The present invention includes an organic resin, the electrical resistivity and the particles of non-oxide ceramics in a specific range, at least a portion of the surface by coating and a rust-preventive pigment is coated, resistance weldability, corrosion resistance, formability It related to automotive coated metal plate having excellent.
BACKGROUND
[0002]
　The following describes the background art of the present invention.
[0003]
　Many automobile body member, a metal plate such as a steel plate or the like as a material, the blank cleaving the [1] metal plate into a predetermined size, Aburaarai washing with oil [2] metal plate, [3] Blank a step of press-molding the [4] joining step of assembling the members of a desired shape molded material by spot welding, bonding or the like, a step of degreasing and washing the press oil [5] member surface, [6] the chemical conversion treatment step, [ It is manufactured through many steps of 7 electrodeposition coating process. Body member to be used as an outer plate, further, [8] the intermediate step, [9] is generally subjected to a coating process such as overcoating process. Thus, in the automotive industry, the manufacturing process, a high need for cost reduction, especially by omitting or simplifying the chemical conversion treatment step and coating step.
[0004]
　Further, corrosion resistance of automobile parts are often secured by the above chemical conversion coating and subsequent electrodeposition coating. However, the joint of the metal plate (the plate engaging portion), especially in such a plate registration unit and the bent hem portion of the inner surface of the bag-like member, which may be part no wraparound of the coating or paint results. In that case, the joint portion of the metal member is likely to be exposed to the corrosive environment naked state. Therefore, body sealer, undercoat, Adohishibu is compensated their corrosion resistance using the rust auxiliary materials such as bag portion wax. These rust secondary materials are not only has the increase factor of the motor vehicle manufacturing cost, poor productivity, because it is also the cause of the body weight increase, the corrosion resistance even if the number of these auxiliary materials can be ensured needs of the automotive coated steel plate was high.
[0005]
　Response to these needs, the omission of the chemical conversion treatment step during car manufacturing, omitted or simplified electrodeposition coating process, research and development of the coated metal plate is omitted and reduction of secondary materials, at the same time can be achieved has been actively carried out . Such coated metal plate, after press forming, are assembled into a desired shape by spot welding or the like, or is subsequently electrodeposition coating, electrodeposition coating process are coated intermediate If is omitted. Therefore, enhanced press formability, resistance welding, or a coating film made conductive to allow further electrodeposition coating covering, and it is necessary to provide sufficient corrosion resistance.
[0006]
　For example, Patent Document 1 (JP-55-17508 JP), has a resin-based conductive coating film containing a zinc powder having a high corrosion resistance, techniques weldable alloyed galvanized steel sheet have been proposed ing. Is preferably zinc powder is contained 30 to 90 wt% in the coating, coating thickness is stated to 2 ~ 30 [mu] m is preferred.
[0007]
　For example, Patent Document 2 (JP-A-9-276788), on the rust-proofing layer composed mainly of a chromium compound, an organic resin film containing 3 to 59 vol% of the conductive powder and the anticorrosive pigment were coated with 0.5 ~ 20 [mu] m thick, technology excellent resistance weldable organic composite plated steel sheet corrosion resistance is disclosed. Type of conductive powder is not limited, in the embodiment iron phosphide as the conductive powder, Fe-Si alloy, and Fe-Co alloy or the like is used, there is a superior corrosion resistance and spot weldability .
[0008]
　Patent Document 3 (JP 2000-70842), on the chromate surface treatment to improve corrosion resistance and paint adherence, conductive pigments and rust from 25 to 45% by weight consisting primarily of iron phosphide the organic resin layer containing a pigment coated with 2 ~ 8 [mu] m thick, corrosion resistance, techniques Ni-containing electro-galvanized steel sheet resistance weldability such excellent automotive spare parts has been proposed. Example, aqueous, since both solvent-based coating resin is illustrated, the coating composition for forming a resin coating layer may be used an aqueous, either solvent-based.
[0009]
　Patent Document 4 (JP-T-2003-513141), after curing on metal surfaces has conductivity, the metal surface coating agent capable of forming a weldable corrosion resistant coating, a specific organic binder 10 to 30 mass % conductive powder 30 ~ aqueous coating agent containing 60% by weight have been proposed, as an example of a suitable conductive powders in the preparation of the coating agent, zinc, aluminum, graphite, carbon black, molybdenum sulfide, phosphide iron are mentioned.
[0010]
　Patent Document 5 (JP 2005-288730), Patent Document 6 (JP 2005-325427), a galvanized steel sheet and an aluminum-based plated steel sheet, the first to enhance the adhesion between the plating through the layer coating, by coating the resin second layer coating comprising a conductive pigment and rust-preventive agent, technology excellent automotive organic coated steel sheet to achieve both corrosion resistance and weldability it has been proposed . The coating composition of the first layer film forming is water, also coating composition for the second layer film formation, the water-based paint resin composition of both solvent systems are shown in the literature from aqueous, any solvent system is applicable. Conductive pigment is contained 5 to 70% by volume in the second layer coating in a thickness of 1 ~ 30 [mu] m, Suitable conductive pigments, metals, alloys, conductive carbon, iron phosphide, carbide, semiconductor oxide It is illustrated.
[0011]
　Patent Document 7 (JP-2004-42622), and an alloy or compound of a metal and metalloid elements as the conductive particles, has the conductive coating film containing a specific urethane resin, weldable with high corrosion resistance technology Do not paint the metal material has been proposed. The conductive particles preferably have alloy or compound containing Si of more than 50 wt%, ferrosilicon containing 70 mass% or more of Si is described as more preferable.
[0012]
　Among the conductive particles other than the metal particles, as a technique using a conductive ceramic particles, for example, in Patent Document 8 (JP 2003-268567), a core metal, titanium, zirconium, tantalum, niobium or their, and coating with the cladding layer made of a corrosion-resistant metal selected from an alloy, consisting of further thereon, a carbon material, a conductive ceramic, at least one or more conductive materials and any resin for binding them selected from metal powders coated with a surface treatment layer, techniques of the conductive material coated corrosion-resistant metal material having excellent corrosion resistance and conductivity have been proposed.
CITATION
Patent Document
[0013]
Patent Document 1: JP 55-17508 Patent Publication
Patent Document 2: JP-A 9-276788 Patent Publication
Patent Document 3: JP 2000-70842 JP
Patent Document 4: JP-T 2003-513141 Patent Publication
Patent Document 5: JP open 2005-288730 JP
Patent Document 6: JP 2005-325427 Patent Publication
Patent Document 7: JP 2004-42622 JP
Patent Document 8: JP 2003-268567 JP
Summary of the Invention
Problems that the Invention is to Solve
[0014]
　As mentioned in the Background of the Invention, it can be resistance welding, or a coating film made conductive to allow further electrodeposition coating coating and to impart sufficient corrosion resistance, use the technique of Patent Document 1 If you were, in the literature 1, although the galvannealing layer and the coating film are described as excellent peeling resistance at the time of molding because it is firmly adhered, actually marked paint film peeling at the time of press molding occurs, the corrosion resistance of the part coated film was peeled is lowered.
[0015]
　When using the technique as described in Patent Documents 2 and 3 must be a base anticorrosive treated layer containing a chromium compound in order to express a desired corrosion resistance. This does not match the current needs to avoid the hazards and environmental impact of hexavalent chromium. Further, powders such as iron phosphide and Fe-Si alloy is used as the conductive pigment, since much conductivity inferior metal powder, the conductive coating film must be added in large amounts of conductive powder , significant coating peeling or galling during press molding occurs, the corrosion resistance of the part coated film was peeled is lowered.
[0016]
　Patent Document 4, Patent Document 5, in the Patent Document 6 described techniques, the zinc of suitable conductive powders, when a metal powder such as aluminum, the metal powder content in the coating film increases, conductivity ( the resistance weldability) is improved, there is conflicting tendency corrosion resistance decreases significantly, incompatible weldability and corrosion resistance. Further, conductive carbon, molybdenum sulfide, iron phosphide, when using a powder such as a semiconductor oxide, since these are remarkably conductivity inferior metal powder, as in the case of Patent Documents 2 and 3 described technique, must be added in large amounts of powder to conductive coating film, significant coating peeling or galling during press molding occurs, corrosion resistance is lowered.
[0017]
　In Patent Document 7 described technique, when a metal or particles of alloys thereof as the conductive powder, as in the case of the electrically conductive due to the increase in particle content of the coating film is improved, significantly corrosion resistance It tends to decrease. In the case of using a ferrosilicon particles, is inferior is much conductive than metal particles, it is necessary to add a large amount of particles in the conductive coating film, as in the case of the significant coating during press molding peeling or galling occurs, the corrosion resistance is lowered.
[0018]
　Patent Document 8 described techniques for the proposed technique for special applications such as separators and electrochemical fuel cell electrodes, corrosion resistant metal used for the cladding layer is very expensive, it is difficult to apply to the automobile body member was.
[0019]
　Thus, in the prior art, it must be used together chromate undercoat order to achieve both a sufficient conductivity and corrosion resistance (Patent Documents 2 and 3), the sacrificial corrosion resistance and formability with the addition of conventional conductive particles become (Patent documents 2-7), it is impossible to obtain an inexpensive coated metal plate that can be applied to automobile body member (Patent Document 8), there are various issues such as.
[0020]
　Above mentioned manner, the omission of the chemical conversion treatment step during car manufacturing, electrodeposition omitted or simplified painting process, omission or reduction of the secondary materials, in order to achieve at the same time, excellent press formability, conductivity, painted metal plate with all the corrosion resistance is required. To provide such a coated metal plate, it was necessary to find a conductive particle having combined the following characteristics. That, (a) in paint coating compositions are stable for long periods of time, (b) express excellent conductivity even in relatively small amounts in addition to the coating film, the addition amount of the (c) coating lowering of the corrosion resistance and formability be increased to be less is.
[0021]
　The present invention has been made in view of the above problems, at least a portion of the surface with a chromate-free coating comprising a non-oxide ceramic particles with a limited electrical resistivity to a very low range is covered, resistance weldability, corrosion resistance, relates to an automotive coated metal plate having excellent moldability.
Means for Solving the Problems
[0022]
　The present inventors have made intensive studies to achieve the above objects, industrially comparatively cheaply available, electrical resistivity × 10 0.1 -6 ~ 185 × 10 -6 [Omega] cm the film containing the non-oxide ceramic particles and rust pigment and an organic resin be formed on the metal surface, conductive, it found that the corrosion resistance, the automotive coated metal sheet excellent in all the moldability is obtained.
[0023]
　The present invention, these findings the by was developed on the basis of, specifically, as follows.
　(1) metal plate, and said a motor vehicle coated metal plate including a coating (alpha) that is on at least one surface of the metal plate,
　the coating film (alpha) is an organic resin (A), the boric product, carbides, nitrides, selected from at least one silicide, the electrical resistivity of 25 ° C. is × 10 0.1 -6 ~ 185 × 10 -6 and the Ωcm non-oxide ceramic particles (B), proof automotive coated metal plate including a rust pigment (C).
　(2) the organic resin (A) comprises an organic resin (A1) having at least one hydrophilic functional group, automotive coated metal plate according to (1).
　(3) the organic resin (A) comprises a derivative (A2) of the organic resin (A1) and the resin (A1) having at least one hydrophilic functional group, automotive coated metal according to (1) plate.
　(4) the organic resin (A1) is a carboxyl group (-COOH), a carboxylate (-COO - M + , M + is a monovalent cation), a sulfonic acid group (-SO 3 H), sulfonate ( -SO 3 - M Tasu , where M TasuThe monovalent cation), primary amino group (-NH 2 ), 2 amino groups (-NHR 1 , wherein R 1 is a hydrocarbon group), a tertiary amino group (-NR 1 R 2 , wherein R 1 and R 2 is a hydrocarbon group), a quaternary ammonium salt (-N + R 1 R 2 R 3 X - , wherein R 1 , R 2 , R 3 is a hydrocarbon group, X - is a monovalent anion), a sulfonium base (-S + R 1 R 2 X - , wherein R 1 , R 2 is a hydrocarbon group, X - is a monovalent anion), a phosphonium salt (-P + R 1 R 2 R 3 X - , wherein R 1 , R 2 , R 3 is a hydrocarbon group, X - is a monovalent anion having at least one functional group selected from), (2) or automotive coated metal plate according to (3).
　(5) the derivative of the resin (A1) (A2) is general formula (I):
[0024]
[Formula 1]

[0025]
　(Wherein "A1" is an organic resin (A1), "Z-" represents a hydrocarbon chain having 1 to 9 carbon atoms, nitrogen atoms 0-2, oxygen atoms 0-2, "A1 . ~ Z "indicates that the" A1 "," Z "is covalently bonded via both functional groups also" - O-'is an ether bond, "- OH" is a hydroxyl group "- X" is a hydrolyzable alkoxy group having 1 to 3 carbon atoms, a hydrolyzable halogeno group or a hydrolyzable acetoxy group, "- R" is an alkyl group of 1 to 3 carbon atoms, a representing the number of substituents, b, c, d is an integer of either 0 to 3, provided that a + b + c + d = 3.)
resin (A2 represented by Si is), in (3) automotive coated metal plate according.
　(6) the non-oxide ceramic particles (B) of 25 ° C. electrical resistivity 0.1 × 10 of -6 ~ 100 × 10 -6 , characterized in that a [Omega] cm, the (1) to (5) automotive painted metal sheet according to any one.
　(7) said of the non-oxide ceramic particles (B), the particle size is 1 [mu] m ~ 24 [mu] m (B1) is 0.8 or on at least one surface of the metal plate / mm 2 ~ 40000 pieces / mm 2 are arranged, (1) automobile coated metal plate according to any one of the - (6).
　(8) the non-oxide ceramic particles (B), boride ceramics: BaB 6 , CeB 6, Co 2 B, CoB, Feb, GdB 4 , GdB 6 , Lab 4 , Lab 6 , Spirit 2 B, Gal, Gal 2 , Spirit 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 country, country, 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, silicides 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 is one or a mixture of two or more selected from the group consisting of, (1 ) automotive coated metal plate according to any one of (1) to (7).
　(9) the anticorrosive pigment (C) comprises, silicate compound, a phosphate compound, vanadate compound, and one selected from metal oxide particles (D) or two or more, (1) automotive coated metal plate according to any one of the - (8).
　(10) The metal oxide fine particles (D) is, Si, Ti, Al, including one or more metal element selected from the group consisting of Zr, automotive coated metal plate according to (9).
　(11) said of the metal oxide particles (D), particle size of the metal oxide nanoparticles (D1) is 1 nm ~ 100 nm, the total volume in the said coating (alpha), the non-oxide ceramic particles ( the ratio to the total volume of B) (D1 / B) is 20 or less, (1) automobile coated metal plate according to any one of the - (10).
　Is before (12) SL non-oxide ceramic particles coating (alpha) of 0.5 to 65 vol% content of at 25 ° C. of (B), according to any one of (1) to (11) automotive painted metal plate.
　(13) the thickness of the coating film (alpha) is 2 - 30 [mu] m, (1) automobile coated metal plate according to any one of the - (12).
　(14) the coating film (alpha) is formed by coating the aqueous coating composition, (1) to an automotive coated metal plate according to any one of (13).
Effect of the invention
[0026]
　According to the present invention can provide a specific conductive particles and anticorrosive pigment requiring only the addition of the coating, sufficient resistance weldability, corrosion resistance, automotive coated metal plate having excellent moldability. Also, the above conductive particles, acidic or alkaline aqueous solution, neutral water, for long-term stability various or non-aqueous solvent, the composition for coating of suitable aqueous and solvent-based in order to obtain a coating film of the present invention it is possible to choose the things freely.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027]
[1] Figure 1 represents a schematic view of a cross section of an automotive coated metal plate of the present invention.
[2] Figure 2 represents a cross-sectional photograph of the coated metal plate. Figure 2 (a) is a surface layer cross-sectional SEM photograph of the coated metal plate, FIG. 2 (b), the coated metal plate engaging portion, a cross-sectional SEM photograph of pressurized welding electrodes.
FIG. 3 is a schematic view showing a state during welding automotive coated metal plate.
FIG. 4 is a metal oxide fine particles (D) is inhibited attached around, or caught in non-oxide ceramic particles (B) between the adjacent energization of the non-oxide ceramic particles (B) it is a schematic view showing a.
DESCRIPTION OF THE INVENTION
[0028]
　Hereinafter, the present invention will be described in detail.
[0029]
　
　coated metal plate of the present invention, a metal plate at least partially coated on the surface at a particular conductive coating. The metal plate, depending on the application, even if both sides of the metal plate is covered with the coating, may be only one side covered, also be part of the surface is covered, the entire surface is covered it may be. Coating film coated portion of the metal plate resistance weldability, corrosion resistance, in which the moldability is excellent.
[0030]
　The constituent metal of the metal plate can be used for coating metal plate of the present invention, for example, aluminum, titanium, zinc, copper, nickel, and steel or the like. Components of these metals is not particularly limited, for example, when using steel, even ordinary steel, may be added element-containing steels such as chromium. However, the metal plate of the present invention is to be press-formed, in either case of the metal plate, so as to provide a desired molding trackability, kind and addition amount of the additive element, and that properly controlled metallographic It is preferred.
[0031]
　In the case of using steel as a metal plate, there may be covering plating layer on the surface, but the kind thereof is not particularly limited. The applicable plating layer, for example, zinc, aluminum, cobalt, tin, plating containing any one of nickel, and these metal elements or even other metal elements, alloy plating containing a nonmetallic element etc. the. In particular, the zinc-based plating layer, for example, plating of zinc, zinc and aluminum, cobalt, tin, nickel, iron, chromium, titanium, magnesium, alloy plating with at least one manganese, or still other metallic elements, various zinc-based alloy plating containing a nonmetallic element (e.g., a zinc, aluminum, magnesium, quaternary alloy plating silicon) but may be mentioned, the alloy component other than zinc are not particularly limited. Furthermore, cobalt as a minor different metal elements or impurities in these plating layers, molybdenum, tungsten, nickel, titanium, chromium, aluminum, manganese, iron, magnesium, lead, bismuth, antimony, tin, copper, cadmium, arsenic, etc. those containing silica, alumina, may include those obtained by dispersing an inorganic material titania.
