WO2006126394A1

WO2006126394A1 - Aqueous surface treating agent for precoated metal material, surface treatment method and method for producing precoated metal material

Info

Publication number: WO2006126394A1
Application number: PCT/JP2006/309391
Authority: WO
Inventors: Tomohiro Iko; Tomoyoshi Konishi; Atsushi Miura
Original assignee: Nihon Parkerizing Co., Ltd.
Priority date: 2005-05-23
Filing date: 2006-05-10
Publication date: 2006-11-30
Also published as: JP2006328445A

Abstract

Disclosed is an aqueous surface treating agent for precoated metal materials which contains a silane coupling agent (A), a cationic urethane resin (B), a Zr compound and/or Ti compound (C), and a fluorine-containing inorganic compound (D). In this aqueous surface treating agent, the mass ratio of (A) to(B) is from 1/50 to 20/1, the mass ratio of Zr and/or Ti atoms to (B) is from 1/1000 to 1/2, and the mass ratio of fluorine atoms to(B) is from 1/1000 to 2/1. Also disclosed are a treatment method and a method for producing a non-chromium precoated metal material. This non-chromium aqueous surface treating agent has good storage stability, and is useful as a foundation-treating agent for producing a precoated metal material which is excellent in adhesion of coating during processing, corrosion resistance and coin-scratch resistance. The corrosion resistance can be further improved by blending a specific metal compound (E) into the aqueous surface treating agent.

Description

Specification

Aqueous surface treatment agent for precoat metal material, surface treatment method, and method for producing precoat metal material

Technical field

[0001] The present invention is useful as a base treatment agent for producing a precoat metal material having excellent coating adhesion (coating adhesion of a coating film), corrosion resistance and coin scratch resistance, and also has storage stability. The present invention relates to a good non-chromium aqueous surface treatment agent, a treatment method, and a method for producing a non-chromium pre-coated metal material. Background art

[0002] Conventional post-coated products that have been coated after processing on parts for home appliances, building materials, automobiles, etc. have been subjected to many pre-treatments such as phosphates. Instead of such pretreatment, precoated metal plates coated with a colored organic film have been used. This metal plate is a metal plate with a base treatment and a metal plate coated with an organic film. It has a good appearance, good workability, and good corrosion resistance. And then.

[0003] For example, Patent Document 1 discloses a precoated steel sheet in which end face corrosion resistance is improved by applying a specific chromate treatment liquid and drying without washing with water. Pre-coated steel sheets with such a chromium-containing pretreatment have corrosion resistance, workability and paint adhesion (coating adhesion of the coating film) due to the combined effects of chromate treatment and organic coating, and are coated after processing. The purpose is to improve productivity and quality, and is currently used for general purposes. However, there is a growing demand for non-chromium anti-glare treatment and non-chromium organic coating due to the toxicity of hexavalent chromium that may be dissolved. .

[0004] The first characteristic required for the pretreatment of precoated steel sheets is paint adhesion (coating adhesion of the paint film), and the two interfaces between the underlying metal as the lower layer and the primer as the upper layer are excellent. Adhesion is required. This coating adhesion may be evaluated after being immersed in boiling water for a predetermined time. This is called the secondary coating adhesion, and it is applied before being immersed in boiling water. Distinguish from primary paint adhesion, which is adhesion. Both the primary and secondary adhesion are extremely important characteristics that are essential for pre-coated steel sheets that are assumed to be processed into complex shapes by post-processing. The T-bending test is an extremely rigorous test and is used to evaluate the adhesion of precoated steel sheets.

[0005] The second characteristic required for the pretreatment of the precoated steel sheet is a coin scratch resistance. This is a property that is influenced not only by adhesion but also by the film hardness of the ground treatment.

[0006] A third characteristic required for the pretreatment of the precoated steel sheet is corrosion resistance. In the case of a pre-coated steel sheet, usually, a base treatment, a primer coating process, and a top coat coating process are sequentially performed on the steel sheet. In the case of a pre-coated steel sheet that has been subjected to conventional chromate treatment, chromate is also contained in the primer layer that consists of only the ground treatment layer. In particular, compared to the surface treatment that is not normally used exceeding 0. 3 to: Primer that is used as thick as LO m One layer contains many chromium components as anti-glare pigments, giving corrosion resistance to pre-coated steel sheets. It plays the main role. However, the actual condition is that the primer in the pre-coated steel sheet not containing chromium can only provide corrosion resistance as much as the primer containing the chromium-based anti-corrosive pigment. Therefore, it can be said that in non-chromated pre-coated steel sheets, the surface treatment part plays a role of imparting corrosion resistance rather than the conventional chromate system.

[0007] Patent Document 2 discloses a non-chromium antifouling treatment method as an alternative to chromate treatment. Surface treatment of zinc and a zinc alloy with an aqueous solution containing tannic acid and a silane coupling agent results in anti-whitening resistance and paint. Although a technique for improving adhesion is disclosed, this method cannot sufficiently ensure the coin scratch resistance and corrosion resistance required for the precoated metal sheet.

[0008] Patent Document 3 discloses a metal surface treatment agent containing a silane coupling agent, a water-dispersible silica, a Zr compound, and an acrylic resin for application to a metal surface such as a zinc-plated steel sheet. This surface treatment agent cannot satisfy the paint adhesion and corrosion resistance required for precoated steel sheets.

[0009] Patent Document 4 discloses a metal comprising a silane coupling agent, silica, and a water-soluble resin. The force S for which a surface treatment agent is disclosed S, and even this surface treatment agent cannot satisfy the paint adhesion and corrosion resistance required for precoated steel sheets.

Patent Document 5 describes that a chemical conversion film containing silica fine particles and a binder such as polyacrylic acid is formed on the surface of a zinc-plated steel sheet. However, the paint adhesion and corrosion resistance achieved using this method is inferior to those achieved with chromate treatment.

[0011] Patent Document 6 describes a surface treatment agent containing a carbon-based polyurethane, a silane coupling agent, and a water-soluble Zr compound. However, this surface treatment agent is used for imparting temporary antifungal properties and cannot achieve the level of paint adhesion required for precoated steel sheets.

[0012] Pre-coated steel plates are required to have paint adhesion that can withstand severe post-processing such as deep drawing. The adhesion achieved by the surface treatment liquid for imparting temporary anti-fouling property is the work adhesion at the Erichsen extrusion level, and the work adhesion at a level that passes the T-bending test is not achieved. The same applies to the case where the anti-fingerprint surface treatment solution or the surface treatment solution for lubrication is diverted to the pretreatment of the pre-coated steel sheet, and the level of processing adhesion that passes the T-bending test is not achieved. As described above, a surface treatment agent having both the level of paint adhesion required for precoated steel sheets and sufficient corrosion resistance has not been put into practical use at present, and rapid development has been desired.

Patent Document 1: Japanese Patent Laid-Open No. 3-100180

Patent Document 2: JP 59-116381

Patent Document 3: Japanese Patent Laid-Open No. 2001-316845

Patent Document 4: Japanese Patent Laid-Open No. 2001-164195

Patent Document 5: Japanese Patent Laid-Open No. 2002-80979

Patent Document 6: Japanese Unexamined Patent Application Publication No. 2004-204333

Disclosure of the invention

Problems to be solved by the invention

[0013] The present invention is an environment-friendly non-chromium material, but when used as a coating base for a pre-coated metal material, the resulting pre-coated metal material has a coating adhesion (coating film). Non-chromium pre-coated metal with excellent processing adhesion, corrosion resistance and coin scratch resistance, aqueous surface treatment agent with excellent storage stability, surface treatment method using the same, and excellent processing adhesion, corrosion resistance and coin scratch resistance The object is to provide a method for producing the material.

