KR20070069169A - Agent for treating metal surface, method of treating surface of metallic material, and surface-treated metallic material - Google Patents

Abstract

An agent for treating metal surfaces which comprises an aqueous medium and, incorporated therein, (A) a cationic urethane resin which is water-soluble or in an aqueous emulsion form, (B) a cationic polycondensation product obtained from a phenol compound and an aldehyde, and (C) a zirconium compound and/or titanium compound. A coating film formed from the treating agent imparts excellent corrosion resistance and alkali resistance to a metallic material. When the proportion of the urethane resin (A) is equal to or higher than that of the polycondensation product (B), yellowing resistance can be also imparted. By incorporating a metal compound (D) containing a specific metal, excellent blacking resistance also can be imparted. Furthermore, by incorporating an acid ingredient (E) and a vanadium compound (F), a further improvement in performances can be attained.

Description

Metal surface treatment agent, surface treatment method of metal material, and surface treatment metal material {AGENT FOR TREATING METAL SURFACE, METHOD OF TREATING SURFACE OF METALLIC MATERIAL, AND SURFACE-TREATED METALLIC MATERIAL}

The present invention provides a sheet coil made of a metal material, excellent corrosion resistance and excellent alkali resistance, and, in some cases, further excellent blackening resistance and excellent yellowing resistance to the surface of the molded article, and furthermore, a coating containing no chromium. A metal surface treatment agent, a metal surface treatment method, and a surface-treated metal material used for forming. More specifically, the present invention provides excellent corrosion resistance and excellent corrosion resistance to molded products, castings, sheet coils, etc. for automobile bodies, automobile parts, building materials, and home appliance parts made of galvanized steel sheets, steel sheets, and aluminum-based metal materials. The present invention relates to a surface treatment agent, a surface treatment method, and a surface-treated metal material used for forming a coating containing no chromium, which can impart alkalinity and, in some cases, further excellent blackening resistance and good yellowing resistance.

Metal materials, such as a galvanized steel plate and a steel plate, are oxidized and corroded by oxygen, moisture, ions contained in moisture, etc. in air | atmosphere. In addition, after the molding process, it may be washed with a degreasing agent showing alkalinity, and if it is not durable against alkali, it will discolor or corrode prematurely when used. In addition, under high temperature and high humidity and under certain circumstances, a phenomenon in which the plated steel material becomes black and discolored occurs, and all of the phenomenon is caused by deterioration of the plated layer metal material, which is problematic in view of quality and designability when made as various products. As a method of preventing such corrosion, conventionally, a chromate coating is formed on a metal surface by contacting a surface of a metal material with a treatment solution containing chromium such as chromic acid chromate to deposit a chromate coating, or applying and drying the coating. There is a way. However, these inorganic chromate coatings alone exhibit short-term rust resistance under relatively mild environments, but have insufficient corrosion resistance in long-term or more stringent environments. In addition, when the sheet coil subjected to the chromate treatment is cut and molded, the formed film is hard, weak, and lacks in lubricity. Thus, the film is not dropped, which damages the appearance, and does not have sufficient processing, and the material is cracked and cracked. Occurs. Therefore, generally, in order to satisfy all these performances, the two-layer process of forming a chromate film on the surface of a metal material and forming a resin film further on the formed chromate film is performed. In addition to the insufficient performance, the chromate coating has harmful hexavalent chromium in the treatment liquid, and thus, wastewater treatment is time-consuming and expensive, and since the formed coating contains hexavalent chromium, it is also environmentally safe. It tends to be light in respect.

In an attempt to satisfy all the performances by the one-layer treatment, a resin chromate for forming chromate and a resin film at one time was examined, and a surface of an aluminum-zinc plated steel sheet with a specific water-dispersible or water-soluble resin and a specific amount of 6 A treatment method for applying a resin composition containing chromium chromium (Japanese Patent Laid-Open No. 4-2672), and hexavalent chromium ions or hexavalent chromium ions and trivalent chromium ions of an inorganic compound and polymerized under specific emulsion polymerization conditions Metal surface treatment compositions (Japanese Patent Laid-Open No. 7-6070) containing an acrylic emulsion are known. However, as described above, the hexavalent chromium contained in the coating, although it is a trace amount, has a slowly melting property and has a problem in terms of environment and safety.

As a method of using the non-chromate treatment liquid which does not have chromium, a polymer composition for surface treatment of metal materials and a surface treatment method containing a phenolic resin polymer and an acidic compound having a specific structure (Japanese Patent Laid-Open No. 7-278410) , Metal surface treatment agents and methods excellent in anti-fingerprint and the like, which contain two or more kinds of silane coupling agents having different kinds and reactive functional groups having a specific structure capable of reacting with each other (Japanese Patent Laid-Open No. 8-73775), Metal surface treatment agent and processing method containing the silane coupling agent of a specific structure and the phenolic resin polymer of a specific structure (Unexamined-Japanese-Patent No. 9-241576), the epoxy resin which has at least 1 nitrogen atom, an acrylic resin, a urethane resin, etc. Surface treatment agent, treatment method and treated metal material containing organic polymer and specific polyvalent anion of 10-1789), (1) a rust preventive agent containing a bisphenol A epoxy resin of a specific structure, (2) a rust preventive agent containing specific resins such as phenolic resins and other polyesters at a specific ratio, (1) and (2) A process method and a process metal material (Japanese Patent Laid-Open No. 10-60233), a phenolic resin compound having a specific structure, a vanadium compound, a specific metal compound, and an organic polymer as an optional component. Metal surface treatment agent, treatment method and treated metal material (Japanese Patent Laid-Open No. 2001-181860), a specific water-soluble resin or an aqueous emulsion resin, a phenolic resin compound having a specific structure, and a metal having a specific metal compound as essential components Surface treatment agents, treatment methods and treated metal materials (Japanese Patent Laid-Open No. 2003-13252) are known.

However, in the metal surface treatment without chromium, while the treatment liquid has the advantage that it does not contain hexavalent chromium, the corrosion resistance is insufficient, particularly the corrosion resistance of the scratches and the processed portion is remarkably inferior to the chromate coating, In addition, the blackening resistance also has the drawback that the performance is insufficient under high temperature and high humidity environment. In general, the resin film has a characteristic (yellowing) that discolors yellow or brown under the influence of heat, and has a defect that discolors under the influence of heat generated during welding or press work. Therefore, in the present situation, no non-chromate-based metal surface treatment agent has been obtained which forms a film capable of simultaneously providing excellent corrosion resistance, alkali resistance and blackening resistance, and in some cases, further excellent yellowing resistance to the metal material surface. .

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art, and does not contain chromium, which is used to impart excellent corrosion resistance and excellent alkali resistance to the metal material and, in some cases, further excellent blackening resistance and excellent yellowing resistance. It is an object to provide a metal surface treatment agent, a metal surface treatment method and a surface treatment metal material.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining about the means which solve the said subject, it is a polycondensation product of cationic water-soluble or aqueous emulsion urethane resin, a phenolic compound, and aldehydes, and it is cationic, and a zirconium compound and / or a titanium compound are essential. By treating the surface of the metal material with an aqueous surface treatment agent as a component, a coating having excellent corrosion resistance and excellent alkali resistance is obtained, and in the case of blending another specific metal compound with the aqueous surface treatment agent, in addition to the above characteristics, Furthermore, it discovered that the outstanding blackening resistance can be provided to the film, and completed this invention.

That is, this invention is a polycondensation product of (1) cationic water-soluble or aqueous emulsion urethane resin (A) (henceforth a cationic urethane resin (A)), a phenolic compound, and aldehydes, and cationic (B) (Hereinafter referred to as cationic phenolic polycondensate (B)) and a zirconium compound and / or a titanium compound (C) (hereinafter referred to as a metal compound (C)) to a metal surface treatment agent formed by blending in an aqueous medium will be. According to this aspect of the present invention, a film having excellent corrosion resistance and excellent alkali resistance can be formed.

In addition, the present invention, (2) the metal compound (C) is a zirconium compound, at least one member selected from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo It is related with the metal surface treating agent of said (1) which mix | blended the compound (D) containing a metal (henceforth a metal compound (D)). According to this aspect of the present invention, in addition to excellent corrosion resistance and excellent alkali resistance, a film having excellent blackening resistance can be formed.

In the aspect of said (1) and (2) of this invention, the compounding ratio of cationic urethane resin (A) and cationic phenolic polycondensate (B) is solid content mass ratio, (A) :( B) = 99: 1 to 1:99 is preferred,

In the case of (A) :( B) = 99: 1 to 50:50, a film having excellent yellowing resistance can be formed in addition to excellent corrosion resistance, excellent alkali resistance, and optionally excellent blackening resistance.

Moreover, (3) this invention is a metal compound (C) is a titanium compound, and is at least 1 sort (s) chosen from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce, and Mo. A compound (D) containing a metal (that is, a metal compound (D)) is blended, and a blending ratio of the cationic urethane resin (A) and the cationic phenolic polycondensate (B) is a solid content mass ratio (A). : (B) = 99: 1-50:50 It is related with the metal surface treating agent of said (1). According to this aspect of the present invention, a film having excellent corrosion resistance, excellent alkali resistance, excellent blackening resistance and excellent yellowing resistance can be formed.