[0032]
　The aluminum-based plating layer, aluminum or aluminum and silicon, zinc, alloy plating with at least one magnesium, (e.g., aluminum and silicon alloy plating, aluminum and zinc alloy plating, aluminum, silicon, ternary magnesium alloy plating), and the like.
[0033]
　Further, the plating and other types of plating such as iron plating, iron and phosphorus alloy plating, nickel plating, multilayered plating in combination with cobalt plating can also be applied.
[0034]
　Method of forming the plating layer is not particularly limited. For example, electroplating, electroless plating, melt plating, vapor deposition plating, it is possible to use a dispersing plating. Plating method, continuous, it may be any of batch type. Also, when using steel plates, as treatment after plating, zero spangle treatment is an external uniform treatment after hot-dip plating, a reforming process is annealing of the plated layer, temper rolling or the like for the surface condition and material adjustment Although may not particularly limit a in the present invention, it is also possible to apply one.
[0035]
　
　coating film to cover the metal plate of the present invention (alpha) is formed on at least one surface of the metal plate, and an organic resin (A), the electrical resistivity of 25 ° C. is 0.1 × 10 -6 ~ 185 × 10 -6 [Omega] cm borides, carbides, nitrides, and non-oxide ceramic particles selected from the silicide (B), contains a rust preventive pigment (C).
[0036]
　The coating, as long as industrially be produced by coating the coating composition, the type of coating solvent, and, film forming method of the metal plate surface, hardening method is not limited. Hereinafter referred to coating compositions to obtain a coating film (alpha) in the present invention coating composition and (beta). The coating composition (beta), for aqueous coating compositions, organic solvent-based paint compositions.
[0037]
　In the present invention, the term "water-based coating composition" refers to a composition where water was constructed using the "aqueous solvent" is not less than 50 wt% of the total solvent. Further, the "organic solvent-based coating composition" refers to an organic solvent constituent compositions using the "organic solvent-based medium" is more than 50 wt% of the total solvent.
[0038]
　The constituent components other than water in the "aqueous solvent" mentioned above, for example, sulfuric acid and mix well in water, nitric acid, hydrochloric acid, phosphoric acid, boric acid, inorganic acids such as hydrofluoric acid, Ya metal salt of the inorganic acid which dissolves in the inner water of the inorganic salts such as ammonium salts, silicates which are soluble in water, thiosulfate, inorganic compounds such as thiocyanate salts, and include organic compounds miscible with water. If necessary, it is also possible to add organic solvents to the "aqueous solvent" mentioned above. However, from the viewpoint of occupational health, the "aqueous coating composition" of the present invention, the Industrial Safety and Health Law Enforcement Order organic solvent as defined in (Prevention of Organic Solvent Poisoning rules Chapter Article) (first seed organic solvent, the two organic solvents, the three organic solvents, or the organic solvent, 5 wt% beyond those containing) such as a coating composition which does not correspond to the type and the addition of an organic solvent it is preferable to adjust the amount.
[0039]
　As film forming method of the metal plate, for example, in the case of water-based or solvent-based coating compositions, roll coating, groove roll coating, curtain flow coating, roller curtain coating, immersion (dipping), known such diaphragm air knife coating composition onto a metal plate by coating method (beta) is applied, then, a method of drying the moisture and solvent wet coating is preferred. As the curing method of dry coating, polymerization by heating baking of the organic resin in the coating film, although curing is preferred, the resin in the coating film polymerization if an ultraviolet polymerization or curing by ultraviolet irradiation, coating resin in the film polymer if an electron beam, or by polymerization or curing by electron beam irradiation.
[0040]
　Wherein in the coating film (alpha) of the adhesion and corrosion resistance further improves purpose to the metal plates, the surface treatment film of the chromate-free may be provided between the coating film and the metal plate surface. In the case of providing a surface treatment coating, the number of the layer, although the composition is not limited, so as not to impair the processability tracking resistance and corrosion resistance of the coating film (alpha) at the time of molding a metal plate, surface treatment coating, the metal plate and it must have a good adhesion to the upper layer coating (alpha). Further, in order to ensure sufficient conductivity in the film thickness direction, preferably a surface treatment coating thickness and 0.5μm or less.
[0041]
　When providing the undercoating film, if the film formation method which can industrially applicable, film forming method of the surface treatment film is not limited. Film forming method of the surface treatment coating, painting surface treatment composition, deposition can be exemplified a method of film application such as, from the viewpoint of film formation costs (productivity) and versatility of aqueous or solvent-based base painting treatment composition, the method according to drying is preferable. When using a surface treatment composition for aqueous or solvent-based, one layer each from the lowest layer of the plurality of coating films including the surface treatment coating to the outermost surface layer, by repeating the drying and recoatability (sequential coating method) it may be formed multilayer coating film. Further, as a method of forming the easily and efficiently coating the metal plate surface, the coating layers from the lowermost layer in contact with the metal plate surface to the outermost layer, in a wet state, sequentially or step of multilayer coated simultaneously (wet-on-wet coating or multilayer simultaneous coating process of coating composition), drying step of simultaneously dry water and solvent in each layer coating wet state, the film-forming step of curing the multilayer coating film in this order film may be formed by lamination methods including. Here, the wet-on-wet coating method, after coating the coating liquid on the metal plate, while the solvent content state before this coating solution dries (wet state), the other coating liquid thereon coated, the solvent at the same time drying of the resulting laminated coating solution was cured, a method of film formation. Further, the multilayer simultaneous coating method, a multilayer slide curtain coater or a slot die coater, after applying the coating liquid a plurality of layers simultaneously on a metal plate in a stacked state, at the same time drying the solvent in the laminated coating liquid, manufactured and cured it is a method of film.
[0042]
　Coating covering the metal sheet of the present invention (alpha) is a non-oxide ceramic particles having an electrical resistivity of a specific range as described later organic resin (A) (B) and anticorrosive pigment (C), or further optionally including a surfactant such as described in the section . Content at 25 ° C. of non-oxide ceramic particles in such coating (α) (B) is preferably from 0.5 to 65 volume%, the electric conductivity at the time of resistance welding, and corrosion resistance more preferably 1 to 40 vol% from the viewpoint of moldability secure, and even more preferably 2 to 20% by volume. In addition to moldability and securing sufficient corrosion resistance, in view of also securing sufficient resistance weldability, particularly preferably from 4 to 20% by volume.
[0043]
　In coated metal plate of the present invention, reasons for coating (alpha) express good conductivity, in the coating film (alpha), non-oxide ceramic particles are conductive particles (B) that is almost aggregation without being sufficiently uniformly distributed throughout the coating film surface is believed that the electrical conduction path to the metal plate at the bottom is because not unevenly distributed in the coating film. When the conductive particles are caused to aggregate in the coating, electric conductive paths in a state of being uniformly SPILL throughout the coated surface is less likely to be formed in the coating film in the coating film, electric conductive path at all likely to occur is the area that gives the trouble to no resistance welding. In such a case, it is necessary to add more conductive material by for securing the conductive path, it is more likely to not be maintained good corrosion resistance and formability. The coated metal plate of the present invention, is very unlikely that such a problem arises.
[0044]
　When the content of the coating film (alpha) in the (B) is more than 65% by volume, can retain sufficient conductivity, the coating peeling or galling occurs easily at the time of press molding, it can hold good formability not, there is a possibility that the corrosion resistance of the coating film peeling site is reduced. If it exceeds 65 vol%, the amount of the conductive particles dispersed in the coating film is increased, the corrosion current excessively increasing conductive point is very easy to flow, even in the presence of anticorrosive pigment (C) coating the whole of corrosion resistance may be insufficient.
[0045]
　Incidentally, 0.5% by volume or more of the coating, 1, in the conductive particle added is less than% by volume, there is a possibility that electrical conductivity during resistance welding is insufficient, also, the coating 40 vol% or more, the conductive particle addition of 65 vol% or less, the formability and the corrosion resistance may be insufficient, the volume ratio of (B) is 1 vol% or more, more preferably added to less than 40% by volume. Further, 1% by volume or more of the coating, even with conductive particles added is less than 2% by volume, there is a possibility that electrical conductivity during resistance welding is somewhat insufficient, and the coating 20 vol% or more, 40 also conductive particles added is less than% by volume, there is a possibility that formability and corrosion resistance is slightly poor, 2% by volume or more, further preferably added to less than 20% by volume. But the coating film 2 vol% or more, the conductive particle added is less than 4 vol%, when changing the resistance welding conditions large, because there is always high and stable risk that can not be ensured weldability, 4 vol% or more, 20 addition of less than% by volume is particularly preferred.
[0046]
　When the content of the coating film (alpha) in the (B) is less than 0.5% by volume, can not ensure good electrical conductivity because a small amount of non-oxide ceramic particles dispersed in the coating, the coating the thickness of the (alpha), may not be provided with sufficient resistance weldability of the coating film. Here has been described the conductivity in terms of loading of non-oxide ceramic particles in the coating film (alpha) (vol%), at the time of resistance welding, the amount of non-oxide ceramic particles occupied in the coated metal plate surfaces ( number) is also electrically conductive (i.e., affect the weldability). In this regard, it will be described later.
[0047]
　The thickness of the coating film to cover the metal plate of the present invention (alpha) is preferably in the range of 2 ~ 30 [mu] m thick, and more preferably in the range of 3 ~ 15 [mu] m thick. In thickness is less than 2 [mu] m, the coating film is too thin, it may not sufficient corrosion resistance can not be obtained. If film thickness exceeds 30 [mu] m, there is the amount of coating composition used (beta) is not only the production cost is increasing, the coating is peeled off or cohesive failure during press molding. Also, increased electrical insulation in the thickness direction for a thick film, resistance welding is difficult. Furthermore, when using an aqueous coating composition, more likely to coating defects such as popping occurs, it is not easy to stably obtain the appearance required as an industrial product.
[0048]
　The thickness of the coating film (alpha) can be measured by cross-section observation, etc. of the coating film. Other, mass of the coating film adhered to the unit area of ​​the metal plate, may be calculated by dividing the specific gravity of the dried specific gravity of the coating or paint composition, (beta). Attachment mass of the coating, the mass difference before and after coating, the presence of the mass difference before and after peeling of the coated coating film, or have been found content in advance the coating by fluorescent X-ray analysis of the coating element etc. to determine the amount can be appropriately selected from existing methods. The specific gravity of the dried specific gravity or coating composition of the coating film (beta) measures the volume and mass of the isolated coating, after drying take appropriate amount of the coating composition for (beta) to the vessel measuring the volume and mass, or the like calculated from the amount and the known specific gravity of the components of the coating components, it can be appropriately selected from existing methods.
[0049]
　
　The organic resin of the present invention (A) is a binder component of the coating (alpha), water may be any of organic solvent-based resin comprises a resin (A1) to be described later, or further including additional to react derivative of the resin (A1) (A2).
[0050]
　Paint composition used to form a coating film (alpha) in the present invention (beta) is aqueous, it is possible to use either an organic solvent-based, 50 to 100 mass of nonvolatile content of the resin (A1) to be described later % including. Resin (A1) is present stably in the coating composition (beta). Such paint compositions (beta) was applied to the metal plate and heated, often resin (A1) is directly dried without reacting. Resin at least part of (A1) is, the coating composition (beta) a silane coupling agent during the curing agent, when containing the crosslinking agent is reacted with their derivatives of the resin (A1) (A2) to form. Therefore, in this case, that includes the reaction derivative of the unreacted resin (A1) and the resin (A1) (A2) becomes the organic resin (A) is a binder component of the coating (alpha).
[0051]
　The resin (A1) is not particularly limited as the type of, for example, polyurethane resins, polyester resins, epoxy resins, and (meth) acrylic resins, polyolefin resins, phenolic resins or their modified products such as. May be used as said mixture of one or more of these resins (A1), wherein a mixture of organic resin obtained by modifying at least one organic resin one or more it may be used as the resin (A1). Thus, in particular it why not limit the type of the resin (A1) in the present invention, even when the coating film (alpha) conductive to easy corrosion current flows to, anticorrosive pigment (C) is co to, it is not necessary to the binder component of the coating film and special corrosion-resistant resin.
[0052]
　It is possible to use various resin wherein the resin (A1). The resin (A1), a polyurethane resin, a polyurethane resin modified product, a polyurethane resin composite, it is preferable to use mixtures of these and other resins. Urethane groups in the polyurethane resin (-NHCOO-), in order to have a high molecular cohesive energy than many other organic groups (8.74kcal / mol), if it contains a polyurethane resin in the resin (A1) coating becomes tough, during press molding, hardly occurs galling flaking or coating, in addition, it enhances the corrosion resistance was improved corrosion factor barrier properties (denseness of the coating film) by a relatively high cohesive energy effect there is. Organic groups other than urethane groups, for example, methylene (-CH 2 -), ether group (-O -), 2 amino group (imino group, -NH-), an ester group (-COO-), a benzene ring molecular cohesive energy, respectively 0.68kcal / mol, was 1.00kcal / mol, 1.50kcal / mol, 2.90kcal / mol, 3.90kcal / mol, molecular cohesive energy of the urethane group (-NHCOO-) is , considerably higher compared to these. Therefore, in many cases, a coating film containing a polyurethane resin, many other resins include polyester resins, (meth) acrylic resins, polyolefin resins, tough than the coating made of phenol resin, and a high corrosion resistance is there.
[0053]
　The resin (A1) is, as already mentioned, as long as it stably present in the coating composition (beta), and there is no particular limitation on the kind. In the structure of the resin (A1), a carboxyl group (-COOH), a carboxylate (-COO - M + , M + is a monovalent cation), a sulfonic acid group (-SO 3 H), sulfonate groups (-SO 3 - M + ; M + is a monovalent cation), primary amino group (-NH 2 ), 2 amino group (-NHR 1 ; R 1 is a hydrocarbon group), a tertiary amino group (-NR 1 R 2 ; R 1 and R 2 is a hydrocarbon group), a quaternary ammonium salt (-N + R 1 R 2 R 3 X - ; R 1 , R 2 , R 3 is a hydrocarbon group, X - is a monovalent anion), sulfonium salt (-S + R 1 R 2 X - ; R 1 , R 2 is a hydrocarbon group, X - is 1 valence anion), a phosphonium salt -P + R 1 R 2 R 3 X - ; R 1 , R 2 , R 3 is a hydrocarbon group, X - structure at least one functional group selected from a monovalent anion) it is preferably a resin containing the. Will be described later these details and examples.
[0054]
　Incidentally, the resin used in the paint composition for obtaining a coating film (alpha) in the present invention (beta) is a water-soluble or solvent soluble type resin completely dissolved in water or an organic solvent, and emulsion or suspension may include a resin are uniformly and finely dispersed in water or in a solvent (a water-dispersible resin or a solvent-dispersible resin) in the form of equal. The term "(meth) acrylic resin" means an acrylic resin and methacrylic resin.
[0055]
　Among the resin (A1), as the polyurethane resin is not particularly limited. For example, by reacting a polyol compound with a polyisocyanate compound, mention may be made subsequently further those obtained by chain extension by chain extender in such. As the polyol compound is not particularly limited as long as it is a compound containing two or more hydroxyl groups per molecule, such as ethylene glycol, propylene glycol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, glycerin, trimethylol ethane, trimethylol propane, polycarbonate polyols, polyester polyols, polyether polyols such as bisphenol hydroxypropyl ether, polyester amides polyol, acrylic polyol, polyurethane polyol, or mixtures thereof. Examples of the polyisocyanate compound is not particularly limited as long as it is a compound containing two or more isocyanate groups per molecule, for example, aliphatic isocyanates such as hexamethylene diisocyanate (HDI), such as isophorone diisocyanate (IPDI) fat alicyclic diisocyanates, aromatic diisocyanates tolylene such diisocyanate (TDI), an aromatic aliphatic diisocyanates such as diphenylmethane diisocyanate (MDI) or mixtures thereof. Examples of the chain extender is not particularly limited as long as it is a compound containing one or more active hydrogen in the molecule, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylene pentamine aliphatic and polyamines such as amine, tolylenediamine, xylylenediamine, and aromatic polyamines such as diaminodiphenylmethane, diamino cyclohexyl methane, piperazine, 2,5-dimethylpiperazine, alicyclic polyamines or hydrazines such as isophorone diamine, succinic acid dihydrazide, adipic acid dihydrazide, hydrazine, such as phthalic acid dihydrazide
[0056]
　If it is desired to obtain an aqueous polyurethane resin, for example, during resin manufacture, after at least a portion of the polyol compounds instead a carboxyl group-containing polyol compound, it is reacted with a polyisocyanate compound by introducing a carboxyl group into the resin chain, the carboxyl group there may be cited those with neutralized aqueous resin with a base. Alternatively, during resin manufacture, instead of the polyol compound having in the molecule at least a portion of the secondary amino group or tertiary amino groups of the polyol compound, it is reacted with a polyisocyanate compound secondary amino group or tertiary resin strand after introducing an amino group, it can be exemplified by the neutralization with an acid aqueous resin. A tertiary amino group if it has the resin chain is quaternized with an alkyl group introduced into the tertiary amino group may be a water-based cation resin having a quaternary ammonium base. These compounds may be used alone or in mixture of two or more.
