[0001]The present invention (also referred to as a pre-coated steel plate or post-coated steel sheet) coated steel sheet having a zinc or zinc alloy plating layer and in the post-coating steel, excellent corrosion resistance, chemical resistance (e.g., alkali resistance, acid resistance, etc.) and molding aqueous treating agent for imparting coating adhesion parts, as well as the by the aqueous treating agent obtained, corrosion resistance, has excellent film on coating adhesion chemical resistance and molding unit, galvanized steel, zinc alloy plating steel, painted galvanized steel and painted zinc alloy plating steel, and methods for their preparation.
Background technique
[0002]
　Appliances, building materials, in the industrial fields such as automobiles, using a steel sheet which has been subjected to a pre-coated with steel manufacturer (pre-coated steel plate), cutting, techniques for manufacturing a product by molding is widely used. Coated steel sheet design of the retention is required, high coating adhesion to withstand working after severe at the end-user is required. Further, excellent corrosion resistance to withstand long-term outdoor exposure, livestock feces and cleaning agents alkali concentration environment in alkali resistance to withstand derived from such acid resistance to withstand acid rain and cleaning agents are required.
　Structure of a typical coated steel sheet, on a plated steel sheet which has been subjected to treatment for imparting coating adhesion, comprise those coated with organic coating film having a two-layer structure of the primer coating and a top coating film. To achieve corrosion resistance described above, the coating comprises a film adhesion chromate treatment to treatment for imparting, also coating material to the primer coating was contained anticorrosive pigment of chromium-based have been used conventionally. However, the environmental impact problems of hexavalent chromium in recent years chromate-free, such as those coatings is strongly desired. Although the indoor-friendly to be used under mild conditions, such as consumer electronics field is progressing chromate-free, in the outdoor-friendly products that are used under severe conditions of outdoor such as building materials, it is difficult to satisfy all the requirements of the end user in it, there is a status quo that the chromate-free is not progressing.
[0003]
　In general, coating adhesion of the coated steel sheet is evaluated by the test by bending. However, in some cases, coating adhesion under more severe working conditions, such as tests by squeezing molding is required. When processing conditions are severe, side portion or edge surface paint adhesion is subjected to a machining load is insufficient, and the like flaw portion coating peeled up turning. For severe working conditions, coating adhesion of the very high processing unit, for processing tracking of the coating film is required, as chromate-free treatment is applicable is the treating agent mainly composed of resin. However, outdoor for alkali resistance, acid resistance, since high corrosion resistance of the required level, the conventional treatment agent composed mainly of resin degradation is unavoidable when exposed to long-term corrosion environments, necessarily required thereof It is not intended to satisfy the performance to be.
[0004]
　When the plating layer composition in coated steel plate is a zinc-based zinc mainly for processing the applied and plating layer is ductile, cracks not enter the plating layer at the time of processing, a large stress to the coating film formed on the plating layer it takes. Since the stress causes the coating film peeling, the coated steel sheet to a zinc or zinc alloy plated steel sheet as a base material, and more is possible to ensure the coating adhesion after subjected to severe working such as the aperture forming process it is more difficult.
[0005]
　As chromate-free painted steel, for example, Patent Documents 1-3, a silane coupling agent and / or a hydrolytic condensation product, water dispersible silica, non-chromate metal surface treating agent comprising a zirconium compound or the like, or an acrylic resin It discloses a technique regarding further comprising a metal surface treatment agent of a water-soluble resin. According to these techniques, it is possible to impart corrosion resistance superior steel material.
[0006]
　Patent Document 4, water and, Mg, Co, Zr, Ni, and carbonate of a metal selected from Zn and Cu, and a water dispersible silica, a surface treatment agent containing a specific organic acid is disclosed there. According to the surface treatment agent, it is possible to provide machining adhesion of the coating film, excellent surface-treated steel sheet corrosion resistance.
CITATION
Patent Literature
[0007]
Patent Document 1: JP 2001-240979 Patent Publication
Patent Document 2: JP 2001-316845 Patent Publication
Patent Document 3: WO 2004/005579 Patent
Patent Document 4: JP 2004-277849 JP
Summary of the Invention
Problems that the Invention is to Solve
[0008]
　The present invention, which has excellent corrosion resistance, it is possible to form a coating having a coating adhesion of chemical resistance and molding unit, chromium-free aqueous treating agent, and having a coating, galvanized steel, it is an object to provide a zinc alloy-plated steel, painted galvanized steel and painted zinc alloy plating steel, and methods for their preparation.
Means for Solving the Problems
[0009]
　The present inventors have, includes the result of extensive studies to achieve the above object, a specific zirconium compound, an epoxy resin, a specific silanol group-containing compound, a phosphate compound, a vanadium compound, containing these by using an aqueous treatment agent satisfies a specific composition ratio for component excellent with having corrosion resistance, paint can be both coating adhesion of chemical resistance and molding unit at a high level galvanized steel and painted zinc alloy plating It found that steel is obtained, and have completed the present invention.
[0010]
　That is, the present invention is as follows.
(1) (A) ammonium zirconium carbonate, potassium zirconium carbonate, zirconium basic carbonate, and zirconium compound selected from zirconium acetate,
(B) an epoxy resin,
a silanol group-containing compound represented by (C) the following formula [I] and / or its
condensate, XY (Z) n Si (OH) 3-n · · ·
(I) (X represents a functional group derived from a glycidoxy group or a glycidoxy group, Y is an alkyl group having 1 to 10 carbon atoms the stands, Z is represents a methoxy group, an ethoxy group, or a methyl group, n represents an integer of 0 ~ 2.) (D)
phosphoric acid compound,
, (E) a vanadium compound
and an aqueous treating agent containing ,
relative to the mass in terms of Zr of the zirconium compound (a),
epoxy resin (B) solid mass ratio of the mass of [(B) / Zr] is 0.7 to 1.5,
a silanol SiO groups-containing compound and / or its condensate (C) 2 a is 0.15-1.5 solid weight ratio [SiO2 / Zr] in terms of mass,
with P reduced mass of phosphoric acid compound (D) solid weight ratio [P / Zr] is 0.025 to 0.1
in terms of solid content mass ratio [V / Zr] of 0.02 to 0.05 at V reduced mass of the vanadium compound (E) there, the water-based treatment agent.
(2) the epoxy resin is a bisphenol A type epoxy resin containing a carboxyl group, and a weight average molecular weight in terms of polystyrene by gel permeation chromatography according to the 30,000 to 150,000 (1) water treatment agent.