Means for solving the problem

The above issues

(1) A silane coupling agent (A), cationic urethane resin (B), Zr compound and Z or Ti compound (C), and an aqueous surface treatment agent for precoated metal materials containing fluorine-containing inorganic compound (D). (A) The mass ratio of Z (B) is 1Z50 to 20Z1, (Zr and Ζ or Ti atom) The mass ratio of Z (B) is lZl, 000 to 1Z2, and the mass ratio of fluorine atom Z (B) The water-based surface treatment agent wherein is 1Z 1,000-2Zl;

(2) Silane coupling agent (A) 5% by mass or more of primary aminoamino group, secondary amino group, tertiary amino group and quaternary ammonium group selected An aqueous surface treating agent according to the above (1), which is a silane coupling agent having a group;

(3) Silane coupling agent (A) consists of silane coupling agents each having functional groups that react with each other, and the equivalent ratio of one functional group to the other functional group is 50: 1 to 1:50 The aqueous surface treating agent according to 1) or (2).

(4) Further, at least one metal compound selected from V compound, Mo compound, W compound, Co compound, A1 compound, Zn compound, Ni compound, Mn compound, Ce compound, Nb compound, Sn compound and Mg compound The aqueous surface treating agent according to any one of (1) to (3) above, which contains (E) in the range of lZl, 000 to 1Z2 as a mass ratio of the metal atom Z (B);

(5) The water-based surface according to any one of (1) to (4) above, wherein the Zr compound and the Z or Ti compound (C) are fluoride, fluoro acid or fluoro acid salt. Processing agent;

(6) Apply the water-based surface treatment agent described in (1) to (5) above on the surface of the metal material and then dry to form a dry film of 10-: L, 000 mg / m ² A surface treatment method of a metal material, characterized by:

(7) A method for producing a pre-coated metal material, wherein the metal material surface-treated by the surface treatment method described in (6) above is further coated with an upper layer coating not containing chromium. Achieved by:

The invention's effect

[0015] The aqueous surface treatment agent for precoated metal materials of the present invention has good storage stability, and further chromium is added to the aqueous surface treatment agent and the metal material surface-treated by the surface treatment method of the present invention. Pre-coated metal material obtained by applying an upper layer coating that does not contain, even though the composite film does not contain chromium, corrosion resistance (X-cut corrosion resistance and end face corrosion resistance), work adhesion (primary bending adhesion and secondary adhesion) Excellent bending adhesion and coin scratch resistance. Therefore, the present invention has extremely high industrial value.

BEST MODE FOR CARRYING OUT THE INVENTION

[0016] The present invention is described in detail below.

The aqueous surface treatment agent for precoated metal materials of the present invention comprises a silane coupling agent (A), a cationic urethane resin (B), a Zr compound and a Z or Ti compound (C), and a fluorine-containing inorganic compound (D). It is an aqueous surface treatment agent contained as an essential component.

[0017] The silane coupling agent forms a strong chemical bond of Si—O—M via the base metal M, which is a base material with high OH activity of the silanol group generated by hydrolysis, and oxygen atoms. . This chemical bond particularly contributes to good adhesion to the base metal. In addition, the reaction with the organic functional group contained in the upper layer may contribute to improving the adhesion with the upper layer. In the case where a polar group having 0, N or the like having a strong polarity as a functional group of the silane coupling agent is introduced, the adhesion with the upper layer is further improved.

[0018] Examples of silane coupling agents applicable to the present invention include N- (2 aminoethyl) 3 -aminopropyltrimethoxysilane, N- (2 aminoethyl) 3 aminopropylmethyldimethoxysilane, N- (2 Aminoethyl) 3 Aminopropyltriethoxysilane, N— (2-Aminoethyl) 3 Aminopropylmethyl jetoxysilane, N— (2 Aminoethyl) 3 — Aminopropylmethyldimethoxysilane, γ-Amino Propyltriethoxysilane, γ-aminopropyltrimethoxysilane, ΝPhenol γ-Aminopropyltrimethoxysilane, Ν-Phenol γ-Aminopropyltriethoxysilane, γ-Methacryloxypropyltrimethoxysilane , Γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropirtrie Toxisilane, _Ύ —Methacryloxypropylmethyl _jetoxysilane , N—j8— ( N-Bulbenylaminoethyl) 3-Aminopropyltrimethoxysilane, N—j8— (N—Bulbenylaminoethyl) 3-aminopropylmethyldimethoxysilane, N—j8— (N Bulbendil) Aminoethyl) 3-Aminopropyltriethoxysilane, N-β- (ΝBulbenylaminoethyl) 3-Aminopropylmethyljetoxysilane, γ-run, グリ -glycidoxypropyltriethoxysilane, γ— Glycidoxypropylmethyldiethoxysilane, 2- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γmercaptopropylmethyljetoxysilane, methyltrimethoxysilane, dimethyl Dimethoxysilane, methyltriethoxysilane, dimethyljetoxysilane, vinyltria Setokishishiran, _I - black port propyl trimethoxysilane down, _I black port methyl dimethoxy silane, _I black port triethoxysilane, gamma black port propyl methyl jet silane, the hexamethyldisilazane, .gamma. Anirinopu port pills trimethoxysilane silane, .gamma. § two Reno propyl methyl dimethoxy silane, .gamma. Anirinopu port pills triethoxysilane, _I - § d Reno propyl methyl jet silane, Isoshianatopu port pills trimethoxysilane, isocyanatopropyltriethoxysilane, ureidopropyltriethoxysilane Silane, bis (trimethoxysilyl) aminovinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyljetoxysilane, octadecyl dimethyl [3- (trimethoxy Silyl) propyl] ammonium chloride, octadecyl dimethyl [3- (methyldimethoxysilyl) propyl] ammonium chloride, octadecyl dimethyl [3- (triethoxysilyl) propyl] ammonium chloride, octadecyldimethyl [3- Toxisilyl) propyl] ammonium chloride, γ-chloropropyl dimethyldimethoxysilane, γ mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane and the like. Of these, only one component or a combination of two or more can be used.

In many cases, the surface treatment agent is somewhat compatible with the primer applied to the upper layer, and depending on the combination, the performance may not appear as expected. Among the above coupling agents, those having an amino functional group are not easily affected by compatibility with the upper layer. Therefore, this departure The bright water-based surface treatment agent (primary treatment agent) preferably contains at least one silane coupling agent (A) having an amino group. Here, in the present invention, the amino functional group refers to a functional group selected from a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group. Examples of counter ions having a quaternary ammonium group include halogen ions such as chlorine ions, phosphate ions, nitrate ions, sulfate ions, and organic acid ions. Silane force having amino functional group The amount of the coupling agent used for the entire silane coupling agent (A) is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 20% by mass. As described above, it is even more preferable that, depending on the type of primer, the adhesion to the primer can be prevented from being adversely affected or minimized.

