[0001]The present invention is, for galvanized steel or zinc base alloy plated steel product for aqueous surface-treating agent, coating method using the treatment agent, and a coating steel obtained using this method.
Background technique
[0002]On the surface of the steel sheet such as galvanized steel sheet, a resin as a main component, the surface treated steel sheet to form a chromium-free rust preventing film with the addition of other organic or inorganic ingredients need, a number of techniques proposed to date ing. These rust preventing film, corrosion resistance, degreasing corrosion resistance after painting adhesion, degreased after coating adhesion, resistance to blackening, anti condensation whitening, treatment agent stability, the performance of the actual operation, etc. are required.
[0003]
　For example, Patent Document 1, the galvanized steel sheet substrate, the cationic resin, a siloxane compound, a titanium compound, vanadium compound, and preferably contains a material of the surface-modified olefin wax with a silicon compound in a specific ratio by coating and baking and drying of the aqueous treatment solution, the total content of the strong electrolyte component remaining in the coating 0.3 mg · m -2 technique of forming a poorly water-soluble coating is below has been proposed.
CITATION
Patent Document
[0004]
Patent Document 1: JP Patent No. 5220050
Summary of the Invention
Problems that the Invention is to Solve
[0005]
　Here, the surface treatment agent for forming the surface treatment film in the surface treated steel sheet described in Patent Document 1, the present inventors have evaluated is not sufficiently considered for the treatment agent Stability It has been found. To improve the treatment agent stability, were studied, when blending the acid in the surface treatment agent described in Patent Document 1, the treatment agent stability of the surface treatment agent has been found to improve.
[0006]
　However, the present inventors have made further studies and findings newly resistant stack whitening resistance and filament tape is deteriorated, the present inventors have found that the when formulating acetic acid surface treatment agent described in Patent Document 1 problem was found to be caused. The resistance stack whitening resistance, in a state simulating the storage conditions during coil storage of surface-treated steel sheet, means resistance to whitening of the surface treatment film, the performance evaluation is fixed to the surface treated steel sheet in a high temperature and high humidity conditions applying a pressure (stack) is performed by evaluating the appearance after the lapse of a certain period. Further, the resistance to filament tape resistance, but of using filament tape for temporarily fixing an end portion of the coil of the surface-treated steel sheet, means a resistance to the filament tape surface treatment film, the performance evaluation is after attaching a filament tape on the surface treated steel sheet is performed by evaluating the appearance after peeling the filament tape after a certain period of time at high temperature and high humidity conditions. The cause of resistance stack whitening resistance is deteriorated, acetic acid remaining in the surface treatment film is high humidity by become hydrated state, by affecting the galvanized layer of the galvanized steel sheet is a base material, white rust Zn It is considered to be due to more likely to occur. As the cause of resistance to filament tape is deteriorated, acetic acid remaining in the surface treatment film is high humidity by become hydrated state, by affecting the adhesive layer of filament tape adhesion of filaments tape is reduced, Firan placement tape attachment unit is considered to be due to film damage.
[0007]
　The present invention has been made in view of the above circumstances, corrosion resistance, degreasing corrosion resistance after painting adhesion, degreased after coating adhesion, resistance to blackening, anti condensation whitening, treatment agent stability, actual operability while satisfying the performance of equal, for formable galvanized steel a coating excellent in stack whitening resistance and filament tape or zinc base alloy plated steel product for aqueous surface-treating agent, coating method using the treatment agent and, and to provide a coated steel material obtained using this method.
Means for Solving the Problems
[0008]
　The present inventor has conducted extensive studies to solve the above problems, and cationic polyurethane resin, and a cationic phenol resin, a silane coupling agent, and acetylacetone complexes of titanium, vanadium compounds, olefin wax When, and acetic acid, by blending the phosphate component in water, for formable galvanized steel a coating excellent in stack whitening resistance and filament tape or zinc base alloy plated steel product for aqueous surface-treating agent It found that obtained, and have completed the present invention based on this finding.
[0009]
　That is, the present invention includes a cationic polyurethane resin (A), the cationic phenolic resin (B), a silane coupling agent (C), and a titanium acetylacetone complex (D), vanadium compound and (E), acetic acid component and (G), a phosphate component (H) and the use galvanized steel by blending in water or zinc base alloy plated steel product for aqueous surface-treating agent, the solid content of the aqueous surface-treating agent (V) for mass, SiO of the silane coupling agent (C) 2 ratio of the mass by conversion (NC) / (NV) is from 0.16 to 0.19, relative to the mass of the solid content (V), of said titanium to the mass ratio between the mass (ND) by Ti conversion acetylacetone complex (D) (ND) / ( NV) is from 0.0170 to 0.0240, the solid (V), the vanadium compound of the (E) The ratio between the mass (NE) by V conversion (NE) / (NV) is 0.0070 to 0.0090, with respect to the mass of the solid content (V), the ratio between the mass of the acid component (G) (NG) / (NV) 0.040 - 0.140 the solids to the weight of (V), the ratio (NH) / (NV) is 0.025 to the mass of the phosphoric acid component (H) 0.075 the vanadium compound to the mass by V conversion (E), the ratio between the mass by terms of Ti of acetylacetone complex of the titanium (D) (ND) / ( NE) is from 2.10 to 2.90, said acid component ( to the mass of G), the ratio between the mass of the phosphoric acid component (H) (NH) / ( NG) from 0.25 to 1.10 mass by Ti conversion acetylacetone complex (D) of the titanium (ND) for the ratio between the mass of the phosphoric acid component (H) ( H) / (ND) is 1.11 to 3.19, which is for galvanized steel or zinc base alloy plated steel product for aqueous surface-treating agent.
[0010]
　The ratio of the galvanized steel product for or zinc base alloy plated steel product for aqueous surface-treating agent is further the olefin wax (F), relative to the mass of the solid content (V), and the mass of the olefin wax (F) (NF) / (NV) as 0.035 to 0.060 may contain. Further, the olefin wax (F) is surface-modified with a silane coupling agent (I), the olefin wax to the mass of (F), the ratio between the mass of the silane coupling agent (I) (NI / NF ) may be a .025-.035. Further, the average particle size of the olefin wax (F) may be 0.05 ~ 0.15 [mu] m.
[0011]
　The vanadium compound (E) may be a acetylacetone complex of vanadium. Further, the olefin wax (F) may be one that is surface-modified with epoxy group-containing silane coupling agent.
[0012]
　In the galvanized steel product for or zinc base alloy plated steel product for aqueous surface-treating agent, in the cationic polyurethane resin (A) is the general formula (1) polycarbonate-based water-dispersible cationic polyurethane resin comprising a structural unit represented by the it may be.
[0013]
[Formula 1]