In addition, in each aspect of said (1), (2), and (3) of this invention, the metal surface treating agent has at least 1 type of acid component (E) chosen from an inorganic acid and an organic acid (Hereafter, an acid component (E) ), Whereby the corrosion resistance and blackening resistance of the formed film are further improved. Moreover, it is preferable to contain a vanadium compound (F) in the said metal surface treating agent of this invention, and also the corrosion resistance and alkali resistance of the film formed by this improve further.

The present invention further provides a coating on the surface of the metal material by applying the metal surface treatment agent of the above aspect (1), (2) or (3) to the surface of the metal material, and then drying. A surface treatment method and a metal material having a film formed using the surface treatment method.

Best Mode for Carrying Out the Invention

The "cationic" in the cationic urethane resin (A) (that is, cationic water-soluble or aqueous emulsion urethane resin (A)) blended in the metal surface treatment agent of the present invention means having a cationic functional group in the molecular structure. . Such cationic functional groups include the following general formulas (I), (II), (III) or (IV).

(Wherein R ¹ , R ² , R ³ , R ⁶ and R ⁷ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, or 1 to 10 carbon atoms, preferably Preferably it represents a 1-6 linear or branched hydroxyalkyl group, R <^4> and R <^5> represent a C2-C10, preferably 2-6, linear or branched alkylene group independently of each other, and A <^-> And B ⁻ represents a hydroxyl ion or an acid ion. The amount of such cationic functional group may be any amount in which the cationic urethane resin (A) can be stably present in the dissolved or dispersed state in the metal surface treatment agent of the present invention.

In general formula (I), (II), (III) and (IV), as a C1-C10 alkyl group which R <^1> , R <^2> , R <^3> , R <^6> and R <^7> represent, a methyl group, an ethyl group, Propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like, as a hydroxyalkyl group having 1 to 10 carbon atoms, hydroxymethyl group, 2 -Hydroxyethyl group, 1-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group, 7-hydroxyheptyl group, 8-hydroxy Octyl group, 9-hydroxynonyl group, 10-hydroxydecyl group, etc. are mentioned. In general formula (III) and (IV), as a C2-C10 alkylene group which R <^4> and R <^5> represent, an ethylene group, a propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene A group, an octamethylene group, 2-ethyl- hexylene group, a decamethylene group, etc. are mentioned. In the general formulas (II) and (IV), examples of acid ions represented by A ^- and B ^- include inorganic acids such as halogen ions (chlorine ions, bromine ions, fluorine ions, etc.), sulfate ions, nitrate ions, and phosphate ions. And organic acid ions such as ions, acetate ions, and formate ions.

In addition, the cationic urethane resin (A) used by this invention is a water-soluble thing or an aqueous emulsion form.

The cationic urethane resin (A) used in the present invention is required to have the above cationic functional group, which is cationic phenolic polycondensate (B) (i.e., polycondensate of phenolic compound and aldehydes). And cationic (B)) or compound (C) (ie, zirconium compound and / or titanium compound (C)) or metal compound (D) (ie, Li, Mg, Al, Ca, Mn, Co, Ni, It contributes to the compatibility of the compound (D)) containing at least one metal selected from Zn, Sr, W, Ce and Mo. The solubility or dispersibility of the cationic urethane resin (A) in water may be achieved based on the self solubility or self dispersibility of the resin in water, and also cationic surfactants (for example, alkyl quaternary ammonium salts, etc.) and / Or with the help of a nonionic surfactant (for example, alkylphenyl ether or the like).

As the cationic urethane resin (A), in the urethane resin which is a polycondensation product of polyols, such as a polyol, a polyether polyol, and a polyester polyol, and an aliphatic, alicyclic, or aromatic polyisocyanate, it is (substituted) The urethane resin obtained by using the polyol which has an amino group, or the polyol which has a nitrogen atom in a principal chain, the urethane resin which quaternized the nitrogen atom of this urethane resin with the quaternization agent, etc. are mentioned.

In the above, as the polyol, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,2-butylene glycol, 1, 3-butylene glycol, 1,4-butylene glycol, hexamethylene glycol, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, 1,2-propanediol, 1,3-propanediol, 2-methyl-1, 3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentylglycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1, 5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1, Aliphatic diol compounds such as 7-heptane diol, 3,5-heptane diol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and trimethyl Olethane, trimethylolpropane, hexitols, pentitols, glycerin, diglycerin, polyglycerin, pentaerythritol, dipenta Discrete erythritol, tetra methylol trivalent or more aliphatic or cycloaliphatic, such as propane and the like can be mentioned alcohol compound.

In the above, as the polyether polyol, for example, ethylene oxide adducts such as ethylene glycol, diethylene glycol, triethylene glycol, propylene oxide adducts such as propylene glycol, dipropylene glycol, tripropylene glycol, and ethylene of the polyol. Oxides and / or propylene oxide adducts, polytetramethylene glycol and the like.

In the above, as the polyester polyol, for example, the direct esterification reaction of the polyol and ester-forming derivatives such as polyhydric carboxylic acid or its anhydrides, halides and esters in an amount less than the stoichiometric amount thereof and / or Obtained by a transesterification reaction; Obtained by ring-opening lactones with the polyol; And polycarbonate polyols. As polyhydric carboxylic acid, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, sumeric acid, azelaic acid, sebacic acid, dodecane diacid, 2-methyl succinic acid, 2 -Methyl adipic acid, 3-methyl adipic acid, 3-methylpentane diacid, 2-methyloctane diacid, 3,8-dimethyldecane diacid, 3,7-dimethyldecane diacid, dimer acid, hydrogenation Aliphatic dicarboxylic acids such as dimer acid; Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid; Tricarboxylic acids, such as trimeric acid, trimesic acid, and trimer of castor oil fatty acid; And tetracarboxylic acids such as pyromellitic acid. As the ester-forming derivative, acid anhydrides of these polyhydric carboxylic acids; Halides such as chlorides and bromides of the polyvalent carboxylic acids; Lower aliphatic esters, such as methyl ester of this polyhydric carboxylic acid, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, amyl ester, etc. are mentioned. Examples of the lactones include lactones such as γ-caprolactone, δ-caprolactone, ε-caprolactone, dimethyl-ε-caprolactone, δ-valerolactone, γ-valerolactone, and γ-butyrolactone. Can be mentioned.

In the above, as a polyol having a (substituted) amino group or a polyol having a nitrogen atom in the main chain, the following general formula (V) or (VI)

Wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ silver The same meaning as defined in the general formulas (I) and (III), R ⁸ represents a straight or branched chain alkylene group having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms. A polyol represented by -NR ¹ R ² group is substituted). Specific examples of such polyols include N, N-dimethylaminodimethylolpropane, N-methyl-N, N-diethanolamine, and the like. As the quaternizing agent, R ³ Cl, R ³ Br, R ⁷ Cl, R ⁷ Br (wherein R ³ and R ⁷ have the same meanings as in General Formulas (II) and (IV)) and the like. Can be mentioned.

Regarding the cationic urethane resin (A), examples of the aliphatic, alicyclic or aromatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, hydrogenated xylene diisocyanate, and 1,4-cyclohexylene di. Isocyanate, 4,4'-dicyclohexyl methane diisocyanate, 2,4'-dicyclohexyl methane 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'-di Phenyl methane diisocyanate, phenylene diisocyanate, xylene diisocyanate, tetramethyl xylene diisocyanate, etc. are mentioned, Among these, , Tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, hydrogenated xylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, 2,4'-dish When using aliphatic or alicyclic polyisocyanate compounds, such as chlorhexyl methane diisocyanate and isophorone diisocyanate, since the film obtained also becomes excellent in weather resistance, it is preferable.

Among the cationic urethane resins (A) described above, the soap-free or the amount thereof which does not use a surfactant as a solubilizer or an emulsifier, which may adversely affect the adhesion to the metal material of the coating or the water resistance of the coating. One is more preferable.

It is preferable that it is 1,000-1,000,000, and, as for the weight average molecular weight of a cationic urethane resin (A), it is more preferable that it is 2,000-500,000. When the molecular weight is less than 1,000, the film formability is insufficient, while when the molecular weight exceeds 1,000,000, the stability of the treatment agent tends to be lowered.

The "cationic" in the cationic phenolic polycondensate (B) (that is, the polycondensation product of the phenolic compound and aldehydes and cationic (B)) contained in the metal surface treatment agent of the present invention is a cationic functional group. It means to have. As such cationic functional group, what is represented by the said general formula (I) or (II) is mentioned. The cationic phenolic polycondensate (B) may have at least one kind of such cationic functional group. These cationic functional groups coexist with ammonia or amine corresponding to the cationic functional group represented by the said general formula (I), for example, when polycondensing a phenol type compound and aldehydes, and are further quaternary as needed. It can introduce | transduce by quaternizing a nitrogen atom with a topical agent. It is preferable that the ratio of the cationic functional group contained in a cationic phenol type polycondensate (B) is 0.2-3 per benzene ring contained in a cationic phenol type polycondensate (B). When the said numerical value is less than 0.2, there exists a tendency for stability of a metal surface treating agent to fall, and when it exceeds 3, there exists a tendency for the corrosion resistance of the film formed to fall. It is preferable that the cationic phenolic polycondensate (B) used by this invention is a novolak-type phenolic polycondensate obtained by performing the said polycondensation reaction in presence of an acidic catalyst. In addition, the cationic phenolic polycondensate (B) used in the present invention may be selected from the above-mentioned novolac phenolic polycondensates such as boron modification, silicon modification, phosphorus modification, heavy metal modification, nitrogen modification, sulfur modification, oil modification, and rosin modification. It may be modified by a known method.

