JP2009185366A - Water base surface treating composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water base surface treating composition which can increase rust prevention performance to zinc or an alloy comprising ≥20% zinc or their plated bodies. <P>SOLUTION: Disclosed is the water base surface treating composition for rust prevention having a chemical structure obtained by bringing a titanium-compounded composite having a chemical structure obtained by reacting a titanium compound oligomer (a), an amine compound (b) and a glycol compound (c) and/or a composition obtained by mixing them into reaction with a silicon compound (d) having one or more alkoxy groups in the molecule and/or a composition obtained by mixing them. Also disclosed is a zinc or an alloy comprising ≥20% zinc or their plated bodies subjected to rust prevention using the water base surface treating composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an aqueous surface treatment composition for use on the surface of zinc or an alloy containing zinc in an amount of 20% or more, or a plated body thereof, and more particularly, an aqueous system using a titanium compound oligomer as a raw material. Or a composition containing at least one selected from a phosphoric acid compound, a vanadium compound and a zirconium compound in the above composition, in particular zinc or an alloy containing 20% or more of zinc, or The present invention relates to a water-based surface treatment composition that improves substrate adhesion, processed part corrosion resistance, heat resistance, paint adhesion, alkali resistance, and solvent resistance with respect to the surface of these plated bodies.

  As a steel material having excellent corrosion resistance, a galvanized steel material subjected to zinc plating, zinc alloy plating, or the like is used. Such a galvanized steel material is oxidized by contact of the zinc layer with air or water, and white rust is generated. For this reason, preventing oxidation by surface treatment, that is, imparting corrosion resistance is performed.

  Further, the steel material subjected to such surface treatment is used under high temperature conditions, and the surface may be scratched during transportation, so that heat resistance and scratch resistance are also required. Furthermore, the surface-treated steel material may be processed or coated before use, and excellent corrosion resistance and paint adhesion after processing are also required. Moreover, since the degreasing process of the press oil used in the process is usually performed with an alkaline degreasing agent, alkali resistance is also required.

  As such a treatment, a chromate treatment using a chromium compound is known. When the chromate treatment is performed, generation of white rust is prevented, and a very good galvanized steel sheet can be obtained. However, in recent years, from the viewpoint of environmental problems, a method of performing chemical conversion treatment with a non-chromate treatment agent that does not use chromium is being changed.

  Patent Document 1 discloses a metal surface treatment agent containing a silicate ester, an inorganic salt of aluminum, and a silane coupling agent. However, since the metal surface treatment agent described in Patent Document 1 cannot provide a stable and sufficient cross-linking reaction due to a siloxane bond, the metal surface treatment plate obtained by the treatment may be inferior in solvent resistance or alkali resistance. There is.

  Patent Document 2 discloses a metal surface treatment agent containing a vanadium compound and a metal compound containing at least one metal selected from cobalt, nickel, zinc, aluminum, calcium, strontium, barium, and lithium. ing. However, the metal surface-treated metal plate obtained by treating with the metal surface treating agent described in Patent Document 2 has a problem that when it is left for a long time under high temperature and high humidity, the adhesion with the substrate is lowered.

  Patent Document 3 discloses a metal surface treatment agent containing a diluted hydrolyzate and / or a silane coupling agent obtained by diluting ethyl polysilicate to a hydrolysis rate of 100% or more and diluting. ing. However, in the metal surface treatment plate obtained by treatment with the metal surface treatment agent described in Patent Document 3, a hard film with poor flexibility is formed, and the processed film is easily cracked. There is a problem that the adhesion to the material is insufficient. In addition, the storage stability of the diluted hydrolyzed solution, the corrosion resistance of the film, and the alkali resistance may be inferior.

  In Patent Document 4, a divalent or higher metal ion such as titanium ion, vanadium ion or zirconium ion, a fluoro acid having at least four fluorine atoms and elements such as titanium or zirconium, an active hydrogen-containing amino group, an epoxy group, etc. A metal surface treatment composition containing a silane coupling agent having a water content and an aqueous emulsion resin is disclosed. However, since the metal surface treatment composition described in Patent Document 4 contains a resin, the metal surface treatment plate obtained by the treatment has a problem that the film has poor heat resistance when left in a high temperature environment.

  Patent Document 5 discloses a water-soluble phosphorus and / or water-soluble resin, a silane coupling agent, phosphoric acid and / or hexafluorometal acid, and water-soluble phosphorus whose cation species is manganese, magnesium, aluminum, or nickel. Metal surface treatment compositions containing acid salts are disclosed. However, since the metal surface treatment agent described in Patent Document 5 contains a resin, the metal surface treatment plate obtained by treatment with this has a problem that it is inferior in corrosion resistance of the film when left in a high temperature environment.

  Patent Document 6 discloses a water-based anticorrosive coating agent for galvanizing containing an silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having a vinyl group, and an acid, A rust prevention treatment method for coating the same and a rust prevention treatment metal material coated with the same are disclosed. However, the anticorrosive metal agent described in Patent Document 6 has good corrosion resistance but has a problem of poor alkali resistance.

JP-A-10-251864 JP 2004-183015 A JP 2005-118635 A JP 2005-120469 A JP 2005-206947 A JP 2007-39715 A

  In view of the above situation, the present invention is an aqueous system that satisfies all of substrate adhesion, processed part corrosion resistance, heat resistance, paint adhesion, alkali resistance, and solvent resistance, which has been difficult with conventional non-chromate coatings. An object is to provide a surface treatment composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has obtained a chemical structure obtained by reacting a titanium compound oligomer, an amine compound and a glycol compound and / or a titanium composite composition having a composition obtained by mixing them. In addition, a chemical structure obtained by reacting a specific silicon compound and / or a composition obtained by mixing, or at least one selected from a phosphoric acid compound, a vanadium compound, and a zirconium compound is further added to the above composition. By applying, baking, drying, curing, etc., such a surface treatment composition that has a composition containing it as a water-based compound (that is, exists as a water-soluble compound) and is dissolved or dispersed in water, zinc or Alloy containing 20% or more of zinc, or substrate adhesion to the surface of the plated body, processed part corrosion resistance, heat resistance, Instrumentation adhesion, alkali resistance, and solvent resistance and completed the present invention have found that significantly improved.

