Technical field [0001] 　The present invention, corrosion resistance, adhesion to a top coating, blackening resistance, and a process of good galvanized steel sheet surface adhesion to the structural adhesive. Background technique [0002] 　Zinc-plated steel sheet building materials, has been applied automobile, to a wide range of applications such as consumer electronics products. [0003] 　Generally, a method of a coating formed by a surface treatment agent to the zinc-based plated steel sheet, as a technique for imparting such corrosion is subjected to chromate treatment with a treating solution containing chromic acid, bichromate or their salts as the main component, method of applying a phosphate treatment, a method of applying an inorganic metal coating process, are known a method of applying an organic resin coating treatment, it has been put to practical use. [0004] 　The mainly technology using an inorganic component, in Patent Document 1, a vanadium compound, zirconium, titanium, molybdenum, tungsten, metal surface treatment agent containing a metal compound containing at least one metal selected from manganese and cerium It is mentioned. Further, in Patent Document 2, the basic zirconium compound, vanadyl-containing compound, phosphoric acid compound, cobalt compound, the composite coating-treated zinc-containing plated steel material is exemplified using a treatment solution containing an organic acid and water. [0005] 　Primarily as a technique of using an organic resin coating treatment, in Patent Document 3, an anionic water-dispersible resin on a metal material surface treatment agent comprising an alkali metal silicate, the patent document 4, ammonium zirconium carbonate, tetravalent vanadium compound, an organic phosphonic acid, a surface treating agent comprising an anionic water-dispersible acrylic resin is disclosed. [0006] 　Zinc has excellent corrosion resistance - a coating provided by a surface treatment agent to the aluminum alloy plated steel sheet, as a technique for improving resistance to corrosion, and the like, in Patent Document 5, a zirconium compound on Zn-Al-Mg-Si alloy plating, vanadium compound zinc is provided a film made of - aluminum alloy plated steel sheet, the patent document 6, on Zn-Al alloy plating, vanadium compound, phosphoric acid compound, a metal component, the configured acrylic resin with a specific monomer component zinc - aluminum alloy coated steel sheet is disclosed. [0007] 　However, these techniques are planar portion corrosion resistance, processing unit corrosion resistance, adhesion to a top coat, poor blackening resistance, in particular, not to satisfy the adhesion between the structural adhesive, problems in practical use ing. Is the surface treatment agent develop totally satisfactory galvanized steel sheet is strongly required in this order a wide variety of applications. CITATION Patent Literature [0008] Patent Document 1: JP 2002-30460 JP Patent Document 2: WO2007 / 123276 Patent Document 3: WO2007 / 069783 Patent Document 4: WO2009 / 004,684 Patent Document 5: JP 2003-55777 JP Patent Document 6: JP 2005 -097,733 JP Summary of the Invention Problems that the Invention is to Solve [0009] 　The present invention is to solve the above problems of the prior art, corrosion resistance, adhesion to a top coating, a surface treatment agent of the galvanized steel sheet satisfying all of adhesion to the blackening resistance, and structural adhesives it is an object to provide a. Means for Solving the Problems [0010] 　When the inventors of the present invention to achieve this objective is further examined by using the zirconium carbonate compound, and a specific acrylic resin, a vanadium compound, a phosphorus compound, a water-based surface treatment agent containing a cobalt compound, zinc was coated on a system plated steel sheet, it found that can achieve the above object by using the heated dry surface treated steel sheet, and have completed the present invention. [0011] 　That is, the present invention provides the following. (1) zirconium carbonate compound (A), copolymerization of a monomer component comprising at least styrene and (b1) (meth) acrylic acid (b2) and (meth) acrylic acid alkyl ester (b3) and acrylonitrile (b4) a resin obtained from that, the amount of acrylonitrile (b4) is, based on the solid weight of the total monomer components of the resin is 20-38 wt%, and a glass transition temperature of -12 ~ 15 ° C. and the water-soluble resin and an aqueous emulsion resin is a acrylic resin (B), 2 ~ 4-valent vanadium compound (C), and the phosphorus compound (D), a cobalt compound and (E), and water, and blended it is pH 8 ~ 11, zinc-plated steel sheet for processing