JPWO2007069783A1 - Surface treatment agent for metal material, surface treatment method and surface treatment metal material - Google Patents

Abstract

An anionic water-dispersible resin (A) having a glass transition temperature of 0 ° C. or higher, and at least one (B) selected from the group consisting of alkali metal silicates and basic zirconium compounds are blended in water, In the alkali metal silicate, a metal material in which the mass ratio M2O / SiO2 between the M2O portion and the SiO2 portion is 1/1000 to 6/10, and M is at least one selected from the group consisting of lithium, sodium, and potassium Surface treatment agent, surface treatment method and surface-treated metal material. According to the present invention, there is provided a surface treatment agent for a metal material containing no chromium, which is used for imparting excellent corrosion resistance, chemical resistance, heat discoloration and weather resistance to a metal material. The performance can be further enhanced by blending a silane coupling agent, a vanadium compound, a titanium compound, a phosphoric acid ester of an organic phosphonic acid or a polyhydric alcohol, an inorganic acid or a salt thereof, a metal fluoride, or an oxide.

Description

  The present invention is a sheet coil made of a metal material, a metal surface treatment agent that can impart corrosion resistance, chemical resistance, heat discoloration and weather resistance to the surface of a molded product, and is used to form a chromium-free film. The present invention relates to a surface-treated metal material. More specifically, iron, zinc, zinc-plated steel, zinc-aluminum alloy-plated steel, aluminum, automotive parts made from aluminum alloys, home appliances, exterior wall materials, construction materials such as agricultural greenhouse posts, guardrails, etc. Provides excellent corrosion resistance, chemical resistance, heat discoloration, and weather resistance for sheet coils, molded products, cast products, etc. used in civil engineering products such as soundproof walls and drainage grooves, and forms a film that does not contain chromium The present invention relates to a surface treatment agent, a surface treatment method, and a surface-treated metal material.

Steel materials such as steel, galvanized steel, and zinc-aluminum alloy plated steel, aluminum materials, and zinc materials are oxidized and corroded by oxygen in the atmosphere, moisture, ions contained in moisture, and the like. As a method for preventing such corrosion, there is a conventional method of forming a chromate film by bringing a metal material surface into contact with a treatment liquid containing chromium such as chromate chromate and phosphate chromate. Films formed using these chromate treatments have excellent corrosion resistance, but contain harmful hexavalent chromium in the treatment liquid, and wastewater treatment takes time and cost. Since hexavalent chromium is contained in the coated film, there are concerns about adverse effects on the environment or the human body, and the environment is in the direction of being regulated.
In addition, when the surface-treated sheet coil is molded in the above various fields, the mold may be damaged or the film may be damaged. Further, the articles may collide with each other when the sheet coil is transported or after the molding process, and a cut may occur. Due to these external factors, when a scratch reaches the metal substrate through the film, it corrodes intensively from that site.
Moreover, press oil is used when molding the surface-treated sheet coil, and degreasing may be performed to remove it. Recently, alkaline degreasing agents are mostly used as types of degreasing agents, but some acidic degreasing agents are also used. In order to improve productivity, the concentration of the degreasing agent and the processing temperature may be increased, and the metal material on which the coating layer is formed may have unevenness due to part of the surface treatment film being removed after degreasing, depending on the case. Occurring phenomena may occur, and the corrosion resistance of the degreased molded product may be significantly reduced. Therefore, the required level of durability after cleaning of the metal material with a film formed, that is, chemical resistance is high.
In addition, there is a case where a molded product is used without being painted, and when it is used outdoors for a long period of time, there is a problem that the metallic material is discolored and corroded by acid rain, and the demand for protecting it is increasing. Therefore, it is important to improve the acid resistance of the film formed on the metal material in relation to the previous chemical resistance.
In addition, a molded product that has been surface-coated with a resin or the like may be applied with a solvent or a water-based paint. When the coating is a clear coating or only one side is coated with a color coating, the unpainted side may turn yellow when baked at a high temperature of about 200 to 280 ° C., and may turn brown when severe. Furthermore, when welding, where higher temperatures of about 400-500 ° C are locally concentrated, or when exposed to a heated atmosphere, the coating will turn brown, and in severe cases, the metal material will corrode and white rust and red rust will occur. There is. For this reason, heat discoloration is required for metal materials.
As a method using a non-chromate treatment liquid that does not contain chromium, JP-A-2004-183015 includes a vanadium compound and at least one metal selected from the group of cobalt, nickel, zinc, magnesium, aluminum, calcium, and the like. A metal surface treatment agent containing a metal compound and further at least one metal compound selected from the group consisting of zirconium, titanium, molybdenum, tungsten, manganese and cerium is disclosed.
JP-A-2003-13252 discloses at least one water-soluble resin or aqueous emulsion resin selected from cationic or nonionic urethane resins, acrylic resins, epoxy resins, polyester resins, and polyamide resins, and a specific structural formula. And a metal surface treatment agent selected from the group consisting of zircon, titanium, vanadium, molybdenum, tungsten and cerium, and a metal compound containing at least one metal selected from the group consisting of zircon, titanium, vanadium, molybdenum, tungsten and cerium.
Japanese Patent Application Laid-Open No. 2005-3069094 discloses a surface-treated metal plate formed from an inorganic filler composed of a carboxyl group-containing polyurethane resin, a silane coupling agent, and a mixture of amorphous silica and scaly silica. .

Japanese Patent Application Laid-Open Nos. 2004-183015 and 2003-13252 have the advantage of not containing hexavalent chromium and are excellent in corrosion resistance, but are sufficient in terms of the technology having both heat discoloration resistance and chemical resistance. I can't say that.
Japanese Patent Application Laid-Open No. 2005-3069094 is a two-stage surface-treated steel sheet formed of a plurality of upper and lower layers, which is not economical and does not have sufficient corrosion resistance at the scratches.
Therefore, at present, metal surface treatment agents and surface-coated metal materials that form a single-layer film that does not use chromium on the surface of metal materials and satisfy all of corrosion resistance, chemical resistance, heat discoloration resistance, and weather resistance are available. Not obtained.
The present invention has been made to solve the problems of the prior art, and is a metal containing no chromium, which is used for imparting excellent corrosion resistance, chemical resistance, heat discoloration and weather resistance to metal materials. It aims at providing a surface treating agent and a surface coating metal material. Regarding the corrosion resistance of the present invention, the performance on a flat plate where the material is not processed or scratched is taken into consideration, as well as the scratched corrosion resistance where the film is scratched and the metal material is exposed, and also the corrosion resistance after alkali cleaning is considered. Yes.
As a means for solving the above problems, the present inventor has excellent corrosion resistance, chemical resistance, heat discoloration resistance and weather resistance by treating a film on a metal material surface using a surface treatment agent having a specific composition. The present inventors have found that a film having the above properties can be obtained, and have completed the present invention.
That is, the present invention provides an anionic water-dispersible resin (A) having a glass transition temperature of 0 ° C. or higher, and at least one metal compound (B) selected from the group consisting of alkali metal silicates and basic zirconium compounds. In the alkali metal silicate salt, the mass ratio M ₂ O / SiO ₂ part of the M ₂ O part and the SiO ₂ part is 1/1000 to 6/10, and M is lithium, sodium and The present invention relates to a surface treatment agent for a metal material that is at least one selected from the group consisting of potassium.
In the present invention, the mass ratio between the anionic water-dispersible resin (A) and the metal compound (B) is in the range of 1/100 to 85/10 as (B) / (A). This is preferable from the viewpoint of improving scratch corrosion resistance and alkali resistance.
In addition, it is preferable that the anionic water-dispersible resin (A) is silyl-modified from the viewpoint of improving all the performances other than the above-described heat-resistant discoloration.
In addition, a silane coupling agent (C) having at least one functional group selected from the group consisting of an epoxy group, an amino group, a vinyl group, a mercapto group, and an isocyanato group bonded to adjacent carbon atoms. ) In such a way that the mass ratio (C) / [(A) + (B)] of component (C) to the sum of component (A) and component (B) is 1/1000 to 3/10. It is preferable from the viewpoint of improving at least one of flat plate corrosion resistance, scratch corrosion resistance, corrosion resistance after alkali cleaning, and chemical resistance.
Further, the vanadium compound (D) is added to the surface treatment agent, and the mass ratio (D) / [(A) + (B)] of the sum of the component (D), the component (A), and the component (B) is 1. It is preferable to blend so as to be / 1000 to 1/5 from the viewpoint of improving at least one of flat plate corrosion resistance, scratch corrosion resistance, and corrosion resistance after alkali cleaning.
Moreover, the mass ratio (E) / [(A) + (B)] of the titanium compound (E) and the sum of the component (E), the component (A), and the component (B) is 1 in the surface treatment agent. It is preferable to blend so as to be / 1000 to 1/5 from the viewpoint of improving at least one of flat plate corrosion resistance, scratch corrosion resistance, and corrosion resistance after alkali cleaning.
Moreover, at least one organic phosphorus compound (F) selected from the group consisting of phosphoric acid esters of organic phosphonic acids and polyhydric alcohols and salts thereof is used as the surface treatment agent, and the components (F) and (A). And it is preferable from a viewpoint of an improvement of plate | board corrosion resistance to mix | blend so that mass ratio (F) / [(A) + (B)] with the sum total of a component (B) may become 1 / 1000-1 / 10.
In addition, the surface treatment agent may include at least one inorganic acid compound (G) selected from the group consisting of inorganic acids and salts thereof, with the sum of component (G), component (A), and component (B). It is preferable from the viewpoint of improving the plate corrosion resistance that the mass ratio (G) / [(A) + (B)] is 1/1000 to 1/10.