  That is, the present invention provides a titanium composite composition having at least a chemical structure obtained by reacting a titanium compound oligomer (a), an amine compound (b) and a glycol compound (c) and / or a composition obtained by mixing them. A chemical structure obtained by reacting a silicon compound (d) having one or more alkoxy groups in the molecule and / or a composition obtained by mixing, or a phosphoric acid compound, a vanadium compound, and zirconium The present invention provides a water-based surface treatment composition characterized by having a composition containing at least one selected from compounds.

  In addition, the present invention is characterized in that zinc or an alloy containing 20% or more of zinc, or the surface of the plated body is formed using the above-described aqueous surface treatment composition. A rust preventive film is provided.

  Further, the present invention provides zinc or an alloy containing 20% or more of zinc, or a plated body thereof, characterized in that a rust prevention layer is formed using the aqueous surface treatment composition described above. To do.

  According to the aqueous surface treatment composition of the present invention, zinc or an alloy containing 20% or more of zinc, or a highly dense composite film of a titanium compound and a silicon compound is formed on the surface of the plated body. Thus, a film satisfying all of substrate adhesion, processed part corrosion resistance, heat resistance, paint adhesion, alkali resistance, and solvent resistance can be obtained.

  Hereinafter, the present invention will be described. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented.

[Titanium composite composition]
The aqueous surface treatment composition of the present invention is a titanium composite having a chemical structure obtained by reacting “titanium compound oligomer (a), amine compound (b) and glycol compound (c)” and / or a composition obtained by mixing them. The composition has a chemical structure obtained by reacting “a silicon compound (d) having one or more alkoxy groups in the molecule” and / or a composition obtained by mixing them.

(Titanium compound oligomer (a))
The titanium compound oligomer (a) is not particularly limited, but “a titanium alkoxide represented by the following formula (1) or a structure in which a chelating agent is coordinated to a titanium alkoxide represented by the following formula (1)” What has the structure which "the titanium chelate compound" condensed is preferable.

［式（１）中、Ｒ^１〜Ｒ^４は、それぞれ独立に炭素数１個以上１８個以下のアルキル基を示す。］

Wherein ^(1), R 1 to R ⁴ represents one or more 18 or less alkyl group having a carbon number independently. ]

The “titanium alkoxide represented by the formula (1)” which is the starting material before the condensation is that each of R ^{1 to} R ⁴ in the formula (1) is independently an alkyl group having 1 to 18 carbon atoms. However, it is preferable that each independently be an alkyl group having 1 to 8 carbon atoms, and it is particularly preferable that each independently be an alkyl group having 1 to 5 carbon atoms.

  Specific examples of the “titanium alkoxide represented by the formula (1)” include, for example, tetramethoxy titanium, tetraethoxy titanium, tetra n-propoxy titanium, tetraisopropoxy titanium, tetra n-butoxy titanium, and tetraisobutoxy titanium. , Diisopropoxydi n-butoxytitanium, ditert-butoxydiisopropoxytitanium, tetratert-butoxytitanium, tetraisooctoxytitanium, and tetrastearoxytitanium. These can be used alone or in admixture of two or more.

  As a starting material before condensation, in addition to the above-mentioned “titanium alkoxide represented by formula (1)”, titanium having a structure in which a chelating agent is coordinated to “titanium alkoxide represented by formula (1)” Chelate compounds are also preferred. Such a chelating agent is not particularly limited, but the hydrolysis of the titanium compound should be at least one selected from the group consisting of β-diketone, β-ketoester, polyhydric alcohol, alkanolamine and oxycarboxylic acid. It is preferable in terms of improving stability against the above.

  The β-diketone compound is not particularly limited as long as it is coordinated as a chelating agent. For example, specifically, 2,4-pentanedione, 2,4-hexanedione, 2,4-heptanedione , Dibenzoylmethane, thenoyltrifluoroacetone, 1,3-cyclohexanedione, 1-phenyl-1,3-butanedione, and the like. These can be used alone or in combination of two or more.

  The β-ketoester is not particularly limited as long as it is coordinated as a chelating agent. Specific examples thereof include methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, and methylpivaloyl acetate. Methyl isobutyroyl acetate, methyl caproyl acetate, and methyl lauroyl acetate. These can be used alone or in combination of two or more.

  The polyhydric alcohol is not particularly limited as long as it is coordinated as a chelating agent. 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol 2,3-butanediol, 2,3-pentanediol, glycerin, diethylene glycol, hexylene glycol and the like. These can be used alone or in combination of two or more.

  The alkanolamine is not particularly limited as long as it is coordinated as a chelating agent, but N, N-dimethylethanolamine, N, N-diethylethanolamine, N- (β-aminoethyl) ethanolamine, N -Methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, Nn-butylethanolamine, Nn-butyldiethanolamine, N-tert-butylethanolamine, N-tert-butyldiethanolamine, triethanolamine, Examples include diethanolamine and monoethanolamine. These can be used alone or in combination of two or more.

  The oxycarboxylic acid is not particularly limited as long as it coordinates as a chelating agent, and examples thereof include glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, and gluconic acid. These can be used alone or in combination of two or more.

  The above-mentioned “titanium alkoxide represented by the formula (1)” or “titanium chelate compound having a structure in which a chelating agent is coordinated to the titanium alkoxide” is condensed to obtain a titanium compound oligomer (a). The method for condensation here is not particularly limited, but the titanium alkoxide or the titanium chelate compound is reacted by reacting water in an alcohol solution, or the amine compound (b) described later in the alcohol solution. A method of reacting in the state where water coexists is preferable.

  Regarding the amount of water used for the oligomerization by condensation, the number of moles of water is 0.2 mol or more per 1 mol of the total amount of titanium alkoxide and / or titanium chelate compound, that is, 1 mol of titanium atom. It is preferably 2 mol or less from the viewpoint of stability to water, film-forming property, coating property, etc., more preferably 0.3 mol or more and 1.7 mol or less, and 0.5 mol or more and 1.6 mol or less. It is particularly preferably at most mol, more preferably at least 1.0 mol and at most 1.5 mol.