[0014]
　In the formula (1), R is an aliphatic alkylene group having 4 to 9 carbon atoms, n is an integer number average molecular weight is equivalent to the range of 500-5000.
[0015]
　Further, it may be a polymer molecule having an average degree of polymerization of 2 to 50 with recurring units of the cationic phenolic resin (B) is represented by the general formula (2).
[0016]
[Formula 2]

[0017]
　Wherein (2), Y1, and Y2 represents a Z group represented by each independently hydrogen or the formula (3) or (4), the average substitution number of Z groups per each benzene ring 0.2 it is ~ 1.0.
[0018]
[Formula 3]

[0019]
　In the formula (3) and (4), R1, R2, R3, R4 and R5 represent each independently a hydrogen atom, an alkyl group or hydroxyalkyl group having 1 to 10 carbon atoms having 1 to 10 carbon atoms, A - represents a hydroxide ion or an oxo acid ions.
[0020]
　Further, the present invention forms a film by coating the galvanized steel product for or zinc base alloy plated steel product for aqueous surface-treating agent described above to galvanized steel or zinc base alloy plated steel, a coating method.
[0021]
　Further, the present invention is obtained by the method of coating a coating steel.
Effect of the invention
[0022]
　According to the present invention, resistance to stack whitening resistance and zinc capable of forming a film excellent in resistance to filament tape resistant plating steel product for or zinc base alloy plated steel product for aqueous surface-treating agent, coating method using the treatment agent, and the how it is possible to provide a coating steel obtained using.
[0023]
　Furthermore, the present invention, in addition to excellent resistance to condensation whitening resistance, etc. is one of the important characteristics required for the surface appearance quality of the surface treated steel sheet used in unpainted, further compounding the olefin wax (F) as an optional component by, it is possible to improve the non-application oil lubricity and handling property (i.e., resistance to coil deformation resistance and 耐切 plate pile collapsing property).
DESCRIPTION OF THE INVENTION
[0024]
　Hereinafter, described in detail preferred embodiments of the present invention. Incidentally, galvanized steel or for zinc-based alloy plated steel material for aqueous surface-treating agent according to the present invention, with respect to the coating method and coating steel are set forth in the following order.
[Galvanized steel for or zinc base alloy plated steel product for aqueous surface-treating agent]
　(component)
　　
　　
　　
　　
　　
　　
　　
　　
　　
　(compounding
　　ratio) <(NC) / 　　(NV)>
<(ND.) / (NV)> <(NE) / 　　(NV)> <(NF) / (NV)> 　　<(NG) / (NV)> <(NH) / 　　(NV)> < 　　(ND.) / (NE)> 　　<(NH) / (NG)> <(NH) / (ND.)>

　(Physical
　　Properties)
[coating process]
　(Substrate: galvanized steel or zinc base alloy plated steel)
　(process step)
[coated steel]
　(film deposition amount)
[0025]
[Galvanized steel for or zinc base alloy plated steel product for aqueous surface-treating agent]
　The present invention according to the galvanized steel for or zinc base alloy plated steel product for aqueous surface-treating agent, at least, a cationic polyurethane resin (A), the cationic and sex phenolic resin (B), a silane coupling agent (C), and a titanium acetylacetone complex (D), vanadium compound and (E), and acetic acid component (G), and a phosphate component (H) in water it is an aqueous surface treatment agent formed by blending. The proportion of each component in the aqueous surface-treating agent are as follows.
(1) to the mass of the solid content of the aqueous surface-treating agent of the present invention (V), SiO silane coupling agent (C) 2 ratio of the mass by conversion (NC) / (NV) is from 0.16 to 0. 19
(2) to the mass of the solid content (V), the ratio between the mass (ND) by Ti conversion acetylacetone complex of titanium (D) (ND) / (NV) is from 0.0170 to 0.0240
(3) solid to the mass of minute (V), vanadium compound ratio between the mass (NE) by V conversion (E) (NE) / (NV) is from 0.0070 to 0.0090
by weight in (4) solid (V) , the ratio of the mass of acetic acid component (G) (NG) / (NV) is 0.040 to 0.140
the ratio between the mass of (5) to the mass of the solid content (V), phosphate component (H) ( NH) / (NV) is 0.025 to 0.075
(6) a vanadium compound With respect to the mass by V in terms of E), the ratio between the mass by terms of Ti of acetylacetone complex of titanium (D) (ND) / ( NE) is 2.10 to 2.90
(7) to the mass of acetic acid component (G), the ratio between the mass of the phosphate component (H) (NH) / (NG) is 0.25 ~ 1.10
Ti (8) acetylacetone complex of titanium (D) relative to the mass (ND) by translation, the ratio between the mass of the phosphate component (H) (NH) / ( ND) is 1.11 to 3.19
[0026]
　Hereinafter, the composition (components, compounding ratio) of galvanized steel for or zinc base alloy plated steel product for aqueous surface-treating agent according to the present invention will be described in detail and physical properties.
[0027]
(Components)
　will be described first component to be blended in the aqueous surface treating agent of the present invention.
[0028]

