Technical field
[0001]
The present invention relates to a surface treated steel sheet and the coating member.
BACKGROUND
[0002]
For example, many automobile body member, and the material of the metal plate such as a steel plate. The automobile body member, for example, the (1) blank cutting the metal plate into a predetermined size, (2) Aburaarai step of blank metal plate washed with oil, metal plate was washed with (3) an oil to obtain a molding material was press-molded, (4) bonding process of assembling the molding material spot welding, to the member of the desired shape with an adhesive or the like, (5) a step of degreasing and washing the press oil of the joined member surface, (6 ) chemical conversion treatment step, and is manufactured through many steps of (7) electrodeposition coating process. Further, the automobile body member when it is in use as the outer plate, automobile body member further example, (8) an intermediate step, and is manufactured through (9) overcoat process like painting process There is common. Thus, in the automotive industry, the manufacturing process, a high need for cost reduction, especially by omitting and simplifying the chemical conversion treatment step and coating step.
[0003]
　Further, the corrosion resistance of automobile body member, the chemical conversion coating by chemical conversion treatment step, and often are secured by electrodeposition coating film by the subsequent electrodeposition coating process. However, the junction of the profiled (plate registration unit), in particular, in such a plate registration unit and bending hem portion of the inner surface of the bag-like member, there may be a wraparound portion without the chemical conversion coating and electrodeposition coating film occurs. In that case, the joint portion of the molding material, may be exposed to corrosive environments naked state increases. Therefore, body sealer, undercoat, Adohishibu, with rust auxiliary materials, such as a bag portion wax is compensated corrosion resistance of the joint portion of the molding material. These rust secondary materials are not only has the increase factor of the motor vehicle manufacturing cost, has also become a cause of productivity reduction and body weight gain. Therefore, to reduce the rust auxiliary materials, and the corrosion resistance was high demand for automobile body member can be secured.
[0004]
　To meet these needs, the omission of the chemical conversion treatment step during car manufacturing, omission and simplification of electrodeposition coating process, as well as research and development of the surface-treated steel sheet that can be achieved omissions and reducing anticorrosive secondary materials simultaneously actively It has been done. Such surface-treated steel sheet, for example, after press forming, are assembled into a desired shape by spot welding or the like, thereafter, are electrodeposition coating, it is coated intermediate When electrodeposition coating is omitted. Therefore, increasing the press formability, the coating film so that it is resistance welding or electrodeposition coating and conductive, and, it is necessary to impart corrosion resistance.
[0005]
　For example, Patent Document 1, alloyed galvanized steel sheet having a resin-based conductive coating film containing zinc powder has a high corrosion resistance, and it is described that can be welded. Patent Document 1, in the alloyed galvanized steel sheet, it is preferred that the zinc powder contains 30 to 90 wt% in the coating, and it is preferable that the thickness of the coating is 2 ~ 30 [mu] m It has been described as.
[0006]
　Further, Patent Document 2, on the rust-proofing layer consisting mainly of chromium compound, the thickness of 0.5 ~ 20 [mu] m an organic resin film containing 3 to 59 vol% of the conductive powder and the anticorrosive pigment coated organic composite plated steel sheet excellent in corrosion resistance, and it has been described that the resistance welding can be of. The Examples of Patent Document 2, the organic composite plated steel sheets, iron phosphide as the conductive powder, Fe-Si alloy, by using a Fe-Co alloy or the like, is also described to be excellent in corrosion resistance and spot weldability ing.
[0007]
　Further, Japanese Patent Document 3, on the chromate surface treatment for improving the corrosion resistance and paint adherence, an organic resin containing a conductive pigment 25 to 45% by weight consisting primarily of iron phosphide and the anticorrosive pigment Ni-containing electro-galvanized steel sheet for automobile repair parts coated with a layer with a thickness of 2 ~ 8 [mu] m is disclosed. Patent Document 3, the Ni-containing electro-galvanized steel sheet, the corrosion resistance, has been described to be excellent in resistance welding and the like. The Examples of Patent Document 3 is exemplified both coating resins of aqueous and solvent-based coating composition for forming a resin coating layer is described that may be either water-based and solvent-based.
[0008]
　Further, Patent Document 4 has conductivity, comprising a metal surface coating agent capable of forming a weldable corrosion resistant coating, and a specific organic binder 10-30% by weight and the conductive powder 30-60% by weight aqueous coating agent. Patent Document 4, as an example of a suitable conductive powders for the preparation of aqueous coating agents, zinc, aluminum, graphite, carbon black, have been described molybdenum and iron phosphide sulfide.
[0009]
　Further, Patent Document 5 and Patent Document 6, the galvanized steel sheet or the surface of an aluminum-based plated steel sheet, through the first layer coating to enhance the adhesion between the plated layer, the conductive pigments and anticorrosive additives taken by coating the resin second layer coating comprising, describes a motor vehicle for organic coated steel sheet to achieve both excellent corrosion resistance and weldability. Patent Document 5 and Patent Document 6, water is illustrated, both water-based and solvent system is illustrated as a coating composition of the second layer film forming a coating composition of the first layer film forming . Further, Patent Document 5 and Patent Document 6, it is described that the conductive pigment in the second layer coating in a thickness of 1 ~ 30 [mu] m is contained 5 to 70 vol%. Patent Document 5 and Patent Document 6, as a suitable electrically conductive pigments, metals, alloys, conductive carbon, iron phosphide, carbide and semiconductor oxides are exemplified.
[0010]
　Further, Patent Document 7, and alloy particles or compound particles of metal and metalloid elements as the conductive particles, the coated metal material having a conductive coating film containing a specific urethane resin has high corrosion resistance, and, it is described that is weldable. Patent Document 7, the conductive particles is described as preferably an alloy or compound containing Si of more than 50 wt%, and more preferably ferrosilicon containing 70 wt% or more Si .
[0011]
　Here, among the conductive particles other than the metal particles, as a technique using a conductive ceramic particles, for example, Patent Document 8, coated with a cladding layer of the core metal from corrosion resistant metal, further thereon, the conductive material conductive material coated corrosion resistant metal material coated with a surface treatment layer made of any resin for binding them and is described to be excellent in corrosion resistance and conductivity. Patent Document 8, a corrosion resistant metal, are mentioned titanium, zirconium, tantalum, niobium or alloys thereof. In Patent Document 8, a conductive material, and at least one or more can be mentioned selected from a carbon material, a conductive ceramic and metal powders.
[0012]
　Patent Document 9, a conductive for application to the metal surface, and weldable anticorrosion composition is disclosed. The anticorrosion composition, based on the entire composition, (a) (aa) at least one epoxy resin, at least one curing agent selected from (ab) cyanoguanidine, benzoguanamine and plasticised urea resin, and, ( ac) ~ organic binder 5 which contains at least one amine adduct selected from polyoxyalkylene triamines and epoxy resin / amine adduct 40 wt%, (b) anti-corrosive pigments 0-15% by weight, zinc and (c) powdered, aluminum, graphite, molybdenum disulfide, conductive pigments 40 to 70 wt% selected from carbon black and iron phosphide, (d) solvent 0-45% by weight, and, optionally, other active up to 50 wt% or contain auxiliary substances.
[0013]
　Patent Document 10, a silane coupling agent having a glycidyl group (a1), tetraalkoxysilane (a2), and, zinc-plated steel sheet obtained from the chelating agent (a3) ​​is a silane compound having a hydrolyzable group ( in a), but zirconium carbonate compound (B), vanadate compound (C), and nitric acid compound (D), contains the water, and is surface treated with a surface treating solution has a pH of 8-10 it has been described that are.
[0014]
　Patent Document 11, on at least one surface of the steel strip surface roughness 0.2 ~ 3μmRa, essentially C and H, or C, H and O or becomes C, H, O and N, and , an inner magnetic shield material thickness has an organic resin coating of 0.1 ~ 6 [mu] m is described. The inner magnetic shield material, the organic resin coating, (a) a total of 2 to 50 mass% of at least one coupling agent, and, (b) the total SiO 2 to 80 wt% 2 , Fe 3 O 4 , Fe 2 O 3 , Ni-O, Zr-O, Cr 2 O 3 and Al 2 O 3 , characterized in that it contains one or both of at least one metal oxide selected from.
[0015]
　Patent Document 12, the surface of the steel sheet, Mg: 1 ~ 10 wt%, Al: 2 ~ 19 wt%, and, Si: contains 0.01 to 2% by weight and, Mg and Al and the Mg (wt%) + Al (mass%) satisfy the ≦ 20 mass%, chromate-free treatment molten zinc having a Zn alloy plating layer the balance of Zn and unavoidable impurities - aluminum alloy coated steel sheet is described. The chromate-free treatment molten zinc - aluminum alloy coated steel sheet, the surface layer of the Zn alloy plating layer, further, 10 to 30% by weight of zirconium compounds as zirconium, coating containing 5 to 20% by weight of vanadyl compound as vanadium and at least one surface 200 ~ 1200 mg / m as a coating weight 2 , characterized in that it has. Thus, the chromate-free treatment molten zinc - aluminum alloy coated steel sheet is excellent in weldability and corrosion resistance.
[0016]
　Patent Document 13, the galvanized steel sheet or the surface of an aluminum-based plated steel sheet, as the first layer coating, and (alpha) and silica, (beta) phosphoric acid and / or phosphoric acid compound, (gamma) Mg, Mn , at least one metal selected from among Al (provided that the containing when included as a compound and / or complex compounds) and, (sigma) 4-valent vanadium compound of describes a surface-treated steel sheet containing there.