  In addition, the above does not limit the manufacturing method of the titanium compound oligomer (a) in the present invention, and the chemical structure such as the condensation degree of the titanium compound oligomer (a) is specified by the manufacturing method such as the condensation method. It is what you are doing. This is because the titanium compound oligomer (a) may have a two-dimensional or three-dimensional chemical structure, and the chemical structure can only be specified by the production method. The titanium compound oligomer (a) having the following chemical structure is also used in the present invention.

When the titanium compound oligomer (a) is represented by a composition formula, when the number of moles of water to react is 2 moles with respect to 2 moles of titanium atoms, the titanium compound oligomer (a) represented by the following formula (2): Usually obtained by condensation.
TiO _{x / 2} (OR) _4-x (2)
[In Formula (2), R represents any of R ^{1 to} R ⁴ in Formula (1). ]

When 1 mol of water is reacted with 1 mol of titanium atom, that is, when 2 mol of water is reacted with 2 mol of titanium atom, x = 2.
TiO ₁ (OR) ₂ (3)
When 1.5 mol of water is reacted with 1 mol of titanium atom, that is, when 3 mol of water is reacted with 2 mol of titanium atom, x = 3, so that the formula (2) Is
TiO _3/2 (OR) ₁ (4)
It becomes.

  The composition having the composition formula obtained by substituting the value of x corresponding to the above-mentioned “preferable amount of water used for condensation and oligomerization” into the formula (2) is the condensation of the titanium compound oligomer (a). The degree is preferable.

  The titanium compound oligomer (a) in the present invention is not particularly limited as long as it is an oligomer. On average, it is preferably 1.1-mer or more and 20-mer or less, and it is preferably dimer or more and 15-mer or less. It is more preferable that it is tetramer or more and 13-mer or less, and it is more preferable that it is pentamer or more and 12-mer or less. From the viewpoint of stability to water, film-forming property, coating property, etc., those having a high degree of condensation are preferred. Although the above formula (3) represents in principle one having a one-dimensional infinite degree of condensation, the actual titanium compound oligomer (a) to be produced has a finite degree of condensation. The titanium compound oligomer (a) in the present invention is more preferably one having a chemical structure produced using an amount of water that has an infinite degree of condensation in principle.

At the time of condensation, a titanium compound oligomer (a) may be obtained by using a solvent such as alcohol and using the titanium alkoxide or the titanium chelate compound as an alcohol solution, and optionally through a heat treatment such as reflux. Although there is no particular limitation on the alcohol used in this case, a monohydric alcohol having an alkyl group R ¹ to R ⁴ in the formula (1) is preferred in that does not change the reactivity of the titanium compound oligomer (a). Specific examples include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, and 2-ethylhexanol. These can be used alone or in combination of two or more.

  The amount of alcohol used is not particularly limited, but the amount of water used for condensation and oligomerization is 0.5% by mass or more and 20% by mass or less based on the total amount of water and the alcohol. It is preferable to dilute using the alcohol as described above in terms of suppressing the occurrence of white turbidity and white precipitates in the chemical solution, and it is more preferable to dilute to a concentration of 0.7% by mass or more and 15% by mass or less. It is particularly preferable to dilute to a concentration of 1.0% by mass or more and 10% by mass or less.

  The above condensation is carried out by reacting titanium alkoxide or titanium chelate compound with water in the presence of the amine compound (b) and in an alcohol solution. It is preferable in terms of easy suppression. The amine compound (b) used at this time is the same as the amine compound (b) used when preparing a titanium composite composition by reacting and / or mixing with a titanium compound oligomer (a) described later. It may or may not be.

  It is also preferable that the titanium compound oligomer (a) has a structure in which a chelating agent is further coordinated with the above-described titanium compound oligomer. That is, a structure obtained by further coordinating a chelating agent to a titanium alkoxide represented by the formula (1) or a structure obtained by condensing a titanium chelate compound having a structure coordinated with a chelating agent. Also preferred are those having That is, a structure in which a chelating agent is reacted before and / or after the condensation is preferable in terms of enhancing the stability of the titanium compound oligomer (a) against hydrolysis.

  Although there is no limitation in particular as a chelating agent used after condensation, the above-mentioned chelating agent can be used conveniently. Particularly preferred are β-diketone, β-ketoester, or alkanolamine.

(Amine compound (b))
The amine compound (b) to be reacted and / or mixed with the titanium compound oligomer (a) for obtaining the titanium composite composition is not particularly limited, but is substituted unsubstituted aliphatic amine or quaternary ammonium hydroxide. It is preferable that it is a thing in order to improve stability with respect to a hydrolysis etc. of a titanium oligomer compound (a), and to make it water-soluble.

  The substituent in the “substituted unsubstituted aliphatic amine” is preferably an alcoholic hydroxyl group. Alkanolamine is particularly preferred as the substituted aliphatic amine.

  Specific examples of the unsubstituted aliphatic amine include aliphatic alkylamines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, and amylamine. , Sec-amylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, and tributylamine; and aliphatic cyclic amines such as piperidine and pyrrolidine. These can be used alone or in combination of two or more.

  Specific examples of the alkanolamine include N, N-dimethylethanolamine, N, N-diethylethanolamine, N- (β-aminoethyl) ethanolamine, N-methylethanolamine, N-methyldiethanolamine, N -Ethylethanolamine, Nn-butylethanolamine, Nn-butyldiethanolamine, N-tert-butylethanolamine, N-tert-butyldiethanolamine, triethanolamine, diethanolamine, monoethanolamine and the like. These can be used alone or in combination of two or more.

  Specific examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, and 2-hydroxyethyl. Examples include trimethylammonium hydroxide. These can be used alone or in combination of two or more.

(Glycol compound (c))
The glycol compound (c) to be reacted and / or mixed with the titanium compound oligomer (a) for obtaining the titanium composite composition is not particularly limited, but a glycol compound having a hydroxyl group at each adjacent carbon atom is preferred. Specifically, for example, 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 2,3-butanediol, 2,3-pentanediol, and Examples include glycerin. Among these, 1,2-ethanediol, 1,2-propanediol, or 2,3-butanediol is particularly preferable in terms of improving the stability of the titanium oligomer compound against hydrolysis and the like, and making it water-soluble.