The phenolic compound used to obtain the cationic phenolic polycondensate (B) used in the present invention is selected from aldehydes in the presence of an acid catalyst and ammonia or amine corresponding to the cationic functional group represented by the general formula (I). It will not specifically limit, as long as it can polycondense and produce a cationic phenolic polycondensate (B). As such phenolic compounds, for example, phenol, m-cresol, m-ethylphenol, m-propylphenol, m-butylphenol, p-butylphenol, o-butylphenol, resorcinol, hydroquinone, catechol, 3-methoxyphenol, 4-methoxyphenol, 3-methylcatechol, 4-methylcatechol, methylhydroquinone, 2-methylresolcinol, 2,3-dimethylhydroquinone, 2,5-dimethylresolci Knol, 2-ethoxyphenol, 4-ethoxyphenol, 4-ethylresolcinol, 3-ethoxy-4-methoxyphenol, 2-propenylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 3,4,5-trimethylphenol, 2-isopropoxyphenol, 4-propoxyphenol, 2-allylphenol, 3,4,5-trimethoxyphenol, 4-isopropyl-3 Methylphenol, pyrogallol, phloroglycinol, 1,2,4-benzenetriol, 5-isopropyl-3-methylphenol, 4-butoxyphenol, 4-t-butylcatechol, t- Butylhydroquinone, 4-t-pentylphenol, 2-t-butyl-5-methylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3-phenoxyphenol, 4-phenoxyphenol, 4-hexyloxyphenol, 4-hexanoyl olecinol, 3,5-diisopropylcatechol, 4-hexyl solcinol, 4-heptyloxyphenol, 3,5-di -t-butylphenol, 3,5-di-t-butylcatechol, 2,5-di-t-butylhydroquinone, di-sec-butylphenol, 4-cumylphenol, nonylphenol, 2-cyclopentylphenol , 4-cyclopentyl phenol, bisphenol A, bisphenol F and the like. These may be used individually or in combination of 2 or more types. Among them, phenol, o-cresol, m-cresol, p-cresol, bisphenol A, 2,3-xylenol, 3,5-xylenol, m-butylphenol, p-butylphenol, o-butylphenol, 4-phenylphenol and resorcinol are preferred, and phenol and bisphenol A are most preferred.

Aldehydes used to obtain the cationic phenolic polycondensate (B) used in the present invention are the phenolic compounds in the presence of an acid catalyst and ammonia or amine corresponding to the cationic functional group represented by the general formula (I). It will not specifically limit, as long as it can polycondense with and produce a cationic phenolic polycondensate (B). As such aldehydes, for example, formaldehyde, trioxane, furfural, paraformaldehyde, benzaldehyde, methylhemiformal, ethylhemiformal, propylhemiformal, butylhemiformal, phenylhemiformal, acetaldehyde , Propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, o-nitrobenzaldehyde, m- Nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde and the like. These may be used individually or in combination of 2 or more types. Of these, formaldehyde, paraformaldehyde, furfural, benzaldehyde, salicyaldehyde are preferred, and formaldehyde and paraformaldehyde are most preferred.

As the amine used to obtain the cationic phenolic polycondensate (B) used in the present invention, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, isopropylamine, di Isopropylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, isobutylamine, diisobutylamine, sec-butylamine, n-amylamine, di-n-amylamine, tri n-amylamine, sec-amylamine, sec-hexylamine, 2-ethylhexylamine, dioctylamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N- Butylethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N-ethyl diethanolamine, Nn-butyl diethanolamine, N, N-di-n-butylethanolamine, N-methyl Propanolamine, triisopropanolamine, etc. are mentioned. As the quaternizing agent, the quaternizing agent described in the production of the cationic urethane resin (A) can be used.

The acidic catalyst used to obtain the cationic phenolic polycondensate (B) used in the present invention is not limited to the following examples, for example, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, butyric acid, lactic acid , Salts with benzenesulfonic acid, p-toluenesulfonic acid, tartaric acid, boric acid, and the like or metals such as zinc chloride or zinc acetate can be used. These may be used individually or in combination of 2 or more types.

The number average molecular weight of the cationic phenolic polycondensate (B) used in the present invention is preferably in the range of 1,000 to 1,000,000, and more preferably in the range of 2,000 to 100,000. If the number average molecular weight is less than 1,000, the barrier property (density) of the formed film is inferior, and the corrosion resistance and alkali resistance tend to be lowered. If the number average molecular weight is more than 1,000,000, the liquid stability of the present metal surface treatment agent may be impaired.

The metal compound (C) (ie, zirconium compound and / or titanium compound (C)) contained in the metal surface treatment agent of the present invention is a salt of an zirconium or titanium oxide, a hydroxide, a complex, an inorganic acid or an organic acid, and the like. It is preferable that compatibility with resin (A) and a cationic phenol type polycondensate (B) is good. Examples of the metal compound (C) include zirconyl nitrate ZrO (NO ₃ ) ₂ , zirconyl acetate, zirconyl sulfate, zirconyl ammonium carbonate (NH ₄ ) ₂ [Zr (CO ₃ ) ₂ (OH) ₂ ], Zirconiumacetylacetonate Zr (OC (= CH ₂ ) CH ₂ COCH ₃ )) ₄ , Fluorozirconic Acid, Titanium Sulfate TiOSO ₄ , Diisopropoxytitaniumbisacetylacetone (C ₅ H ₇ O ₂ ) ₂ Ti [ OCH (CH ₃ ) ₂ ] ₂ , reactant of lactic acid and titanium alkoxide, titanium laurate, titanium acetylacetonate Ti (OC (= CH ₂ ) CH ₂ COCH ₃ )) ₃ , fluorotitanic acid, and the like. These metal compounds (C) can be used individually or in combination of 2 or more types, respectively.

Metal surface treatment agent of this invention which mix | blends said cationic urethane resin (A), a cationic phenolic polycondensate (B), and a metal compound (C) (As already mentioned, this invention of this aspect is an aspect ( The coating film obtained by coating 1) on a metal surface has excellent corrosion resistance and excellent alkali resistance. In this metal surface treatment agent, a zirconium compound is used as the metal compound (C), and Li, Mg, Al In the case of compounding a compound (D) (hereinafter referred to as a metal compound (D)) containing at least one metal selected from Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo, In addition to the excellent corrosion resistance and the excellent alkali resistance, the film formed can be provided the outstanding blackening resistance. The aspect of this invention in this case is set as aspect (2) as already mentioned.

In aspect (1) and (2), the compounding ratio of cationic urethane resin (A) and cationic phenolic polycondensate (B) is solid content mass ratio, (A) :( B) = 99: 1-1 It is preferable that it is: 99. As for this compounding ratio, it is more preferable that it is (A) :( B) = 99: 1-50: 50 as solid content mass ratio, In this case, the formed film has the outstanding corrosion resistance and the outstanding alkali resistance, and in some cases In addition to being able to impart excellent blackening resistance, more excellent yellowing resistance can be imparted.

Furthermore, the metal surface treatment agent (namely, this invention of aspect (1)) of this invention formed by mix | blending said cationic urethane resin (A), a cationic phenolic polycondensate (B), and a metal compound (C) is made into the metal surface. The film obtained by coating on the layer has excellent corrosion resistance and excellent alkali resistance. In this metal surface treatment agent, a titanium compound is used as the metal compound (C), and Li, Mg, Al, Ca, Mn, Co, Ni , Compound (D) (that is, metal compound (D)) containing at least one metal selected from Zn, Sr, W, Ce, and Mo; and further, a cationic urethane resin (A) and a cationic phenol In the case where the blending ratio of the system polycondensate (B) is set to (A) :( B) = 99: 1 to 50:50 as the solid content mass ratio, in addition to the excellent corrosion resistance and excellent alkali resistance to the formed film, Excellent blackening resistance and excellent yellowing resistance can be imparted. The aspect of this invention in this case is called aspect (3) as already mentioned.

In the metal compound (D) (i.e., Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo) contained in the metal surface treatment agent of the embodiments (2) and (3) of the present invention The compound (D) containing at least one metal selected is a salt of an oxide, a hydroxide, a complex, an inorganic acid or an organic acid of the metal, and the like. The cationic urethane resin (A) and the cationic phenol polycondensate (B) ) And good compatibility.