[0017]
　Patent Document 14, metallic tin layer in sequence from the steel sheet side, 0.3 ~ 2.5mC / cm as the amount of electricity required for reduction 2 tin oxide layer, Sn, Fe, Al, Mg , Ca, Ti, Ni, Co , 0.1 ~ 5mg / m 1 or more kinds of the phosphate or polymetaphosphate salt as P amount of Zn 2 plated steel sheet for cans characterized by having at least a chemical conversion treatment layer having is described .
[0018]
　Patent Document 15, a main resin, a hardening agent, Ni, Co, Mn, Fe , Ti, Cu, Al, Zn, Sn and Fe 2 1 or more single metal powders selected from the group consisting of P or coated precoated steel sheet coating resin metal composition comprising, with these alloy powders are described.
[0019]
　Patent Document 16, a metal plate, and automotive coated metal plate including a coating (alpha) that is on at least one surface of the metal plate is described. The automotive coated metal plate, the coating film (alpha) is an organic resin (A), the borides, carbides, selected from at least one of nitrides and silicides, electrical resistivity of 25 ° C. 0.1 10 × -6 ~ 185 × 10 -6 comprising the Ωcm non-oxide ceramic particles (B), and anticorrosive pigment (C).
[0020]
　Patent Document 17, a metal plate, and automotive coated metal plate including a coating (alpha) that is on at least one surface of the metal plate is described. And in the automotive coated metal plate, and the coating film, the organic resin (A), the borides, carbides, and conductive pigment selected from at least one of nitrides and silicides (B), anticorrosive pigment (C ) and includes a metal oxide fine particles (D).
[0021]
　Patent Document 18, on at least one surface of the metal plate, and an organic resin (A), the electrical resistivity of 25 ° C. is × 10 0.1 -6 ~ 185 × 10 -6 is [Omega] cm, borides, carbides, nitrides non-oxide ceramic particles (B) and corrosion resistance coated metal plate coating (alpha) is formed containing are described selected from at least one object and silicides.
[0022]
　Patent Document 19, galvanized steel sheet for the back cover of the display device using a thin display panel is described. The zinc-plated steel sheet, the surface of the surface on the side serving as the inner surface of the back cover, coating amount is 0.3 ~ 0.7 g / m 2 inorganic organic composite based treatment film is formed is.
CITATION
Patent Document
[0023]
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
Patent Document 9: JP-T 2003-532778 Patent Publication
Patent Document 10: JP 2013-60647 JP
Patent Document 11: JP 2004-83922 JP
Patent Document 12: JP 2003-55777 JP
Patent Document 13: JP 2005-154812 JP
Patent Document 14: JP 2007-239004 JP
Patent Document 15: JP-T 2013-515854 Patent Publication
JP 16: JP 2015-91657 Patent Publication No.
Patent Document 17: JP 2015-202686 JP
Patent Document 18: WO 2012/029988 Patent
Patent Document 19: JP 2008-23975 JP
Summary of the Invention
Problems that the Invention is to Solve
[0024]
　Automobile parts, mechanical components, consumer electronics member, a surface-treated steel sheet is widely used in applications building materials are conductive when ChakumakuAtsu is thin, in order to increase the corrosion resistance when the flaw has entered electrodeposition coating film, electrodeposition it is necessary to increase the corrosion resistance of before wearing paint. On the other hand, weldability is also required.
[0025]
　However, for electrodeposition coating prior to corrosion resistance, and weldability, it has been researched and developed in the technology described in the literature, among which increasing recent required level, that further improvement is desired in the present circumstances.
[0026]
　An object of the present invention, the surface-treated steel sheet electrodeposition coating prior to corrosion resistance, and weldability is excellent in both, as well as to provide a coating member using a surface-treated steel sheet.
Means for Solving the Problems
[0027]
<1>
　A surface-treated steel sheet having a coating on at least one surface of the plated steel sheet,
　the coating film,
　a binder resin,
　a non-oxide ceramic particles containing V (excluding VC particles),
　doped zinc oxide and a particle
　content relative to the coating film of the non-oxide ceramic particles and the doped zinc oxide particles containing the V is, satisfies the following equation, surface-treated steel sheet.
　　C Zn　≧ 10.0 · · · (1)
　　C V　≦ 0.5　　· C Zn · · ·
　　(2) C V　≦ 70-C　　　Zn · · ·
　　(3) C V　≧ 0.125 · C Zn · · ·
　　(4) C V　≧ 2.0 · · · (5)
　However, C V , the content of non-oxide ceramic particles containing the V (wt%), C Zn is the doped zinc oxide It means the content of the particles (by mass%), respectively.
[0028]
<2>
　the coating film,
　containing anticorrosive pigments,
　surface-treated steel sheet according to <1>.
[0029]
<3>
　The binder resin is
　a water-soluble or water-dispersible aqueous resin,
　surface-treated steel sheet according to <1> or the <2>.
[0030]
<4>
　non-oxide ceramic particles containing the V is
　one vanadium boride particles (VB particles),
　diboride, vanadium particles (VB 2 particles), and,
　at least is selected from vanadium nitride particles (VN particles) it is one,
　the surface treated steel sheet according to any one of the items <1> to the <3>.
[0031]
<5>
　the coating film,
　a non-doped zinc oxide particles,
　magnesium oxide particles,
　calcium oxide particles, and,
　at least one selected from strontium oxide particles, a total of 1.0 to respect the coating film 10 .0 including mass%,
　the surface treated steel sheet according to any one of the items <1> to the <4>.
[0032]
<6>
　the coating
　film, the anticorrosive pigments containing Mg, the coating comprises from 5.0 to 40.0 wt% with respect to the film,
　according to any one of the items <1> to <5>, wherein surface-treated steel sheet.
[0033]
<7>
　The plated steel sheet is
　a zinc-plated steel sheet or an aluminum-plated steel sheet,
　surface-treated steel sheet according to any one of the items <1> to <6>, wherein.
[0034]
<8>
　made from the surface treated steel sheet according to any one of the items <1> to the <7>, and molding material having the coating film,
　and a the coating film on the formed electrodeposition coating film,
　paint Element.
Effect of the invention
[0035]
　According to the present invention, the surface-treated steel sheet electrodeposition coating prior to corrosion resistance, and weldability is excellent both well, it is possible to provide a coating member using a surface-treated steel sheet.
DESCRIPTION OF THE INVENTION
[0036]
　The following describes a is an embodiment example of the present invention.
[0037]

　surface-treated steel sheet according to the present embodiment, on at least one surface of the plated steel sheet having a coating film (hereinafter referred to as "resin film"), wherein the coating film contains a binder resin, a V a non-oxide ceramic particles (excluding VC particles), and a doped zinc oxide particles, the content relative to the coating film of the non-oxide ceramic particles and the doped zinc oxide particles containing said V satisfies the following formula to satisfy.
　　C Zn　≧ 10.0 · · ·
　　(1) C V　≦ 0.5　　· C Zn · · · (2)
　　C V　≦ 70-C　　　Zn · · ·
　　(3) C V　≧ 0.125 · C Zn · · ·
　　(4) C V　≧ 2.0 · · · (5)
[0038]
　However, C V , the content of non-oxide ceramic particles containing the V (wt%), C Zn is meant the content of the doped zinc oxide particles (mass%), respectively.
[0039]
　Surface-treated steel sheet according to the present embodiment, the above-described configuration, electrodeposition coating prior to corrosion resistance, and weldability is excellent both. The reason for this, is estimated as follows.
[0040]
　As a method of expressing the weldability surface treated steel sheet, in general, to reduce the film thickness of the resin coating film formed on the surface of the steel sheet, the electrode surface during the spot electrode during spot welding is applied to the resin film, a thin film the resin film or contacting the surface of the steel sheet through, or, a method of expressing the spot weldability by direct contact with a portion where the steel sheet surface is exposed. Alternatively, by adding a conductive pigment having excellent conductivity in the resin coating film, when the spot electrode during spot welding is applied to the resin film, the conductive pigment in the spot electrode and the resin coating film There contact, by further and the conductive pigment and the steel sheet surface in contact, and a method of expressing the spot weldability. In the former, by further reducing the thickness of the resin coating film, it can improve the weldability. In the latter, by increasing the addition amount of the conductive pigments to be added, it can be improved weldability.
[0041]
　However, the former, because the thin resin coating film capable of spot welding, it is difficult to secure the corrosion resistance of the pre excellent electrodeposition coating. For the latter, the resin coating film is not contribute to the corrosion resistance, and includes a conductive pigment having a particle size across the resin coating section. Therefore, when carrying out the corrosion test and the like, a binder resin and the interface of the conductive pigment in the resin coating is water, tends to be permeating path saline etc., it is difficult to secure the corrosion resistance of the pre excellent electrodeposition coating.
[0042]
　As a method for solving these, a conductive pigment having both conductive properties and corrosion resistance by adding to the resin coating, a surface-treated steel plate, while ensuring the weldability, ensuring the corrosion resistance of the pre electrodeposition coating considered possible is. As a result of searching a conductive pigment having excellent corrosion resistance, the exception of vanadium carbide particles (VC particles) have a non-oxide ceramic particles is excellent conductivity performance containing V, and also is excellent in corrosion resistance It was confirmed.