  By using the glycol compound (c), the stability of the titanium oligomer compound (a) against hydrolysis and the like can be improved and water-solubilized.

(Ratio of each component in the titanium composite composition)
The use ratio of “titanium compound oligomer (a)”, “amine compound (b)” and “glycol compound (c)” is not particularly limited, but the molar ratio of (b) and (a) is (b) / (A) = 0.1 / 10 to 10 / 0.1 is preferable, (b) / (a) = 0.3 / 10 to 10 / 0.3 is more preferable, and 0.5 / 10 to 10/0 .5 is particularly preferred. If the amount of (a) is too small relative to the total amount of (a) and (b), it will cause a decrease in crosslinkability, film-forming property, adhesiveness, etc., while if too much (a), it will dissolve in water. And stability such as hydrolysis may be insufficient.

  The molar ratio of (c) to (a) is preferably (c) / (a) = 0.1 / 10 to 10 / 0.1, and (c) / (a) = 0.5 / 10 to 10 /0.5 or less is more preferable, and 1/10 or more and 10/1 or less is particularly preferable. If the amount of (a) is too small relative to the total amount of (a) and (c), it will cause a decrease in crosslinkability, film-forming properties, adhesiveness, etc. On the other hand, if (a) is too large, it will dissolve in water. The stability may be insufficient, such as inadequate properties or hydrolysis.

  Regarding the chemical structure of a compound having a structure obtained by the reaction of a titanium compound oligomer (a), an amine compound (b) and a glycol compound (c) (hereinafter abbreviated as “compound A”) in the titanium composite composition As long as it has a structure obtained by the above production method, it is not limited to one produced by a specific production method.

  As the chemical structure of Compound A, a structure in which the titanium compound oligomer (a) reacts with the amine compound (b) and the glycol (c) to coordinate the titanium chelate oligomer glycol chelate or amino group to titanium is preferable. . In particular, an alkoxyl group at the end of the titanium compound oligomer (a) reacts with the amine compound (b) and / or glycol compound (c) to form a chelated structure or an amino group or glycol compound present in the amine compound. A structure in which the hydroxyl group present in is coordinated to a titanium atom is preferred.

  The titanium composite composition in the present invention contains the compound A, a titanium compound oligomer (a), an amine compound (b) and / or a glycol (c). The titanium composite composition may have a composition in which the amine compound (b) and the glycol compound (c) are mixed at room temperature with the titanium compound oligomer (a), or the titanium compound oligomer (a). On the other hand, it may have a composition obtained by heating and refluxing the amine compound (b) and the glycol compound (c). The “mixed composition” includes the case where the whole amount of the reaction does not proceed and the unreacted remaining material is mixed, and the case where only a part is reacted.

The titanium composite composition in the present invention is not particularly limited as long as it is a composition obtained by the above method, but the following eight forms are preferable.
(1) Compound A;
(2) Mixture of compound A and titanium compound oligomer (a);
(3) a mixture of compound A and amine compound (b);
(4) a mixture of compound A and glycol compound (c);
(5) Mixture of compound A, titanium compound oligomer (a) and amine compound (b);
(6) Mixture of compound A, titanium compound oligomer (a) and glycol compound (c);
(7) Mixture of compound A, amine compound (b) and glycol compound (c);
(8) A mixture of a titanium compound oligomer (a), an amine compound (b) and a glycol compound (c);
Among these, form (1) and form (8) are preferable in that the above-described effects of the present invention can be suitably obtained.

[Silicon compound (d)]
The water-based surface treatment composition of the present invention further includes a “silicon compound (d) having one or more alkoxy groups in the molecule” (hereinafter abbreviated as “silicon compound (d)”) in the titanium composite composition. It has a chemical structure obtained by reacting and / or a composition obtained by mixing.

  Although there is no limitation in particular as a silicon compound (d), A silane coupling agent, the alkyl silicate which four alkoxy groups couple | bonded with the silicon atom, etc. are preferable at the point which improves film forming property. Among these, those containing an amino group, a mercapto group, or an epoxy group are preferable from the viewpoint of further improving coating adhesion and heat resistance. Further, those having a structure in which an alkyl group is directly bonded to a silicon atom are preferable from the viewpoint of improving paint adhesion and heat resistance. In this case, the alkyl group is preferably a methyl group or an ethyl group. Moreover, the partial hydrolysis-condensation product of the said compound can also be used conveniently.

  Specific examples of the silicon compound (d) include monomethyltrimethoxysilane, dimethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetranormalpropoxysilane, γ-aminoethylaminopropyltrimethoxysilane, and γ-aminopropyl. Aminoethyltrimethoxysilane, γ-aminopropylaminoethylmethyldimethoxysilane, γ-aminopropylaminoethyltriethoxysilane, γ-aminopropylaminoethylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltri Ethoxysilane, bis- (trimethoxysilylpropyl) amine, bis- (triethoxysilylpropyl) ethylenediamine, γ-ureidopropyltrimethoxysilane, γ-ureidopropylate Ethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxy Propylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyl Examples thereof include methyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. These can be used alone or in admixture of two or more.

  When the silicon compound (d) is used in combination with the titanium composite composition described above to obtain an aqueous titanium oligomer composition, the structure and / or the mixture obtained by reacting the titanium compound composition with the silicon compound (d) It is preferable that it has a composition obtained by making it. Here, the reaction method is not particularly limited, but it is preferable that the titanium composite composition and the silicon compound (d) are mixed and then refluxed at the boiling point of the solvent used to advance the reaction. There is no regulation in the order of blending.

  The use ratio of the titanium composite composition and the silicon compound (d) is not particularly limited, but the mass ratio of the titanium composite composition and the silicon compound (d) is 0.1 / 10 or more and 10 / 0.1 or less. It is preferable that it is 0.5 / 10 or more and 10 / 0.5 or less, and it is especially preferable that it is 1/10 or more and 10/1 or less. If the amount of the titanium composite composition is too small relative to the total amount of the titanium composite composition and the silicon compound (d), the film forming property is reduced. On the other hand, if the amount of the titanium composite composition is too large, the film forming property is reduced. And stability such as hydrolyzability may be insufficient.

