JP2000026980A - Metal surface treating agent, surface-treated metallic material and resin coated metallic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a chromium-free metal surface treating agent excellent in corrosion resistance and adhesion of a coating material by using an aluminum salt, a salt of a metal other than aluminum, a phosphorus compd. and a resin and/or its precursor as constituent components. SOLUTION: The metal surface treating agent contains an aluminum salt, a salt of a metal other than aluminum, a phosphorus compd. and a resin and/or its precursor, has a phosphorus to aluminum equiv. ratio of >=0.1 and does not contain chromium. The resin and its precursor fix all the other components in the treating agent except a solvent on a metal surface as a tough film. The resin preferably has a mol.wt. >=1,000. The content of the resin and its precursor is preferably 30-80 wt.% of the total amt. of all the constituent components in the treating agent. The resin is preferably an acrylic resin, polyester resin, acrylic modified polyester resin, epoxy modified polyester resin or urethane modified polyester resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is applied to surfaces of metals, plated steel sheets, alloy plated steel sheets, alloy sheets, silicon steel sheets, stainless steel sheets, shaped steels, pipes, wires and molded metal bodies of these materials. The present invention relates to a surface-treated metal material having a rust-preventive film formed by drying, and further relates to a metal material obtained by coating a resin on a surface-treated metal material. And a metal surface treating agent.

[0002]

[Prior Art] Cold rolled steel sheet, Zn plated steel sheet, Zn-Ni type, Zn
-Ni-Co, Zn-Ni-Cr, Zn-Fe, Zn-Co, Zn-Cr
Series, Zn-Mn series and other Zn-based alloy plated steel sheets or Ni, Cu,
In order to improve the corrosion resistance of a metal-plated steel sheet of Pb, Sn, Cd, Al, Ti or the like or an alloy-plated steel sheet of these metals, it is common practice to perform a chromate treatment to form a chromate film.

The chromate treatment can be roughly classified into an electrolytic chromate treatment and a coating chromate treatment. Electrolytic chromate contains chromic acid as a main component, and forms a chromate film by subjecting a steel sheet to cathodic electrolytic treatment with addition of various compounds. Trivalent and 6 for coating type chromate
A chromate film is formed by applying a liquid containing valent chromium as a main component and an inorganic colloid compound, an inorganic anion, an inorganic cation compound, and the like.

[0004] One type of coating type chromate is
A coating type chromate to which an organic resin is added, that is, a so-called resin type chromate, has recently been developed. For example, a treatment method (JP-A-2-163385) in which chromic acid is composed of amorphous silica, a phosphate compound, and polyacrylic acid, and the C / Si ratio of the outermost layer of the film is specified (JP-A-2-163385) A method in which an emulsion of an acrylic copolymer of a copolymer such as methyl methacrylate is added and treated under specific conditions (see
JP-A 2-179883), a method of applying a liquid containing chromic acid, a chromate reduction product, an acrylic emulsion, and a silica sol under specific conditions (JP-A-3-215683), a chromic acid, a chromate reduction product, A method for treating a liquid containing an acrylic emulsion or a wet-type silica sol under specific conditions (Japanese Patent Laid-Open No. 3-215681), comprising an ethylenically unsaturated carboxylic acid component, a hydroxyl group-containing monomer component, and other ethylenically unsaturated compounds. Metal surface treatment composition obtained by mixing an aqueous emulsion, an aqueous colloid of a water-soluble chromium compound and an inorganic compound, and an inorganic substance that forms a poorly water-soluble salt by reacting with an amphoteric metal (Japanese Patent Application Laid-Open No. 5-230666), and the like. Can be mentioned.

[0005] Of the chromate films, the chromate film formed by electrolysis has little elution of Cr, but cannot be said to have sufficient corrosion resistance, and the film has poor scratch resistance at the time of processing, and therefore has extremely poor corrosion resistance after processing. To decline. Further, if the chromate film formed by the coating die is used as it is after the treatment, the chromium component in the chromate film is easily eluted, which is not preferable because it causes pollution.
In addition, corrosion resistance and paint adhesion are not always sufficient,
Even during processing, the film is easily scratched and the corrosion resistance after processing is considerably reduced. Further, the resin-type chromate treatment is insufficient in that the treatment liquid easily gels or separates layers, the bath life is short, and the chromium elution resistance of the formed film is insufficient.

On the other hand, regulations on chromium (especially hexavalent chromium) have been greatly strengthened due to recent environmental and pollution problems. Correspondingly, corrosion-resistant coating compositions that do not use chromium have been developed. For example, those coated with an emulsion polymer obtained by polymerizing a polymerizable unsaturated monomer containing a specific amount of unsaturated carboxylic acid (JP-A-5-223223)
No. 24), an acetoacetyl group-containing synthetic resin aqueous dispersion is coated as a main agent (Japanese Patent Application Laid-Open No. 5-148432),
Coating a mixture of a substantially water-insoluble mono- or poly-basic salt of a special keto acid with a base selected from cations, amines, guanidines and amidines (JP-A-5-7071)
No. 5), a resin coated with a copolymer resin of an unsaturated carboxylic acid-an unsaturated monomer having a glycidyl group-a monomer copolymerizable with an alkyl acrylate-an alkyl acrylate (JP-A-3-192166) Publication). All of them are coated with special resin or a mixture of special resin and inorganic compound, but the corrosion resistance is poor and it is not possible to secure sufficient corrosion resistance even if a fairly thick (eg 3-5μ) film is formed. In addition, adhesion to various metals such as iron and various plated steel sheets is not always good, especially in a wet environment, adhesion is significantly reduced,
The film peels off and falls off. There is no film capable of maintaining excellent adhesion even in a wet environment. Further, the formed film is easily broken at the time of processing and is easily peeled.

[0007]

On the other hand, the present invention solves the above-mentioned drawbacks of the prior art, and provides a metal, a plated steel plate, an alloy plated steel plate, a plated steel plate in which an inorganic substance is dispersed, an alloy plate, a silicon steel plate, and a stainless steel plate. Extremely excellent corrosion resistance and paint adhesion applied to cold rolled steel sheets, hot-rolled hot-rolled steel sheets, hot-rolled pickled steel sheets, thick plates, shaped steel, pipes, wires, etc. It is an object of the present invention to provide a chromium-free surface treatment agent, a surface-treated metal material, and a resin-coated metal material shown below.

[0008]

SUMMARY OF THE INVENTION The present invention is as follows. (1) A chromium-free metal surface treating agent containing the following (i) to (iv) and having an equivalent ratio of phosphorus / aluminum elements of 0.1 or more. (I) Aluminum salt (ii) Salt of metal other than aluminum (iii) Phosphorus compound (iv) Resin and / or precursor thereof (2) Metal material surface-treated with the surface treating agent of (1) above. (3) A resin-coated metal material obtained by laminating a surface-treated layer and a resin-coated layer on a metal substrate, wherein the surface-treated layer comprises the surface-treating agent of (1).

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The surface treating agent of the present invention comprises an aluminum salt, a salt of a metal other than aluminum, a phosphorus compound, a resin and / or a precursor thereof, and contains no chromium. The surface treatment layer is formed by applying this on a cold rolled steel sheet or various metals including a Zn or Zn-based alloy-plated steel sheet.

The formed surface treatment layer secures extremely excellent adhesion to various metals, has excellent bare corrosion resistance after processing, and also has excellent adhesion to various coating films with organic resins. To achieve this excellent adhesion, it is preferable to include an organic resin. The adhesion between the excellent metal material and the coating film is at least one of an organic resin, an aluminum salt and inorganic oxide particles, and / or aluminum and oxygen.
Aluminum-containing inorganic oxide particles containing various kinds of elements,
It is ensured by a combination of a salt of a metal other than aluminum and a phosphorus compound. In addition, the presence of inorganic oxide particles such as colloidal silica or aluminum-containing inorganic oxide particles containing aluminum and oxygen and at least one element other than these two, such as aluminum surface-treated colloidal silica, in the treated layer is extremely high. It is preferable to ensure excellent bare corrosion resistance. Due to the presence of these, the organic resin in the treatment layer, aluminum salts, salts of metals other than aluminum, and phosphorus compounds, interact with the treatment layer components are less likely to fall off the steel sheet surface, bare corrosion resistance is improved it is conceivable that.

First, the surface treating agent used to obtain the coated metal material and the surface treated metal material of the present invention will be described. The metal surface treatment agent of the present invention is an aluminum salt, a salt of a metal other than aluminum, a phosphorus compound,
A metal surface treatment agent containing a resin and / or a precursor thereof as a component and containing no chromium.

The resin and / or its precursor according to the present invention comprises an aluminum salt, a salt of a metal other than aluminum, a phosphorus compound and other components other than a solvent in a metal surface treating agent, which are firmly bonded to the metal surface. It plays the role of fixing as a membrane. The resin in the present invention has a molecular weight of 1,000 or more and is not particularly limited. The molecular weight is preferably 1500 or more, more preferably 2,000 or more. Although the resin precursor of the present invention does not have a molecular weight that can be expressed as a resin per se, after adhering to a metal surface, it is left naturally,
It reacts by heat, electromagnetic waves, etc., and has the ability to form a resin film. Specific examples include monomers and oligomers of various resins.