[0043]
　That is, except of vanadium carbide particles (VC particles), non-oxide ceramic particles containing V, while high conductivity, water, when in contact with salt water or the like part of the pigment is eluted, release the V ion it is, express chromium-free surface-treated steel sheet and also excellent corrosion protection and V based compound and V-based anticorrosive pigment used in the painted steel. Therefore, the non-oxide ceramic particles containing V except vanadium carbide particles (VC particles) increases the corrosion resistance of the resin coating itself. On the other hand, in the vanadium carbide particles (VC particles), but to release the non-oxide ceramic particles as well as V ion containing other V, after V ion release, since the C adversely affects the corrosion resistance, as a result , it would not be exhibited were superior corrosion protection compared with the conductive pigments containing other V.
[0044]
　Furthermore, surface-treated steel plate, except for the vanadium carbide particles (VC particles), and non-oxide ceramic particles containing V, and a doped zinc oxide particles allowed to coexist in the resin coating film, and contains the V by adjusting the content of the non-oxide ceramic particles (excluding VC particles) and doped zinc oxide particles in a predetermined range, while securing the conductivity, and it is possible to improve the welding of the electrode Therefore, it is considered possible to improve the weldability.
[0045]
　From the above, the surface-treated steel sheet according to the present embodiment, electrodeposition coating prior to corrosion resistance, and weldability are presumed to be excellent both. That is, the surface-treated steel plate, the corrosion resistance before electrodeposition coating, it is estimated that both the weldability is realized.
[0046]
　The surface-treated steel sheet according to the present embodiment, except for the vanadium carbide particles (VC particles), the non-oxide ceramic particles containing V, since the corrosion resistance of the resin coating film itself is high, before electrodeposition coating corrosion resistance , and while both weldability, thinning of the resin film can be realized. Therefore, it not reduced the amount of resin of the resin coating, reducing the gas generation amount generated when welding the surface-treated steel sheet can be realized. Further, by thinning the resin film, variations in the membrane resistance of the resin coating film is suppressed, uniform weldability can be achieved.
[0047]
　Incidentally, the surface-treated steel sheet according to the present embodiment, the resin coating film, depending on the application, may be formed on both surfaces of the plated steel sheet, may be formed on only one surface of the plated steel sheet. Further, the resin coating film is also formed in a part of the surface of the plated steel sheet, the entire surface of the plated steel sheet may be coated. Site of the plated steel sheet in which the resin coating film is formed, electrodeposition coating prior to corrosion resistance, and weldability is excellent.
[0048]
　Hereinafter, the surface-treated steel sheet according to the present embodiment will be described in detail.
[0049]

　The plated steel sheet, zinc-plated steel sheet, and known coated steel sheet of the aluminum-based plated steel sheet or the like. Steel sheet, even Sheet steel, may be added element-containing steel sheet such as chromium. However, when press forming, the steel sheet is to comprise a desired molding trackability, kind and addition amount of the additive element, and properly controlled steel sheet metal structure is preferable.
[0050]
　The zinc-based plated layer of galvanized steel sheet, for example, plating layer of zinc, zinc and aluminum, cobalt, tin, nickel, iron, chromium, alloy plating layer of at least one of titanium, magnesium and manganese, Furthermore various zinc alloy plated layer containing other metallic or non-metallic elements (e.g., zinc, aluminum, quaternary alloy plating layer of magnesium and silicon) and the like. However, the zinc-based plating layer, the alloy component other than zinc are not particularly limited.
[0051]
　Incidentally, these zinc-based plating layer, further, a small amount of different metal elements, cobalt, molybdenum, tungsten, nickel, titanium, chromium, aluminum, manganese, iron, magnesium, lead, bismuth, antimony, tin, copper, cadmium, impurities such as arsenic, or silica, alumina, and may include an inorganic material titania.
[0052]
　The aluminum-based plating layer of an aluminum-based plated steel sheet, for example, plating layer of aluminum, aluminum and silicon, zinc, alloy plating layer of at least one of magnesium (e.g., an alloy plating layer of aluminum and silicon, aluminum and alloy plating layer of zinc, aluminum, ternary alloy plating layer of silicon and magnesium) and the like.
[0053]
　Zinc-plated steel sheet, aluminum-plated steel sheets, other types of plating layer (e.g., an iron plating layer, the alloy plating layer of iron and phosphorus, nickel plating layer, cobalt plating layer, etc.) was a double layer plated steel sheet in combination with it may be.
[0054]
　Method of forming the plating layer of the plated steel sheet is not particularly limited. For example, formation of the plating layer, electroplating, electroless plating, melt plating, vapor deposition plating, utilizes distributed plating. Formation of the plating layer is continuous, it may be any of batch type. Further, after the plating layer formation, zero spangle treatment is an external uniform treatment, a reforming process is annealing treatment of the plating layer, the process may be subjected to the temper rolling or the like for the surface condition or material adjustment.
[0055]

　resin coating comprises a binder resin, a non-oxide ceramic particles containing V except vanadium carbide particles (VC particles), and a doped zinc oxide particles. Resin coating, if necessary, may contain other ingredients.
[0056]
(Binder resin)
　The binder resin is water-soluble or water-dispersible aqueous resin is dissolved or dispersed in water, and may be any of solvent-based resin dissolved or dispersed in an organic solvent, but the production cost, in terms of environmental suitability , aqueous resin is preferable.
[0057]
　The aqueous resin, polyester resin, urethane resin, polyolefin resin, acrylic resin, epoxy resin, phenolic resin, water-soluble or water-dispersible resin of a mixed resin of two or more of these resins. In the case of using the polyester resin preferably has a molecular weight of 10,000 to 30,000. It may become difficult to molecular weight to ensure sufficient workability is less than 10000. On the other hand, if the molecular weight exceeds 30000 binding sites of the resin itself is lowered, is to ensure excellent adhesion to the electrodeposition coating film may be difficult. Further, when to be crosslinked using a curing agent such as melamine, crosslinking reaction is not sufficiently performed, the performance of the resin film may be degraded. In the case of using the urethane resin, the form of the urethane resin preferably (preferably 20 ~ 60 nm) emulsion particle size of 10 ~ 100 nm is an emulsion of. Those emulsion particle diameter is excessively small, it may become costly. On the other hand, those emulsion particle diameter is excessively large, the gap of the emulsion between increases upon film coating, there is the barrier of the resin coating film is lowered. The types of urethane resin, ether-based, polycarbonate-based, ester-based, and acrylic graphite type or the like. These may be used alone or may be used in combination.
[0058]
　On the other hand, the solvent-based resins, polyester resins, urethane resins, epoxy resins, acrylic resins, mixed resins of two or more of these resins.
[0059]
　Here, the binder resin may be a crosslinked resin having a crosslinked structure, it may be a non-crosslinked resin not having a crosslinked structure, in terms of low-temperature film formation of the resin coating film, a non-crosslinked resin it is preferable that. Crosslinking agent which imparts a crosslinked structure into the binder resin as (a curing agent) is preferably water-soluble crosslinking agent. Specifically as crosslinking agents, melamine, isocyanate, silane compounds, zirconium compounds, titanium compounds and the like are preferable.
[0060]
　The amount of the crosslinking agent added is 5 to 30 parts by mass of the resin solid content 100 parts by mass is preferred. When the amount of the crosslinking agent is less than 5 parts by mass, reduces the cross-linking reaction with the resin, there is the performance of the coating film becomes insufficient. On the other hand, when the amount of the crosslinking agent is more than 30 parts by weight, crosslinking reaction proceeds excessively, the resin coating film becomes excessively hard, in addition to formability is lowered, a silane compound, a zirconium compound, a titanium compound, Furthermore sometimes paint stability is reduced.
[0061]
　The content of the binder resin is 10.0 to 60.0 wt% with respect to the resin coating film (the total solid fraction of the paint film) is preferable. When the content of the binder resin is less than 10.0 mass%, the function as a binder without expression, it decreases the cohesive force of the resin coating film, when subjected to adhesion test and molding, the interior of the coating film destruction (cohesive failure of the coating film) may easily occur in. Both the content of the binder resin exceeds 60.0 wt%, the ratio of the pigment component contained in the resin coating film is reduced, weldability, electrodeposition coating prior to corrosion resistance, the adhesion between the electrodeposition coating film it may be difficult to. The content of the binder resin, expressed binder function, and weldability, from the viewpoint of achieving both the adhesion between the electrodeposition coating prior to corrosion resistance and electrodeposition coating film, (the total solid fraction of the paint film) resin film 15.0 to 50.0 wt% with respect to more preferred.
[0062]
(Non-oxide ceramic particles containing V)
　non-oxide ceramic particles containing V in the present embodiment, the electrical resistivity of 25 ° C. (volume resistivity, resistivity) of 0.1 × 10 -6 ~ 185 × 10 -6 [Omega] cm range non-oxide ceramics in (boride ceramics, nitride ceramics, silicide ceramics, etc.) is preferably.
[0063]
　Here, the non-oxide ceramic containing V, a ceramic consisting of elements or compounds containing no oxygen. Moreover, boride ceramics, and nitride ceramics and silicide ceramics, respectively, is that the non-oxide ceramic containing boron B, nitrogen N, V for silicon Si as a main non-metallic element. These electrical resistivity of either 25 ° C. is 0.1 × 10 -6 is a non-oxide ceramics of less than [Omega] cm.