  The aqueous surface treatment composition of the present invention is not limited to those produced by the production method described above, and any aqueous surface treatment composition can be used as long as it has a chemical structure and composition produced by the production method described above. Even if the manufacturing method is different, it is included in the present invention. However, the aqueous titanium oligomer composition of the present invention is preferably produced by the production method described above. That is, reacting and / or mixing the titanium compound oligomer (a), the amine compound (b) and the glycol compound (c) is preferable as a method for producing a titanium composite composition and a method for producing an aqueous titanium oligomer composition. Moreover, it is preferable as a manufacturing method of a water-system titanium oligomer composition to make a titanium compound composition react and / or mix the silicon compound (d) which has a 1 or more alkoxy group in a molecule | numerator.

  The content ratio of the titanium composite composition in the aqueous surface treatment composition of the present invention is not particularly limited, but the titanium composite composition is 0.1% by mass to 30% by mass as titanium in 100% by mass of the surface treatment agent. It is preferable to contain, it is especially preferable to contain 0.3 to 20 mass%, and it is still more preferable to contain 0.5 to 10 mass%.

  The aqueous surface treatment composition of the present invention may further contain at least one selected from a phosphoric acid compound, a vanadium compound, and a zirconium compound. Thereby, excellent corrosion resistance can be obtained.

  Examples of the phosphoric acid compound include phosphoric acids such as orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid, triammonium phosphate, diammonium hydrogen phosphate, trisodium phosphate, disodium hydrogen phosphate, And phosphates such as aluminum phosphate. These may be used alone or in combination of two or more. When the phosphoric acid compound is used, the phosphate ions can form a phosphate layer on the surface of the metal substrate to be passivated, thereby improving corrosion resistance, such as being effective in preventing white rust.

  When the aqueous surface treatment composition of the present invention contains a phosphoric acid compound, the content of the phosphoric acid compound is 0.01% by mass or more and 10% by mass or less in 100% by mass of the surface treatment agent. It is preferable. If it is less than 0.01% by mass, the corrosion resistance is insufficient, and if it exceeds 10% by mass, it may be gelled and cannot be applied depending on the aqueous titanium oligomer composition used. More preferably, it is 0.05 mass% or more and 5 mass% or less.

  Examples of the vanadium compound include ammonium metavanadate, sodium metavanadate, potassium metavanadate, vanadium oxyacetylacetonate, vanadium acetylacetonate, and the like. These may be used alone or in combination of two or more. When the above vanadium compound is used, it is passivated by forming a vanadium layer on the surface of the metal base as in the case of chromium compounds that have been used to impart corrosion resistance. Corrosion resistance can be improved.

  When the aqueous surface treatment composition of the present invention contains the vanadium compound, it is preferably contained in an amount of 0.05% by mass to 10% by mass in 100% by mass of the surface treatment agent. If it is less than 0.05% by mass, the corrosion resistance is insufficient, and if it exceeds 10% by mass, the corrosion resistance is saturated and uneconomical, and depending on the aqueous titanium oligomer composition used, it becomes gelled and cannot be applied. Sometimes. More preferably, they are 0.1 mass% or more and 5 mass% or less.

  Examples of the zirconium compound include ammonium hexafluorozirconate, sodium hexafluorozirconate, potassium hexafluorozirconate, zirconium nitrate, zirconium acetate, ammonium zirconium carbonate, and zirconium acetylacetonate. These may be used alone or in combination of two or more. When the above vanadium compound is used, it is passivated by forming a zirconium layer on the surface of the metal base as in the case of chromium compounds that have been used to impart corrosion resistance. Corrosion resistance can be improved.

  When the aqueous surface treatment composition of the present invention contains the zirconium compound, it is preferably contained in an amount of 0.05% by mass to 10% by mass in 100% by mass of the surface treatment agent. If it is less than 0.05% by mass, the corrosion resistance is insufficient, and if it exceeds 10% by mass, the corrosion resistance is saturated and uneconomical, and depending on the aqueous titanium oligomer composition used, it becomes gelled and cannot be applied. Sometimes. More preferably, they are 0.1 mass% or more and 5 mass% or less.

  The aqueous surface treatment composition of the present invention can further use a rust preventive agent in order to enhance the rust preventive effect as necessary. Specifically, triazole compounds such as 1,2,3-benzotriazole, 1-N, N bis (2-ethylhexyl) aminoethylbenzotriazole, and carboxybenzotriazole; orthomolybdate, paramolybdate, and And molybdenum compounds such as metamolybdate; and hydrazine compounds such as carbohydrazide, propionic acid hydrazide, and salicylic acid hydrazide. When using these rust preventives, although not particularly limited, it is preferably used in a range of 0.01 to 10% by mass in 100% by mass of the surface treatment composition of the present invention, and mixed or reacted. Can be used.

  The aqueous surface treatment composition of the present invention can be suitably used for zinc or an alloy containing 20% or more of zinc, or a plated body thereof. Any of these can be used without any particular limitation. Specifically, for example, the present invention can be applied to galvanized steel sheets such as galvanized steel sheets, zinc-nickel plated steel sheets, zinc-iron plated steel sheets, and zinc-aluminum plated steel sheets. . The plating method is not particularly limited, and any known method such as electroplating, hot dipping, vapor deposition, dispersion plating, and vacuum plating may be used.

  The aqueous surface treatment composition of the present invention may use an antifoaming agent, an organic solvent, a leveling agent, and a pH adjusting agent in order to form a more uniform and smooth film. The organic solvent is not particularly limited as long as it is generally used in paints, and examples thereof include alcohol-based, ketone-based, ester-based, and ether-based hydrophilic solvents. Examples of the leveling agent include silicone-based, acetylenic diol-based, and fluorine-based compounds. Examples of the pH adjuster include inorganic acids such as hydrofluoric acid, sulfuric acid, and nitric acid, organic acids such as acetic acid, lactic acid, and phosphonic acid, ammonium salts, and amines.

