JP2001329379A - Metal surface treatment agent, surface treatment method for metal material, and surface treated metal material - Google Patents

Abstract

(57) [Summary] [PROBLEMS] Excellent corrosion resistance for metal materials (planar parts, processed parts,
It is an object of the present invention to provide a chromium-free metal surface treatment agent, a metal surface treatment method, and a surface-treated metal material used for imparting a flaw. SOLUTION: This is an organic compound having a resonance structure in a molecule and having an electrophilic functional group (a1), a phosphoric acid group, a phosphonic acid group, a silanol group, an alkoxysilyl group, a mercapto group and a sulfonium group. At least one selected from at least one functional group (a2) selected from
A metal surface treatment agent containing an organic compound (A) having a kind of functional group (a), a metal surface treatment method, and a surface-treated metal material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet coil made of metal, and to a surface of a molded product having excellent corrosion resistance.
The present invention relates to a metal surface treatment agent, a metal surface treatment method, and a surface-treated metal material used for forming a film which can impart a processed portion and a flaw and which does not contain chromium. More specifically, the present invention provides excellent corrosion resistance for molded articles, cast articles, sheet coils, etc. of automobile bodies, automobile parts, building materials, parts for home appliances, etc. using zinc-based plated steel sheets, steel sheets, aluminum-based metal materials as materials. The present invention relates to a surface treatment agent, a surface treatment method, and a surface-treated metal material that can be provided with (a flat portion, a processed portion, and a flaw portion) and are used to form a chromium-free film.

[0002]

2. Description of the Related Art Metal materials such as galvanized steel sheets, steel sheets, and aluminum metal materials are oxidized and corroded by oxygen, moisture, ions contained in moisture, and the like in the atmosphere. As a method of preventing such corrosion, a method of forming a chromate film by contacting the surface of a metal material with a treatment solution containing chromium such as chromate chromate or phosphoric acid chromate, There is a coating type chromate treatment or a resin chromate treatment in which a film is formed by heating and drying after coating on the surface. Although the film formed by using such a chromate treatment has corrosion resistance and paint adhesion, since the treatment solution contains harmful hexavalent chromium, wastewater treatment is troublesome and costly. Environmentally friendly because hexavalent chromium is contained in the
They tend to be shunned from safety.

Japanese Patent Application Laid-Open No. 7-278410 discloses a method for using a chromium-free non-chromate treating solution, which is disclosed in Japanese Patent Application Laid-Open No. 7-278410. And a surface treatment method disclosed in Japanese Patent Application Laid-Open No. H8-73775, which include two or more silane coupling agents having a reactive functional group having a specific structure which is different from each other and can react with each other. Metal surface treatment agent and treatment method, JP-A-9-24
No. 1576 discloses a metal surface treating agent containing a silane coupling agent having a specific structure and a phenolic resin-based polymer having a specific structure and a processing method. Japanese Patent Application Laid-Open No. 10-1789 discloses a method having at least one nitrogen atom. Epoxy resin,
Acrylic resin, metal surface treatment agent containing an organic polymer such as urethane resin and a specific polyvalent anion, a treatment method and a treated metal material, JP-A-10-60233,
(1) a rust inhibitor containing a bisphenol A epoxy resin having a specific structure; (2) a solid content ratio of a phenolic resin and another specific resin such as polyester when mixed is 4:
Disclosed are a rust preventive contained in a ratio of 1 to 1: 4, a treatment method using (1) and (2), and a treated metal material.

[0004] When the surface of a metal material sheet such as a zinc-based plated steel sheet, a steel sheet, or an aluminum-based metal is treated by a coil coating method, scratches are often generated when winding or transporting the coil. In order to be cut, bent, overhanged, etc. when forming into the target product, scratches, cut end faces, bending,
It is truly necessary and important to control corrosion of parts that have undergone processing such as overhang.

However, the metal surface treating agent containing no chromium as described above has the advantage of not containing hexavalent chromium, but the corrosion resistance of the obtained film is inferior to that of the conventional chromate film. There is almost no corrosion resistance on the scratches on the surface generated after the treatment, the end faces cut after the treatment, and the parts that have been bent, overhanged, etc. after the treatment. The resulting treating agent has not been obtained.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art, and
An object of the present invention is to provide a chromium-free metal surface treatment agent, a metal surface treatment method, and a surface-treated metal material used for imparting excellent corrosion resistance (a flat portion, a processed portion, and a scratch portion) to a metal material. .

[0007]

Means for Solving the Problems The present inventors have intensively studied the means for solving the above-mentioned problems, and as a result, have found that a metal material surface is treated with a surface treating agent containing an organic compound having a specific structure. As a result, it was found that a film having excellent corrosion resistance (a flat portion, a processed portion, a scratch portion) was formed, and the present invention was completed. That is, the metal surface treating agent of the present invention is an organic compound having a resonance structure in the molecule and having an electrophilic reactive functional group (a1) and / or a phosphoric acid group, a phosphonic acid group, a silanol group, an alkoxysilyl group. Organic compound (A) having at least one functional group (a2) selected from a group, a mercapto group and a sulfonium group.

The organic compound (A) is preferably an aromatic compound. The functional group (a1) is preferably a group represented by the following general formula (1) and directly bonded to the resonance structure, or a group represented by the following general formula (2). —CH ₂ X (1) —ψ—CH ₂ X (2) (where X is —OR ¹ , —NR ² R ³ , —N ⁺ R ⁴ R ⁵ R ⁶ A ⁻
Or a halogen atom, and R ^{1 to} R ⁶ are each independently
A hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms or a linear or branched hydroxyalkyl group having 1 to 5 carbon atoms, A ^- is a hydroxyl ion or an acid ion;
Is a group having an electron donating inducing effect).