[0064]
　The non-oxide ceramic particles containing V in the present embodiment, for example, one vanadium boride particles (VB particles, electrical resistivity 35 × 10 -6 [Omega] cm), diboride, vanadium particles (VB 2 particles, the electrical resistance rate × 10 0.99 -6 [Omega] cm), vanadium nitride particles (VN particles, electrical resistivity × 10 0.99 -6 [Omega] cm), and, V 5 Si 3 particles (electrical resistivity 115 × 10 -6 [Omega] cm) and VSi 2 particles ( electrical resistivity of 9.5 × 10 -6 silicide vanadium particles, etc. [Omega] cm), and the like.
[0065]
　Here, the non-oxide ceramic particles containing V in the present embodiment, except for the VC particles. Non-oxide ceramic particles containing V in the present embodiment, in addition to the VC particles, V 2 may be omitted vanadium carbide particles such as C particles.
[0066]
　The electric resistivity was appended in parentheses non-oxide ceramic containing exemplified V are representative of those sold as an industrial raw material used (literature value). These electrical resistivity increases and decreases depending on the type and amount of impurity elements entering into the crystal lattice of the non-oxide ceramics. Constant Therefore, for example, using a 4-terminal 4-probe method in accordance with the Corporation Mitsubishi Chemical Analytic Tech Ltd. resistivity meter Loresta EP (MCP-T360 type) and ESP probe (flat 2mm diameter of the head of the pin) a current application method, in compliance with JIS K7194 by measuring the electrical resistivity of ° C. 25, 0.1 × 10 -6 ~ 185 × 10 -6 better be used after confirming that it is within the Ωcm .
[0067]
　In the present embodiment, the non-oxide ceramic particles containing V (excluding VC particles) is often dissolution of V ions, with corrosion protection is also very good, a very low resistance value as the conductive pigment in view illustrating one vanadium boride particles (VB particles), diboride, vanadium particles (VB 2 particles), and is preferably at least one selected from vanadium nitride particles (VN particles).
[0068]
　Then, (excluding VC particles) non-oxide ceramic particles containing V is the viewpoint of the electrodeposition coating before improving corrosion resistance, diboride, vanadium particles (VB 2 and particularly preferably particles). By applying the diboride vanadium particles in the conductive pigment, it is possible to further improve the electrodeposition coating prior to corrosion resistance, and weldability. This is because, 1) Double the amount of elution of V ions vanadium boride particles is large, 2) as well as V ions released, B ions are affecting the corrosion resistance, 3) of the eluted V ions This is because the valence is presumed, affecting the corrosion resistance.
[0069]
　Present here, and the non-oxide ceramic particles containing these V (excluding VC particles), in a state of being dissolved in the composition of the resin coating film formation (for example, in the case of titanium oxide, the state of the titanium chelate) instead of, means a material mainly composed of non-oxide containing V present in a dispersed state in the composition at a few μm or more solid as primary particles.
[0070]
　The following describes the characteristics of the non-oxide ceramic particles containing V in this embodiment (excluding VC particles).
[0071]
　Particle shape of the non-oxide ceramic particles containing V in this embodiment (excluding VC particles), spherical, pseudo-spherical (e.g. elliptical spherical, egg-shaped, rugby ball shape or the like), or, polyhedral (e.g. football ball-shaped, cubes, such as various gem brilliant shape), is preferably a shape close to a sphere. Conductive particles having a shape close to a sphere is uniformly dispersed in the resin coating film, it becomes easy to form an effective conduction path penetrating the thickness direction of the resin film, the bonding property is further improved. On the other hand, an elongated shape (eg, a bar, a needle-like, fibrous, etc.), or the planar shape (e.g. flakes, plate-like, flaky, etc.) conductive particles is parallel to the coated surface during the formation of the resin film or arranged in, plated steel sheet (if there is a surface treatment on the surface of the plated steel sheet surface treatment layer) to or deposited in the vicinity of the interface between the resin coating film, effective through penetrating the thickness direction of the resin film to become difficult to form an electrical path, it may bondability is degraded.
[0072]
　The average particle size of the non-oxide ceramic particles containing V in this embodiment (excluding VC particles) is preferably 0.5 ~ 10 [mu] m. When the average particle size of the non-oxide ceramic particles containing the V is less than 0.5 [mu] m, it is difficult to obtain, with an disadvantageous in cost, resistance of the resin coating film becomes high at the time of spot welding, spot weldability it may be reduced. When the average particle diameter of the non-oxide ceramic particles containing said V exceeds 10 [mu] m, since the existence ratio of the non-oxide ceramic particles containing the V occupying in the resin coating film is reduced, good electrodeposition coating before sometimes corrosion resistance is difficult to obtain.
[0073]
　The average particle size of the non-oxide ceramic particles containing V in this embodiment (excluding VC particles), the previous corrosion resistance electrodeposition coating, from the viewpoint of improving the weldability further more not less 1μm or more preferably, and more preferably 5μm or less. The surface treated steel sheet of the present embodiment, the coating is within the range of the average particle diameter of 0.5 ~ 10 [mu] m, the inclusion by blending non-oxide ceramic particles containing different particle sizes the case of V, and better it can be expressed name electrodeposition coating prior to corrosion resistance, and weldability. The non-oxide ceramic particles containing V used in this embodiment (excluding VC particles), enough to become a small particle size, corrosion resistance is improved, as the become large grain size, conductivity is improved.
[0074]
　The "average particle diameter" of the non-oxide ceramic particles containing V in this embodiment (excluding VC particles), non-oxide ceramic particles containing the V present in the resin coating is present alone If refers to an average primary particle size, when the non-oxide ceramic particles to each other containing the V exists aggregate means the average secondary particle diameter represents the particle diameter of the oxide particles at the time of aggregation . The average particle size of the non-oxide ceramic particles containing the V are preferably obtained by the following measuring method. First, by cutting the surface treated substrate resin film is formed to expose the cross section and further polishing the cross section thereof. The thus obtained cross section was observed with a scanning electron microscope and the observation image of the cross section in the resin coating film. Non-oxide ceramic particles optionally picked several from existing in the visual field of the observation image, to measure the long side and short side length of each of the non-oxide ceramic particles. Finally, the long side length of the average value and the calculated average value of the short side length, yet, by averaging the average value of the average value and the short side length of the long side length, the average to calculate the particle size.
[0075]
　The numerical values ​​of the average particle size varies somewhat by the measuring method. For example, the measurement principle in the case of using a particle size distribution meter, in the case of the image analysis may vary by the image processing method. However, the range of particle diameter of the oxide particles as defined herein, is obtained by considering such variations. Even particle size obtained by any method, as long as it is defined herein, can be obtained the desired effect stably.
[0076]
　The following describes the content of the non-oxide ceramic particles containing V in this embodiment (excluding VC particles).
[0077]
　The content of non-oxide ceramic particles containing V in this embodiment (excluding VC particles) is 2.0 mass% or more based on the resin coating film (the total solid fraction of the paint film). When the content of the non-oxide ceramic particles containing the V is less than 2.0 wt%, it can not be sufficiently obtained corrosion resistance and weldability before electrodeposition coating. On the other hand, the content of the non-oxide ceramic particles containing V in this embodiment (excluding VC particles), be the resin coating film (the total solid fraction of the paint film) is 25.0 wt% or less preferable. When the content of non-oxide ceramic particles containing said V exceeds 25.0 mass%, with a decrease in the ratio of the binder resin in the resin coating film, the cohesive force of the resin coating film is lowered. As a result, the adhesion between the electrodeposition coating film after electrodeposition coating may be lowered.
[0078]
　Free of oxide ceramic particles, electrodeposition coating prior to corrosion resistance, weldability, and terms such as (corrosion resistance after electrodeposition coating) adhesion between the electrodeposition coating film, the resin coating containing the V more preferably 2.5 to 15.0 mass% relative to the (total solid content of the coating film).
[0079]
(Doped zinc oxide particles)
　resin coating comprises doped zinc oxide particles (i.e., conductive zinc oxide particles). When containing doped zinc oxide particles having conductivity in the resin coating film, thereby improving the adhesion between the resin coating film and the electrodeposition coating film. In addition to this, also improves weldability.
[0080]
　The doped zinc oxide particles, for example, at least one element selected from the group consisting of periodic table Group 13 element and Periodic Table Group 15 element (hereinafter also referred to as "doping element"), the zinc oxide particles particles was expressed conductivity like by doping.
[0081]
　The element of Group 13 of the Periodic Table, B, Al, Ga, In, and the like. The Periodic Table Group 15 element, P, As, and the like. Among these, from the viewpoint of improving conductivity, the doping element is preferably Al or Ga. Further, from the viewpoint of cost, doping elements is more preferably is Al.
[0082]
　The content of the doping element is from the viewpoint of improving conductivity, relative to the zinc oxide particles undoped, preferably from 0.05 ~ 5 atom%, and more preferably 0.1 ~ 5 atom%.
[0083]
　The average particle size of doped zinc oxide particles is preferably 0.2 ~ 5 [mu] m, more preferably from 0.3 ~ 4 [mu] m, further preferably 0.4 ~ 2.5 [mu] m. When the average particle diameter of doped zinc oxide particles in 0.2 ~ 5 [mu] m, the crystal of the chemical conversion coating that forms (e.g., crystalline acid chloride such as phosphate) is likely to grow in a wedge shape, the chemical conversion coating by the anchor effect of the crystal can be the adhesion between the resin coating film and the electrodeposition coating film further improve. Also improved weldability.