Further, the surface treatment agent contains at least one oxide (H) selected from the group consisting of calcium oxide, magnesium oxide, manganese oxide, zinc oxide, aluminum oxide, niobium oxide, boron oxide and zinc borate. It is preferable from the viewpoint of improving all the performances that the mass ratio (H) / (B) of (H) to the component (B) is 1/1000 to 1/10.
The present invention also provides a surface of a metal material, wherein the surface treatment agent is applied to at least one surface of the metal material and dried to form a film having a dry film mass of 0.1 to 3 g / m ^2. The present invention relates to a treatment method and a metal material surface-treated by the surface treatment method.
The metal material is preferably a steel material, a zinc material, a galvanized steel material, a zinc-aluminum alloy plated steel material, an aluminum material, or an aluminum alloy material.
The metal surface treatment agent of the present invention is a non-chromate type that does not contain harmful chromium compounds, and the surface coating metal material formed from this surface treatment agent is generally compared with conventional chromate films and conventional non-chromate films. It has excellent corrosion resistance, chemical resistance, heat discoloration and weather resistance, and the surface treatment agent, surface treatment method and surface treatment metal material of the present invention have extremely great industrial utility value. I can say that.

The improvement effect of the metal surface treatment agent of the present invention is most exerted on steel, zinc, and galvanized steel that are easily corroded, and is generally used as a material in many cases. A specific explanation will be given centering on an example adapted to.
The anionic water-dispersible resin (A) to be blended with the surface treatment agent of the present invention has a glass transition temperature of 0 ° C. or higher. The glass transition temperature is a temperature at which the resin changes from a glass state to a rubber state. Basically, when a resin having a high glass transition temperature is used, corrosion resistance and chemical resistance are often excellent. When the glass transition temperature is low, the resin is soft and the degree of freedom is large, so that water and chemicals are likely to penetrate, and discoloration and corrosion of metal materials are often promoted. Therefore, in the urethane resin (A) used in the present invention, the glass transition temperature is set to 0 ° C. or higher so that a corrosion-resistant and chemical-resistant film that hardly penetrates water and chemicals can be formed. The glass transition temperature is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 100 ° C. or higher, from the viewpoint of corrosion resistance and chemical resistance. If the temperature is lower than 0 ° C., the resin is too flexible, and therefore, the stickiness of the film and the water permeability increase under high temperature and high humidity. On the other hand, if it exceeds 130 ° C., the film-forming property may be poor and the adhesion may be poor. In any case, it leads to a decrease in corrosion resistance and chemical resistance, and the effect of the present invention cannot be obtained. Moreover, it becomes easy to hold | maintain the metal compound (B) and also component (C)-(F) mix | blended as an arbitrary component in a film | membrane by setting glass transition temperature to 0 degreeC or more, and the effect of each component is made more. Can be increased.
The reason why the resin component (A) used in the present invention is anionic is that when a cationic water-dispersible resin is used, the liquid stability of the surface treatment agent of the present invention is low, and the nonionic water-dispersible resin is the resin itself. This is because the water resistance is relatively low, which leads to a decrease in corrosion resistance, whereas the anionic water-dispersible resin does not have such a problem.
Examples of the type of the anionic water-dispersible resin (A) of the present invention include anionic urethane resins, anionic acrylic resins, anionic epoxy resins, anionic fluororesins, anionic polyester resins, and the like. is not. Among these resins, an anionic urethane resin, an anionic acrylic resin, and an anionic epoxy resin are preferable from the viewpoint of corrosion resistance and chemical resistance, and an anionic urethane resin is particularly preferable. These resins will be described below.
The anionic water-dispersible resin (A) of the present invention is preferably silyl-modified using a silane coupling agent at the stage of synthesis. Silyl modification refers to reacting a silane coupling agent with a functional group present in the resin raw material in the resin synthesis stage, and the reaction product of the silane coupling agent is present in the skeleton of the anionic water-dispersed resin. . When it exists in the principal chain of the resin skeleton, it may be either present in the side chain. There is no restriction | limiting in particular about the kind of silane coupling agent at the time of silyl modification | denaturation, and the amount of silyl modification | denaturation. The amount of silyl modification is defined as the mass ratio of silicon atoms to the resin (solid content). The ratio of silicon atoms to the anionic water-dispersible resin (A) is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and more preferably 0.1% by mass or more. Even more preferred. The upper limit of the silyl modification amount is not particularly limited, but is about 5% by mass. If it exceeds 5% by mass, the effect of silyl modification is saturated, which is economically wasteful. Due to the silyl modification, the adhesion to the metal material is increased at the time of film formation, and further, the film becomes dense, so that the planar corrosion resistance, scratch corrosion resistance, post-cleaning corrosion resistance and chemical resistance are improved. Since the silane coupling agent is highly reactive, the amount of silyl modification can usually be determined from the amount charged, but it can also be measured by NMR analysis of the resin. In addition, the method of silyl modification | denaturation is demonstrated in description of each resin.
The acid value of the anionic urethane resin used as the anionic water-dispersible resin (A) is not particularly limited, but in order to make the resin water-dispersible, the physical properties of the film formed from the resin are further limited. From the point of view, the range is preferably 10 to 50, more preferably 15 to 40, and still more preferably 20 to 30. When the acid value is in the range of 10 to 50, the adhesion with the metal material, the corrosion resistance and the chemical resistance are further improved. If the acid value is less than 10, the adhesion to the metal substrate is inferior, and the chemical resistance and scratch resistance are reduced. When the acid value exceeds 50, the hydrophilicity of the film increases, it becomes easy to draw water, and the corrosion resistance and chemical resistance may decrease.
Although there is no restriction | limiting in particular about the molecular weight of an anionic urethane resin, When it measures by a gel permeation chromatography, it is preferable that it is about 10,000-1,000,000, About 50,000-1,000,000. It is more preferable that it is about 100,000 to 1,000,000.
By increasing the molecular weight, the metal compound (B) or other optional components (C) to (G) can be held in the film, and the effect of each component can be further enhanced.
Anionic urethane resins are generally made from polyisocyanates (particularly diisocyanates), polyols (particularly diols), carboxylic acids having two or more, preferably two hydroxyl groups, or reactive derivatives thereof, and polyamines (particularly diamines). Obtained by various synthesis methods. More specifically, although not limitedly interpreted, for example, a urethane prepolymer having an isocyanate group at both ends is produced from a diisocyanate and a diol, and a carboxylic acid having two hydroxyl groups or a reactivity thereof. By reacting the derivative to form a derivative having an isocyanato group at both ends, and then adding triethanolamine or the like to form an ionomer (triethanolamine salt), adding it to water to make an emulsion, and further adding a diamine to extend the chain, An anionic urethane resin can be obtained.
Examples of the polyisocyanate used when producing the anionic urethane resin include aliphatic, alicyclic and aromatic polyisocyanates, and any of them can be used. Specifically, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, hydrogenated xylylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 2,4′-dicyclohexylmethane diisocyanate, Isophorone diisocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4, , 4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, phenylene diisocyanate, xylylene diisocyanate, tetra Chill xylylene diisocyanate. Among these, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, hydrogenated xylylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate When an aliphatic or alicyclic polyisocyanate such as the above is used, a film excellent not only in chemical resistance and corrosion resistance but also in heat discoloration resistance and weather resistance is preferable.
Examples of polyols used in the production of an anionic urethane resin include polyester polyols and polyether polyols. In the present invention, any of those usually used for the production of urethane resins can be used. In particular, polyester polyol is preferable.
As the polyester polyol, a polyester polyol obtained by subjecting a glycol component and a dicarboxylic acid or a reactive derivative thereof (an acid anhydride) to a dehydration condensation reaction; a cyclic ester compound such as ε-caprolactone, a polyhydric alcohol as an initiator And polyester polyols obtained by ring-opening polymerization.
Examples of the glycol component used for producing the polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl-1,5-pentane. Diol, 1,6-hexanediol, neopentyl glycol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300 to 6,000), dipropylene glycol, tripropylene glycol, bis (hydroxy Ethoxy) benzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, hydroquinone and the like.
Examples of the dicarboxylic acid and its reactive derivative used in the production of polyester polyol include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4 -Cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (Phenoxy) ethane-p, p′-dicarboxylic acid and anhydrides of these dicarboxylic acids.
A carboxylic acid having two or more, preferably two, hydroxyl groups used in the production of an anionic urethane resin or a reactive derivative thereof introduces an acidic group into the urethane resin, and makes the urethane resin water-dispersible. Used for. Examples of carboxylic acids having two or more, preferably two, hydroxyl groups include dimethylol alkanoic acids such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolpentanoic acid, and dimethylolhexanoic acid. it can. Examples of the reactive derivative include acid anhydrides. Thus, by making the urethane resin self-water dispersible and not using an emulsifier or using it as much as possible, a film having excellent water resistance can be obtained.
Examples of the polyamine used for producing the anionic urethane resin include hydrazine, ethylenediamine, propylenediamine, 1,6-hexanediamine, tetramethylenediamine, isophoronediamine, xylylenediamine, piperazine, 1,1'-bicyclohexane- 4,4′-diamine, diphenylmethanediamine, ethyltolylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine and the like can be mentioned.
In order to improve the stability of the resin during the synthesis of the anionic urethane resin and the film-forming property when the ambient environment during the film-forming is under low temperature drying, it is preferable to add a film-forming aid during the synthesis. Examples of the film forming aid include butyl cellosolve, N-methyl-2-pyrrolidone, butyl carbitol, and texanol, and N-methyl-2-pyrrolidone is more preferable.