[0020] When two or more kinds of silane coupling agents (A) are used, the corrosion resistance can be further improved by using silane coupling agents each having a functional group that reacts with each other to form a new bond. it can. For example, a silane coupling agent having a primary amino group or a secondary amino group and a functional group capable of reacting with the amino group, for example, an epoxy group bonded to an adjacent carbon atom (glycidyl group, 3, 4 epoxy cyclohexane). It is preferable to use in combination with a silane coupling agent having a hexyl group or the like, and a silane coupling agent having or capable of generating a hydroxyl group (for example, having an epoxy group bonded to an adjacent carbon atom). And a silane coupling agent having an isocyanato group is preferably used in combination. The usage ratio of the silane coupling agents each having a functional group that reacts with each other is such that the amount of the functional groups that react with each other does not need to be sufficient. The equivalent ratio between the primary amino group and the other functional group (for example, an epoxy group bonded to an adjacent carbon atom) is preferably in the range of 50: 1 to 1:50 30: 1 to 1 : More preferably, the range is 30.

[0021] The cationic urethane resin (B) used in the present invention is water-soluble or water-based emulsion type. The dissolution or dispersion of the cationic urethane resin (B) in water may be achieved on the basis of self-solubility or self-dispersibility, and cationic surfactants (eg tetraalkyl ammonium salts) And may be dispersed in the presence of Z or a non-ionic surfactant (such as alkyl ether). [0022] The cationic urethane resin (B) imparts flexibility to the base film and contributes to the improvement of coating adhesion, and thus effectively acts to improve bending adhesion and coin scratch resistance.

The cationic urethane resin (B) in the surface treating agent composition of the present invention is at least one cationic functional selected from the primary forces of primary to tertiary amino groups and quaternary ammonium salts. As long as it has a group, the polyol component and the polyisocyanate component, which are constituent monomer components, and the polymerization method are not particularly limited. For example, aliphatic, cycloaliphatic or aromatic diisocyanates such as hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI) and polyester Cationic urethane resin by polymerizing polyols such as polyols, polyether polyols, polycarbonate polyols, etc., in which amino groups are introduced into the chain by a known method, and partially quaternizing the amine with alkyl sulfuric acid or the like. (B) can be obtained. The substituent on nitrogen in the cationic functional group includes, but is not limited to, a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkyl group, and a hydroxyalkyl group. The cationic urethane resin (B) can be used alone or in combination of two or more.

In the above, examples of the aliphatic, alicyclic or aromatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, hydrogenated xylylene diisocyanate. Cyanate, 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 3, 3 , -Dimethoxy 4,4, -biphenol-diisocyanate, 1,5 naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate 4,4'-dimethanemethane diisocyanate, 2,4'-dimethanemethane diisocyanate, phenolic diisocyanate Powers such as xylylene diisocyanate, tetramethylxylylene diisocyanate, etc. Among these, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, hydrogenated xylylene diisocyanate 1,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylenemethane When using aliphatic or alicyclic polyisocyanate compounds such as diisocyanate, 2,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, etc., chemical resistance, anticorrosion, etc. It is preferable because a film excellent in weather resistance is obtained.

In the above, examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2 propylene glycol, 1,3 propylene glycol, neopentyl glycol, 1,2 butylene glycol, and 1,3 butylene glycol. 1,4-butylene glycol, hexamethylene glycol, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, 1,2 propanediol, 1,3 propanediol, 2-methyl-1,3 propanediol, 2 butyl 2-ethyl-1,3-prononediol, 1,4 butanediol, neopentylglycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2- Methyl-2,4 pentanediol, 2,4 di 1,5-pentanediol, 1,6 hexanediol, 1,7 heptanediol, 3,5 heptanediol, 1,8 octanediol, 2-methyl-1,8 octanediol, 1,9-nonanediol, 1,10 Trivalent diol compounds such as decane diol, trimethylol ethane, trimethylol propane, hexitols, pentitols, glycerol, diglycerol, polyglycerol, pentaerythritol, dipentaerythritol, tetramethylol propane, etc. Examples include the above aliphatic or alicyclic alcohol compounds.

In the above, examples of the polyether polyol include ethylene oxide adducts such as ethylene glycol, polyethylene glycol, and triethylene glycol, propylene oxide adducts such as propylene glycol, dipropylene glycol, and tripropylene glycol. Examples of the polyol include ethylene oxide and Z- or propylene oxide-attached carbohydrate, polytetramethylene glycol, and the like.

[0026] In the above, the polyester polyol includes, for example, the above polyol and the like, an ester-forming derivative such as a polycarboxylic acid having an amount less than the stoichiometric amount or its ester, anhydride, halide, and the like, and Direct esterification reaction and Z or transesterification with Z or ratatones or hydroxycarboxylic acid compounds obtained by hydrolyzing them Examples include polyester polyols obtained by the reaction. Examples of the polyvalent carboxylic acid include oxalic acid, malonic acid, succinic acid, dartaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2 —Methyl adipic acid, 3 methyl adipic acid, 3-methylpentanedioic acid, 2 methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, dimer acid, hydrogenated dimer monoacid, etc. Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid; trimellitic acid, trimesic acid, castor oil fatty acid 3 Examples include tricarboxylic acids such as trimers, and polycarboxylic acids such as tetracarboxylic acids such as pyromellitic acid. Examples of the conductor include acid anhydrides of these polyvalent carboxylic acids; halides of the polyvalent carboxylic acids such as chlorides and bromides; methyl esters of the polyvalent carboxylic acids, ethyl esterol, propinoreesterol, isopropinoreesterol, And lower aliphatic esters such as butinoreesterol, isobutinol ester and amyl ester. Examples of the latatones include latones such as y-one-strength prolatatone, δ-one-strength pro-latatone, ε-one-strength pro-latatone, γ-norralatataton, and δ-valerolatatone.

[0027] As the cationic urethane resin (wax), a surfactant as a solubilizer or emulsifier should not be used because it may adversely affect adhesion to metal materials and water resistance!ヽ Soap-free or those with reduced usage are preferred.

[0028] The weight average molecular weight of the cationic urethane resin (榭) is preferably 1,000 to 1,000,000, more preferably 2,000-500,000! / ヽ. When the molecular weight force is less than ^ 1,000, the film-forming property is insufficient, while when it exceeds 1,000,000, the stability of the aqueous surface treatment agent tends to decrease.

[0029] In addition, as long as it is compatible with the cationic urethane resin (resin), other resin such as acrylic resin, ester resin, amino resin, epoxy resin, phenol resin can be used. You may mix and use. In addition, an organic solvent may be used to improve the film forming property of the cationic urethane resin (soot) and form a more uniform and smooth coating film.

[0030] The blending amount of the silane coupling agent (Α) is required to be 1Ζ50 to 20Ζ1 as a mass ratio (Α) Ζ (Β) with respect to the cationic urethane resin (Β). : L0Z1 More preferably, it is more preferably 1Z10 to 5Z1. If the amount of the silane coupling agent (A) is less than 1Z50, the coating hardness will decrease, making it difficult to obtain sufficient coin scratch resistance.If it is more than 20Z1, the adhesion to the underlying metal will decrease. As a result, processing adhesion deteriorates.