[0084]
　Definition and measurement method of the "average particle size" of the doped zinc oxide particles is the same as the definition and measurement method of the "average particle diameter" of the non-oxide ceramic particles containing V in the present embodiment.
[0085]
　The content of doped zinc oxide particles is 10.0% by mass or more with respect to the resin coating film (the total solid fraction of the paint film). When the content of the doped zinc oxide particles is less than 10.0 mass%, the component crystals of the chemical conversion coating formed (e.g., acid chloride, such as phosphate crystals) formed in the surface layer inside the resin film hard to be, chemical conversion by the anchor effect of the treatment film with adhesion between the resin coating film and the electrodeposition coating film is difficult to obtain, it is not obtained improvement in weldability. On the other hand, the content of doped zinc oxide particles, it is preferred for the resin coating film (the total solid fraction of the paint film) is 45.0 mass% or less. When the content of doped zinc oxide particles exceeds 45.0 mass%, formation of the component crystals of the chemical conversion coating to be formed by saturated, adhesion between the resin coating film and the electrodeposition coating film is saturated together, by allowing the ratio of the conductive pigments and anticorrosive pigment occupies in the coating is reduced, weldability, properties such as corrosion resistance before electrodeposition coating may be insufficient. The content of doped zinc oxide particles, the chemical conversion film further improve the adhesion between the resin coating film and the electrodeposition coating film by the anchoring effect of the crystal, and from the viewpoint of further improving the weldability, 15.0 more preferably to 25.0% by weight.
[0086]
　Here, the resin film, as well as doped zinc oxide particles, may contain anticorrosive pigments containing Mg, which will be described later. In a resin coating, to include a rust-preventive pigment containing doped zinc oxide particles and Mg, corrosion resistance before electrodeposition coating is further improved. The reason for this, and Mg is the reaction of doped zinc oxide and anticorrosive pigment, by forming a composite oxide of poorly soluble is presumed that it is possible to improve the corrosion resistance of the pre electrodeposition coating.
[0087]
　The rust preventive pigment containing Mg, magnesium treatment of dihydrogen tripolyphosphate aluminum, magnesium ion exchange silica, magnesium phosphate, and the like. Among these, from the viewpoint of electrodeposition coating prior to improving corrosion resistance of magnesium treated tripolyphosphate aluminum are preferred.
[0088]
　The content of the anticorrosive pigment containing Mg when used in combination with doped zinc oxide particles is preferably 5.0 to 40.0 wt% with respect to the resin coating film (the total solid fraction of the paint film) . When the content of the anticorrosive pigment containing Mg is less than 5.0 mass%, the improvement effect of the combination according to the electrodeposition coating prior to corrosion resistance and anticorrosive pigments containing Mg can not be obtained. On the other hand, if the content of the anticorrosive pigment containing Mg exceeds 40.0% by mass, the proportion of the conductive pigments occupying in the resin coating film becomes insufficient weldability by lowering. The content of the anticorrosive pigment containing Mg when used in combination with doped zinc oxide particles, from the viewpoint of electrodeposition coating before improving the corrosion resistance, and more preferably 10.0 to 30.0 wt%.
[0089]
　Content relative to the coating film of the non-oxide ceramic particles and the doped zinc oxide particles containing said V satisfies the following expression.
　　C Zn　≧ 10.0 · · ·
　　(1) C V　≦ 0.5　　· C Zn · · ·
　　(2) C V　≦ 70-C　　　Zn · · ·
　　(3) C V　≧ 0.125 · C Zn · · ·
　　(4) C V　≧ 2.0 · · · (5)
[0090]
　However, C V , the content of non-oxide ceramic particles containing the V (wt%), C Zn is meant the content of the doped zinc oxide particles (mass%), respectively.
[0091]
　By content relative to the coating film of the non-oxide ceramic particles and the doped zinc oxide particles containing the V satisfies the above expression, the surface treated steel sheet of the present embodiment, while securing the conductivity, and , it is possible to improve the welding of the electrode can be further improved weldability.
[0092]
(Anticorrosive pigment)
　as still another component is preferably contained in the resin film, and a rust-preventive pigment. In a state where the resin coating film contains a non-oxide ceramic particles containing V in the present embodiment, the inclusion of anti-rust pigment, corrosion resistance before electrodeposition coating is further improved.
[0093]
　Anticorrosive pigments include, but are not limited to, aluminum tripolyphosphate, Zn phosphate and phosphorous acid, Mg, Al, Ti, Zr and Ce salts, hydrocalumite treated phosphoric acid compound (as an example, zinc phosphate a hydrocalumite processing Toho pigment manufactured by EXPERT NP-530 N5) of, Ca ion exchange silica and oil absorption 100 ~ 1000 ml / 100 g, a specific surface area of 200 ~ 1000 m 2 / g, average particle size 2 ~ 30 [mu] m amorphous of is preferably at least one selected from the group consisting of quality silica.
[0094]
　Among these, anticorrosive pigments, flaw portion, in terms of both the corrosion resistance of the flat portion, phosphate-based anticorrosive pigment (aluminum tripolyphosphate, phosphoric acid compounds are hydrocalumite processing, etc.), silica-based rust pigments or, is preferably a combination of both. In particular, rust pigments, aluminum tripolyphosphate, hydrocalumite treated phosphoric acid compound, Ca exchange silica, an oil absorption of 100 ~ 1000 ml / 100 g, a specific surface area of 200 ~ 1000 m 2 / g, the non-average particle size of 2 ~ 30 [mu] m more preferably at least one selected from the group consisting of crystalline silica.
[0095]
　Incidentally, the oil absorption of the silica can be measured in accordance with JIS K 5101-13-2. The specific surface area of ​​silica can be measured by the BET method. The average particle size of the silica can be measured by the average particle diameter and the same method of the non-oxide ceramic particles containing V.
[0096]
　The content of the anticorrosive pigment is preferably the resin coating film (the total solid fraction of the paint film) is from 5.0 to 40.0% by weight. When the content of the anticorrosive pigment is less than 5 wt%, it may not be obtained the effect of improving the prior electrodeposition coating corrosion resistance. When the content of anticorrosive pigment is more than 40.0% by mass, the decrease of the workability of the resin coating film, reduction in cohesive force. The content of the anticorrosive pigment, electrodeposition coating prior to corrosion resistance, from the viewpoint of workability, more preferably 10.0 to 30.0 wt% with respect to the resin coating film (the total solid fraction of the paint film) .
[0097]
(Oxide particles)
　as still another component is preferably contained in the resin film, a non-doped zinc oxide particles (i.e., zinc oxide particles of the non-conductive), magnesium oxide particles, calcium oxide particles, and oxide at least one oxide particles are selected from strontium particles. If the resin coating film is contained the oxide particles, the adhesion between the electrodeposition coating film after electrodeposition coating is improved. The reason for this, is estimated as follows. On the resin coating film containing the oxide particles, when subjected to a chemical conversion treatment by the chemical conversion treatment liquid acidic, the chemical conversion treatment liquid acidic, oxide particles exposed to the surface of the resin film is dissolved. Then, to increase the pH of near the component of the chemical conversion solution (e.g., acid chlorides such as phosphate) precipitates and growth. Accordingly, chemical conversion coating on the surface of the resin film is formed. At this time, the oxide particles present in the surface layer inside the resin coating film also was dissolved by chemical conversion treatment liquid acidic, the components of the chemical conversion treatment liquid is deposited on the surface layer inside the resin film, the surface from the surface layer inside the resin coating film It grows in a wedge shape so as to protrude. When forming a chemical conversion film electrodeposition coating film by coating on the state, in addition to the high adhesion due to the chemical conversion film itself, the chemical conversion coating grown in a wedge shape crystal (e.g., acid chloride, such as phosphate adhesion between the resin coating film and the electrodeposition coating film by the anchoring effect of the crystals) (especially secondary adhesion after hot water test) is further enhanced.
[0098]
　Oxide particles, from the viewpoint of improving adhesion between the resin coating film and the electrodeposition coating film, a non-doped zinc oxide particles (i.e., non-conductive zinc oxide particles), particles of magnesium oxide, calcium oxide particles and, is preferably at least one selected from strontium oxide particles.
[0099]
　Undoped zinc oxide particles were dissolved by chemical conversion treatment solution, crystals of the chemical conversion coating (e.g., crystalline acid chloride such as phosphate) to promote the growth of crystals of the anchor effect of the chemical conversion coating the adhesion between the resin coating film and the electrodeposition coating film can be further improved by.
[0100]
　Undoped zinc oxide particles, magnesium oxide particles, calcium oxide particles, and, strontium oxide particles (especially particles of magnesium and calcium oxide particles oxidation), after dissolved by the chemical conversion treatment liquid, is incorporated into the chemical conversion film. Therefore, Mg, is the chemical conversion coating having a Ca or Sr formed to have a corrosion resistance after electrodeposition coating, thereby improving the corrosion resistance after electrodeposited coating.
[0101]
　The average particle diameter of the oxide particles is preferably 0.2 ~ 5 [mu] m, more preferably from 0.3 ~ 4 [mu] m, further preferably 0.4 ~ 2.5 [mu] m. When the average particle diameter 0.2 ~ 5 [mu] m of oxide particles, crystals of the chemical conversion coating that forms (e.g., crystalline acid chloride such as phosphate) is likely to grow in a wedge shape, the crystals of the chemical conversion coating it can further improve the adhesion between the resin coating film and the electrodeposition coating film by the anchoring effect.
