95 M2 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 96 M3 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 97 M3 8 A1 100 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 98 M3 8 A1 70 A3 30 B1 70 C9 20 D2 10 E3 3 5 200 Ex. 99 M3 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 100 M4 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 101 M4 8 A1 100 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 102 M4 8 A1 70 A3 30 B1 20 C9 20 D2 10 E3 3 5 200 Ex. 103 M4 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 104 M5 8 A1 70 A3 30 Bl 20 C2 20 D2 10 E3 3 5 200 Ex. 105 M5 8 A1 100 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 106 M5 8 A1 70 A3 30 B1 20 C9 20 D2 10 E3 3 5 200 Ex. 107 M5 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 108 M6 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 109 M6 8 A1 100 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 110 M6 8 A1 70 A3 30 B1 20 C9 20 D2 10 E3 3 5 200 Ex. 111 M6 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 112 M7 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 113 M7 8 A1 100 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 114 M7 8 A1 70 A3 30 B1 20 C9 20 D2 10 E3 3 5 200 Ex. 115 M7 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 116 M8 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 117 M8 8 A1 100 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 118 M8 8 A1 70 A3 30 B1 20 C9 20 D2 10 E3 3 5 200 Ex. 119 M8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 5 200 Ex. 120 M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 1.5 200 Comp. M1 8 A1 70 A3 30 B1 20 C17 20 D2 10 E3 3 5 200 Ex. 1 Comp. M1 8 A1 70 A3 30 B1 20 C18 20 D2 10 E3 3 5 200 Ex. 2 Comp. M1 8 A1 70 A3 30 B1 20 C19 20 D2 10 E3 3 5 200 Ex. 3 Comp. M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 1 200 Ex. 4 Comp. M1 8 A1 70 A3 30 B1 20 C2 20 D2 10 E3 3 12 200 Ex. 5 Comp. M1 8 A1 70 A3 30 B1 20 D2 10 E3 3 5 200 Ex. 6 *1: Percentage in the organic resin (% by mass of solid content) *2: Percentage relative to 100% by mass of organic resin solid content (% by mass of solid content) *3: Percentage in the coating film () (% by mass of solid content)

(5) Evaluation Test

[0141] The design characteristics, corrosion resistance, coating film adhesion (processing adhesion and water resisting adhesion), chemical resistance, and scratch resistance of the coated metal sheet (test sheet), which was prepared as explained in (3) above, were evaluated in accordance with the evaluation method and evaluation standards below. The results are shown in Table 16.

(Design Characteristics)

[0142] The design characteristics of the test sheet was visually observed and evaluated in accordance with the following evaluation standards. Moreover, G value (Glossiness) was evaluated using a 60/60 gloss meter in accordance with JIS Z 8741.

5: Both of metallic color and surface burnish are uniform, the substrate is not completely seen through, and the G value is 25 or more
4: Both of metallic color and surface burnish are uniform, the substrate is not completely seen through, and the G value is 20 or more and less than 25
3: Both of metallic color and surface burnish are uniform, the substrate is not completely seen through, and the G value is less than 20
2: The substrate is slightly seen through (the substrate could be confirmed by staring) or fine cracking is generated in the coating film (the cracking could be confirmed by staring)
1: The substrate is seen through (the substrate could be easily observed), or cracking is generated in the coating film (the cracking could be easily observed)

(Corrosion Resistance)

[0143] After sealing a tape on the end surface of the test sheet, salt spray test (SST) was carried out for 120 hours in accordance with JIS Z 2371. The rust generation conditions were observed, and evaluated along the following evaluation standards.

5: White rust and blackening are not generated
4: A ratio of an area at which white rust and blackening were generated is less than 1%
3: A ratio of an area at which white rust and blackening were generated is 1% or more and less than 2.5%
2: A ratio of an area at which white rust and blackening were generated is 2.5% or more and less than 5%
1: A ratio of an area at which white rust and blackening were generated is 5% or more

(Coating Film Adhesion (Processing Adhesion))

[0144] After bending the test sheet at 180, tape peeling test (in accordance with JIS K 5600-5-6) was carried out at the outside of the bent pan of the test sheet. Then, the appearance of the area from which the tape was peeled was evaluated in accordance with the following standards. Moreover, the bending was carried out by inserting a space of 0.5 mm in thickness at 20 C. (in general, it is called 1T bending)

5: Peeling is not observed in the coating film
4: Peeling is observed only at a small part of the coating film (peeling is barely observed using a loupe)
3: Peeling is observed at a part of the coating film (peeling is observed using a loupe)
2: Partial peeling is observed in the coating film (peeling is observed with eyes)
1: Peeling is observed in almost all of the coating film (peeling is easily observed with eyes)

(Coating Film Adhesion (Water Resisting Adhesion))

[0145] The test sheet was immersed in boiling water for 30 minutes, and removed. After leaving it at room temperature for 24 hours, 100 cut flaws were made in the test sheet at intervals of 1 mm in a checkerboard pattern. Then tape peeling test was carried out using the test sheet. Making cut flaws in a checkerboard pattern, and peeling the tape were carried out in accordance with JIS-K 5400. 8. 2 and JIS-K 5400. 8. 5. The results were evaluated using the following standards.