  The application method in the case of applying the aqueous surface treatment composition of the present invention to zinc or an alloy containing 20% or more of zinc, or an adherend such as a plated body thereof is not particularly limited and is generally used. Roll coating, air spray, airless spray, immersion and the like can be appropriately employed. In order to enhance the curability of the rust-preventing film, it is preferable to heat the object to be coated in advance or to heat-dry the object after coating. The heating temperature of the object to be coated is 50 ° C. or higher and 250 ° C. or lower, preferably 70 ° C. or higher and 220 ° C. or lower. When the heating temperature is less than 50 ° C., the evaporation rate of moisture is slow and sufficient film forming properties cannot be obtained, so that the solvent resistance and alkali resistance are lowered. On the other hand, when it exceeds 250 degreeC, corrosion resistance will fall. The drying time in the case of heat drying after coating is preferably from 1 second to 5 minutes.

The coating amount in the case of applying the aqueous surface treatment composition of the present invention to zinc or an alloy containing 20% or more of zinc, or an adherend such as a plated body thereof is not particularly limited, but preferably after drying The coating amount is 0.5 g / m ² or more and 3 g / m ² or less. If it is less than 0.5 g / m ² , the corrosion resistance and alkali resistance may decrease. On the other hand, when the amount of the film is too large, not only the substrate adhesion is lowered but also uneconomical. More preferably, it is 0.5 g / m ² or more and 2 g / m ² or less.

  The anticorrosive film of the present invention can also be used by forming a coating film by applying a top coating onto the film. Examples of the top coat include paints made of acrylic resin, acrylic-modified alkyd resin, epoxy resin, urethane resin, melamine resin, phthalic acid resin, amino resin, polyester resin, vinyl chloride resin, and the like.

  The film thickness of the coating film of the top coating is appropriately determined depending on the application of the rust-proof metal product, the type of top coating used, and the like, and is not particularly limited. Usually, it is about 5 μm to 300 μm, more preferably about 10 μm to 200 μm. Formation of the coating film of the top coating material can be performed by applying the top coating material on the coating film formed from the aqueous surface treatment composition, heating, drying and curing. The drying temperature and time are appropriately adjusted according to the type of top coat to be applied, the film thickness of the coating film, and the like. Usually, the drying temperature is preferably 50 ° C. or higher and 250 ° C. or lower, and the drying time. Is preferably 5 minutes to 1 hour. As a method for applying the top coat, it can be performed by a conventionally known method according to the form of the paint.

  The aqueous surface treatment composition of the present invention is preferably used for treating the surface of zinc or an alloy containing 20% or more of zinc, or in order to enhance the rust prevention performance of such a plated body. That is, it is preferable to use the aqueous surface treatment composition of the present invention for rust prevention of these surfaces. The rust preventive film formed using the aqueous surface treatment composition of the present invention can enhance the rust preventive performance of these surfaces.

  Rust prevention using the aqueous surface treatment composition of the present invention, zinc or an alloy containing 20% or more of zinc, or a plated body thereof, even under severe conditions, substrate adhesion, processed part corrosion resistance, Heat resistance, paint adhesion, alkali resistance, and solvent resistance can be maintained.

  The action and principle of the surface treatment composition of the present invention exhibiting an excellent antirust effect is not clear, and the present invention is not limited to the scope of the following action and principle, but the following may be considered. That is, by using a titanium oligomer compound, it is considered that a film to be formed is densified, and by using a silicon compound (d) having one or more alkoxy groups in the molecule, It is thought that the adhesiveness with the metal plate which is a base material is improved. From these events, it is thought that the causative substances that generate rust such as water and air are less likely to come into direct contact with the metal plate, and the rust prevention performance is enhanced.

  Next, the present invention will be described more specifically with reference to titanium composite compositions, production examples of titanium compounds, examples using the production examples, and comparative examples. In addition,% in each example means the mass%.

<Production Example 1>
After 28.4 g (0.10 mol) of tetraisopropoxytitanium was dissolved in 50.0 g of 2-propanol, a mixed solution of 2.7 g (0.15 mol) of water and 50.0 g of 2-propanol was added dropwise. After completion of dropping, the mixture was stirred for 1 hour to obtain “titanium compound oligomer (a) A”. Next, after adding 8.9 g (0.10 mol) of N, N-dimethylmonoethanolamine, the mixture was stirred for 1 hour, and then 30.4 g (0.40 mol) of 1,2-propanediol was added. The mixture was stirred for an hour and further refluxed for 1 hour to obtain “titanium composite composition A”.

<Production Example 2>
After 28.4 g (0.10 mol) of tetraisopropoxytitanium was dissolved in 50.0 g of 2-propanol, 2.7 g (0.15 mol) of water, 50.0 g of 2-propanol and Nn-butylethanol were used. A mixed solution of 5.9 g (0.05 mol) of amine was added dropwise. After completion of dropping, the mixture was stirred for 1 hour to obtain “titanium compound oligomer (a) B”. Next, 36.8 g (0.40 mol) of glycerin was added, stirred for 1 hour, and further refluxed for 1 hour to obtain “titanium composite composition B”.

<Production Example 3>
After dissolving 28.4 g (0.10 mol) of tetraisopropoxytitanium in 50.0 g of 2-propanol, 0.9 g (0.05 mol) of water, 50.0 g of 2-propanol, and N, N-dimethylmono A mixed solution of ethanolamine 4.5 g (0.05 mol) was added dropwise. After completion of dropping, the mixture was stirred for 1 hour to obtain “titanium compound oligomer (a) C”. Next, after stirring for 1 hour, 36.0 g (0.40 mol) of 1,2-butanediol was added, stirred for 1 hour, refluxed for further 1 hour, and 87 g of 2-propanol was further removed. “Titanium composite composition C” was obtained.