(3) plating layer composition Zn: on at least one surface of the galvanized steel sheet or zinc alloy plated steel sheet is 80% by mass or more, the (1) or is formed by using an aqueous treatment agent according to (2), Zr 1 ~ 40 mg / m as a coating weight 2 galvanized steel or zinc alloy plated steel with a treatment coating layer.
(4) the (3) galvanized steel or zinc alloy plated steel is the treatment film total thickness painted galvanized steel or painted with at 1 ~ 50 [mu] m a multilayer coating film comprising at least one layer on top of the layer having the described zinc alloy plated steel.
(5)
　the aqueous treatment agent according to (1) or (2), the plating layer composition Zn: 80 at least is applied on one surface of the mass% or more in a galvanized steel sheet or zinc alloy plated steel sheet, treated film layer formed,
　and dried by heating the treatment film layer, 1 ~ 40 mg / m as a Zr coating weight 2 to form a treated film layer of the method of manufacturing a galvanized steel or zinc alloy plated steel.
(6)
　the aqueous treatment agent according to (1) or (2), the plating layer composition Zn: 80 at least is applied on one surface of the mass% or more in a galvanized steel sheet or zinc alloy plated steel sheet, treated film layer formed,
　and dried by heating the treatment film layer, 1 ~ 40 mg / m as a Zr coating weight 2 to form a treated film layer of,
　further, on the treated film layer, coating the multilayer coating film of at least one layer was applied,
　the heated drying the multilayer coating film of at least one layer to form a multilayer coating film of the total thickness 1 ~ 50 [mu] m,
coated galvanized steel or method for manufacturing a coated zinc alloy plating steel.
Effect of the invention
[0011]
　Aqueous treating agent of the present invention, even though it does not contain chromium, which has excellent corrosion resistance, to form a film having a film adhesion of the chemical resistance and molding unit. Therefore, it is possible to significantly reduce the environmental impact of the coated steel plate used outdoors for. Accordingly, the aqueous treating agent of the present invention has a very large industrial value. Painted galvanized steel and painted zinc alloy plating steel of the present invention not only pre-coated steel sheet laminated coating film is subjected in advance steel manufacturer, in those after delivery of any specification of post-coating steel sheet which is applied on the user side also, it can be expected the effect of the aqueous treating agent of the present invention.
DESCRIPTION OF THE INVENTION
[0012]
　Hereinafter, the present invention will be described in detail. Aqueous treating agent of the present invention, the zirconium compound (A), and the epoxy resin (B), the silanol group-containing compound and / or its condensate (C), and phosphoric acid compound (D), vanadium compound (E) containing. The following describes each component.
[0013]
　Zirconium compound (A), ammonium zirconium carbonate, potassium zirconium carbonate, selected basic zirconium carbonate, and zirconium acetate. Zirconium compound (A) in the film-forming (printing) process, by condensation with the elimination of hydrolysis and volatile acids such as carbonic or acetic acid, at a film-forming component capable of forming a film of a three-dimensional crosslinked zirconium oxide There, processability adhesion, corrosion resistance, contributes to the expression of the chemical resistance. Also, zirconium activated by elimination of the acid, in order to firmly bonded through the plated layer surface and an oxygen atom, which contributes to adhesion expression. Operation and effect of such a zirconium compound (A), zircon hydrofluoric acid or fluoro zirconate, zirconium nitrate, not obtained by such a zirconium sulfate, zirconium oxychloride, stabilized carbonate, acetate is a volatile acid it is obtained only zirconium compounds.
[0014]
　Epoxy resin (B) is a film-forming component, a zirconium compound (A) and the silanol group-containing compound and / or its condensate (C) and complex entanglement, giving toughness and moderate processability followability to conversion film by contributing to the processability adhesion expression. Further, the formation of hydrolysis resistance is high dense coating structure, processability adhesion, chemical resistance, contributes to the expression of the corrosion resistance. The epoxy group and a hydroxyl group in the resin by reaction or hydrogen bonding effect between the organic functional groups of the layer of the laminated coating film, which contributes to adhesion expression of the upper layer. Operation and effect of the epoxy resin (B) can not be obtained in resin species other than epoxy resin. For example, the acrylic resin is not processed adhesion obtained is inferior in hard working follow-up property is film, polyurethane resin moisture or ultraviolet, not long-term corrosion resistance is obtained because the poor durability against heat, the polyester resin undergoes hydrolysis easy not alkali resistance can not be obtained.
[0015]
　Epoxy resins to be contained in the aqueous treating agent (B) of the present invention, it can be obtained by known production methods, and is not particularly limited. Epoxy resin (B) is bisphenol A commonly used for the manufacture of aqueous epoxy resin, bisphenol F, and the like novolak resins, addition reaction and condensation reaction of an epoxy compound having an epihalohydrin or glycidyl group, such as epichlorohydrin two or more the epoxy resin obtained by repeating the repeated or addition reaction can be obtained by aqueous dispersion.
[0016]
　Epoxy resin (B) may be one obtained by the modifying agent reacted epoxy group or hydroxyl group in the resin. For example, unsaturated fatty acid epoxy ester resin obtained by reacting (meth) silane reacted acrylic-modified epoxy resin obtained by reacting an acrylic acid or its ester, urethane-modified epoxy resin obtained by reacting an isocyanate compound, a silane coupling agent modified epoxy resins, such as phosphoric acid-modified epoxy resin obtained by reacting phosphoric acid or its esters. The above epoxy resin (B) may be used alone or may be used in combination of two or more thereof.
[0017]
　The the epoxy resin (B), the bisphenol A type epoxy resin containing a carboxyl group is preferable. The rigidity and appropriate flexibility derived from bisphenol A structural unit in the resin contributes to the improvement of the processing adhesion of the coating film. Furthermore, hydrolysis occurs hardly, the chemical resistance, which contributes to improvement in the corrosion resistance. Carboxyl groups in the epoxy resin, the polarity by binding strongly with the plated metal surface, which contributes to the improvement of the adhesion between the plated metal surface. Further, in the formation process of the treated film, the carboxyl groups in the epoxy resin, the zirconium compound and the silanol group-containing compound and cross-linking action, improved toughness of the treated film, chemical resistance, which contributes to improvement in the corrosion resistance. Carboxyl groups in the resin, from the viewpoint of maintaining the zirconium compound in the treating agent (A) and miscible stability, are preferably neutralized with a basic neutralizing agent. The basic neutralizing agent, in that hardly remain in the film formation process, it is more preferable to use a volatile amine or ammonia.