Further, the metal surface treating agent of the present invention comprises, as a further component, a metal compound (B) containing at least one metal selected from the group consisting of vanadium, zirconium, titanium, molybdenum, tungsten, manganese and selenium. It is preferable to contain it in order to further improve the corrosion resistance of the film. Further, the metal surface treating agent of the present invention comprises, as a further component, a weight average molecular weight of 1,0.
The addition of the organic polymer (C) of from 0 to 1,000,000 in a solution or dispersion state is intended to further improve the corrosion resistance of the film, and to improve the fingerprint resistance, alkali resistance and solvent resistance of the film. ,preferable. Further, it is preferable that the metal surface treating agent of the present invention contains an etching agent (D) as a further component in order to promote a metal surface reaction and increase the adhesion of a film.

According to the present invention, the temperature of the material may be 50 to 2 after the surface of the metal material is treated with the metal surface treating agent.
The present invention relates to a method for treating a surface of a metal material, which is characterized by drying by heating to 50 ° C. The present invention also relates to a metal material having a film formed using the surface treatment method.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The organic compound (A) used in the surface treating agent of the present invention is a basic compound having a resonance structure in which the groups a1 and / or a2 are substituted.

As such a basic compound, an aromatic compound,
Conjugated polyene compounds and the like. The aromatic compound is
It includes homocyclic compounds and heterocyclic compounds, and examples of homocyclic compounds include phenol, cresol, bisphenols (bisphenol A, bisphenol F, etc.), phenolic compounds such as naphthol, aniline, naphthylamine, toluidine, sulfanilic acid, etc. Examples of the heterocyclic compound include furan compounds such as furan, furfuryl alcohol, furfural, and coumarone; pyrrole compounds such as pyrrole, indole and carbazole; and thiophene. , Thiophene-based compounds such as 2-methylthiophene and thianaphthene, oxazole-based compounds such as oxazole and benzoxazole, imidazole-based compounds such as imidazole and benzimidazole, pyrazole and indazole Pyrazole compounds such as thiazole and benzothiazole; triazole compounds such as triazole and benzotriazole; pyridine compounds such as pyridine and quinoline; pyrimidine compounds such as pyrimidine, quinazoline and pteridine; pyrazine and quinoxaline. And triazine compounds such as triazine, melamine and guanamine, and thiamine, pyridoxine and menadiol. Examples of the conjugated polyene compound include conjugated polyene compounds such as retinol and retinene.

[0013] Examples of such basic compounds include oligomers and polymers containing a resonance structure as a part of a repeating structural unit. Examples of such oligomers and polymers include oligomers and polymers obtained by condensing the above homocyclic compounds and heterocyclic compounds with aldehyde compounds such as formaldehyde, and polyhydroxystyrene, aminated polystyrene, polyvinylimidazole, and polyacetylene.

The electrophilic reactive functional group (a1) to be substituted on the basic compound as described above is a group represented by the following general formula (1) and directly bonded to the resonance structure, or a group represented by the following general formula (2) include groups _{represented: -CH 2 X (1) -ψ} -CH 2 X (2) ( wherein, X is ^{-OR 1, -NR 2 R 3,} -N + R 4 R 5 R 6 A ^-
Or a halogen atom, and R ^{1 to} R ⁶ are each independently
A hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms or a linear or branched hydroxyalkyl group having 1 to 5 carbon atoms, A ^- is a hydroxyl ion or an acid ion;
Is a group having an electron donating inducing effect).

In the above definition of R ^{1 to} R ⁶ , the alkyl group having 1 to 5 carbon atoms is a methyl group, an ethyl group, a propyl group,
Isopropyl group, butyl group, pentyl group and the like,
Examples of the hydroxyalkyl group having 1 to 5 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, and a hydroxypentyl group. In the definition of A ⁻ , acid ions include halogen ions (chlorine ions, bromine ions, fluorine ions, etc.),
Examples include inorganic acid ions such as sulfate ion, nitrate ion and phosphate ion, and organic acid ions such as acetate ion and formate ion. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. As the group は, -NH-, -CO
NH- (in the formula (2), CH ₂ X is bonded to the right side). If the number of carbon atoms of the alkyl group or hydroxyalkyl group in R ^{1 to} R ⁶ exceeds 5, the stability of the organic compound (A) in the treating agent is undesirably reduced.

The functional group (a2) substituted on the basic compound as described above is a phosphate group (—OPO ₃ H ₂ , —OPO ₃ HR)
¹⁰ or —OPO ₃ (R ¹⁰ ) ₂ ), a phosphonic acid group (—PO ₃
H ₂ , —PO ₃ HR ¹¹ or —PO ₃ (R ¹¹ ) ₂ ), a silanol group (—Si (OH) ₃ ), an alkoxysilyl group (—S
iH ₂ (OR ¹² ), —SiH (OR ¹² ) ₂ or —Si (O
R ¹² ) ₃ ), a mercapto group and a sulfonium group (—S
⁺ (R ¹³ ) (R ¹⁴ ) B ⁻ ) at least one type of functional group. Here, R ^{10 to} R ¹⁴ are each independently:
Represents an alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. B ⁻ in the sulfonium group represents a hydroxyl ion or an acid ion. Examples of the acid ion include inorganic ions such as a halogen ion (chlorine ion, bromine ion, fluorine ion), sulfate ion, nitrate ion, phosphate ion, and acetic acid. ion,
Organic acid ions such as formate ion are exemplified.