As described above, the anionic urethane resin is preferably silyl-modified. This silyl modification is performed by using a silane coupling agent in the synthesis step of the anionic urethane resin, and a more specific modification method is not particularly limited. For example, a silane coupling agent having an amino group or a glycidyl group as a polyol. Is reacted with polyisocyanate after the reaction, or a polysilane of polyol and polyisocyanate is reacted with a silane coupling agent having an amino group or an epoxy group. The silane coupling agent can also react with a silanol group generated by hydrolysis of an alkoxy group bonded to a silicon atom.
There is no restriction | limiting in particular about the kind of silane coupling agent at the time of carrying out silyl modification | denaturation, As a silane coupling agent, the silane coupling agent included by the below-mentioned silane coupling agent (C) can be used. A silane coupling agent having an amino group (primary or secondary amino group) or a glycidyl group is preferable as a silane coupling agent for silyl modification, but a silane coupling agent having a mercapto group or an isocyanato group is also used. In addition, a silane coupling agent having no special functional group can also be used by utilizing a reaction with a silanol group. There is no restriction | limiting in particular about the reaction temperature at the time of carrying out silyl modification | denaturation, For example, you may react at 0-150 degreeC.
Next, the anionic acrylic resin used as the anionic water-dispersible resin (A) will be described. The acid value and molecular weight of the anionic acrylic resin can be in the same numerical range from the same viewpoint as in the case of the anionic urethane resin.
Although there is no restriction | limiting in particular in the monomer seed | species which synthesize | combines an acrylic resin, It can combine arbitrarily so that a glass transition temperature may be 0 degreeC or more using a monomer as shown below. As monomer components, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, Hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, maleic acid, itaconic acid, acrylamide, N-methylol acrylamide, diacetone acrylamide, glycidyl (meth) acrylate, styrene, vinyl acetate, acrylonitrile, glycidyl (meth) acrylate, etc. Is mentioned. The acid value can be adjusted with, for example, acrylic acid or methacrylic acid.
Furthermore, chemical resistance is improved by combining the following modified acrylic monomers. For example, a polyester (meth) acrylate obtained by reaction of a polyol such as those mentioned in the description of an anionic urethane resin with an organic acid (for example, phthalic acid) of 2 or more basic acids and (meth) acrylic acid; a polyol and a polyisocyanate And polyurethane (meth) acrylate obtained by reaction with (meth) acrylic acid; epoxy (meth) acrylate obtained by reaction between epoxy resin and (meth) acrylic acid; polyether resin and eg (meth) acrylic acid And polyether (meth) acrylate obtained by the reaction.
As described above, the anionic acrylic resin is preferably silyl-modified. As silyl-modified acrylic resins, silyl-modified acrylate monomers obtained by reacting silane coupling agents having amino groups and the like with (meth) acrylic acid or glycidyl (meth) acrylate are copolymerized with other acrylic monomers. An acrylic resin obtained by adding a silane coupling agent having an amino group capable of reacting with a carboxyl group or a glycidyl group at the final stage of synthesis of an acrylic resin containing a (meth) acrylic acid unit or a glycidyl (meth) acrylate unit. An acrylic resin obtained by the above can be exemplified. The anionic property of the silyl-modified acrylic resin can be adjusted with (meth) acrylic acid or the like as described above. The silyl modification can be performed by the same method using the same silane coupling agent as mentioned in the silyl modification of the anionic urethane resin.
In the silyl-modified acrylic resin, the alkoxy group bonded to the silicon atom may be partially or entirely hydrolyzed. However, from the viewpoint of improving adhesion with a metal material during film formation and improving corrosion resistance and chemical resistance due to the dense film, the residual ratio of alkoxy groups bonded to silicon atoms in the silyl-modified acrylic resin is 50. It is preferable that it is -95 mol%, and it is more preferable that it is 60-90 mol%.
Next, the anionic epoxy resin used as the anionic water-dispersible resin (A) of the present invention will be described. Examples of the anionic epoxy resin include phenol novolak, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcin novolak, bisphenol A novolak, bisphenol F novolak and the like obtained by reaction of epichlorohydrin. An anionic thing is mentioned in a glycidyl ether compound. Since the phenolic hydroxyl group is anionic, the anionicity is maintained by leaving the phenolic hydroxyl group during glycidylation. These epoxy resins can be made into an aqueous dispersion by a conventional method.
The epoxy equivalent of the epoxy resin (the chemical formula amount of the epoxy resin per epoxy group, in other words, the value obtained by dividing the molecular weight of the epoxy resin by the number of epoxy groups contained in the epoxy resin) is preferably 100 to 5000. 500 to 2000 is more preferable. When the epoxy equivalent is less than 100, the film to be formed becomes soft and chemical resistance may be lowered. On the other hand, if it is larger than 5000, the coating film to be formed becomes brittle and may adversely affect various performances.
The epoxy resin may be an epoxy resin in which a part of the glycidyl group is modified. Examples of the modification of the epoxy resin include silyl modification and phosphoric acid modification. The silyl modification can be performed by adopting the above-described method of silyl modification of urethane resin or acrylic resin.
Phosphoric acid modification is performed by reacting an epoxy resin having a phenolic novolak structure as described above with phosphoric acid or an ester thereof. As phosphoric acids, metaphosphoric acid, phosphonic acid, orthophosphoric acid, pyrophosphoric acid and the like can be used. As esters of phosphoric acids, monoesters such as metaphosphoric acid, phosphonic acid, orthophosphoric acid, pyrophosphoric acid, such as monomethyl phosphoric acid, Monooctyl phosphoric acid, monophenyl phosphoric acid and the like can be used. The degree of modification of phosphoric acid is not particularly limited as long as the effect of modification is recognized, but usually P-OH group equivalent (chemical formula amount of epoxy resin per P-OH group, in other words, epoxy resin) The molecular weight of the epoxy resin is divided by the number of P-OH groups contained in the epoxy resin) is preferably modified to be in the range of 150 to 1,000, and modified to be in the range of 300 to 800. Is more preferable.
The effect of silyl modification has already been described. As for phosphoric acid modification, the phosphoric acid modification improves the adhesion to the metal material during film formation, and further improves the chemical resistance because the film becomes dense. However, when silyl modification and phosphoric acid modification are compared, silyl modification is more preferable from the viewpoint of improving chemical resistance.
The metal compound (B) to be blended in the surface treatment agent of the present invention, that is, at least one selected from the group consisting of an alkali metal silicate salt and a basic zirconium compound is a plate corrosion resistance, a scratch corrosion resistance, and an acid resistance in chemical resistance. Contributes to the improvement of sex.
First, the alkali metal silicate used as the metal compound (B) will be described. M of alkali metal silicate ₂ O portion (M represents an alkali metal such as lithium, sodium, potassium) and SiO ₂ Mass ratio M ₂ O / SiO ₂ Needs to be in the range of 1/1000 to 6/10, and is preferably in the range of 1/100 to 1/2. M ₂ If the ratio of O is less than 1/1000, the effect of mitigating corrosion due to dissolution of the metal material generated at the interface between the film and the metal material becomes poor, leading to a general decrease in corrosion resistance. M ₂ When the proportion of O is more than 6/10, the alkali metal is easily dissociated from the film, and this leads to a general decrease in corrosion resistance and a decrease in alkali resistance due to a phenomenon in which water resistance decreases.
Examples of the basic zirconium compound used as the metal compound (B) of the present invention include zirconium ammonium carbonate, lithium zirconium carbonate, sodium zirconium carbonate, potassium zirconium carbonate, zirconium hydroxide and the like.
The mass ratio (B) / (A) of the metal compound (B) and the anionic water-dispersible resin (A) is 1/100 to 85/10 from the viewpoints of improvement in flat plate corrosion resistance, scratch corrosion resistance and alkali resistance. The range is preferably 10/90 to 80/20, and more preferably 15/85 to 40/60.
If the proportion of the metal compound (B) (excluding zirconium ammonium carbonate) is less than 1/100, the effect of mitigating corrosion due to dissolution of the metal material generated at the interface between the film and the metal material becomes poor, and overall corrosion resistance and alkali resistance Leading to a decline. Moreover, when the ratio of a metal compound (B) becomes more than 85/10, an alkali metal will be easily dissociated from a film, and it will lead to a general fall in corrosion resistance or alkali resistance by the phenomenon that water resistance falls.
In the case of a basic zirconium compound, carbonate ions are removed when a film is formed, and the above effects are also obtained by increasing the barrier properties of the film by binding zirconium through oxygen to increase the molecular weight. In the case of ammonium zirconium carbonate, when the ratio is less than 1/100, this barrier property cannot be sufficiently exhibited, and when it exceeds 85/10, the liquid stability of the surface treatment agent of the present invention is lowered. In the case of a basic zirconium compound, when the anionic water-dispersible resin has a carboxyl group, a crosslinking reaction occurs to improve water resistance and lead to improvement in corrosion resistance.
When the silane coupling agent (C) is blended with the surface treatment agent of the present invention, at least one of flat plate corrosion resistance, scratch corrosion resistance, corrosion resistance after alkali cleaning, and chemical resistance can be further improved. Examples of the silane coupling agent (C) include vinyltrichlorosilane, vinyltris (2-methoxyethoxysilane), vinyltriethoxysilane, vinyltrimethoxysilane, 3- (methacryloyloxypropyl) trimethoxysilane, 2- (3 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glyoxydoxypropyltrimethoxysilane, 3-glyoxydoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltri Toxisilane, 3-mercaptopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, ureidopropyltriethoxysilane, tetra or trimethoxysilane (tetramethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane Etc.). Moreover, a glycidyl group-containing partial condensate obtained by a demethanol reaction of tetra or trimethoxysilane and glycidol can also be used.
The compounding amount of the silane coupling agent (C) is the mass ratio (C) / [(A) + (B) between the component (C) and the total of the anionic water-dispersible resin (A) and the metal compound (B). ] Is preferably in the range of 1/1000 to 3/10, and more preferably in the range of 1/100 to 1/5. If the ratio of the component (C) is less than 1/1000, the blending effect does not appear, and if it exceeds 3/10, the effects of the present invention may be inhibited.