Specific examples of the metal compound (D) include lithium nitrate, lithium phosphate, lithium fluoride, lithium hydroxide, lithium sulfate, lithium carbonate, lithium 2 oxalate, lithium oxide, magnesium nitrate, magnesium sulfate, magnesium carbonate and magnesium hydroxide. Magnesium fluoride, magnesium ammonium phosphate, magnesium hydrogen phosphate, magnesium oxide, aluminum nitrate, aluminum sulfate, potassium aluminum sulfate, sodium aluminum sulfate, aluminum ammonium sulfate, aluminum phosphate, aluminum carbonate, aluminum oxide, aluminum hydroxide, aluminum iodide, calcium acetate, Calcium fluoride, calcium phosphinate [Ca (PH ₂ O ₂ ) ₂ ], calcium nitrate, calcium hydroxide, calcium oxalate, calcium oxide, calcium acetate, permanganate HMnO ₄ , potassium permanganate, sodium permanganate, manganese dihydrogen phosphate Mn (H ₂ PO _{4) 2,} manganese nitrate Mn (NO _{3) 2,} manganese sulfate (ⅱ), (ⅲ), or (ⅳ), manganese fluoride (ⅱ) or (ⅲ), tan Manganese acetate, manganese (Ⅱ) or (Ⅲ), ammonium sulfate, manganese, manganese acetylacetonate _{Mn (OC (= CH 2)} CH 2 COCH 3)) 3, iodide, manganese, manganese oxide, manganese hydroxide, cobalt chloride, chloro-penta Amine Cobalt Chloride [CoCl (NH ₃ ) ₅ ] Cl, Hexaamine Cobalt Chloride [Co (NH ₃ ) ₆ ] Cl ₂ , Cobalt Chromate, Cobalt Sulfate, Ammonium Cobalt Sulfate, Cobalt Nitrate, Cobalt Oxide 2 Aluminum CoO · Al ₂ O ₃ , cobalt hydroxide, cobalt phosphate, nickel nitrate, nickel sulfate, nickel carbonate, nickel acetylacetonate Ni (OC (= CH ₂ ) CH ₂ COCH ₃ )) ₃ , nickel chloride, hexaamine nickel chloride [Ni (NH ₃ ) ₆ ] Cl ₂ , nickel oxide, nickel hydroxide, zinc sulfate, zinc carbonate, zinc chloride, zinc iodide, zinc acetylacetonate Zn (OC (= CH ₂ ) CH ₂ COCH ₃ )) ₂ , dihydrogen phosphate, strontium nitrate , Strontium sulfate, strontium carbonate, strontium chloride, strontium acetylacetonate Sr (OC (= CH ₂ ) CH ₂ COCH ₃ )) ₂ , metatungstic acid H ₆ [H ₂ W ₁₂ O ₄₀ ], ammonium metatungstate (NH ₄ ) ₆ [H ₂ W ₁₂ O ₄₀ ], sodium metatungstate, paratungstic acid H ₁₀ [ W ₁₂ O ₄₆ H ₁₀ ], ammonium paratungstate, sodium paratungstate, cerium oxide, cerium acetate Ce (CH ₃ CO ₂ ) ₃ , cerium nitrate (III) or (IV), cerium sulfate, cerium chloride, molybdenum oxide , Molybdate H ₂ MoO ₄ , ammonium molybdate, ammonium paramolybdate, sodium molybdate, molybdate phosphoric acid compound (eg ammonium molybdate (NH ₄ ) ₃ [PO ₄ Mo ₁₂ O ₃₆ ] 3H ₂ O, sodium molybdate phosphate Na ₃ [PO ₄ .12MoO ₃ ] .nH ₂ O, and the like. These metal compounds (D) can be used individually or in combination of 2 types or more, respectively. Regarding the molybdenum (VI) compound, the tungsten (VI) compound, and the manganese (VI) compound, those reduced by using reducing agents such as alcohols and organic acids can be used. Among these metal compounds, it is particularly preferable to use a compound of Mg, Ni or Co in improving corrosion resistance and blackening resistance.

The above-mentioned cationic urethane resin (A), cationic phenolic polycondensate (B) and metal compound (C) (ie, zirconium compound and / or titanium compound), and optionally a metal compound (D) The film obtained by applying the metal surface treatment agent of the aspects (1) to (3) of the present invention on the metal surface has excellent corrosion resistance and excellent alkali resistance, and in some cases excellent blackening resistance and excellent yellowing resistance. By further mix | blending an acid component (E) (that is, at least 1 acid component (E) chosen from an inorganic acid and an organic acid) in a processing agent, the corrosion resistance and blackening resistance of the formed film can be improved further.

As the inorganic acid as the acid component (E), water-soluble ones can be used, and for example, phosphoric acid systems such as orthophosphoric acid, metaphosphoric acid, phosphonic acid, and polyphosphoric acid (particularly orthophosphoric acid multimers such as pyrroline acid and triphosphate). Acid of; Hydrofluoric acid; Fluoro metal acids such as fluorozirconium acid and fluorotitanic acid; Nitric acid; Sulfuric acid, and the like. Moreover, as an organic acid, what is water soluble can be used, such as having a carboxyl group or a sulfone group, For example, acetic acid, propionic acid, oxalic acid, tartaric acid, malic acid, gluconic acid, tannic acid, formic acid, ascorbic acid, etc. are mentioned. These acid components (E) can be used individually or in combination of 2 types or more, respectively. Of these, hydrofluoric acid, nitric acid, sulfuric acid and phosphoric acid are particularly preferable. The acid component (E) is mainly responsible for the function of etching the surface of the metal material when the metal surface treatment agent of the present invention is in contact with the metal material, and further improves the corrosion resistance and the film adhesion (adhesiveness to the metal surface). . In particular, nitric acid also has the effect of further improving the black resistance under high wet conditions. In addition, the acid component (E) further improves the liquid stability of the metal surface treatment agent of the present invention.

By mix | blending a vanadium compound (F) further in the metal surface treatment agent of the said (1)-(3) aspect of this invention, the corrosion resistance and alkali resistance of the film formed can further be improved. The vanadium compound (F) roneun, is the oxidation number of vanadium 5, and 4 is or can be used to trivalent vanadium compounds such as 5-vanadium oxide V ₂ O _5, metavanadate HVO _3, metavanadate, ammonium Vanadium compounds having pentavalent oxides such as sodium metavanadate and oxytrivanadium vanadium VOCl ₃ ; Vanadium trioxide V ₂ O ₃ , Vanadium dioxide VO ₂ , Vanadium oxysulfate VOSO ₄ , Vanadiumoxyacetylacetate VO (OC (= CH ₂ ) CH ₂ COCH ₃ )) ₂ , Vanadiumacetylacetate V (OC (= CH ₂ ) CH ₂ COCH ₃ )) ₃ , oxidized water such as vanadium trichloride VCl ₃ , invanad molybdate H _15-X [PV _12-x Mo _x O ₄₀ ] · nH ₂ O (6 <x <12, n <30) A trivalent or tetravalent vanadium compound is mentioned. These vanadium compounds can be used individually or in combination of 2 types or more, respectively.

The metal surface treatment agent of the aspect (1) to (3) of the present invention preferably contains a trivalent or tetravalent vanadium compound as the vanadium compound (F) in view of further improved high corrosion resistance maintenance and alkali resistance. Do. That is, the ratio of the trivalent or tetravalent vanadium compound in the vanadium compound (F) is (V ³⁺ + V ⁴⁺ ) / V (wherein V ³⁺ , V ⁴⁺ , V are vanadium compounds ( It is preferable that it is 0.1-1.0, It is more preferable that it is 0.2-1.0, and it is most preferable that it is the vanadium mass which is trivalent oxide number, the vanadium mass which is tetravalent oxide number, and the total vanadium mass in F).

As a method of containing a trivalent or tetravalent vanadium compound in the metal surface treatment agent of the said (1)-(3) aspect of this invention, pentavalent vanadium other than using said trivalent or tetravalent vanadium compound is used. A trivalent or quadruple reduced compound can be used beforehand using a reducing agent. Although the reducing agent to be used may be either an inorganic type or an organic type, an organic type is preferable, and alcohols, such as methanol, ethanol, isopropanol, and ethylene glycol; Aldehyde compounds such as formaldehyde, acetaldehyde and furfural; Carbonyl compounds such as acetylacetone, ethyl acetoacetate, dipivaloyl methane and 3-methylpentanedione; Organic acids such as formic acid, acetic acid, propionic acid, tartaric acid, ascorbic acid, gluconic acid, citric acid and malic acid; Amine compounds such as triethylamine, triethanolamine, ethylenediamine, pyridine, imidazole, pyrrole, morpholine and piperazine; Acid amide compounds such as formamide, acetamide, propionamide, and N-methylpropionamide; Amino acids such as glycine, alanine, pyrroline and glutamic acid; Monosaccharides such as glucose, mannose and galactose; Natural polysaccharides such as maltose, sucrose, starch and cellulose; Organic phosphoric acids such as aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1'-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid) and phytic acid; Natural polymers such as gallic acid, tannic acid, humic acid, lignin sulfonic acid and polyphenols; Synthetic polymers such as polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylamide, polyethyleneimine, and water-soluble nylon; Aminocarboxylic acids, such as EDTA, etc. are mentioned.

The organic reducing agent not only has a function of reducing the vanadium compound, but also significantly improves the stability of the vanadium compound in the treatment liquid, and provides an excellent corrosion resistance effect of the metal surface treatment agent of the aspect (1) to (3) of the present invention. Can be maintained for a long time. Moreover, since the said organic type reducing agent is effective also in forming a uniform film, improvement of corrosion resistance can also be anticipated.