[0031] The Zr compound and the Z or Ti compound (C) used in the present invention impart or improve the corrosion resistance of the metal material. Zr compounds and Z or Ti compounds (C) include Zr or Ti carbonate, oxide, nitrate, sulfate, phosphate, fluoride, fluoro acid (salt), organic acid salt Organic complex compounds and the like can be used, and among them, a fluoride also serving as a fluorine-containing inorganic compound (D) described later, and a fluoro acid (salt) are preferable. Specifically, basic zirconium carbonate, zirconium oxide carbonate, zirconium carbonate ammonium, zirconium carbonate ammonium (NH) [Zr (CO) (OH)], zirconium oxide (IV) (zirconia) , Titanium oxide (IV)

4 2 3 2 2

(Titer), zirconium nitrate, zirconium nitrate ZrO (NO), titanium nitrate, zirconium sulfate

3 2

Conium (IV), zirconyl sulfate, titanium (III) sulfate, titanium (IV) sulfate, titanyl sulfate Ti OSO, zirconium oxyphosphate, zirconium pyrophosphate, zirconium dihydrogen phosphate

Four

, Zirconium fluoride, titanium fluoride (チタン), titanium fluoride (IV), hexafluorozirco-humic acid (H ZrF), hexafluorozirconate ammonium [(NH) ZrF )],

2 6 4 2 6 Hexafluorotitanate (H TiF), Hexafluorotitanate ammonium [(NH) T

2 6 4 2 iF)], zirconium acetate, titanium laurate, zirconium acetyl cetate Zr (OC

6

(= CH) CH COCH)) Diisopropoxytitanium bisacetylacetone (C H O

2 2 3 4, 5 7

) Ti [OCH (CH)], Titanium Acetylacetonate Ti (OC (= CH) CH COC

2 2 3 2 2 2 2

H))) and the like. These may be anhydrides or hydrates if present

3 3

Good. These compounds may be used alone or in combination of two or more.

[0032] The blending amount of the Zr compound and the Z or Ti compound (C) is 1/1 / mass ratio of (Zr and Z or Ti atom) Z (B) to the cationic urethane resin (B). It is necessary to be 1,000 to 1Z2, and it is preferably 1Z500 to 1Z4, more preferably 1Z250 to 1Z10. If the amount of Zr compound and Z or Ti compound (C) is less than 1Z1,000, the corrosion resistance is insufficient, and if more than 1Z2, the work adhesion or liquid stability decreases. Become a trend. When the Zr compound and Ti compound are used in combination, the above compounding amount is the total compounding amount.

[0033] The fluorine-containing inorganic compound (D) contained in the aqueous surface treatment agent of the present invention releases free fluorine ions or complex fluorine ions into the liquid and serves as an etching agent for the substrate. The fluorine-containing inorganic compound (D) is not particularly limited, and examples of those that release free fluorine ions include hydrofluoric acid, ammonium fluoride, sodium fluoride, and the like. Tetrafluoro-borate, hexafluorosilicate, zinc hexafluorosilicate, manganese hexafluorosilicate, magnesium hexafluorosilicate, nickel hexafluorosilicate, hexafluorozirconate, hexafluoro A titanic acid etc. can be mentioned. One of the above compounds may be used alone, or two or more may be used in combination.

[0034] The compounding amount of the fluorine-containing inorganic compound (D) must be lZl, 000 to 2Zl as a mass ratio of the fluorine atom Z (B) to the cationic urethane resin (B). 1/50 0 to lZl is preferred and 1Z250 to 1Z2 is more preferred. When the blending amount of the fluorine-containing inorganic compound (D) is less than 1Z1,000, the work adhesion becomes insufficient, and when it exceeds 2Z1, the stability of the aqueous surface treatment agent decreases.

[0035] The aqueous surface treatment agent of the present invention further includes, as optional components, V compound, Mo compound, W compound, Co compound, Ni compound, A1 compound, Zn compound, Mn compound, Ce compound, Nb compound, Sn At least one metal compound (E) selected from a compound and an Mg compound can be blended. These metal compounds (E) have the effect of improving the corrosion resistance especially at the end face portions. Examples of the metal compound (E) include carbonates, oxides, hydroxides, nitrates, sulfates, phosphates, fluorides, chlorides, fluoroacids (salts), oxygen acids (salts), and organic acids of the above metals. Examples thereof include salts and organic complex compounds.

[0036] Specific examples of the V compound, Mo compound, W compound, Co compound, Ni compound, A1 compound and Zn compound include pentanoic acid vanadium, metavanadate HVO, metavanadate.

Three

Monium, sodium metavanadate, vanadium trichloride VOC1, vanadium trioxide

Three

Um V O, vanadium dioxide VO, vanadium oxysulfate VOSO, vanadium oxide

2 3 2 4

Ciacetylacetonate VO (OC (= CH) CH COCH)), vanadium acetylacetate Tonate V (OC (= CH) CH COCH)), vanadium trichloride VC1; lymphadromib

2 2 3 3 3

Deacid H [PV Mo O] · ηΗ 0 (6 <x <12, n <30), molybdenum oxide, molybdenum

15- X 12- 40 2

De-acid H MoO, ammonium molybdate, ammonium paramolybdate, molybdenum

twenty four

Sodium denoate and molybdophosphoric acid compounds (eg, ammonium molybdophosphate (NH) [

4 3

PO Mo O] · 3Η 0, sodium molybdate Na [PO · 12ΜοΟ] · ηΗ Η etc.);

4 12 36 2 3 4 3 2 Tungstic acid H [H W Ο], ammonium metatungstate (ΝΗ) [H W Ο

6 2 12 40 4 6 2 12

], Sodium metatungstate, paratungstic acid H [W Ο Η], paratanda

40 10 12 46 10

Ammonium stearate, sodium paratungstate; cobalt chloride, black-open pentaamminecobalt chloride [CoCl (NH)] C1, hexamminecobalt chloride [Co (NH)]

3 5 3 6

C1, cobalt chromate, cobalt sulfate, ammonium cobalt sulfate, cobalt nitrate, oxidation

2

Cobalt dialuminum CoO 'Al O, cobalt hydroxide, cobalt phosphate, etc .;

twenty three

, Nickel sulfate, nickel carbonate, nickel acetylacetonate Ni (OC (= CH) C

2

H COCH)), nickel chloride, hexammine nickel chloride [Ni (NH)] C1, acid

2 3 3 3 6 2 Nickel fluoride, nickel hydroxide; aluminum nitrate, aluminum sulfate, potassium aluminum sulfate, sodium aluminum sulfate, ammonium aluminum sulfate, aluminum phosphate, aluminum carbonate, aluminum oxide, Aluminum hydroxide, aluminum iodide; zinc sulfate, zinc carbonate, zinc chloride, zinc iodide, zinc acetylylacetonate Zn (OC (= CH) CHCOCH)), zinc dihydrogen phosphate, etc. .

2 2 3 2

Specific examples of Mn compounds, Ce compounds, Nb compounds, Sn compounds, and Mg compounds include HMnO permanganate, potassium permanganate, sodium permanganate, and dihydrogen phosphate.

Four

Manganese Mn (H PO), manganese nitrate Mn (NO), manganese sulfate (11), (III) or

2 4 2 3 2

(IV), manganese fluoride (Π) or (III), manganese carbonate, manganese acetate (Π) or (III), ammonium manganese sulfate, manganese acetyl cetate Mn (OC (= CH) CH

twenty two

COCH)), Manganese iodide, Manganese oxide, Manganese hydroxide; Cerium oxide, Ce acetate

3 3

Ce (CH 2 CO 3), cerium nitrate (IV) or (IV), cerium nitrate ammonium, sulfur

3 2 3

Cerium acid, cerium chloride, niobium pentoxide (Nb 2 O 3), sodium niobate (NaNbO 2)

2 5 3

, Niobium fluoride (NbF), ammonium hexafluoroniobate (NH4) NbF;

5 6 (IV), sodium stannate (Na SnO), tin chloride (Π), tin chloride (IV), tin nitrate (Π),

twenty three Tin nitrate (IV), ammonium hexafluorosuccinate (NH4) NbF; magnesium nitrate

6

, Magnesium sulfate, magnesium carbonate, magnesium hydroxide, magnesium fluoride, ammonium magnesium phosphate, magnesium hydrogen phosphate, magnesium oxide and the like.