When the vanadium compound (D) is blended with the surface treatment agent of the present invention, at least one of plate corrosion resistance, scratch corrosion resistance and corrosion resistance after alkali cleaning can be further improved. Examples of the vanadium compound (D) include vanadium compounds having an oxidation number of pentavalent, tetravalent, trivalent or divalent, such as vanadium pentoxide (V ₂ O ₅ ), Metavanadic acid (HVO) ₃ ), Ammonium metavanadate, sodium metavanadate, vanadium oxytrichloride (VOCl) ₃ ) And the like, and vanadium trioxide (V ₂ O ₃ ), Vanadium dioxide (VO) ₂ ), Vanadium oxysulfate (VOSO) ₄ ), Vanadium oxyacetylacetonate [VO (OC (CH ₃ ) = CHCOCH ₃ )) ₂ ], Vanadium acetylacetonate [V (OC (CH ₃ ) = CHCOCH ₃ )) ₃ ], Vanadium trichloride (VCl ₃ ), Molybdic acid {H ₁₅ -X [PV ₁₂ -XMoxO ₄₀ ] NH ₂ O (6 <x <12, n <30)}, vanadium sulfate (VSO ₄ ・ 8H ₂ O), vanadium dichloride (VCl ₂ ), Vanadium oxide (VO) and the like, and vanadium compounds having an oxidation number of 4 to 2 are listed.
As for the vanadium compound (D), the oxidation number of vanadium is equally effective with respect to the corrosion resistance, but the tetravalent vanadium compound is superior to the pentavalent vanadium compound with respect to water resistance. As a method of blending the 4- to 2-valent vanadium compound with the surface treatment agent of the present invention, the 4-valent vanadium compound is used in addition to the 5-valent vanadium compound in advance using a reducing agent in advance. What was divalently reduced can be used. The reducing agent to be used may be either inorganic or organic, but it is particularly preferable to use an organic acid among organic ones. It is preferable to mix the pentavalent vanadium compound after reducing it to tetravalent, trivalent or divalent because the stability of the vanadium compound can be improved.
The compounding quantity of a vanadium compound (D) is as mass ratio (D) / [(A) + (B)] of a sum total of a component (D), anionic water-dispersible resin (A), and a metal compound (B). The range of 1/1000 to 1/5 is preferable, and the range of 1/500 to 1/10 is more preferable. When the ratio of the component (D) is less than 1/1000, the blending effect is not expressed, and when it exceeds 1/5, the heat discoloration and weather resistance may be deteriorated.
When the titanium compound (E) is blended with the surface treatment agent of the present invention, at least one of flat plate corrosion resistance, scratch corrosion resistance and corrosion resistance after alkali cleaning can be further improved. Examples of the titanium compound (D) include titanyl sulfate TiOSO. ₄ , Diisopropoxytitanium bisacetylacetone (C ₅ H ₇ O ₂ ) ₂ Ti [OCH (CH ₃ ) ₂ ] ₂ , Reaction product of lactic acid and titanium alkoxide, titanium laurate, titanium acetylacetonate Ti (OC (= CH ₂ ) CH ₂ COCH ₃ ) ₃ , Tetraisopropyl titanate [Ti (OCH (CH ₃ ) ₂ ) ₄ ], Tetranormal butyl titanate [Ti (O (CH ₂ ) ₃ (CH ₃ )) ₄ ], Butyl titanate dimer [((CH ₃ ) (CH ₂ ) ₃ O) ₃ -Ti-O-Ti (O (CH ₂ ) ₃ (CH ₃ )) ₃ ], Tetraoctyl titanate [Ti (O (CH ₂ ) ₇ (CH ₃ )) ₄ ], Titanium octyl glycolate, titanium tetraacetylacetonate, titanium ethylacetoacetate and the like can be used.
The compounding quantity of a titanium compound (E) is as mass ratio (E) / [(A) + (B)] of a component (E), and the sum total of anionic water-dispersible resin (A) and a metal compound (B). The range of 1/1000 to 1/5 is preferable, and the range of 1/500 to 1/10 is more preferable. When the ratio of the component (E) is less than 1/1000, the blending effect is not exhibited, and when it exceeds 1/5, the heat discoloration and weather resistance may be deteriorated.
When the surface treatment agent of the present invention is blended with at least one organic phosphorus compound (F) selected from the group consisting of organic phosphonic acid and polyhydric alcohol phosphates and salts thereof, the plate corrosion resistance is further improved. Can be made. Examples of the organic phosphonic acid include aminotri (methylenephosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, ethylenediamine-N, N, N ′, N′-tetra (methylenephosphonic acid), hexamethylenediamine-N, N, N ′, N′-tetra (methylenephosphonic acid), diethylenetriamine-N, N, N ′, N ″, N ″ -penta (methylenephosphonic acid), 2-phosphonobutane-1,2,4-tricarboxylic acid An acid etc. are mentioned, and inositol hexaphosphate ester etc. are mentioned as a phosphate ester of a polyhydric alcohol. Examples of the salts of organic phosphonic acid and phosphoric acid ester of polyhydric alcohol include alkali metal salts (sodium salt, potassium salt, etc.), ammonium salts and the like. When the phosphoric acid ester of organic phosphonic acid or polyhydric alcohol has two or more phosphonic groups or phosphoric acid groups, the alkali metal salt or ammonium salt may be a partial salt or a total salt. .
The compounding amount of the component (F) is 1 as a mass ratio (F) / [(A) + (B)] of the component (F) and the total of the anionic water-dispersible resin (A) and the metal compound (B). It is preferably in the range of / 1000 to 1/10, and more preferably in the range of 1/500 to 1/20. When the proportion of the component (F) is less than 1/1000, the blending effect is not exhibited, and when it exceeds 1/10, the corrosion resistance and chemical resistance after alkali cleaning may be deteriorated.
When at least one inorganic acid compound (G) selected from the group consisting of inorganic acids and salts thereof and metal fluorides is blended in the surface treatment agent of the present invention, the plate corrosion resistance can be further improved. Ingredient (G) contributes to improving the corrosion resistance of the flat plate by etching the metal material to remove the oxide film or eluting zinc and the like (zinc ions form a hardly soluble salt with the metal compound (B)). In addition, the component (G) has an effect of insolubilizing the metal compound (B) itself, that is, suppressing the dissociation of alkali metal ions, and the water resistance is increased, which leads to improvement of corrosion resistance.
Inorganic acids include phosphoric acid, tetrafluoroboric acid (HBF) ₄ ), Hexafluorosilicic acid (H ₂ SiF ₆ ), Hexafluorozirconic acid (H ₂ ZrF ₆ ), Hexafluorotitanic acid (H ₂ TiF ₆ These salts include ammonium salts and alkali metal salts (sodium salt, potassium salt, etc.), and metal fluorides include tin (I) fluoride (SnF). ₂ ), Tin (II) fluoride (SnF) ₄ ), Ferrous fluoride, ferric fluoride and the like.
The compounding amount of the component (G) is 1 as a mass ratio (G) / [(A) + (B)] of the component (G) and the total of the anionic water-dispersible resin (A) and the metal compound (B). It is preferably in the range of / 1000 to 1/10, and more preferably in the range of 1/500 to 1/20. When the ratio of the component (G) is less than 1/1000, the blending effect does not appear, and when it exceeds 1/10, the corrosion resistance and chemical resistance after alkali cleaning may be lowered.
When the surface treatment agent of the present invention contains at least one oxide (H) selected from the group consisting of calcium oxide, magnesium oxide, manganese oxide, zinc oxide, aluminum oxide, niobium oxide, boron oxide and zinc borate. All of the effects of the present invention can be further improved. These oxides may be hydrates. The component (H) is used by previously blending it in an aqueous solution of the metal compound (B). Among the metal compounds (B), it is preferable to use an alkali metal silicate, which is preferable in order to maximize the effects of the surface treatment agent of the present invention.
The oxide (H) reacts with the metal compound (B) to form a salt that is hardly soluble in water, thereby fixing the ammonium ion or alkali metal ion, particularly the alkali metal ion, thereby exhibiting the above effect. . That is, the water resistance of the whole film can be increased by suppressing or delaying alkali metal ions and the like from flowing out of the film. As a result, when it is immersed in a corrosive environment containing water or in chemicals, a highly water-resistant film can be formed, leading to the suppression of permeation of corrosive factors, improving overall corrosion resistance, and chemical resistance. A coated metal material having excellent properties can be obtained. In addition, the immobilized alkali metal ions have an effect of neutralizing the acid content that has penetrated into the film when acid rain comes into contact with the coated metal material, and can suppress corrosion of the metal material. Furthermore, when the anodic reaction in which the metal dissolves locally on the surface of the metal material proceeds, the site becomes acidic, but alkali metal ions act to neutralize it (so-called corrosion phenomenon buffering action to dissolve the metal) ). Therefore, the oxide (H) can improve all the performances related to the present invention. Moreover, since the said hardly soluble or insoluble salt exists as a gel-like substance, it has the effect | action which accelerates | stimulates gelatinization in the stage of film formation.
The compounding amount of the component (H) is preferably in the range of 1/1000 to 1/10 as the mass ratio (H) / (B) of the component (H) and the metal compound (B), A range of 1/20 is more preferable. When the ratio of the component (H) is less than 1/1000, the blending effect does not appear, and when it exceeds 1/10, the liquid stability of the surface treatment agent tends to decrease.