[0018]
　The weight average molecular weight in terms of polystyrene by gel permeation chromatography of the epoxy resin (B) is preferably 30,000 to 150,000. The weight average molecular weight by defining the above range contributes to the expression of excellent chemical resistance, also contributes to the processability adhesion, corrosion resistance of the expression.
[0019]
　The acid value of the epoxy resin (B) is not particularly limited, is preferably 10 to 40. The acid value by defining in the above range, processability adhesion treatment coating, improves the solution stability can be improved chemical resistance.
[0020]
　In aqueous treating agent of the present invention, a zirconium compound (A) Weight solids weight ratio of the mass of the epoxy resin (B) for at Zr Conversion [(B) / Zr] is an 0.7-1.5 , preferably, from 1.0 to 1.5. If it is less than 0.7, sufficient processing adhesion can not be obtained corrosion resistance, whereas, if it exceeds 1.5, sufficient processing adhesion, chemical resistance can not be obtained corrosion resistance.
[0021]
　Silanol group-containing compound as component (C) is represented by the following formula [I].
[0022]
　XY (Z) n Si (OH) 3-n · · · [I]
[0023]
　Wherein [I], X represents a functional group derived from a glycidoxy group or a glycidoxy group, Y represents an alkylene group of 1 to 10 carbon atoms, Z is represents a methoxy group, ethoxy group, or a methyl group, n represents 0 to represent two of the integer.
[0024]
　Silanol-containing compound used in the present invention is a compound obtained by hydrolyzing the organic silicon compound having a glycidoxy group. Hydrolysis of the organic silicon compound is generally water or alcohol containing water, ketone, a water-soluble organic solvent cellosolve, performed by the addition of hydrolysis aid. Hydrolysis aids are used to in the range of 3-5 pH value of the solvent used without any known is particularly limited. The hydrolysis aids such as hydrochloric acid, sulfuric acid, mineral acids such as nitric acid, acetic acid, lactic acid, tartaric acid, carboxylic acids such as citric acid. Among these, acetic acid is volatilized in the film formation process, particularly preferred in view that it is difficult to remain in the processed film.
[0025]
　The organic silicon compound having a glycidoxy group, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl methyl diethoxy silane, 3-glycidoxypropyl and methyl diethoxy silane. These compounds may be used alone or may be used in combination of two or more thereof.
[0026]
　Silanol-containing compound and / or its condensate is used in the present invention (C) is a film-forming component, complex intertwined zirconium compound (A) and the epoxy resin (B), the moderate processability and toughness to the conversion film by providing trackability, contributing to processability adhesion expression treatment film. Further, the formation of a dense film structure, contributes to the expression of the chemical resistance. Further, silanol groups (-Si-OH) is used to form a firm chemical bond -Si-O-M via the plated metal surface and oxygen atoms, it contributes to the improvement of adhesion between the plated metal surface. Functional group derived from a glycidoxy group or a glycidoxy group is responsible for maintaining the miscibility stability of zirconium compound in the treating agent (A) and epoxy resin (B). Silanol group-containing compound, ends highly active amino group or a vinyl group, if having a functional group such as methacryl group, miscibility stability of zirconium compound in the treating agent (A) and epoxy resin (B), the coercive since no, these functional groups can not be applied.
[0027]
　In aqueous treating agent of the present invention, zirconium compound silanol group-containing compound to the mass in terms of Zr of (A) and / or its condensate (C) SiO of 2 solid mass ratio in terms of mass [SiO 2 / Zr] is 0.15 to 1.5, preferably 0.2 to 1.0. If it is less than 0.15, sufficient processing adhesion can not be obtained corrosion resistance, whereas, if it exceeds 1.5, sufficient processing adhesion, chemical resistance can not be obtained corrosion resistance.
[0028]
　Phosphoric acid compound (D) and vanadium compound (E) contributes to corrosion resistance as dissolution inhibitor (corrosion inhibitor). In the corrosion of the cutting end face and the wound of the coated steel plate, first, although the anode dissolution reaction of the plated layer by sacrificial protection action takes place, and the phosphoric acid compound and the vanadium compound contained in the treated film layer during elution, the plating layer forming a zinc corrosion products eluting from inhibiting the progress of corrosion of the plated layer surface by passivation. When containing both phosphoric acid compound (D) and vanadium compound (E), is formed corrosion products having a higher electrical insulating property, and is immobilized on the plating layer surface, corrosion inhibiting effect is enhanced significantly.
[0029]
　The phosphoric acid compound (D), is not particularly limited, for example, phosphoric acid, ammonium salts of phosphoric acid, alkali metal salts of phosphoric acid, alkaline earth metal salts of phosphoric acid.
[0030]
　In aqueous treating agent of the present invention, zirconium compound phosphate compound to the mass of at Zr Conversion (A) (D) solid mass ratio of P reduced mass of the [P / Zr] is in 0.025-0.1 , preferably, it is 0.03 to 0.07. If it is less than 0.025, chemical resistance, the effect does not appear for corrosion resistance, whereas, if it exceeds 0.1, no sufficient corrosion resistance can not be obtained.
[0031]
　The vanadium compound (E), is not particularly limited, for example, vanadium pentoxide, metavanadate HVO 3 , ammonium metavanadate, oxytrichloride, vanadium VOCl 3 , vanadium trioxide V 2 O 3 , vanadium dioxide, vanadium oxysulfate VOSO 4 , vanadium oxy acetylacetonate VO (OC (= CH 2 ) CH 2 COCH 3 ) 3 , vanadium acetylacetonate V (OC (= CH 2 ) CH 2 COCH 3 ) 3 , vanadium trichloride VCl 3 and the like.
[0032]
　In aqueous treating agent of the present invention, zirconium compound, vanadium compound to the mass of at Zr Conversion (A) (E) solid mass ratio in V reduced mass of [V / Zr] is in the 0.02-0.05 preferably a 0.02-0.03. If it is less than 0.02, chemical resistance, the effect does not appear for corrosion resistance, whereas, if it exceeds 0.05, sufficient acid resistance can not be obtained.
[0033]
　Aqueous treating agent of the present invention preferably does not contain a metal component (F) nobler than zinc. Such metal components (F), for example, Fe, Co, Ni, Sn, Pb, Bi, Cu, and the like. It is preferable zirconium compound solid mass ratio in terms of metal element mass of the metal component (F) relative to the mass in terms of Zr of (A) [F / Zr] is 0.01 or less. This is because, after the metal component (F) is eluted from the treated film layer in a corrosive environment, and displace deposition galvanized layer, to promote the corrosion of the zinc plating layer, alkali resistance and acid resistance, corrosion resistance decreases This is because there is a tendency to be.