5: A number of peeled square is 0
4: A number of peeled square is 1 or 2
3: A number of peeled square is in a range of 3 to 5
2: A number of peeled square is in a range of 6 to 10
1: A number of peeled square is II or more

(Chemical Resistance)

[0146] After setting the test sheet in a rubbing tester, the surface of the test sheet was rubbed using a cotton impregnated with ethanol back and forth 10 times with a load of 49.03 kPa (0.5 kgf/cm.sup.2). Then the conditions of the coating film of the test sheet were evaluated using the following standards.

5: Rubbed surface has not tracks at all
4: Rubbed surface has very slight tracks (rubbed tracks can be barely observed by staring)
3: Rubbed surface has light tracks (rubbed tracks can be easily observed by staring)
2: Rubbed surface has clear tracks (rubbed tracks can be easily observed in a moment)
1: Coating film is dissolved in the rubbed surface, and the substrate was exposed

(Scratch Resistance)

[0147] The test sheet was scratched by 5 lines by a lead pencil at an angle of 45 and the scratch resistance was evaluated by the pencil hardness by which no scratches were formed at 2 lines or more. As the lead pencil. Uni pencil marketed by Mitsubishi Pencil Co., Ltd. was used. The test was carried out in accordance with JIS K 5600-5-4 at 20 C. with a load of 4.903 N (500 gf). The results were evaluated using the following standards.

5: Pencil hardness of 3H or more
4: Pencil hardness of 2H
3: Pencil hardness of H
2 Pencil hardness of F
1: Pencil hardness of HB or less

TABLE-US-00016 TABLE 16 Coating film adhesion Water- Design Corrosion Processing resisting Chemical Scratch No. characteristics resistance adhesion adhesion resistance resistance Example 1 5 3 5 4 3 3 Example 2 5 3 5 5 5 3 Example 3 5 4 5 4 3 3 Example 4 5 3 5 4 3 3 Example 5 5 5 5 5 5 4 Example 6 5 3 5 5 5 4 Example 7 5 4 5 4 3 4 Example 8 5 5 5 5 5 5 Example 9 5 4 5 4 5 5 Example 10 5 3 5 3 3 4 Example 11 5 4 5 4 4 5 Example 12 5 5 4 5 3 5 Example 13 4 3 4 4 3 4 Example 14 5 3 3 4 3 5 Example 15 5 4 3 3 5 4 Example 16 5 5 5 5 4 5 Example 17 5 4 5 5 5 5 Example 18 5 5 5 5 5 5 Example 19 5 4 5 5 4 4 Example 20 5 3 5 5 5 5 Example 21 5 5 5 5 5 5 Example 22 5 5 5 5 5 5 Example 23 3 5 5 5 5 5 Example 24 4 4 5 5 5 5 Example 25 5 3 5 5 5 5 Example 26 5 3 5 5 5 5 Example 27 5 5 5 5 5 5 Example 28 4 5 5 5 5 5 Example 29 5 5 5 5 5 5 Example 30 5 5 5 5 5 5 Example 31 5 5 5 5 5 5 Example 32 5 5 5 5 5 5 Example 33 4 5 5 5 5 5 Example 34 4 4 5 5 5 5 Example 35 3 5 5 5 5 5 Example 36 4 5 5 5 5 5 Example 37 5 5 5 5 5 5 Example 38 5 5 5 5 5 5 Example 39 5 5 5 5 5 5 Example 40 5 4 5 4 5 5 Example 41 5 3 4 3 5 5 Example 42 3 5 5 5 5 5 Example 43 4 5 5 5 5 5 Example 44 4 5 5 5 5 5 Example 45 4 5 5 5 5 5 Example 46 4 5 5 5 5 5 Example 47 4 4 5 4 5 5 Example 48 4 3 4 3 5 5 Example 49 5 5 5 5 5 5 Example 50 5 5 5 5 5 5 Example 51 5 4 5 5 5 5 Example 52 5 4 5 5 5 5 Example 53 4 3 5 5 5 5 Example 54 5 4 5 5 5 5 Example 55 5 5 5 5 5 5 Example 56 5 5 5 5 5 5 Example 57 5 5 4 4 5 5 Example 58 5 5 5 5 5 4 Example 59 5 5 5 5 5 5 Example 60 5 5 5 5 5 5 Example 61 4 4 5 5 5 5 Example 62 5 5 5 5 5 5 Example 63 5 5 5 5 5 4 Example 64 5 5 5 5 5 5 Example 65 5 5 5 5 5 5 Example 66 5 5 5 5 5 5 Example 67 4 4 5 5 5 5 Example 68 3 3 5 5 5 4 Example 69 4 4 5 5 5 5 Example 70 5 5 5 5 5 5 Example 71 4 4 4 5 5 5 Example 72 5 3 3 4 5 4 Example 73 5 3 3 4 5 4 Example 74 5 3 3 3 3 4 Example 75 5 3 3 4 5 5 Example 76 5 3 4 4 5 5 Example 77 5 3 4 4 5 5 Example 78 5 3 4 4 5 5 Example 79 5 3 4 4 5 5 Example 80 5 4 5 4 5 5 Example 81 5 4 5 5 5 5 Example 82 5 4 5 5 5 5 Example 83 5 3 4 4 5 5 Example 84 5 4 4 4 5 5 Example 85 5 4 4 4 5 5 Example 86 5 5 4 5 5 5 Example 87 5 5 4 5 5 5 Example 88 5 5 4 5 5 5 Example 89 5 5 4 5 5 5 Example 90 5 5 5 5 5 5 Example 91 5 5 5 5 5 5 Example 92 5 5 5 5 5 5 Example 93 5 4 5 4 5 5 Example 94 4 5 5 5 5 5 Example 95 5 3 3 4 5 5 Example 96 5 5 5 5 5 5 Example 97 5 4 5 4 5 5 Example 98 4 5 5 5 5 5 Example 99 5 3 3 4 5 5 Example 100 5 5 5 5 5 5 Example 101 5 5 5 4 5 5 Example 102 4 5 5 5 5 5 Example 103 5 4 3 4 5 5 Example 104 5 5 5 5 5 5 Example 105 5 5 5 4 5 5 Example 106 4 5 5 5 5 5 Example 107 5 4 3 4 5 5 Example 108 5 5 5 5 5 5 Example 109 5 5 5 4 5 5 Example 110 4 5 5 5 5 5 Example 111 5 5 3 4 5 5 Example 112 5 5 5 5 5 5 Example 113 5 5 5 4 5 5 Example 114 4 5 5 5 5 5 Example 115 5 5 3 4 5 5 Example 116 5 5 5 5 5 5 Example 117 5 5 5 4 5 5 Example 118 4 5 5 5 5 5 Example 119 5 5 3 4 5 5 Example 120 3 3 5 5 5 3 Comparative 5 1 5 5 5 5 Example 1 Comparative 5 1 5 5 5 5 Example 2 Comparative 5 1 5 5 5 5 Example 3 Comparative 1 2 5 5 5 2 Example 4 Comparative 2 3 2 4 5 5 Example 5 Comparative 1 5 5 5 5 4 Example 6