[0102]
　Definition and measurement method of the "average particle diameter" of the oxide particles is the same as the definition and measurement method of the "average particle diameter" of the non-oxide ceramic particles containing V in the present embodiment.
[0103]
　The content of the oxide particles is preferably 1.0 to 10.0 mass% relative to the resin film (the total solid fraction of the paint film). If the content of the oxide particles is less than 1.0 wt%, the component crystals of the chemical conversion coating formed (e.g., crystalline acid chloride such as phosphoric acid salt) formed in the surface layer inside the resin coating film hardly , adhesion between the resin coating film and the electrodeposition coating film by the anchoring effect of the chemical conversion coating is difficult to obtain. On the other hand, if the content of the oxide particles is more than 10.0 mass%, formation of the component crystals of the chemical conversion coating to be formed by saturated, adhesion between the resin coating film and the electrodeposition coating film is saturated together, by the ratio of the conductive pigments and anticorrosive pigment occupies in the resin coating film is lowered, weldability, properties such as corrosion resistance before electrodeposition coating may be insufficient. The content of the oxide particles, from the viewpoint of the crystal of the anchor effect of the chemical conversion coating to further improve the adhesion between the resin coating film and the electrodeposition coating film, and more to be 2.5 to 7.5 wt% preferable.
[0104]
(Other additives)
　The resin film, in addition to the aforementioned other components, may contain other additives. Other additives, for example, extender pigments, solid lubricants, rust inhibitors, known additives such as leveling agents.
[0105]
　Examples of the extender pigment include silica (containing colloidal silica), and the like.
[0106]
　If the resin coating film containing a solid lubricant, it is possible to impart excellent lubricating properties to the resin coating film, it can improve the powdering resistance of the resin coating film. As solid lubricant, for example, solid lubricant following (1) to (2).
[0107]
(1) polyolefin wax, paraffin wax: for example, polyethylene wax, synthetic paraffin, natural paraffin, micro wax, chlorinated hydrocarbons, etc.
(2) a fluorine resin-based wax: for example polyfluoroethylene resin (polytetrafluoroethylene resin), polyvinyl fluoride resins, polyvinylidene fluoride resins, etc.
[0108]
　When using a polyethylene wax as a solid lubricant, the average particle diameter is preferably 0.5 ~ 10 [mu] m. When the average particle size of the polyethylene wax is less than 0.5 [mu] m, the adhesion of the surface segregation of the polyethylene wax, it tends many area occupied by the polyethylene wax occupying the surface of the resin film, the resin coating film and the electrodeposition coating film sex may be reduced. On the other hand, when the average particle size of the solid lubricant is more than 10 [mu] m, easily occur separation of polyethylene wax from the resin coating film, a predetermined hard lubricity is obtained, corrosion resistance after electrodeposition coating may be lowered . The average particle size of the solid lubricant, excellent adhesion between the resin coating film and the electrodeposition coating film, electrodeposition corrosion resistance after painting, lubricity, from the viewpoint of obtaining a powdering resistance, it is 1 ~ 5 [mu] m more preferable.
[0109]
　The softening point of the solid lubricant is preferably 100 ° C. ~ 135 ° C., and more preferably 110 ~ 130 ° C.. When the softening point of the solid lubricant is at 100 ℃ ~ 135 ℃, lubricity and powdering resistance of the resin coating film is further improved.
[0110]
　The content of the solid lubricant is preferably 0.1 to 10% by weight based on the resin coating film (the total solid fraction of the paint film). When the content of the solid lubricant is less than 0.1% by mass, the lubricity can not be sufficiently obtained. When the content of the solid lubricant exceeds 10% by mass, the adhesion between the resin coating film and the electrodeposition coating film, the corrosion resistance after electrodeposition coating decreases. The content of the solid lubricant, 0 adhesion to the resin coating film and the electrodeposition coating film, lubricity, in view of corrosion resistance after electrodeposition coating, the resin coating film (the total solid fraction of the paint film). more preferably 5 to 5 wt%, and more preferably 0.5 to 2.5 mass%.
[0111]
　Examples of the rust inhibitor include inorganic corrosion inhibitors, organic corrosion inhibitors and the like.
[0112]
　The inorganic corrosion inhibitors include phosphate compounds such water-soluble. If the phosphoric acid compound is contained in the resin coating film, as in the phosphoric acid-based rust preventive pigment, by forming a phosphate film on a metal base material surface, to improve the rust resistance. Examples of the phosphoric acid-based compounds in water-soluble, for example, orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphate, phosphoric acids and their salts such as tetraphosphate, as well, include phosphonic acids and salts thereof.
[0113]
　The organic corrosion inhibitor, for example, guanidino group-containing compound, Piguanijino group-containing compounds, thiocarbonyl group-containing compounds. Since these easily adsorbed on the metal surface, it is effective to white rust inhibition, such as galvanized steel sheet.
[0114]
　The content of the rust inhibitor, the resin coating film (the total solid fraction of the paint film) is preferably 0.5 to 5 mass%. When the content of the anticorrosive agent is less than 0.5 wt%, it may not be allowed to sufficiently improve the corrosion resistance. If the content of the rust inhibitor is more than 5 mass%, the reduction in liquid stability, sometimes paint it becomes difficult. The content of the rust inhibitor, from the viewpoint of corrosion resistance and paint stability, the resin coating film (the total solid fraction of the paint film), and more preferably 1 to 3% by weight.
[0115]
(Adhesion amount of the resin coating film)
　adhered amount of the resin coating film (coating weight of total solids of the resin film) is, 1 ~ 25 g / m 2 is preferably. Adhesion amount of the resin coating film is 1 g / m 2 if less than the adhesion between the resin coating film and the electrodeposition coating film, and corrosion resistance before electrodeposition coating may not be sufficiently obtained. Adhesion amount of the resin coating film is 25 g / m 2 if it exceeds, by cohesion of the coating film is lowered, weldability may not be sufficiently obtained. Adhesion amount of the resin coating film, adhesion between the resin coating film and the electrodeposition coating film, weldability, in terms of electrodeposition coating prior to corrosion resistance, 1.5 ~ 20 g / m 2 and more preferably from 2 ~ 20 g / m 2 more preferably, 2 ~ 15 g / m 2 and particularly preferably.
[0116]
(Resin coating film formation)
　method for forming a resin coating film is not particularly limited, it can be used known methods. For example, a binder resin, a non-oxide ceramic particles containing V (excluding VC particles), if necessary, the other components, and other additives, the composition of the resin coating film formed of a mixture in a solvent get a (paint). Solvents may be water, but may be an organic solvent, production costs, the environmental suitability point is preferably water. In other words, the composition of the resin coating film is preferably an aqueous composition. Then, a composition for a resin coating film formed, at least coated on one side of the plated steel sheet, followed by drying and heating to form a resin coating film.
[0117]

　surface-treated steel plate, between the plated steel sheet and the resin film, surface treatment film or the like for adhesion and further improve the electrodeposition coating before corrosion resistance to coated steel sheet of resin film known functional film may be interposed in the.
[0118]
　The surface treatment film, rather than a chromate conversion coating, it is preferred chromium is substantially free primed film (chromate-free conversion coating). The chromate-free treatment solution for use in the chromate-free treatment, zircon system for liquid silica, vapor phase silica, silica-based treatment liquid silicon compound such silicates as the main film component, zircon-based compound as a main film component treatment solution and the like. These treatment liquid may be processing liquid coexisting organic resin together with the main film component. Incidentally, chromate-free treatment liquid is not limited to silica-based processing liquid and zirconate-based treatment liquid. Chromate-free treatment liquid, silica processing liquid and besides zircon-based treatment liquid, chromate-free treatment solution for various for use in the painting surface treatment has been proposed. It is also possible to use a chromate-free treatment liquid is expected to be proposed in the future.
[0119]
　Adhesion amount of surface treatment coating, according to the processing solution used may be selected a suitable adhesion amount. For example, if the surface treatment coating by silica treating solution, conventional deposition amount, in terms of Si 1 ~ 20 mg / m 2 is preferably.
[0120]

　coating member according to the present embodiment is made of surface-treated steel sheet according to the present embodiment, the comprises a molded material having a coated film, and a electrodeposition coating film formed on the coating film.
[0121]
　Coating member according to the present embodiment, for example, it is manufactured as follows. First, for example, using well known molding techniques cutting and press molding, by molding a surface treated steel sheet to obtain a green body of the desired shape. Molding material, if desired, welding may be assembled into a desired shape by (spot welding, etc.).
[0122]
　Next, the resin film of the forming material is subjected to electrodeposition coating process. Thus, on the resin coating film, electrodeposition coating film is formed. Electrodeposition coating process may be either anionic electrodeposition coating and a cationic electrodeposition coating, the corrosion resistance viewpoint, it is preferred that the cationic electrocoating.