Next, the usage-amount of each component in the metal surface treating agent of aspect (1)-(3) of this invention is demonstrated. The blending ratio of the cationic urethane resin (A) and the cationic phenolic polycondensate (B) to be blended in the metal surface treatment agent of the aspects (1) and (2) of the present invention is (A) :( B ) = 99: 1 to 1:99. If the blending ratio of the cationic phenolic polycondensate (B) is less than 99: 1, the corrosion resistance of the formed film is insufficient. On the other hand, if the cationic urethane resin (A) is less than 1:99, the corrosion resistance and alkali resistance are insufficient. There is a tendency to lose. When the said ratio was in the range of (A) :( B) = 99: 1-50: 50, in addition to the effect mentioned previously, it was discovered that the outstanding yellowing resistance can be provided to the obtained film. The ratio is still more preferably (A) :( B) = 90: 10 to 60:40. When the blending ratio of the cationic phenolic polycondensate (B) exceeds 50:50, yellowing resistance is insufficient.

In the case of aspect (3) of this invention, the compounding ratio of cationic urethane resin (A) and cationic phenolic polycondensate (B) mix | blended in a metal surface treating agent is (A) :( B) as solid content mass ratio. It is required that it is = 99: 1 to 50:50, and excellent yellowing resistance can be imparted to the resulting film. It is preferable that the said ratio is (A) :( B) = 90: 10-60: 40. If the blending ratio of the cationic phenolic polycondensate (B) is less than 99: 1, the corrosion resistance of the formed film tends to be insufficient, while the blending ratio of the cationic phenolic polycondensate (B) is 50:50. If it exceeds, yellowing resistance will become inadequate.

Metal compound (C) when the total solid content of the cationic urethane resin (A) and cationic phenolic polycondensate (B) contained in the metal surface treatment agent of aspect (1)-(3) of this invention is 100 mass parts. It is preferable that it is 0.1-20 mass parts as a metal (zirconium and / or titanium), and, as for the compounding quantity of, it is more preferable that it is 1-10 mass parts. When the compounding quantity of a metal compound (C) is in the said range, sufficient corrosion resistance and liquid stability can be ensured.

Metal compound (D) when the total solid content of the cationic urethane resin (A) and cationic phenol type polycondensate (B) contained in the metal surface treatment agent of aspect (2) and (3) of this invention is 100 mass parts. (Ie, compound (D) containing at least one metal selected from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce and Mo) When the above metal is contained, it is preferable that it is 0.01-10 mass parts, and, as for the metal as a whole, it is more preferable that it is 0.1-5 mass parts. If the compounding amount of the metal compound (D) is less than 0.01 part by mass, black deformation resistance cannot be imparted to the metal surface, and if it exceeds 10 parts by mass, the barrier property (density) of the film is lowered and the corrosion resistance tends to be lowered.

Acid component (E) as an optional component in the metal surface treatment agent of aspects (1)-(3) of this invention

(That is, when blending at least one acid component (E) selected from inorganic and organic acids), the blending amount is 100% of the total solid content of the cationic urethane resin (A) and the cationic phenolic polycondensate (B). When it is set as a mass part, it is preferable that it is 1-30 mass parts as an acid component itself which does not contain water, and it is more preferable that it is 5-20 mass parts. When the content of the acid component (E) is less than 1 part by mass, the etching action on the metal surface becomes insufficient, and as a result, the adhesion between the metal material and the coating is inferior and the corrosion resistance tends to be lowered. Moreover, when the said content of an acid component (E) exceeds 30 mass parts, it becomes difficult to form a uniform film by etching action excessively, and there exists a tendency for each performance, such as corrosion resistance and blackening resistance, to fall.

When mix | blending the vanadium compound (F) as an arbitrary component with the metal surface treatment agent of aspect (1)-(3) of this invention, the compounding quantity is cationic urethane resin (A) and cationic phenol type polycondensate (B). When total solid content of this is made into 100 mass parts, it is preferable that it is 0.01-20 mass parts as vanadium, and it is more preferable that it is 0.1-10 mass parts. If the content of the vanadium compound (F) is less than 0.01 parts by mass, the effect of the vanadium compound (F) to further improve the corrosion resistance and alkali resistance is not exerted, and when it exceeds 20 parts by mass, the barrier property (density) of the film is lowered and the corrosion resistance And alkali resistance tends to be rather impaired.

Moreover, in order to improve the lubricity and workability of the film formed, at least 1 chosen from water-based waxes, such as a polyolefin wax, ester wax, and hydrocarbon wax, to the metal surface treatment agent of aspects (1)-(3) of this invention. Species can be blended. When the total solid content of the cationic urethane resin (A) and the cationic phenolic polycondensate (B) contained in the metal surface treatment agent of the present invention is 100 parts by mass, the amount of the aqueous wax is preferably 0.5 to 30 parts by mass as a solid content. And it is more preferable that it is 1-20 mass parts.

Moreover, in order to further improve the corrosion resistance and alkali resistance of the film formed, a silane coupling agent can be mix | blended with the metal surface treatment agent of aspects (1)-(3) of this invention. The kind of such a silane coupling agent is not specifically limited, For example, vinyl trichlorosilane, vinyl tris ((beta) -methoxyethoxysilane), vinyl triethoxysilane, vinyl trimethoxysilane, (gamma)-(methacrylo) Yloxypropyl) trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N- (β-aminoethyl) γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltri Methoxysilane, (gamma)-mercaptopropyl trimethoxysilane, (gamma) -chloropropyl trimethoxysilane, ureidopropyl triethoxysilane, etc. are mentioned. These can be used individually or in combination of 2 or more types, respectively. When the total solid content of the cationic urethane resin (A) and the cationic phenolic polycondensate (B) contained in the metal surface treatment agent of the present invention is 100 parts by mass, the amount of the silane coupling agent is 0.5 to 15 parts by mass as the solid content. It is preferable and it is more preferable that it is 1-10 mass parts.

The aqueous medium used in the metal surface treatment agent of the aspects (1) to (3) of the present invention is usually water, but a small amount of alcohol (for example, 10% by volume or less of the entire aqueous medium) is used for the purpose of improving the dryness of the coating. You may use together the water-soluble organic solvent of a ketone, a cellosolve system. In addition, a surfactant, an antifoaming agent, a leveling agent, an antibacterial agent, a coloring agent, etc. can be added in the range which does not impair the liquid stability and the film performance of the metal surface treatment agent of this invention.

The lower limit of the total solid concentration of the metal surface treatment agent of the aspects (1) to (3) of the present invention is not particularly limited as long as the effect of the present invention can be achieved. However, the upper limit is limited in terms of liquid stability. do. It is preferable to adjust the total solid content concentration of the metal surface treating agent of this invention to the range of 0.1-40 mass%, It is more preferable to adjust to the range of 1-30 mass%, and to adjust to the range of 5-25 mass% Most preferred.

Next, the surface treatment method of this invention is described.

The metal surface treatment agent and surface treatment method of aspects (1)-(3) of this invention are suitable for steel sheets, such as a cold rolled sheet steel, a carbon steel plate, and a silicon steel plate, a plated steel plate, and an aluminum type metal material. The plated steel sheet includes, for example, a zinc-containing plated steel sheet subjected to plating treatment such as electro galvanizing, hot dip galvanizing, 55% aluminum zinc plating, 5% aluminum zinc plating, aluminum plating, iron zinc plating and the like. An aluminum metal material contains the metal material which has aluminum or aluminum alloy as a main component, such as a pure aluminum material, an aluminum alloy material, and an aluminum die-cast material.

Although there is no restriction | limiting in particular about the pretreatment process prior to the process by the metal surface treatment agent of aspect (1)-(3) of this invention, Usually, the oil adhering to a to-be-processed metal and contamination are removed before this process is performed. In order to do this, it wash | cleans with an alkali degreasing agent or an acidic degreasing agent, hot water washing | cleaning, solvent washing, etc. are performed, and surface adjustment by acid, an alkali, etc. are then performed as needed after that. In the washing | cleaning of the metal material surface, it is preferable to wash with water after washing so that a washing | cleaning agent may not remain so that it may remain on the metal material surface.

The process by the metal surface treating agent of aspect (1)-(3) of this invention is performed by drying, after apply | coating a metal surface treating agent. There is no restriction | limiting in particular about a coating method, The roll coat method which roll-transfers a coating agent to a metal material surface, and apply | coats, or the method removes water with a roll, removes water with an air knife, and flows out by a shower ringer etc., processing liquid What is necessary is just to select suitably from the method of immersing a metal material in the inside, the method of spraying a processing agent to a metal material, etc. Since the solvent of this treatment agent is water mainly, it is preferable that it is 0-60 degreeC, and, as for the process liquid temperature, it is more preferable that it is 5-40 degreeC.

With regard to the drying step after applying the metal surface treatment agent of the aspects (1) to (3) of the present invention, it is not necessary to promote curing of the cationic urethane resin (A) and the cationic phenolic polycondensate (B). In the case of removing only the adhering water, physical removal such as air drying or air blow may be performed without necessarily heat, but the curing of the cationic urethane resin (A) and the cationic phenol polycondensate (B) is accelerated or In order to enhance the coating effect by softening, it is necessary to heat-dry. 50-250 degreeC is preferable and, as for the temperature in that case, 60-220 degreeC is more preferable.