The organic compound (A) has at least one type of functional group (a) selected from a functional group (a1) and a functional group (a2). The number of such functional groups is not particularly limited, but is preferably 0.1 to 0.1 per resonance hybrid structure (for example, a carbon ring such as a benzene ring or a naphthalene ring, a furan ring, a pyridine ring, or a heterocyclic ring such as a quinoline ring). ~ 7, especially 0.2 ~ 5
Is appropriate. In addition, the position where the functional group (a1) and the functional group (a2) are substituted is not particularly limited (-C
H ₂ X), and may be directly bonded to the resonance structure of the organic compound (A), or may be bonded to a side chain.

The organic compound (A) is not particularly limited as long as it has a resonance structure in the molecule and has at least one kind of the above-mentioned functional group (a). It is preferably a compound represented by (I), (II) or (III).

[0019]

Embedded image

(General formula (I), (II) or (III)
In the formula, φ represents a resonance hybrid structure, and Y represents —OR ⁹ a,
-R ⁹ a, selected from -Oa and -a, wherein R ⁹ is a linear or branched alkylene group having 1 to 5 carbon atoms, 1 to carbon atoms
5 straight-chain or branched hydroxyalkyl groups or polyoxyalkylene groups having a degree of polymerization of 1 to 10 (each alkylene group is a straight-chain or branched alkylene group having 1 to 5 carbon atoms)
A represents an electrophilic functional group (a1) and at least one functional group (a2) selected from a phosphoric acid group, a phosphonic acid group, a silanol group, an alkoxysilyl group, a mercapto group and a sulfonium group. At least one chosen
R ⁷ is a linear or branched alkylene group having 1 to 5 carbon atoms, a linear or branched hydroxyalkylene group having 1 to 5 carbon atoms, or a polyoxy group having a polymerization degree of 1 to 10; An alkylene group (each alkylene group is a linear or branched alkylene group having 1 to 5 carbon atoms), R ⁸ is a hydrogen atom or a methyl group, n1 is 0 or an integer of 1 to 30, and n2 is 1 An integer of 15 to 15, n3 is an integer of 3 to 100, m1 is an integer of 0 or 1 to 7, m2 is an integer of 0 or 1 to 7, m3 is an integer of 1 to 7, p is an integer of 0 or 1 to 30 And n3 / (n3 + p) = 0.6 to 1.0,
Z is a group formed by opening the ethylenic double bond of a compound having an ethylenic double bond, which is different from the structure enclosed by n3).

For both terminal groups of the general formula (III),
AIBN (azobisisobutyronitrile), BPO (benzoyl peroxide), persulfate and the like can be used as the polymerization initiator, which may have different terminal structures, and both terminal groups are not particularly limited. , Hydrogen atom, -C
(CH ₃ ) ₂ (CN), a phenyl group, a benzoyloxy group and the like.

In the general formulas (I), (II) and (III), examples of the compound giving the resonance hybrid structure φ include the basic compounds having the above-mentioned resonance structure, and in the definition of R ⁷ and R ⁹ , Examples of the linear or branched alkylene group of 1 to 5 include a methylene group, an ethylene group, a propylene group,
-Butylene group, 1,4-butylene group, pentamethylene group and the like. Examples of the linear or branched hydroxyalkylene group having 1 to 5 carbon atoms include hydroxymethylene group, hydroxyethylene group, hydroxypropylene group and hydroxy-1. , 2-butylene group, hydroxy-1,4-butylene group, hydroxypentamethylene group and the like. The polyoxyalkylene group having a polymerization degree of 1 to 10 includes a polymerization degree of 1 to 1.
And the functional groups (a1), (a2) and (a) have the same meanings as described above, and are different from the structure enclosed by n3 in the definition of Z Examples of the compound having an ethylenic double bond include (meth) acrylic acid, (meth) acrylic acid esters (such as alkyl or hydroxyalkyl esters having 1 to 5 carbon atoms), styrene, acrylonitrile, and maleic acid.

The compound corresponding to the general formula (I) includes
Phenol resin, toluene resin, aniline resin, xylene resin, furan resin, guanamine resin, mercaptoimidazole, methylolthiophene, pyridinethiol
1-oxide and the like. Examples of the compound corresponding to the general formula (II) include a mercapto-modified bisphenol epoxy compound and a phosphoric acid-modified compound. The general formula (I
Examples of the compound corresponding to II) include a Mannich-modified product (dialkylaminomethylated product) of polyhydroxystyrene, a phosphoric acid-modified product, and a methylol-modified product of polyvinylimidazole.

Specific examples of the organic compound (A) include methylolmelamine, methoxymethylated melamine, methylolguanamine, a copolymer of vinylimidazole and N-methylolacrylamide, and a copolymer of vinylphenol and N-butoxymethylmethacrylamide. Copolymers, condensates of imidazole and formaldehyde, mercaptotriazine, and the like.