In the present invention, the content of the resin and / or its precursor is preferably 30 to 80% by weight, more preferably 40 to 80% by weight, based on all components in the metal surface treating agent.
% By weight.

Examples of the resin include a polymer resin, a polycondensation resin, an addition polymer resin, a cellulose resin, a natural rubber, and a polysiloxane.

Examples of the polymer resin include polyacrylate and its copolymer, polymethacrylate and its copolymer, polystyrene and its copolymer, polyvinyl acetate and its copolymer, polyacrylonitrile and its copolymer. Polymer, polyvinyl chloride and its copolymer,
Double bonds such as polyvinylpyrrolidone and its polymer, polybutadiene and its copolymer resin, polyisoprene and its copolymer resin, polyneoprene and its copolymer, polyethylene and its copolymer, polypropylene and its copolymer Ring-opening polymerization type resins such as polymers of contained compounds, polyethylene oxide and its copolymer, polypropylene oxide and its copolymer, polytetramethylene oxide and its copolymer, polyethyleneimine and its copolymer. These precursors include monomers and oligomers of these resins.

Polycondensation resins include polyesters, polyamides, polyimides, polycarbonates, and copolymers thereof, and precursors include these monomers and oligomers. Examples of the addition polymerization resin include an epoxy resin, a urethane resin, and a polyether resin. Examples of the precursor include an epoxy compound, an isocyanate compound and a block thereof.
In addition, resin modified products such as polyester polyamide, polyurethane modified polyester, and epoxy modified polyester are also included.

Further, after attaching these resins and their precursors to the metal surface, a phenol resin, an amino resin,
It goes without saying that curing with an epoxy compound, an isocyanate compound or the like also falls within the category of the resin of the present invention and / or its precursor.

In the present invention, the resin and / or its precursor is contained in the treatment liquid in a dissolved or dispersed state. Solvent is not particularly selected organic solvent or aqueous solvent, but usually, the processing solution is used in an aqueous solvent,
The resin is preferably in a form dissolved or dispersed in water.

In order to dissolve the resin and / or its precursor in an aqueous solvent, a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group,
And a hydrophilic functional group such as a salt thereof, an ether group, or the like. Among these, a hydroxyl group is particularly preferred. Resin and / or
Alternatively, in order to disperse the precursor, the above functional group is introduced or a surfactant is added. As a method for introducing these functional groups into the resin and / or the precursor thereof, a known method such as a method using a monomer containing each functional group or a method after introducing the resin after synthesis can be used, and those methods are particularly limited. is not.

Examples of the method of dissolving or dispersing the resin and / or its precursor include a method of directly dissolving and dispersing the resin and / or its precursor in water or hot water, and a method of dissolving water after dissolving in water and an organic solvent to be used. A known method such as a method of addition and a method of using the polymer resin as it is after the emulsion polymerization is used.

Among these resins and / or precursors thereof, the treatment liquid of the present invention includes acrylic resins, polyester resins, acrylic-modified polyester resins, epoxy-modified polyester resins, urethane-modified polyester resins, acrylic-modified polyurethanes, acrylic-modified polyurethanes, and the like. Modified polyester polyurethane resins are preferred.

In the present invention, in the acrylic resin, a resin comprising a hydroxyl group-containing acrylic monomer alone, a resin obtained by copolymerizing a hydroxyl group-containing acrylic monomer and another monomer, or a polymer comprising these monomers is bonded to another resin. Those that have been made are more preferred.

In the following, when simply indicating%, it means% by weight, and "part" indicates "part by weight". Examples of the hydroxyl group-containing acrylic monomer component include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 2,2-bis (hydroxymethyl acrylate). )ethyl,
2,3-dihydroxypropyl (meth) acrylate,
Hydroxy group-containing monomers such as (meth) acrylic acid hydroxyalkyl esters such as (meth) acrylic acid-3-chloro-2-hydroxypropyl, allyl alcohols and N-methylolacrylamides, as well as hydroxyl groups in acidic liquids and in acidic liquids Glycidyl (meth) acrylate allyl glycidyl ether, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and other monomers having a glycidyl group, and aldehyde group of acroleinamide And monomers can be used, but 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are particularly preferred. The expression (meth) acrylic acid refers to methacrylic acid and / or acrylic acid.

It is preferable to use one or two of ethylenically unsaturated carboxylic acids and other ethylenically unsaturated compounds simultaneously as another organic monomer. Examples of the ethylenically unsaturated carboxylic acid component include, for example, acrylic acid, methacrylic acid, ethylenically unsaturated monocarboxylic acids such as crotonic acid, itaconic acid, maleic acid, and ethylenically unsaturated dicarboxylic acids such as fumaric acid. The alkali metal salts, ammonium salts and organic amine salts of carboxylic acids can be used. Further, the other ethylenically unsaturated compounds include, as the ethylenically unsaturated carboxylic acid compounds, ethylenically unsaturated compounds other than those exemplified as the ethylenically unsaturated carboxylic acid component and the hydroxyl group-containing monomer component, and (meth) Examples include alkyl acrylates and other vinyl compounds and aromatic vinyl compounds.

The resin to which a polymer composed of these monomers is bonded includes the above-mentioned polymerization resins, polycondensation resins, addition polymerization resins, cellulose resins, natural rubbers, polysiloxanes and the like.

As a method of bonding a polymer comprising the above monomer to a resin, a functional group capable of undergoing radical polymerization with the above monomer may be introduced into the resin, or a radical may be generated in the resin to form a radical in the presence of the resin. A method by graft polymerization for polymerizing the monomer, a method of directly reacting a functional group introduced into the polymer of the monomer with a functional group in the resin after polymerizing the monomer, a method of introducing a functional group into the polymer of the monomer, A method in which a functional group in the resin is bonded with an isocyanate compound, an epoxy compound, or the like is used.

In the present invention, the polyester resin is obtained by reacting a dicarboxylic acid component with a glycol component. As the aromatic dicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid,
Biphenyl dicarboxylic acid, sodium sulfoisophthalic acid and the like can be mentioned. Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecandionic acid, and dimer acid.Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Examples thereof include 3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and acid anhydrides thereof. Examples of the dicarboxylic acid containing an unsaturated double bond include α, β-unsaturated dicarboxylic acids such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and an alicyclic dicarboxylic acid containing an unsaturated double bond. Examples of the acid include 2,5-norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride and the like. Further, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, or hydroxycarboxylic acids such as hydroxypivalic acid, γ-butyrolactone, and ε-caprolactone can be used if necessary.

On the other hand, the glycol component comprises an aliphatic glycol having 2 to 10 carbon atoms and / or an alicyclic glycol having 6 to 12 carbon atoms and / or an ether bond-containing glycol. Glycols containing saturated bonds can also be used. Examples of the aliphatic glycol having 2 to 10 carbon atoms include ethylene glycol, 1,2-propylene glycol,
3-propanediol, 1,4-butanediol, 1,
5-pentaneddiol, neopentyl glycol, 1,
6-hexanediol, 3-methyl-1,5-pentaneddiol, 1,9-nonandiol, 2-ethyl-2-
Examples thereof include butyl propanediol, neopentyl glycol hydroxypivalate, and dimethylol heptane. Examples of the alicyclic glycol having 6 to 12 carbon atoms include 1,4-cyclohexanedimethanol and tricyclodeyl. Candimethylol and the like can be mentioned.

Examples of the ether bond-containing glycol include diethylene glycol, triethylene glycol, dipropylene glycol, and ethylene oxide or propylene oxide in two phenolic hydroxyl groups of bisphenols. Glycols obtained by adding one to several moles each, for example, 2,2-bis (4-hydroxyethoxyphenyl) propane and the like can be mentioned. Polyethylene glycol, polypropylene glycol and polytetramethylene glycol may be used if necessary.

Examples of the glycol containing an unsaturated bond include glycerin monoallyl ether, trimethylolpropane monoallyl ether, and pentaerythritol monoallyl ether.

In the polyester resin used in the present invention, 0 to 5 mol% of a trifunctional or higher polycarboxylic acid and / or polyol is copolymerized. Trimellitic acid, pyromellitic anhydride (anhydride), benzophenonetetracarboxylic anhydride,
Trimesic acid, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate) and the like are used. On the other hand, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like are used as trifunctional or higher functional polyols. The tricarboxylic or higher polycarboxylic acid and / or polyol is used in an amount of 0 to all acid components or all glycol components.
The copolymerization is carried out in a range of from 5 to 5 mol%, preferably in a range of from 0 to 3 mol%, but if it exceeds 5 mol%, sufficient processability cannot be imparted. In a preferred composition, the dicarboxylic acid component contains 50 to 100 mol% of aromatic dicarboxylic acid and 0 to 50 mol% of aliphatic and / or alicyclic dicarboxylic acid. Further, as the polyester resin used in the present invention, those obtained by adding an acid anhydride such as maleic anhydride or trimellitic anhydride to the molecular terminal can also be used.