　The cationic polyurethane resin (A) is blended as an essential component in the aqueous surface-treating agent of the present invention are formed using an aqueous surface treatment agent of the present invention (i.e., the aqueous surface and the coating of the treatment agent is formed by drying) poorly water-soluble film (hereinafter, it is simply referred to as "hardly water-soluble film") resin forming a main body of the. Since the process used is water, using an aqueous resin as a cationic polyurethane resin to be contained in the treatment agent (A). Aqueous resin, water-dispersible, emulsion, and are roughly classified into water-soluble, in the present invention, anti-condensation whitening resistance, in order to obtain a film having a water resistance, it is preferred to use a water-dispersible resin . Water-soluble resins are the equilibrium dissolution system, strong electrolyte component as a counter cation or counter anion (fluorine, lithium, sodium, potassium, chlorine, bromine, sulfate, sulfite, nitrate, nitrite, acetic acid, formic acid, propionic acid, When ion) is required (strong electrolyte components such as sulfonic acids are substantially remain in the coating, whitening is likely to occur condensation), also emulsions, surfactant remains in the film, there is a possibility that water resistance is deteriorated.
[0029]
　The water-dispersible resin, the type of the resin particle surface by amine modified were cationically dispersed, i.e., the preferred cationic water-dispersible resin. Be to cationic dispersion, it is possible to coexist with later-described silane coupling agent (C). Anionic dispersion treatment agent becomes alkaline, the silane coupling agent becomes unstable. In this case, lithium hydroxide as a counter cation, to dissolve the silane coupling agent with sodium hydroxide or the like, can be added a silane coupling agent in the alkaline processing agent, the addition of strong electrolyte ions such as lithium or sodium It is not preferable because resistance condensation whitening deteriorates.
[0030]
　The particle size of the water-dispersible resin 9nm above, is preferably the range of 200 nm. As the particle size of the water-dispersible resin is large, it can be reduced adverse effects of hydrophilic by amine modified, inhibiting film formation in the baking and drying process too much.
[0031]
　Cationic water-dispersible resins described above, in the present invention, incorporating the cationic polyurethane resin (A) to the processing agent. Film whose main component is a cationic polyurethane resin (A) is excellent in balance of tensile strength and elongation, adhesiveness becomes good and processability.
[0032]
　Cationic polyurethane resin (A) is preferably a water-dispersible cationic polyurethane resin of polycarbonate-based, including a structural unit represented by the following general formula (1). When the cationic polyurethane resin (A) contains a structural unit represented by the following general formula (1), it is assigned a better barrier property, resistance to dew whitening resistance is improved.
[0033]
[Chemical Formula 4]

[0034]
　The formula (1), R is an aliphatic alkylene group having 4 to 9 carbon atoms, n is the number average molecular weight of carbonate-based polyol as a raw material for the polycarbonate-based cationic polyurethane resin (A) 500 to is an integer that corresponds to the range of 5000.
[0035]

　The aqueous surface-treating agent of the present invention, in addition to the cationic polyurethane resin (A), the further cationic phenolic resin (B) is blended as an essential component. When aqueous surface-treating agent of the present invention contain cationic phenolic resin (B), the stability of the treatment agent is improved. Further, when the poorly water-soluble film of the present invention contain cationic phenolic resin (B), it improves topcoat water secondary adhesiveness.
[0036]
　Cationic phenolic resin (B) preferably has a repeating unit represented by the following general formula (2), and more preferably a polymer molecule having an average degree of polymerization of 2 to 50 of the repeating units. If the average polymerization degree is within this range, improved water resistance of the coating. The average degree of polymerization of the repeating unit of formula (2), 1 can be determined from the area ratio by H-NMR.
[0037]
[Formula 5]

[0038]
　In the above formula (2), Y1, and Y2 represents a Z group represented by each independently hydrogen or the formula (3) or (4), the average substitution number of Z groups per each benzene ring 0. from 2 to 1.0. The average number of substituents Z group 1 can be obtained from the area ratio by H-NMR.
[0039]
[Formula 6]

[0040]
　The formula in (3) and (4), R1, R2, R3, R4 and R5 represent each independently a hydrogen atom, an alkyl group or hydroxyalkyl group having 1 to 10 carbon atoms having 1 to 10 carbon atoms, a - represents a hydroxide ion or an oxo acid (e.g., nitric acid, sulfuric acid, phosphoric acid, carbonic acid, carboxylic acids, etc.) ions.
[0041]
　As described above, the counter anion of the cationic resin used in the present invention (cationic polyurethane resin (A) and cationic phenolic resin (B)) is an anion that volatilizes under dry filming, specifically or formic acid acetate ions are preferred. When counter anion of the cationic resin is a hydroxide ion, treatment agent tilt alkaline, silane coupling agent as described above is liable to gelation, the liquid becomes unstable.
[0042]
　If the counter anion of the cationic resin is formic acid or acetic acid ion, formic acid or acetic acid is volatilized during drying film formation. Thus, in the cationic resin, amine loses charge, irreversible agglomeration of the film-forming reaction occurs by hydrophobic resin particles. At the same time the volatile counter anion increases the pH, silane coupling agent silanol by hydrolysis is allowed to proceed irreversible gelling and condensation as film-forming reaction. In this case further, reaction of the side chain and a silane coupling agent of the cationic polyurethane resin (A) and cationic phenolic resin (B), as well as by the reaction of the silanol and the plating base, a network of a resin-siloxane metalloxane bond to form the adhesion, corrosion resistance, a strong film with excellent solvent resistance can be formed.
[0043]

　The aqueous surface-treating agent of the present invention, a silane coupling agent (C) is blended as an essential component. Silane coupling agent (C), to form a three-dimensional crosslinked siloxane-type film by siloxane bonds via hydrolysis and condensation in the film-forming (printing) process. In other words, hardly water-soluble film of the present invention includes a siloxane compound (C '). As film-forming component, not only the cationic polyurethane resin (A) and cationic phenolic resin (B), the siloxane compound (C ') also be used in combination, of the formed film corrosion resistance, adhesion, solvent resistance performance is significantly improved.
[0044]
　The siloxane compound (C ') of the material to become a silane coupling agent (C), 2 or more, preferably using an alkoxysilane having 3 or more alkoxy groups. It is also possible to use a partial hydrolyzate thereof.
[0045]
　Alkoxy groups of the silane coupling agent (C) is hydrolyzed by the addition of an aqueous, a silanol (-Si-OH). Dispersion stability of the silanol is obtained in pH6.5 or less. The pH of the treatment agent is more than 6.5, no pot life is obtained by gelation.
[0046]
　The silane coupling agent (C), may be commercially available products. As commercially available products, for example, N- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropyl trimethoxy silane, and the like. Preferred silane coupling agent (C), those having a functional group reactive with the cationic polyurethane resin (A) used and the cationic phenolic resin (B) (for example, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane Sid trimethoxysilane, 3-mercaptopropyl trimethoxysilane and the like are preferable, 3- aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane and the like are particularly preferred.). Type of reaction of these cationic resins, polymerization reaction, condensation reaction, well in addition reaction is not particularly limited.
[0047]