[0057]
　Thus, the polyurethane resin can be used as the resin (A1) is not particularly limited. The resin (A1), no aromatic ring, or preferably used an aromatic ring is less a polyurethane resin. Such polyurethane resins, since the glass transition temperature is lower than the polyurethane resin containing a large amount of aromatic rings, there is a tendency that the mobility of the molecular chains is superior in film-forming property at the time of high film formation, and the elongation deformation index of the coating film high order, processability followability during press molding, if better than a polyurethane resin containing a large amount of aromatic rings is large. Accordingly, the polyol compound used in the resin production, polyisocyanate compound, but there is no particular limitation on the chain extender, aliphatic or alicyclic no aromatic ring, or an aromatic ring is less araliphatic or aromatic alicyclic preferably used compounds such.
[0058]
　Among the resin (A1), as the polyester resin is not particularly limited. For example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, diethylene glycol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, bisphenol hydroxypropyl ether, 2-methyl-1 , 3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 2-methyl-1,4-butanediol , 2-methyl-3-methyl-1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1 , 3-cyclohexanedimethanol, 1,2-cyclohexane dimethanol Nord, hydrogenated bisphenol -A, dimer diol, trimethylolethane, trimethylolpropane, glycerol, and polyols such as pentaerythritol, phthalic acid, phthalic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic phthalic anhydride, methyltetrahydrophthalic phthalate, methyl tetrahydrophthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, sebacic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, himic anhydride, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, azelaic acid, succinic acid, succinic anhydride, lactic acid, dodecenylsuccinic acid, dodecenylsuccinic anhydride, cyclohexane-1,4-dicarboxylic acid, and anhydride end acid A polycarboxylic acid, may be mentioned those obtained by dehydration polycondensation. Further, mention may be made of these was neutralized with ammonia or an amine compound such as, such as those with aqueous resin.
[0059]
　Among the resin (A1), the epoxy resin is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resins, resorcin type epoxy resins, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resins, resorcin type epoxy resins, epoxy resins such as novolac epoxy resin diethanolamine , obtained by reacting an amine compound such as N- methylethanolamine. Additionally, neutralizing them with an organic or inorganic acid, those with aqueous resin and, in the presence of the epoxy resin, after the high acid value acrylic resin by radical polymerization, an aqueous reduction neutralized with ammonia or an amine compound such as and the like can be mentioned those.
[0060]
　Among the resin (A1), as the (meth) acrylic resin is not particularly limited. For example, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n- butyl (meth) alkyl (meth) acrylates such as acrylate, 2-hydroxyethyl (meth) hydroxyalkyl (meth) acrylates such as acrylate alkoxysilane (meth) acrylate of a (meth) acrylic acid esters include those obtained by radical polymerization using a polymerization initiator in water together with (meth) acrylic acid. The polymerization initiator is not particularly limited, for example, can be used potassium persulfate, persulfates such as ammonium persulfate, azobiscyanovaleric acid, azo compounds such as azobisisobutyronitrile. Here, means acrylate and methacrylate and "(meth) acrylate", "(meth) acrylic acid" means acrylic acid and methacrylic acid.
[0061]
　Among the resin (A1), as the polyolefin resin is not particularly limited. For example, ethylene and methacrylic acid, acrylic acid, maleic acid, fumaric acid, itaconic acid, obtained by radical polymerization of unsaturated carboxylic acids such as crotonic acid under high temperature and high pressure. Further, mention may be made of these further ammonia or amine compound, KOH, NaOH, and neutralized with LiOH ammonia or an amine compound containing a basic metal compound or the metal compound such as such, and the like that produce a water-based resin.
[0062]
　Among the resin (A1), as the phenol resin is not particularly limited. For example, phenol, resorcinol, cresol, bisphenol A, phenol resins such as methylolated phenolic resin obtained by addition reaction in the presence of an aromatic compound with formaldehyde, such as para-xylylene dimethyl ether catalyst, diethanolamine, N- methylethanolamine those obtained by reacting an amine compound such as an amine, and the like. Furthermore, it can be exemplified such that the aqueous resin neutralized with an organic or inorganic acid.
[0063]
　The resin (A1) may be used alone or in combination of two or more. Further, the main component of the coating composition (beta), in the presence of at least one resin (A1), one type of composite resin obtained by modifying at least a part of the resin (A1) or are collectively of two or more may be used as the resin (A1).
[0064]
　Further, if necessary, in formulating the coating composition comprising the resin (A1) (beta), but described in detail below, it may be added a curing agent or a crosslinking agent for the resin (A1) it may be introduced a crosslinking agent to the resin structure. The is not particularly restricted but includes crosslinking agents, for example, amino resins, polyisocyanate compounds, blocked polyisocyanate, epoxy compounds, at least one cross-linking agents are selected from the group consisting of a carbodiimide group-containing compound. By blending these crosslinking agents, it is possible to enhance the adhesion to the crosslinking density and the metal surface of the coating film (alpha), corrosion resistance and, thereby improving coating film followability during processing. These crosslinking agents may be used alone or in combination of two or more thereof.
[0065]
　As the amino resin is not particularly limited, examples thereof include melamine resins, benzoguanamine resins, urea resins, glycoluril resins and the like.
[0066]
　Examples of the polyisocyanate compound is not particularly limited, examples thereof include hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate and the like. Furthermore, blocked polyisocyanates are blocked product of the polyisocyanate compound.
[0067]
　The epoxy compound is, if a compound having a plurality of epoxy groups (oxirane rings) is a cyclic ether group of three-membered ring is not particularly limited, for example, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, diglycidyl terephthalate esters, sorbitan polyglutarimide glycidyl ether, pentaerythritol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl glycol polyglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 2,2-bis - (4'-glycidyloxyphenyl) propane, tris (2,3 Epoxypropyl) isocyanurate, bisphenol A diglycidyl ether, and hydrogenated bisphenol A diglycidyl ether and the like. Many of these epoxy compounds, -CH one group to epoxy group 2 - to have a glycidyl group is added, containing the word "glycidyl" in the compound name.
[0068]
　Examples of the carbodiimide group-containing compounds, for example, aromatic diisocyanates, aliphatic diisocyanates, the condensation reaction accompanying decarboxylation of diisocyanate compounds such as alicyclic diisocyanate, after synthesizing the isocyanate-terminated polycarbodiimide, further with an isocyanate group and the like compounds obtained by adding a hydrophilic system segment having a functional group having reactivity.
[0069]
　The amount of these crosslinking agents, resin (A1) for forming a coating film (α) 1 ~ 40 parts by weight is preferable with respect to 100 parts by weight. If it is less than 1 part by mass, there is a possibility that the effect of the amount of addition is added insufficiently not obtained, the coating film becomes brittle with excess curing in an amount of more than 40 parts by mass, corrosion resistance and processability followability at the time of molding there is likely to decrease.
[0070]
　As already mentioned, since the rust-preventive pigment in the coating film (alpha) in the present invention (C) coexist, with the conductive coating film, it is necessary to the coating constituent resin and a specific high corrosion resistance resin, Not particularly. However, to broaden the scope of coated metal plate of the present invention to enhance the corrosion resistance of the coating film, the organic resin (A), the resin (A1) alone or additionally to the following general formula of the derivatives, (I ) resin (A2 shown in Si a) a total of the to contain 50 to 100 wt% of the organic resin (a) is particularly preferred.
[0071]
[Formula 2]

[0072]
　(Wherein, notation "A1" represents the resin (A1), "Z-" means 1-9 carbon atoms, nitrogen atoms 0-2, hydrocarbon chain oxygen atoms having 0 to 2, "A1 . the notation ~ Z ", indicating that the" A1 "," Z "is covalently bonded via both functional groups also" - O-'is an ether bond, "- OH" represents a hydroxyl group , and the "- X" is a hydrolyzable alkoxy group having 1 to 3 carbon atoms, a hydrolyzable halogeno group or a hydrolyzable acetoxy group, "- R" is an alkyl group of 1 to 3 carbon atoms, There, a representing the number of substituents, b, c, d is an integer of either 0 to 3, provided that a + b + c + d = 3.)
[0073]
　As already mentioned, the coating composition used to form the coating film of the present invention (α) (β) comprises a resin (A1) 50 ~ 100 wt% of nonvolatile matter. Nonvolatile component other than the resin (A1) included the painting composition (beta), such as described in detail later, anticorrosive pigment (C) and a silane coupling agent (s), curing agent, crosslinking agent it is. The content of these compounds in the film after the coating film (alpha), as described later, the resin (A1) alone or, (A2 Si because of the total mass with respect to the preferred range of the), these in formulating paint compositions comprising a compound of (beta), to adjust the amount so that they fit into the preferred content range in the coating film after the film (alpha).
[0074]
　In the present invention, resin contained in the organic resin (A) (A2 Si ), for example, coating composition containing a resin (A1) and a silane coupling agent (s) and (beta), a metal plate used in the present invention the coating, and drying. In general, a silane coupling agent, or a metal surface having a functional group such as a hydroxyl group, it is possible to chemically bind to many functional organic resins, metal surfaces, functional organic resins, in the presence of silane coupling agents, metal surface crosslinking or functional organic resin, it is possible to intermolecular or intramolecular crosslinking of each other functional organic resins. In the present invention, the resin (A1) and paint compositions comprising a silane coupling agent (s) is a (beta) was applied to the metal plate, followed by drying, at least one functional group of the resin (A1) and parts, at least some of the functional groups of the metal surface is reacted respectively silane coupling agent (s), the resin (A2 Si ) is produced. Formula resin shown in (I) (A2 Si at least a portion of) -O- (ether bond) or -OH (hydroxyl group) is bonded to the metal surface. The coating film (alpha) and the case of providing a surface treatment film between the metal sheet surface, the resin shown by the general formula (I) (A2 SiAt least part of) the -O- (ether bond) or -OH (hydroxyl group) is bonded with the surface treatment film surface. Binding of the ether bond and the metal surface, and the binding of the ether bond and the surface treatment component is a covalent bond, the bond between the hydroxyl group and the metal surface, and, between the hydroxyl group and the surface treatment coating component binding is often a hydrogen bond or a coordinate bond. Such a chemical bond between the coating resin constituting the metal surface or by chemical bonding to the upper layer coating component resins and the underlying conversion film increases the adhesion between them, the film when the metal plate is deformed by the molding process to demonstrate excellent processing followability, without impairing the appearance of the processed portion, and the corrosion resistance of the machined portion is increased.
[0075]
　Coating of the silane coupling agent (s) coating composition comprising (beta), if during the coating (alpha) and metal plate surface obtained by drying, further provide the base treatment film, as already stated , one layer each from the ground processing layer to the outermost layer, may be formed multilayer film by a sequential coating method is repeated drying and recoating. Furthermore, a convenient and efficiently coating as a method of forming the metal plate surface, it is also possible to use a wet-on-wet coating method or multilayer simultaneous coating method described above. In these methods, stacked from the lowermost layer to the uppermost layer, once formed on the metal plate in water or 含溶 agent state (wet state). In such a state, due to the high mobility of the silane coupling agent contained in the outermost layer (s), at least a portion of the silane coupling agent (s) are functional compounds both contained in the base layer immediately below the efficiently react. These chemical bonds (interlayer crosslinking accelerator), tend to increase than that of the outermost layer and the underlayer adhesion sequential coating method, and the film followability when the metal plate is deformed by the molding process, the processing unit to improve compared to the case where corrosion resistance was formed into a film in a sequential coating method.
[0076]
　In the present invention, the general formula resin (A2 in (I) Si silane coupling agent used to form the) (s) have the general formula Y-Z-SiX m R 3-m silane having a molecular structure represented by it can be a one or more selected from a coupling agent. Wherein among the functional groups of molecular structure, -X group mainly comprising a reaction point of the metal surface or other silane coupling agent, a hydrolyzable alkoxy group having 1 to 3 carbon atoms or a hydrolyzable halogeno group (fluoro group (-F), chloro group (-Cl), such as a bromo group (-Br)), or hydrolyzable acetoxy group (-O-CO-CH 3 is). Of these, the hydrolyzable alkoxy group having 1 to 3 carbon atoms, preferably for easily adjusting a hydrolyzable by changing the number of carbon atoms of the alkoxy group include a methoxy group (-OCH 3 ) or ethoxy group (- OCH 2 CH 3 ) is particularly preferred. Silane coupling agents -X group is a functional group other than above, because either a low hydrolyzable -X group, or hydrolyzable too high, undesirable in the present invention. In the case coating composition (beta) is not an aqueous, in order to decompose the silane coupling agent of hydrolysable functional groups, previously small amount of water paint composition (beta), the further hydrolysis catalyst is added it may be.
[0077]
　-R group in the molecular structure an alkyl group having 1 to 3 carbon atoms. If -R group is a methyl group or an ethyl group, compared to the bulky n- propyl group or an isopropyl group does not interfere with the access of water molecules to the -X group in the composition, relatively easily is -X group preferably for the hydrolysis, among them a methyl group is particularly preferred. Silane coupling agent -R group is a functional group other than above, since whether the extremely low hydrolyzable -X groups, or reactive is too high, undesirable in the present invention.
[0078]
　At the molecular structure, m indicating the number of substituents is an integer of 1-3. Because many reaction sites with hydrolyzable -X groups are often more metal surface, m indicating the number of substituents is 2 or 3 are preferred.
[0079]
　-Z- in the molecular structure of the silane coupling agent (s) is 1 to 9 carbon atoms, nitrogen atoms having 0 to 2, the hydrocarbon chain of an oxygen atoms 0-2. Of these, 2 to 5 carbon atoms, nitrogen atoms 0 or 1, hydrocarbon chain oxygen atoms 0 or 1, for the balance of reactivity and dispersibility in water or solvent of the silane coupling agent is good ,preferable. -Z- carbon atoms of 10 or more, the number of nitrogen atoms is 3 or more, or when the number of oxygen atoms is 3 or more, the balance of reactivity and dispersibility in water or solvent of the silane coupling agent for defects, undesirable in the present invention.
[0080]
　The molecular structure Y-Z-SiX silane coupling agent (s) m R 3-m in, -Y group as a reaction point with the functional groups of the resin (A1) or other coexisting resin, the resin (A1 ) and is not particularly limited as long as it reacts with other coexisting resin, high reactivity, epoxy group, amino group, mercapto group or methylidene group (H, 2 C =) are preferred, epoxy group or amino groups are particularly preferred.
[0081]
　During the coating film formation of the present invention, the molecular structure-Z-Y SiX m R 3-m -SiX silane coupling agent represented by (s) molecule m group reacts with the metal surface and the like. Further, when -Y groups are reacted with the resin (A1) or the like, the resin (A2 shown in the general formula (I) Si becomes). That is, at least partially generates the hydrolyzed to -Si-OH (silanol group), at least a portion of the metal surface or other silane coupling the -Si-X of the silane coupling agent (s) molecular end combined hydroxyl and dehydration condensation of the coupling agent (s) molecules, covalently linked through ether bonds one Si-O-Me (Me is a metal atom) or -Si-O-Si * - ( Si * other silane coupling generating a Si atom) from molecules. Is -Y group at the other end of the silane coupling agent (s) molecule reacts with the functional groups of the resin (A1), to generate a binding A1 ~ Z, as a result, shown in the following general formula (I) resin (A2 having the structure Si becomes). End of these reactions, the resin (A2 Si (A2 after) is produced Si are bonded to Si atoms in) -O -, - OH, -X, the number of -R group each a, b, c , When d, which is a + b + c = m. Further, since -R group of the silane coupling agent (s) are to remain in the resin (A2) does not participate in the reaction, the number of -R group, d = 3-m = 3- (a + b + c), a + b + c + d = 3. Incidentally, notation "A1 ~ Z" in formula (I) indicates that A1 and Z is covalently bound through both the functional groups.
[0082]
　Specific examples of the silane coupling agent (s), the general formula:
Y-Z-SiX m R 3-m (-X
group is a hydrolyzable alkoxy group of 1 to 3 carbon atoms, hydrolyzable halogeno group or a hydrolyzable acetoxy group, -R group is an alkyl group having 1 to 3 carbon atoms, m is an integer 1 to 3 indicating the number of substituents, -Z- is 1-9 carbon atoms, a nitrogen atom, number 0-2, hydrocarbon chain oxygen atoms 0-2, -Y group is a functional group) which reacts with the resin (A1)
as having a molecular structure shown in, for example, vinyltrimethoxysilane, vinyltriethoxysilane , 3-aminopropyltrimethoxysilane, 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyl diethoxy silane, 3- Metakurirokishipu Pills triethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl methyl diethoxy silane, 3-glycidoxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane silane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyl methyl dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane silane, N- phenyl-3-aminopropyltrimethoxysilane may be mentioned 3-mercaptopropyl trimethoxysilane.
[0083]
　In the present invention, when a coating film (alpha) containing the organic resin (A) is formed on the metal surface, the coating composition used (beta), the resin (A1) relative to 100 parts by weight of a silane coupling agent (s ) preferably contains 1 to 100 parts by weight. Small amount of silane coupling agent (s) is less than 1 part by mass, the crosslinking structure with a silane coupling agent is not well developed, possibly not obtained sufficiently 繊密 coating film corrosion resistance is slightly poor and, it may become insufficient processability adhesion between the metal surface and the like at the time of molding. When it exceeds 100 parts by weight, the adhesion improving effect is saturated, but also uneconomical for use unnecessarily expensive silane coupling agent, which may reduce the stability of the coating composition (beta) .
[0084]
　Organic resin (A) in the present invention, the resin (A1) alone, or even add to the resin (A2 Si preferably contains 50 to 100 wt% of the resin (A) a) in total, the resin (A1 ) and the resin (A2 Si ) total and more preferably contains 75 to 100 wt% of the organic resin (a) in the. Resin (A1) and the resin (A2 Si when the total) is less than 50% by weight of the organic resin (A), the may be insufficient adhesion to the繊密property and the metal surface of the coating, the desired corrosion resistance and paint adherence, may not be obtained coating film followability at the time of molding.