In order to dissolve or disperse the polyester in the aqueous solvent, at least one of the above-mentioned dicarboxylic acid component containing a hydrophilic group and the diol component is copolymerized.

Examples of the hydrophilic group-containing dicarboxylic acid include sulfonic acid group-containing polycarboxylic acids and derivatives such as 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium sulfoisophthalic acid, and sodium sulfosuccinic acid, and methyl-2,3. -Polycarboxylic acids containing a phosphoric acid group such as dicarboxypropylphosphoric acid.

Examples of the hydrophilic group-containing diol include 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium,
Alkylene oxide adducts such as sulfoisophthalic acid and sodium sulfosuccinic acid, sulfonic acid group-containing diols and derivatives thereof such as sodium sulfobisphenol A and 2-sodium sulfo-1,4-butanediol, and sodium bis (hydroxymethyl) phosphate; Screw (2
(Hydroxyethoxymethyl) sodium phosphate and the like. Examples of the hydrophilic group-containing diol include polyethylene glycol having a molecular weight of 100 or more. Among these, 5-sodium sulfoisophthalic acid is particularly preferred.

Further, as a method for dissolving or dispersing the polyester in the aqueous solvent, it is possible to add trimellitic anhydride or pyromellitic anhydride to the molecular terminal of the polyester as described above.

The polyurethane resin used in the present invention includes a polyol (a), an organic diisocyanate compound
(b) and, if necessary, a chain extender having an active hydrogen group (c)
It is composed of As the polyol (a), various polyols can be used, and examples thereof include, in addition to polyester polyol, polyether polyol, polycarbonate polyol, and polyolefin polyol, an epoxy resin, a phenoxy resin, a cellulose resin, a phenol resin, and a butyral resin. Can be used, or one or more of these can be used. Preferred polyols are polyester polyols in which the dicarboxylic acid component contains an aromatic dicarboxylic acid, more preferably 30 to 100 mol% of an aromatic dicarboxylic acid, A polyester polyol containing 0 to 40 mol% of an aliphatic and / or alicyclic dicarboxylic acid.
It is desirable to contain 100wt%.

As the organic diisocyanate compound (b), hexamethylene diisocyanate, tetramethylene diisocyanate, 3,3′-dimethoxy-4,4′-biphenylenediisocyanate, p-xylylene diisocyanate,
m-xylylene diisocyanate, 1,3-diisocyanate methyl cyclohexane, 4,4'-diisocyanate dicyclohexane, 4,4'-diisocyanate cyclohexylmethane, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate , P-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, 2,4-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 4,4'-diisocyanate diphenyl ether, 1,5-naphthalene diisocyanate And the like.

Examples of the chain extender (c) having an active hydrogen used as required include ethylene glycol, propylene glycol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, diethylene glycol, and spiroglycol. In addition to glycols such as glycol and polyethylene glycol, amines such as hexamethylenediamine, propylenediamine and hexamethylenediamine, and compounds having two or more active hydrogens such as dimethylolpropionic acid and other functional groups No.

The polyurethane resin used in the present invention comprises a polyol (a), an organic diisocyanate (b) and, if necessary, a chain extender (c) having an active hydrogen, and the active hydrogen of (a) + (c) It is necessary that the polyurethane resin be obtained by reacting at a mixing ratio of 0.4 to 1.3 (equivalent ratio) in a ratio of / isocyanate group.

The unsaturated bond in the polyurethane resin can be contained in the above (a), (b) and (c). For example, when (c) contains an unsaturated bond, Glycols such as allyl ether and glycerol monomethacrylate can be used.

The polyurethane resin used in the present invention is produced in a known manner at a reaction temperature of 20 to 150 ° C. in a solvent in the presence or absence of a catalyst. As the solvent used at this time, for example, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, and esters such as ethyl acetate and butyl acetate can be used. As a catalyst for accelerating the reaction, amines, organotin compounds and the like are used.

As a method for dissolving or dispersing the polyurethane in the aqueous solvent, a method using a polyol dissolvable or dispersible in the aqueous solvent for the polyol (a), specifically, the above-mentioned polyester dissolvable or dispersible in the aqueous solvent is used. , A method using polyethylene glycol having a molecular weight of 100 or more, and a method using the above-mentioned hydrophilic group-containing chain extender (c).

Examples of the hydrophilic group-containing chain extender include the hydrophilic group-containing diol described in the above-mentioned polyester section, and glyceric acid, dimethylolpropionic acid, N, N-diethanolglycine, and hydroxyethyloxybenzoic acid. And aminocarboxylic acids such as diaminopropionic acid and diaminobenzoic acid, and derivatives thereof.

As another method, there is a method of producing an isocyanate-terminated polyurethane by using an isocyanate compound so that an isocyanate group becomes excessive during the production of the polyurethane, and reacting the polyurethane with a polyhydric alcohol compound. As the polyhydric alcohol compound, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like can be used.

As the epoxy resin, an epoxy compound itself having a plurality of epoxy groups in a molecule, or an epoxy compound capable of reacting with an epoxy group such as a hydroxyl group, a mercapto group, a carboxyl group, an acid anhydride, an amino group, etc. It is a reaction product with a compound having a plurality of groups. Epoxy compounds include dihydric alcohols, phenols, hydrogenated and halogenated products of these phenols,
Novolaks (reaction products of polyhydric phenols and aldehydes such as formaldehyde in the presence of an acidic catalyst)
Epoxy compounds obtained from the above, one or a mixture of two or more acid-modified products thereof such as fatty acids can be used,
Among them, preferred are bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, and modified products thereof.

An epoxy-modified polyester resin obtained by reacting a polyester as it is or at the above-mentioned acid terminal with an epoxy compound can also be used.

For the introduction of unsaturated bonds, an unsaturated compound having a functional group highly reactive with an epoxy group or a hydroxyl group in an epoxy resin, such as an unsaturated acid compound or an unsaturated amine compound, is reacted. Is possible.
As unsaturated acid compounds, acrylic acid, methacrylic acid,
Fumaric acid, maleic acid and its anhydride, itaconic acid and its anhydride, acid phosphooxyethyl (meth) acrylate (trade name: Phosmer M, manufactured by Unichemical) and the like can be used. As unsaturated amine compounds, amino acrylate Ethyl, aminoethyl methacrylate and the like can be used. In that case, it is also possible to carry out the reaction under various catalysts such as pyridine. In the case of an epoxy-modified polyester resin, it is also possible to introduce an unsaturated group into the polyester.

As a method for dissolving or dispersing an epoxy resin in an aqueous solvent, a method in which a hydrophilic group-containing polycarboxylic acid or polyhydric diol described in the above-mentioned polyester section is used as a reaction partner of an epoxy compound, Examples include a method using an aminocarboxylic acid such as propionic acid and diaminobenzoic acid and a derivative thereof. In the case of an epoxy-modified polyester resin, a method using a polyester that can be dissolved or dispersed in an aqueous solvent described above is used.
Further, it is also possible to make the epoxy resin having an epoxy terminal by making the epoxy group excessive, and then reacting with a polycarboxylic acid compound to form a carboxylic acid terminal, and in some cases, neutralizing this to form a salt. Examples of the polycarboxylic acid include trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, trimesic acid, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate) and the like.

Acrylic-modified polyester resin is
A resin in which a polyester resin (A) having a weight average molecular weight of 1,000 to 100,000 having an unsaturated bond of 1000 mol / 10 ⁶ g and a polymer (B) obtained from an unsaturated monomer mixture are chemically bonded, B) is 15
An unsaturated monomer (B-1) capable of dissolving (A) at a temperature of 0 ° C. or lower, a water-soluble unsaturated monomer (B-2) containing a functional group such as a hydroxyl group, an acid Or an ionic unsaturated monomer neutralized with a base (B-3)
And an acrylic-modified polyester resin.

Each item will be described below. (Resin A) The polyester resin A in the present invention has an unsaturated bond in the molecule and has a weight average molecular weight of 1,000 to
0000, a polyester resin forming the main chain of the graft. The amount of unsaturated bonds contained in the molecule is preferably 5 to 1000 mol / 10 ⁶ g. If the amount is less than 5 mol / 10 ⁶ g, it is difficult to perform sufficient grafting, so that the effect of acrylic modification is not seen. If the amount exceeds 1000 mol / 10 ⁶ g, gelation or the like is observed at the time of grafting. Therefore, it is not preferable.

As for the introduction of the unsaturated bond, a copolymerizable dicarboxylic acid or glycol having an unsaturated bond in the polyester can be used as described above. It is possible to introduce by reacting an unsaturated compound containing a functional group reactive to the group. For example, an epoxy group-containing unsaturated monomer such as glycidyl methacrylate, an isocyanate group-containing unsaturated monomer such as methacryloyl isocyanate, and an unsaturated acid anhydride such as maleic anhydride can be used.