The surface treatment agent of the present invention may further contain a lubricant such as polyethylene wax, polypropylene wax, microcrystalline wax, carnauba wax, polytetrafluoroethylene. Sliding property, moldability, and scratch resistance can be imparted by blending the lubricant. 1-20 mass% of all the non-volatile components of the surface treating agent of this invention are preferable, and, as for the compounding quantity of a lubricant, 3-15 mass% is more preferable.
The surface treatment agent of the present invention may further contain a surfactant, an antifoaming agent, a leveling agent, an antibacterial and antibacterial agent, a colorant, and the like within a range not impairing the gist and film performance of the present invention.
Although the medium used in the surface treatment agent of the present invention is mainly water, a small amount (for example, 10% by volume or less of the entire aqueous medium) of alcohol, ketone, cellosolve water-soluble, if necessary, such as improvement of the drying property of the film. An organic solvent may be used in combination.
In addition, description of the essential component which comprises the surface treating agent of this invention, and an arbitrary component represents the state at the time of a mixing | blending, and even if it reacts between components after a mixing | blending, it does not remove | deviate from the scope of the present invention.
Although there is no restriction | limiting in particular about the total solid content concentration of the surface treating agent of this invention as long as the effect of this invention can be achieved, Usually, it is preferable to adjust to the range of 1-35 mass%, and 5-25 mass%. It is more preferable to adjust to the range.
The surface treatment agent of the present invention can be applied to various metal materials, but is preferably applied to metal materials whose materials are steel, zinc, galvanized steel, zinc-aluminum alloy plated steel, aluminum or aluminum alloy. Metal materials include metal plates, sheet coils, pipes, round bars, square materials, etc .; including molded products or cast products (automobile members, home appliances, outer wall materials, building material products, civil engineering products, etc.) made from these primary materials To do.
There is no particular limitation on the pre-treatment process of the surface treatment agent of the present invention, but usually, alkaline degreasing is performed to remove oil and dirt adhering to the metal material (hereinafter sometimes referred to as “raw material”) before performing this treatment. Wash with an agent or acidic degreasing agent, or wash with hot water or solvent. Thereafter, surface adjustment with acid, alkali or the like is performed as necessary. In cleaning the surface of the material, it is preferable to wash with water after cleaning so that the cleaning agent does not remain on the surface of the material as much as possible. Of course, if the surface is not dirty, it may not be washed.
The treatment with the metal surface treatment agent of the present invention is performed by applying the metal surface treatment agent and then drying. There are no particular restrictions on the application method, a roll coating method in which a treatment agent is roll-transferred and applied to the surface of a metal material, or a method of squeezing with a roll after pouring with a shower ringer or the like, or draining with an air knife, in the treatment liquid What is necessary is just to select suitably from the method of immersing a metal material in this, the method of spraying a processing agent on a metal material, etc. Since the solvent of this treatment agent is mainly water, the treatment liquid temperature is preferably 0 to 60 ° C, more preferably 5 to 40 ° C.
The drying step does not necessarily require heat and may be air-dried or physical removal such as air blow, but may be heat-dried in order to improve film-forming properties and interlayer adhesion. The temperature in that case is preferably in the range of 30 to 250 ° C, more preferably in the range of 60 to 220 ° C, and still more preferably in the range of 80 to 200 ° C.
The amount of film formed is 0.1 to 3 g / m in dry film amount. ² Is preferably 0.2 to 2.5 g / m ² Is more preferable. 0.1 g / m ² If it is less than 1, the chemical resistance and the corrosion resistance after alkali washing may decrease. 3g / m ² If it exceeds 1, the effect of the present invention is saturated, which is economically undesirable.
On the film formed from the surface treatment agent of the present invention, the dry film amount is 0.3 to 50 g / m in order to impart further functionality or further enhance the effects of the present invention. ² It is also possible to provide such a resin layer. Thereby, in addition to improving the corrosion resistance and chemical resistance of the metal material to be treated, fingerprint resistance, solvent resistance and surface lubricity can be improved.
Examples of a method for providing such a resin layer include a method in which a solvent-based paint or a water-based paint in which a resin is dissolved or dispersed in advance is applied and dried at 30 to 280 ° C .; a method in which a film-like resin is laminated, and the like. Examples of the resin include polyester resin, vinyl chloride resin, acrylic resin, epoxy resin, polyimide resin, polyamide resin, polyolefin resin, polyamide resin, urethane resin, and phenol resin.
The water-based paint preferably contains water-dispersible silica in order to improve the toughness and fingerprint resistance of the film, and preferably contains water-based wax in order to improve lubricity. The content of each component in the water-based paint is 50 to 100 parts by weight of resin, 0 to 40 parts by weight of water-dispersible silica, and 0 to 0 to water-based wax when the total solid content is 100 parts by weight. The amount is preferably 30 parts by mass. Moreover, it is also possible to contain the crosslinking agent which can bridge | crosslink resin.
The reason why the coating obtained by applying the surface treatment agent of the present invention to the surface of a metal material and drying it exhibits excellent corrosion resistance, chemical resistance, heat discoloration resistance and weather resistance is estimated as follows, but the present invention Is not limited in any way by such an estimate, and such an estimate has no adverse effect on the patentability of the present invention.
First, when a surface treatment agent is applied to the surface of a metal material, at least one (B) selected from the group consisting of a metal compound (B), that is, an alkali metal silicate salt and a basic zirconium compound, is present on the surface of the metal material. A hardly soluble composite film comprising a metal oxide or a complex oxide (oxyacid salt) containing alkali metal, silicon and metal or a complex oxide (oxyacid salt) containing alkali metal, zirconium and metal by reacting with metal oxide or metal Formed, thereby reducing the activity of the metal material. Furthermore, when a corrosive factor such as water or chlorine penetrates through the film in a corrosive environment and a corrosion reaction of the metal material occurs, an anode reaction of the metal material occurs and the acidity increases locally. A buffering effect against corrosion of the metal material is exhibited by dissociating and neutralizing the alkali metal ions (some of which may be ammonium ions) present in the component (B) with respect to the site. In addition, dissociation of alkali metal ions further increases the barrier property of the film formed by the metal compound (B) (for example, the barrier property is increased by binding zirconium to each other through oxygen to increase the molecular weight). In addition, the filling effect (physical shielding effect) of the component (B) itself leads to improvement of water resistance, and the effect of the present invention is further enhanced.
However, since the metal compound (B) alone easily flows out and this effect does not last for a long time, the anionic water-dispersible resin (A) is indispensable. By using a resin component having a high glass transition temperature and excellent chemical resistance, the effect of the component (B) can be maintained over a long period of time. Since component (B) generally exhibits a considerably strong alkalinity, it is necessary to use a resin having excellent alkali resistance. When the glass transition temperature is lower than the minimum temperature defined in the present invention, the resin is flexible, so that the film has fluidity in a corrosive environment and the water resistance is lowered, and further, the retainability of the component (B) is impaired.
In addition, adhesiveness with a metal material increases by carrying out silyl modification | denaturation of a component (A), and also chemical resistance increases.
With regard to scratch corrosion resistance, even when the film is damaged and the metal material is exposed, the neutralization effect of dissociating alkali metal ions, and the dissociation of alkali metal (partially ammonium component) allows silicon compounds and zirconium compounds to It has an effect of covering active sites from which the metal material is eluted in a corrosive environment, and delays the progress of corrosion.
Corrosion resistance after alkali cleaning is manifested by the formation of a film with a high barrier property, and the alkali metal silicate or zirconium compound held in the resin film is filled with alkali (physical shielding effect). It is expressed by the component (B) remaining in the film even after washing.
The effects of the optional components (C) to (H) are as described above, and the effects of the components (A) and (B) can be further enhanced.
With regard to the weather resistance, there is an effect of protecting the metal material by neutralizing the alkali metal ions present in the film even when the acid content caused by acid rain penetrates through the film.
Regarding the heat discoloration, the surface treatment agent of the present invention exhibits heat discoloration particularly for a metal material exhibiting a passive state region on the alkali side. In general, when a film containing a resin is heated to a temperature of 300 ° C. or higher, the resin is broken as the resin is decomposed to expose the metal, and discoloration due to corrosion of the metal occurs. In the surface treatment agent of the present invention, in particular, the metal compound (B) plays a role of preventing or delaying thermal discoloration.