[0034]
　More (A), (B), the component of (C), (D), (E), by dissolving or dispersing in water or an aqueous solvent, it is possible to prepare an aqueous treatment agent of the present invention. Each component is adjusted to a composition ratio of specified non-volatiles excluding the solvent and volatile components (processing film). While the solvent is usually water, for the purpose of improving the drying properties of the resulting treated film layer, a small amount (e.g., less than 10% by volume of the total aqueous medium) alcohols, ketones, water-soluble organic solvent cellosolve it may be used in combination. Further, in order to form a more uniform treated layer, does not impair the effects of the present invention the surfactant to improve wettability, the additives which are customary for coating processes such as antifoaming agents to suppress foaming range in can be formulated.
[0035]
　The pH of the aqueous treatment agent of the present invention, as long as it can achieve the effect of the present invention, but particularly the never limited, is preferably in the range of 7-10. By adjusting the pH to this range, in addition to improving the storage stability, it is possible to improve corrosion resistance. Incidentally, the adjustment of the pH, volatile alkali component such as ammonia, or acetic acid, can also be used volatile acid component such as formic acid.
[0036]
　For solid concentration of the aqueous treatment agent of the present invention is not to be particularly limited as long as it can achieve the effect of the present invention, it is preferably in the range of 1 to 20 mass%. Can solid concentration of the aqueous treatment agent to form efficiently coating by in this range, also can improve the storage stability of the water-based treatment composition.
[0037]
　By using an aqueous treatment agent of the present invention, it estimates below why the process coating layer excellent in coating adhesion of chemical resistance and molding unit is obtained. However, the effect of the present invention and the present invention should not be limitatively interpreted by such estimation.
[0038]
　Aqueous treating agent of the present invention, as a main component, containing a particular zirconium compound, and an epoxy resin, and a specific silanol group-containing compound and / or its condensate.
　The zirconium compound is stabilized Jirukonimu compounds volatile acids (A) is applied, in the treatment film formed (baking) process, and three-dimensionally crosslinked by condensation with the elimination of hydrolysis or volatile acids forming a coating of zirconium oxide. Such film comprising zirconium oxide chemical resistance is very high, difficult also eluted in concentrated acid or alkali environments. However, due to its hard and brittle properties, the molding process does not follow treated film at all, it just does not paint adherence is obtained.
　Therefore, the inventors have found that as a component to impart toughness to the film, it was found that epoxy resin (B) is optimal. Epoxy resins are structurally combines rigidity and flexibility, have a high hydrolytic resistance. Further, the reaction or hydrogen bonding effect between the organic functional groups of the top coat of epoxy groups or hydroxyl groups in the epoxy resin contributes to the adhesion-expression with the multilayer coating film. Also, cross-linked with the zirconium compound to form a compact structure. Therefore, the epoxy resin by blending in the appropriate ratio to the zirconium compound, without reducing the high chemical resistance of zirconium oxide film, is inferred that it was possible to impart toughness to the film.
[0039]
　Furthermore, in order to impart adhesiveness to withstand molding processing, it is necessary to mix the silanol-containing compound and / or its condensate. The silanol group-containing compound, compounds known as silane coupling agents are generally known, the molecular terminus of silanol groups (-Si-OH) are oriented in the vicinity of the material, via the plated metal surface and oxygen atoms - to form a strong chemical bond of Si-O-M, it is firmly adhered. Organic functional group of opposite ends contribute to adhesion expression of the multilayer coating film. However, when applying a silane coupling agent commonly used, it is very high reactivity of the terminal organic functional group, mixing stability of zirconium compound in the treating agent (A) and epoxy resin (B) sex can not be maintained. The present inventors have found that the silanol group-containing compound containing an organic functional group to work most effectively in order to impart adhesion and miscibility stability is derived from a glycidoxy group or a glycidoxy group and / or its condensate It was found to be (C). Glycidoxy groups can keep mixing stability for poor reactivity, also, adhesion between the multilayer coating film through hydrogen bonding, with moderate flexibility, plated metal surfaces from silanol groups derived from the organic group It could also confer adhesion.
[0040]
　Mixing ratio of the zirconium compound and the silanol group-containing compound is also important. Silanol-containing compound itself is concentrated acid, easily eluted under alkaline environment, chemical resistance and the amount of the silanol group-containing compounds is excessive decreases, suitable silanol-containing compound to a zirconium compound by blending in a ratio, a silanol group and zirconium crosslinked three-dimensionally, to infer the elution of the silanol group-containing compound can be suppressed.
　Above, a specific zirconium compound, an epoxy resin, a specific silanol group-containing compound and / or its condensate, a by blending in a specific ratio, chemical resistance, excellent coating adhesion of the molded part It estimates that it was possible to form a treated film layer.
[0041]
　It will now be described galvanized steel and zinc alloy plating steel having a treated film layer formed by using an aqueous treatment agent of the present invention.
[0042]
　The aqueous treating agent of the present invention, the plating layer composition Zn: can be applied to 80 wt% or more in a galvanized steel sheet or zinc alloy plated steel sheet. As the galvanized steel and zinc alloy plating steel, it may be a known galvanized steel sheet and zinc alloy-plated steel sheet. For example, hot-dip galvanized steel sheet, galvannealed steel sheet, electro-galvanized steel sheet, molten Zn-Al plated steel sheet, hot-dip Zn-Al-Mg plated steel sheet, an electric Zn-Ni plated steel sheet and the like.
[0043]
　Prior to forming the treatment film layer with the aqueous treatment agent of the present invention, although not necessarily normal, oil adhering to the treated metal materials, to remove dirt, cleaning with degreasing agent, washed with hot water, acid washing, can be carried out alkali washing, a combination of such solvent washing appropriately. In the cleaning of the metal surface, it is preferable that the cleaning agent is rinsed after washing so as not to remain on the metal surface.
[0044]
　Galvanized steel or zinc alloy plated steel material treated film layer of the present invention, after contacting the aqueous treating agent of the present invention in coated steel sheet, is formed on the surface and dried by heating without rinsing.
[0045]
　As the contact method of the aqueous treatment agent of the present invention is not particularly limited, for example, a roll coater method, dipping method, and a known method such as spraying. As heat drying method is not particularly limited, a hot-air furnace, induction furnace, heat drying by an electric furnace is preferred. As the arrival temperature of the steel sheet during drying is not particularly limited, preferably 50 ~ 0.99 ° C..