The dicarboxylic acids and glycols used as the polyester resin A have been described above, but the most preferred for introducing a double bond are fumaric acid, maleic acid, itaconic acid and 2,5-norbornene dicarboxylic anhydride. .

(Resin B) Resin B is a water-soluble resin containing a functional group such as an unsaturated monomer (B-1) or a hydroxyl group capable of dissolving the polyester resin (A) at a temperature of 150 ° C. or lower. Unsaturated monomer (B-2), an ionic unsaturated monomer (B-
It is characterized by comprising a monomer containing 3).

The unsaturated monomer (B-1) capable of dissolving the resin (A) at a temperature of 150 ° C. or less improves the compatibility between the resin (A) and the resin (B) in the coating film. Work as a thing to do. The unsaturated monomer capable of dissolving the resin (A) at a temperature of 150 ° C. or lower is defined as resin (A) 1
200 parts of unsaturated monomer was added to
It refers to an unsaturated monomer that can dissolve the resin (A) at a temperature of not more than ° C. As a rough guide for solubility,
An aromatic solvent capable of dissolving the polyester resin (A),
The solvent can be selected from ester solvents, ketone solvents, ether solvents, and unsaturated monomers having a structure similar to those of these solvents. Examples are given below.

Unsaturated monomers similar in structure to general-purpose aromatic solvents: styrene, styrene derivatives Unsaturated monomers similar in structure to general-purpose ester solvents:
Lower alkyl esters and vinyl esters of (meth) acrylic acid Unsaturated monomers similar in structure to common ether solvents:
Vinyl ethers, glycol ether (meth) acrylates Unsaturated monomers similar in structure to other solvents: N, N-
Dimethylacrylamide, vinylpyridine, vinylpyrrolidone, acryloylmorpholine, etc.

One or more of these unsaturated monomers can be used. Of these, preferred are styrene and its derivatives and alkyl esters of (meth) acrylic acid having 1 to 6 carbon atoms, more preferably styrene and its derivatives and 1 to 6 carbon atoms of (meth) acrylic acid. Is a mixture of alkyl esters. A water-soluble unsaturated monomer containing a functional group such as a hydroxyl group (B
-2) contributes to imparting curability and adhesion to the coating film due to the functional groups such as hydroxyl groups. As the water-soluble unsaturated monomer containing a functional group such as a hydroxyl group, a known unsaturated monomer can be used. Water solubility is 1
It refers to being completely miscible with water in any proportion at temperatures below 00 ° C. Examples are given below.

Hydroxyl group-containing unsaturated monomers: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- (meth) acrylate
Hydroxybutyl, diethylene glycol mono (meth)
Acrylate, dipropylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, allyl alcohol, glycerin monoallyl ether, N-
Methylol (meth) acrylamide, etc. Carboxyl group-containing unsaturated monomer: acrylic acid, methacrylic acid, etc. Amino group-containing unsaturated monomer: N, N-dimethyl (meth)
Acrylamide, etc.

These are used in one kind or in a mixture of two or more kinds. Preferred are one or more kinds of unsaturated monomers containing a hydroxyl group, one or more kinds of unsaturated monomers containing a hydroxyl group and one or more kinds of unsaturated monomers containing a hydroxyl group. A mixture of a carboxyl group-containing unsaturated monomer, a mixture of one or more hydroxy group-containing unsaturated monomers and one or more amino group-containing unsaturated monomers,
In the two components, the content of the hydroxyl group-containing unsaturated monomer is preferably 30% by weight or more.

The ionic unsaturated monomer (B-3) neutralized with an acid or a base has an effect of easily causing the association of the polymer of the unsaturated monomer mixture in the coating film. Although it is effective in improving the curing efficiency and suppressing the decrease in adhesion, it is desirable to keep the amount to a minimum because an excessive amount may cause a decrease in water resistance. Examples of these unsaturated monomers include unsaturated carboxylic acid compounds, unsaturated phosphoric acid compounds, unsaturated sulfonic acid compounds, and quaternary ammonium group-containing unsaturated monomers neutralized with a base. For example, alkali metal salts of (meth) acrylic acid, ammonium salts, organic amine salts, sodium styrenesulfonate, alkali metal salts of acid phosphooxyethyl (meth) acrylate (trade name: Phosmer M, etc., manufactured by Unichemical) , Ammonium salts, organic amine salts, alkali metal salts of acrylamidomethylpropanesulfonic acid, ammonium salts, organic amine salts,
(Meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium sulfate,
(Meth) acryloyloxyethyltriethylammonium sulfate, (meth) acryloyloxyethyltrimethylammonium phosphate, (meth) acryloyloxyethyltriethylammonium phosphate, acetate, hydrochloride, N, N-dimethylaminoethyl (meth) acrylate Acid salt, sulfate, acetate, hydrochloride of N, N-diethylaminoethyl (meth) acrylate,
Phosphates, sulfates and the like may be mentioned, but more preferred are unsaturated monomers in combination of strong acids and strong bases,
For example, sodium styrenesulfonate and the like can be mentioned. The unsaturated monomer B-3 can be converted into an alkali metal salt, an ammonium salt, or an organic amine salt after polymerization.

In the resin (B), various other known unsaturated monomers including a polyfunctional unsaturated monomer can be used if necessary. Examples of the various unsaturated monomers include various vinyl compounds, vinyl ester compounds, vinyl ether compounds, (meth) acrylic acid esters, and the like.
g, other reactivity, etc. can be adjusted / provided. Examples of the polyfunctional unsaturated monomer include ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate.

The resin (B) is an unsaturated monomer (B-B) capable of dissolving (A) at a temperature of 150 ° C. or lower.
1), including a water-soluble unsaturated monomer (B-2) containing a functional group such as a hydroxyl group, and an ionic unsaturated monomer (B-3) neutralized with an acid or a base. The weight ratio of resin (B) / resin (A) is (Y / X), where X is the weight of resin (A) and Y is the weight of resin B.
Is preferably in the range of 1/99 to 90/10, and more preferably 10/90 to 80/20. When the ratio of the resin (A) is lower than this ratio, the characteristics of the resin (A) are hardly exhibited, and when the ratio is higher than this ratio, the effect of improving the curability is small.

At a temperature of 150 ° C. or less, (A)
The weight of the unsaturated monomer (B-1) capable of dissolving the compound is Y1, the weight of the water-soluble unsaturated monomer (B-2) containing a functional group such as a hydroxyl group is Y2, the acid or Assuming that the weight of the ionic unsaturated monomer (B-3) neutralized with a base is Y3, 0.6 ≦ (Y1 + Y2 + Y3) /
It is preferable that Y ≦ 1.0, and (Y1 + Y2 + Y
3) When / Y is smaller than this range, effects such as improvement in curability are small. The unsaturated monomer (B-1) preferably satisfies 0.005 ≦ Y1 / X and 0.3 ≦ Y1 / Y ≦ 0.7, and Y1 / X or Y1 / Y is smaller than this range. In this case, it becomes difficult to provide compatibility. The unsaturated monomer (B-2) preferably satisfies 0.005 ≦ Y2 / X and 0.3 ≦ Y2 / Y ≦ 0.7.
When 2 / X or Y2 / Y is smaller than this range, the curability of the resin (B) is reduced. For the unsaturated monomer (B-3), Y3 / X ≦ 0.05 and 0.0001 ≦ Y3 /
It is preferable that Y ≦ 0.1, and Y3 / X or Y3
If / Y is larger than this range, the water resistance and the like are undesirably reduced.

In the present invention, the acrylic-modified polyurethane resin is obtained by using a double bond-containing polyurethane resin instead of the double bond-containing polyester A described above, and the polyurethane resin includes glycerin monoallyl ether, Trimethylolpropane monoallyl ether,
Glycerin containing a double bond such as pentaerythritol monoallyl ether is used.

In the present invention, the acrylic-modified polyester polyurethane is obtained by using a double bond-containing polyester polyurethane resin in place of the double bond-containing polyester (A) described above. Others are the same as the acrylic-modified polyester.

The aluminum salt in the present invention is
For example, aluminum phosphate, aluminum hydrogen phosphate, aluminum dihydrogen phosphate, aluminum acetate, aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum bromide, aluminum fluoride, aluminum oxalate, aluminum formate, aluminum nitrite, aluminum sulfite Aluminum bisulfite, aluminum silicate, aluminum bioxalate, aluminum bifluoride, aluminum carbonate, aluminum hydrogen carbonate, aluminum hydrogen sulfate, aluminum hydroxide, aluminum oxide, aluminum polyphosphate, aluminum hypophosphite, aluminum tripolyphosphate , Aluminum hexametaphosphate, polyaluminum metaphosphate, aluminum phosphonate and the like. Hydrogen aluminum, dihydrogen aluminum phosphate are preferred.