<Production Example 4>
Tetra n-butoxytitanium (34.0 g, 0.10 mol) was dissolved in 1-butanol (30.0 g), and then a mixture of water (2.7 g, 0.15 mol) and 1-butanol (60.0 g) was added dropwise. . After completion of dropping, the mixture was stirred for 1 hour to obtain “titanium compound oligomer (a) D”. Next, after adding 8.9 g (0.10 mol) of N, N-dimethylmonoethanolamine, the mixture was stirred for 1 hour, and then 36.0 g (0.40 mol) of 2,3-butanediol was added. The mixture was stirred for an hour and further refluxed for 1 hour to obtain “titanium composite composition D”.

<Production Example 5>
“Titanium compound oligomer (a)” was prepared in the same manner as in Production Example 4 except that the amount of water relative to 28.4 g (0.10 mol) of tetraisopropoxytitanium was changed to 2.2 g (0.12 mol) of water. E "and" titanium composite composition E "were obtained.

<Production Example 6>
After dissolving 36.4 g (0.1 mol) of diisopropoxybisacetylacetonate titanium in 50.0 g of 2-propanol, a mixed solution of 2.7 g (0.15 mol) of water and 100.0 g of 2-propanol. Was dripped. After completion of dropping, the mixture was stirred for 1 hour and further refluxed for 1 hour to obtain "titanium compound oligomer (a) F". Next, after adding 5.1 g (0.05 mol) of triethylamine and stirring for 1 hour, 30.4 g (0.40 mol) of 1,2-propanediol was added and stirred for 1 hour, and further for 1 hour. The mixture was refluxed to obtain “titanium composite composition F”.

<Production Example 7>
After 28.4 g (0.10 mol) of tetraisopropoxytitanium was dissolved in 50.0 g of 2-propanol, a mixed solution of 2.7 g (0.15 mol) of water and 50.0 g of 2-propanol was added dropwise. After completion of dropping, the mixture was stirred for 1 hour to obtain “titanium compound oligomer (a) G”. Next, after adding 8.9 g (0.10 mol) of N, N-dimethylmonoethanolamine, the mixture was stirred for 1 hour, and then 30.4 g (0.40 mol) of 1,2-propanediol was added. Stir for hours and reflux for an additional hour. Thereafter, 13.6 g (0.10 mol) of monomethyltrimethoxylane was further added, and the mixture was further refluxed for 1 hour to obtain “titanium composite composition G”.

<Production Example 8>
To 28.4 g (0.10 mol) of tetraisopropoxy titanium, 8.9 g (0.10 mol) of N, N-dimethylmonoethanolamine was added. After the addition, the mixture was stirred for 1 hour. Further, 30.4 g (0.40 mol) of 1,2-propanediol was added, stirred for 1 hour, and further refluxed for 1 hour to obtain “titanium compound a”.

<Production Example 9>
To 34.0 g (0.10 mol) of tetra-n-butoxytitanium, 5.1 g (0.05 mol) of triethylamine was added, followed by stirring for 1 hour. Thereafter, 30.4 g (0.40 mol) of 1,2-propanediol was added, stirred for 1 hour, and further refluxed for 1 hour to obtain “titanium compound b”.

<Production Example 10>
To 28.4 g (0.1 mol) of tetraisopropoxytitanium, 10.1 g (0.1 mol) of triethylamine was added over 30 minutes. Subsequently, 52.9 g (0.2 mol) of γ- (2-aminoethyl) aminopropylmethyldiethoxysilane was added, and then 49.6 g (0.8 mol) of 1,2-ethanediol was added. The mixture was stirred for 1 hour and further refluxed for 1 hour to obtain “titanium compound c”.

<Examples 1-84, Comparative Examples 1-24 Creation of surface-coated steel sheets>
[Create test plate]
An electrogalvanized steel sheet with a thickness of 0.8 mm (zinc adhesion amount: 20 g / m ² ) was sprayed for 60 seconds using a 60% alkaline degreasing agent (Surf Cleaner 155, manufactured by Nippon Paint Co., Ltd.) 2% aqueous solution. Degreased. Next, the titanium composite composition obtained in the above production example and the substances shown in Tables 1 to 4 were prepared according to the formulations shown in Tables 5 and 6, and an aqueous coating agent was prepared using a bar coater. It applied so that it might become the quantity of 0.5 g / m < ² >, and it baked to the ultimate board temperature of 80 degreeC using the hot air drying furnace with an atmospheric temperature of 500 degreeC, and created the test board.

<Evaluation method>
Substrate adhesion, processed part corrosion resistance, heat resistance, paint adhesion, alkali resistance, and solvent resistance were evaluated. The results are shown in Tables 5 and 6. Evaluation was performed according to the following method.

[Base material adhesion]
The test plate was extruded 8 mm with an elixir tester, and then a cellophane tape (registered trademark, manufactured by Nichiban Co., Ltd.) was applied to the extruded portion and forcedly peeled off. The test plate was immersed in a methyl violet staining solution, the state of the film was observed and evaluated according to the following criteria.
◎: No peeling ○: Slightly peeling △: Partial peeling ×: Complete peeling

[Processed part corrosion resistance]
The test plate was processed by extruding 7 mm with an elixir tester, the edge and back surface of the test plate were tape-sealed, and a salt spray test SST (JIS-Z-2371) was performed. The occurrence of white rust after 120 hours was observed and evaluated according to the following criteria.
◎: No white rust occurrence ○: White rust occurrence area is less than 10% △: 10% or more and less than 30% ×: 30% or more

[Heat-resistant]
After heating the test plate at 250 ° C. for 1 hour, the edge and the back surface were tape-sealed, and a salt spray test SST (JIS-Z-2371) was performed. The occurrence of white rust after 72 hours was observed and evaluated according to the following criteria.
◎: No white rust occurrence ○: White rust occurrence area is less than 10% △: 10% or more and less than 30% ×: 30% or more

[Coating adhesion]
A melamine alkyd paint (Super Rack 100, manufactured by Nippon Paint) was applied to the surface of the test plate with a bar coater to a dry film thickness of 20 μm, and baked at 120 ° C. for 25 minutes to prepare a coated plate. After being left for a day and night and then immersed in boiling water for 30 minutes, taken out and left for a day, extrude the coated plate 7mm with an elixir tester, paste cellophane (registered trademark, made by Nichiban) on the extruded part and forcibly peel off The coating state of was evaluated according to the following evaluation criteria.
◎: No peeling ○: Slightly peeling △: Partial peeling ×: Complete peeling