[0046]
　By contact with an aqueous treatment agent of the present invention, the coating amount of galvanized steel or zinc alloy plated steel material to form a treatment coating layer, 1 ~ 40 mg / m as a Zr coating weight 2 is, preferably, 5 ~ 30 mg / M 2 is. Zr coating weight of 1 mg / m 2 can not obtain the effect of the treatment film layer is less than, 40 mg / m 2 and formed film exceeds becomes susceptible to cohesive destruction, processability adhesiveness is lowered.
[0047]
　Painted galvanized steel or painted zinc alloy plating steel of the present invention, on the treatment film layer with galvanized steel or zinc alloy plated steel material, those having a multilayer coating film comprising at least one layer, typically precoated steel sheet and it refers to the painted steel sheet called post-coated steel sheet. The total thickness of the multilayer coating film of the coated galvanized steel or painted zinc alloy plating steel of the present invention is 1 ~ 50 [mu] m. By adjusting the film thickness in this range, it is possible to improve chemical resistance, corrosion resistance, processability adhesion.
[0048]
　There is no particular restriction on the structure of the multilayer coating film, the outdoor-friendly for use in harsh conditions, on the treated film layer, an intermediate coating layer in formulated with anticorrosive pigment for the purpose of improving corrosion resistance are stacked, it can be applied further on a structure formed by laminating a top coat layer obtained by blending a coloring pigment for the purpose of design imparting its. The Indoor used under relatively mild conditions, on the treated film layer to form a top coat layer for the purpose of design properties imparted without using the intermediate coating layer in blended anticorrosive pigments or anything structures, can be applied as functional pigments to form a coating film containing a combination structure such as a conductive pigment. The anticorrosive pigment can be a known chromate-free pigments, such as zinc phosphate, iron phosphate, aluminum phosphate, phosphoric acid-based rust preventive pigment, calcium molybdate, magnesium phosphate, molybdate aluminum, molybdate anticorrosive pigments such as barium molybdate, vanadium oxide, vanadium anticorrosive pigments such as calcium vanadate, water-dispersible silica, fine silica anticorrosive pigments such as fumed silica.
[0049]
　The coloring pigment may be a known inorganic and organic colored pigments, such as inorganic coloring as a pigment titanium oxide (TiO 2 ), zinc oxide (ZnO), zirconium oxide (ZrO 2 ), calcium carbonate (CaCO 3 ), barium sulfate (BaSO 4 ), alumina (Al 2 O 3 ), kaolin clay, carbon black, iron oxide (Fe 2 O 3 , Fe 3 O 4 , etc.), Hansa as organic color pigments, pyrazolone orange, azo such as system pigment, and the like.
[0050]
　Regarding the method for forming a multilayer coating film is not particularly limited. For example, a roll coater method, dipping method, after contacting the paint by a known method such as spraying method, a hot-air furnace, an induction heating furnace, by a known method such as an electric furnace include forming method of repeating the step of performing heating and drying. The arrival temperature of the steel sheet during drying is not particularly limited, preferably 80 ~ 250 ° C..
Example
[0051]
　The following examples illustrate the present invention by, but the present invention is not limited by these examples.
[0052]

　Preparation (No.1 ~ 31 and 35-39) the aqueous treating agent 1
　combination of raw materials shown in Table 1, under the compounding ratio, the components (A is selected from the following in deionized water ) was added ~ to (F) sequentially to give example for aqueous treating agent (No.1 ~ 14,35 ~ 38) and comparative examples for the aqueous treating agent (No.15 - 31, 39). Adding deionized water was adjusted to a nonvolatile content becomes 7 wt%.
[0053]
A1: ammonium zirconium carbonate
　A2: Zirconium Acetate
　a1: Jirukonfu' ammonium
[0054]

　B1: carboxyl group-containing bisphenol type epoxy resin
　200 parts by weight of bisphenol A type liquid epoxy resin in the reaction vessel, 30 parts by weight of polyethylene glycol diglycidyl Jiri ether, were charged 80 parts by mass of butyl cellosolve, nitrogen reflux and stirring lower, was dissolved by heating to 100 ° C., was added triethylamine 3 parts by weight, was allowed to react for 5 hours at 120 ° C.. Then, 30 parts by weight of butyl acrylate, 10 parts of acrylic acid, 10 parts of methyl methacrylate, styrene 25 parts by mass, and a mixed solution of butyl cellosolve 30 parts by weight, using a dropping funnel was added dropwise over 2 hours. After completion of the dropwise addition, heating was continued, nitrogen reflux and agitated for 4 h. After cooling to 80 ° C., 10 parts by weight of triethylamine were mixed deionized water 580 parts by mass. The weight average molecular weight of the obtained carboxyl group-containing bisphenol A type epoxy resin (B1) molecular weight 61,000, acid value was 20 mgKOH / g.
[0055]
　B2: carboxyl-containing bisphenol type epoxy resin
　200 parts by weight of bisphenol A type liquid epoxy resin in the reaction vessel, 30 parts by weight of polyethylene glycol diglycidyl Jiri ether, were charged 80 parts by mass of butyl cellosolve, nitrogen reflux-stirring, to 100 ° C. heating after dissolved, was added triethylamine 5 parts by weight, it was allowed to react for 5 hours at 120 ° C.. Then, 100 parts by weight of bisphenol A type liquid epoxy resin was continued for 4 hours heating and nitrogen reflux, stirred with 80 parts by mass of methyl isobutyl diketimine. After then cooling to 80 ° C. by adding 50 parts by mass of methyl isobutyl diketimine, 10 parts by weight of triethylamine were mixed 550 parts by weight of deionized water. The weight average molecular weight of the obtained carboxyl-containing bisphenol type epoxy resin (B2) molecular weight 18,000, acid value was 25 mg KOH / g.
[0056]
　B3: carboxyl group-containing bisphenol type epoxy resin
　200 parts by weight of bisphenol A type liquid epoxy resin in the reaction vessel, 30 parts by weight of polyethylene glycol diglycidyl Jiri ether, were charged 80 parts by mass of butyl cellosolve, nitrogen reflux-stirring, and heated to 100 ° C. after dissolution, triethylamine was added 5 parts by weight, was allowed to react for 5 hours at 120 ° C.. Then, 30 parts by weight of butyl acrylate, 20 parts acrylic acid, 10 parts of methyl methacrylate, styrene 25 parts by mass, and a mixed solution of butyl cellosolve 30 parts by weight, using a dropping funnel was added dropwise over 2 hours. After completion of the dropwise addition, heating was continued, nitrogen reflux, stirred for 4 hours. After cooling to 80 ° C., 10 parts by weight of triethylamine were mixed deionized water 560 parts by mass. The weight average molecular weight of the obtained carboxyl group-containing bisphenol A type epoxy resin (B3) molecular weight 84,000, acid value was 41mgKOH / g.