These salts may not be compounded as salts, but may be compounded with an aluminum compound which can be converted to an aluminum salt in a metal surface treatment solution containing a solvent.
Further, it is preferable that these aluminum salts can be dissolved in a solvent used for the surface treatment liquid.

The salt of a metal other than aluminum in the present invention is preferably a divalent or higher valent metal salt. Examples of the metal other than aluminum include Cu, Co, Fe, M
n, Sn, V, Ba, Mg, Zr, W, Mo, Ca, S
r, Nb, Y and Zn, preferably M
n, Mg, Zr, W, Mo, Ca and Sr. Most preferred is Mn. Salts include phosphate, hydrogen phosphate, dihydrogen phosphate, acetate, formate, nitrate,
Sulfate, chloride, bromide, fluoride, oxalate, nitrite, sulfite, bisulfite, silicate, bioxalate, bicarbonate, bifluoride, bisulfate, carbonate, carbonate Hydrogen salts, hydrogen sulfates, polyphosphates, hypophosphites, tripolyphosphates, hexametaphosphates, polymetaphosphates, phosphonates, and the like, particularly phosphates, hydrogen phosphates, phosphoric acid 2 Hydrogen salts are preferred. In addition, these salts may not be compounded as a salt, but may be compounded with a compound that can be changed into a salt in a metal surface treatment solution containing a solvent. Further, it is preferable that these salts of metals other than aluminum can be dissolved in the surface treatment solution.

The salts of metals other than aluminum used here are exemplified by phosphoric acid compounds, such as copper phosphate, cobalt phosphate, iron phosphate, manganese phosphate, tin phosphate, vanadium phosphate, and phosphorus phosphate. Barium phosphate, calcium phosphate, magnesium phosphate, tungsten phosphate, zirconium phosphate, molybdenum phosphate, strontium phosphate, niobium phosphate, yttrium phosphate, zinc phosphate, copper hydrogen phosphate, cobalt hydrogen phosphate, hydrogen phosphate Iron, manganese hydrogen phosphate, tin hydrogen phosphate, vanadium hydrogen phosphate,
Barium hydrogen phosphate, calcium hydrogen phosphate, magnesium hydrogen phosphate, tungsten hydrogen phosphate, zirconium hydrogen phosphate, molybdenum hydrogen phosphate, strontium hydrogen phosphate, niobium hydrogen phosphate, yttrium hydrogen phosphate, zinc hydrogen phosphate, Copper dihydrogen phosphate, cobalt dihydrogen phosphate, iron dihydrogen phosphate, manganese dihydrogen phosphate, tin dihydrogen phosphate, vanadium dihydrogen phosphate, barium dihydrogen phosphate, calcium dihydrogen phosphate, phosphoric acid Magnesium dihydrogen, tungsten dihydrogen phosphate, zirconium dihydrogen phosphate, molybdenum dihydrogen phosphate, strontium dihydrogen phosphate, niobium dihydrogen phosphate, yttrium dihydrogen phosphate, zinc dihydrogen phosphate, copper polyphosphate, Cobalt polyphosphate, iron polyphosphate, manganese polyphosphate, tin polyphosphate, poly Phosphate vanadium, barium polyphosphate, calcium polyphosphate, magnesium polyphosphate,
Tungsten polyphosphate, zirconium polyphosphate, molybdenum polyphosphate, strontium polyphosphate, niobium polyphosphate, yttrium polyphosphate, zinc polyphosphate, copper hypophosphite, cobalt hypophosphite, iron hypophosphite, hypophosphorous acid Manganese, tin hypophosphite, vanadium hypophosphite, barium hypophosphite, calcium hypophosphite, magnesium hypophosphite, tungsten hypophosphite, zirconium hypophosphite, molybdenum hypophosphite,
Strontium hypophosphite, niobium hypophosphite, yttrium hypophosphite, zinc hypophosphite, copper tripolyphosphate, cobalt tripolyphosphate, iron tripolyphosphate, manganese tripolyphosphate, tin tripolyphosphate, vanadium tripolyphosphate, tripolyphosphate Barium, calcium tripolyphosphate, magnesium tripolyphosphate, tungsten tripolyphosphate, zirconium tripolyphosphate,
Molybdenum triphosphate, strontium tripolyphosphate, niobium tripolyphosphate, yttrium tripolyphosphate, zinc tripolyphosphate, copper hexametaphosphate, cobalt hexametaphosphate, iron hexametaphosphate, manganese hexametaphosphate, tin hexametaphosphate, vanadium hexametaphosphate, barium hexametaphosphate, hexametaphosphate Calcium, magnesium hexametaphosphate, tungsten hexametaphosphate, zirconium hexametaphosphate, molybdenum hexametaphosphate, strontium hexametaphosphate, niobium hexametaphosphate, yttrium hexametaphosphate, zinc hexametaphosphate,
Cobalt polymetaphosphate, polyiron iron phosphate, polymanganese phosphate, tin polymetaphosphate, polyvanadium polyphosphate, barium polymetaphosphate, calcium polyphosphate, magnesium polymetaphosphate, tungsten polymetaphosphate, zirconium polyphosphate, molybdenum polyphosphate, strontium polyphosphate, polymetaphosphate Niobium, polyyttrium metaphosphate, zinc zinc metaphosphate, copper phosphonate, cobalt phosphonate, iron phosphonate, manganese phosphonate, tin phosphonate, vanadium phosphonate, barium phosphonate,
Calcium phosphonate, magnesium phosphonate, tungsten phosphonate, zirconium phosphonate, molybdenum phosphonate, strontium phosphonate, niobium phosphonate, yttrium phosphonate, zinc phosphonate and the like can be used.

In the present invention, the amount of the aluminum salt is 0.1 to 100 g of the above resin and / or its precursor.
005 to 10 mol, preferably 0.01 to 5 mol, more preferably 0.015 to 1.5 mol, and most preferably 0.05 to 1.0 mol. In addition, the amount of the salt of a metal other than aluminum is determined according to the above resin and / or its precursor 1
0.005 to 10 mol, preferably 0.
The amount is from 0.01 to 5 mol, more preferably from 0.015 to 1.5 mol, and most preferably from 0.05 to 1.0 mol. Further, the total amount of the aluminum salt and the salt of a metal other than aluminum is 0.005 to 10 mol, preferably 0.01 to 5 mol per 100 g of the above resin and / or its precursor.
Mole, more preferably 0.015 to 1.5 mole, most preferably 0.02 to 1.0 mole.

The surface treating agent of the present invention preferably contains inorganic oxide particles. As the inorganic oxide particles, Si, Fe, Ge, Ti, Zr, Mg, S
Oxide particles of n, Sb, and Al are preferred, for example, colloidal silica, SiO ₂ powder, SnO ₂ , Fe ₂ O ₃ ,
It is possible to use one or more of colloids (sols) or powders of Fe ₃ O ₄ , MgO, Al ₂ O ₃ and ZrO ₂ . Among them, it is most preferable that SiO ₂ is contained. These are effective not only in improving corrosion resistance and paint adhesion, but also in improving scratch resistance and the like.

Further, a plurality of types of elements other than oxygen may be contained. Further, the surface of the inorganic oxide particles may be different from the internal composition. An example of this is an aluminum surface-treated colloidal silica obtained by treating colloidal silica produced by a sol-gel method with aluminate ions (Al (OH) ^4- ). A specific production method is described in U.S. Pat. No. 2,892,797. Has been described.

The particle size of the inorganic oxide particles is preferably 1 to 2
0 nm, most preferably 4-6n
m.

The content of the above-mentioned inorganic oxide particles is preferably 2 to 80 parts by weight, more preferably 2 to 70 parts by weight, further preferably 10 to 100 parts by weight with respect to 100 parts by weight of the resin.
70 parts by weight, most preferably 20 to 70 parts by weight.

The metal surface treating agent of the present invention contains a phosphorus compound in addition to the above components. Examples of the phosphorus compound include phosphoric acids. Phosphoric acids dissolve the metal surface and roughen the surface, and therefore have a function of improving the adhesion between the metal and the resin. Examples of the phosphoric acids include phosphoric acid, polyphosphoric acid, hypophosphorous acid, tripolyphosphoric acid, hexametaphosphoric acid, polymetaphosphoric acid, and salts thereof. Further, phosphoric acid such as methyl phosphate, dimethyl phosphate, or the like to which an alkyl group or a phenyl group is attached may be used. Further, the above-mentioned aluminum salts and salts of metals other than aluminum may also serve as the phosphoric acid compound (for example, aluminum salts and salts of metals other than aluminum are salts of phosphoric acids).

The amount of phosphorus in the metal surface treating agent of the present invention is such that the equivalent ratio of phosphorus / aluminum is 0.1 or more, preferably 0.5 or more, more preferably 1.0 or more.
That is all. The equivalent ratio of phosphorus / aluminum elements is 0.
If it is less than 1, the effect of the phosphorus compound on the metal material may be weakened, the adhesion of the surface treatment agent to the metal material may be reduced, or the rust prevention effect may be reduced.