２．前処理及び表面処理剤による表面処理
（１）供試板
ａ：溶融亜鉛メッキ鋼板（板厚：０．６ｍｍ、片面めっき量８０ｇ／ｍ^２）
ｂ：５５質量％アルミニウム−亜鉛系合金メッキ鋼板（板厚：０．５ｍｍ、片面めっき量１２０ｇ／ｍ^２）
ｃ：４．５質量％マグネシウム−アルミニウム合金板（Ａ５１８２）、（板厚０．３ｍｍ）
（２）脱脂処理
日本パーカライジング（株）製アルカリ脱脂剤パルクリーンＮ３６４Ｓ（２０ｇ／Ｌ建浴、６０℃、１０秒スプレー、スプレー圧５０ｋＰａ）で供試板を脱脂した後、スプレー水洗を１０秒行った。
（３）表面処理及び乾燥
上記で調製した実施例及び比較例の表面処理剤を、それぞれ表１〜７に示した乾燥皮膜量が得られるように、バーコーターで、脱脂処理後の供試板の表面に塗布した。ついで、熱風乾燥炉でそれぞれ表１〜７に示す到達板温になるように乾燥した。
３．評価試験
上記で作製した表面処理供試板を以下に示す試験に付した。
（１）耐食性
（１）−１ 平板耐食性
塩水噴霧試験法ＪＩＳ−Ｚ−２３８１に基づき塩水噴霧１２０時間後、２４０時間後の白錆発生面積の割合を目視で求めて評価した。本発明では２４０時間で評価基準の□以上を満たすものを実用レベルと判断した。
評価基準：白錆発生面積 ◎１％未満、○１％以上５％未満、□５％以上１５％未満 △１５％以上３０％未満、×３０％以上
（１）−２ Ｘカット部耐食性（傷部耐食性）
ＮＴカッターで処理板にクロスカットを付した。ついで塩水噴霧試験法ＪＩＳ−Ｚ−２３８１に基づき塩水噴霧１２０時間後、２４０時間後に白錆が発生している箇所で錆幅の長い方から最大３点の平均値を求めて評価した。本発明では２４０時間で評価基準の□以上を満たすものを実用レベルと判断した。
評価基準：◎１ｍｍ未満、○１ｍｍ以上２ｍｍ未満、□２ｍｍ以上４ｍｍ未満、△４ｍｍ以上８ｍｍ未満、×８ｍｍ以上
（１）−３ アルカリ洗浄後耐食性
日本パーカライジング（株）製アルカリ脱脂剤パルクリーンＮ３６４Ｓを２０ｇ／Ｌに建浴し、６０℃に調整した脱脂剤水溶液を処理板に２分間スプレーした。水洗した後、８０℃で乾燥した。この板について、上記（１）−１及び（１）−２に記載した条件、評価法で耐食性を評価した。本発明では２４０時間で評価基準の□以上を満たすものを実用レベルと判断した。
（２）耐薬品性
（２）−１ 耐酸性
０．５質量％濃度に調整した２５℃の硫酸水溶液に処理板を３０分間浸漬した。水洗した後に８０℃で乾燥し、処理板の外観を目視判定した。本発明では耐酸性が□以上を満たすものを実用レベルと判断した。
評価基準：変色面積（皮膜及び素材変色を含む）：◎１％未満、○１％以上５％未満、□５％以上１５％未満、△１５％以上３０％未満、×３０％以上
（２）−２ 耐アルカリ性
１質量％濃度に調整した２５℃の水酸化ナトリウム水溶液に処理板を１時間浸漬した。水洗した後、８０℃で乾燥し、処理板の外観を目視判定した。本発明では耐アルカリ性が□以上を満たすものを実用レベルと判断した。
評価基準：変色面積（皮膜及び素材変色を含む）：◎１％未満、○１％以上５％未満、□５％以上１５％未満、△１５％以上３０％未満、×３０％以上
（３）耐熱変色性
処理板を２５０℃もしくは４００℃で３０分間加熱し、加熱前後の処理板の変色度合いを目視判定した。本発明では耐熱変色性が○以上を満たすものを実用レベルと判断した。
評価基準：変色面積：◎殆ど変色なし、○僅かに変色が認められる、□変色が明らかに認められる、△黄変あるいは黒変が認められる、×褐変、赤変あるいは黒変が認められる
（４）耐候性
処理板を平塚市で屋外暴露し、１年経過した後の変色度合いを目視判定した。本発明では耐候性が○以上を満たすものを実用レベルと判断した。
評価基準：変色面積：◎殆ど変色なし、○僅かに変色が認められる、□変色が明らかに認められる、△黄変あるいは黒変が認められる、×褐変、赤変あるいは黒変が認められる
４．評価結果
処理板の評価結果を表８〜１４に示す。表８〜１４より特定のアニオン性水分散性樹脂（Ａ）と金属化合物（Ｂ）とを配合する本発明の表面処理剤を用いた実施例１〜実施例８０は、平板耐食性、傷部耐食性、アルカリ洗浄後耐食性、耐薬品性、耐熱変色性及び耐候性において総合的に優れた結果を示すことが分かる。そのなかでも、実施１〜３２と比較して、実施例３３〜４１はアニオン性水分散性樹脂（Ａ）をシリル変性しており、平板耐食性、傷部耐食性、アルカリ洗浄後耐食性、耐薬品性及び耐候性が全体的に向上することが分かる。また、シランカップリング剤（Ｃ）を配合した実施４２〜４４のなかで、ウレタン樹脂を使用した場合は傷部耐食性が向上し、アクリル樹脂もしくはエポキシ樹脂を使用した場合は平板耐食性、アルカリ洗浄後耐食性及び耐薬品性が向上することが分かる。
また、本発明の成分（Ｄ）〜成分（Ｈ）を配合した実施例４５〜７２は、平板耐食性、傷部耐食性及び洗浄後耐食性のいずれかが向上していており、全ての項目で○以上の評点であることが分かる。
また、本発明の処理条件において、皮膜量と到達板温を変動した実施例７３〜７５及び供試材の種類を変更した実施例７６〜８０は、全ての項目で○以上の評点であることが分る。
一方、アニオン性水分散性樹脂（Ａ）もしくは金属化合物（Ｂ）を配合しない比較例１〜２、金属化合物（Ｂ）に占めるアルカリ金属の量が本発明の範囲外となる比較例３〜４、金属化合物（Ｂ）の替わりにコロイダルシリカを配合した比較例５、クロメート皮膜を形成した比較例６では、全ての性能を満足するものはなかった。

金属材料の中で最も腐食し易い鋼板を用いた実施例を比較例と共に示す。実施例４３、比較例５及び比較例６の表面処理剤を使用し、金属材料を溶融亜鉛めっき鋼板（ａ）から冷延鋼板（板厚：０．８ｍｍ）に変更し、表１５に示す処理条件で処理板を作製した。
鋼板は溶融亜鉛めっき鋼板と比較して、赤錆が発生し易いため、前記評価方法では実用性の判断としては厳しいため、次のような評価方法に変更した。すなわち、耐食性は塩水噴霧試験を６時間とした。冷延鋼板の場合、上層として上塗り塗装やラミネート等を施す場合を除いて、本発明の表面処理剤より形成されるような皮膜に対して、前記評価方法で示すような厳しい耐薬品性や耐候性は要求されない。従って、耐食性、耐熱変色性のみで試験、評価を実施した。なお、耐熱変色性の評価は前記評価方法で行った。評価結果を表１５に示す。
表１５から、実施例８１は比較例７及び比較例８と比較し、傷部耐食性、アルカリ洗浄後耐食性、耐熱変色性に優れることが分かる。特に、４００℃に加熱した場合、比較例７及び比較例８は全面に赤錆が発生しているのに対して、実施例８１は全面にマグネタイトの形成に由来すると推定される黒色の安定錆により全面が黒化しているが、赤錆の発生はなかった。

EXAMPLES Hereinafter, the present invention will be described more specifically together with effects thereof by giving examples and comparative examples. However, these examples are exemplifications, and the present invention is not limited by these examples.
Hereinafter, preparation of surface treatment agents of Examples and Comparative Examples (Tables 1 to 7), test materials, when a hot-dip galvanized steel plate, an aluminum-zinc alloy-plated steel plate or a magnesium-aluminum alloy plate is used as the test material In addition, the pretreatment and surface treatment, explanation of the evaluation method, explanation of the evaluation result, and evaluation result (Tables 8 to 14) will be described in this order. Next, the test about the case where a cold-rolled steel plate is used as a test material and the result will be described.
1. Manufacture of surface treatment agents The surface treatment agents of Examples and Comparative Examples shown in Tables 1 to 7 were prepared using the components shown below in combinations and proportions shown in Tables 1 to 7. That is, in deionized water, an anionic water-dispersible resin (A), a metal compound (B), and a silane coupling agent (C), a vanadium compound (D), a titanium compound (E), an organic phosphorus when used. The compound (F), the inorganic acid compound (G) and the oxide (H) were added in this order, and finally the solid content concentration was adjusted to 15% by mass using deionized water.
<Anionic water dispersible resin (A)>
A1: Tg 40 ° C. Polyester polyol urethane resin A2: Tg 80 ° C. Polyester polyol urethane resin A3: Tg 120 ° C. Polyester polyol urethane resin A4: Tg 80 ° C. Polyether polyol urethane resin A5: Tg 80 ° C. Polycarbonate polyol urethane resin A6: Tg 70 ° C. Acrylic resin A7: Tg 100 ° C. Epoxy resin A8: Tg 90 ° C. Silyl-modified polyester polyol urethane resin A9: Tg 90 ° C. Silyl-modified polycarbonate polyol urethane resin A10: Tg 70 ° C. Production of silyl-modified acrylic resin polyester polyol urethane resin (A1) Reactor Polyester polyol 100 having a number average molecular weight of 5000 obtained from 1,6-hexanediol and adipic acid Parts, 2,2-dimethyl-1,3-propanediol 5 parts by mass, 2,2-dimethylolpropionic acid 20 parts by mass, 4,4-dicyclohexylmethane diisocyanate 100 parts by mass, N-methyl-2-pyrrolidone 100 parts by mass A urethane prepolymer having a free isocyanato group content of 5% based on the nonvolatile content was obtained by adding a part. Next, 16 parts by mass of tetramethylene diamine and 10 parts by mass of triethylamine are added to 500 parts by mass of deionized water and stirred with a homomixer. The urethane prepolymer is added and emulsified and dispersed, and finally deionized water is added. A water dispersible urethane resin having a nonvolatile content of 25% by mass was obtained.
Production of Polyester Polyol Urethane Resin (A2) Number average obtained from 1,6-hexanediol and adipic acid instead of 100 parts by mass of polyester polyol having a number average molecular weight of 5000 obtained from 1,6-hexanediol and adipic acid A water-dispersible urethane resin having a nonvolatile content of 25% by mass was obtained in the same manner as in the production of A1, except that 100 parts by mass of a polyester polyol having a molecular weight of 2000 was used.