　The aqueous surface-treating agent of the present invention are formulated as acetylacetone complex (D) is also an essential component of titanium. Are processed blending titanium acetylacetone complex (D) is in the of the present invention, by a poorly water-soluble film formed contains titanium compound is a reaction precipitates acetylacetone complexes of titanium (D) a (D '), corrosion resistance is greatly improved.
[0048]
　The treatment agent, the acetylacetone complex of titanium is blended, corrosion resistance of the poorly water-soluble film formed is further improved, Further, acetylacetonate and acetylacetone remaining in dry film-forming coating weak ionic, condensation It does not adversely affect the whitening. Acetylacetone complex of titanium, react with plated substrate in a dry film-forming precipitated to form a poorly water-soluble film. Of the chelate compounds of titanium, triethanolamine complexes with cationic is preferred in that no adverse effect on condensation whitening, since triethanolamine remaining after drying film formation even during the film exhibits water absorption, corrosion resistance improving effect is larger in the acetylacetone complex. Titanium hydrofluoric acid and Chitanfu' ammonium Since fluorine is deteriorated resistance to condensation whitening liberated, is unsuitable.
[0049]

　The aqueous surface-treating agent of the present invention, the vanadium compound (E) is also incorporated as an essential component. Are processed blending vanadium compound (E) is the of the present invention, by a poorly water-soluble film formed contains vanadium compound is the reaction precipitate vanadium compound (E) to (E '), the corrosion resistance is very improves.
[0050]
　The vanadium compound (E), vanadium pentoxide contains no strong electrolyte, metavanadate and its salts (e.g., ammonium metavanadate), vanadium trioxide, vanadium dioxide, vanadium oxy acetylacetonate, vanadium acetylacetonate, etc., and acetic acid and vanadium salts with volatile acids. Considering the corrosion resistance improving effect, vanadium acetylacetonate in this, vanadium acetylacetone complex such as vanadium oxy acetylacetonate is preferred. As described below, the vanadium compound (E ') is fixed as an oxide or acetylacetone complex in the film.
[0051]

　aqueous surface-treating agent of the present invention, it is preferable that the olefin wax (F) is also incorporated as an optional component. The olefin wax (F) is more preferably surface-modified with a silane coupling agent (I). When containing olefin wax hardly water-soluble film has been surface-modified with a silane coupling agent (I) of the present invention (F), it is to disperse the coating in the not exposed on the surface, no oil coating lubricity and handling properties, i.e. resistance to coil deformation resistance, it is possible to achieve both耐切plate pile collapsing resistance. The olefin wax (F) is dispersed in the coating, the surface tension of the wax is increased by surface modification with a silane coupling agent (I), probably because the wettability to the processing agent is increased.
[0052]
　In general, lubricating coat the solid lubricant were added, such as waxes, dry enrichment of coating the surface of the wax by the liquid convection is generated in the film-forming temperature, it is not easy to uniformly disperse in the coating wax. However, it is possible to uniformly disperse in the coating by surface modification of wax particles with a silane coupling agent.
[0053]
　The silane coupling agent (I), it is preferable to use a silane coupling agent having a reactive functional group. Surface modification with a silane coupling agent (I) can be carried out by mixing the olefin wax emulsion silane coupling agent (I) directly. Thus, the cationic polyurethane resin, stable surface-modified olefin wax is obtained by cationic phenolic resin and pH6.5 following acidic treatment solution containing a silane coupling agent. The olefin wax (F) that can be used, polyethylene wax, polyethylene wax oxide, and polypropylene oxide wax. As the silane coupling agent of the present invention (I) by surface-modified olefin wax (F) a silane coupling agent containing an epoxy group to a polyethylene wax emulsion having a stable carboxyl group with an acidic treatment liquid (e.g. , surface-modified olefin wax obtained by mixing the glycidyl-propyl trimethoxy silane) directly is preferred.
[0054]
　Further, with respect to the weight of the olefin wax (F), the ratio (NI / NF) between the mass of the silane coupling agent (I) is preferably from 0.025 to 0.035. The NI / NF by 0.025 or more, it is possible to improve the handling properties. Also, the NI / NF by 0.035 or less, it is possible to improve the workability. The addition amount of the silane coupling agent (I) is preferably not wax dispersion having an acid value of equimolar or more.
[0055]
　Further, the average particle size of the olefin wax (F) is preferably 0.05 ~ 0.15 [mu] m. If the wax particle size is 0.15μm or less, improved handleability volume of wax present on the film surface is reduced, if 0.05μm or more, the treatment composition according to wax agglomeration with improved processability stable adverse effect on the sex is also small. As the average particle size of the olefin wax (F), and the use of a value measured by a laser diffraction scattering method.
[0056]

　The aqueous surface-treating agent of the present invention, acetic acid component (G) is blended as an essential component. By blending the acid component (G), liquid stability of the treatment agent (treatment agent stability) is improved. This is because the pH buffering action of the acetate component (G), pH of the treatment agent is stabilized in the vicinity of 3.5-4.0, a condensation reaction of the silane coupling agent (C) is presumed to become slow . Incidentally, the study of the present inventors, pH of the condensation reaction is the slowest of the silane coupling agent (C) is found to be around 3.5-4.0. Further, acetic acid is a boiling point of 118 ° C., a low boiling point among the organic acids having a buffer action, remaining on the film is relatively difficult. Therefore, as the organic acid to be contained in the surface treatment agent is preferred.
[0057]
　The acid component (G), for example, acetic acid, ammonium acetate, potassium acetate, sodium acetate and the like. Considering the effect of improving the treatment agent stability, acetate is particularly preferred.
[0058]