The functional group (a1) and / or
Alternatively, the introduction of the functional group (a2) can be performed using a known organic chemical reaction. For example, for phosphorylation and phosphonation, phosphorylation is performed by a dehydrohalogenation reaction with a phosphorus halide or phosphorus oxyhalide, or phosphorus trichloride is added to a highly nucleophilic site using a Friedel-Crafts reaction. A nucleus-substituted derivative can be obtained by a method of phosphorylation by the action of phosphorus oxychloride and then hydrolysis. Further, a phosphorus-containing acid group can be introduced using a Grignard reaction. Introduction of silanol group
For example, it can be achieved by reacting a hydroxyl group or an amino group of the basic compound with a trialkylchlorosilane to perform silylation, followed by hydrolysis.Introduction of an alkoxysilyl group is performed, for example, by introducing a hydroxyl group or an amino group of the basic compound. It can be achieved by allowing a silane coupling agent such as trialkoxychlorosilane or epoxysilane to act on a group or the like.

The introduction of a mercapto group can be achieved, for example, by reacting a halogenated aromatic compound with hydrogen sulfide or an alkali metal salt of sulfur to remove hydrogen halide. Introduction of a mercapto group can also be achieved by a Friedel-Crafts reaction.
Introduction of a sulfonium group can be achieved, for example, by reacting an aromatic compound such as phenol with sulfoxide in the presence of a condensing agent such as concentrated sulfuric acid.

Further, the compound represented by the general formula (1), namely, -CH ₂ X
For the introduction of the group represented by the formula, for example, methylol can be formed by allowing formalin to act on a site having a high electron density such as an aromatic ring. Aminomethylation can be achieved by reacting formalin with ammonia or an amine. In addition, halomethylation involves formalin and hydrohalic acid (hydrochloric acid, hydrofluoric acid, etc.)
Can be achieved. Also,
Introduction of the group represented by the general formula (2), that is, -ψ-CH ₂ X is performed by a basic compound having the above-described resonance structure, for example, an aromatic primary amine, an aromatic secondary amine, or an aromatic secondary amine.
It can be achieved by allowing formalin or formalin and hydrohalic acid to act on the lower amide.

The metal surface treating agent of the present invention contains, as a further component, a metal compound (B) containing at least one metal selected from the group consisting of vanadium, zirconium, titanium, molybdenum, tungsten, manganese and cerium. Is preferable for further improving the corrosion resistance of the coating. Such a metal compound (B) is an oxide, a hydroxide, a complex compound, a salt with an inorganic acid or an organic acid, or the like of the metal, and preferably has good compatibility with the organic compound (A). .

As the metal compound (B), specifically,
Vanadium oxide V_TwoO_Five, Vanadium trioxide V_TwoO_Three, Diacid
Vanadium VO_Two, Metavanadate HVO_Three, Metabana
Ammonium formate, sodium metavanadate, oki
Vanadium sulphate VOSO_Four, Vanadium oxyacetyl
Luacetonate VO (OC (CH_Three) = CHCOC
H_Three))_Two, Vanadium acetylacetonate V (OC
(CH_Three) = CHCOCH_Three)_Three, Vanadium oxytrichloride
VOCl_Three, Vanadium trichloride VCl_Three, Zirconi nitrate
Le ZrO (NO_Three)_Two, Zirconyl sulfate, zirconium acetate
, Zirconyl ammonium carbonate (NH_Four)_Two[Zr (C
O_Three)_Two(OH)_Two], Fluorozirconate H_TwoZrF
₆, Titanyl sulfate TiOSO_Four, Diisopropoxy titani
Umbisacetylacetone (C_FiveH₇O_Two)_TwoTi [OCH
(CH_Three)_Two]_TwoThe reaction between lactic acid and titanium alkoxide
Corresponding substance, fluorotitanic acid H_TwoTiF₆, Titanium lactate
Ti (OH) _Two(C_ThreeH_FiveO_Three)_Two, Molybdic acid H_TwoMoO
_Four, Ammonium molybdate, sodium molybdate
Molybdophosphate compounds (eg, molybdophosphate compounds)
Ammonium (NH_Four)_Three[PO_FourMo₁₂O₃₆] ・ 3H_TwoO,
Sodium molybdophosphate Na _Three[PO_Four・ 12Mo
O_Three] ・ NH_TwoO), metatungstic acid H₆[H_TwoW₁₂
O₄₀], Ammonium metatungstate (NH_Four)
₆[H_TwoW₁₂O₄₀], Sodium metatungstate,
Latungstic acid H_Ten[W₁₂O₄₆H_Ten], Palatungs
Ammonium formate, sodium paratungstate,
Permanganate HMnO_Four, Potassium permanganate, perma
Sodium ganganate, manganese dihydrogen phosphate Mn (H_Two
PO_Four)_Two, Manganese nitrate Mn (NO_Three)_Two, Sulfuric acid manga
Manganese fluoride, manganese carbonate, manganese acetate, vinegar
Cerium Ce (CH)_ThreeCO_Two)_Three, Cerium nitrate, chloride
Cerium and the like.

The metal surface treating agent of the present invention comprises, as an additional component, a weight average molecular weight of 1,000 to 1,000,000.
Containing the organic polymer (C) in a solution or dispersion state, further improves the corrosion resistance of the film, the fingerprint resistance of the film,
It is preferable for improving alkali resistance and solvent resistance. A more preferred molecular weight is from 2,000 to 500,000. If the molecular weight is less than 1,000, the film-forming property is insufficient, and if it exceeds 1,000,000, the stability of the treating agent may be reduced. Such an organic polymer (C) can be mixed with a processing agent and can be dissolved in water, or can be a dispersion form such as an emulsion or a dispersion in itself or in the presence of an emulsifier. It is preferable that the agent is stable and uniform in the agent and can take a form that can be diluted with water. Examples of the emulsifier include, but are not particularly limited to, anionic surfactants such as alkyl sulfates, cationic surfactants such as alkyl quaternary ammonium salts, nonionic surfactants such as alkyl phenyl ethers, and water-soluble surfactants. A molecule or the like can be used.