As a dry film mass, 30-5,000 mg / m <2> is preferable and 50-3,000 mg / m <2> of an adhesion amount of the film formed is more preferable. When the dry film mass is less than 30 mg / m 2, sufficient corrosion resistance and blackening resistance are not obtained. When the dry film mass is more than 5,000 mg / m 2, the adhesion to the metal material and the yellowing resistance decrease.

Next, the operation of the present invention will be described. Although it is inferred that each component has the following functions in the metal surface treating agent of aspect (1)-(3) of this invention, this invention is not restrict | limited at all by the following speculation.

In the process of apply | coating to a metal material and drying, the metal surface treating agent of aspect (1)-(3) of this invention reacts with a metal material surface, forms a film with favorable adhesiveness, and a resin component forms a film. It is considered to give the material excellent corrosion resistance. The cationic phenolic polycondensate (B) and the metal compound (C) (i.e., zirconium compound and / or titanium compound) form a dense three-dimensional structure and form a film on the surface of the metal at the time of coating of the treatment agent or in a heat drying step. To react and stick. At this time, when the acid component (E) is contained in the metal surface treatment agent, the etching action is increased and the reactivity with the metal surface is higher, whereby a stronger film is formed at the interface with the metal surface.

The coating formed in this way has excellent corrosion resistance, and the following can be considered in addition to the metal surface barrier property (density) of the formed coating. That is, the cationic phenolic polycondensate (B) contained in the treatment agent of the present invention is a compound having a resonance stabilizing structure, and Mn in the metal compound (C) (ie, zirconium compound and / or titanium compound) and the metal compound (D). , Co, Ni, W, Ce or Mo-containing compound, and vanadium compound (F) are transition metal compounds. The film formed of the cationic phenolic polycondensate (B), the metal compound (C) and the compound containing Mn, Co, Ni, W, Ce or Mo, and the optional vanadium compound (F) reacts with the metal surface. By being attached to the outer surface of the material metal so as to be close enough to overlap with the outer track of the raw metal, and as a result, the electrons generated by the corrosion are delocalized by using the Φ track, whereby the surface potential is kept uniform. It is thought to give excellent corrosion resistance (not only a flat part but a cut section and a flaw part). As a conventional chromate coating anticorrosive mechanism, soluble hexavalent chromium melts and a self-repairing effect of reprecipitation on a metal surface exposed portion is generally known. It is considered to be the same anticorrosive mechanism as the treatment agent of the present invention due to its properties (high fixation reactivity to the metal surface) and excellent (corrosive electron) delocalization.

In addition, the metal compound (D) inactivates the metal substrate surface by forming a basic compound on the metal substrate surface or by modifying the metal substrate surface, prevents blackening of the metal substrate, and further improves corrosion resistance.

On the other hand, cationic urethane resin (A) is formed on the said film formed in the metal interface (that is, it has a two-layer structure), and has the effect of improving corrosion resistance by improving barrier property (density), and workability It is effective to increase.

In addition, by combining the cationic urethane resin (A) and the cationic phenolic polycondensate (B) and limiting the ratio of both, the water resistance is improved, and the coating becomes difficult to dissolve, leading to improvement in alkali resistance.

Regarding yellowing resistance (heat resistance), since the cationic phenolic polycondensate (B) has an aromatic ring, it tends to be discolored by heating, but the cationic urethane resin (A) and the cationic phenolic polycondensate By using the cationic urethane resin (A) in the ratio of (B) to be equal or more, yellowing resistance can be imparted / enhanced while maintaining corrosion resistance, blackening resistance and alkali resistance.

Although an Example and a comparative example demonstrate this invention below, this Example is only a mere example and does not limit this invention. The metal material to be processed, the components (A) to (F) and the treatment method (pretreatment and the present invention treatment) used in the Examples and Comparative Examples, the evaluation method, the explanation of the evaluation result, the treatment agent composition and the treatment method (Tables 1 to 2). 4, 8-10, 13-15) and evaluation result (Tables 5-7, 11-12, 16-17) are described below in this order.

(1) metal material to be treated

Ⅰ Electro galvanized steel sheet (plate thickness: 0.8 mm)

Ⅱ Hot dip galvanized steel sheet (plate thickness: 0.8 mm)

Ⅲ 5% aluminum galvanized steel sheet (plate thickness: 0.6㎜)

Ⅳ 55% aluminum galvanized steel sheet (plate thickness: 0.4㎜)

(2) metal surface treatment agent components

(2-1) Cationic Urethane Resin (A)

Cationic Urethane Resin (A1)

150 parts by mass of polyether polyol (synthetic component: tetramethylene glycol and ethylene glycol, molecular weight 1500), 6 parts by mass of trimethylolpropane, 24 parts by mass of N-methyl-N, N-diethanolamine, 94 parts by mass of isophorone diisocyanate And 135 mass parts of methyl ethyl ketones were put into the reaction container, and it reacted for 1 hour, keeping at 70-75 degreeC, and produced the urethane prepolymer. Subsequently, 15 mass parts of dimethyl sulfate was put into the reaction container, it was made to react at 50-60 degreeC for 30 to 60 minutes, and the cationic urethane prepolymer was produced. Subsequently, 576 mass parts of water were put into the reaction container, the mixture was emulsified uniformly, methyl ethyl ketone was collect | recovered, and water-soluble cationic urethane resin (A1) was obtained.

Cationic Urethane Resin (A2)

Polyester polyol (synthetic component: isophthalic acid, adipic acid and 1,6-hexanediol, ethylene glycol, molecular weight 1700) 135 parts by mass, 5 parts by mass of trimethylolpropane, N-methyl-N, N-diethanolamine 22 Mass part, 86 mass parts of isophorone diisocyanate, and 120 mass parts of methyl ethyl ketone were put into the reaction container, and it reacted for 1 hour, keeping at 70-75 degreeC, and produced the urethane prepolymer. 17 mass parts of dimethyl sulfate was put into the reaction container, and it reacted at 50-60 degreeC for 30 to 60 minutes, and produced the cationic urethane prepolymer. Subsequently, 615 mass parts of water were put into the reaction container, the mixture was emulsified uniformly, methyl ethyl ketone was collect | recovered, and water-soluble cationic urethane resin (A2) was obtained.

Cationic Polyurethane Resin (A3)

130 parts by mass of polycarbonate polyol (synthetic component: 1,6-hexanecarbonate diol, ethylene glycol, molecular weight 2000), 4 parts by mass of trimethylolpropane, 21 parts by mass of N-methyl-N, N-diethanolamine, and isophorone di 75 parts by mass of isocyanate and 115 parts by mass of methyl ethyl ketone were placed in a reaction vessel, and reacted for 1 hour while maintaining at 70 to 75 ° C to produce a urethane prepolymer. Subsequently, 22 mass parts of dimethyl sulfate was put into the reaction container, and it reacted at 50-60 degreeC for 30 to 60 minutes, and produced the cationic urethane prepolymer. Subsequently, 633 mass parts of water were put into the reaction container, the mixture was emulsified uniformly, methyl ethyl ketone was collect | recovered, and water-soluble cationic polyurethane resin (A3) was obtained.

(2-2) Cationic Phenol-based Polycondensate (B)

Cationic Phenolic Polycondensate (B1)

Into a 1000 mL flask equipped with a reflux condenser, 0.3 g of p-toluenesulfonic acid was added as a mole of bisphenol A1 (228 g) and a catalyst, the internal temperature was raised to 100 ° C, and 0.85 mole (69 g) of aqueous formaldehyde solution was added over 1 hour. And reacted under reflux at 100 ° C. for 2 hours. Thereafter, the reaction vessel is left to cool with water, and after the turbidity of the water layer separated into the upper layer disappears, it is decanted to remove the water layer, and the mixture is heated and stirred until it reaches 170 to 175 ° C. Removed.

Next, the temperature was lowered to 100 ° C., 234 g of butyl cellosolve was added to completely dissolve the polycondensate, and then 234 g of pure water was added, and 1 mole (75 g) of diethanolamine was added when the temperature in the system dropped to 50 ° C. ) Was added, and 1 mol (81.1 g) of formaldehyde aqueous solution was dripped at 50 degreeC over about 1 hour to this. Furthermore, the temperature was raised to 80 degreeC and reaction was continued, stirring for about 3 hours, and cationic phenolic polycondensate (B1) was obtained.

Cationic Phenolic Polycondensate (B2)

Into a 1000 mL flask equipped with a reflux condenser, 1 mole (96 g) of phenol and 0.3 g of p-toluenesulfonic acid were added as a catalyst, the internal temperature was raised to 100 ° C., and 0.7 mole (56.8 g) of aqueous formaldehyde solution over 1 hour. It added and reacted at 100 degreeC under reflux for 2 hours. Thereafter, the reaction vessel is left to cool with water, and after the turbidity of the water layer separated into the upper layer disappears, it is decanted to remove the water layer, and the mixture is heated and stirred until it reaches 170 to 175 ° C. Removed.