[Alkali resistance]
The film state after the test plate was immersed for 30 minutes in a 2% aqueous solution of 55 ° C. alkaline degreasing agent (Surf Cleaner 53, Nippon Paint) was evaluated according to the following evaluation criteria.
◎: No peeling ○: Slightly peeling △: Partial peeling ×: Complete peeling

[Solvent resistance]
After placing the test plate on a rubbing tester, the absorbent cotton impregnated with ethanol was loaded 10 times (reciprocating) with a load of 0.5 kgf / cm ² , and the absorbent cotton impregnated with methyl ethyl ketone (MEK) was loaded with 0.5 kgf / cm ² . The coating state after rubbing 10 times (reciprocating) was evaluated according to the following evaluation criteria.
◎: No trace on the rubbing surface ○: Slight trace on the rubbing surface Δ: White trace on the rubbing surface ×: No film on the rubbing surface

The results of evaluation and measurement by the above test are shown in Tables 4 and 5 below.

  From the results of Tables 4 and 5, any of the adherends obtained by treating the surface of each adherend with the aqueous surface treatment composition of the examples is substrate adhesion, processed part corrosion resistance, solvent resistance, paint adhesion, It was excellent in all of alkali resistance and heat resistance. On the other hand, an aqueous surface treatment composition (Comparative Examples 1 to 3) obtained from the titanium compounds a to c, and an aqueous surface treatment that does not cause the silicon compound (d) to react (mix) with the titanium composite compositions A, E, and G. It is obtained from the composition (Comparative Examples 4 to 6), the aqueous surface treatment composition (Comparative Examples 7 to 9) obtained by reacting (mixing) the silicon compounds with the titanium compounds a to c, and the silicon compound (d). In addition, none of the adherends obtained by treating the surface of each adherend with the aqueous surface treatment composition (Comparative Examples 10 to 12) were excellent in all of the above performances.

  The aqueous surface treatment composition of the present invention is suitable for adhesion to substrates, corrosion resistance of processed parts, heat resistance, and coating adhesion to zinc or alloys containing 20% or more of zinc, or adherends such as plated bodies thereof. Since alkali resistance and solvent resistance can be remarkably improved, it can be suitably used in industrial fields such as home appliances, office equipment, building materials, and automobiles.

Claims (15)

  The titanium composite composition having a chemical structure obtained by reacting a titanium compound oligomer (a), an amine compound (b), and a glycol compound (c) and / or a composition obtained by mixing them with one or more alkoxy compounds in the molecule Zinc or an alloy containing 20% or more of zinc, or a plating thereof, characterized by having a chemical structure obtained by reacting a silicon compound having a group (d) and / or a composition obtained by mixing them An aqueous surface treatment composition, which is used on the surface of a body.   The aqueous surface treatment composition according to claim 1, further comprising at least one selected from a phosphoric acid compound, a vanadium compound, and a zirconium compound. The titanium compound oligomer (a) is a titanium alkoxide represented by the following formula (1) or a titanium chelate compound having a structure in which a chelating agent is coordinated to a titanium alkoxide represented by the following formula (1): The aqueous surface treatment composition according to claim 1 or 2, which has a condensed structure.

Wherein ^(1), R 1 to R ⁴ represents one or more 18 or less alkyl group having a carbon number independently. ] The titanium compound oligomer (a) is a titanium alkoxide represented by the following formula (1) or a titanium chelate compound having a structure in which a chelating agent is coordinated to a titanium alkoxide represented by the following formula (1): The aqueous surface treatment composition according to claim 1 or 2, wherein the composition has a structure obtained by further coordinating a chelating agent to a condensed structure.

Wherein ^(1), R 1 to R ⁴ represents one or more 18 or less alkyl group having a carbon number independently. ]   The aqueous surface treatment composition according to claim 3 or 4, wherein the condensation of the titanium alkoxide or the titanium chelate compound is performed by reacting the titanium alkoxide or the titanium chelate compound with water in an alcohol solution. .   The condensation of the titanium alkoxide or the titanium chelate compound is carried out by reacting 0.2 mol or more and 2 mol or less of water in an alcohol solution with respect to 1 mol of the titanium alkoxide and / or titanium chelate compound. The water-based surface treatment composition according to any one of claims 3 to 5.   The condensation of the titanium alkoxide or the titanium chelate compound is carried out by reacting the titanium alkoxide or the titanium chelate compound with water in an alcohol solution in the presence of the amine compound (b). The aqueous surface treatment composition according to claim 6.   The aqueous surface treatment composition according to any one of claims 1 to 7, wherein the amine compound (b) is a substituted or unsubstituted aliphatic amine or a quaternary ammonium hydroxide.   The glycol compound (c) is at least one selected from the group consisting of 1,2-ethanediol, 1,2-propanediol, and 2,3-butanediol. The water-based surface treatment composition according to any of claims.   The claim according to any one of claims 3 to 7, wherein the chelating agent is at least one selected from the group consisting of β-diketone, β-ketoester, polyhydric alcohol, alkanolamine, and oxycarboxylic acid. The aqueous surface treatment composition as described. The aqueous surface treatment composition according to any one of claims 3 to 7, wherein R ^{1 to} R ⁴ in the formula (1) are each independently an alkyl group having 1 to 8 carbon atoms.   The aqueous surface according to any one of claims 1 to 11, wherein the silicon compound (d) having one or more alkoxy groups in the molecule has a structure in which an alkyl group is directly bonded to a silicon atom. Treatment composition.   The silicon compound (d) having one or more alkoxy groups in the molecule contains an amino group, mercapto group, epoxy group, vinyl group, or (meth) acryloyloxy group. The aqueous surface treatment composition according to claim 12.   Using zinc or an alloy containing 20% or more of zinc, or the surface of the plated body thereof, a film is formed using the aqueous surface treatment composition according to any one of claims 1 to 13. A rust preventive film characterized by comprising   A rust preventive layer is formed using the aqueous surface treatment composition according to any one of claims 1 to 13, wherein zinc or an alloy containing 20% or more of zinc, or , Those plated bodies.