[0057]
　B4: carboxyl group-containing bisphenol type epoxy resin
　200 parts by weight of bisphenol A type liquid epoxy resin in the reaction vessel, 30 parts by weight of polyethylene glycol diglycidyl Jiri ether, were charged 80 parts by mass of butyl cellosolve, nitrogen reflux-stirring, and heated to 100 ° C. after dissolution, the addition of 0.5 part by weight of triethylamine, was reacted for 5 hours at 120 ° C.. Then, 30 parts by weight of butyl acrylate, 10 parts of acrylic acid, 10 parts of methyl methacrylate, styrene 25 parts by mass, and a mixed solution of butyl cellosolve 30 parts by weight, using a dropping funnel was added dropwise over 2 hours. After completion of the dropwise addition, heating was continued, nitrogen reflux, stirred for 4 hours. After cooling to 80 ° C., 10 parts by weight of triethylamine were mixed deionized water 580 parts by mass. The weight average molecular weight of the obtained carboxyl group-containing bisphenol A type epoxy resin (B4) molecular weight 22,000, acid value was 26 mg KOH / g.
[0058]
　B5: carboxyl group-containing novolac type epoxy resin
　200 parts by weight novolak type liquid epoxy resin in the reaction vessel, 30 parts by weight of polyethylene glycol diglycidyl Jiri ether, were charged 80 parts by mass of butyl cellosolve, nitrogen reflux-stirring, dissolved by heating to 100 ° C. after triethylamine was added 3 parts by weight, it was allowed to react for 5 hours at 120 ° C.. Then, 30 parts by weight of butyl acrylate, 10 parts of acrylic acid, 10 parts of methyl methacrylate, styrene 25 parts by mass, and a mixed solution of butyl cellosolve 30 parts by weight, using a dropping funnel was added dropwise over 2 hours. After completion of the dropwise addition, heating was continued, nitrogen reflux, stirred for 4 hours. After cooling to 80 ° C., 10 parts by weight of triethylamine were mixed deionized water 580 parts by mass. The weight average molecular weight of the obtained carboxyl group-containing novolac type epoxy resin (B5) molecular weight 33,000, acid value was 28 mg KOH / g.
[0059]
　b1: polyurethane resin
　in the reaction vessel, 1,6-hexanediol and the polyester polyol 66 parts by weight obtained by reacting adipic acid and terephthalic acid, 44 parts by weight of dicyclohexylmethane 4,4'-diisocyanate, dimethylol 6 parts by weight of propionic acid, N- methyl-2-pyrrolidone 30 parts by mass of the nitrogen reflux-stirring, the urethane prepolymer obtained by reaction for 5 hours while maintaining the 70 ° C., triethylamine 4 parts by mass was added, It reacted for 30 minutes at 30 ° C. to obtain an anionic urethane prepolymer. Then, after emulsification-dispersed in deionized water 110 parts by mass, it continued 10 hours at 40 ° C., to obtain an anionic polyurethane resin emulsion.
[0060]
　b2: Acrylic resin
　100 parts by weight of deionized water in a reaction vessel, the reactive surfactant (manufactured by Aqualon KH-10 from Dai-ichi Kogyo Seiyaku Co.,) 3 parts by weight, nitrogen reflux-stirring and heated to 50 ° C.. Then, 20 parts by weight of butyl acrylate, 2 parts by weight of acrylic acid, 15 parts by weight of methyl methacrylate, and a monomer mixture solution of styrene 13 parts by weight, 0.2 part by weight of ammonium persulfate, and a mixture of ion-exchanged water 4 parts by weight , respectively, using a dropping funnel was added dropwise over 2 hours. After completion of the dropwise addition, heating was continued, nitrogen reflux, stirred for 3 hours. It cooled to 30 ° C., continuing the stirring for 5 hours to obtain an acrylic resin emulsion (b2).
[0061]
　b3: polyester resin
　in the reaction vessel, terephthalic acid (41 mol%), isophthalic acid (40 mol%), total acid component 1mol consisting of dimethyl isophthalate-5-sodium sulfonate (2 mol%) and trimellitic anhydride (17 mol%) If, ethylene glycol (90 mol%) and the total amount of the alcohol component of 2mol consisting of trimethylolpropane (10 mol%), placed in a calcium acetate 0.25g and N- butyl titanate 0.1g as a catalyst, nitrogen reflux, in the system It stirred and melted the contents were heated to 180 ° C.. After heating to 200 ° C., and continued for about 2 hours stirring, was carried out esterification or transesterification. Then heated to 260 ° C., under reduced pressure in the system until 0.5mmHg after about 15 minutes to about 3 hours polycondensation reaction. After completion of the reaction, allowed to cool under nitrogen introduction, the contents were taken out. The appropriate amount of aqueous ammonia and deionized water final pH in the retrieved content is 6-7 was added, in an autoclave, and heated and stirred for 2 hours at 100 ° C., the solids in the final deionized water 30% to obtain a polyester resin (b3) adjusting the aqueous emulsion.
[0062]
C1: 0.02 parts by weight acetic acid in 80 parts of deionized water, 3-glycidoxypropyltrimethoxysilane 25 parts by mass was added, by stirring for 2 hours at 25 ° C. to give a silanol group-containing compound (C1).
[0063]
　C2: 0.02 parts by weight acetic acid in 60 parts of deionized water, ethanol 20 parts, 3-glycidoxypropyl triethoxysilane 25 parts by mass of the silanol group-containing compound by stirring for 2 hours at 60 ° C. (C2) was obtained.
[0064]
　C3: 0.02 parts by weight acetic acid in 60 parts of deionized water, 20 parts by weight of isopropyl alcohol, 3-glycidoxypropyl methyldimethoxysilane 25 parts by mass of the silanol group-containing by stirring for 2 hours at 60 ° C. to give the compound (C3).
[0065]
　c1: N-2- (aminoethyl) in 70 parts of deionized water aminopropyl triethoxysilane 30 parts by weight was added, resulting silanol-containing compound (c1) by stirring for 2 hours at 25 ° C. It was.