agents. (2) the 20 to 60 mass% blending amount relative to the total solid content of the surface treatment agent of the acrylic resin (B), 　and the mass when converted the vanadium compound (C) in V, the zirconium carbonate compound the (a) the mass ratio [(V) / (Zr)] 0.07 to 0.69 mass when converted into Zr, 　and the mass when the phosphorus compound (D) in terms of P the zirconium carbonate compound (a) and the mass ratio [(P) / (Zr)] 0.04 to 0.58 mass when converted into Zr, 　converted the cobalt compound (E) to Co the mass ratio of the mass and the zirconium carbonate compound when the (a) and mass when converted into Zr [(Co) / (Zr)] is from 0.005 to 0.08 according to (1) zinc-plated steel sheet for surface-treating agent. (3) the amount of each monomer component of the acrylic resin (B), based on the solid weight of the total monomer components of the resin, styrene (b1) is 15 to 25 wt%, (meth) acrylic acid (b2) There 1 to 10 mass%, (meth) acrylic acid alkyl ester (b3) is from 40 to 58 wt%, wherein (1) or zinc-plated steel sheet for surface-treating agent according to (2). (4) zinc-based plating layer of the galvanized steel sheet, in addition to zinc and unavoidable impurities, 60 wt% or less of Al, 10 mass% of Mg, 2 wt% of one or more of the following Si also be compositions contain the (1) to galvanized steel sheet for surface treatment agent according to (3). (5) at least a portion of the phosphorus compound (D) is an inorganic phosphoric acid and / or salts thereof, surface treatment agent according to (1) to (4). Effect of the invention [0012] 　The present invention, corrosion resistance, adhesion to a top coating, a surface treatment agent of the galvanized steel sheet satisfying all of adhesion to the blackening resistance, and structural adhesives. DESCRIPTION OF THE INVENTION [0013] 　Hereinafter, the present invention will be specifically described. [0014] 　Aqueous surface-treating agent used in the present invention zirconium carbonate compound (A) as one starting material. Zirconium carbonate compound (A), disconnected carbonate ions when forming the coating film, zirconium bonded to each other through an oxygen barrier property of the film is increased by high molecular weight. Also, zirconium carbonate compound undergoes a crosslinking reaction with the acrylic resin (B), it is possible to increase the barrier properties of the coating. Type of zirconium carbonate compound (A) is not particularly limited, for example, zirconium carbonate, ammonium zirconium carbonate, potassium zirconium carbonate, etc. sodium zirconium carbonate and the like, can be used one or more of these. Among them, zirconium carbonate, and ammonium zirconium carbonate preferable because corrosion resistance is excellent. [0015] 　Aqueous surface-treating agent used in the present invention as one raw material of acrylic resin (B). Acrylic resin is believed to high molecular weight by a regular arrangement and the zirconium carbonate (A), that confers a property that the organic-based film has usually a zirconium coating sparingly soluble. In particular, it is possible to express the performance necessary for adhesion to the acrylic resin has characteristics derived from the monomer components constituting is granted, the structural adhesives in molecular weight was coated by ordered array . The content of the acrylic resin (B) it is preferred that the total solid content of the surface treatment agent is 20 to 60 mass%. More preferably 20 to 40 mass%. If less than 20 wt%, the adhesion is lowered, if it exceeds 60 wt%, corrosion resistance decreases. [0016] 　Acrylic resin (B) is at least styrene (b1), and (meth) acrylic acid (b2), (meth) acrylic acid alkyl ester (b3), copolymerizing a monomer component comprising acrylonitrile (d4) a resin obtained from the amount of acrylonitrile (b4) is, based on the solid weight of the total monomer components of the resin is 20-38 wt%, and a glass transition temperature of -12 ~ 15 ° C. it is a water-soluble resin and an aqueous emulsion resin. Here, acrylonitrile (b4) other than, the monomer component as a raw material (composition), with respect to the total mass of the total monomer component, styrene (b1) 15 ~ 25 wt%, (meth) acrylic acid (b2 ) 1 to 10 wt%, it is preferable to contain 40 to 58% by weight of (meth) acrylic acid alkyl ester (b3). [0017] 　Since styrene (b1) is an effect of enhancing the adhesion and corrosion resistance, preferably contains 15 to 25 wt%, more preferably 17-23 wt%. It is less than 15 wt% reduces the adhesion and corrosion resistance, greater than 25 wt%, the film becomes hard, the processing unit corrosion resistance decreases. [0018] 　(Meth) acrylic acid (b2) has the effect of