The metal surface treating agent of the present invention is used by dissolving and / or dispersing each component in a solvent. Solvents that can be used in the present invention include organic solvents and aqueous solvents, with aqueous solvents being preferred. Water, as an aqueous solvent,
Alternatively, a mixture with a solvent compatible with water can be used.
Examples of the solvent compatible with water include tetrahydrofuran, methyl ethyl ketone, isopropanol, methanol, ethanol, propanol, acetone, dimethylformaldehyde, dimethylacetaldehyde, dimethyl sulfoxide, dioxane, ethylene glycol, propylene glycol, cellosolves, carbitols and the like. Can be

Further, the surface treating agent of the present invention includes various acids.
Add corrosion agent to further improve corrosion resistance
be able to. As the oxidizing agent, N_TwoO_Four, N_TwoO_Three, N_TwoO, Cu
(NO_Three) _Two, AgNO_Three, NH_FourNO_Three, BaO_Two, FeCl_Two, CuSO_Four, Cu (CH_ThreeC
OO)_Two, Hg (CH_ThreeCOO)_Two, Bi (CH_ThreeCOO)_Three, Ag_TwoO, CuO, Bi_TwoO_Three,
HMnO_FourAnd MnO_TwoIt is preferable to use Also these
One or more of these may be used. Effect of oxidizer
Is considered to passivate the metal surface.

The pH of the surface treating agent of the present invention is 1.5 to 1.5.
3.5, more preferably 2.0 to 3.0.
It is preferred that By adjusting the pH to this range, a trace amount of metal is dissolved from the metal surface, and by its action, the metal element in the processing solution and the eluted metal are deposited on the metal surface again to form a composite metal film on the metal surface. At the same time, the resin is pseudo-crosslinked with Al, another metal, or the like, and these form a solid surface treatment film.

The effect of the above surface treatment agent is that, among various metals, the cold-rolled steel sheet, black scale steel sheet, pickled hot-rolled steel sheet, thick sheet,
Steels such as shaped steel and pipe wires, copper or copper alloys, titanium or titanium alloys, nickel or nickel alloys, aluminum or aluminum alloys, magnesium or magnesium alloys, metals that are easily passivated such as stainless steel, or Fe, Ni, Cr, Cu The effect tends to be more effective when applied to a plating layer containing an element that is easily passivated, such as Al, Mg, Ti.

Although the reason for this is not necessarily clear at the local point, when the surface treatment agent is applied to various metals, the metal elements on the surface of the metal material are partially eluted as ions into the metal surface treatment layer. Excessive elution results in adsorption or binding to any of the components of the metal surface treatment layer, deteriorating the function of these components, and often deteriorating the function of the entire coating. On the other hand, when an oxidizing agent coexists in the surface treatment agent and the metal surface is passivated during coating, excessive elution of ions into the surface treatment film is suppressed as much as possible. It seems that more excellent film performance is stably secured.

The present invention relates to a metal such as Zn, Ni, Cu, Fe, A
Plated steel sheet in which one kind of metal such as l, Co, Cr, Ti, Mg, Mn, Sn, Pb, etc. is plated on steel sheet, or alloy in which two or more of these metals or two or more of these metals are plated Plated steel sheets, furthermore, a plated metal sheet in which inorganic substances such as a third metal or / and silica, alumina, zirconia, titania and the like are dispersed in these plated layers, or alloy plates made of two or more of the above metals, for example, Zinc or zinc alloy plate, copper or copper alloy plate, aluminum or aluminum alloy plate, magnesium or magnesium alloy plate, titanium or titanium alloy plate, nickel or nickel alloy plate, silicon steel plate, stainless steel, etc.
Also, for steel materials, it is not necessary to select a coated material such as a cold-rolled steel sheet, a hot-rolled hot-rolled steel sheet, a pickled hot-rolled steel sheet, a thick plate, a shaped steel, a pipe, a wire, etc. I can do it. A metal having a chromium-free surface treatment film that exhibits excellent adhesion to the material by applying, drying, and post-curing, if necessary, on these metal coated objects, and that exhibits extremely excellent corrosion resistance and paint adhesion. Material can be provided.

To apply the surface treating agent of the present invention to various metal materials, any coating method such as roll coating, spray coating, brush coating, dip coating, curtain flow and the like may be used.

The thickness of the surface-treated layer of the surface-treated metal material and the resin-coated metal material of the present invention is preferably 5 μm or less. If the thickness of the surface treatment layer exceeds 5 μm, the surface treatment layer is carbonized by the heat of welding when welding, and the welding characteristics are poor. It is not preferable because it cannot be performed uniformly. The thickness of the surface treatment layer is more preferably 3 μm or less, further preferably 2 μm, and most preferably 1.5 μm.

Further, this surface-treated metal material is provided with a top-coated resin coating film on the surface metal-treated layer, and is used practically as a resin-coated metal material.

For the resin coating layer, known materials such as an alkyd resin, a polyester resin, a polyurethane resin, an epoxy resin, an acrylic resin, and modified resins thereof can be used. The resin coating layer contains various pigments, an ultraviolet absorber, and a stabilizer. Can be. Further, crosslinking and curing may be performed with various curing agents such as an isocyanate compound, an alkyl etherified formaldehyde compound, an epoxy compound, and a radical polymerizable compound.

The coating layer can be provided by a method of applying an organic solvent or water-based coating, a method of fixing a powder coating by heat, a method of electrodeposition, or the like.

The coated metal material and the surface-treated metal material of the present invention include, in particular, parts for home appliances such as an electric washing machine, a television, a personal computer, a word processor and the like, office parts, a roof / wall material, a guardrail, various iron poles and the like. And construction materials, and automotive parts such as bodies and gasoline tanks.

Further, shipbuilding members, bridge-type steel formed from thick plates and shaped steel, wire ropes formed from wire rods, various transport pipes formed from pipes, steel furniture formed from cold-rolled steel sheets, Examples include simple furniture, containers such as drums formed from hot-rolled hot-rolled steel sheet and pickled hot-rolled steel sheet, boxes including containers, and members for vehicles.

Further, since it is a pollution-free surface treatment agent that does not use chromium, it can be used for containers and toys, such as food cans and cans, and its use is greatly expanded.

The form of the coated metal material of the present invention may be a post-coated product in which a surface-treated metal material is molded and then coated with a resin paint, but may be a roll before cutting or molding the metal material. It is preferably a precoated metal in which a coating layer is provided on a metal steel sheet wound in a shape.

Further, since the formed film exhibits excellent insulation properties, it can be used as a coating agent for an electromagnetic steel sheet (silicon steel sheet), especially a non-oriented electromagnetic steel sheet.

(Operation) There has been a description about an Al compound in a steel sheet surface treatment material. However, there is no mention of resin, aluminum and other elements. We have demonstrated for the first time that a combination of (i) an aluminum salt, (ii) a salt of a metal other than aluminum, (iii) a phosphorus compound, and (iv) a resin and / or a precursor thereof exhibits high corrosion resistance.

[0093]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to embodiments. In Examples, “parts” means “parts by weight” and “%” means “% by weight”. Each measurement item followed the following method.

(1) Weight average molecular weight 0.005 g of resin was added to 10 cc of tetrahydrofuran.
And measured with a GPC-LARLS apparatus low angle light scattering photometer LS-8000 (manufactured by Tosoh Corporation, tetrahydrofuran solvent, reference: polystyrene).

(2) Particle Size of Aqueous Dispersion The aqueous dispersion was prepared by using ion-exchanged water to obtain a solid content of 0.1
wt%, and a laser light scattering particle size distribution analyzer Cou
liter model N4 (Coulter)
Was measured at 20 ° C.