[0038] The compounding amount of the metal compound (E) is preferably lZl, 000 to lZ2 as a mass ratio of the metal atom Z (B) to the cationic urethane resin (B). 1Z4 is more preferable 1Z50 to 1Z8 is even more preferable. If the compounding amount of the metal compound (E) is less than 1Z1,000, the effect of improving the corrosion resistance is not exhibited, while if it exceeds 1Z2, the work adhesion tends to be lowered. The metal compound (E) may be used alone or in combination of two or more. When two or more types are used in combination, the above blending amount is the total blending amount.

[0039] In the aqueous surface treatment agent of the present invention, as an optional component, a surfactant called a wettability improver for forming a uniform film on the coated surface; a thickener; for improving weldability In order to improve the design properties of the conductive material, coloring pigments and the like can be blended within a range that does not impair the liquid stability and film performance of the aqueous surface treatment agent.

[0040] The medium used in the aqueous surface treatment agent of the present invention is usually water, but a small amount (for example, 10% by volume or less of the entire aqueous medium) of alcohol, ketone, or mouth-solve is used for the purpose of improving the drying property of the film. Use a water-soluble organic solvent.

[0041] The pH of the aqueous surface treatment agent of the present invention is not particularly limited, but is preferably in the range of 3-12, more preferably in the range of 4-8. When the pH is less than 3, the etching becomes excessive and the function as a surface treatment agent cannot be fully exerted, and the liquid stability tends to be lowered. When the pH is higher than 12, especially the dissolution rate of amphoteric metal zinc and the like increases, and the storage stability of the silane coupling agent tends to be adversely affected. When pH adjustment is necessary, alkaline components such as ammonia, dimethylamine, and triethylamine, or acidic components such as acetic acid and phosphoric acid can be added.

[0042] The lower limit of the total solid content concentration of the aqueous surface treating agent of the present invention is not particularly limited as long as the effect of the present invention can be achieved, but the upper limit is limited from the viewpoint of liquid stability. The total solid concentration of the metal surface treatment agent of the present invention is preferably adjusted to a range of 0.1 to 40% by mass, more preferably adjusted to a range of 1 to 30% by mass, and 5 to 25% by mass. It is even more preferable to adjust to the range of%.

[0043] The aqueous surface treatment agent of the present invention includes a silane coupling agent (A), a cationic raw urethane resin (B), a Zr compound and a Z or Ti compound (C), a fluorine-containing inorganic compound. It can be produced by adding (D) and, if necessary, the metal compound (E) and optionally other optional components to water as a dispersion medium and stirring. There is no particular limitation on the order of addition of each component.

Next, the surface treatment method of the present invention will be described.

Examples of the metal material to which the water-based surface treatment agent of the present invention is applied include cold-rolled steel sheets, hot-rolled steel sheets, hot-dip galvanized steel sheets, electrogalvanized steel sheets, molten alloyed zinc-plated steel sheets, aluminum-plated steel sheets, aluminum zinc Commonly known metal materials such as alloyed steel plates, stainless steel plates, aluminum plates, copper plates, titanium plates, magnesium plates and the like are mentioned, and particularly suitable metal materials are zinc-containing steel plates.

[0045] The pretreatment step prior to the treatment with the water-based surface treatment agent of the present invention is not particularly limited, but usually an alkali is used to remove oil and dirt adhering to the metal material to be treated before the main treatment. Wash with a degreasing agent or acidic degreasing agent, or wash with hot water or solvent, and then adjust the surface with acid or alkali as necessary. In cleaning the surface of the metal material, it is preferable to wash with water after cleaning so that the cleaning agent does not remain on the surface of the metal material.

[0046] The treatment with the aqueous surface treatment agent of the present invention is performed by applying the aqueous surface treatment agent and then drying. There are no particular restrictions on the application method. For example, usual application methods such as roll coating, curtain flow coating, air spray, airless spray, dipping, bar coating, and brush coating can be employed. There is no particular limitation on the temperature of the processing solution, but since the solvent of this processing agent is mainly water, the processing solution temperature is preferably 0 to 60 ° C, preferably 5 to 40 ° C. More preferred.

[0047] Regarding the drying step after the application of the aqueous surface treating agent of the present invention, it is not necessary to accelerate the curing of the cationic urea resin (B), and it is not always necessary to remove the adhering water. However, air drying or physical removal such as air blowing may be used. However, heating and drying are required to accelerate the curing of the cationic urethane resin (B) or to enhance the coating effect of soft wrinkles. . In this case, the temperature is preferably 50 to 250 ° C, more preferably 60 to 220 ° C.

[0048] The amount of the base film formed is 10 to L, OOOmgZm ² as dry film mass, more preferably ^{20 to} 500 mg / m ² force, and more preferably 30 to 250 mg / m ² force ^! / ヽ. Dry film mass is not sufficient corrosion resistance is obtained when less than lOmgZm ^{^2,} 1, OOOmg Zm ² by weight, the mosquito卩工adhesion property is lowered, it becomes disadvantageous in terms of cost.

[0049] The base film formed as described above is usually used as a base film for a pre-coated metal material. However, since it has excellent adhesiveness, it imparts fingerprint resistance, lubricity, and the like. It can also be used as an undercoat for high-performance coatings having one to three coating layers on top.

[0050] Next, a method for producing the precoated metal material of the present invention will be described. The precoat metal material is produced by further forming an upper film layer on the metal film surface on the base film formed as described above using the aqueous surface treatment agent of the present invention. The top coating layer can be formed by applying a non-chromate primer on the base coating and then drying, then applying a top coat, or applying a top coat directly without using a primer, or using a laminate film. It can be performed using a coating method generally used for pre-coated steel sheets such as affixing method.

[0051] As the non-chromate primer, any primer can be used as long as it is a primer that does not contain a chromate anti-mold pigment. The non-chromate primer usually contains a resin and, if necessary, a colored pigment or an antifungal pigment. The resin can be in any form such as aqueous, solvent-based, or powder-based. Generally, the types of resin are known, such as polyacrylic resin, polyolefin resin, polyurethane resin, epoxy These can be used singly or in combination, such as a polyester resin, a polyester resin, a polypropylene resin, a melamine resin, and a fluorine resin.

[0052] Examples of the color pigment include inorganic pigments such as titanium oxide, zinc oxide, zirconium oxide, calcium carbonate, barium sulfate, alumina, kaolin clay, carbon black, iron oxide, and the like. Known color pigments such as machine pigments can be used. Commonly known anti-fouling pigments include, for example, phosphoric acid-based anti-fouling pigments such as zinc phosphate, iron phosphate, and aluminum phosphate, and molybdate-based defenses such as calcium molybdate, aluminum molybdate, and barium molybdate. Pigments, vanadium-type anti-bacterial pigments such as acid vanadium, and the like can be used. In addition, finely divided silica such as water-dispersible silica and fumed silica can be used as appropriate. Further, an antifoaming agent, a dispersion aid, a diluent for lowering the viscosity of the paint, and the like can be appropriately used.