　The aqueous surface-treating agent of the present invention, phosphoric acid component (H) is blended as an essential component. Blended phosphate component (H), poorly water-soluble film to be formed by containing a phosphoric acid component (H), reacting with the zinc plating layer of the galvanized steel or zinc base alloy plated steel which is a base material , from generating a zinc phosphate coating, it is possible to suppress the zinc elution from galvanized layer. As a result, the occurrence of zinc white rust is suppressed, resistance to stack whitening resistance is improved. In addition, by phosphoric acid component in the treatment agent (H) is blended, it is possible to reduce the amount of acid remaining in the film, as a result, the adhesive layer of filament tape is not affected, the adhesion of the filament tape it is possible to suppress the sexual decline.
[0059]
　The phosphoric acid component (H), for example, inorganic phosphoric acids such as phosphoric acid and ammonium phosphate, potassium phosphate, sodium phosphate, and inorganic phosphate compounds such as dihydrogen phosphate monosodium. Considering the effect of improving stack whitening resistance and filament tape resistance, inorganic phosphoric acid compounds and inorganic phosphate are preferred, and phosphoric acid are particularly preferred.
[0060]

　The aqueous surface-treating agent of the present invention, it is preferred that the colloidal silica is not blended. When colloidal silica aqueous surface-treating agent of the present invention is blended, since the silane coupling agent (C) reacts with the colloidal silica, the treatment agent stability decreases, undesirably. Further, the aqueous surface-treating agent of the present invention are preferably basic alkali silicate is not blended. Aqueous surface-treating agent of the present invention are acidic and basic alkali silicate is alkaline is blended, since the treatment agent stability decreases, undesirably.
[0061]
(Mixing ratio)
　will now be described compounding ratio of the components to be blended in the aqueous surface-treating agent of the present invention.
[0062]
<(NC) / (NV) >
　to the mass of the solid content of the aqueous surface-treating agent of the present invention (V), SiO silane coupling agent (C) 2 ratio of the mass by conversion (NC) / (NV) is a 0.16 to 0.19, preferably from 0.16 to 0.18. When (NC) / (NV) is more than 0.19, it reduces the primary adhesion and less than 0.16, sufficient planar portion corrosion resistance can be obtained.
[0063]
<(ND) / (NV) >
　the solid to the mass of (V), the ratio between the mass (ND) by Ti Conversion acetylacetone complex of titanium (D) (ND) / ( NV) is 0.0170 ~ is 0.0240, preferably from 0.0190 to 0.0230. When (ND) / (NV) is less than 0.0170, corrosion resistance after degreasing is deteriorated, if it is 0.0240, more than with the effect of improving the degreasing after corrosion resistance is saturated, reduced adhesion after degreasing to.
[0064]
<(NE) / (NV) >
　to the mass of the solid content (V), vanadium compound (E) the ratio of the mass (NE) by V Conversion (NE) / (NV) is from 0.0070 to 0. it is 0090, and preferably from 0.0075 to 0.0090. (NE) / (NV) is less than 0.0070, can not be obtained sufficiently cut portion corrosion resistance improving effect, if it is 0.0090, greater than with cuts improving the corrosion resistance effect is saturated, the secondary adhesion There is reduced.
[0065]
<(NF) / (NV) >
　to the mass of the solid content (V), the ratio of the mass of the olefin wax (F) (NF) / ( NV) are preferably be from 0.035 to 0.060 , more preferably from 0.040 to 0.055. When (NF) / (NV) is 0.035 or more, a sufficient non-application Oil lubrication is obtained, thereby improving the workability. On the other hand, if (NF) / (NV) is at 0.060 or less, the resistance coils deformability and耐切plate pile collapsing property is improved, thereby improving the handleability.
[0066]
<(NG) / (NV) >
　to the mass of the solid content (V), the ratio of the mass of acetic acid component (G) (NG) / ( NV) is 0.040 to 0.140, preferably it is from 0.050 to 0.130, more preferably 0.060 to 0.120. When (NG) / (NV) is less than 0.040, a sufficient treatment agent stability enhancement effect can be obtained, if it is 0.140 greater, together with the processing agent stability enhancement effect is saturated, anti-condensing whitening resistance is lowered.
[0067]
<(NH) / (NV) >
　to the mass of the solid content (V), the ratio between the mass of the phosphate component (H) (NH) / ( NV) is 0.025 to 0.075 preferably it is from 0.030 to 0.070, more preferably 0.035 to 0.065. When (NH) / (NV) is less than 0.025, can not be obtained zinc dissolution suppressing effect from sufficient plating layer, if it is 0.075 greater, with zinc elution suppressing effect is saturated,耐黒modified is reduced.
[0068]
<(ND) / (NE) >
　Further, the ratio of the mass by V in terms of vanadium compound (E), the mass according to terms of Ti of acetylacetone complex of titanium (D) (ND) / ( NE) is 2.10 ~ is 2.90, preferably 2.20 ~ 2.80 and more preferably 2.30 to 2.70. When (ND) / (NE) is less than 2.10, and reduced fixed rate to the coating of the vanadium compound (E), the processing unit corrosion resistance decreases. On the other hand, (ND) / (NE) is the is 2.90 greater than lowered a fixed rate to the coating of titanium acetylacetone complex (D), the processing unit corrosion resistance decreases.
[0069]
<(NH) / (NG) >
　Further, with respect to the mass of acetic acid component (G), the ratio between the mass of the phosphate component (H) (NH) / ( NG) is 0.25 to 1.10. (NH) / If (NG) is less than 0.25 and 1.10, more than resistance stack whitening resistance decreases. To enhance the effect of improving the stack whitening resistance, (NH) / preferably (NG) is 0.30 to 1.00 and more preferably 0.35 to 0.90.
[0070]
<(NH) / (ND) >
　Further, with respect to mass (ND) by Ti Conversion acetylacetone complex of titanium (D), the ratio between the mass of the phosphate component (H) (NH) / ( ND) is 1. it is a 11-3.19. When (NH) / (ND) is less than 1.11 and 3.19, greater than resistance to filament tape is lowered. To enhance the effect of improving filament tape resistance, (NH) / preferably (ND) is 1.40 to 3.00 and more preferably 1.80 to 2.81.
[0071]
　The above ingredients by dissolving or dispersing in an aqueous solvent, can be prepared a surface treatment agent for forming a film in the present invention. Each component to a predetermined ratio in the film, therefore, adjusted to a predetermined ratio with respect to the total amount of solvent and non-volatile content excluding volatile components (solids). Because the treatment agent used in the present invention are aqueous, the solvent may only water, but for the purpose of improving the drying property of the film, does not include strong electrolytes mentioned above water-soluble organic solvent (e.g., alcohols) a small amount (e.g., less than 30 wt% of the total solvent) may be contained. It can also be added a leveling agent, an additive that is commonly used coating treatment liquid, such as antifoaming agents in the processing agent.
[0072]
(Physical Properties)
　will now be described physical properties of the components to be blended in the aqueous surface-treating agent of the present invention.
[0073]