(3) Bare corrosion resistance The surface treatment liquid was applied to an electrogalvanized steel sheet (a zinc adhesion amount of 30 g).
/ M ² ), the total solid content is 1.0 g / m ² (thickness 1.0 μm).
m), dried at 300 ° C. for 10 seconds, and then sprayed with a salt water spray device (salt water concentration 5%, tank temperature 35 ° C., spray pressure 200 P) in accordance with JIS Z-2371 standard.
SI) to evaluate the occurrence of white rust.
The bare corrosion resistance of the processed portion was evaluated by performing a 6 mm Erichsen extrusion process and evaluating the occurrence of white rust in the Erichsen portion. ◎: White rust occurrence area 0%, ○: White rust occurrence area 5% or less,
△: White rust generation area within 10%, ×: White rust generation area 50%
Within, XX: White rust generation area 50% or more

(4) Adhesion to Material The surface treatment liquid was applied to an electrogalvanized steel sheet (a zinc adhesion amount of 30 g /
m ² ) so that the total solid content is 1.0 g / m ² (film thickness 1.0 μm), and then the steel plate obtained by drying is immersed in boiling water for 30 minutes, and then 2 mm square Cut the film into
The tape was peeled off, and the peeled area of the coating film was evaluated. ◎: peeled area 0%, ○: peeled area 5% or less, Δ: peeled area 10% or less, ×: peeled area 50% or less, XX: peeled area 50% or more

(5) Adhesion of paint after boiling water treatment A surface treatment solution was applied to an electrogalvanized steel sheet (a zinc adhesion amount of 30 g).
/ M ² ) and the total solid content is 1.0 g / m ² (film thickness 1.0 μ).
After drying at 200 ° C. for 10 seconds, a melamine-based low-temperature baking paint (Amilac 1000, manufactured by Kansai Paint Co., Ltd.) was applied so that the film thickness after baking became 30 μm. I baked it for a minute. After that, it was immersed in boiling water for 1 hour to perform the treatment.
The film was cut on the square, the tape was peeled off, and the peeled area of the film was evaluated. ◎: peeled area 0%, ○: peeled area 5% or less, Δ: peeled area 10% or less, ×: peeled area 50% or less, XX: peeled area 50% or more

(6) Cross-cut test A surface treatment solution was applied to an electrogalvanized steel plate (zinc adhesion amount 30 g / m ² ) having a total solid content of 70 mm × 150 mm.
g / m ² (film thickness 1.0 μm).
After drying at 10 ° C. for 10 seconds, a melamine-based low-temperature baking paint (Amilac 1000, manufactured by Kansai Paint Co., Ltd.) was applied so that the film thickness after baking became 30 μm.
Bake for 0 minutes. Make a cut in this coating film up to the plating layer with an Olfa cutter knife (length about 10c).
The two cuts of m intersect at an angle of about 45 degrees at the center of the length), and the salt spray test was performed for 360 hours. After the test, the maximum swollen width from the cross cut portion was measured. The maximum swollen width was measured with a Nokis. When the swollen width was unclear, the swollen coating layer was peeled off with a needle or the like and measured.

Production Example of Resin (A-1) 360 parts of water, 1.5 parts of sodium styrenesulfonate, and 2 parts of potassium persulfate were charged into a reactor equipped with a stirrer, a thermometer, and a reflux device. After heating to 16 parts, styrene 16 parts, methyl methacrylate 36 parts, glycerin monomethacrylate 20 parts, methacrylic acid 16 parts
, And added to the system over 3 hours. Thereafter, the reaction was continued at 70 ° C. for 3 hours, and then cooled to room temperature to obtain an aqueous dispersion of an acrylic resin (A-1) having a solid content of 20%. The average particle diameter of the obtained aqueous dispersion is 200 n.
m.

Production Example of Resin A-2 262 parts of dimethyl terephthalate, 262 parts of dimethyl isophthalate, 89 parts of dimethyl 5-sodium sulfoisophthalate were placed in a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser. , 279 parts of ethylene glycol, 672 parts of ethylene oxide adduct of bisphenol A (manufactured by Sanyo Chemical Industries, BPE20F), and 0.52 part of tetra-n-butyl titanate, and transesterification reaction was performed at 160 ° C to 220 ° C for 4 hours. Was performed. Next, the temperature was raised to 255 ° C., and the pressure of the reaction system was gradually reduced. Then, the reaction was performed under a reduced pressure of 0.2 mmHg for 1 hour and 30 minutes to obtain a polyester. The obtained polyester was light yellow and transparent, and the weight average molecular weight was 11,000.
Met. Next, 80 parts of the obtained polyester, 40 parts of methyl ethyl ketone, and 40 parts of tetrahydrofuran were charged into a reactor equipped with a stirrer, a thermometer, and a reflux device, and dissolved under reflux. After the resin was dissolved, 200 parts of water was added and stirring was continued for 10 minutes. Thereafter, the solvent remaining in the medium was distilled off by heating to obtain a final aqueous dispersion of the polyester resin (A-2). The resulting aqueous dispersion was milky white and had an average particle size of 150 nm.

Production Example of Resin (A-3) In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 456 parts of dimethyl terephthalate, 456 parts of dimethyl isophthalate, and dimethyl 5-sodium sulfoisophthalate were added. 59 parts, 233 parts of ethylene glycol, 443 parts of 3-methyl-1,5-pentanediol, 1120 parts of an ethylene oxide adduct of bisphenol A (manufactured by Sanyo Chemical Industries, BPE20F), and 0.52 part of tetra-n-butyl titanate Preparation,
The transesterification reaction was performed from 160 ° C to 220 ° C over 4 hours. Next, 11.6 parts of fumaric acid was added and 20
The temperature was raised from 0 ° C to 220 ° C over 1 hour to carry out an esterification reaction. Then

The temperature was raised to 255 ° C., and the pressure in the reaction system was gradually reduced. Thereafter, the reaction was carried out under a reduced pressure of 0.2 mmHg for 1 hour and 30 minutes to obtain a polyester. The obtained polyester was pale yellow and transparent. The obtained polyester has a weight average molecular weight of 18,000 and an unsaturated bond content of 51 mol /
Was 10 ⁶ g. Next, in a reactor equipped with a stirrer, thermometer and reflux device, 66 parts of the obtained polyester,
18 parts of methyl methacrylate, 10 parts of glycerin monomethacrylate, 8 parts of methacrylic acid, 16 parts of isopropyl alcohol, and 0.01 part of hydroquinone were added, and 90 ° C.
To dissolve. After the resin is dissolved, 8 parts of styrene is added. Then, while maintaining the solution temperature at 70 ° C., water 180
Was added and stirring was continued for 10 minutes. Next, after adding an aqueous solution obtained by dissolving 0.6 part of sodium styrenesulfonate in 40 parts of water, 0.9 part of potassium persulfate and 10 parts of water were added to initiate polymerization. After continuing the reaction at 70 ° C. for 4 hours, the mixture was cooled to room temperature to obtain an aqueous dispersion of an acrylic-modified polyester resin (A-3) having a solid content of 30%. The average particle diameter of the obtained aqueous dispersion was 150 nm.

Production Example of Resin (A-4) A bisphenol A epoxy resin (manufactured by Toto Kasei Co., Ltd.,
YD-017), 60 parts, and methyl ethyl ketone, 100 parts, were heated, stirred, and dissolved under reflux. After the resin was completely dissolved, 2 parts of maleic anhydride was added, and after confirming that the resin was dissolved, 0.01 parts of pyridine was added and reacted under reflux for 2 hours. Next, under reflux, 10 parts of styrene,
6 parts of 2-hydroxyethyl acrylate, 8 of methacrylic acid
Part, acrylamidomethylpropanesulfonic acid 2 parts, dibutyl fumarate 4 parts, azosubutyronitrile 2 parts, α
-2 parts of methylstyrene dimer, 6 of methyl ethyl ketone
A mixture of 0 parts and 3 parts of water was dropped into the reactor over 1.5 hours, and then the reaction was continued for 2.5 hours to polymerize the unsaturated monomer mixture. Next, 20 parts of triethylamine was added to neutralize the mixture, and then isopropyl alcohol 6 was added.
0 parts and 200 parts of ion-exchanged water were added and stirred for 30 minutes. Thereafter, the solvent remaining in the medium was distilled off by heating to obtain a final aqueous dispersion of the epoxy resin (A-4). The resulting aqueous dispersion is milky white and has an average particle size of 50 nm,
The B-type viscosity at 25 ° C. was 50 cps. In addition,
The polystyrene-equivalent weight average molecular weight of the polymer of the unsaturated monomer mixture is 8,000, the hydroxyl group content is 0.17 equivalent / 100 g, and the carboxyl group content is 0.31 equivalent / 10
0 g and the amount of sulfonic acid groups were 0.03 equivalent / 100 g.

Example 1 70 g / l of an acrylic resin (A-1) and 3 g of aluminum acetate were applied to an electro-zinc-plated steel sheet (basis weight: 30 g / m ² ).
/ G, 10 g / l of manganese (II) phosphate, and 10 g / l of colloidal silica (Snowtex ST-OS, manufactured by Nissan Chemical Industries, particle size: 8 to 11 nm). C. and dried at 1.degree.
A film was formed so as to have a thickness of 00 g / m ² (1.0 μm in film thickness).

Example 2 70 g / l of acrylic resin (A-1), 4 g / l of aluminum dihydrogen phosphate, 12 g / l of iron (III) phosphate were applied to an electro-zinc plated steel sheet (basis weight: 30 g / m ² ). , Colloidal silica (Nissan Chemical Industries, Snowtex ST-O-XS,
An aqueous solution blended so as to have a particle size of 4 to 6 nm (10 g / l) is applied by a roll, dried at 200 ° C., and coated so that the total adhesion amount becomes 1.00 g / m ² (film thickness 1.0 μ). Was formed.