Examples of the organic polymer (C) include synthetic polymers which can be contained in a solution or dispersion state, for example, alkyl (meth) acrylate (C1-8) ester (methyl acrylate, methyl methacrylate, ethyl Acrylate, ethyl methacrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, etc.), hydroxyalkyl (meth) acrylate (1 to 4 carbon atoms) ester (2-
Hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, etc.), homo- or copolymers of acrylic monomers such as (meth) acrylic acid, such acrylic monomers (30% by weight or more) and styrene,
Acrylic resins such as copolymers with addition-polymerizable unsaturated monomers such as acrylonitrile and vinyl acetate; homo- or copolymers of olefins (1-8 carbon atoms) (ethylene, propylene, butene, hexene, octene, etc.); A polyolefin-based resin such as a copolymer of such an olefin (50% by weight or more) and (meth) acrylic acid;

Alkylene (C1-6) glycol (ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexamethylene glycol, etc.), polyether polyol (polyethylene glycol such as diethylene glycol, triethylene glycol, etc., polyethylene / propylene glycol) And polyester polyols (such as the above-mentioned alkylene glycols or polyether polyols, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, glycerin, and other polyols with succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, and isophthalic acid). Polyester polyol having a hydroxyl group at the terminal obtained by polycondensation with polybasic acids such as acid, terephthalic acid, trimellitic acid) Polycondensates of polyols such as carbonate polyols with aromatic, alicyclic or aliphatic polyisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, dicyclohexyl methane diisocyanate, cyclohexylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, etc.) A urethane resin;

Bisphenols, especially bisphenol A
Of bisphenol-type epoxy resin obtained by reacting phenol novolak resin with glycidyl ether of phenol novolak resin, glycidyl ester of aromatic carboxylic acid, and ethylenically unsaturated compound. Epoxy resins such as peroxyepoxy epoxy resins in which heavy bonds are epoxidized with peracid; polyesters which are condensates of polyol components such as ethylene glycol and neopentyl glycol with polybasic acids such as terephthalic acid and trimellitic anhydride Resin; and the like.

In these organic polymers (C), it is more preferable to use a soap-free one which does not use a surfactant as a solubilizer or an emulsifying dispersant, or one in which the amount used is as small as possible. Sulfonic acid groups, phosphoric acid groups, phosphonic acid groups, anionic hydrophilic groups such as carboxyl groups, primary to tertiary amino groups, cationic hydrophilic groups such as quaternary ammonium groups, hydroxyl groups, polyoxyethylene chains,
Monomers having at least one hydrophilic group selected from nonionic hydrophilic groups such as amide groups are copolymerized to make them water-soluble or self-emulsified, or a reactive surfactant having an unsaturated bond is polymerized. It is more preferable that the emulsion is self-emulsified by occasional addition. For the polyolefin-based resin, the monomer having the hydrophilic group is used as a copolymer component. In the urethane resin, one of the polyol groups having a hydrophilic group that does not react during polymerization is used as one of the polyol components. In, to introduce the hydrophilic group by modifying part or all of the glycidyl ether, in the polyester resin, by using a polybasic acid having the hydrophilic group in part of the polybasic acid used, water-soluble, A self-emulsifying resin can be obtained.

The surface treating agent of the present invention may further comprise
Therefore, the content of the etching agent (D) can
Etching, metal surface reaction acceleration, increase of film adhesion?
Preferred. As such an etching agent (D),
Acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, boric acid, etc.
Luorodisilconic acid H_TwoZrF₆, Fluorotitanic acid H
_TwoTiF₆, Hydrofluorosilicic acid H_TwoSiF₆, Hydrogen borofluoride
Acid HBF_Four, Tin fluoride, ferrous fluoride, ferric fluoride, etc.
Complex fluoride / fluoride, formic acid, acetic acid, tartaric acid, funils
Use of organic acids such as sulfonic acid and phenylphosphonic acid
Can be.

The amount of each component in the treating agent of the present invention is as follows, assuming that the total of the metal and the organic polymer (C) in the organic compound (A) and the metal compound (B) is 100% by mass.
(A) is preferably 3 to 99% by mass, (B) is preferably 0.05 to 30% by mass, more preferably 0.1 to 20% by mass as a metal, and (C) is preferably 5 to 95% by mass. , 10 to 90% by mass. (A),
For (B) and (C), it is desirable to select the above preferable range in order to maintain high corrosion resistance. The amount of the etching agent (D) in the treatment agent of the present invention is preferably 0.05 to 30 g / L, and more preferably 0.1 to 20 g / L. 0.05
If the amount is less than g / L, the reaction with the metal material is insufficient, and the
If / L is exceeded, the adhesion tends to be impaired due to excessive etching.

In the treatment agent of the present invention, a water-dispersible silica sol, and / or an alumina sol, a zirconia sol, and the like are used to improve the corrosion resistance of the film and adjust the film properties such as tensile strength.
It is effective to add a metal sol such as titania sol,
In this case, the amount to be added is 5 to 40% by mass of the total nonvolatile components.
Is preferable, and 10 to 30% by mass is more preferable. Also,
An organic crosslinking agent and an inorganic crosslinking agent capable of crosslinking the organic polymer (C) can be added to the surface treatment agent of the present invention. Epoxy, melamine, aldehyde, and isocyanate-based organic crosslinking agents are used. Examples of the inorganic crosslinking agent include compounds of metals such as iron, cobalt, nickel, niobium, tantalum, and zinc other than the metal compounds specified in the present invention.