[0085]
　In the present invention, the resin (A1) and the resin (A2 Si coating containing) membranes (alpha), the resin (A1) and (A2 Si relative to the total 100 parts by weight of), the resin (A2 Si ) in the the Si atoms forming the -C-Si-O-bond preferably contains 0.1 to 30 parts by weight. Is less than 0.1 part by weight,繊密resistance of the coating film, adhesion between the metal surface and the like, a smaller amount of the coating process followability the influence -C-Si-O- bond when forming a metal plate , there is a possibility that no sufficient corrosion resistance and adhesion can be obtained. If it exceeds 30 parts by weight, the adhesion improving effect of the metal surface or the like is saturated, for use unnecessarily expensive silane coupling agent for forming a coating film, or uneconomical, the composition for coating which may reduce the stability of the object (beta). For identification and quantification of Si atoms forming the -C-Si-O-bonds, and FT-IR spectrum of the coating on the metal plate, 29 be performed using analytical methods such as Si-NMR it can.
[0086]
　As already mentioned, the resin (A1) is contained 50 to 100% by weight of the nonvolatile content as a component of the coating composition used to form the coating film of the present invention (α) (β), and, after coating (alpha) formed by coating on the metal plate, the organic resin in the coating film (a), the include resin (A1), or further include additional to reactive derivative thereof (A2). The resin (A1) is, as already mentioned, as long as that is stable in an aqueous or organic solvent-based coating composition (beta), is not particularly limited in its type and structure, its structure during, a carboxyl group (-COOH), a carboxylate (-COO - M + , M + is a monovalent cation), a sulfonic acid group (-SO 3 H), sulfonate (-SO 3 - M + ; M + is a monovalent cation), primary amino group (-NH 2 ), 2 amino group (-NHR 1 ; R 1 is a hydrocarbon group), a tertiary amino group (-NR 1 R 2 ; R 1 and R 2Is a hydrocarbon group), a quaternary ammonium salt (-N + R 1 R 2 R 3 X - ; R 1 , R 2 , R 3 is a hydrocarbon group, X - 1 monovalent anion), sulfonium salt (-S + R 1 R 2 X - ; R 1 , R 2 is a hydrocarbon group, X - is a monovalent anion), a phosphonium salt -P + R 1 R 2 R 3 X - ; R 1 , R 2, R 3 is a hydrocarbon group, X - is preferred that at least one functional group selected from a monovalent anion). That is, the coating film (alpha) the organic resin in (A), the above carboxyl group, carboxylate, sulfonic acid, sulfonate, secondary amino group, tertiary amino group, quaternary ammonium salt, sulfonium comprising a base, at least one functional group selected from phosphonium salt (hereinafter collectively referred to as "polar functional groups" in the present invention) of the resin (A1), or even the resin derivative (A2) containing the structure it is preferred that.
[0087]
　The resin (A1) is, for the preferred reason to include the polar functional groups in its structure, described below.
[0088]
　The coating composition (beta), which contains a resin (A1) constituting at least a part of the film after the organic resin (A). If paint composition (beta) is aqueous, in many environments of the water after storage in or paint coating composition (beta), while low polarity structure of the resin (A1) mainly composed of hydrocarbon chains When polar functional groups are present, the polar functional groups showing an extremely high hydrophilicity in highly polar elongation in water, water and hydration of the peripheral. As a result, the resin (A1) is easily stably dispersed in the coating composition (beta). These polar functional Motogun is adsorbed on the surface of the non-oxide ceramic particles present in the coating composition (B), it prevents aggregation of the non-oxide ceramic particles (B), keeping the dispersion effective.
[0089]
　In general, for water-based coating compositions, unlike an organic solvent-based coating compositions, immediately after storage or during paint coating compositions but high polarity comprise a large amount of water, the water evaporates in the film-forming process , polar environment during coating composition largely changes from the high polarity to low polarity. For the present invention, because of the structure polar functional groups in the resin (A1), when the water in the coating film forming process vaporized polarity is rapidly reduced, at least a portion of the polar functional groups of the water of hydration It shrinks into a coil to desorb from and the metal surface. On the other hand, elongation low polarity resin chain portion of the resin (A1), to form a steric hindrance layer, is believed to play a role in preventing the aggregation of non-oxide ceramic particles (B).
[0090]
　Thus, during the low polarity structure of the resin (A1) mainly composed of hydrocarbon chains, if any polar functional groups showing an extremely high hydrophilicity in highly polar, and during storage of the aqueous coating composition, the coating its polarity elongation group or chain adapted in accordance with the polarity change in the coating composition at the time of film formation (coating film), easily maintaining the dispersibility of the non-oxide ceramic particles.
[0091]
　If paint composition (beta) is an organic solvent-based, in the low polarity structure of the resin (A1) mainly composed of hydrocarbon chains, if said polar functional groups showing an extremely high hydrophilicity in highly polar, these are adsorbed on the surface of the non-oxide ceramic particles present in the coating composition (B), and the polar functional in the organic solvent and elongation low polarity resin chain portion of the resin (A1) a resin structure to distance the group together with each other, in and film formation process coating composition to prevent aggregation of the non-oxide ceramic particles (B), it is effective to maintain the dispersion.
[0092]
　Other benefits resin (A1) contains a polar functional groups of the, by containing these functional groups, the adhesion of the metal plate is a base material (if there is surface treatment coating the coating) and improved corrosion resistance of the coating film (alpha), the processing follow-up property of the coating during molding (film adhesion processing portion during sheet metal forming process, crack resistance, colorfastness drop, etc.), scratch resistance, etc. but I like to be improved.
[0093]
　A sulfonic acid group structural formula -SO 3 is a functional group represented by H. Further, sulfonate group, structural formula -SO 3 - M + (M + is a functional group represented by the monovalent cation), alkali metals sulfonic acid groups and neutralized with amines such as containing ammonia it is intended.
[0094]
　Resin (A1) is, in the case of a polyester resin containing a sulfonic acid group or a sulfonate group in the structure, the polyol used as a starting material for the synthesis of the resin, polycarboxylic acid, sulfonic acid group-containing compounds, is limited to the sulfonate group-containing compound Absent. The polyol and a polycarboxylic acid, can be used those already exemplified. As the sulfonic acid group-containing compounds, for example, 5-sulfoisophthalic acid, 4-sulfo-naphthalene-2,7-dicarboxylic acid, 5 (4-sulfophenoxy) dicarboxylic acids containing a sulfonic acid group, such as isophthalic acid, or 2-sulfo-1,4-butanediol, 2,5-dimethyl-3-sulfo-2,5-diols such as hexyl diol can be used. The sulfonate group-containing compounds, e.g., 5-sulfo sodium sulfoisophthalic acid, 5-sulfo sodium isophthalic acid dimethyl and the like can be used. If it is desired to obtain a sulfonic acid group is neutralized resin, already neutralized sulfonic acid groups may be incorporated into the resin, may be neutralized sulfonic acid groups after incorporation into the resin. If paint composition (beta) is an aqueous, for resin uniformly finely dispersed in water, compared to radix of the sulfonic acid groups are not neutralized, neutralized with amines such as containing alkali metals, ammonia Write radix sulfonate group often preferred. It is because, alkali metals, sulfonate neutralized with amines such as including ammonia, in order to easily ionized hydrated in water, the resin containing a large amount of these groups in its structure is uniformly and finely dispersed in water This is because easy. Among these, Li, Na, alkali metal neutralized sulfonic acid metal salt such as K is, water-based coating composition and during storage of the (beta), non-oxidized in many environments with water immediately after painting or suppress aggregation of objects ceramic particles (B), particularly preferred in enhancing the adhesion between the substrate and the coating film (alpha), sulfonate Na bases are most preferred.
[0095]
　The amount of the dicarboxylic acid or diol containing a sulfonic acid or sulfonate group based on all the polycarboxylic acid components or the total polyol component, the sum of the dicarboxylic acid or diol containing a sulfonic acid group or a sulfonate group preferably contains 0.1 to 10 mol%. If it is less than 0.1 mol%, water-based paint composition during storage and the (beta), in many environments with water immediately after coating, stable dispersion of the resin containing carboxyl group or a sulfonic acid group, a sulfonic acid salt sulfonic acid for reduction, acid base moiety is small, there is a possibility that sufficient resin dispersion is obtained. Further, a sulfonic acid group that adsorbs to the non-oxide ceramic particles coexisting in the coating composition (B), since the amount of the sulfonic acid salt is small, if the effect of preventing the aggregation of each other non-oxide ceramic particles is insufficient is there. Further, the metal plate is a base material (if surface treatment is surface treatment layer) for a sulfonic acid group which acts on, the amount of sulfonate group is small, the effect of improving the adhesion and corrosion resistance can not be obtained. If it is 10 mol percent, a sulfonic acid group, the amount of water coating holds increases the sulfonate group, there is a case where the corrosion resistance is lowered. Considering the balance of the performance, and more preferably in the range of 0.5 to 5 mol%.
[0096]
　The carboxyl group is a functional group represented by the structural formula -COOH. Further, the carboxylic acid salt structural formula -COO - M + (M + is a functional group which is a monovalent cation) represented by, is obtained by neutralizing the carboxyl group alkali metals, amine and the like containing ammonia .
[0097]
　Resin (A1) is, when in the structure of the polyester resin containing carboxyl groups or carboxylate is not particularly limited as method of deploying the carboxyl group or carboxylate in the polyester resin. For example, after polymerization of the polyester resin, atmospheric pressure, under a nitrogen atmosphere, trimellitic anhydride, phthalic anhydride, pyromellitic anhydride, succinic anhydride, 1,8-naphthalic anhydride, 1,2-cyclohexanedicarboxylic acid , cyclohexane-1,2,3,4-tetracarboxylic acid-3,4-anhydride, ethylene glycol bisanhydrotrimellitate, 5- (2,5-dioxo-3-furanyl) -3-methyl 3-cyclohexene-1,2-dicarboxylic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride and select one or two or more, such as high how and polyester append put these acid anhydrides in those oligomeric state before the molecular weight, then a method in which a high molecular weight by polycondensation under reduced pressure, and the like.
[0098]
　If the carboxyl group is used neutralized resin, already neutralized carboxyl groups may be incorporated into the resin, it may be neutralized carboxyl groups after incorporation into the resin. If paint composition (beta) is an aqueous, for resin uniformly finely dispersed in water, compared to radix of carboxyl groups which are not neutralized, neutralized with amines such as containing alkali metals, ammonia carboxylic Write radix acid base is often preferred. Is because, alkali metals, carboxylate groups neutralized with amines such as including ammonia, in order to easily ionized hydrated in water, the resin containing a large amount of these groups in its structure is uniformly and finely dispersed in water This is because easy.
[0099]
　There is no particular limitation on the introduction amount of the carboxyl group or carboxylate. Acid value corresponding to the total amount of carboxyl groups and carboxylate salt is preferably in the range of 0.1 ~ 50mgKOH / g. If it is less than 0.1 mg KOH / g, water paint composition (beta) of the storage or during at high environment of the water after painting, to stabilize the dispersion resin containing a carboxyl group or a sulfonic acid group fewer carboxyl group moiety, there is a possibility that sufficient resin dispersion is obtained. Further, since the amount of the non-oxide ceramic particles carboxyl or carboxylate adsorbed on (B) to coexist in the coating composition is less, the effect of preventing the aggregation of non-oxide ceramic particles is insufficient . Further, the metal plate is a base material (if surface treatment is surface treatment layer) for a small amount of the carboxyl group or carboxylate acting on, the effect of improving the adhesion and corrosion resistance can not be obtained. Acid value is 50 mg KOH / g greater, more amount of water retained coating film carboxyl group or a carboxylic acid base, in some cases corrosion resistance decreases. Considering the balance of the performance, the acid value is more preferably in the range of 0.5 ~ 25mgKOH / g.
[0100]
　Primary amino groups of the two amino groups, tertiary amino groups, quaternary ammonium bases are, respectively, -NH 2 , -NHR 1 , -NR 1 R 2 , -N + R 1 R 2 R 3 X - in a functional group represented by. R 1 , R 2 , R 3 is a hydrocarbon group, X - is a monovalent anion.
[0101]
　Resin (A1) is, if it contains a primary amino group or secondary amino group (imino group), no particular restriction on the method of deploying these groups in the resin backbone. For example, urea, melamine, hexamethoxymethylmelamine, a compound with formaldehyde having two or more primary amino groups of benzoguanamine and condensation polymerization, methanol some or all of the methylol groups of the product obtained, ethanol, method in which the amino resin is etherified with a lower alcohol such as butanol.
[0102]
　Resin (A1) is a secondary amino group, when the cationic resin containing a tertiary amino group or a quaternary ammonium salt, is not particularly limited as method of deploying the functional group into the resin skeleton. For example, primary three-membered cyclic ether group in which the epoxy groups in the epoxy resin chains (oxirane ring) is reacted with a secondary or tertiary amine compound, respectively, secondary amino group in the resin chain, a tertiary amino group, and a method of introducing a quaternary ammonium group. Furthermore, can be exemplified those groups organic acid, it was neutralized with an inorganic acid such as aqueous resin of the thing and the like.
[0103]
　Secondary amino groups of the tertiary amino groups, quaternary ammonium salt, sulfonium salt, the structural formula of the phosphonium salt, respectively, -NHR 1 , -NR 1 R 2 , -N + R 1 R 2 R 3 X - , -S + R 1 R 2 X - , -P + R 1 R 2 R 3 X - is represented by wherein, R 1 , R 2 , R 3 is a hydrocarbon group, X - is a monovalent anion . R 1, R 2 , R 3 and,, X - is a resin having a functional group is stably present in the coating composition (beta), has good coating property and film forming property of the metal plate, resistance welding of coated metal plates after film, corrosion resistance, if the formability is good and is not particularly limited.
[0104]
　R 1 , R 2 , R 3 include, for example, an alkyl group, an aryl group, an alkyl group substituted with a hydroxyl group or an alkoxy group, an aryl group or an aralkyl group having a straight-chain or branched having 1 to 18 carbon atoms it can be mentioned. As these specific examples, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, alkyl groups such as dodecyl group, phenyl, tolyl, xylyl, or similar aryl groups, benzyl, aralkyl groups such as phenethyl group, hydroxyl groups, such as those substituted with an alkoxy group, and the like. R 1 , R 2 , R 3 may be either the same group different groups. X - may be, for example, fluorine, chlorine, halide ions bromine or iodine, sulphate, phosphate, perchlorate ions, and the like.
[0105]
　The organic resin (A) is preferably a resin cured with a curing agent. Wherein the curing agent is not particularly limited as long as curing the organic resin (A). Wherein in the resin of those already exemplified as the crosslinking agent (A1), is preferably used at least one crosslinking agent selected from one melamine resin or polyisocyanate compound is an amino resin as the curing agent.
[0106]
　Melamine resin, some or all of the methylol groups of the product obtained by condensation of melamine and formaldehyde is methanol, ethanol, resins etherified with lower alcohols as butanol. No particular limitation is imposed on the polyisocyanate compound. For example, hexamethylene diisocyanate already exemplified as a crosslinking agent for the resin (A1), isophorone diisocyanate, xylylene diisocyanate, can be mentioned tolylene diisocyanate and the like. Moreover, the blocked product can be mentioned the blocked product of hexamethylene diisocyanate is a blocked product of a polyisocyanate compound, blocked product of isophorone diisocyanate, blocked product of xylylene diisocyanate, blocked product of tolylene diisocyanate and the like. These curing agents may be used alone or in combination of two or more thereof.
[0107]
　The content of the curing agent, it is preferable that the 5 to 35% by weight of the organic resin (A). If the amount is less than 5 wt%, bake hardenability is insufficient, corrosion resistance, may scratch resistance is lowered, if it is more than 35 wt%, bake hardenability becomes excessive, if the corrosion resistance, workability decreases there is.
[0108]
　From the viewpoint of scratch resistance of the coating film (alpha), preferably contains a melamine resin in the curing agent. The content of the melamine resin is preferably 30 to 100 mass% of the curing agent. If it is less than 30 mass%, the scratch resistance of the resulting coating film (alpha) is reduced.
[0109]
　
　In the present invention, as the conductive particles in the coating film (alpha), and using a non-oxide ceramic particles (B). In the present invention, even if paint composition for obtaining a coating film (α) (β) is an aqueous composition, these non-oxide ceramic particles (B) is not deteriorated in the composition, high electrical Den'no permanently hold. Therefore, conductive particles deteriorated by moisture, for example, compared with the base metal particles and ferrosilicon particles, etc., can be very long period retain excellent resistance weldability.
[0110]
　Non-oxide ceramics constituting the non-oxide ceramic particles contained in the coating film (alpha) (B) of the present invention, the electrical resistivity of 25 ° C. (volume resistivity, resistivity) of 0.1 × 10 -6 ~ 185 × 10 -6 boride ceramic is in the range of [Omega] cm, carbide ceramics, a nitride ceramic or silicide ceramic. The non-oxide ceramics which here means the ceramics consisting of elements and compounds that do not contain oxygen. Also, here referred boride ceramics, carbides ceramics, nitrides ceramics, and the silicide ceramics, respectively, boron B, that of non-oxide ceramics to carbon C, nitrogen N, silicon Si principal nonmetallic construction elements it is. Of these, the electrical resistivity of 25 ° C. is 0.1 × 10 -6 do not see of less than [Omega] cm. Further, non-oxide 25 ° C. electrical resistivity of the ceramic (the volume resistivity, the resistivity) of 185 × 10 -6 large amounts when excess of [Omega] cm, the coating film in order to impart sufficient conductivity to the resin coating film addition is required, the coated metal plate coated film peeling and galling occurs significant when press molding of the present invention, is unsuitable for corrosion resistance decreases.