[0148] Examples of the present invention had excellent design characteristics, corrosion resistance, coating film adhesion (processing adhesion and water resisting adhesion), chemical resistance, and scratch resistance in which the evaluation standard was 3 or more in all of the evaluation tests. Moreover, when the coating composition having a solid content of 30% among all coating compositions used in Examples was left at rest at 40 C., and thereby the storage stability was examined, the coating composition in Example 11 gelated after 2 weeks, and the coating composition in Example 13 gelated after 3 days. In other words, the coating composition containing the polyester resin A2 having a carboxyl group and no sulfonic acid group, and the coating composition containing the polyurethane resin A4 having a cationic functional group had inferior storage stability to that of other coating compositions.

[0149] On the other hand, Comparative Examples 1 to 3, which were out of the scope of the present invention, and used the aluminum pigment, the surface of which was not subjected to the deactivation treatment, had inferior corrosion resistance. Comparative Example 4 of which the thickness of the coating film was 1 m, which was out of the scope of the present invention, had inferior design characteristics and corrosion resistance. Comparative Example 5 of which the thickness of the coating film was 12 m, which was out of the scope of the present invention, had inferior design characteristics and processing adhesion. Comparative Example 6, which did not contain the aluminum pigment, had an inferior design characteristics.

[0150] The preferable embodiments of the present invention were explained above. However, the present invention is not limited to these embodiments. It is clear that a person skilled in the art can make various changes or modifications to the embodiments and still be within the scope of the claims, and that such changes or modifications are deservingly included in the technical scope of the present invention.

INDUSTRIAL APPLICABILITY

[0151] The chromate-free coated metal sheet having metallic appearance according to the present invention does not contain hexavalent chromium having a high environmental load, is cheap, and extremely excellent in design characteristics (luster and concealing properties), corrosion resistance, coating film adhesion (processing adhesion, water resisting adhesion), scratch resistance, chemical resistance and the like. Therefore, the chromate-free coated metal sheet according to the present invention is promising as a metallic tone raw material which is cheap, is highly designable, adds a high amount of value, is compatible with the environment, and significantly contributes to various industries.