Next, the temperature was lowered to 100 ° C, 234 g of butyl cellosolve was added to completely dissolve the polycondensate, and then 234 g of pure water was added, and 1 mole of N-methylpropanolamine was added when the temperature in the system dropped to 50 ° C. (89g) was added and 0.7 mol (56.8g) of formaldehyde aqueous solution was dripped at 50 degreeC over about 1 hour to this. Moreover, the temperature was raised to 80 degreeC and reaction was continued, stirring for about 3 hours, and cationic phenolic polycondensate (B2) was obtained.

Cationic Phenolic Polycondensate (B3)

In a 1000 mL flask equipped with a reflux condenser, 1 mole (108 g) of O-cresol and 0.3 g of p-toluenesulfonic acid were added as a catalyst, the internal temperature was raised to 100 ° C, and 0.85 mole (69 g) of aqueous formaldehyde solution was added for 1 hour. Added over and reacted under reflux at 100 ° C. for 2 hours. Thereafter, the reaction vessel is left to cool with water, and after the turbidity of the water layer separated into the upper layer disappears, it is decanted to remove the water layer, and the mixture is heated and stirred until it reaches 170 to 175 ° C. Removed.

Next, the temperature was lowered to 100 ° C., 234 g of butyl cellosolve was added to completely dissolve the polycondensate, and then 234 g of pure water was added, and N, N-diethylethanol was added when the temperature in the system dropped to 50 ° C. 1 mol (117 g) of amine was added, and 1 mol (81.1 g) of formaldehyde aqueous solution was dripped at this at 50 degreeC over about 1 hour. Furthermore, the temperature was raised to 80 degreeC, reaction was continued, stirring for about 3 hours, and cationic phenolic polycondensate (B3) was obtained.

(2-3) Metal Compound (C)

C1: zirconium ammonium carbonate

C2: fluorozirconium acid

C3: titan lactate

C4: fluoro titanoic acid

(2-4) Metal Compound (D)

D1: lithium oxide

D2: Magnesium Nitrate

D3: Magnesium Oxide

D4: Aluminum Acetyl Acetate

D5: calcium fluoride

D6: Cobalt Nitrate

D7: Nickel Nitrate

D8: Nickel Carbonate

D9: strontium nitrate

D10: Molybdenum Oxide

D11: ammonium metatungstate

D12: Cerium Oxide

D13: Zinc Oxide

D14: zinc acetylacetonate

D15: Manganese Carbonate

D16: Manganese Oxide

D17 Manganese Phosphate Dihydrogen

(2-5) Acid Component (E)

E1: hydrofluoric acid

E2: Phosphoric Acid

E3: nitric acid

E4: citric acid

E5: Oxalic acid

(2-6) Vanadium Compound (F)

F1: ammonium metavanadate

F2: Vanadiumacetylacetonate

F3: Vanadium Phosphate

F4: vanadium oxysulfate

(3) processing method

(3-1) Degreasing

Nippon Parkarizing Co., Ltd. make alkaline degreasing agent Parclin 364S (20 g / L dry bath, 60 degreeC, 10 second spray, spray pressure 0.5 kg / cm <2>), and wash | cleaned the material for 10 seconds after spray dehydration.

(3-2) Application and drying

I: The metal surface treatment agent (medium: water) adjusted to 10 mass% of solid content concentration was bar code-coated so that dry mass might be 700 mg / m <2>, and it dried at 80 degreeC (PMT: reaching plate temperature).

II: The metal surface treatment agent (medium: water) adjusted to 16 mass% of solid content concentration was bar code-coated so that dry mass might be 1000 mg / m <2>, and it dried at 150 degreeC (PMT).

(4) evaluation method

(4-1) corrosion resistance

The processed plate sample prepared in the Examples and Comparative Examples was processed (plane), crosscut to reach the base material with an NT cutter (crosscut), and extruded 7mm hexane ( Processed part), a corrosion resistance test was carried out. The evaluation method is as follows.

(Planar part) Salt spray test method Based on JIS-Z-2371, the white rust generation area after 360 hours of salt spray was calculated | required and evaluated.

Evaluation criteria: White rust generating area ◎ Less than 5%, ○ 5% or more and less than 10%, △ 10% or more and less than 30%, × 30% or more and less than 50%, × 50% or more.

(Cross cut part) Based on the salt spray test method JIS-Z-2371, the situation of white rust occurrence after 360 hours of salt spray was visually evaluated.

Evaluation Criteria: White rust occurs ◎ Almost no rust, ○ Many parts where white rust does not occur in the crosscut part, △ The whole crosscut part is made of white rust, but there is no rust that flows down, × rust that flows from the crosscut part occurs.

(Processing part) Based on the salt spray test method JIS-Z-2371, the white-blue generation after 360 hours of salt spray was evaluated visually.

Evaluation Criteria: White rust generated ◎ Almost no rust, ○ Many parts where white rust has not occurred in the processing part, △ The whole processed part is made of white rust, but no rust flowing down, × Rust flowing from the processing part is generated.

(4-2) alkali resistance

Nihon Parkarizing Co., Ltd. alkali degreasing agent Parclin 364S was dripped in 20 g / L of water, The degreasing agent aqueous solution adjusted to 65 degreeC was sprayed for 5 minutes, and it washed with water, and dried at 80 degreeC to the process board sample. About this board, corrosion resistance was evaluated by the conditions and evaluation method as described in said (4-1).

(4-3) blackening resistance

After leaving a process board sample for 12 days in the temperature of 70 degreeC, and the humidity of 95% of atmospheres, the appearance was visually observed and evaluated.

Evaluation criteria: ◎ No white rust, no black stools, ○ No white rust, slight black stools, △ White rust occurs, slight black stools, × White rust occurs, Black stools are quite significant

(4-4) yellowing resistance

After leaving a process board sample for 2 hours in 250 degreeC atmosphere, external appearance was visually observed and evaluated.

Evaluation criteria: ◎ no discoloration, ○ slightly yellowing, yellowing △ overall, yellowish brown ×.

Composition and treatment method of metal surface treatment agent according to aspect (1) of the present invention, and test evaluation results

The compositions and treatment methods of the metal surface treatment agents of Examples 101 to 177 and Comparative Examples 101 to 105 are shown in Tables 1 to 4 and the test evaluation results are shown in Tables 5 to 7. As is clear from Tables 5 to 7, the metal materials of Examples 101 to 143 and 145 to 177 having a film formed using the metal surface treatment agent of the aspect (1) of the present invention have good corrosion resistance, alkali resistance, and yellowing resistance. In addition, since it does not contain harmful chromium, it turns out that safety is high and the flat part, the cross cut part, and the processed part have the outstanding corrosion resistance equivalent to or more than chromate treatment. Moreover, although the metal material of Example 144 with a higher ratio of (B) than (A) was inferior to yellowing resistance, it was excellent in corrosion resistance and alkali resistance. On the other hand, the metal material of the comparative example 101 which does not contain a cationic urethane resin (A), and the metal of the comparative example 102 which does not contain the cationic phenolic polycondensate (B) which is an essential component of the metal surface treatment agent of this invention. The metal material of Comparative Example 104, which does not contain the material, the metal compound (C) (ie, the zirconium compound and / or the titanium compound), is outside the scope of the present invention. There was a clear fall in both alkaline and yellowing resistance. In addition, the alkali-resistant metal material of the comparative example 105 which processed the chromate (jinchrome 3360H) was inferior.

In Tables 1-4, (A) is a cationic urethane resin, (B) is a cationic phenol type polycondensate, (C) is a metal compound (zirconium compound and / or titanium compound), (E) is an acid component, (F) represents a vanadium compound. In addition, * 1 is solid content compounding ratio (mass ratio), * 2 and * 4 are compounding ratios as zirconium and / or titanium and vanadium, respectively, with respect to 100 mass parts of total solids of a component (A) and a component (B), respectively. (Part) and * 3 represent the compounding ratio (mass part) as the acid component itself which does not contain water with respect to 100 mass parts of total solids of a component (A) and a component (B), respectively. * 5 is the reaching plate temperature. * 6 It roll-coated so that the chromium adhesion | attachment chromium 3360H which is the coating chromate of Nippon Parker Co., Ltd. made to be 20 mg / m <2> in chromium adhesion amount was heat-dried at 100 degreeC (PMT).

Composition and treatment method of metal surface treatment agent according to aspect (2) of the present invention, and test evaluation results

The compositions and treatment methods of the metal surface treatment agents of Examples 201 to 251 and Comparative Examples 201 to 206 are shown in Tables 8 to 10, and the test evaluation results are shown in Tables 11 and 12. As is clear from Tables 11 and 12, the metal materials of Examples 201 to 250 having a coating formed using the metal surface treatment agent of the present invention have good corrosion resistance, alkali resistance, blackening resistance and yellowing resistance, and contain harmful chromium. Since it does not exist, it is high in safety, and it turns out that all the planar part, a crosscut part, and a process part have the outstanding corrosion resistance equivalent to chromate treatment or more. In addition, the metal material of Example 251 having a higher ratio of (B) than (A) was inferior in yellowing resistance, but was excellent in corrosion resistance, alkali resistance and blackening resistance. On the other hand, the metal material of Comparative Example 201 in which the film does not contain a cationic urethane resin (A), and the metal of Comparative Example 202 in which the film does not contain a cationic phenolic polycondensate (B) which is an essential component of the metal surface treatment agent of the present invention. The metal material of Comparative Example 203 in which the material, the film does not contain a zirconium compound (C), and the Comparative Example 205 in which the ratio of (A) / (B) is outside the scope of the present invention are resistant to corrosion, alkali, black and yellowing. In all, it fell clearly. In addition, the film is a metal compound (D) (that is, a compound (D) containing at least one metal selected from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce, and Mo)). In Comparative Example 204, which does not contain the, black resistance was insufficient. In addition, the alkali-resistant metal material of the comparative example 206 which processed the chromate (jinchrome 3360H) was inferior.