[0123]
　In particular, a resin [e.g., a carboxyl group, a hydroxyl group, methylol group, an amino group, a sulfonic acid group, a hydrophilic group such as polyoxyethylene bond, aqueous resin (acrylic resin having a functional group such as a hydroxyl group which reacts with a curing agent , polyester resins, alkyd resins, epoxy resins, and known aqueous resin) such as polyurethane resin, and a curing agent (melamine resin, blocked polyisocyanate), and other additives (coloring pigment, light interference pigments, extender pigments , dispersing agents, anti-settling agents, reaction accelerators, defoamers, thickeners, rust preventives, UV absorbers, known additives such as surface modifier) ​​and a cationic electrodeposition coating using the aqueous coating material comprising the process, to form a electrodeposition coating film, tends to improve the adhesion between the resin coating film and the electrodeposition coating film.
[0124]
　Thereafter, the electrodeposition coating film on the molding material, if necessary, intermediate coating film, other coating film such as a topcoating film may be formed.
[0125]
　Through these steps, paint member according to the present embodiment is manufactured.
[0126]
　Note that, before electrodeposition coating, the molding material resin coating film is formed, degreasing of the resin coating film, after the surface conditioning, chemical conversion treatment (e.g., phosphate treatment, Zr treatment or the like) be subjected to good. Chemical conversion treatment by the applied, hardly the resin coating film is formed chemical conversion film is, but the area in need other resin film chemical conversion coating is formed. Therefore, the whole forming material (coating member), it is possible to improve the adhesion of the electrodeposition coating film.
[0127]
　Coating member according to the present embodiment, the mobile member (automobile body, suspension members, etc.), mechanical component (housing, etc.), consumer electronics member (casing or the like), widely used in building materials (roofing, walls, etc.) and the like applications It is.
Example
[0128]
　Hereinafter, the present invention will be described more specifically by way of Examples. However, these examples are not intended to limit the present invention.
[0129]
Production of surface-treated steel
　sheet] 1. Preparation of coated steel sheet
　was prepared following galvanized steel sheet GA and AL plate, an aqueous alkaline degreasing agent 2.5% by weight of (Nippon Parkerizing Co. FC-301), was immersed for 2 minutes in 40 ° C. solution surface after degreasing and the metal plate for coating by washing and drying.
· GA: alloyed hot-dip galvanized steel sheet (thickness 0.8 mm, 10 wt% Fe, coating weight 45 g / m
2 ) · EG: electric galvanized steel (thickness 0.8 mm, coating weight 40 g / m 2 )
· ZL: electrical Zn-10 wt% Ni alloy plated steel sheet (sheet thickness 0.8 mm, coating weight 40 g / m
2 ) · GI: galvanized steel sheet (thickness 0.8 mm, coating weight 60 g / m 2 )
· SD: molten Zn-11 wt% Al-3 mass% Mg-0.2 wt% Si alloy-plated steel sheet (sheet thickness 0.8 mm, coating weight 60 g / m
2 ) · AL: dip Al-plated steel sheet (plate thickness 0.8 mm, coating weight 40 g / m 2 )
[0130]
　2. Deposition of the base treated film
　was then prepared following two undercoating film forming composition, the composition thickness of the coating so that the 0.08 .mu.m, and bar coating to a plated steel sheet. In a hot air oven plated steel sheet to form a film, after drying at a metal surface temperature reached 70 ° C., by air drying, to form a surface treatment film on the surface of the plated steel sheet.
· P1: Zr compound, a silane coupling agent, comprising silica fine particles aqueous coating composition
· P2: polyester resin, silica fine particles, aqueous coating composition comprising a silane coupling agent
[0131]
　3. Film of the resin coating film
　Next, in order to form a resin coating film having a composition shown in Tables 2 to 5, by mixing each component having the same solid matter concentration as in Table 2 to Table 5, the resin It was prepared an aqueous composition for forming a coating film. According to Table 6 to Table 9, was coated with a bar coater and the resulting aqueous composition on the plated steel sheet, followed by drying using an oven in such conditions are maintained for 8 seconds at a maximum temperature 140 ° C., the resin coating film It was formed. Adhesion amount of the resin coating film, so that the total adhesion amount of the solid of the aqueous composition fraction (non-volatile content) to a number shown in Table 6 to Table 9, were prepared by count of dilution and bar coater aqueous composition . In Table 2 to Table 5, the solid concentration of each component is solid entire aqueous composition content ratio (unit of solids of each component with respect to (nonvolatile content) (nonvolatile content): mass%, per surface value It was described as.) at.
[0132]
　Table 2 Each component in ~ Table 5 (symbols) details are as follows.
[0133]
　(A) non-oxide ceramic particles
· VB　2 : diboride vanadium particles (VB 2 particles) (average particle size 1 ~ 3 [mu] m, a specific gravity 5.1 g = / cm
3 ) · VB: one vanadium boride particles (VB particles )
· VC: vanadium carbide particles (average particle size 1 ~ 3 [mu] m, a specific gravity 5.8 g = / cm
3 ) · VN: vanadium nitride particles (average particle size 1 ~ 3 [mu] m, a specific gravity 6.1 g = / cm
3 ) · TN: titanium nitride particles (average particle size 1 ~ 3 [mu] m, a specific gravity 6 g =
/ cm 3 ) · SUS: SUS particles (average particle size 3 ~ 7 [mu] m, a specific gravity = 7.7 g / cm 3 )
[0134]
　(B) anticorrosive pigment
· PA: tripolyphosphate aluminum (Zn coating) (Tayca condensed phosphate aluminum K-105) (mean particle size 1 ~ 3 [mu]
m) · PM: magnesium phosphate (average particle size 1 ~ 3 [mu] m)
· SC: calcium ion exchange silica (average particle size ~ 3 [mu] m
1) · Si: silica (oil absorption 100 ~ 1000ml / 100g, a specific surface area of ~ 1000 m 200 2 / g, amorphous silica having an average particle diameter of 1 ~ 30 [mu] m) (Fuji Silysia silos mask
02) · HP: hydrocalumite treated zinc phosphate (manufactured by Toho pigment EXPERT NP-530 N5) (average particle size 1 ~ 3 [mu]
m) · PMA: tripolyphosphate aluminum (Mg coating) (Tayca condensation aluminum phosphate K-450H) (average particle size 1 ~ 3 [mu] m)
[0135]
　(C) a binder resin
· U1: urethane resin emulsion (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Superflex (R)
E-2000) · U2: urethane resin emulsion (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Superflex (registered trademark ) E-2000) + silane coupling agent (JNC Corporation silane coupling agent S510) in solid content 95: mixed resin was blended in 5
· U3: urethane resin emulsion (Dai-ichi Kogyo Seiyaku Co., Super fLEX (TM) E-2000) + silane coupling agent (JNC Corporation silane coupling agent S510) + zirconium compound (Kishida chemical Co., 90 ammonium zirconium carbonate) at a solid content ratio: 5: blend 5 the mixed resin
· P1: polyester resin emulsion (Toyobo Co., Ltd. bus Ronaru (R)
MD1985) · P2: polyester resin emulsion (Toyobo Co., Ltd. Vylonal (R)
MD1245) · P3: polyester resin (Toyobo Co., Ltd., Byron (registered trademark) Byron 290) + melamine resin (Orunekkusu Japan Ltd. mixed resin obtained by blending the imino type melamine resin Cymel 325) 80:20 by solid content ratio
[0136]
　(D) oxide particles
· MgO: Magnesium oxide particles (average particle size = 1.0
.mu.m) · CaO: Calcium oxide particles (average particle size 1.0 .mu.m
=) · ZnO (1): Zinc oxide particles (average particle size = 1.0
.mu.m) · SrO: strontium oxide particles (average particle size = 1.0
.mu.m) · ZnO (2): doped zinc oxide particles (Hakusui Tech Co., aluminum doped conductive zinc oxide 23-Kt, average particle size = 0.5μm)
[0137]
　Incidentally, the various oxide particles are dispersed in water with the addition of resin, it was used after pulverized by a ball mill. The average particle diameter of the oxide particles, and adjusting the grinding time, was determined an average particle size in the resin coating film.
[0138]
　(E) Other Additives
· WAX1: Polyethylene wax (Mitsui Chemicals, Inc. Chemipearl S650) (average particle size of less than 0.1 [mu] m
=) · WAX2: Polyethylene wax (Mitsui Chemicals, Inc. Chemipearl S120) (average particle size = 0
.5Myuemu) · WAX3: polyethylene wax (Mitsui Chemicals, Inc. Chemipearl W700) (average particle size 1.0 .mu.m
=) · WAX4: polyethylene wax (Mitsui Chemicals, Inc. Chemipearl W400) (average particle size = 4.0 .mu.m)
· WAX5: polyethylene wax (Mitsui chemicals, Inc. Chemipearl W310) (average particle size = 9.5
.mu.m) · CS: colloidal silica (manufactured by Nissan chemical Industries, Ltd. silica sol ST-O)
[0139]
　5. Production of surface treated steel sheet
　according to Tables 1 to 5, and, according to the above method of operation, on the plated steel sheet, surface treatment coating to form a resin film, each sample No. The surface treated steel sheet of manufactured.
[0140]
[Chemical conversion treatment Evaluation Test]
- zinc phosphate chemical conversion -
　Each sample No. To the surface treated steel sheet of using a Nihon Parkerizing surface conditioning treatment agent Co., Ltd. Prepalene X (trade name), the surface conditioning was performed for 20 seconds at room temperature. In addition, Japan Parkerizing chemical conversion treatment solution Co., Ltd. (zinc phosphate treatment solution) using the "PALBOND 3020 (trade name)", was carried out the zinc phosphate treatment. Conversion temperature of the treatment liquid was set to 43 ° C., after 120 seconds immersion the surface treated steel sheet in a chemical conversion treatment solution was then washed with water and dried.