The treating agent of the present invention may further contain an aqueous wax such as an ester wax, a polyolefin wax, or a hydrocarbon wax such as microcrystalline, methyl methacrylate, polystyrene, or melamine for the purpose of preventing scratching or imparting lubricity. Slip agents such as resin powders, matting agents and the like can be contained within a range that does not impair the object of the present invention. The treating agent of the present invention can further contain a surfactant, an antifoaming agent, a leveling agent, a germicidal and antifungal agent, a pigment, a coloring agent, and the like as long as the object of the present invention is not impaired.

The solvent used in the surface treatment agent of the present invention is usually water. However, if necessary for improving the drying property of the film, a water-soluble organic solvent of alcohol, ketone or cellosolve may be used, based on the sum of water and water. The content can be preferably 20 v / v% or less, more preferably 10 v / v% or less.

Next, the surface treatment method of the present invention will be described. Regarding the treatment method, after applying the treatment liquid to the surface of the metal material, it is sufficient if the treatment liquid can be dried by heating at 50 to 250 ° C.
The method of application and the method of drying are not specified. Usually, a roll coating method in which the treatment agent is transferred to the material surface by roll transfer, or a method of squeezing with a roll after pouring with a shower ringer or the like, or a method of draining with an air knife, a method of immersing the material in the treatment liquid, A method of spraying a treatment agent on a material is used. The temperature of the treatment liquid is not particularly limited, but since the solvent of the treatment agent is mainly water, the treatment temperature is preferably from 0 to 60 ° C, and from 5 to 40 ° C.
C is more preferred.

Although there is no particular limitation on the treatment step, usually, before this treatment, the material is washed with an alkaline degreaser or an acidic degreaser to remove oil and dirt attached to the material, or washed with hot water. Perform solvent cleaning, etc. Thereafter, if necessary, the surface is adjusted with an acid, an alkali, or the like. In the cleaning of the material surface, it is preferable to wash with water after cleaning so that the cleaning agent does not remain on the material surface as much as possible.

In the drying step, when it is not necessary to promote the curing of the organic polymer (C) and only the adhering water is removed, heat is not necessarily required and air drying or physical removal such as air blowing may be used. , Curing of organic polymer (C),
Alternatively, it is necessary to heat and dry in order to enhance the coating effect by softening. In that case, the temperature is preferably from 50 to 250C, more preferably from 60 to 220C.

The coating weight of the formed film was 3 in the total weight of the film.
0 to 5,000 mg / m ² , preferably 50 to 3,000 mg / m ²
0 mg / m ² is more preferred. If it is less than 30 mg / m ² , sufficient corrosion resistance and adhesion to the top coat cannot be obtained, and if it is more than 30 mg / m ² , cracks or the like occur in the film, and the adhesion of the film itself decreases.

[0044]

The film formed by using the surface treatment agent and the surface treatment method of the present invention has excellent corrosion resistance. The mechanism is described below. Specified organic compound (A)
Has two main functions. That is, (1) a function of reacting and fixing with the metal surface, and (2) a function of delocalizing corrosion electrons. Anode reaction, which is a corrosion reaction from film defects and scratches (ie, dissolution reaction of base metal)
When electrons generated by the anodic reaction are localized, a corrosion reactant is generated by the dissolved metal ions, oxygen, and water at the site (cathode reaction). The organic compound (A) having the resonance structure specified in the present invention is capable of converting corrosion electrons generated by dissolution of metal into resonance π of the organic compound (A).
Since the delocalization is performed using the orbit, the corrosion product forming reaction can be suppressed, and the surface potential difference caused by the dissolution of the metal can be reduced. In order for the organic compound (A) to take in corrosive electrons into its π orbit and delocalize it, the metal surface and the organic compound (A) must be aligned with the π orbit of the metal surface and the π orbit of the organic compound (A). Must be close enough to overlap.

The functional group (a) in the organic compound (A) has a function of reacting with the metal surface at the time of applying a treating agent and / or forming a film, thereby fixing the organic compound (A) to the metal surface. This has the effect of keeping a sufficient distance to take in corrosive electrons. The functional group (a) capable of reacting with a metal is a cationion that reacts electrophilically with an electron-rich site on the metal surface. Expressed as an acid-base, it is considered that the metal surface is a base that supplies electrons, and the organic compound (A) is an acid.
The functional group (b), that is, the phosphoric acid group, the phosphonic acid group, the silanol group, the alkoxysilyl group, the mercapto group, and the sulfonium group are also considered to be a kind of cationoid group utilizing the d orbital of phosphorus, silicon, and sulfur. . The metal compound (B) is a compound of a transition metal having an incomplete electron shell, and is considered to be a kind of cationoid. Therefore, similarly to the organic compound (A), the organic compound (A) undergoes an electrophilic fixation reaction on the metal surface, and has an effect of delocalizing corrosion electrons by using the incomplete electron orbitals of the organic compound (A). .