In Tables 8-10, (A) is a cationic urethane resin, (B) is a cationic phenolic polycondensate, (C) is a zirconium compound, (D) is a metal compound, (E) is an acid component, (F ) Represents a vanadium compound. In addition, * 1 is solid content compounding ratio (mass ratio), * 2, * 3, and * 5 are compounding ratios (mass) as zirconium, a metal, and vanadium, respectively with respect to 100 mass parts of total solids of a component (A) and a component (B). (Part) and * 4 represent the mixture ratio (mass part) as the acid component itself which does not contain water with respect to 100 mass parts of total solids of a component (A) and a component (B), respectively. * 6 is the reaching plate temperature. * 7 The roll coating of chromium 3360H which is the coating chromate of Nippon Parker Co., Ltd. product was made into 20 mg / m <2> by chromium adhesion amount, and it heat-dried at 100 degreeC (PMT).

Composition and treatment method of metal surface treatment agent according to aspect (3) of the present invention, and test evaluation results

The compositions and treatment methods of the metal surface treatment agents of Examples 301 to 342 and Comparative Examples 301 to 306 are shown in Tables 13 to 15, and the test evaluation results are shown in Tables 16 and 17. As is clear from Tables 16 and 17, the metal materials of Examples 301 to 342 having a coating formed using the metal surface treatment agent of the present invention had good corrosion resistance, alkali resistance, blackening resistance and yellowing resistance, and contained harmful chromium. Since it does not exist, it is high in safety, and it turns out that all the planar part, a crosscut part, and a process part have the outstanding corrosion resistance equivalent to chromate treatment or more. On the other hand, the metal material of Comparative Example 301 in which the film does not contain a cationic urethane resin (A), and the metal material of Comparative Example 302 in which the film does not contain a cationic phenolic polycondensate (B), and the film contains a titanium compound (C) The metal material of Comparative Example 303, which is not, and the metal material of Comparative Example 305, in which the ratio of (A) / (B) is outside the scope of the present invention, were clearly inferior in all of corrosion resistance, alkali resistance, blackening resistance, and yellowing resistance. . In addition, the film is a metal compound (D) (that is, a compound (D) containing at least one metal selected from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce, and Mo)). The metal material of Comparative Example 304 containing no was insufficient in black denaturation. Further, the metal material of Comparative Example 306 subjected to chromate treatment (jin chrome 3360H) was inferior in corrosion resistance of the processed portion after alkali degreasing.

In Tables 13-15, (A) is a cationic urethane resin, (B) is a cationic phenolic polycondensate, (C) is a titanium compound, (D) is a metal compound, (E) is an acid component, (F ) Represents a vanadium compound. In addition, * 1 is solid content compounding ratio (mass ratio), * 2, * 3, and * 5 are compounding ratios (mass, as titanium, a metal, and vanadium, respectively) with respect to 100 mass parts of total solids of a component (A) and a component (B), respectively. (Part) and * 4 represent the mixture ratio (mass part) as the acid component itself which does not contain water with respect to 100 mass parts of total solids of a component (A) and a component (B), respectively. * 6 is the reaching plate temperature. * 7 The roll coating of chromium 3360H which is the coating chromate of Nippon Parker Co., Ltd. product was made into 20 mg / m <2> by chromium adhesion amount, and it heat-dried at 100 degreeC (PMT).

Claims (16)

Cationic water-soluble or aqueous emulsion urethane resin (A) (hereinafter referred to as cationic urethane resin (A)), a polycondensate of phenolic compound and aldehydes and cationic (B) (hereinafter cationic phenolic polycondensate) (B)) and a zirconium compound and / or a titanium compound (C) (hereinafter referred to as a metal compound (C)) as a metal surface treatment agent formed by blending an aqueous medium, including a cationic urethane resin (A) and a cation. The blending ratio of the phenolic polycondensate (B) is (A) :( B) = 99: 1 to 1:99 as the solid content mass ratio, and the blending ratio of the metal compound (C) is cationic urethane resin (A ) Metal surface treatment agent which is 0.1-20 mass parts as zirconium and / or titanium with respect to 100 mass parts of total solids of the cationic phenol type polycondensate (B). The metal compound (C) is a zirconium compound and contains at least one metal selected from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce, and Mo. The compound (D) (henceforth a metal compound (D)) to which the said compounding ratio is based on 100 mass parts of total solids of a cationic urethane resin (A) and a cationic phenolic polycondensate (B) As a metal surface treatment agent mix | blended so that it may be 0.01-10 mass parts. The metal surface of Claim 1 whose compounding ratio of cationic urethane resin (A) and cationic phenolic polycondensate (B) is (A) :( B) = 99: 1-50: 50 as solid content mass ratio. Treatment Article 1. The metal surface of Claim 2 whose compounding ratio of cationic urethane resin (A) and cationic phenolic polycondensate (B) is (A) :( B) = 99: 1-50: 50 as solid content mass ratio. Treatment agent. The metal compound (C) is a titanium compound, and further contains at least one metal selected from Li, Mg, Al, Ca, Mn, Co, Ni, Zn, Sr, W, Ce, and Mo. Compound (D) (that is, metal compound (D)) to be blended, and the blending ratio of the cationic urethane resin (A) and the cationic phenolic polycondensate (B) is (A) :( B ) = 99: 1 to 50:50 metal surface treatment agent. The at least 1 type of acid component (E) (henceforth an acid component (E)) chosen from an inorganic acid and an organic acid is mix | blended with cationic urethane resin (A) and a cationic phenol. The metal surface treatment agent mix | blended so that it may be 1-30 mass parts as the acid component itself which does not contain water with respect to 100 mass parts of total solids of a system polycondensate (B). The at least 1 type of acid component (E) (henceforth an acid component (E)) chosen from an inorganic acid and an organic acid is the compounding ratio of cationic urethane resin (A) and cationic phenol. The metal surface treating agent mix | blended so that it may be 1-30 mass parts as the acid component itself which does not contain water with respect to 100 mass parts of total solids of a system polycondensate (B). The at least 1 type of acid component (E) (henceforth an acid component (E)) chosen from inorganic acid and organic acid is the compounding ratio of cationic urethane resin (A) and cationic phenol of Claim 5 The metal surface treatment agent mix | blended so that it may be 1-30 mass parts as the acid component itself which does not contain water with respect to 100 mass parts of total solids of a system polycondensate (B). The vanadium compound (F) according to claim 1, wherein the blending ratio is 0.01 to 20 masses as vanadium with respect to 100 parts by mass of the total solids of the cationic urethane resin (A) and the cationic phenolic polycondensate (B). Metal surface treatment agent mix | blended so that it might be added. The vanadium compound (F) according to claim 2, wherein the blending ratio is 0.01 to 20 masses as vanadium with respect to 100 parts by mass of the total solids of the cationic urethane resin (A) and the cationic phenolic polycondensate (B). Metal surface treatment agent mix | blended so that it might be added. The vanadium compound (F) according to claim 5, wherein the blending ratio is 0.01 to 20 masses as vanadium with respect to 100 parts by mass of the total solids of the cationic urethane resin (A) and the cationic phenolic polycondensate (B). Metal surface treatment agent mix | blended so that it might be added. The cationic urethane resin (A) according to any one of claims 1, 2, and 5, wherein the functional groups giving cationicity to the resin are represented by the following general formulas (I), (II), ( III) or (IV)

Wherein R ¹ , R ² , R ³ , R ⁶ and R ⁷ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or a linear or branched hydroxyalkyl group having 1 to 10 carbon atoms And R ⁴ and R ⁵ independently of each other represent a linear or branched alkylene group having 2 to 10 carbon atoms, and A ^- and B ^- represent hydroxyl ions or acid ions. The urethane resin according to any one of claims 1, 2 or 5, wherein the cationic urethane resin (A) is a polycondensate of a polyol and a polyisocyanate, and is unsubstituted or substituted as part of the polyol to be used. The metal surface treating agent which is a urethane resin obtained by using the polyol which has an amino group, or the polyol which has a nitrogen atom in a principal chain, or a urethane resin which quaternized the nitrogen atom of this urethane resin. The polycondensate according to any one of claims 1, 2 or 5, wherein the cationic phenolic polycondensate (B) is a polycondensate obtained by coexisting ammonia or amine when polycondensing a phenolic compound and an aldehyde, Or the metal surface treating agent which quaternized the nitrogen atom of the polycondensate. The coating method is formed on the metal material surface by apply | coating and drying the metal surface treatment agent in any one of Claims 1-11 on the metal material surface, The surface treatment method of the metal material characterized by the above-mentioned. The metal material which has a film formed using the surface treatment method of Claim 15.