[0111]
　Non-oxide ceramic particles contained in the coating film (alpha) of the present invention (B) has a high conductivity, the amount for imparting sufficient conductivity to the resin coating film well in smaller amounts, the result, adverse effects on the corrosion resistance and formability of the coated metal plate is less. For reference, the electrical resistivity of the pure metal is × 10 1.6 -6 [Omega] cm (Ag alone) ~ 185 × 10 -6 is in the range of [Omega] cm (Mn alone), non-used as conductive particles in the present invention oxide ceramics (electrical resistivity × 10 0.1 -6 ~ 185 × 10 -6 [Omega] cm) is found to have excellent conductivity of pure metal the same degree.
[0112]
　The non-oxide ceramics which can be used in the present invention includes the followings. That is, the boride ceramic, IV of the periodic table (Ti, Zr, Hf), V group (V, Nb, Ta), VI group (Cr, Mo, W) each transition metal, Mn, Fe, Co, Ni, rare earth or be, alkaline earth metals other than Mg (Ca, Sr, Ba) a boride of, can be exemplified.
　However, in the electrical resistivity of the 25 ° C. of Be boride is 185 × 10 -6 to exceed [Omega] cm (e.g., Be 2 B, BeB 6 , etc.), application to the present invention for conducting performance is not sufficient it is not suitable for. Further, it borides Mg (Mg 3 B 2 , MgB 2 , etc.) because unstable to water and acid, is not suitable for application to the present invention.
　The carbide ceramics, IV, Group V, Group each transition metal Group VI, Mn, Fe, Co, carbides Ni can be exemplified. However, a hydrolyzing risk under a humid atmosphere, a rare earth element or an alkaline earth metal carbide (eg, YC 2 , LaC 2 , CEC 2 , PrC 2 , Be 2 C, Mg 2 C 3 , SrC 2 , etc.) is not suitable for application to the present invention.
　As the nitride ceramics, IV, Group V, Group each transition metal Group VI or Mn, Fe, Co, nitrides Ni, can be exemplified. However, a hydrolyzing risk under a humid atmosphere, a rare earth element or nitride of alkaline earth metal (e.g., LaN, Mg 3 N 2 , Ca 3 N 2 , etc.) are not suitable for application to the present invention . The silicide ceramics, IV, Group V, Group each transition metal Group VI or Mn, Fe, Co, a silicide of Ni, can be exemplified. However, a possibility of generating hydrogen reacts with water under a humid atmosphere, a rare earth element or an alkaline earth metal silicide (e.g., LaSi, Mg 2 Si, SrSi 2 , BaSi 2 , etc.), to the present invention it is not suitable to apply.
　Furthermore, these borides, carbides, nitrides, mixtures of two or more selected from silicides, or can be exemplified by those ceramic mixed with binder metal sintered cermet.
[0113]
　When fabricating the coating film (alpha) from the aqueous coating composition, the standard electrode potential of the metal constituting a part of the cermet is preferably water degradation resistance at least -0.3 V. If the standard electrode potential of the metal constituting a part of the cermet is less than -0.3 V, this cermet particles are present long time in an aqueous paint composition, Sabiso and thick oxide insulating layer on the surface of the particles occurs , there is a possibility that the conductive particles are lost. Examples of water-degradation of cermet particles, WC-12Co, WC-12Ni, TiC-20TiN-15WC-10Mo 2 C-5Ni the like. Co, respectively the standard electrode potential of Ni -0.28V, and both noble than -0.3V at -0.25 V, any metal is also water-degradable.
[0114]
　Of the non-oxide ceramics of the, Cr-based ceramics (CrB, CrB 2 , Cr 3 C 2 , Cr 2 N, CrSi, or the like) from concerns over the environmental impact, also, Hf-based ceramics (HfB 2 , HfC, HfN etc.), many of the ceramic of Jumaredo side of rare-earth than Tb is expensive, also because it is not on the market, in the present invention, the non-oxide excluding those from the group of the ceramic, or, it is preferable to use a mixture of two or more selected from these.
[0115]
　Furthermore, stability distribution of the presence or absence and abroad markets for industrial products, prices, in terms of electrical resistivity, etc., and more preferably less non-oxide ceramics. That, BaB 6 (electric resistivity × 10 77 -6 [Omega] cm), CeB 6 (same × 10 30 -6 [Omega] cm), Co 2 B (same × 10 33 -6 [Omega] cm), CoB (the 76 × 10 -6 [Omega] cm ), FeB (same × 10 80 -6 [Omega] cm), GdB 4 (same × 10 31 -6 [Omega] cm), GdB 6 (same × 10 45 -6 [Omega] cm), LaB 4 (same × 10 12 -6 [Omega] cm), LaB 6 (same × 10 15 -6 [Omega] cm), Mo 2 B (same × 10 40 -6 [Omega] cm), MoB (the 35 × 10 -6 [Omega] cm), MoB 2 (with 10 × 45 -6 [Omega] cm), of Mo 2 B . 5 (with 10 × 26 is -6 [Omega] cm), of Nb . 3 B 2 (with 10 × 45 -6 [Omega] cm), NbB (6 same. × 10. 5 -6 [Omega] cm), of Nb . 3 B . 4 (with 10 × 34 is -6 [Omega] cm), NbB 2 (with 10 × 10 -6 [Omega] cm), NdB . 4 (with 10 × 39 -6 [Omega] cm), NdB . 6 (with 10 × 20 is -6 [Omega] cm), PrB . 4 (with 10 × 40 -6 [Omega] cm), PrB 6 (with 10 × 20 is -6 [Omega] cm), SrB 6 (with 10 × 77 -6 [Omega] cm), TaB (with 10 × 100 -6 [Omega] cm), TaB 2 (10 × with 100 -6 [Omega] cm), of TiB (with 40 10 × -6 [Omega] cm), of TiB 2 (with 10 × 28 -6 [Omega] cm), VB (with 10 × 35 -6 [Omega] cm), VB 2 (with 10 × 150 -6 [Omega] cm), W is 2 B . 5 (with 80 × 10 -6 [Omega] cm), YB . 4 (with 10 × 29 -6 [Omega] cm), YB . 6 (with 10 × 40 -6 [Omega] cm), YB 12 is(With 10 × 95 -6 [Omega] cm), of ZrB 2 (with 10 × 60 -6 [Omega] cm), of MoC (with 10 × 97 -6 [Omega] cm), of Mo 2 C (with 10 × 100 -6 [Omega] cm), of Nb 2 C ( with 10 × 144 -6 [Omega] cm), of NbC (with 10 × 74 -6 [Omega] cm), Ta 2 C (with 10 × 49 -6 [Omega] cm), TaC (with 10 × 30 -6 [Omega] cm), of TiC (with 180 × 10 -6 [Omega] cm), V 2 C (with 10 × 140 -6 [Omega] cm), the VC (with 10 × 150 -6 [Omega] cm), the WC (with 10 × 80 -6 [Omega] cm), W is 2 C (with 10 × 80 -6Ωcm), ZrC (with 10 × 70 -6 [Omega] cm), of Mo 2 N (with 10 × 20 is -6 [Omega] cm), of Nb 2 N (with 10 × 142 -6 [Omega] cm), of NbN (with 10 × 54 is -6 [Omega] cm) , ScN (with 10 × 25 -6 [Omega] cm), Ta 2 N (with 10 × 135 -6 [Omega] cm), of TiN (with 10 × 22 is -6 [Omega] cm), of ZrN (with 10 × 14 -6 [Omega] cm), CoSi 2 ( with 10 × 18 is -6 [Omega] cm), of Mo . 3 Si (with 10 × 22 is -6 [Omega] cm), of Mo . 5 Si . 3 (with 10 × 46 is -6 [Omega] cm), MoSi 2 (with 10 × 22 is -6[Omega] cm), NbSi 2 (same × 10 6.3 -6 [Omega] cm), Ni 2 Si (same × 10 20 -6 [Omega] cm), Ta 2 Si (same × 10 124 -6 [Omega] cm), TaSi 2 (same 8.5 10 × -6 [Omega] cm), TiSi (same × 10 63 -6 [Omega] cm), TiSi 2 (same × 10 123 -6 [Omega] cm), V 5 Si 3 (same × 10 115 -6 [Omega] cm), VSi 2 (same 9. × 10 5 -6 [Omega] cm), W 3 Si (same × 10 93 -6 [Omega] cm), WSi 2 (same 33 × 10 -6[Omega] cm), ZrSi (same × 10 49 -6 [Omega] cm), ZrSi 2 (same 76 × 10 -6 [Omega] cm), or, it is preferable to use a mixture of two or more selected from these.
[0116]
　Among these, the electric resistivity of 25 ° C. is × 10 0.1 -6 ~ 100 × 10 -6 in [Omega] cm, non-oxide ceramics are particularly preferred. Is because they are electrical resistivity of 25 ° C. is 100 × 10 -6 185 × 10 exceeds the [Omega] cm -6 has a high conductivity than non-oxide ceramics in the range of up to [Omega] cm, sufficient resin film well with less amount of particles added amount for imparting conductivity is not formed conductive paths of corrosion current passing through the coating film little, corrosion resistance because almost unchanged. Further, without inducing coating peeling or galling during press molding for a small amount of particles added, because moldability is not lowered little.
[0117]
　Electrical resistivity which is appended in the parentheses non-oxide ceramics of the are respectively representative value of those sold as an industrial raw material used (literature value). These electrical resistivity, to increase or decrease depending on the type and amount of non-oxide impurity element that enters into the crystal lattice of the ceramic, in use in the present invention include, for example, (Corporation) Mitsubishi Chemical Analytic Tech Ltd. resistivity meter Loresta EP (MCP-T360 type) and ESP probe 4-terminal 4-probe method using a (2mm diameter flat head of the pin), a constant current application system, the electrical resistivity of in compliance with JIS K7194 25 ° C. actually measured, 0.1 × 10 -6 ~ 185 × 10 -6 may be used after confirming that in the range of [Omega] cm.
[0118]
　Particle shape of the non-oxide ceramic particles (B), spherical particles, or pseudo-spherical particles (e.g., elliptical spherical, egg-shaped, rugby ball shape or the like) or a polyhedron particles (eg a soccer ball shape, cubes, various jewels such as brilliant-cut shape or the like), preferably a shape close to a sphere. Elongated shape (eg, a bar, a needle-like, fibrous, etc.) or a planar shape (for example flakes, plate-like, flaky, etc.), those of or arranged in parallel to the coated surface in coating processes, in paint base certain metal plate (if surface treatment to a metal surface primed layer) to or deposited in the vicinity of the interface coating and, since it is difficult to form an effective conduction path penetrating the thickness direction of the coating film, of the present invention not suitable for use.
[0119]
　The average particle size of the non-oxide ceramic particles (B) is not particularly limited, C. in coating composition of the present invention (beta), is preferably a volume average diameter is present in the particles of 0.2 ~ 20 [mu] m , more preferably is present in particles having a volume average diameter of 0.5 ~ 12 [mu] m, a volume average diameter is particularly preferably present in the particles of 1 ~ 8 [mu] m. Dispersed particles, coating compositions having these volume mean diameter step of the production (beta), and during storage and transportation, a paint base metal plate (surface treatment layer if there is a surface treatment on the metal surface) at coating process or the like to, if present stably in the coating composition (beta), it is a single particle, or may be a secondary particle in which a plurality of single particles are aggregated strongly. At coating process to the substrate of the coating composition, drying the coating film, and the (B) particles agglomerate during film formation, no problem even when the volume-average diameter in the coating film is large.
[0120]
　Here, the volume average diameter referred is that the average diameter on a volume basis obtained from the volume distribution data of the particles. This generally may be obtained by using any particle size distribution measuring method are known, to use a mean value of the sphere volume equivalent diameter distribution measured by the Coulter method (a pore electrical resistance method) preferable. Because Coulter method, other particle size distribution measuring method (for example, (a) is calculated from the volume distribution obtained by laser diffraction scattering method, the volume distribution circle area equivalent diameter distribution obtained in (b) Image analysis converted to, is calculated from the mass distribution obtained in (c) centrifugal sedimentation method, compared to the like), measuring manufacturers and the difference almost no measurements depending on the model, since it is precise and accurate measurement. The Coulter method, the aqueous electrolyte solution to suspend the test particles, the pores of the glass tube passing a constant current is set so that the particles by negative pressure to pass through the pores. When particles pass through the pores, by volume of the aqueous electrolyte solution particles were excluded (= volume of the particles), the electrical resistance of the pores increases. By applying a constant current, the resistance change at the time of the particles pass it is reflected in a voltage pulse changes, by measuring process of this voltage pulse height one by one, directly measuring the volume of individual particles. Since the particles are many cases of irregular shape, assuming a sphere of the same volume and the particle is converted to the diameter of the sphere (= sphere volume equivalent diameter). Method of measuring the sphere volume equivalent diameter by such Coulter method are well known and, for example, the literature: on the Beckman Coulter, Inc. Internet official website web page [http: // www. beckmancoulter. co. jp / product / product03 / Multisizer3. In html (precision particle size distribution measurement apparatus Multisizer 3)], are described in detail.
[0121]
　Non-oxide ceramic particles less than a volume average diameter of 0.2μm is expensive in general larger non-oxide ceramic particles having a volume average diameter than, less those on the market as an industrial product. Further, since the specific surface area is relatively large, when preparing the coating composition of the aqueous or organic solvent-based, be used wetting and dispersing agent is difficult to wet dispersing the entire particle surface, rub water or an organic solvent no lump (lump), because they often lumps occurs, it is better not to use the present invention. The volume non-oxide ceramic particles having an average diameter exceeds 20μm, from the volume average diameter is smaller than the non-oxide ceramic particles, fast and easy to settle in the coating composition of the aqueous or organic solvent-based (Stokes equation the obvious). Therefore, since it is possible to ensure the dispersion stability by devising a dispersant difficult, sometimes precipitated in a short time without suspended particles, resulting in problems such as re-dispersion may become difficult to aggregate and solidifying, it is better not to use in the present invention.
[0122]
　The coating film (α) cμm a volume average diameter of the non-oxide ceramic particles dispersed (B) in case where, was bμm the thickness of the coating film (α), 0.5 ≦ c / b ≦ it is preferable to satisfy the relationship of 1.5. Figure 1 represents a schematic view of a cross section of an automotive coated metal plate of the present invention. (A) an organic resin, (B), (B ') is a non-oxide ceramic particles, (C) represents the anticorrosive pigment, (gamma) represents a metal plate. (B) is a particle ratio c / b of particle size to thickness becomes 0.5 or more, the conductivity of this thickness direction is ensured. (B ') is the ratio c / b is less than 0.5 particles having a particle diameter to thickness, in this case, there are cases where conductivity is not sufficiently secured. If the ratio c / b of particle diameter to the thickness is more than 1.5, there are cases where corrosion resistance and press formability decreases.
[0123]
　Available non-oxidizing ceramic particles (B) is generally because raw materials were classified as required crushed often be prepared to a predetermined particle size, mixed different particle particle sizes It has a particle size distribution. Accordingly, even in a size range having a volume average diameter described above, depending on its particle size distribution, it affects the weldability. Among the non-oxidizing ceramic particles (B), each volume particle diameter of 1 ~ 24μm (B1) is, in particular showing the effect on good weldability.
[0124]
　The amount of non-oxidizing ceramic grains accounting for coating the surface of the metal plate (B) also affects the weldability. In the present invention, a non-oxidizing ceramic particles particles having a particle diameter of 1μm ~ 24μm (B1) is 0.8 pieces / mm painted metal plate surface 2 ~ 40000 / mm 2 that are arranged, the welding of coated metal plate in a preferred gender. Particle size 1μm of less than (B) has a small contribution to the weldability, the particle diameter 24μm than (B) are particularly difficult to show the effect to fall off from the coating film easily welded if the thin film thickness. Number is 0.8 pieces / mm 2 smaller effect on the improvement in weldability is less than, 40000 / mm 2 provides a small effect of improving the weldability for the amount in excess.
[0125]
　
　it is not particularly restricted but the kind of anticorrosive pigment used in the present invention (C), silicate compounds, phosphate compounds, vanadate compound, and metal oxide particles (D) preferably includes one or more selected from.
[0126]
　Silicate compound, a phosphate compound, vanadate compound, in coating compositions (beta) and coating (alpha), moisture in the composition or coating, coexisting substances and the base material surface contact, depending on the environmental changes such as pH, release respectively, silicic acid ion, phosphoric acid ion, vanadate ion, and the counter cation of these anionic (e.g., an alkaline earth metal ion, Zn ion, Al ion, etc.) can do. Among these ions, the ions were eluted already in coating composition (beta), incorporated into the coating (alpha) during film, increase or decrease in water content in the coating, coexisting materials and substrate surface contact with, depending on the pH change, to form a film of other atoms or atomic groups and sparingly soluble salt or oxide coexisting believed to inhibit corrosion. Further, the coating film (alpha) has been incorporated into a silicate compound, a phosphate compound, as in the case of vanadate compounds, according to the environmental changes after film formation, the above anion, the cation gradually released and, to form a coating of sparingly soluble salt or oxide, it is believed to inhibit corrosion.