　aqueous surface-treating agent of the present invention as described above, since is a cationic polyurethane resin (A) and cationic phenolic resin (B) as essential components, also the dispersion stability of the silane coupling agent (C) it is preferable that the pH of 6.5 or less in the acidic range for reduction. The preferred pH range of the aqueous surface treatment agent is 2.0 to 6.5. If necessary, acetic acid, it is possible to adjust the acidity of the additive to the treatment agent a volatile acid such as formic acid (pH).
[0074]
[Coating process]
　has been described in detail galvanized steel for or zinc base alloy plated steel product for aqueous surface-treating agent according to the present invention, followed by the above-mentioned galvanized steel for or zinc base alloy plated steel product for aqueous surface-treatment agent was used, described coating method according to the present invention. Coating method according to the present invention, by coating the galvanized steel product for or zinc base alloy plated steel product for aqueous surface-treating agent described above to galvanized steel or zinc base alloy plated steel (more specifically, galvanized steel or after contacting the zinc based alloy-plated steel, by drying), a surface treatment method for forming a coating on galvanized steel or zinc-based alloy surface of the plated steel material.
[0075]
(Base galvanized steel or zinc base alloy plated steel)
　The galvanized steel or zinc base alloy plated steel used in the present invention, for example, zinc - nickel plating steel, zinc - iron plating steel, zinc - chromium plated steel , zinc - aluminum plating steel, zinc - titanium plated steel, zinc - magnesium-plated steel, zinc - manganese plated steel, zinc - aluminum - magnesium plated steel, zinc - aluminum - magnesium - galvanized steel such as silicon plated steel, further these plating layer, as a minor different metal elements or impurities, cobalt, molybdenum, tungsten, nickel, titanium, chromium, aluminum, manganese, iron, magnesium, lead, bismuth, antimony, tin, copper, cadmium, arsenic, etc. those but has been contained, Siri Include those of alumina, inorganic titania or the like is dispersed.
[0076]
　Furthermore, the plating layer and other types of plating layer, such as iron plating, iron - phosphorus plating, nickel plating, a plating layer such as a cobalt plating, combined is also applicable to multi-layer plating. Formation of the plating layer is not particularly limited, a known electroplating method, hot dipping, vapor deposition plating, dispersion plating method can be performed using any method such as vacuum plating method. Coating weight is not particularly limited, and may be in a conventional general range. Plating, it may be either a single-sided plating and double-sided plating. The surface treatment method according to the present invention, when the substrate is a double-sided plated steel sheet, it is possible to form a coating on one or both sides of the plated steel sheet.
[0077]
(Processing step)
　in the galvanized steel or zinc base alloy plated steel material, after contacting the aqueous surface-treating agent described above, coating on galvanized steel or zinc-based alloy surface of the plated steel material by drying (poorly water-soluble to form a film). The coating is formulated in the processing agent of the present invention, the cationic polyurethane resin (A), the cationic phenolic resin (B), a silane coupling agent (C), acetylacetone complexes of titanium (D), vanadium compound (E ), derived from the acid component (G) and phosphoric acid component (H), cationic polyurethane resin (a), the cationic phenolic resin (B), the siloxane compound (C '), the titanium compound (D'), vanadium compound (E '), it includes acid component (G) and phosphate component (H) at least.
[0078]
　Contacting method to a substrate the treating agent is galvanized steel or zinc base alloy plated steel of this invention can be carried out dipping, spraying, roll coating, a method of contacting any conventional. Perform baking and drying after contact. The heating temperature at the time the volatile components in the treatment agent (e.g., acetic acid or formic acid from the counter anion of the cationic resin) is chosen to be volatilized. It is preferable that peak metal temperature (PMT) performs drying so as to be in the range of 60 ~ 0.99 ° C.. Baking and drying can be carried out by hot air drying or oven drying.
[0079]
　In baking and drying process, volatile acid component such as acetic acid from the liquid film of the treatment agent is volatilized, pH is raised. Thus, acetylacetone complex plating substrate and the titanium, silane coupling agent, a cationic polyurethane resin dispersion, the cationic phenolic resin undergoes hydrolysis and condensation reactions, plating the substrate surface, the resin, an organic silane compound, a titanium compound , and vanadium compounds ionomer attached form a strong network of metalloxane bond or a siloxane bond, there has a an olefin wax vanadium compound is fixed structure, sparingly water-soluble film is formed.