Organic polymer (C) used in the treating agent of the present invention
Is a film-forming resin, which forms a film so as to cover a reaction film composed of an organic compound (A) and a metal compound (B) formed on a metal surface when a processing liquid is applied or / and dried, and It has a barrier effect of blocking permeation of moisture, corrosion promoting ions, etc., and when the reaction film layer is present at the interface with the base metal, the corrosion resistance is further improved. At the same time, there is an effect of improving fingerprint resistance, alkali resistance, solvent resistance, and the like of the film. The etching agent (D) has an effect of etching the material metal to increase the electron density on the surface, and has an effect of promoting a fixing reaction between the organic compound (A) and the metal compound (B). By the above mechanism, the surface treatment agent of the present invention can impart excellent corrosion resistance to the surface of the metal material, and it is considered that the surface treatment agent of the present invention is particularly excellent in corrosion resistance even in a flaw portion and a processed portion.

[0047]

EXAMPLES Next, the present invention will be described with reference to examples and comparative examples. However, the present examples are merely examples and do not limit the present invention. 1. Material (a) Galvanized steel sheet (sheet thickness 0.6 mm) (b) Hot-dip galvanized steel sheet (sheet thickness 0.8 mm) (c) Hot-dip galvanized steel sheet containing 55% aluminum (sheet thickness 0.
5 mm) Treatment agent (1) Treatment agent component The organic compound (A) used is as follows.

[0048]

[Table 1]

The metal compound (B) used is as follows. B1: ammonium zirconium carbonate B2: fluorozirconate B3: titanium lactate B4: ammonium metavanadate B5: ammonium metatungstate

The organic polymer (C) used is as follows. C1: Water-based ionomer resin (manufactured by Mitsui Chemicals, Inc., Chemipearl S-10) (polyolefin resin having a carboxyl group) C2: Water-based acrylic resin (Polysol AP-6530, manufactured by Showa Polymer Co., Ltd.) C3: Water-based anion-modified Epoxy resin (Adeka Resin EM-0433, manufactured by Asahi Denka Kogyo Co., Ltd.) C4: Aqueous urethane resin (Daiichi Kogyo Seiyaku Co., Ltd., Superflex 150P) C5: Aqueous urethane resin (Asahi Denka Kogyo, Adeka) Bon Titer HUX680)

The etching agent (D) used is as follows. D1: HF D2: H ₂ TiF ₆ D3: H ₂ SiF ₆ D4: H ₃ PO ₄

(2) Preparation of treatment agent The organic compound (A), the metal compound (B), the organic polymer (C) and the etching agent (D) are separately solubilized or dispersed in water and diluted. (B) to liquid (D)
The liquid and the liquid (A) were mixed in this order, and this mixed liquid was added to the liquid (C) and mixed.

3. Treatment method (1) Degreasing The material was degreased with an alkali degreasing agent PALCLEAN 364S (manufactured by Nippon Parkerizing Co., Ltd., 20 g / L bath, 60 ° C., 10 seconds spray, spray pressure 50 kPa), and then spray-washed for 10 seconds. . (2) Coating and drying I: The treatment liquid adjusted to a concentration of 16% by mass was applied with a bar coater # 3 and dried at 80 ° C. (PMT). II: The treatment liquid adjusted to a concentration of 20% by mass was applied with a bar coater # 5 and dried at 100 ° C. (PMT). III: The treatment liquid adjusted to a concentration of 16% by mass was applied with a bar coater # 3 and dried at 150 ° C. (PMT).

4. Evaluation method For the treated plate samples produced in the examples and comparative examples,
Unprocessed (flat part), cross cut with NT cutter until reaching the substrate (cross cut part), Erichsen 7mm
The extruded product (worked portion) was subjected to a corrosion resistance test. The evaluation method is as follows. (Planar part) The area of white rust occurrence 72 hours after salt spraying was determined and evaluated based on the salt spray test method JIS-Z-2371. Evaluation criteria: White rust generation area ◎ Less than 10%, ○ 10% or more to less than 30%, Δ30% or more to less than 60%, × 60% or more (Cross cut part) Salt spray test method JIS-Z-237
Based on No. 1, the state of white rust generation 72 hours after spraying with salt water was visually evaluated. Evaluation criteria: White rust generation status ◎ Almost no rust, ○ Slight rust, △ Rust generation is recognized, × Rust generation is remarkable (Processed part) 72 hours after salt water spray based on salt water spray test method JIS-Z-2371 Was visually evaluated for the occurrence of white rust. Evaluation criteria: White rust occurrence ◎ Almost no rust, ○ Slight rust, △ Rust generation observed, × Rust generation remarkable

Table 2 shows the compositions and processing conditions of the processing agents used in the examples and comparative examples.

[0056]

[Table 2]

In Table 2, each numerical value for (A) to (C) is the total of (A) to (C) as the mass of the non-volatile component (however, the mass of the metal compound of (B) is a metal). % By mass. The numerical values for (D) and other components represent the amount (g) of the active ingredient added to 1 kg of the treating agent. Comparative compound of component A, ratio 1 was phenol as an aromatic compound having no methylol group, and ratio 2 was N-methylolacrylamide as a methylol compound having no resonance structure.

(Comparative Example 5) ZM-1300AN, a coating type chromate treatment agent manufactured by Nippon Parkerizing Co., Ltd., was added to the material (a) degreased under the above degreasing conditions in an amount of 20 m in chromium adhesion amount.
g / m ² , and dried at 80 ° C. PMT (material arrival temperature).

The treated samples prepared in Examples 1 to 9 and Comparative Examples 1 to 5 were subjected to a corrosion resistance test. Table 3 shows the evaluation results.