[0127]
　The silicate compound that can be used in the present invention, for example, magnesium silicate, alkaline earth silicates metal such as calcium silicate, lithium silicate, sodium silicate, alkali metal such as potassium silicate silicates, aluminum silicates, and the like. Of these, lithium silicate, sodium silicate, as potassium silicate, silicon oxide (SiO 2 ) and lithium oxide (Li 2 configuration molar ratio of O) is ≦ 0.5 (SiO 2 / Li 2 O) ≦ 8 is a lithium silicate, silicon oxide (SiO 2 ) and sodium oxide (Na 2 constituting molar ratio of 0.5 ≦ (SiO the O) 2 / Na 2 sodium silicate is O) ≦ 4, silicon oxide (SiO 2 ) and potassium oxide (K 2 constituting molar ratio of 0.5 ≦ (SiO the O) 2 / K 2 potassium silicate is O) ≦ 4, and it can be exemplified by hydrates of these silicates. Specific examples thereof include lithium orthosilicate (Li 4 SiO 4; 2Li 2 O · SiO 2 ), ortho disilicate six lithium (Li 6 Si 2 O 7 ; 3Li 2 O · 2SiO 2 ), lithium metasilicate (Li 2 SiO 3 ; Li 2 O · SiO 2 ), disilicate lithium acid (Li 2 Si 2 O 5 ; Li 2 O · 2SiO 2 ), seven silicic tetracalcium lithium (2Li 2 O · 7SiO 2 ), four lithium silicate (Li 2 Si 4 O 9 ; Li 2O · 4SiO 2 ), nine silicic tetracalcium lithium (2Li 2 O · 9SiO 2 ), fifteen silicic tetracalcium lithium (2Li 2 O · 15SiO 2 ), and, sodium orthosilicate (Na 4 SiO 4 ; 2Na 2 O · SiO 2 ), sodium metasilicate (Na 2 SiO 3 ; Na 2 O · SiO 2 ), sodium disilicate (Na 2 Si 2 O 5 ; Na 2 O · 2SiO 2 ), sodium tetraborate silicate (Na 2 Si 4 O 9; Na 2 O · 4SiO 2 ), potassium orthosilicate (K 4 SiO 4 ; 2K 2 O · SiO 2 ), potassium metasilicate (K 2 SiO 3 ; K 2 O · SiO 2 ), potassium disilicate (K 2 Si 2 O 5 ; K 2 O · 2SiO 2 ), potassium tetraborate silicate (K 2 Si 4 O 9 ; K 2 O · 4SiO 2), And, hydrates of these silicates and the like. Incidentally, many of the hydrates of these silicates by environmental changes such as pH, temperature and remains readily gelled state of hydration, part of which may be polysilicate salt and polymerized. A silicate compound that can be applied to the present invention also includes such a polysilicate salt.
[0128]
　The phosphate compound which can be used in the present invention, for example, orthophosphoric acid, polyphosphoric acid (single linear polymer to the polymerization degree 6 of orthophosphoric acid or a mixture of two or more thereof), metaphosphate (single cyclic polymer until the polymerization degree of 3 to 6 orthophosphoric acid or a mixture of two or more thereof), tetrametaphosphoric acid, metal salts such as hexametaphosphate, phosphorus pentoxide, monetite, Torufiru stone, whitlockite , xenotime, star copolymers light, Sutorubu stone, phosphate minerals such as orchids iron ore, a commercial complex phosphate pigment, phytic acid, such as polyphosphoric acid silica and tripolyphosphate, phosphonic acid (phosphorous acid), phosphinic acid (hypophosphorous acid) metal salts such as or, and mixtures of two or more thereof. The orthophosphate here, the monohydrogen (HPO 4 2- salt), dihydrogenphosphate (H 2 PO 4 - ) including. Further, the polyphosphate containing hydrogen salt. There is no particular limitation on the cation species to form a phosphate, for example, Co, Cu, Fe, Mn , Nb, Ni, Sn, Ti, V, Y, Zr, Al, Ba, Ca, Mg, Sr and Zn metal ions etc., vanadyl, titanyl, including but oxo cations such as zirconyl, Al, Ca, Mg, Mn, to use Ni preferred. The phosphate compound may be used alone or in combination of two or more thereof.
[0129]
　As cationic species to form the phosphate, a large amount of use of the alkali metal is undesirable. When using the phosphate of the alkali metal tends to products obtained by firing at an industrial production process is too soluble in water. However, in the case of using a phosphate of an alkali metal, the solubility of control to the water, when anticorrosive pigment production, during the production of the coating composition, during film to the metal plate, or a coated metal plate if you can practice to use or the like, may be used slightly larger amount. Such control may, for example, of the anticorrosive pigment, or coexist with other additives to prevent solubility in water, coexist with a polymer of highly resin and inorganic systems were crosslinked water controlling the dissolution rate, the method of and the like.
[0130]
　Vanadate compounds which can be used in the present invention, the valence of vanadium any one valency 0, 2, 3, 4 or 5, or a composite compound having two or more valences, e.g. these oxides, hydroxides, oxyacid salt of various metals, vanadyl compound, halides, sulfates, and metal powders. It decompose in the presence of heat or when water reacts with oxygen coexisting. For example, metal powders or compounds of divalent vanadium, eventually changes to any of the compounds of the 3,4,5-valent. 0-valent ones, e.g., vanadium metal powder, but can be used in the above reasons, since the oxidation reaction has a problem of insufficient or the like, it is not preferable for practical use. Pentavalent vanadium compounds have a vanadate ion, heated react with phosphate ions, liable to make a heteropolymeric contribute to rust, contain a pentavalent vanadium compound as one component are preferred. Specific examples of the vanadium compounds are vanadium oxide (II), vanadium (II) compounds such as vanadium hydroxide (II), vanadium (III) compounds such as vanadium oxide (III), vanadium oxide (IV), halogenated vanadyl vanadium (IV) compounds such as vanadium oxide (V), vanadate (orthovanadate various metals, metavanadate salt, pyrovanadates salts, etc.) vanadium (V) compounds such as, or mixtures thereof and the like. Preferred metal species constituting the vanadate is the same as the metal that shown in phosphate.
[0131]
　When using a vanadate of an alkali metal, for products obtained by firing at an industrial production process tends to be too soluble in water, as in the case of phosphate, vanadate of an alkali metal large amount of use is not desirable of. However, if control solubility in water in the same manner as in the case of using a phosphate of an alkali metal, no problem even their use. Halides vanadium, the same applies to the case of sulphate.
[0132]
　The coated metal plate of the present invention, the silicate compound, a phosphate compound, the total amount of vanadate compound is 1 to 40% by volume of the coating (alpha), it is the 1 to 20% by volume , more preferably from 2 to 15% by volume. Silicate compound is less than 1 vol%, the phosphate compound, because the action of vanadate compound is insufficient, there is a lowering of the corrosion resistance is lowered. More than 20% by volume, the coating becomes brittle, lowered coating film adhesion and coating film followability at the time of molding by coating cohesive failure, the welding may be decreased.
[0133]
　Anticorrosive pigment (C) is a silicate compound, a phosphate compound, preferably comprises one or more of the vanadate compound, a phosphate compound (phosphate ion source), Kay salt compound (silicate ion source) or vanadate compound that at least one (vanadate ion source) coexist, and more preferable in enhancing the corrosion protection. A source of phosphate ions to be blended, silicic acid ion source, the ratio of the total amount of vanadate ion source, [P 2 O 5 moles of]: [SiO 2 and V 2 O 5 ratio of the total moles of] 25: 75-99: more preferably 1. A source of phosphate ions, silicic acid ion source, the molar ratio of the total amount of silicate ion source and vanadate ion source to the total amount of vanadate ion source is more than 75%, that corrosion protection by phosphate ions is reduced There, when the molar ratio of the total amount of silicate ion source and vanadate ion source is less than 1%, that the peripheral species oxidation and fixing effect by silicate ions (or vanadate ions) becomes insufficient is there.
[0134]
　As anticorrosive pigment (C) used in the present invention, it is possible to use Si, Ti, Al, metal oxide particles comprising one or two or more metal elements selected from the group consisting of Zr and (D). Or use of these metal oxide fine particles and (D) alone or silicate compound, a phosphate compound, by blending with the vanadate compound, it is possible to increase the corrosion resistance. Silicate compound, a phosphate compound, coexists vanadate compound and silica, the corrosion resistance is preferable for further improvement. As silica, for example, fumed silica, colloidal silica, agglomerated silica. It is also possible to use calcium deposits silica.
[0135]
　As the metal oxide fine particles which can be used in the present invention (D), for example, silica fine particles, alumina fine particles, titania fine particles, there may be mentioned zirconia fine particles, the volume average diameter of the metal oxide of about 1 ~ 100 nm nanoparticles (D1) is furthermore preferable. These may be used alone or in combination of two or more. Among these, silica fine particles can be both improving corrosion resistance and toughness of the coating film may be added if necessary.
[0136]
　Particle size as 100nm than metal oxide nanoparticles or 1 nm (D1), can be used, for example colloidal silica, colloidal titania, colloidal zirconia. Since these process are different from those fine particles by grinding the metal oxide, dispersed in the coating film remain paint and coated metal material after coating of fine primary particles (particle diameter 1 nm ~ 100 nm) easy. These metal oxide nanoparticles (D1), the rust prevention effect is higher than the metal oxide fine particles is larger than the same composition in particle diameter. However, such metal oxide nanoparticles (D1), for example, such as spot welding, may inhibit the weldability by energization resistance welding for welding by Joule heat by energization while applying a load at the electrode.
[0137]
　Figure 2 represents a cross-sectional photograph of the coated metal plate. Figure 2 (a) is a surface layer cross-sectional SEM photograph of the coated metal plate. 2 (b) is a coated metal plate engaging portion, a cross-sectional SEM photograph of pressurized welding electrodes, coated metal plate matching unit cross section in the state that received pressure when energized welding is shown. Non-oxide ceramic particles (B) with each other through the coating contacted by the arrow position, it is understood that the current path.
[0138]
　3, overlap automotive coated metal plate when energized welding is a schematic view showing a state in which applied a load at the electrode. Position of the coated metal plate alignment unit shown in FIG. 2 (b), represented by the square frame in FIG. Automotive coated metal plate at the time of welding, when applied load by two or more coated metal plates overlapped welding electrodes, electrode and non-oxide ceramic particles (B) are in contact, and the coating film (alpha) non-oxide ceramic particles (B) with each other or with the non-oxide ceramic particles (B) and the metal plate to form a conduction path in contact, in, it is possible to energization resistance welding.
[0139]
　Figure 4 shows that the metal oxide nanoparticles (D1) is inhibited attached around, or caught in non-oxide ceramic particles (B) between the adjacent energization of the non-oxide ceramic particles (B) it is a schematic view. Thus, the coating film (alpha) metal oxide having a particle size of less than is 1nm or more 100nm in the nanoparticles (D1) is present in large amounts, electrode and non-oxide ceramic particles (B), non-oxide ceramics particles ( B) each other, or metal oxide nanoparticles (D1) inhibits energization between the metal plate non-oxide ceramic particles (B), adversely affects the weldability. For example, a metal material or a coating film with excessive heat generation due to the electrical resistance of the weld is too high scatters some cases adverse effects such as appearance degradation due to deposition of the weld of insufficient strength and scattering substance occurs. If more pronounced in some cases can not be welded because the electrical resistance is too high. Thus, relative to the amount of the coating film (B) (D1) it is not too much preferred to ensure the weldability.
[0140]
　The amount of the metal oxide nanoparticles (D1) is in the coating film, the total volume of the metal oxide nanoparticles (D1), the ratio (D1 / B) to the total volume of the non-oxide ceramic particles (B) is 20 or less it is preferable to be. More preferably 10 or less in the case of emphasizing weldability. Preferably 0.1 or more as a lower limit of (D1 / B). In (D1 / B) is less than 0.1, the non-oxide ceramic particles in the coating film (B) is too large, or a state metal oxide nanoparticles (D1) is too small. In the former, the coating film becomes brittle due the amount of non-oxidized ceramic particles in the coating film (B) is too large, the coating film cracking and coating falling off may occur during molding. Coating cracking and coating missing, leading to poor appearance of degradation or coated metal plate of corrosion resistance coating. In the latter, the amount of metal oxide nanoparticles in the coating film (D1) is insufficient, it may not effect sufficient to obtain increase the corrosion resistance. Particularly preferred range of (D1 / B) is 0.5 to 6. Corrosion resistance to decrease by suppressing the amount of the metal oxide nanoparticles (D1) in order to ensure the weldability can be compensated by adding a particle diameter 100nm or more anticorrosive pigments (C). As the particle diameter 100nm or more anticorrosive pigments (C), or the entire amount or a part as a particle diameter 100nm or more of the metal oxide fine particles (D2). Particle size 100nm or more anticorrosive pigments (C), the state coating was coated on a metal plate, or in a state where the coating film is deformed by the load due to the welding electrodes, and the electrode (B), (B) with each other or a so unlikely enters between the metal plate (B), a small adverse effect on the energization resistance welding as compared with the metal oxide nanoparticles (D1).
[0141]
　The amount of the rust-preventive pigment (C) is 1 to 40% by volume of the coating (alpha), and it is preferred that the total of the amount of non-oxide ceramic particles (B) does not exceed 80% by volume. More preferably an amount of 1 to 20% by volume of anticorrosive pigment (C) in the case that emphasizes weldability of the coated metal plate, more preferably 2-15% by volume. When importance is attached to corrosion resistance of the coated metal plate is more preferably an amount of anticorrosive pigment (C) is 3 to 40 vol%, more preferably from 7.5 to 40 vol%. If you even more emphasis on the corrosion resistance of the layer of coated metal plates, it is more preferable amount of anticorrosive pigment (C) is 13 to 40 vol%. Because it is less than 1% by volume is insufficient amount of anticorrosive pigment (C), there is the effect of enhancing the corrosion resistance is not sufficiently obtained. For film adhesion drop to embrittlement and metal plate than when the coating 40 vol%, the exposed metal plate by coating destruction or coating delamination during forming occurs, Ya appearance deterioration of the coated metal plate there is a decline in the corrosion resistance improving effect by the coating occurs.
[0142]
　The amount of non-oxidizing ceramics particles (B), the particle size is the amount of less than 100nm or more 1nm metal oxide nanoparticles (D1), particle size 100nm or more anticorrosive pigments (C) an amount, and particle size 100nm or more the amount of the metal oxide fine particles (D2) may be calculated in terms of the coating film cross-section counts the number per cross-section in terms of identifying the respective particles by electron microscopy, in terms of the number per coating volume it can. In this case, it is possible to identify each particle by using a EDX spectrometer as needed. Included in the before painting paint (B), it is also possible to calculate each amount of particles in the coating film from the coating deposition amount on the amount and the metal plate (C), (D1), and (D2) . Before painting in the paint (B), each particle amount in the coating film from when the charged amount is long known, coating weight of the charged amount and the metal plate (C), (D1), and (D2) It can be calculated. If the charged amount is not known, for example, by using an apparatus such as Malvern Co. particle image analyzer Morphologi G3, the individual identified by counting at an appropriate concentration on the particle image analysis in diluted paint, can be calculated it is. This approach can also be used when counting the number of particles by dissolving a coating film adhered to the metal plate.
[0143]
　The various anti-corrosion pigments, previously dissolved an appropriate amount to the coating composition (beta), or dispersed stabilizer, preferably introduced into the coating film (alpha) of the organic resin (A).
[0144]
　
　method for producing a coating film (alpha) coating composition used to form the present invention (beta) is not particularly limited. For example, each of the coating film (alpha) formed component was added to the water or in an organic solvent, and stirred at a dispersing machine such as disper, dissolution, and a method of dispersing or crushing dispersion. For water-based coating composition, in order to improve each of the solubility of the coating film (alpha) forming component, or a dispersion, if necessary, may be added known hydrophilic solvent or the like.
[0145]
　Particularly, in the case of water-based paint composition (beta), the resin (A1), the non-oxide ceramic particles (B), optionally in addition to the rust-preventive pigment (C), paints of aqueous and coating various water-soluble or water-dispersible additives in a range not to impair the sex may be added. For example, various anti-corrosion agent and form a taken not water-soluble or water-dispersible pigments, defoamers, antisettling agents, leveling agents, surface active agents such as wetting and dispersing agents, and, thickeners, viscosity modifiers such as agents and the like may be added. Furthermore, in order to stabilize such components of the coating composition such as a resin or other organic compounds (beta), it is defined by the Industrial Safety and Health Law Enforcement Order (Prevention of Organic Solvent Poisoning rules Chapter Article) organic solvent (first type organic solvent, the two organic solvents, the three organic solvents, or, the organic solvent, those containing more than 5 wt%) in a range that does not correspond to a small amount of organic solvent it may be added.
[0146]
　The coating film (alpha) of the present invention, when forming the aqueous coating composition (beta), since an aqueous, high surface tension compared to organic solvent-based coating compositions, the metal plate is a base material (the surface treatment layer when there underlying process) or a non-oxide ceramic particles (B), poor wettability to anticorrosive pigment (C), when performing a predetermined amount of the coating to the substrate, uniform coatability it may or not be obtained particle dispersibility. In such a case, it is preferable to add the wetting and dispersing agents and thickeners. The wetting and dispersing agents, may be used a surfactant to reduce surface tension, molecular weight is better to use a 2000 or more polymeric surfactants (polymer dispersant). Low molecular surfactants, because it can relatively easily move the resin coating film containing moisture, or water adsorbed on the polar group of the surfactant, dissolved oxygen through the water, corrosion factors such as dissolved salts easily attract metal surface, also its own bleed out, liable to elute, often degrade the rust resistance of the coating film. In contrast, polymeric surfactants, metal, once hardly separated from the adsorbed since it multipoint adsorbed on the surface of the ceramic particles and pigment, it is effective to also improve wettability at a low concentration. Furthermore, molecules are less likely to move bulky fried resin coating film, hardly attract corrosion factors metal surface. Wherein in the section of , Some acrylic resin recommends the addition to the organic resin (A), the the ability of such a polymeric surfactant, a water-based paint in the composition, non-oxide ceramics to suppress the sedimentation of such particles (B) and anticorrosive pigment (C), and there is uniformly dispersed to effect.