[0141]
- zircon-based processing (Zr process) -
　Each sample No. To the surface treated steel sheet of, in place of the zinc phosphate treatment, and Zr ions, containing a fluorine and an aqueous solution containing free fluorine ions of 100 ~ 1000 ppm (hereinafter, referred to as FF chemical conversion treatment liquid.) It was performed Zr processing using.
[0142]
　To obtain a Zr treatment solution, H 2 ZrF 6 placed in a container so that the (hexafluorozirconate) Then placed hydrofluoric acid and aqueous sodium hydroxide in a container, the fluorine concentration and the free fluorine concentration in the solution was adjusted to be a predetermined value. Measurement of free fluorine concentration was performed using a commercially available densitometry. After adjusting the fluorine concentration and the free fluorine concentration, and a constant volume container with ion-exchanged water, Zr treatment solution (specific composition see Table 1) was.
[0143]
　Then, Zr treatment was performed as follows. First, as a pre-treatment, alkali degreasing agent (manufactured by Nippon Paint Co., Ltd. EC90), 2 minutes at 45 ° C., was carried out dipping degreasing the surface treated steel sheet. Thereafter, the surface-treated steel sheet was immersed for 120 seconds at 40 ° C. to Zr treatment solution shown in Table 1, it was carried out conversion treatment. After chemical conversion treatment, it was washed with water and dry the surface treated steel sheet.
[0144]
[Table 1]

[0145]
[Electrocoating before corrosion resistance testing]
　The surface-treated steel sheet before carrying out the above chemical conversion treatment, cut into a predetermined size, the corrosion resistance test method of plating based samples were tape sealed end face to JIS H 8502 ((1) salt spray (35 ° C., 2h), (2) drying (60 ℃, 25% RH, 4h), was used, the planar portion (3) wetting (50 ℃, 98% RH, 2h) are sequentially carried corrosion resistance test method) corrosion occurrence of the observation. Test time, the (1) to (3) one cycle, than the plane portion corroded area ratio at 60 cycles time, to evaluate the relative merits of the electrodeposition coating before corrosion resistance using the following rating. In such electrodeposition coating before the test, scores may be 3 or more was judged to be excellent in electrodeposition coating prior to testing.
　6: corroded area ratio of 2.5% or less
　5: corroded area ratio of 2.5 percent 5% or less
　4: corroded area ratio of 5 percent to 10%
　3: corroded area ratio is more than 10% to 20%
　2 : less corroded area ratio of 20 percent 50
　1: corroded area ratio of 50 percent
[0146]
[Weldability test (contact resistance)
　The surface-treated steel sheet before carrying out the chemical conversion treatment using a CF type Cr-Cu electrode tip diameter 5 mm, R40, pressure 1.96KN, welding current 2A, voltage 10V in using the constant current generator, by measuring the voltage value of the steel sheet under pressure, to calculate the contact resistance value. Using the following scores were evaluated relative merits of spot weldability. In such spot weldability, if score is 3 or greater was judged to be excellent in spot weldability.
　4: 10 m [Omega less than
　3: 10 m [Omega least 50mΩ less
　2: less than 50mΩ than 100 m [Omega
　1: 100 m [Omega than
[0147]
[Weldability test (continuous dotting property)
　The surface-treated steel sheet before carrying out the chemical conversion treatment using a CF type Cr-Cu electrode tip diameter 5 mm, R40, pressure 1.96KN, welding current 8 kA, the energizing time provides continuous dotting test of spot-welded at 12 cycles / 50 Hz, the nugget diameter 3√t (t is thickness) was determined number RBI immediately before below. It was to evaluate the relative merits of the spot weldability using the following scores. In such spot weldability, if score is 3 or greater was judged to be excellent in spot weldability.
　4: 1500 Dot least
　3: 1000 Dot 1,500 RBI less than
　2: 200 points or more, less than 1000 points
　less than 1: 200 RBI
[0148]
[Coating film adhesion test]
　after performing the zinc phosphate treatment or Zr process as the chemical conversion treatment, to the surface treated steel sheet, a cationic electrodeposition paint made by Nippon Paint Co., electrostatic Slope energizing voltage 160V was deposited coating was further baking 20 minutes at baking temperature 170 ° C.. The average film thickness of the electrodeposition coating film after electrodeposition coating, either Test No. was also 8 [mu] m. After the electrodeposition coating, a surface-treated steel sheet, the aqueous 5% NaCl solution having a temperature of 50 ° C., were immersed for 500 hours. After immersion, the test surface 60 mm × 120 mm in area (area = 60 mm × A10 120 mm = 7200Mm 2 ) on the entire surface, was attached polyester tape. Then, I pulled off the tape. Area of the peeled electrodeposition coating film by tape peeling A2 (mm 2 seeking), was determined paint film peeling rate on the basis of the following formula (%).
· Formula: paint film peeling rate = (A2 / A10) × 100
[0149]
　Using the following scores were evaluated relative merits of coating adhesion. In such coating film adhesion evaluation test, if the score is 3 or greater was judged to be excellent in coating film adhesion.
　5: The coating film peeling rate is less than 5%
　4: The coating film peeling rate is less than 5% to 10%
　3: coating film peeling rate is less than 10% or more 20%
　2: The coating film peeling rate is less than 20% or more 40%
　1 : the coating film peeling of 40% or more
[0150]
[Electrodeposition coating after the corrosion resistance test]
　After performing the zinc phosphate treatment as the chemical conversion treatment, to the surface treated steel sheet, a cationic electrodeposition paint made by Nippon Paint Co., electrodeposition Slope energizing voltage 160V paint and, further, to baking for 20 minutes at the baking temperature 170 ° C.. The average film thickness of the electrodeposition coating film after electrodeposition coating, either Test No. was also 8 [mu] m. Performing the electrodeposition coating, to paint evaluation surface, cutter knife (load 500 gf, 1 gf is about 9.8 × 10 -3 to samples scored with a N.), Based on JIS H 8502 Plating corrosion resistance test method ((1) salt spray (35 ℃, 2h), ( 2) drying (60 ℃, 25% RH, 4h), sequentially carried out (3) wetting (50 ℃, 98% RH, 2h) with corrosion resistance test method), and observed the width of blistering of the coating film generated at the cut portion. Test time, the above (1) to (3) as one cycle, than the paint film blister width from the cut portion at 240 cycles time, to evaluate the relative merits after electrodeposition painting corrosion resistance by using the following rating. In such electrodeposition coating after the corrosion resistance test, scores may be 3 or more, it is determined that the excellent corrosion resistance after electrodeposition coating.
　6: blister very extremely fine coating of less than 0.5mm
　5: very small coating of less than 0.5mm or 1.0mm blister
　4: fine coating of less than 1.0mm or 1.5mm blister
　3: 1. swelling coating of less than 2.0mm 5 mm
　2: swelling coating of less than 2.0mm or 3.0mm
　1: blister 3.0mm or more coating
[0151]
　Hereinafter, the details of the embodiments in the list in Table 2 to Table 9.

The scope of the claims
[Requested item 1]
A surface-treated steel sheet having a coating on at least one surface of the plated steel sheet,
the coating film,
a binder resin,
　a non-oxide ceramic particles containing V (excluding VC particles),
　and a doped zinc oxide particles wherein,
　the content relative to the coating film of the non-oxide ceramic particles and the doped zinc oxide particles containing the V is, satisfies the following equation, surface-treated steel sheet.
　　C Zn　≧ 10.0 · · ·
　　(1) C V　≦ 0.5　　· C Zn · · ·
　　(2) C V　≦ 70-C　　　Zn · · ·
　　(3) C V　≧ 0.125 · C Zn · · ·
　　(4) C V　≧ 2.0 · · · (5)
　However, C V , the content of non-oxide ceramic particles containing the V (wt%), C Zn is the doped zinc oxide It means the content of the particles (by mass%), respectively.
[Requested item 2]
　The coating film,
　containing anticorrosive pigments,
　surface-treated steel sheet according to claim 1.
[Requested item 3]
　Said binder resin is
　a water-soluble or water-dispersible aqueous resin,
　surface treated steel sheet according to claim 1 or claim 2.
[Requested item 4]
　Non-oxide ceramic particles containing the V is
　one vanadium boride particles (VB particles),
　diboride, vanadium particles (VB 2 particles), and,
　at least one selected from vanadium nitride particles (VN particles) there,
　the surface treated steel sheet according to any one of claims 1 to 3.
[Requested item 5]
　The coating film,
　a non-doped zinc oxide particles,
　magnesium oxide particles,
　calcium oxide particles, and
　at least one kind of 1.0 to 10.0 mass in total with respect to the coating film is selected from strontium oxide particles % comprising,
　a surface treated steel sheet according to any one of claims 1 to 4.
[Requested item 6]
　The coating film,
　the anticorrosive pigments containing Mg, the comprising from 5.0 to 40.0 wt% of the coating film,
　the surface treated steel sheet according to any one of claims 1 to 5.
[Requested item 7]
　The plated steel sheet is
　a zinc-plated steel sheet or an aluminum-plated steel sheet,
　surface-treated steel sheet according to any one of claims 1 to 6.
[Requested item 8]
　Made from the surface treated steel sheet according to any one of claims 1 to 7, wherein the molded material having a coated film,
　and a the coating film on the formed electrodeposition coating film,
　coating member.