improving adhesion of the coating to the steel sheet of the resin, preferably contains 1 to 10 wt%, more preferably from 2 to 6% by weight. If less than 1 wt%, the adhesion is lowered, the corrosion resistance and water resistance is lowered and when it exceeds 10 wt%. [0019] 　(Meth) acrylic acid alkyl ester (b3) has an effect of the resin coating workability improved, preferably contains from 40 to 58 wt%, more preferably 40 to 55 wt%. If less than 40 wt%, the processing unit corrosion resistance is lowered, if it exceeds 58 mass%, the planar portion corrosion resistance decreases. (Meth) Type of acrylic acid alkyl esters (b3) is not limited, for example, (meth) acrylate, (meth) acrylate, butyl (meth) acrylate, 2-methylhexyl, and these such isomers may be mentioned, it is possible to use one or more of these. Among them, in terms of corrosion resistance superior ethyl acrylate, and butyl acrylate are preferred. [0020] 　Acrylonitrile (b4) is effective to improve the adhesion between the structural adhesive contains 20-38% by weight, preferably 20 to 35 wt%. With 20 mass% or more, it is possible to improve adhesion. On the other hand, if it exceeds 38 wt%, water resistance is lowered and the corrosion resistance is lowered. [0021] 　Acrylic resin (B) has a glass transition temperature that is calculated is -12 ~ 15 ° C.. If the glass transition temperature is above -12 ° C., it can be improved corrosion resistance. On the other hand, decreases adhesiveness exceeds 15 ° C.. The glass transition temperature is calculated by the following formula wherein, i is an integer of at least 1, Wi is the mass fraction of the i homopolymer, Tgi represents a Tg (K) of the i homopolymer. [0022] (Formula 1) [0023] 　Acrylic resin (B), if it is copolymerized with at least styrene (b1) and (meth) acrylic acid and (b2) (meth) acrylonitrile (b4) and the appropriate amount of acrylic acid alkyl esters (b3), it is also possible to use other vinyl group-containing monomer as a raw material monomer. Is not particularly restricted but includes such vinyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth ) acrylate, 4-hydroxybutyl (meth) acrylate, ethoxy - diethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) allyl ether, 3-hydroxypropyl (meth) allyl ether, 4-hydroxybutyl (meth) allyl ether, 2-dimethylaminoethyl acrylate, acrylamide, allyl alcohol, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, citraconic acid, cinnamic acid, vinyl trimethoxysilane, vinyl triethoxysilane Toki Silane, allyl glycidyl ether, glycidyl (meth) acrylate, 2- (1-aziridinyl) ethyl acrylate, Imi Nord methacrylate, acryloyl morpholine, vinyl formate, vinyl acetate, vinyl butyrate, vinyl acrylate, vinyl toluene, cinnamic acid nitrile, (meth) acryloxyethyl phosphate, and bis - (meth) include such acryloxyethyl phosphate, can be used one or more of these. Among these, from the viewpoint of excellent stability of the emulsion, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, ethoxy - glycol acrylate and acrylamide are preferred. [0024] 　The polymerization process of the polymer used in the present invention is not particularly limited, suspension polymerization, emulsion polymerization, and solution polymerization method. It is also possible to use solvent, and a polymerization initiator upon copolymerization. The polymerization initiator is not particularly limited, it can be used a radical polymerization initiator such as azo compound or peroxide-based compound, relative to the total solids content of the resin, 0.1 to 10 weight % of use is preferred. The reaction temperature is 200 ° C. usually room, preferably 40 ~ 0.99 ° C., the reaction time is 30 minutes to 8 hours, it is preferable that preferably about 2-4 hours. [0025] 　Aqueous surface-treating agent used in the present invention is a divalent to tetravalent vanadium compound (C) and one starting material. Vanadium compound is 2 to pentavalent vanadium compound. Vanadium compounds preferentially eluted in a corrosive environment, in order to suppress the pH rise due to the dissolution of the plating components, is effective in improving corrosion resistance. Although the oxidation number of the vanadium is effective as either, pentavalent vanadium has high solubility, it is necessary to use a divalent to tetravalent vanadium compound. [0026] 　These divalent to tetravalent vanadium compound (C), the mass ratio [(V) / (Zr)] 0.07 to 0 when the zirconium carbonate compound (A) Zr, vanadium compound (C) and V terms a .69, and preferably from 0.14 to 0.56. Is [(V) / (Zr)] For 0.07 or more, it is possible to improve the processing unit corrosion. On the other hand, when it exceeds 0.69 [(V) / (Zr)] it is not preferable