[0066]
D1: phosphate
　D2: ammonium dihydrogen phosphate
[0067]
E1: vanadyl oxalate
　E2: ammonium metavanadate
[0068]
F1: Nickel nitrate
[0069]
　The preparation of the aqueous treating agent 2 (No.32)
　to prepare an aqueous treatment composition according for the comparative example to the embodiment of the Patent Document 1.
　In 1 liter of deionized water, .gamma. 1.5 parts by weight aminopropyltriethoxysilane, water-dispersible silica; a (Snowtex N made by Nissan Chemical Industries, Ltd.) 0.5 parts by mass, a zirconium ammonium carbonate of zirconium ions in terms 0.02 part by mass, to obtain the aqueous treating agent (No.32).
[0070]
　Preparation of the aqueous treating agent 3 (No.33)
　to prepare an aqueous treatment composition according for the comparative example to the embodiment of Patent Document 4.
　100 parts by weight of deionized water, 25 parts by weight of ammonium zirconium carbonate, water-dispersible silica (Snowtex N; manufactured by Nissan Chemical Industries, Ltd.) 25 parts by weight, were mixed tartaric acid 5 parts by weight, the aqueous treating agent (No.33) Obtained.
[0071]
　Preparation of the aqueous treating agent 4 (No.34)
　is applied chromate agent ZM-1300AN (Japan Pas - mosquito manufactured Rising Corporation) was used as a comparative example. This is an example of the prior art chromate treatment composition.
[0072]

　S1: Polyester resin 70 parts by weight 10 parts by weight of a melamine resin, zinc-based anticorrosive pigment 5 parts by weight of phosphoric acid, 5 parts by mass of magnesium phosphate anticorrosive pigment, tripolyphosphate dihydrogen aluminum 5 mass parts and modified silica 5 parts by weight were mixed to obtain a intermediate coating.
[0073]

　T1: Polyester resin 60 parts by weight 15 parts by weight butylated melamine resin, a mixture of 10 parts by weight of titanium oxide and carbon black 15 parts by weight, to obtain a top coat paint.
[0074]
1. Material
　M1: galvanized steel sheet
thickness 0.6 mm, coating weight per side 40 g / m 2 (two-sided
　plating) M2: galvanized steel sheet
thickness 0.6 mm, coating weight per side 20 g / m 2 (two-sided plating )
　M3: galvannealed steel sheet
thickness 0.6 mm, coating weight per side 45 g / m 2 (two-sided
　plating) M4: molten Zn-11% Al-3% Mg-0.2% Si alloy-plated steel
plate thickness 0.6 mm, the coating weight per side 40 g / m 2 (two-sided
　plating) M5: electrical Zn-Ni plated steel sheet
thickness 0.6 mm, the coating weight per side 20 g / m 2 (two-sided plating)
[0075]
　2. Pretreatment
　alkaline degreasing agent at a FC-E6406 - Concentration (Japan Pas mosquito Rising Co.) was 20 g / L, the variety of steel sheet at a temperature 60 ° C. was sprayed for 10 seconds, was degreased. Then, after washing with tap water, squeezed with a draining roll, and dried with hot air.
[0076]
　3. Formation of treated film layer
　as shown in Table 2, Zr coating weight (Cr: represents the Cr deposition amount) so that a predetermined amount, on the surface of various steel plates after the pretreatment, the water using a bar coater treatment agent was applied. It was then heated and dried so that peak metal temperature is 80 ° C. in a hot air drying furnace.
[0077]
　4. Formation of intermediate coating film layer
　after the formation of the treated film layer, the intermediate coating was applied using a bar coater to a dry thickness of 5 [mu] m. Then, peak metal temperature in the hot air drying furnace heated drying such that the 210 ° C..
[0078]
　5. Formation of the topcoat coating layer
　after forming the intermediate coating layer, said top coat paint was applied with a bar coater to a dry thickness of 15 [mu] m. Then, peak metal temperature in the hot air drying furnace heated drying such that the 220 ° C..
[0079]
1. Bending adhesion
　after each test plate was immersed for 2 hours in boiling water, subjected to 0T bending test pinch the inner spacers to according to each test plate in the test method of JIS-G3312 at 20 ° C., after tape peeling the coating film peeling state was visually observed and evaluated according to the following criteria.
[0080]

◎: No peeling
○: less than peeling area 10%
△: peeled area 10% or more but less than 50%
×: Peeling area of 50% or more
[0081]
　2. Drawing adhesion
　drawing ratio: 2.0, blank holder pressure: after deep drawing at 0.5 t, putting a cutter flaws reaching the metal base material to the side surface portion "X" type, 1 in boiling water after time dipping, I stuck the tape to the "X" type flaw part. Then, to observe the coating film peeling state with the naked eye peeling the tape was evaluated according to the following criteria.
[0082]

◎: no peeling
○: peeling of less than 2mm from the cut portion
△: peeling of less than 10mm than 2mm more than the cut
×: peeling of 10mm or more than the cut part
[0083]
　3. Alkali resistance
　after immersion for 24 hours at room temperature the test panels to 5 mass% sodium hydroxide aqueous solution, to observe the size and generation density of the generated blisters with the naked eye was evaluated for alkali resistance in accordance with the following criteria.
[0084]

◎: No blister.
○: less than one blister 1.0 mm, and generation density of F.
△: a single blister 1.0mm or more, and generation density of F. Or, in less than 1.0mm size of one blister, and generation density of M.
×: This type is 1.0mm or more magnitude of one blister, and generation density of M. Or, generation density regardless of the size of the blister is D.
[0085]
　Generation density of blisters evaluated as defined in ASTM D 714, the symbols used have the following meanings.
F: Blister density less
M: blister density Medium
D: blister density dense
[0086]
　4. Acid resistance
(1) sulfuric acid test
　after each test plate was immersed for 24 hours at room temperature 5% by weight aqueous solution of sulfuric acid, the size and generation density of generated blister was observed with the naked eye, evaluated in the same criteria and alkali resistance It was carried out.
[0087]
(2) hydrochloric acid test
　after each test plate was immersed for 24 hours at room temperature 5% by weight aqueous hydrochloric acid, the size and generation density of generated blister was observed with the naked eye, and evaluated by the same criteria and alkali resistance It was.