[0053] The method of applying the non-chromate is not particularly limited, and a commonly used dipping method, spray method, roll coat method, air spray method, airless spray method, or the like can be used. The coating film thickness of the primer is preferably 1 to 30 m as a dry film thickness, more preferably 2 to 20 μm. If the thickness is less than 1 μm, the corrosion resistance decreases, and if it exceeds 30 m, the adhesion during processing tends to decrease. The baking and drying conditions of the non-chromate primer are not particularly limited, for example, 130 to 250 ° C., and the time can be 10 seconds to 5 minutes.

[0054] The topcoat is not particularly limited, and any ordinary topcoat for coating can be used. That is, the top coat contains rosin and, if necessary, a colored pigment, an antifungal pigment, and the like. As the resin, coloring pigment and anti-bacterial pigment, those similar to those used in the non-chromate primer can be used, and other optional components which can be used in the non-chromate primer can also be used. The top coat application method and baking drying conditions may be the same as those for the non-chromate primer. The coating thickness of the top coat is preferably 3 to 50 m, more preferably 5 to 40 m as the dry film thickness. If it is less than 3 μm, the corrosion resistance decreases, and if it exceeds 50 m, the adhesion tends to decrease, and the cost is disadvantageous.

Example

[0055] The present invention will be specifically described below with reference to examples and comparative examples of the present invention. However, the present invention is not limited to these examples.

[0056] 1. Preparation of test plate

1.1 Sample material • Electrogalvanized steel sheet (hereinafter referred to as EG)

Plate thickness 0.6mm, plating coverage 20gZm ² per side (mesh on both sides)

• Hot-dip galvanized steel sheet (hereinafter referred to as GI)

Thickness 0.6mm, Zinc adhesion 50gZm ² per side

• Aluminum zinc alloy plated steel sheet (Symbol: GL)

Plate thickness 0.6mm, plating coverage 50gZm ² per side (with double sided)

[0057] 1.2 Pre-processing

CL-N364S (manufactured by Nihon Parkerizing Co., Ltd.), an alkaline degreasing agent, is made into an aqueous solution with a concentration of 20gZL and a temperature of 60 ° C. After EG or GL material is immersed in this for 10 seconds and washed with pure water Dried. For GI materials, after degreasing in the same manner as above using CL-N364S, it was immersed in an aqueous solution at a temperature of 50 ° C that was built at 100 g / L using LN-4015 (Nihon Parkerizing Co., Ltd.). and it was subjected to the original surface conditioning conditions Ni deposition amount is 5mgZm ^2.

[0058] 1.3 Surface treatment

Non-chromate aqueous surface treatment

Apply the aqueous surface treatment agent with the composition shown in Table 1 on the surface (one side) of the pre-treated sample using a roll coater so that the dry film amount is lOOmgZm ² and arrive in a hot air drying oven. The plate temperature was dried to 80 ° C. In Table 1, Nos. 1 to 26 are aqueous surface treatment agents of the present invention, and Nos. 27 to 40 are aqueous surface treatment agents outside the scope of the present invention. • Coating chromate treatment

Apply ZM-1300AN (manufactured by Nihon Parkerizing Co., Ltd.) as an applied chromate agent to the surface (one side) of the pretreated sample using a roll coater so that the Cr adhesion amount is 0 mg / m ^2. Then, it was dried in a hot air drying oven so that the ultimate plate temperature was 80 ° C.

[0059] 1.4 Application of undercoat and topcoat

1. Primer and top coat were applied to the treated surface of each surface-treated plate prepared in 3 by the following two combinations.

<Upper layer F1>: After applying a commercially available primer coating (Dai Nippon Paint Co., Ltd., V Knit # 200) (film thickness 5.5 m), baking at 200 ° C, then further on top of the baking surface Coat paint (Dai Nippon Paint Co., Ltd., V Knit # 500) was applied (after film thickness, baked at 220 ° C) A test plate was prepared by soldering.

Upper layer F2>: After applying a commercially available primer paint (Nippon Paint Co., Ltd., Flexcoat 600) (film thickness 5.5 m), baking at 200 ° C, then topcoat paint ( After applying Nippon Paint Co., Ltd. (Flexcoat 5030) (film thickness 7 m), it was baked at 220 ° C to prepare a test plate.

[0060] 2. Evaluation test

2.1 Corrosion resistance

The coating film of each test plate was scratched to reach the metal substrate with a cutter, and the salt spray test specified in JIS-Z2371 was conducted for 480 hours. Judgment criteria were measured for the swollen width (maximum value on one side) of the cut part force. The end face corrosion resistance was measured by measuring the swollen width (maximum value) of the coating film from the end face.

: Less than 2mm

○: 2mm or more and less than 5mm

Δ: 5 mm or more and less than 10 mm

X: 10mm or more

©: Less than 4mm

○: 4mm or more, less than 8mm

△: 8mm or more and less than 12mm

X: 12mm or more

[0061] 2.2 Bending adhesion test

2. 2. 1 Primary bending adhesion test (paint primary adhesion)

In accordance with the test method of JIS-G3312, each test plate was subjected to a 2T bending test with two inner spacing plates at 20 ° C, and the peeled state of the coating after tape peeling was observed with the naked eye. The coating adhesion was evaluated according to the above criteria.

◎: No peeling ○: Peeling area less than 10%

Mouth: peeling area 10% or more, less than 50%

Δ: peeling area 50% or more and less than 80%

X: peeling area 80% or more

[0062] 2. 2. 2 Secondary bending adhesion (paint secondary adhesion)

The test plate was immersed in boiling water for 2 hours and then allowed to stand for one day, and then the same test as the primary bending adhesion test was performed. Judgment criteria are as follows.

◎: No peeling

○: Peeling area less than 10%

Mouth: peeling area 10% or more, less than 50%

Δ: peeling area 50% or more and less than 80%

X: peeling area 80% or more

[0063] 2.3 Coin scratch resistance

A 10-yen coin was installed at an angle of 45 ° to each test plate, the coating film was rubbed at a constant speed with a load of 3 kg, and the degree of damage to the coating film was observed with the naked eye. Sexuality was evaluated.

◎: 0% substrate exposure (primer only exposed)

〇: Substrate exposure is less than 10%

Mouth: The substrate exposure is 10% or more and less than 50%

△: Base exposure is 50% or more and less than 80%

X: The substrate exposure is 80% or more

[0064] 2.4 Storage stability of aqueous surface treatment agent

After storage of the water-based surface treatment agent in a thermostat at 40 ° C for 3 months, the state of gely gel precipitation was observed with the naked eye, and the storage stability was evaluated according to the following criteria.

○: No change Δ: Thickening

X: Gelly or precipitated

[0065] 3. Evaluation results

Table 2 shows the evaluation results of the above test. Examples 1-28 in Table 2 are metal materials of any one of EG, GI, and GL, which were coated with the aqueous surface treatment agent of the present invention (Nos. 1-27 in Table 1) and dried to form a film. However, the corrosion resistance (X cut part and end face corrosion resistance), primary bending adhesion, secondary bending adhesion and coin scratch resistance are all good regardless of the metal material, and water-based The storage stability of the surface treatment agent was also good, and almost the same performance as the chromate treatment of Comparative Examples 16 to 18 was shown.