Production of Polyester Polyol Urethane Resin (A3) 100 parts by mass of polyester polyol having a number average molecular weight of 1,500 obtained from 1,4-butanediol and adipic acid in the reactor, 2,2-dimethyl-1,3-propanediol 5 parts by mass, 15 parts by mass of 2,2-dimethylolpropionic acid, 100 parts by mass of 4,4-dicyclohexylmethane diisocyanate, and 120 parts by mass of N-methyl-2-pyrrolidone are reacted to form a free isocyanato group with respect to the nonvolatile content. A urethane prepolymer having a content of 5% was obtained. Next, 16 parts by mass of piperazine and 10 parts by mass of triethylamine are added to 500 parts by mass of deionized water, and while stirring with a homomixer, the urethane prepolymer is added and emulsified and dispersed. 25 mass% water-dispersible urethane resin was obtained.
Production of Polyether Polyol Urethane Resin (A4) 100 parts by mass of a polyether polyol having a number average molecular weight of 2000 obtained from polyethylene glycol and polypropylene glycol, 2,2-dimethyl-1,3-propanediol 5 Mass parts, 20 parts by mass of 2,2-dimethylolpropionic acid, 100 parts by mass of 4,4-dicyclohexylmethane diisocyanate, and 120 parts by mass of N-methyl-2-pyrrolidone are reacted to form a free isocyanato group with respect to the nonvolatile content. A urethane prepolymer having a content of 5% was obtained. Next, 16 parts by mass of tetramethylene diamine and 10 parts by mass of triethylamine are added to 500 parts by mass of deionized water and stirred with a homomixer. The urethane prepolymer is added and emulsified and dispersed, and finally deionized water is added. A water dispersible urethane resin having a nonvolatile content of 25% by mass was obtained.
Production of Polycarbonate Polyol Urethane Resin (A5) 100 parts by mass of polycarbonate polyol (synthesis component: 1,6-hexane carbonate diol, ethylene glycol, number average molecular weight 2000) in the reactor, 2,2-dimethyl-1,3- 5 parts by mass of propanediol, 20 parts by mass of 2,2-dimethylolpropionic acid, 100 parts by mass of 4,4-dicyclohexylmethane diisocyanate, and 120 parts by mass of N-methyl-2-pyrrolidone were allowed to react and release to the non-volatile content. A urethane prepolymer having an isocyanato group content of 5% was obtained. Next, 16 parts by mass of tetramethylene diamine and 10 parts by mass of triethylamine are added to 500 parts by mass of deionized water and stirred with a homomixer. The urethane prepolymer is added and emulsified and dispersed, and finally deionized water is added. A water dispersible urethane resin having a nonvolatile content of 25% by mass was obtained.
Production of acrylic resin (A6) While adding 300 parts by weight of deionized water and 2 parts by weight of an anionic reactive surfactant to the reactor and stirring with a homomixer, 50 parts by weight of deionized water and 1 part by weight of potassium persulfate Part mixture, 287 parts by weight of deionized water, 4 parts by weight of reactive emulsifier, 60 parts by weight of methyl methacrylate, 158 parts by weight of styrene, 18 parts by weight of 2-ethylhexyl acrylate, 4.5 parts by weight of methacrylic acid, 2-hydroxyethyl A mixture of 4.5 parts by weight of methacrylate and 45 parts by weight of glycidyl methacrylate was blended little by little to obtain a water-dispersible acrylic resin. Further, 30 parts by mass of butyl cellosolve was added, and finally deionized water was added to adjust the nonvolatile content to 25% by mass.
Production of Epoxy Resin (A7) 680 parts by mass of an epoxy equivalent of 1950 bisphenol A type epoxy resin, 132 parts by mass of propylene glycol monomethyl ether, and 168 parts by mass of a reactive emulsifier were placed in a reactor, and deionized while stirring with a homomixer. 1000 parts by mass of water was added little by little to obtain a water-dispersible epoxy resin having an epoxy equivalent of 3500, and finally deionized water was added to adjust the nonvolatile content to 25% by mass.
Production of Silyl-Modified Polyester Polyol Urethane Resin (A8) 100 mass parts of polyester polyol having a number average molecular weight of 2000 obtained from 1,6-hexanediol and adipic acid in the reactor, 2,2-dimethyl-1,3- 5 parts by mass of propanediol, 6 parts by mass of 3-aminopropyltriethoxysilane, 20 parts by mass of 2,2-dimethylolpropionic acid, 100 parts by mass of 4,4-dicyclohexylmethane diisocyanate, 150 parts by mass of N-methyl-2-pyrrolidone To obtain a urethane prepolymer having a free isocyanato group content of 5% based on the nonvolatile content. Next, 16 parts by mass of tetramethylene diamine and 10 parts by mass of triethylamine are added to 500 parts by mass of deionized water and stirred with a homomixer. The urethane prepolymer is added and emulsified and dispersed, and finally deionized water is added. A water dispersible urethane resin having a nonvolatile content of 25% by mass was obtained.
Production of Silyl-modified Polycarbonate Polyol Urethane Resin (A9) In the reactor, 100 parts by mass of 1,6-hexanediolene glycol having a number average molecular weight of 2000, 1 part by mass of 3-glycidoxypropyltrimethoxysilane, 2,2- 5 parts by mass of dimethyl-1,3-propanediol, 20 parts by mass of 2,2-dimethylolpropionic acid, 100 parts by mass of 4,4-dicyclohexylmethane diisocyanate, and 150 parts by mass of N-methyl-2-pyrrolidone are added and reacted. Thus, a urethane prepolymer having a free isocyanato group content of 5% based on the nonvolatile content was obtained. Next, 16 parts by mass of tetramethylene diamine and 10 parts by mass of triethylamine are added to 500 parts by mass of deionized water and stirred with a homomixer. The urethane prepolymer is added and emulsified and dispersed, and finally deionized water is added. A water dispersible urethane resin having a nonvolatile content of 25% by mass was obtained.
Production of silyl-modified acrylic resin (A10) In a reactor, 400 parts by mass of deionized water and 2 parts by mass of an anionic reactive surfactant are added, and 50 parts by mass of deionized water and potassium persulfate are stirred with a homomixer. 1 part by weight of mixture, 287 parts by weight of deionized water, 4 parts by weight of reactive emulsifier, 60 parts by weight of methyl methacrylate, 158 parts by weight of styrene, 18 parts by weight of 2-ethylhexyl acrylate, 4.5 parts by weight of methacrylic acid, 2- A mixture of 4.5 parts by mass of hydroxyethyl methacrylate, 45 parts by mass of glycidyl methacrylate and 7.5 parts by mass of 3- (methacryloyloxypropyl) trimethoxysilane was added little by little to obtain a water-dispersible acrylic resin. Further, 30 parts by mass of butyl cellosolve was added, and finally deionized water was added to adjust the nonvolatile content to 25% by mass.
<Metal compound (B)>
Used in Examples B1: Ammonium zirconium carbonate B2: Potassium zirconium carbonate B3: Lithium silicate Li ₂ O / SiO ₂ = 0.15
B4: Sodium silicate Na ₂ O / SiO ₂ = 0.01
B5: Sodium silicate Na ₂ O / SiO ₂ = 0.15
B6: Sodium silicate Na ₂ O / SiO ₂ = 0.33
B7: Sodium silicate Na ₂ O / SiO ₂ = 0.48
B8: Potassium silicate K ₂ O / SiO ₂ = 0.44
Used in Comparative Example B9: Sodium silicate Na ₂ O / SiO ₂ = 0.0005
B10: Sodium silicate Na ₂ O / SiO ₂ = 0.8
B11: Colloidal silica Average particle size 10 nm
<Silane coupling agent (C)>
C1: 3-glycidoxypropyltriethoxysilane C2: 3-glycidoxypropyltrimethoxysilane C3: 3-aminopropyltriethoxysilane C4: vinyltrimethoxysilane <Vanadium compound (D)>
D1: Sodium metavanadate D2: Ammonium metavanadate D3: Vanadyl sulfate D4: Vanadyl acetylacetonate <Titanium compound (E)>
E1: Titanyl sulfate E2: Tetraisopropyl titanate E3: Titanium acetylacetonate E4: Titanium octyl glycolate <Organic phosphorus compound (F)>
F1: 1-hydroxyethylene-1,1-diphosphonic acid F2: 2-butanephosphonic acid-1,2,4-tricarboxylic acid F3: Inosit hexaphosphonic acid <Inorganic acid compound (G)>
G1: Nimmonium hydrogen phosphate G2: Ammonium fluoride G3: Ammonium hexafluorosilicate <Oxide (H)>
H1: Magnesium oxide H2: Calcium oxide H3: Zinc borate

2. Pretreatment and surface treatment with surface treatment agent (1) Test plate a: hot-dip galvanized steel sheet (plate thickness: 0.6 mm, single-sided plating amount 80 g / m ² )
b: 55% by mass aluminum-zinc alloy-plated steel sheet (plate thickness: 0.5 mm, single-sided plating amount 120 g / m ² )
c: 4.5 mass% magnesium-aluminum alloy plate (A5182), (plate thickness 0.3 mm)
(2) Degreasing treatment The test plate was degreased with an alkaline degreasing agent Pulclean N364S (20 g / L building bath, 60 ° C., 10 seconds spray, spray pressure 50 kPa) manufactured by Nihon Parkerizing Co., Ltd., followed by spray water washing for 10 seconds. It was.
(3) Surface treatment and drying Sample plates after degreasing treatment with a bar coater so that the dry coating amounts shown in Tables 1 to 7 were obtained for the surface treatment agents of Examples and Comparative Examples prepared above, respectively. It was applied to the surface. Subsequently, it dried so that it might become the ultimate board temperature shown in Tables 1-7, respectively with a hot air drying furnace.
3. Evaluation Test The surface-treated test plate prepared above was subjected to the following test.
(1) Corrosion Resistance (1) -1 Flat Plate Corrosion Resistance Based on the salt spray test method JIS-Z-2381, the ratio of white rust generation area after 240 hours after salt spray was visually determined and evaluated. In the present invention, those satisfying the evaluation standard □ or more in 240 hours were judged as practical levels.