[0080]
Covering steel]
　Next, with the film formed using the coating methods described above (poorly water-soluble coating), describes coating steel material according to the present invention.
[0081]
(Film adhesion amount)
　adhering amount of the slightly water-soluble coating, for the purpose of primary rust (rust protection during delivery period to the user) is 100 mg / m 2 may be at least, but bare use (final when intended for painting shown) of the product, 300 mg / m 2 is preferably not less than. The upper limit of the film coating weight 3000 mg / m 2 is. When the amount of adhesion than increases, top coating property is lowered, even without containing coating wax, handling property becomes poor. When performing spot welding, the film deposition amount 1500 mg / m 2 is preferably not more than.
[0082]
　Coated steel of the present invention, at least a cationic polyurethane resin (A), the cationic phenolic resin (B), the siloxane compound (C '), the titanium compound (D'), vanadium compound (E '), acetic acid component (G ) and a galvanized steel or zinc-based alloy surface of the plated steel material a poorly water-soluble film formed from the phosphate component (H). Therefore, not only excellent in condensation whitening resistance and corrosion resistance, and excellent resistance stack whitening resistance and filament tape resistance. Also in a preferred embodiment, the film comprises an olefinic wax, further, when containing a silane coupling agent (I) with surface-modified olefin wax (F), Munuri oil lubricity coating granted, and since the wax is dispersed in the coating during not exposed on the surface, resistance to coil deformation resistance, is excellent in 耐切 plate pile collapsing resistance.
Example
[0083]
　The following examples and comparative examples of the present invention, the present invention will be described in detail, the present invention should not be construed as being limited thereto.
[0084]
1. Test material
　galvanized steel or zinc base alloy plated steel used in Examples and Comparative Examples are shown below.
　Manufactured by Nippon Steel Sumitomo Metals Co., Ltd., electro-galvanized steel sheet "NS zinc-coated (registered trademark)" (hereinafter, referred to as "EG".), Hot-dip galvanized steel sheet "NS Silver zinc (registered trademark)" (hereinafter, "GI . referred to as "), a galvannealed steel sheet" NS Silver alloy (registered trademark) "(hereinafter referred to as" GA "), zinc -. aluminum - magnesium - silicon alloy plated steel sheet" SuperDyma® (registered trademark) "( hereinafter referred to as "SD"), and zinc -. nickel alloy plated steel sheet "NS zinc light (registered trademark)" (hereinafter, referred to as "ZL"), as well as Nippon steel Sumitomo Metals steel plate manufactured by zinc -. aluminum alloy plating steel plate "Galvalume steel plate (registered trademark)" (hereinafter, referred to as "GL".), and Nippon steel Sumitomo Metals steel plate manufactured by zinc - aluminum - magnesium alloy plating Plate "Esujieru steel plate (registered trademark)" (hereinafter, referred to as "SGL".) Was used as the original plate.
　The original plate, the plate thickness was used for 0.8 mm. The EG, amount plating deposition on one side 20 g / m 2 was used for. Further, GI, GA, SD, as GL and SGL, the amount of plating deposited on one side 60 g / m 2 was used for. The ZL, the amount of plating deposited on one side 20 g / m 2 is, the amount of nickel plating layer is used as a 12 wt%.
[0085]
2. Aqueous surface-treating agent
　to the raw materials used are described below.
[0086]
[Cationic urethane resin
(A)] A1: polycarbonate-based cationic polyurethane resin
　　　Dai-ichi Kogyo Seiyaku Co., Ltd. Superflex
650 A2: polyester-based cationic polyurethane resin
　　　Co., Ltd. ADEKA Adeka
Bontighter-680 A3: polyether-based cationic polyurethane resin
　　　Dai-ichi Kogyo Seiyaku Co., Ltd. Superflex
600 A4: polyether-based anionic polyurethane resin
　　　Co., Ltd. manufactured by ADEKA Adeka Bontighter HUX-350
[0087]
Cationic phenolic resin
(B)] B1: cationic phenolic resin
　　　average polymerization degree of n = 5 repeating units of formula (2), Y1 = -CH equation (2) 2 N (CH 3 ) 2 , the equation (2 ) of Y2 = H, Z substitution degree of formula (2) =
0.5 B2: cationic phenolic resin
　　　average polymerization degree n = 10 repeating units of formula (2), formula (2) Y1 = -CH 2 n (CH 3 ) (C 2 H 4 OH), Y2 = H of formula (2), Z substitution degree of formula (2) = 1.0
[0088]
[Silane coupling agent
(C)] C1: 3- aminopropyltriethoxysilane
C2: 3- glycidoxypropyltrimethoxysilane
C3: 3- mercaptopropyltrimethoxysilane
[0089]
[Acetylacetone complex of titanium (D)]
D1: Titanium diisopropoxy bis acetylacetonato
D2: titanium tetrakis acetylacetonato
D3: titanium diisopropoxy Sibi string aminate
[0090]
[Vanadium compound
(E)] E1: vanadium acetylacetonate
E2: ammonium metavanadate
[0091]
[Olefin wax (F)]
　were used olefin wax shown in Table 1 were surface-modified with a silane coupling agent (3-glycidoxypropyltrimethoxysilane).
[0092]
[Table 1]