[0060]

[Table 3]

As is clear from Table 3, in Examples 1 to 9 in which a film was formed using the surface treatment agent of the present invention, since the surface treatment agent and the film did not contain harmful chromium, the safety was high. It shows that all of the flat part, the cross cut part, and the processed part have better corrosion resistance than the chromate treatment. In Comparative Examples 1 and 2 in which a film was formed using a surface treatment agent not containing the organic compound (A), which is an essential component of the surface treatment agent of the present invention, the flat portion, the cross cut portion, and the processed portion In each case, the corrosion resistance was remarkably inferior. Also, in the case of Comparative Examples 3 and 4 in which the organic compound having no structure specified in the present invention was used instead of the organic compound (A), almost no development of corrosion resistance was observed. In the case of Comparative Example 5 using the coating type chromate, the corrosion resistance of the processed portion was slightly inferior.

[0062]

The surface treating agent of the present invention is of a non-chromate type containing no harmful chromium compound.
The scratched part and the processed part also have the same or higher corrosion resistance as the conventional chromate film, and the surface treatment agent, surface treatment method and surface treated metal material of the present invention have extremely high industrial utility value. Things.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) // C09D 5/08 C09D 5/08 (72) Inventor Mayumi Yamamoto 1-15-1 Nihonbashi, Chuo-ku, Tokyo No. Japan Parkerizing Co., Ltd. F-term (reference) 4J038 CB011 CB081 CB121 CC021 CC091 CG071 CG141 CG161 CH031 CH041 CH121 CK021 CN001 DA001 DA041 DA061 DA101 DA131 DA141 DA161 DA171 DB061 DB191 DD041 DG012 GA01 DG071 DG071 GA13 GA14 GA15 HA096 HA126 HA216 HA246 HA296 HA336 HA376 HA416 JA37 JA39 JA43 JC02 JC13 JC17 JC23 JC24 JC26 JC32 JC33 JC38 MA14 NA03 NA27 PA19 PC02 4K026 AA02 AA07 AA12 AA13 AA22 BA01 BA03 CA04 CA18 CA29 AB02 BA10 BA21 BB03 BC02 CA11 CA18 CA53

Claims (9)

[Claims] 1. An organic compound having a resonance structure in its molecule and having an electrophilic functional group (a1), a phosphoric acid group, a phosphonic acid group, a silanol group, an alkoxysilyl group, a mercapto group and a sulfonium. At least one selected from at least one functional group (a2) selected from
A metal surface treating agent containing an organic compound (A) having a kind of functional group (a). 2. The metal surface treating agent according to claim 1, wherein the organic compound (A) is an aromatic compound. 3. The functional group (a1) has the following general formula (1):
3. The metal surface treating agent according to claim 1, wherein the group is a group represented by the following formula and directly bonded to the resonance structure, or a group represented by the following general formula (2). —CH ₂ X (1) —ψ—CH ₂ X (2) (where X is —OR ¹ , —NR ² R ³ , —N ⁺ R ⁴ R ⁵ R ⁶ A ⁻
Or a halogen atom, and R ^{1 to} R ⁶ are each independently
A hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms or a linear or branched hydroxyalkyl group having 1 to 5 carbon atoms, A ^- is a hydroxyl ion or an acid ion;
Is a group having an electron donating inducing effect). 4. The organic compound (A) is represented by the following general formula (I):
The metal surface treating agent according to any one of claims 1 to 3, which is a compound represented by (II) or (III): (In the general formula (I), (II) or (III), φ represents a resonance hybrid structure, Y is selected from —OR ⁹ a, —R ⁹ a, —Oa, and −a,
Here, R ⁹ is a straight-chain or branched alkylene group having 1 to 5 carbon atoms, a straight-chain or branched hydroxyalkylene group having 1 to 5 carbon atoms, or a polyoxyalkylene group having a polymerization degree of 1 to 10 (each alkylene group is A is a linear or branched alkylene group of formulas 1 to 5, and a is an electrophilic reactive functional group (a1), and a phosphoric acid group, a phosphonic acid group, a silanol group, an alkoxysilyl group, a mercapto group and At least one functional group (a) selected from at least one functional group (a2) selected from a sulfonium group, R ⁷ is a linear or branched alkylene group having 1 to 5 carbon atoms,
A straight-chain or branched hydroxyalkylene group having 1 to 5 carbon atoms or a polyoxyalkylene group having a polymerization degree of 1 to 10 (each alkylene group is a straight-chain or branched alkylene group having 1 to 5 carbon atoms); ⁸ is a hydrogen atom or a methyl group, n1 is 0 or an integer of 1 to 30, n2 is an integer of 1 to 15,
n3 is an integer of 3 to 100, m1 is 0 or an integer of 1 to 7,
m2 is 0 or an integer of 1 to 7, m3 is an integer of 1 to 7, p is 0 or an integer of 1 to 30, and n3 / (n3 + p) =
Z is a group formed by opening the ethylenic double bond of a compound having an ethylenic double bond, which is different from the structure enclosed by n3). 5. The method according to claim 1, further comprising a metal compound (B) containing at least one metal selected from the group consisting of vanadium, zirconium, titanium, molybdenum, tungsten, manganese and cerium. The metal surface treating agent according to the above item. 6. The weight average molecular weight of 1,000 to
The metal surface treating agent according to any one of claims 1 to 5, comprising 1,000,000 organic polymers (C) in a solution or dispersion state. 7. The metal surface treating agent according to claim 1, further comprising an etching agent (D). 8. After the metal material surface is treated with the metal surface treating agent according to any one of claims 1 to 7, the material is heated and dried so that the temperature of the material is 50 to 250 ° C. Characteristic surface treatment method for metal materials. 9. A metal material having a film formed by using the surface treatment method according to claim 8.