PRECOATED METAL SHEET FOR AUTOMOBILE USE EXCELLENT IN RESISTANCE WELDABILITY, CORROSION RESISTANCE, AND FORMABILITY
Precoated metal sheet for automobile use which is excellent in resistance weldability, corrosion resistance, and formability is provided. The present invention provides precoated metal sheet for automobile use comprising a metal sheet and a coat (α) on at least one surface of the metal sheet, wherein the coat (α) comprising an organic resin (A), non-oxide ceramic particles (B) selected from at least one type of borides, carbides, nitrides, and silicides and which have an electrical resistivity at 25° C. of 0.1×10 −6 to 185×10 −6 Ωcm, and an anti-corrosive pigment (C).
1 . Precoated metal sheet for automobile use comprising a metal sheet and a coat (α) on at least one surface of said metal sheet, wherein said coat (α) comprises an organic resin (A), non-oxide ceramic particles (B) selected from at least one type of borides, carbides, nitrides, and silicides and which have an electrical resistivity at 25° C. of 0.1×10 −6 to 185×10 −6 Ωcm, and an anti-corrosive pigment (C).
2 . The precoated metal sheet for automobile use according to claim 1 wherein said organic resin (A) comprises an organic resin (A1) having at least one type of hydrophilic functional group.
3 . The precoated metal sheet for automobile use according to claim 1 wherein said organic resin (A) comprises an organic resin (A1) having at least one type of hydrophilic functional group and a derivative (A2) of said resin (A1).
4 . The precoated metal sheet for automobile use according to claim 2 or 3 wherein said organic resin (A1) has at least one type of functional group which is selected from a carboxyl group (—COOH), a carboxylate group (—COO − M + , where M + is a monovalent cation), sulfonic acid group (—SO 3 H), sulfonate group (—SO 3 − M + , where M + is a monovalent cation), primary amino group (—NH 2 ), secondary amino group (—NHR 1 , where R 1 is a hydrocarbon group), tertiary amino group (—NR 1 R 2 , where R 1 and R 2 are hydrocarbon groups), quaternary ammonium salt group (—N + R 1 R 2 R 3 X − , where R 1 , R 2 , and R 3 are hydrocarbon groups, and X − is a monovalent anion), sulfonium salt group (—S + R 1 R 2 X − , where R 1 and R 2 are hydrocarbon groups, and X − is a monovalent anion), phosphonium salt group (—P + R 1 R 2 R 3 X − , where R 1 , R 2 , and R 3 are hydrocarbon groups, and X − is a monovalent anion).
5 . The precoated metal sheet for automobile use according to claim 3 wherein the derivative (A2) of said resin (A1) is a resin (A2 Si ) of the following general formula (I):
(where, “A1” indicates the organic resin (A1), “Z-” indicates a hydrocarbon chain having C 1 to C 9 , N 0 to N 2 , and O 0 to O 2 , and “A1˜Z” indicates “A1” and “Z” which are covalently bonded through functional groups of the two. Further, “—O—” is an ether bond, “—OH” is a hydroxyl group, “—X” is a C 1 to C 3 hydrolyzable alkoxy group, hydrolyzable halogeno group, or hydrolyzable acetoxy group, “—R” is a C 1 to C 3 alkyl group, and a, b, c, and d which show the numbers of substituents are all integers of 0 to 3, where a+b+c+d=3).
6 . The precoated metal sheet for automobile use according to any one of claims 1 to 5 wherein said non-oxide ceramic particles (B) have an electrical resistivity at 25° C. of 0.1×10 −6 to 100×10 −6 Ωcm.
7 . The precoated metal sheet for automobile use according to any one of claims 1 to 6 wherein among said non-oxide ceramic particles (B), the particles (B1) with a particle diameter of 1 μm to 24 μm are arranged on at least one surface of said metal sheet at a rate of 0.8/mm 2 to 40000/mm 2 .
8 . The precoated metal sheet for automobile use according to any one of claims 1 to 7 wherein said non-oxide ceramic particles (B) are a mixture of one or more particles selected from the group consisting of boride ceramics: BaB 6 , CeB 6 , Co 2 B, CoB, FeB, GdB 4 , GdB 6 , LaB 4 , LaB 6 , Mo 2 B, MoB, MoB 2 , Mo 2 B 5 , Nb 3 B 2 , NbB, Nb 3 B 4 , NbB 2 , NdB 4 , NdB 6 , PrB 4 , PrB 6 , SrB 6 , TaB, TaB 2 , TiB, TiB 2 , VB, VB 2 , W 2 B 5 , YB 4 , YB 6 , YB 12 , and ZrB 2 , carbide ceramics: MoC, Mo 2 C, Nb 2 C, NbC, Ta 2 C, TaC, TiC, V 2 C, VC, WC, W 2 C, and ZrC, nitride ceramics: Mo 2 N, Nb 2 N, NbN, ScN, Ta 2 N, TiN, and ZrN, and silicide ceramics: CoSi 2 , Mo 3 Si, Mo 5 Si 3 , MoSi 2 , NbSi 2 , Ni 2 Si, Ta 2 Si, TaSi 2 , TiSi, TiSi 2 , V 5 Si 3 , VSi 2 , W 3 Si, WSi 2 , ZrSi, and ZrSi 2 .
9 . The precoated metal sheet for automobile use according to any one of claims 1 to 8 wherein said anti-corrosive pigment (C) comprises one or more types selected from silicate compounds, phosphate compounds, vanadate compounds, and metal oxide microparticles (D).
10 . The precoated metal sheet for automobile use according to claim 9 wherein said metal oxide microparticles (D) comprise one or more types of metal elements selected from the group consisting of Si, Ti, Al, and Zr.
11 . The precoated metal sheet for automobile use according to any one of claims 1 to 10 wherein among said metal oxide microparticles (D), the ratio (D1/B) of the total volume of the metal oxide nanoparticles (D1) with a particle diameter of 1 nm to 100 nm in said coat (α) to the total volume of said non-oxide ceramic particles (B) is 20 or less.
12 . The precoated metal sheet for automobile use according to any one of claims 1 to 11 wherein the content of said non-oxide ceramic particles (B) in the coat (α) at 25° C. is 0.5 to 65 vol %.
13 . The precoated metal sheet for automobile use according to any one of claims 1 to 12 wherein said coat (α) has a thickness of 2 to 30 μm.
14 . The precoated metal sheet for automobile use according to any one of claims 1 to 13 wherein said coat (α) is formed by coating a water-based coating composition.