Example 3 70 g / l of acrylic resin (A-1) and 15 g of aluminum nitrate were added to an electro-galvanized steel sheet (basis weight: 30 g / m ² ).
g / l, copper phosphate 10 g / l, phosphoric acid 10 g / l, colloidal silica (Nissan Chemical Industries, Snowtex ST-O-
(XS, particle size: 4 to 6 nm) An aqueous solution blended so as to have a concentration of 15 g / l is applied by a roll, and dried at 150 ° C. so that the total adhesion amount becomes 1.00 g / m ² (film thickness: 1.0 μ). A film was formed on the substrate.

Example 4 Acrylic resin (A-1) 70 g / l and aluminum sulfate 10 were added to an electro-zinc plated steel sheet (basis weight: 30 g / m ² ).
g / l, magnesium hydrogen phosphate 12 g / l, phosphoric acid 1
An aqueous solution formulated to be 2 g / l and 10 g / l of colloidal silica (Snowtex ST-O-XS, manufactured by Nissan Chemical Industries, particle size: 4 to 6 nm) is applied by a roll, and 150 ° C.
And the total adhesion amount is 1.00 g / m ² (film thickness 1.0
μ).

Example 5 An acrylic resin (A-1) 60 g / l and aluminum chloride 2 g were applied to an electro-zinc plated steel sheet (basis weight: 30 g / m ² ).
/ L, calcium dihydrogen phosphate 4 g / l, manganese (II) phosphate 4 g / m ² , phosphoric acid 12 g / l, colloidal silica (Nissan Chemical Industries, Snowtex ST-O-XS, particle diameter 4 to 6 nm) An aqueous solution formulated to be 10 g / l was applied by a roll and dried at 200 ° C., so that the total adhesion amount was 1.
A film was formed so as to have a thickness of 00 g / m ² (1.0 μm in film thickness).

Example 6 The procedure of Example 1 was repeated except that the resin was changed to polyester resin (A-2). Example 7 It carried out similarly to Example 2 except having changed the resin into polyester resin (A-2). Example 8 It carried out like Example 3 except having changed resin into polyester resin (A-2). Example 9 It carried out similarly to Example 4 except having changed the resin into polyester resin (A-2). Example 10 It carried out like Example 5 except having changed resin into polyester resin (A-2).

Example 11 The procedure of Example 1 was repeated, except that the resin was changed to an acrylic-modified polyester resin (A-3). Example 12 It carried out like Example 2 except having changed the resin into acrylic modified polyester resin (A-3). Example 13 It carried out like Example 3 except having changed the resin into the acrylic modified polyester resin (A-3). Example 14 It carried out like Example 4 except having changed the resin into the acrylic modified polyester resin (A-3). Example 15 It carried out similarly to Example 5 except having changed the resin into the acrylic modified polyester resin (A-3).

Comparative Example 1 Acrylic resin (A-1) 70 g / l, aluminum nitrate 8 g were prepared on an electro-zinc plated steel sheet (basis weight: 30 g / m ² ).
/ L, colloidal silica (Snowtex S manufactured by Nissan Chemical Industries, Ltd.)
(TOS, particle size: 8 to 11 nm) An aqueous solution blended to be 10 g / l was applied by a roll, dried at 200 ° C., and the total adhesion amount was 1.00 g / m ² (film thickness: 1.0 μm). ) Was formed.

Comparative Example 2 70 g / l of a polyester resin (A-2) and manganese phosphate (I) were coated on an electro-galvanized steel sheet (basis weight: 30 g / m ² ).
I) 5 g / l, calcium dihydrogen phosphate 4 g / m2, phosphoric acid 5 g / l, colloidal silica (Nissan Chemical Industries, Snowtex ST-O-XS, particle diameter 4 to 6 nm) 15 g / l
Apply the aqueous solution blended so that it becomes
C. and dried at a total adhesion of 1.00 g / m ² (film thickness 1.0
μ).

Comparative Example 3 Acrylic-modified polyester resin (A-3) 70 g / l, calcium dihydrogen phosphate 10 g / l, and phosphoric acid 10 g / l were prepared on an electro-galvanized steel sheet (basis weight: 30 g / m ² ). The aqueous solution mixed as described above is applied by a roll and dried at 200 ° C., so that the total amount of coating is 1.00 g / m ² (film thickness 1.0 μ).
A film was formed such that

COMPARATIVE EXAMPLE 4 An electro-galvanized steel sheet (basis weight: 30 g / m ² ) was prepared so that acrylic-modified polyester resin (A-3) 70 g / l, aluminum sulfate 20 g / l, and phosphoric acid 0.1 g / l. Was coated with a roll and dried at 200 ° C. to form a film so that the total amount of coating was 1.00 g / m ² (film thickness 1.0 μ).

[0116]

[Table 1]

Example 16 Acrylic resin (A-1) 70 g / l and manganese (II) phosphate 12 g were coated on Zn-plated steel sheet (basis weight: 30 g / m ² ).
/ L, aluminum nitrate 5g / l, colloidal silica surface-treated with Al (Nissan Chemical Snowtex ST-
(CXS-9, particle size: 4 to 6 nm) An aqueous solution blended to be 10 g / l was applied by a roll, dried at 200 ° C., and a film was formed so that the total adhesion amount became 1.00 g / m ² . .

Example 17 An acrylic resin (A-1) 70 g / l, phosphoric acid 10 g / l, and Zn-Ni-plated steel sheet (basis weight: 30 g / m ² )
Colloidal silica surface-treated with aluminum phosphate 4 g / l, calcium dihydrogen phosphate, and Al (Nissan Chemical Industries, Snowtex ST-C, particle size 10 to 20 n)
m) An aqueous solution formulated to be 12 g / l was applied by a roll, dried at 200 ° C., and the total adhesion amount was 1.00 g / m
^A film was formed so as to be ² .

[0119] Example 18 Zn-plated steel sheet (basis weight: 30g / m ^2), the acrylic resin (A-1) 70g / l , aluminum sulfate 6 g /
l, iron (II) phosphate 12 g / l, colloidal silica surface-treated with Al (Nissan Chemical Industries, Snowtex ST-C
XS-9, particle size 4 to 6 nm) An aqueous solution formulated to be 12 g / l was applied by a roll, and dried at 200 ° C.
A film was formed so that the total amount of adhesion was 1.00 g / m ² .

Example 19 A Zn-plated steel sheet (basis weight: 30 g / m ² ) was coated with 70 g / l of an acrylic resin (A-1) and 12 g of manganese (II) phosphate.
/ L, aluminum phosphate 6g / l, phosphoric acid 12g /
1, Colloidal silica surface-treated with Al (Nissan Chemical Industries, Snowtex ST-CXS-9, particle size 4-6n)
m) An aqueous solution formulated to be 10 g / l was applied by a roll, dried at 150 ° C., and the total adhesion amount was 1.00 g / m
^A film was formed so as to be ² .

Example 20 The procedure of Example 16 was repeated except that the resin was changed to polyester resin (A-2). Example 21 It carried out similarly to Example 17 except having changed resin into polyester resin (A-2). Example 22 It carried out similarly to Example 18 except having changed the resin into polyester resin (A-2). Example 23 It carried out similarly to Example 19 except having changed the resin into the polyester resin (A-2).

Example 24 The procedure of Example 16 was repeated, except that the resin was changed to an acrylic-modified polyester resin (A-3). Example 25 It carried out similarly to Example 17 except having changed the resin into the acrylic modified polyester resin (A-3). Example 26 It carried out similarly to Example 18 except having changed the resin into the acrylic modified polyester resin (A-3). Example 27 It carried out similarly to Example 19 except having changed the resin into polyester resin (A-3).

Example 28 The procedure of Example 16 was repeated, except that the resin was changed to epoxy resin (A-4). Example 29 It carried out similarly to Example 17 except having changed the resin into the epoxy resin (A-4). Example 30 It carried out similarly to Example 18 except having changed the resin into the epoxy resin (A-4). Example 31 It carried out similarly to Example 19 except having changed the resin into the epoxy resin (A-4).

[0124]

[Table 2]

[0125]

As described above, the surface treating agent according to the present invention does not use chromium, and is a so-called non-polluting non-chromating agent. It is a coating type chromate, an electrolytic chromate and a resin conventionally used in the fields of automobiles, home appliances and building materials. It can be used as a replacement for all chromating agents such as chromate and reactive chromate. In addition, since it is a pollution-free surface treatment agent that does not use chromium, it can be used in a wide range of applications, including containers, tableware, toys, and indoor building materials.

Claims (3)

[Claims] 1. A chromium-free metal surface treating agent comprising the following (i) to (iv) and having an equivalent ratio of phosphorus / aluminum element of 0.1 or more. (I) Aluminum salt (ii) Salt of metal other than aluminum (iii) Phosphorus compound (iv) Resin and / or precursor thereof 2. A surface-treated metal material which has been surface-treated with the surface treatment agent according to claim 1. 3. A resin-coated metal material obtained by laminating a surface-treated layer and a resin-coated layer on a metal substrate, wherein the surface-treated layer is formed by using the surface-treating agent according to claim 1. Resin painted metal material.