[0147]
　Thickeners, if wetting and dispersing agent sufficient surface coverage only to sections repelling base material surface can not be obtained, or, securing the necessary coating thickness viscosity of the aqueous coating composition is too low it can be added as a countermeasure If not. Many a molecular weight of thousands to tens of thousands, and multi-point adsorption on the surface of the pigment, thickener itself form a weak network structure associated with one another, it is possible to increase the viscosity of the coating composition.
[0148]
　If water-based paint composition (beta) comprises a high density non-oxide ceramic particles (B) and anticorrosive pigment (C) or the like, if necessary, the viscosity can be imparted thixotropic properties (thixotropic) to the paint it is preferable to add a modifier. Viscosity modifier, as in the case of the thickening agent, and multi-point adsorption on the surface of the pigment in the aqueous coating composition, making the network structure. Since such the molecular weight of the viscosity modifier is very high at hundreds of thousands to millions, creating a strong network structure having a large yield value in aqueous paint composition (beta), therefore, the coating composition (beta) is resistant to deformation at low shear rates and high viscosity. If Kuwaware large shear stress above the yield value to paint composition (beta), the viscosity falls sharply network structure collapses. Accordingly, if added viscosity modifier, water-based coating composition (beta) is the substantially during storage and transportation to remain stationary, inhibit sedimentation of heavy pigments to increase the viscosity of the coating composition (beta) and, and when flowing in the piping paint shop, during coating to the substrate or the like, when a high shear stress (high shear rate) is applied to facilitate flow by lowering the viscosity of the coating composition (beta) .
[0149]
　When the organic solvent-based coating composition for the (beta) is paint composition containing dissolved resin in an organic solvent relatively high viscosity, and is easy to adjust the viscosity. Therefore, the coating composition viscosity, can be easily and held stably in the above advantage and is the 100 mPa · s to the pigment settling suppressed. Further, since the non-oxide ceramics is used as the conductive material is a material having also hydrophobic site on the surface, generally in the easy dispersion in organic solvent-based coating composition (beta), coating since it painted without at the non-oxide ceramic particles in the coating composition (β) (B) is precipitated, which is preferable.
[0150]
　When paint composition of the organic solvent system to form a coating film, the viscosity of the (beta), dried baked 100 to coating composition is 2000 mPa · s after application onto a metal plate by a roll coater or a curtain coater, non-oxide ceramic particles (B) is less likely to settle, it is more preferable. If the viscosity of the coating composition (beta) is less than 100 mPa · s, a non-oxide ceramic particles (B) tends to settle, in the case of more than 2000 mPa · s, commonly referred to as a living, etc. excessively high viscosity paint there is a risk of poor appearance of the time. More preferably, a 250 ~ 1000mPa · s. The viscosity of the organic solvent-based coating composition (beta) can be measured using a B-type viscometer at the same temperature as the temperature of the coating composition when coated by a roll coater or a curtain coater.
[0151]
　Viscosity adjustment can be the type of organic solvent used is adjusted with a solvent amount. The organic solvent is typically can be used known solvents, organic solvent having high boiling point is preferred. In the production line of the metal plate of the present invention, since the baking time is short, the use of low boiling point solvent, there is a possibility that coating defects commonly referred to as boiling occurs. Boiling point of the solvent, it is preferred to use more than 120 ° C.. The organic solvent having high these boiling known solvents, e.g., cyclohexane, (product name of ExxonMobil YK) Solvesso aromatic hydrocarbon-based organic solvent or the like can be used.
[0152]
　
　the coating film of the present invention (alpha), as described in the section , coating composition (beta) is an aqueous or organic solvent-based composition for a roll coating, a groove roll coating, curtain flow coating, roller curtain coating, immersion (dip), by a known coating method such as diaphragm air knife coating composition for (beta) was coated on a metal plate then film forming method of drying the moisture and solvent content of the wet coating is preferred. Of these, in the case of aqueous and organic solvent-based UV-curable composition and an electron beam-curable composition, after application to the metal plate with the coating method, the water or solvent component is dried, ultraviolet rays or electron beams It is preferable to irradiate the polymerization.
[0153]
　Baking and drying method for the case of the coating composition (beta) is aqueous or bake-curable composition of the organic solvent-based, specifically described. If paint composition (beta) is aqueous or bake-curable composition of the organic solvent, baking and drying method is not particularly limited, either keep heat in advance the metal plate, or to heat the metal plate after application, or it may be dried in combination. The heating method is not particularly limited, hot air, induction heating, near infrared, can be used alone or in combination with open flame or the like.
[0154]
　The baking and drying temperature, when coating composition (beta) is a baking-curable composition of the aqueous is preferably 120 ° C. ~ 250 ° C. In the metal sheet surface temperature reached, to be 0.99 ° C. ~ 230 ° C. more preferably, and most preferably from 180 ℃ ~ 220 ℃. Is less than the ultimate temperature is 120 ° C., a coating film curing is insufficient, there is a case where the corrosion resistance is lowered, if it is 250 ° C. greater than bake hardenability becomes excessive, the corrosion resistance and moldability may decrease. Preferably baking and drying time is 1 to 60 seconds, more preferably 3 to 20 seconds. If it is less than 1 second, bake hardenability is insufficient, there is a case where the corrosion resistance is lowered, and when it exceeds 60 seconds, there is a case where the productivity is lowered.
[0155]
　If paint composition (beta) is a baking-curable composition of the organic solvent, it is preferable that the metal plate surface temperature reached is 180 ° C. ~ 260 ° C., further preferably 210 ℃ ~ 250 ℃. Is less than the ultimate temperature is 180 ° C., a coating film curing is insufficient, there is a case where the corrosion resistance is lowered, if it is 260 ° C. greater than bake hardenability becomes excessive, the corrosion resistance and moldability may decrease. Preferably baking and drying time is 10 to 80 seconds, more preferably 40 to 60 seconds. If it is less than 10 seconds, bake hardenability is insufficient, there is a case where the corrosion resistance is lowered, and when it exceeds 80 seconds, there is a case where the productivity is lowered.
[0156]
　Paint composition (beta) is film forming method in the case of water-based or organic solvent-based UV-curable composition and an electron beam-curable composition specifically described below. These compositions, after coating in a similar way the aqueous and organic solvent-based composition, drying the moisture and solvent content of the wet coating, then irradiated with ultraviolet rays or electron beam. The coatings for primarily cured film formation starting from the radicals generated by the ultraviolet light or electron beam irradiation, the drying temperature may be a low drying temperatures than in the case of baking-curable composition. At the drying step, it is preferable to irradiate ultraviolet rays or electron beams after evaporate much water or solvent at a relatively low metal surface reaches a temperature of about 80 ~ 120 ° C..
[0157]
　UV irradiation of the ultraviolet curable resin in the coating film by radical polymerization with UV curing, usually in the air atmosphere, an inert gas atmosphere is performed in a mixed atmosphere secondary air and an inert gas. The ultraviolet curing of the present invention, a mixed atmosphere or the oxygen concentration of 10 vol% or less adjusted air and inert gas, preferably UV irradiation in an inert gas atmosphere. Since oxygen as the inhibitor of the radical polymerization, when the atmosphere oxygen concentration during UV irradiation low, less deactivation or crosslinking reaction inhibition due to oxygen added to the generated radicals, the ultraviolet-curable composition used in the present invention, the radical enough to polymerized through the polymerization and cross-linking. Therefore, the adhesion is increased to the non-oxide ceramic particles (B) and the metal plate surface, as a result, compared with the case of UV curing in an air atmosphere, thereby improving the corrosion resistance of the coating film. The inert gas used here, nitrogen gas, carbon dioxide gas, argon gas, and mixed gas thereof can be exemplified.
[0158]
　The ultraviolet light source, for example, a high pressure mercury lamp of the metal vapor discharge method, a metal halide lamp, xenon lamp or the like of the rare gas discharge method, by using an electrodeless lamp using a microwave can be irradiated with ultraviolet rays. In coated metal plate of the present invention, a coating film of the ultraviolet curable be sufficiently cured, the desired resistance weldability, corrosion resistance, as long as moldability is obtained, may be used any lamp. In general, peak irradiance and the integrated light quantity of ultraviolet light coating film receives the influence of the curing of the coating film, the coating film of the ultraviolet curable be sufficiently cured, in which the desired corrosion resistance and formability can be obtained if, irradiation conditions of the ultraviolet ray is not particularly limited.
[0159]
　Paint composition (beta) is, in the case of electron beam curing composition, the electron beam curing, use printing, painting, film coating, packaging, the usual electron beam irradiation apparatus which is used in the field of sterilization, such as be able to. These are those that accelerate while applying a high voltage to a heat electron generated from the hot filament in a high vacuum, take out the resultant electron flow in an inert gas atmosphere, irradiating the polymerizable substance. In coated metal plate of the present invention, it can be sufficiently cured coating film of the electron beam curing type, desired resistance weldability, corrosion resistance, as long as moldability is obtained, may be used any device. In general, the acceleration voltage of the electron beam coating absorbs is to affect the depth of the electron beam to penetrate the paint film, absorbed dose affects the polymerization rate (curing of the coating film), electron beam curing type coating can be sufficiently cured, and as long as the desired corrosion resistance and formability can be obtained is not particularly limited irradiation condition of the electron beam. However, in the case of radical polymerization by electron beam, even if there is a small amount of oxygen, deactivation or crosslinking reaction inhibition by oxygenation occurs to generate radicals, the curing is insufficient, the oxygen concentration is below 500ppm not preferably electron beam irradiation in an inert gas atmosphere. The inert gas used here, nitrogen gas, carbon dioxide gas, argon gas, and mixed gas thereof can be exemplified.
Example
[0160]
　 Example I
　below, the present invention is specifically described by Example I using an aqueous coating composition.
[0161]
　1. Preparation of the metal plate
　was prepared following five galvanized steel sheet, an aqueous alkaline degreasing agent 2.5% by weight of (Nippon Parkerizing Co. FC-301), the surface is immersed for 2 minutes in 40 ° C. solution after degreasing, washed with water and a metal plate for dried paint.
[0162]
　EG: galvanized steel sheet (thickness 0.8 mm, coating weight 40 g / m 2 )
　ZL: Electrical Zn-10% Ni alloy plated steel sheet (sheet thickness 0.8 mm, coating weight 40 g / m 2 )
　GI: melting galvanized steel sheet (thickness 0.8 mm, coating weight 60g / m 2 )
　SD: molten Zn-11% Al-3% Mg-0.2% Si alloy-plated steel sheet (sheet thickness 0.8 mm, coating weight 60g / m 2 )
　GA: alloyed hot-dip galvanized steel sheet (thickness 0.8mm, 10% Fe, coating weight 45 g / m 2 )
[0163]
　2. Film underlying conversion film
　as described in the section , in the present invention need not be provided necessarily undercoating film between the coating film (alpha) and the metal plate surface, the coating it is sometimes used film adhesion and corrosion resistance to the metal plate (alpha) in order to further improve. Here, we evaluated provided surface treatment film on a portion of the coated plate.
[0164]
　As coating compositions for forming a film of the surface treatment coating, were prepared following.
p1: Zr compound, a silane coupling agent, water-based coating composition comprising silica particles
p2: polyester resin, silica fine particles, aqueous coating composition comprising a silane coupling agent
[0165]
　The p1 or p2 was bar coated on the coated metal plate such that the film thickness 0.08 .mu.m, which was dried at a metal surface temperature reached 70 ° C. in a hot air oven, air dried.
[0166]
　3. Preparation and film formation of the water-based coating composition
　for the preparation of aqueous coating compositions, first, the resin (A1), non-oxide ceramic particles ((B), (B) conductive particles other than, anticorrosive pigment ( C), was prepared a silane coupling agent (s).
[0167]
　(1) Resin (A1)
　was synthesized resin A11 ~ A13, was also prepared commercial resin A14, A15. All of these are resin used in the present invention.
[0168]
　 A11: carboxyl group-containing polyester urethane resin (prepared in Production Example 1, recovered as an aqueous dispersion)
　[Production Example 1]
　stirrer, reflux condenser, nitrogen gas inlet tube and a thermometer, the reaction of 10L equipped with a thermostat the vessel, 2,2-dimethylol g of butanoic acid 1628g and the ε- caprolactone 3872G, with the addition of stannous 27.5mg chloride as a catalyst, the temperature was maintained in the reaction vessel 120 ° C., 3 hours It was allowed to react. This gave a hydroxyl value 225.5mgKOH / g, a carboxyl group-containing polyester diol of the liquid acid value 114.6mgKOH / g (a11).
[0169]
　Next, stirrer, reflux condenser, nitrogen gas inlet tube and a thermometer, the reaction vessel 2L having a thermostat, 2,4-tolylene charged an isocyanate 149.9g of acetone 140.0 g, under a stream of nitrogen in stirring, the carboxyl group-containing polyester diol (a11) 124.6 g, a number polycaprolactone diol (manufactured by Daicel Chemical Industries, Ltd. PLACCEL210) of average molecular weight 1000 273.1G and 1,4-butanediol 12.4g added. The temperature inside the reaction vessel was held for 4 hours 60 ° C. to proceed urethanization reaction, to prepare an NCO group-terminated urethane prepolymer. While stirring the urethane prepolymer 168.3 g, was added to deionized water 230g of triethylamine was added 6.1 g, was added ion exchange water 230g was added hexamethylenediamine 1.67 g. Then, under reduced pressure, over a period of 3 hours at 60 ° C. to distill off acetone, the solid content concentration of 35%, water acid value 24.6mgKOH / g (solid basis) carboxyl group containing polyester urethane resin (A11) to obtain a dispersion.
[0170]
　 A12: sulfonic acid group-containing polyester urethane resins (synthesized in Production Example 2, an aqueous dispersion
recovered as liquid)
　[Production Example 2]
　stirrer, reflux condenser, nitrogen gas inlet tube and a thermometer, pressure-resistant reaction with a thermostat the vessel, with stirring under nitrogen gas stream, and adipic acid 1100g and 3-methyl-1,5-pentanediol 900 g, were charged and tetrabutyl titanate 0.5g, keeping the temperature in the reaction vessel 170 ° C., acid value was allowed to react until the following 0.3mgKOH / g. Next, 180 ° C., for 2 hours under a reduced pressure condition of at most 5 kPa, to give a hydroxyl value 112 mg KOH / g, the polyester having an acid value of 0.2 mgKOH / g.
[0171]
　Next, another reaction vessel equipped with the same apparatus as the above-mentioned reaction vessel, the polyester polyol 500 g, were charged 5-sulfo sodium isophthalic acid dimethyl 134g and tetrabutyl titanate 2g, in the same way as described above, under a stream of nitrogen stirring performs esterification reaction by maintaining the temperature of the reaction vessel to 180 ° C., and finally molecular weight 2117, hydroxyl value 53 mg KOH / g, acid value 0.3 mg KOH / g of sulfonic acid group-containing polyester (a12) It was obtained.
[0172]
　The sulfonic acid group-containing polyester (a12) 280 g, polybutylene adipate 200 g, 1,4-butanediol 35 g, hexamethylene diisocyanate 118g and methyl ethyl ketone 400 g, stirrer, reflux condenser, nitrogen gas inlet tube and a thermometer, a thermostat were charged under a nitrogen stream to a reaction vessel equipped performs urethanization reaction to hold the liquid temperature with stirring 75 ° C., NCO content was obtained with 1% of the urethane prepolymer. Subsequently, by lowering the temperature in the reaction vessel 40 ° C., sufficiently stirred and uniformly dropwise deionized water 955g while, it was phase inversion emulsification. Then, the internal temperature is lowered to room temperature and was added to the amine extending the adipic acid hydrazide 13g and adipic acid hydrazide solution of a mixture of ion-exchange water 110g. Some under reduced pressure, after distilling off the solvent at 60 ° C., add the deionized water, the solid content concentration of 35%, acid value 11 mg KOH / g (solid basis) of sulfonic acid group-containing polyester urethane resin (A12 ) was obtained of the aqueous dispersion.
[0173]
　 A13: sulfonic acid group-containing polyester resin (synthesized in Production Example 3, recovered as an aqueous dispersion)
　[Production Example 3]
　stirrer, reflux condenser, nitrogen gas inlet tube and a thermometer, a pressure-resistant reaction vessel equipped with a thermostat with stirring under a nitrogen stream, terephthalic acid 199g and isophthalic acid 232g and adipic acid 199g, 5-sulfo sodium sulfoisophthalic acid 33 g, and ethylene glycol 312g and 2,2-dimethyl-1,3-propanediol 125 g 1, 5 - pentanediol 187 g, were charged and tetrabutyl titanate 0.41 g, the temperature inside the reaction vessel was increased over a period of 4 hours 160 ° C. to 230 ° C., the esterification reaction was carried out. Then, the vessel pressure was gradually reduced to 5mmHg over 20 minutes, further 0.3mmHg below was carried out polycondensation reaction for 40 minutes at 260 ° C.. To the resulting copolymerized polyester 100 g, was added butyl cellosolve 20g, methyl ethyl ketone 42 g, for 2 hours with stirring dissolved at 80 ° C., further addition of ion-exchanged water 213 g, were subjected to water dispersion. Thereafter, the solvent was distilled off under heating to obtain an aqueous dispersion having a solid concentration of 30% of the sulfonic acid group-containing polyester resin (A13).