Evaluation criteria: Area where white rust occurs ◎ <1%, ○ 1% or more and less than 5%, □ 5% or more and less than 15% △ 15% or more and less than 30%, × 30% or more (1) -2 X-cut corrosion resistance (scratches Corrosion resistance)
A cross cut was given to the processing board with an NT cutter. Then, based on the salt spray test method JIS-Z-2381, the average value of up to three points was calculated from the longer rust width at the location where white rust was generated after 120 hours of salt spray and 240 hours later. In the present invention, those satisfying the evaluation standard □ or more in 240 hours were judged as practical levels.
Evaluation criteria: ◎ Less than 1 mm, ○ 1 mm or more and less than 2 mm, □ 2 mm or more and less than 4 mm, Δ4 mm or more and less than 8 mm, × 8 mm or more (1) -3 Corrosion resistance after alkali cleaning Nippon Parkerizing Co., Ltd. Alkali degreasing agent Pulclean N364S The treatment plate was sprayed for 2 minutes with a degreasing agent aqueous solution that had been placed at 20 g / L and adjusted to 60 ° C. After washing with water, it was dried at 80 ° C. About this board, corrosion resistance was evaluated by the conditions and evaluation methods described in (1) -1 and (1) -2 above. In the present invention, those satisfying the evaluation standard □ or more in 240 hours were judged as practical levels.
(2) Chemical resistance (2) -1 Acid resistance The treated plate was immersed in a 25 ° C. sulfuric acid aqueous solution adjusted to a concentration of 0.5% by mass for 30 minutes. After washing with water and drying at 80 ° C., the appearance of the treated plate was visually judged. In the present invention, those having acid resistance satisfying □ or more were judged as practical levels.
Evaluation criteria: Discolored area (including coating and material discoloration): ◎ <1%, ○ 1% or more and less than 5%, □ 5% or more and less than 15%, △ 15% or more and less than 30%, × 30% or more (2) -2 Alkali resistance The treated plate was immersed in a 25 ° C. aqueous sodium hydroxide solution adjusted to a concentration of 1% by mass for 1 hour. After washing with water, it was dried at 80 ° C., and the appearance of the treated plate was visually determined. In the present invention, those having alkali resistance satisfying □ or more were judged as practical levels.
Evaluation criteria: Discolored area (including coating and material discoloration): ◎ <1%, ◯ 1% to less than 5%, □ 5% to less than 15%, △ 15% to less than 30%, x30% or more (3) Heat discoloration The treated plate was heated at 250 ° C. or 400 ° C. for 30 minutes, and the degree of discoloration of the treated plate before and after heating was visually judged. In the present invention, a material having a heat discoloration satisfying ◯ or more was judged as a practical level.
Evaluation criteria: Discolored area: ◎ Almost no discoloration, ○ Slight discoloration observed, □ Discoloration observed clearly, △ Yellowing or black discoloration observed, × Browning, red discoloration or black discoloration observed (4 ) Weather resistance The treated plate was exposed outdoors in Hiratsuka City, and the degree of discoloration after 1 year was visually judged. In the present invention, those satisfying a weather resistance of ◯ or more were judged as practical levels.
Evaluation criteria: Discolored area: ◎ Almost no discoloration, ○ Slight discoloration observed, □ Discoloration observed clearly, △ Yellowing or black discoloration observed, × Browning, red discoloration or black discoloration observed Evaluation result The evaluation result of a process board is shown to Tables 8-14. From Tables 8 to 14, Examples 1 to 80 using the surface treatment agent of the present invention containing a specific anionic water-dispersible resin (A) and a metal compound (B) are flat plate corrosion resistance and scratch corrosion resistance. It can be seen that the results after the alkali cleaning show excellent results in terms of corrosion resistance, chemical resistance, heat discoloration resistance and weather resistance. Among them, compared with Examples 1 to 32, Examples 33 to 41 are silyl-modified anionic water-dispersible resins (A), flat plate corrosion resistance, scratch corrosion resistance, corrosion resistance after alkali cleaning, chemical resistance It can also be seen that the weather resistance is improved overall. Moreover, in Examples 42-44 which mix | blended the silane coupling agent (C), when a urethane resin is used, a crack part corrosion resistance improves, and when an acrylic resin or an epoxy resin is used, flat plate corrosion resistance, after alkali washing It can be seen that the corrosion resistance and chemical resistance are improved.
Moreover, Examples 45-72 which mix | blended the component (D)-component (H) of this invention have improved any of flat plate corrosion resistance, scratch part corrosion resistance, and corrosion resistance after washing | cleaning, and are more than (circle) in all the items. It turns out that it is a grade of.
Moreover, in the processing conditions of the present invention, Examples 73 to 75 in which the coating amount and the reached plate temperature were varied, and Examples 76 to 80 in which the types of the test materials were changed were rated as “good” or better in all items. I understand.
On the other hand, Comparative Examples 1 to 2 in which the anionic water-dispersible resin (A) or the metal compound (B) is not blended, and Comparative Examples 3 to 4 in which the amount of alkali metal in the metal compound (B) falls outside the scope of the present invention. In Comparative Example 5 in which colloidal silica was blended in place of the metal compound (B), and in Comparative Example 6 in which a chromate film was formed, none of the performances were satisfied.

The Example using the steel plate which is most easily corroded in a metal material is shown with a comparative example. Using the surface treating agent of Example 43, Comparative Example 5 and Comparative Example 6, the metal material was changed from a hot-dip galvanized steel sheet (a) to a cold-rolled steel sheet (plate thickness: 0.8 mm), and the treatment shown in Table 15 A treated plate was produced under the conditions.
Since the steel sheet is more susceptible to red rust than the hot dip galvanized steel sheet, the evaluation method described above was severely judged as practical, and thus the following evaluation method was used. That is, the corrosion resistance was 6 hours in the salt spray test. In the case of cold-rolled steel sheets, except for the case where a top coat or a laminate is applied as an upper layer, severe chemical resistance and weather resistance as shown in the evaluation method described above for a film formed from the surface treatment agent of the present invention Sex is not required. Therefore, tests and evaluations were carried out only with corrosion resistance and heat discoloration. The evaluation of heat discoloration was performed by the above evaluation method. The evaluation results are shown in Table 15.
From Table 15, it can be seen that Example 81 is superior in scratch corrosion resistance, corrosion resistance after alkali cleaning, and heat discoloration resistance as compared with Comparative Example 7 and Comparative Example 8. In particular, when heated to 400 ° C., Comparative Example 7 and Comparative Example 8 show red rust on the entire surface, whereas Example 81 is due to black stable rust estimated to be derived from the formation of magnetite on the entire surface. Although the entire surface was blackened, no red rust occurred.

Claims (12)

An anionic water-dispersible resin (A) having a glass transition temperature of 0 ° C. or higher, and at least one metal compound (B) selected from the group consisting of alkali metal silicates and basic zirconium compounds are blended in water. In the alkali metal silicate salt, the mass ratio M ₂ O / SiO ₂ between the M ₂ O portion and the SiO ₂ portion is 1/1000 to 6/10, and M is selected from the group consisting of lithium, sodium, and potassium. A surface treatment agent for a metal material, which is at least one selected. The surface treating agent according to claim 1, wherein the mass ratio (B) / (A) of the component (B) to the component (A) is from 1/100 to 85/10. The surface treating agent according to claim 1 or 2, wherein the component (A) is silyl-modified. A silane coupling agent (C) having at least one functional group selected from the group consisting of an epoxy group, an amino group, a vinyl group, a mercapto group, and an isocyanato group bonded to adjacent carbon atoms, and a component (C) Any one of Claims 1-3 mix | blended so that mass ratio (C) / [(A) + (B)] with the sum total of a component (A) and a component (B) may become 1 / 1000-3 / 10. Item 1. The surface treatment agent according to item 1. In the vanadium compound (D), the mass ratio (D) / [(A) + (B)] of the component (D) and the sum of the components (A) and (B) is 1/1000 to 1/5. The surface treating agent according to any one of claims 1 to 4, formulated as described above. In the titanium compound (E), the mass ratio (E) / [(A) + (B)] of the component (E) and the sum of the components (A) and (B) is 1/1000 to 1/5. The surface treating agent according to any one of claims 1 to 5, formulated as described above. At least one organic phosphorus compound (F) selected from the group consisting of organic phosphonic acid and phosphoric acid esters of polyhydric alcohols and salts thereof, the sum of component (F), component (A) and component (B) The surface treatment agent according to any one of claims 1 to 6, which is blended so that the mass ratio (F) / [(A) + (B)] is 1/1000 to 1/10. At least one inorganic acid compound (G) selected from the group consisting of an inorganic acid and a salt thereof and a metal fluoride is a mass ratio of the component (G) to the sum of the component (A) and the component (B) (G ) / [(A) + (B)] is a surface treatment agent according to any one of claims 1 to 7, which is blended so as to be 1/1000 to 1/10. At least one oxide (H) selected from the group consisting of calcium oxide, magnesium oxide, manganese oxide, zinc oxide, aluminum oxide, niobium oxide, boron oxide and zinc borate, component (H) and component (B) The surface treatment agent according to any one of claims 1 to 8, which is blended so that a mass ratio (H) / (B) to 1/1000 to 1/10. The surface treatment agent according to any one of claims 1 to 9 is applied to at least one surface of a metal material surface and dried to form a film having a dry film mass of 0.1 to 3 g / m ^2. A surface treatment method for a metal material. A metal material surface-treated by the surface treatment method according to claim 10. The metal material according to claim 11, wherein the metal material is a steel material, a zinc material, a galvanized steel material, a zinc-aluminum alloy plated steel material, an aluminum material, or an aluminum alloy material.