because the top coating is lowered. [0027] 　2 ~ kinds of tetravalent vanadium compound (C) is not particularly limited, for example, vanadium pentoxide (V 2 O 5 ), metavanadate (HVO 3 ), ammonium metavanadate, sodium metavanadate, vanadium oxytrichloride (VOCl 3 ) a pentavalent vanadium compound such as those reduced to divalent to tetravalent with a reducing agent, vanadium trioxide (V 2 O 3 ), vanadium dioxide (VO 2 ), vanadium oxysulfate (VOSO 4 ), oxy oxalate vanadium [VO (COO) 2 ], (vanadium oxy acetylacetonate [VO (OC (CH 3 ) = CHCOCH 3 )) 2 ], vanadium acetylacetonate [V (OC (CH 3 ) = CHCOCH 3 )) 3 ], vanadium trichloride (VCl 3 ), phosphovanadomolybdic acid H { 15-X [PV 12-x Mo x O 40 ] · nH 2 O (6 　shows compositions of the processing solutions of Examples and Comparative Examples in Table 3A and Table 3B. Processing solution while stirring the solution using a propeller stirrer for a certain amount of deionized water prepared in advance, was added and the components were sequentially prepared such that the solid content concentration became 15 mass%. The modifiers pH, carbonate was used and ammonia. In the case of combined use of D1 and D2 as a phosphorus compound (D), the mass when converted into P in the processing solution, D1: D2 = 85: was prepared as a 15. [0056] 3. Processing method (1) Degreasing 　Nippon Parkerizing Co. alkaline degreaser Fine Cleaner E6406 (20g / L bath preparation, 60 ° C., 10 sec spray, spray pressure 50 kPa) was degreased material in was subjected to spray washing for 10 seconds . (2) applying and drying of the treatment liquid 　to the treatment liquid using a bar coater, and dried with hot air circulating oven. So that the target Zr coating weight was properly selected count of density adjustment and the bar coater process liquid. Incidentally, Zr coating weight was measured by fluorescence X-ray analyzer ZSX-PrimusII (manufactured by Rigaku Corporation). [0057] 　The following shows the evaluation items and test methods. Further, the evaluation results are shown in Table 4A and Table 4B. Corrosion resistance 　to flat and height 7mm specimens subjected to Erichsen processing was to salt spray test conforming to JIS Z 2371 until the predetermined time. The corrosion resistance was determined by white rust area ratio after the salt spray test. 　The evaluation criteria for the corrosion resistance as follows. 　Flat specimen (after the salt spray test for 240 hours) 　◎: White rust 0% 　○: white rust over 0% and 5% 　○ -: white rust over 5% to 15% 　△: white rust than 15% to 30% 　×: white rust 30% ultra 　Erichsen working specimen (after the salt spray test 72 hours) 　◎: White rust 0% 　○: white rust over 0% and 15% or less 　○ -: white rust than 15% to 30% 　△: white rust 30% ultra 50 percent less 　×: white rust than 50% [0058] · Blackening 　using constant temperature and humidity testing machine to visually observe the appearance of the specimen was allowed to stand for 144 hours in an atmosphere of 70 ℃ × RH85%. 　The evaluation criteria for the blackening resistance are shown below. 　◎: completely no change 　○: little change is not observed 　○ -: some discoloration in the end is observed 　△: some discoloration is observed 　×: is observed obvious discoloration [0059] - coating adhesion 　using a bar coater to the test piece coated with AMILAC 1000 white (manufactured by Kansai Paint Co., Ltd.), to give a dry film thickness of 20μm and dried by heating at 125 ° C. 20 min. Subsequently, it immersed for 30 minutes in boiling water, for 24 hours allowed to stand after removal. Then subjected to cross-cut processing of 1 mm, 100 squares using a cutter knife, the tape peeling test to determine the coating film remaining number. 　The evaluation criteria of paint adhesion are shown below. 　◎: remaining few hundred 　○: remaining number 98 or more than 100 　△: residual number 50 or more 98 than 　×: remaining number less than 50 [0060] 　The treatment agent allowed to stand for 3 months in a thermostat at temperature 40 ° C., was observed Ekigaikan. 　