[0174]
A14: Amino group-containing epoxy resin ((Ltd.) ADEKA Co. Adecaresin EM-0718, aqueous
solution) A15: nonionic polyether-based urethane resin (DIC (KK) Bonn Dick 1520, aqueous dispersion)
[0175]
　(2) non-oxide ceramic particles (B)
　using commercially available fine particles (reagent). The volume average diameter was measured using a Beckman Coulter Co. Multisizer 3 (precision particle size by Coulter principle distribution measuring apparatus). Electrical resistivity, length 80mm from each particle, width 50 mm, to produce a sintered plate having a thickness of 2 ~ 4 mm, ESP and Co. Mitsubishi Chemical Analytic Tech Ltd. resistivity meter Loresta EP (MCP-T360 type) probe 4-terminal 4-probe method using a (2mm diameter flat head of the pin), a constant current application method, was measured at 25 ° C. in conformity with JIS K7194.
[0176]
　TiN: TiN fine particles (manufactured by Wako Pure Chemical Industries, Ltd., the volume average diameter 1.6 [mu] m, the electrical resistivity × 10 20 -6 [Omega]
cm) TiB: TiB 2 particles (KK highly purified Research Laboratory TII11PB, volume average diameter 2.9 .mu.m, the electrical resistivity × 10 30 -6 [Omega]
cm) VC: VC particles (manufactured by Wako Pure Chemical Industries, Ltd., the volume average diameter 2.3 .mu.m, the electrical resistivity × 10 140 -6 [Omega]
cm) ZrB: ZrB 2 fine particles (manufactured by Wako Pure chemical Industries, Ltd., the volume average diameter 2.2 .mu.m, the electrical resistivity × 10 70 -6 [Omega]
cm) MoB: Mo 2 B particles (Mitsuwa chemicals Co., Ltd. boride dimolybdate, volume average diameter 5.2 .mu.m, the electrical resistivity × 10 30 -6 [Omega]
cm) LaB: LaB 6 fine particles (Tenkawa Rikagaku Co. lanthanum hexaboride, volume average diameter 2.8 .mu.m, the electrical resistivity of 20 × 10 -6 [Omega]
cm) NiSi : Ni 2Stirring was added Si particles (Co., Ltd. Kojundo Chemical Laboratory Ltd. NII11PB water, suspended, used was filtered off fine particles Note suspended after the elapse of 5 minutes. The volume average diameter 4.8 .mu.m, electrical resistivity 40 × 10 -6 [Omega]
cm) TiC: TiC particles (manufactured by Wako Pure Chemical Industries, Ltd., the volume average diameter 3.2 .mu.m, the electrical resistivity × 10 180 -6 [Omega]
cm) TiN + VC: mixture of the said TiN VC (volume ratio of 1:
1) VC + ZrB: mixture of the said VC ZrB (volume ratio
1: 1) ZrB + TiC: mixture of the said ZrB TiC (volume ratio 1: 1)
[0177]
　(3) (B) other than the conductive particles
　using a commercially available fine particles (reagent). Of these, TaN, VN, CrSi 2 volume mean diameter of each particle of the (non-oxide ceramics), electrical resistivity was measured in the same manner as in (2). Al (aluminum), C (isotropic graphite), ZnO (electroconductive zinc oxide), FSi 2 volume mean diameter of the particles of (ferrosilicon No.2 defined components in JIS G 2302) are the (2) measured in the same manner as the electrical resistivity has been described with literature values.
[0178]
TaN: TaN particles (Tenkawa Rikagaku Co. tantalum nitride, the volume average diameter 3.7 .mu.m, the electrical resistivity × 10 205 -6 [Omega]
cm) VN: VN particles (Tenkawa Rikagaku Co. nitride vanadium, volume mean diameter 5.8 [mu] m, the electrical resistivity × 10 220 -6 [Omega]
cm) CrSi: CrSi 2 particles stirring was added (Tenkawa Rikagaku Co. chromium silicide in water, was suspended, the fine particles should be noted floating in after 5 minutes filtered and used volume average diameter 4.2 .mu.m, the electrical resistivity × 10 900. -6 [Omega]
cm) Al: aluminum particles (Co. Kojundo Chemical Laboratory Ltd. ALE11PB, volume mean diameter 3.3 [mu] m, the electrical resistivity 2.7 × 10 -6 [Omega]
cm) C: isotropic graphite particles (Ltd. highly purified Research Laboratory CCE03PB, volume mean diameter 6.5 [mu] m, the electrical resistivity × 10 1200 -6 [Omega]
cm) ZnO: conductive zinc oxide particles ( Hakusui Tech Co., Ltd. Pazetto 23-K, the volume average diameter 6.6 [mu] m, the electrical resistivity × 10 190 -6 [Omega]
cm) FSi2: ferrosilicon No.2 particles agglomerated product obtained from (Nihonjukagakukogyo Ltd. (size 5 ~ 50mm, Si-containing using an amount 78 wt%) was micronized with a jet mill. the volume average diameter 4.4 [mu] m, the electrical resistivity of 1000 × 10 -6Ωｃｍ）
[0179]
　(4) anticorrosive pigment (C)
　commercially available reagents, industrial products or used by blending them.
i1: magnesium pyrophosphate (Tenkawa Rikagaku Co., Ltd. Reagent, Mg 2 P 2 O 7 )
i2: calcium silicate (manufactured by Wako Pure Chemical Industries, Ltd. Reagent, CaSiO 3 )
i3: magnesium hydrogen phosphate (Kanto Chemical (Co. ) manufactured MgHPO 4 ): silica particles (manufactured by Nissan Chemical Industries, Ltd. Snowtex N) = 50: 50 (mixture of molar ratio)
i4: manufactured magnesium hydrogen phosphate (manufactured by Kanto Chemical Co., MgHPO 4 )
i5: phosphoric acid tricalcium (manufactured by Kanto Chemical Co., Ca 3 (PO 4 ) 2 ): vanadium pentoxide (Kanto Chemical Co., Ltd. V 2 O 5 ): silica particles (manufactured by Nissan Chemical Industries, Ltd. Snowtex N) = 25 : 25: mixture of 50 (molar ratio)
[0180]
　(5) Silane coupling agent
(s) s1: 3- glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.
KBM-403) s2: 3- aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., KBM-903)
[0181]
　Next, the resin (A1), non-oxide ceramic particles (B), with distilled water and (B) other than the conductive particles, anticorrosive pigment (C), a silane coupling agent (s), various the aqueous coating composition was prepared in a ratio of formulation.
[0182]
　Non-oxide ceramic particles (B), (B) other than the conductive particles, for anticorrosive pigment (C), contained in a nonvolatile content of the aqueous coating composition, the resin (A1), non-oxide ceramic particles (B), were formulated in the desired volume ratio to the total amount of (B) other than the conductive particles, anticorrosive pigment (C). In the case of using a silane coupling agent s1 or s2, it was added to the aqueous coating composition to be 5 parts by weight per 100 parts by weight of the resin (A1) in the non-volatile content. Nonvolatile matter concentration of the aqueous coating composition, to obtain a coating film adhering amount and good paintability aim, was adjusted by changing the amount of water added. Here, "non-volatile content", means that the components remaining after evaporation of the formulated by being water or an organic solvent such as a solvent in the coating and the composition.
[0183]
　Table 1 to Table 6, Table 8, contained in a nonvolatile content of each aqueous coating composition, the resin (A1), non-oxide ceramic particles (B), (B) other than the conductive particles, anticorrosive pigment (C), indicating the type of the silane coupling agent (s). Non-oxide ceramic particles (B), (B) other than the conductive particles, the anticorrosive pigment (C), the content in the coating film (vol%) is also shown.
[0184]
　After uniformly dispersing the components to prepare the aqueous coating composition was applied using a roll coater to a metal plate coated metal plate, or the surface treatment film provided in the metal surface it in a hot air oven dried ultimate temperature 200 ° C., water-cooled and air-dried. Tables 1 to 6 are shown in Table 8, coating thickness after film a ([mu] m unit). Incidentally, the film thickness was calculated by dividing the mass difference before and after peeling of the coated coating film in coating density. Coating density was calculated from the amount and the known specific gravity of the components of the coating constituents.
[0185]
　4. Preparation and film formation of an organic solvent-based coating compositions
　for the preparation of organic solvent-based coating composition was prepared following organic resin (A).
[0186]
　ExxonMobil YK made of a high-boiling aromatic hydrocarbon solvent in which Solvesso 150: cyclohexanone = 50: 50 in a mixed solvent (mass ratio), amorphous polyester resin of the organic solvent-soluble (Toyobo (strain ) made by Byron GK140) was dissolved. Next, with respect to the resin 100 parts by weight of curing agent (hexamethoxymethylmelamine, Mitsui Cytec Co., Ltd. Cymel 303) 15 parts by weight, an acid catalyst (block type of dodecylbenzenesulfonic acid, Mitsui Cytec Co. Cat list 6003 b) stirring 0.5 part by weight was added into the solution to obtain a solution of a melamine-curing polyester resin (a *).
[0187]
　Then, a solution of the resin (A *), the three. Non-oxide ceramic particles prepared in Section aqueous coating composition (B), (B) other than the conductive particles, the anticorrosive pigment (C), wherein the Solvesso 150: cyclohexanone = 50: 50 (weight ratio) using a mixed solvent of an organic solvent-based coating compositions were prepared with various mixing ratio.
[0188]
　As with the water-based coating composition, a non-oxide ceramic particles (B), (B) other than the conductive particles, for anticorrosive pigment (C), in a non-volatile content of the organic solvent-based coating compositions contained, the resin (a *), a non-oxide ceramic particles (B), were formulated in the desired volume ratio to the total amount of (B) other than the conductive particles, anticorrosive pigment (C). Nonvolatile matter concentration of the organic solvent-based coating composition, to obtain a coating film adhering amount and good paintability aim, was adjusted by changing the addition amount of the mixed solvent of the.
[0189]
　Table 7, contained in a non-volatile content of the organic solvent-based coating composition, the resin (A *), a non-oxide ceramic particles (B), the (B) other than the conductive particles, anticorrosive pigment (C) indicating the type. Non-oxide ceramic particles (B), also showed (B) other than the conductive particles, the content in the coating film for anticorrosive pigment (C) (vol%).
[0190]
　The prepared organic solvent-based coating compositions, were uniformly disperse each component, using a roll coater applied to painted metal plate of the, which dried metal surface temperature reached 230 ° C. in a hot air furnace, cured, water-cooled and air-dried. Table 7 shows the film thickness after film ([mu] m units). Coating thickness, as in the case of coating of the aqueous coating composition was calculated by dividing the mass difference before and after peeling of the coated coating film in coating density. Coating density was calculated from the amount and the known specific gravity of the components of the coating constituents.
[0191]
　5. Performance evaluation
　the three. And 4. Using the coated metal plate produced by the method, weldability, formability, it was evaluated corrosion resistance. Hereinafter, a method for evaluation and each test.
[0192]
　(1) Weldability
　using CF type Cr-Cu electrode tip diameter 5 mm, R40, pressure 1.96KN, welding current 8 kA, provides continuous dotting test of spot welding at weld time of 12 cycles / 50 Hz, the nugget diameter There 3√t (t is the thickness) was determined by the number of RBI immediately before the cut. It was evaluated relative merits of spot weldability using the following evaluation points.
[0193]
　5: Number of hitting point above 2,000
　4: 1000 points or more and less than 2,000
　3: 500 points or more, less than 1000 points
　2: less than 500 points
　1: nugget can not be welded even one point does not produce
[0194]
　(2) moldability
　by hydroforming test machine, punch diameter 50 mm, punch shoulder radius 3 mm, die diameter 50 mm, die shoulder radius 3 mm, at a drawing ratio of 1.8, the blank-holder pressure of 1 ton conditions, by applying a processing oil It went a cylindrical cup molded test. Evaluation of moldability, was based on the following indicators.
[0195]
5: the paint film processing portion after molding, gloss sink or surface flaws of the coating film, cracks, the coating film defects such as peeling was not observed at all.
4: formable, but slight scratches or color change in the coating process section is seen, not seen at all cracking or peeling of the coating film.
3: but formable, clear flaws or the coating processing section, a little of the coating film cracking or delamination is observed.
2: but formable, large flaws or the coating processing section, a large coating cracks or peeling is observed.
1: molding are not allowed.
[0196]
　(3) corrosion resistance
　the three. And 4. Cut rectangular specimens from the coated metal plate produced by the method of 0.99 × 70 mm size to obtain a test piece of the flat portion corrosion resistance ends by resin sealing. Further, 2% by weight of said cylindrical cup shaped article an aqueous degreasing agent (2) (Nippon Paint Co., Ltd. EC-92), was immersed for 2 minutes in 40 ° C. solution, after degreasing the surface, washed with water, dried It was evaluated specimen processing portion corrosion resistance after molding Te.
[0197]
　For these specimens, salt spray for two hours, dried for 4 hours, was carried out cycle corrosion test as one cycle a total of 8 hours of moist 2 hours. Conditions of the salt spray is in compliance with JIS-Z2371. Drying conditions, temperature 60 ° C., and RH or less 30% humidity, humid conditions, temperature 50 ° C., and the humidity of 95% RH or more. Examine the red rust occurrence condition of the processing unit, to evaluate the relative merits of the processed portion corrosion resistance by using the following evaluation points.
[0198]
　5: 600 cycles rust without generating
　4: No 450 cycles red rust
　3: 300 None cycles red rust
　2: No red rust at 150 cycles
　1: red rust at 150 cycles

WE claims

Metal plate, and a motor vehicle coated metal plate including a coating (alpha) that is on at least one surface of the metal plate,
　the coating film (alpha) is an organic resin (A), the borides, carbides , nitrides, selected from at least one silicide, the electrical resistivity of 25 ° C. is × 10 0.1 -6 ~ 185 × 10 -6 and Ωcm non-oxide ceramic particles (B), anticorrosive pigment ( C) and car coated metal plate containing.
[Requested item 2]
　The organic resin (A) comprises an organic resin (A1) having at least one hydrophilic functional group, automotive coated metal plate according to claim 1.
[Requested item 3]
　The organic resin (A) comprises a derivative (A2) of the organic resin (A1) and the resin (A1) having at least one hydrophilic functional group, automotive coated metal plate according to claim 1.
[Requested item 4]
　The organic resin (A1) is a carboxyl group (-COOH), a carboxylate (-COO - M + , M + is a monovalent cation), a sulfonic acid group (-SO 3 H), sulfonate (-SO 3 - M + , wherein M + is a monovalent cation), primary amino group (-NH 2 ), 2 amino groups (-NHR 1 , wherein R 1 is a hydrocarbon group), a tertiary amino group (-NR 1 R 2 , wherein R 1 and R 2 is a hydrocarbon group), a quaternary ammonium salt (-N + R 1 R 2 R 3 X - , wherein R 1, R 2 , R 3 is a hydrocarbon group, X - is a monovalent anion), sulfonium salt (-S + R 1 R 2 X - , wherein R 1 , R 2 is a hydrocarbon group, X - is a monovalent anion ), a phosphonium salt (-P + R 1 R 2 R 3 X - , wherein R 1 , R 2 , R 3 is a hydrocarbon group, X - has at least one functional group is selected from monovalent anion) automotive coated metal plate according to claim 2 or 3.
[Requested item 5]
　Said resin derivative (A1) (A2), the following general formula (I):
[Chemical formula 1]

　(In the formula, "A1" represents an organic resin (A1), "Z-" number of 1 to 9 carbon atoms , nitrogen atoms 0-2, a hydrocarbon chain oxygen atoms having 0 to 2, "A1 ~ Z" is that the "A1", "Z" is covalently bonded via both functional groups . shown also "- O-'is an ether bond," - OH "is hydroxyl group," - X "is a hydrolyzable alkoxy group having 1 to 3 carbon atoms, hydrolyzable halogeno group or a hydrolyzable a sexual acetoxy group, "- R" is an alkyl group having a carbon number of 1 to 3 a representing the number of substituents, b, c, d are each a integer of 0 to 3, provided that it is a + b + c + d = 3.)
resin (A2 represented by Si is), automotive coated metal plate according to claim 3.
[Requested item 6]
　The 25 ° C. electrical resistivity of the non-oxide ceramic particles (B) is × 10 0.1 -6 ~ 100 × 10 -6 , characterized in that it is [Omega] cm, in any one of claims 1 to 5, automotive coated metal plate according.
[Requested item 7]
　Wherein of the non-oxide ceramic particles (B), the particle size is 1 [mu] m ~ 24 [mu] m is (B1), 0.8 pieces / mm on at least one surface of the metal plate 2 ~ 40000 / mm 2 is arranged and has, automotive coated metal plate according to any one of claims 1-6.
[Requested item 8]
　Wherein the non-oxide ceramic particles (B) is, 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, silicides 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 1 kind or 2 selected from the group consisting of a mixture of more species, automotive coated metal plate according to any one of claims 1 to 7.
[Requested item 9]
　The anticorrosive pigment (C) is a silicate compound, a phosphate compound, vanadate compound, and one or more selected from metal oxide particles (D), according to claim 1 to 8 automotive coated metal plate according to any one.
[Requested item 10]
　The metal oxide fine particles (D) is, Si, Ti, Al, including one or more metal element selected from the group consisting of Zr, automotive coated metal plate according to claim 9.
[Requested item 11]
　 Among the metal oxide particles (D), particle size of the metal oxide nanoparticles (D1) is 1 nm ~ 100 nm, the total volume in the coating film (alpha) in the non-oxidized ceramic particles (B) the ratio to the total volume of (D1 / B) is 20 or less, an automobile coated metal plate according to any one of claims 1 to 10.
[Requested item 12]
　The content of the coating film (alpha) in at 25 ° C. of non-oxide ceramic particles (B) is from 0.5 to 65 volume%, automotive paint according to any one of claims 1 to 11 metal plate.
[Requested item 13]
　The thickness of the coating film (alpha) is 2 ~ 30 [mu] m, automotive coated metal plate according to any one of claims 1 to 12.
[Requested item 14]
　The coating film (alpha) is formed by coating a water-based coating compositions, automotive coated metal plate according to any one of claims 1 to 13.