On the other hand, in Comparative Examples 1 to 15 in Table 2 using No. 28 to 41 aqueous surface treatment agents in Table 1 that are outside the scope of the present invention, corrosion resistance (X-cut portion and end surface corrosion resistance), primary bending adhesion Performance, secondary bending adhesion and coin scratch resistance, and storage stability of the water-based surface treatment agent were inferior, and the performance was not balanced.

[0066] Further, for comparison between Examples, even though Examples 1 to 19 using an amino group-containing silane coupling agent used silane coupling agents having a glycidyl group or a mercapto group V, Compared to Examples 20 to 28, the primary coating adhesion was generally excellent, and even when a silane coupling agent having an amino group was used, the silane coupling agent / Depending on the ratio of urethane resin, the primary coating adhesion may be the same as when a silane coupling agent having a glycidyl group or a mercapto group is used. Therefore, when a silane coupling agent having an amino functional group is used, it can be said that at least the primary coating adhesion is hardly influenced by the compatibility with the upper layer. Further, Example 13 in which an amino group-containing silane coupling agent and a glycidyl group-containing silane coupling agent are used in combination has superior end face corrosion resistance compared to Example 5 using an amino group-containing silane coupling agent. Te!

[0067] [Table 1] Zr compound Fluorine-containing metal compound

And inorganic compounds Silane force Z or

(E)

T "匕" thing (C) (D) Pulling agent Urethane (A) / (B)

Zr or metal Fluorine (A) Resin (B)

Type Ti atom Type atom Type atom / (B) / (B) / (B)

A1 B1 10/1 C1 2/5 E1 1/50 C1 1/2

A1 B1 2/1 C3 1/20 E1 1/50 C3 1/5

A1 B1 2/1 C1 1/20--C1 1/20

A1 B1 1/1 C1.C3 1/10--C1.C3 1/3

A1 B1 1/1 C2 1/10 E3 1/200 C2, D1 1/5

A1 B1 1/1 C1 1/10 E4 1/50 C1.C3 1/10

A1 B1 1/1 C1 1/10 E5 1/50 C1.C3 1/10

A1 B1 1/1 C1 1/10 E6 1/50 C1.C3 1/10

A1 B1 1/1 C1 1/10 E7 1/50 C1.C3 1/10

A1 B1 1/2 C1 1/5 E3 1/50 Cl'Dl 2/5

A1 B1 1/5 C3 1/10--C3, D1 2/5

A1.A3 B1 1/1 C1.C3 1/10--C1.C3 1/3

A1 B2 1/20 C3 1/25 ― ― C3 1/10

A1 B2 1/30 C4 1/10 E1 2/5 C4, D1 1/1

A2 B2 2/1 C1 1/10 E2 1/25 C1.D2 1/5

A2 B2 2/1 C3 1/10 E2 1/25 C3 1/3

A2 B3 1/5 C3 1/10--C3, D2 1/2

A2 B3 1/20 C4 1/10--C4 1/4

A3 B3 2/1 C1 2/5--C1 1/2

A3 B1 2/1 C1 1/30 E1 1/50 C1 1/30

A3 B1 1/5 C3 1/10 E1 1/25 C3.D2 2/5

A3 B2 1/5 C2 1/20 E1 1/10 C2 1/10

A3 B2 1/20 C3 1/10--C3.D3 2/1

A3 B2 1/20 C5 1/200 E1 1/10 D1 1/200

A3 B3 1/30 C1 1/10--C1 1/10

A4 B3 1/5 C4 1/5 ― ― C4, D3 2/5

A4 B3 1/20 C6 1/10--D3 1/1

A1 ― ― ― ― ― ― ― ―

A1 B1 30/1 C1 1/25 E1 1/50 C1 1/25

A1 B1 1/200 C1 1/25 E1 1/50 C1 1/25

A1 B1 2/1 ― ― ― ― ― ―

A1 B1 2/1 ― ― ― ― One 1/25

A1 B1 2/1 C1 3/5--C1 3/1

A1 B1 2/1 C3 1/2 E1 1/1 C3.D1 1/1

A1 B4 1/5 C5 1/10----

A1 B1 2/1 C1 2/5--C1 1/2

A1 ― ― C1 2/5 ― ― C1 1/2

A1 ― ― C1 2/5 ― ― C1.D1 3/5

A1 ― ― ― One ― One D1 1/10

A1 B1 1/5 ― ― ― ― D1 1/1

A1 B5 1/5 C6 1/3 ― ― ― ― (A) / (B), Zr or Ti atom Z (B), metal atom Z (B) and fluorine source Each child Z (B) is in mass ratio. The equivalent ratio of the A1 amino group of No. 12 to the glycidyl group of A3 was 5: 1. The C1: C3 (mass ratio) of No. 4 and 12 was 2: 1.

[Table 2]

Aqueous surface Test resistance Paint; Wear resistance Coin resistance

Paint:

Storage stability Treatment material X-cut part End face Primary Secondary Scratch Example 1 No. 1 GI Fl ◎ ○ ○ ◎ ◎ ○ Example 2 No. 2 GI Fl ◎ ○ ○ ◎ ◎ Example 3 No. 2 GI F2 ○ ○ ○ ◎ ◎ Example 4 No. 3 GI Fl 〇〇〇 © ◎ 〇 Example 5 No. 4 GI Fl © 〇 © ◎ ◎ 〇 Example 6 No. 5 GL Fl 〇〇 © ◎ ◎ 〇 Example 7 No. 6 EG Fl © 〇 ◎ ◎ ◎ Example 8 No. 7 GI Fl © 〇 © ◎ ◎ 〇 Example 9 No. 8 GI Fl ◎ 〇 ◎ ◎ ◎ Ο Example 10 No. 9 GI Fl ◎ ○ ◎ ◎ ◎ ○ Example 11 No. 10 GI Fl © ○ ◎ ◎ © ○ Example 12 No. 11 GI Fl ○ ○ ◎ ◎ ◎ ◎ Example 13 No. 12 GI Fl ◎ ◎ ◎ ◎ ◎ 〇 Example 14 No. 13 GI Fl ◎ o ◎ ◎ ◎ ○ Example 15 No. 14 GI Fl ® ○ ○ ◎ ◎ ○ Example 16 No. 15 GI Fl ◎ ○ ○ ◎ ◎ ○ Example 17 No. 16 GI Fl ○ ○ ◎ ◎ © 〇 Example 18 No. 17 GI Fl ◎ 〇 ◎ ◎ ◎ 〇 Example 19 No. 18 GI Fl ◎ 〇〇 © © Ο Example 20 No. 19 GI Fl ○ ○ ○ ◎ ◎ ○ Example 21 No. 20 GI F2 ○ o ○ ○ ◎ ○ Example 22 No. 21 GI Fl ◎ ○ ○ © ◎ ○ Example 23 23 No. 22 GI Fl ○ ○ ◎ ◎ ○ Example 24 No. 23 G and Fl ◎ ○ ○ ◎ © ○ Example 25 No. 24 GI Fl ◎ © ○ © ◎ ○ Example 26 No. 25 GI Fl ○ ○ ○ ◎ ◎ ◎ Example 27 No. 26 EG Fl ◎ ○ ○ © ◎ ○ Example 28 No. 27 GI Fl © ○ ○ ◎ ◎ ○ Comparative Example 1 No. 28 GI Fl ○ Δ XXX ○ Comparative Example 2 No. 29 GI Fl ○ ○ Δ Δ 〇〇 Comparative example 3 No. 30 GI Fl 〇〇 □ □ Δ ο Comparative example 4 No. 31 GI Fl o Δ □ Δ □ 〇 Comparative example 5 No. 32 GI Fl 〇 Δ □ □ □ 〇 Comparative example 6 No. 33 GI Fl ◎ ○ ○ Ο ○ Δ Comparative Example 7 No. 34 GI Fl ◎ ◎ Δ □ ◎ X Comparative Example 8 No. 35 GI Fl ◎ ○ □ □ □ ○ Comparative Example 9 No. 35 EG Fl ◎ ○ Δ Δ Δ 〇 Comparative Example 10 No. 36 GI Fl ◎ ○ □ □ □ ○ Comparative Example 11 No. 37 GI Fl ○ ○ Δ Δ Δ, ○ Comparative Example 12 No. 38 GI Fl ○ ○ Δ Δ Δ ○ Comparative Example 13 No. 39 GI Fl ○ Δ Δ Δ X ○ Comparative Example 14 No. 40 GI Fl ○ Δ □ □ ○ ○ Comparative Example 15 No. 41 GI Fl ○ ○ Δ □ ○ ○ Comparative Example 16 Chromate EG Fl ◎ ◎ 〇 ◎ ◎ 〇 Comparative Example 17 Chromate GI Fl ◎ ◎ 〇 ◎ 〇 Comparative Example 18 Chromate GL Fl ◎ ◎ Ο ◎ ◎ 〇 The contents of each component in 1 are as follows. Silane coupling agent (A)