[0088]
　5. Corrosion
　for each test plate was cut into 150 mm × 70 mm, while exposing the cut edge of the longitudinal section, and 200 cycles of a defined combined cycle test JASO M609-91. Coating blister width (maximum value) was measured from the cut end face was evaluated according to the following criteria.
[0089]

◎: less than 2mm
￮: less than 2mm more than 5 mm
△: 5 mm or more 10mm less than
×: 10mm or more
[0090]
　6. Storage stability
　of each aqueous treatment agent shown in Table 1 was allowed to stand for 30 days at 40 ° C.. Then, to evaluate the respective aqueous treating agent according to the following evaluation criteria.
[0091]

◎: No change
○: a very small amount of precipitation was observed.
△: a small amount of precipitation was observed, the viscosity is increased.
×: a large amount of precipitate or seen, or gelled.
[0092]

　As shown in Table 2, Examples 1 to 24 is coated zinc and zinc alloy plated steel sheet having a treated film layer of the present invention, processability adhesion (bending adhesion, drawing adhesiveness, etc.) , chemical resistance (alkali resistance, acid resistance, etc.), showed excellent results in all of the performance of corrosion resistance, showed equivalent performance to Comparative example 21 is a chromate-based. Also, all of the aqueous treating agent used in Examples 1 to 24 were superior in storage stability.
[0093]
　Comparative Example does not contain a zirconium compound (A) 1, the processing adhesion, corrosion resistance, markedly inferior any chemical resistance. In Comparative Example 2 containing range of the zirconium compound of the present invention in place of the zirconium compound (A), the processing adhesion, and corrosion resistance was remarkably inferior.
[0094]
　Comparative Example not containing an epoxy resin (B) 3, all of the performance is insufficient. Further, Comparative Examples 4 and 5 containing the outside of the resin of the present invention instead, processability adhesion, corrosion resistance, chemical resistance and the like is insufficient.
[0095]
　Comparative Example does not contain the silanol group-containing compound (C) 6 are significantly inferior processability adhesion. In Comparative Example 7 including the range of the silanol group-containing compound of the present invention instead, processability adhesion and corrosion resistance was insufficient.
[0096]
　Comparative Example 8 not containing phosphate compound (D), Comparative Example 9 containing no vanadium compound (E) is the corrosion resistance was insufficient.
[0097]
　Comparative Example compounding ratio of the epoxy resin (B) is outside the range of the present invention 10 and 11, the processing adhesion and corrosion resistance was insufficient.
[0098]
　Comparative Example blending ratio is outside the range of the present invention of the silanol group-containing compound (C) 12, 13 are processed adhesion and corrosion resistance was insufficient.
[0099]
　Comparative Example 14 and 15 blending ratio of phosphoric acid compound (D) is outside the range of the present invention, corrosion resistance was extremely inferior.
[0100]
　The blending ratio of the vanadium compound (E) is a comparative example 16 and 17 is outside the scope of the present invention, corrosion resistance was extremely inferior.
[0101]
　Comparative Example Zr coating weight is outside the range of the present invention 18, the processing adhesion and corrosion resistance was remarkably inferior.
[0102]
　In Comparative Example 19 and 20 according to the Patent Document 1 and 4 as the prior art, processing adhesion, corrosion resistance, either chemical resistance was insufficient.
[0103]
[Table 1]

[0104]
[Table 2]

claims

[Claim 1](A) ammonium zirconium carbonate, potassium zirconium carbonate, zirconium basic carbonate, and zirconium compound selected from zirconium acetate,
　(B) an epoxy resin,
　(C) a silanol group-containing compound represented by the following formula [I] and / or
　　　　　　condensates, XY (Z) n Si (OH) 3-n · · ·
(I) (X represents a functional group derived from a glycidoxy group or a glycidoxy group, Y represents an alkylene group having 1 to 10 carbon atoms, Z represents a methoxy group, an ethoxy group, or a methyl group, n represents an integer of 0 ~ 2.)
　(D) phosphoric acid compound,
　, (E) a vanadium compound
and an aqueous treating agent containing,
　zirconium compounds to the mass of at Zr conversion (a),
epoxy resin (B) solid mass ratio of the mass of [(B) / Zr] is 0.7 to 1.5,
　a silanol group-containing Containing compound and / or its condensate (C) SiO of 2 solid mass ratio in terms of mass [SiO 2 / Zr] is 0.15 to 1.5,
　with P reduced mass of phosphoric acid compound (D) solid weight ratio [P / Zr] is 0.025 to 0.1
　in terms of solid content mass ratio [V / Zr] of 0.02 to 0.05 at V reduced mass of the vanadium compound (E) there,
the water-based treatment agent.
[Claim 2]
　The epoxy resin (B) is a bisphenol A type epoxy resin containing a carboxyl group, and an aqueous of claim 1 the weight average molecular weight in terms of polystyrene by gel permeation chromatography is 30,000 to 150,000 Processing agent.
[Claim 3]
　Plating layer composition Zn: on at least one surface of the galvanized steel sheet or zinc alloy plated steel sheet is 80 wt% or more, it is formed using aqueous treating agent according to claim 1 or 2, 1 ~ 40 mg of Zr coating weight / m 2 galvanized steel or zinc alloy plated steel material with a treatment coating layer.
[Claim 4]
　Painted galvanized steel or painted zinc alloy plating steel having a multilayer coating film comprising at least one layer on top of the treatment film layer with a total thickness of 1 ~ 50 [mu] m having the galvanized steel or zinc alloy plated steel material according to claim 3 .
[Claim 5]
　The aqueous treating agent according to claim 1 or 2, plating layer composition Zn: 80 at least applied to one side of a mass% or more in a galvanized steel sheet or zinc alloy plated steel sheet, to form a treated film layer,
　wherein the treatment film dried by heating the layer, 1 ~ 40 mg / m as a Zr coating weight 2 to form a treated film layer of the method of manufacturing a galvanized steel or zinc alloy plated steel.
[Claim 6]
　The aqueous treating agent according to claim 1 or 2, plating layer composition Zn: 80 at least applied to one side of a mass% or more in a galvanized steel sheet or zinc alloy plated steel sheet, to form a treated film layer,
　wherein the treatment film dried by heating the layer, 1 ~ 40 mg / m as a Zr coating weight 2 to form a treated film layer of,
　further, on the treated film layer is coated with a multilayer coating film for coating at least one layer,
　said at least dried by heating the multilayer coating film of the first layer to form a multilayer coating film of the total thickness 1 ~ 50 [mu] m,
method for manufacturing a coated galvanized steel or painted zinc alloy plating steel.