The evaluation criteria are shown below. ◎: almost no change ○: There is a slight turbidity △: Yes precipitation ×: gelling, there is a large amount of precipitation [0061] Adhesive Evaluation 　using various adhesives was conducted adhesion between the galvanized steel sheets or galvanized steel sheets and other materials by the evaluation method 1-4. Other material test piece used in adhesives and the evaluation method 2 below. A: Epoxy (Konishi Co., Ltd., E2300J) other materials specimens: the mortar specimens B: Acrylic (manufactured by Denki Kagaku Kogyo, Hard Rock 8) other materials specimens: the mortar specimens C: silicon (Toray Dow Corning, PV8303) other materials specimen: float glass D: silicon (Cemedine manufactured, PM210) other materials specimen: for ceramic tiles, float glass E: silicon (Cemedine manufactured by Super X No.8008) other materials test piece; float glass F: phenol (Cemedine manufactured, 110) other materials specimen: No G: urethane (Cemedine manufactured, UM700) other materials specimen: MDF (medium-density fibreboard) H: vinyl acetate (Konishi Co., Ltd., CH18) other materials specimen: MDF (medium-density fibreboard) I: chloroprene rubber (Cemedine manufactured, 575F) other materials specimen: MDF (medium density fiber board) Evaluation method 1: test piece (25 ± 0.5mm × 100 ± × 1.6mm thickness) adhered portion two with adhesive (25 ± 0.5mm × 12.5 ± 0.5mm ) and was prepared lap shear specimens, after a predetermined time curing was evaluated primary adhesion. Evaluation Method 2: adhesion by the test piece (25 ± 0.5mm × 100 ± 0.5mm × 1.6mm thick) and other materials test piece (25 ± 0.5mm × 100 ± 0.5mm × arbitrary thickness) adhesive portion was prepared (25 ± 0.5mm × 12.5 ± 0.5mm ) and the lap shear specimens, after a predetermined time curing was evaluated primary adhesion. Evaluation Method 3: After curing the specimens of evaluation method 1, 50 ° C., after a predetermined time at 85%, was evaluated secondary adhesion. Evaluation 4: after curing the specimens of evaluation method 1, 85 ° C., after a predetermined time at 85%, was evaluated secondary adhesion. 　The adhesion was evaluated and the tensile shear load cohesive failure rate. Tensile shear load is a tensile speed: 100 mm / min, room temperature: carried out at 25 ° C., was evaluated by a tensile shear load ratio of the test piece untreated (tensile shear load of the tensile shear load / untreated material test materials). The evaluation criteria of the tensile shear load is shown below. ◎: 1.1 or higher ○: 1.0 and less than ~ 1.1 △: 1.0 (untreated test piece equivalent) ×: less than 1.0 Also, the zinc-based plated steel sheet side after the tensile shear test remaining area of adhesive (cohesive failure rate) were evaluated in comparison with untreated material. The evaluation criteria of cohesive failure rate below. ◎: a clear increase in residual area of the adhesive ○: increased residual area of the adhesive △: non-treated material equivalent ×: decrease residual area of the adhesive [0062] [Table. 3A] [0063] [Table 3B] [0064] [Table 4A] [0065] [Table 4B] [Claim 1] 　Zirconium carbonate compound (A), 　at least styrene (b1), and (meth) acrylic acid (b2), and (meth) acrylic acid alkyl ester (b3), copolymerizing a monomer component comprising acrylonitrile (b4) a resin obtained from that, the amount of acrylonitrile (b4) is, based on the solid weight of the total monomer components of the resin is 20-38 wt%, and a glass transition temperature of -12 ~ 15 ° C. and the water-soluble resin and an aqueous emulsion resin is a acrylic resin (B), 　2 ~ 4-valent vanadium compound (C), and 　the phosphorus compound (D), 　a cobalt compound and (E), 　and water becomes blended with a pH 8 ~ 11, zinc-plated steel sheet for surface-treating agent. [Claim 2] 　Wherein 20 to 60 mass% the amount is based on the total solid content of the surface treatment agent of the acrylic resin (B), 　and the mass when converted the vanadium compound (C) in V, the zirconium carbonate compound (A ) the mass ratio of the mass when converted into Zr [(V) / (Zr)] is 0.07 to 0.69 　mass when the phosphorus compound (D) in terms of P, the zirconium carbonate compound (a) the mass ratio of the mass when converted into Zr [(P) / (Zr)] is 0.04 to 0.58 　when converted the cobalt compound (E) to Co mass and the zirconium carbonate compound of the mass ratio of the mass when the (a) in terms of Zr [(Co) / (Zr)] is from 0.005 to 0.08 zinc system according to claim 1 surface treatment agent for the coated steel sheet. [Claim 3] 　The amount of each monomer component of the acrylic resin (B), based on the solid weight of the total monomer components of the resin, styrene (b1) is 15 to 25 wt%, and 1 is (meth) acrylic acid (b2) 10 wt%, (meth) acrylic acid alkyl ester (b3) is from 40 to 58 mass%, zinc-plated steel sheet for surface-treating agent according to claim 1 or 2. [Claim 4] 　Galvanized layer of said galvanized steel sheet, in addition to zinc and unavoidable impurities, and containing one or more of 60 mass% or less of Al, 10 mass% of Mg, 2 wt% or less of Si also may composition have a zinc-plated steel sheet for surface-treating agent according to any one of claims 1 to 3. [Claim 5] 　At least a portion of the phosphorus compound (D) is an inorganic phosphoric acid and / or its salts, zinc-plated steel sheet for surface-treating agent of any one of claims 1-4.