[0093]
[Acetate component
(G)] G1: acetate
G2: Ammonium acetate
[0094]
[Phosphate component
(H)] H1: phosphate
H2: Ammonium phosphate
[0095]
　By mixing in the composition indicating the respective components listed above in Table 2, to prepare a treating agent used in the following examples and comparative examples. Incidentally, the solid content in the treatment agent was adjusted to 11 mass%. In Table 2, the content of component (C) SiO 2 is the content by conversion, the content of the component (D) is a content by terms of Ti, by the content of the component (E) V conversion it is the content.
[0096]
[Table 2]

[0097]
3. Test plate making process
　concentration 20 g / L Fine Cleaner silicate-based alkali degreasing agent dissolved in water so that the E6406 using (Nippon Parkerizing Co., Ltd.), the test for 10 seconds spraying at a temperature of 60 ° C. subjecting the wood were further those dried after washing with water for 30 seconds with pure water used in the following tests. Each treatment agent was applied by a bar coater, and dried to a predetermined peak metal temperature (PMT) in a hot air drying furnace. Details of deposition amount, etc. shown in Table 3 below.
[0098]
[table 3]

[0099]
[Table 4]

[0100]
[table 5]

[0101]
[Evaluation Method]
(1) corrosion resistance
　to the test plate, unprocessed ones (flat portion), that cross-cut with NT cutter until the matrix reaches (crosscut portions), Erichsen 7mm extruded ones for (processing unit), corrosion resistance test was carried out. The evaluation method is as follows.
1-1 (flat portion corrosion resistance):
　Based on the salt spray test method JIS-Z-2371, were evaluated seeking white rust area ratio of 72 hours after the salt spray. The evaluation criteria are shown below.
　　◎: white rust area ratio is less than 10%
　　○: white rust area ratio of 10% or more and less than 30%
　　△: white rust area ratio of 30% to less than 60%
　　×: white rust area ratio of 60 % or more
(△ above is the practical performance.)
1-2 (cross-cut portion corrosion resistance):
　based on the salt spray test method JIS-Z-2371, it was evaluated white rust occurrence of 72 hours after the salt spray with the naked eye . The evaluation criteria are shown below.
　　◎: No rust occurred almost
　　○: rust was slightly recognized
　　△: rust is observed
　　×: rust is remarkable
(. △ above is the practical performance)
1-3 (processing unit corrosion resistance):
　Based on the salt spray test method JIS-Z-2371, it was evaluated white rust occurrence of 72 hours after the salt spray with the naked eye. The evaluation criteria are shown below.
　　◎: No rust occurred almost
　　○: rust was slightly recognized
　　△: rust is observed
　　×: rust significant
(△ above is the practical performance.)

claims

[Claim 1]A cationic polyurethane resin (A), the cationic phenolic resin (B), a silane coupling agent (C), and a titanium acetylacetone complex (D), vanadium compound and (E), and acetic acid component (G), a phosphate component (H) and the use galvanized steel by blending in water or zinc base alloy plated steel product for aqueous surface-treating agent,
　to the mass of the solid content (V) of the aqueous surface-treating agent, the silane SiO coupling agent (C) 2 ratio of the mass by conversion (NC) / (NV) is from 0.16 to 0.19,
　relative to the mass of the solid content (V), acetylacetone complexes of (D) of the titanium the ratio between the mass (ND) by terms of Ti (ND) / (NV) is from 0.0170 to 0.0240,
　with respect to the mass of the solid content (V), mass by V in terms of the vanadium compound (E) (N E) the ratio of (NE) / (NV) is from 0.0070 to 0.0090,
　with respect to the mass of the solid content (V), the ratio between the mass of the acid component (G) (NG) / ( NV) is 0.040 to 0.140,
　with respect to the mass of the solid content (V), wherein the ratio of the mass of phosphoric acid component (H) (NH) / ( NV) is 0.025 to 0.075,
　the vanadium compound ( with respect to the mass by V in terms of E), the ratio between the mass by terms of Ti of acetylacetone complex of the titanium (D) (ND) / ( NE) is from 2.10 to 2.90,
　relative to the weight of the acid component (G) , the ratio between the mass of the phosphoric acid component (H) (NH) / ( NG) from 0.25 to 1.10
　Relative to the mass (ND) by Ti Conversion acetylacetone complex (D) of the titanium, the ratio between the mass of the phosphoric acid component (H) (NH) / (ND) is 1.11 to 3.19, galvanized steel for or zinc base alloy plated steel product for aqueous surface-treating agent.
[Claim 2]
　Further, the olefin wax (F), relative to the mass of the solid content (V), 0.035 ~ 0.060 containing as the ratio of the mass of the olefin wax (F) (NF) / (NV), galvanized steel or for zinc-based alloy plated steel material for aqueous surface-treating agent according to claim 1.
[Claim 3]
　The olefin wax (F) is surface-modified with a silane coupling agent (I), relative to the weight of the olefin wax (F), the ratio between the mass of the silane coupling agent (I) (NI / NF) is it is 0.025 to 0.035 galvanized steel for or zinc base alloy plated steel product for aqueous surface-treating agent according to claim 2.
[Claim 4]
　Average particle diameter of 0.05 ~ 0.15 [mu] m, galvanized steel or for zinc-based alloy plated steel material for aqueous surface-treating agent according to claim 2 or 3 wherein the olefin-based wax (F).
[Claim 5]
　The vanadium compound is (E) is acetylacetone complexes of vanadium, galvanized steel or for zinc-based alloy plated steel material for aqueous surface-treating agent according to any one of claims 1 to 4.
[Claim 6]
　The olefin wax (F) are those that are surface modified with an epoxy group-containing silane coupling agent, galvanized steel or for zinc-based alloy plated steel for water according to any one of claims 2-5 surface treatment agent.
[Claim 7]
　The cationic polyurethane resin (A) is a general formula (1) Water-dispersible cationic polyurethane resin of polycarbonate-based, including a structural unit represented by, galvanized steel according to any one of claims 1 to 6, use or zinc base alloy plated steel product for aqueous surface-treating agent.
[Formula 1]

wherein, R is an aliphatic alkylene group of 4-9 carbon atoms, n is an integer number average molecular weight is equivalent to the range of 500-5000. ]
[8.]
　The average is a polymer molecule having a degree of polymerization of 2 to 50, galvanized steel according to any one of claims 1 to 7 having repeating units of the cationic phenolic resin (B) is represented by the general formula (2) use or zinc base alloy plated steel product for aqueous surface-treating agent.
[Formula 2]

wherein, Y1, and Y2 represents a Z group represented by each independently hydrogen or the formula (3) or (4), the average substitution number of Z groups per each benzene ring 0 a .2 to 1.0. ]
[Formula 3]

in [formula (3) and (4), R1, R2, R3, R4 and R5 are each independently a hydrogen atom, a hydroxyl alkyl group or 1 to 10 carbon atoms having 1 to 10 carbon atoms It represents an alkyl group, a - represents a hydroxide ion or an oxo acid ions. ]
[Claim 9]
　Forming a film by coating the galvanized steel product for or zinc base alloy plated steel product for aqueous surface-treating agent according to galvanized steel or zinc base alloy plated steel in any one of claims 1 to 8, the coating method.
[Claim 10]
　Obtained by the method of coating according to claim 9, coated steel.