A1: γ-Aminopropyltriethoxysilane

Α2: Ν- (2 aminoethyl) 3 aminopropyltrimethoxysilane

Α4: γ-Mercaptopropyltrimethoxysilane

[0071] Cationic Urethane Resin (Amber)

B1: Cationic polyether urethane urethane (water dispersion)

Β2: Cationic polyester urethane resin (water dispersion)

Β3: Cationic polycarbonate-based urethane resin (water dispersion)

Β4: Superflex 410 (A-on polycarbonate polyurethane dispersion, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Β5: Primal Κ-3 (Polyacrylic resin, manufactured by ROHM AND HAAS)

[0072] Cationic urethane resin Bl, B2 and B3 were prepared by the following method.

Cationic polyether urethane resin (water dispersion) B1

Polyether polyol (synthesis components: polytetramethylene glycol and ethylene glycol, molecular weight 1500) 150 parts by mass, 6 parts by mass of trimethylolpropane, 24 parts by mass of N-methyl N, N diethanolamine, isophorone diisocyanate 94 Mass parts and 135 parts by mass of methyl ethyl ketone are placed in a reaction vessel, and 15 parts by mass of dimethyl sulfuric acid is added to the urethane prepolymer obtained by reaction while maintaining the temperature at 70 to 75 ° C. Cationic urethane prepolymers were obtained by reacting for ~ 60 minutes. Further, 576 parts by mass of water was added to the cationic urethane prepolymer and uniformly emulsified, and then methyl ethyl ketone was recovered to obtain a cationic polyether urethane resin (aqueous dispersion) (B1). .

[0073] Cationic polyester urethane resin (aqueous dispersion) B2

Polyester polyol (Synthetic components: isophthalic acid, adipic acid and 1,6 hexanediol, ethylene glycol, molecular weight 1700) 135 parts by mass, trimethylolpropane 5 parts by mass, N-methyl N, N diethanolamine 22 parts by mass, isophorone Add 86 parts by weight of diisocyanate and 120 parts by weight of methyl ethyl ketone to a reaction vessel and add 17 parts by weight of dimethyl sulfate to the urethane prepolymer obtained by reacting while maintaining at 70 to 75 ° C. A cationic urethane prepolymer was obtained by reacting at 50 to 60 ° C. for 30 to 60 minutes. Further, 615 parts by mass of water was added to the cationic urethane prepolymer and uniformly emulsified, and then methyl ethyl ketone was recovered to obtain a cationic polyester urethane resin (water dispersion) (B2). .

[0074] Cationic polycarbonate urethane resin (aqueous dispersion) B3

Polycarbonate polyol (synthesis component: 1, 6 hexane carbonate diol, ethylene glycol, molecular weight 2000) 130 parts by mass, 4 parts by mass of trimethylolpropane, 21 parts by mass of N-methyl N, N diethanolamine, isophorone diisocyanate 75 parts by mass and 115 parts by mass of methyl ethyl ketone were placed in a reaction vessel, and 22 parts by mass of dimethyl sulfate was added to a urethane polymer obtained by reacting while maintaining at 70 to 75 ° C., and 50 to 60 A cationic urethane prepolymer was obtained by reacting at 30 ° C. for 30 to 60 minutes. Further, 633 parts by mass of water was added to the cationic urethane prepolymer and uniformly emulsified, and then methyl ethyl ketone was recovered to obtain a cationic polycarbonate urethane resin (aqueous dispersion) (B3).

[0075] Zr compound and Z or Ti compound (C)

C1: Hexafluorozirconic acid

C2: Hexafluoro zirconate ammonium

C3: Hexafluorotitanic acid

C4: Hexafluorotitanate ammonium

C5: Zirconium carbonate ammonia

C6: Ginoleconiazonore

[0076] Fluorine-containing inorganic compound (D)

D1: Ammonium fluoride

D2: Hydrofluoric acid

D3: Key hydrofluoric acid

[0077] Metallic compound (E)

E1: Vanadium oxycetylacetonate

E2: Ammonium molybdate E3: Ammoni metatungstate

E4: Cobalt nitrate

E5: Aluminum hydroxide

E6: Cerium ammonium nitrate

E7: Nickel carbonate

Claims

The scope of the claims

[1] Aqueous surface for precoated metal materials containing silane coupling agent (A), cationic urethane resin (B), Zr compound and Z or Ti compound (C) and fluorine-containing inorganic compound (D) (A) The mass ratio of Z (B) is 1Z50 to 20Z1, (Zr and Ζ or Ti atoms) The mass ratio of Z (B) is 1Z1,000 to 1Z2, and the fluorine atom Z (B ) Is a water-based surface treatment agent having a mass ratio of lZl, 000 to 2Zl.

[2] Silane coupling agent (A) 5% by mass or more of primary amino group, secondary amino group, tertiary amino group and quaternary ammonium group selected 2. The aqueous surface treating agent according to claim 1, which is a silane power peeling agent having a group.

[3] The silane coupling agent (A) also has a silane coupling agent having functional groups that react with each other, and the equivalent ratio of one functional group to the other functional group is 50: 1 to 1:50. The water-based surface treatment agent according to claim 1 or 2.

[4] Further, at least selected from V compound, Mo compound, W compound, Co compound, A1 compound, Zn compound, Ni compound, Mn compound, Ce compound, Nb compound, Sn compound and Mg compound The water-based surface treatment agent according to any one of claims 1 to 3, which contains one metal compound (E) in a range of lZl, 000 to 1 Z2 as a mass ratio of the metal atom Z (B).

[5] The aqueous surface treating agent according to any one of claims 1 to 4, wherein the Zr compound and the Z or Ti compound (C) are fluoride, fluoro acid or fluoro acid salt.

[6] The water-based surface treatment agent according to any one of claims 1 to 5 is applied to the surface of the metal material and then dried to form a dry film of 10 to 1,000 mg / m ^2. Surface treatment method for metallic materials.

[7] A method for producing a precoated metal material, wherein the metal material surface-treated by the surface treatment method according to [6] is further coated with an upper layer coating not containing chromium.