KR100676602B1 - Metal surface treatment chemical providing the metal with excellent corrosion resistance and method for surface treatment of metal using the chemical - Google Patents

Abstract

The object of this invention is to form a coating having excellent corrosion resistance and paint adhesion on the metal surface by using a treatment solution containing no chromium ion.

In order to solve this problem, (a) a surface treatment agent containing a compound having two or more functional groups represented by the following formula (1) and a compound selected from (b) organic acids, phosphoric acid and complex fluorides is used. Furthermore, the molecular weight per one functional group of (a) is 100-30000. (C) It is possible to further contain a resin having a functional group selected from tertiary amino groups and quaternary amino groups in the skeleton. And (d) fluorine compounds of metals such as Co, W, V, Mg, Al, Mn, Ti, and the like. In addition, (e) further contain compounds having functional groups containing C═O, C═C, C≡C, C═N, C≡N, N═N, NN, and S groups. There is a number. This surface treating agent is applied to a metal surface and dried to form a film having a thickness of 0.1 to 3.0 g / m ² .

In the above formula, R ¹ , R ² , and R ³ each independently represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms.

Description

TECHNICAL SURFACE TREATMENT CHEMICAL PROVIDING THE METAL WITH EXCELLENT CORROSION RESISTANCE AND METHOD FOR SURFACE TREATMENT OF METAL USING THE CHEMICAL}

The present invention relates to a surface treatment agent for forming a film that provides excellent corrosion resistance and top coat adhesion to surfaces of metal materials such as steel, galvanized steel sheets, and aluminum sheets, and a method for surface treatment of metal materials using the same. .

Metallic materials, especially galvanized steel sheets, are used in various fields such as automobiles, home appliances, and building materials, and have the drawback of forming corrosion products called white rust by corrosion in the atmosphere. Therefore, in the prior art, a method called a chromate treatment for forming a coating layer containing hexavalent chromium and trivalent chromium using a treatment solution containing an aqueous solution of chromic acid on the surface of a galvanized steel sheet for the purpose of improving corrosion resistance is generally known. It is carried out.

However, the aqueous solution used for the chromate treatment has hexavalent chromium that is harmful to the human body, so the drainage treatment needs to be subjected to a special treatment prescribed by the Water Pollution Prevention Act. Therefore, as the awareness of global environmental conservation increases in recent years, there has been a strong movement to avoid the use of compounds harmful to the human body.

On the other hand, as a surface treatment method other than chromate treatment, the treatment method by the surface treating agent containing tannic acid is well known. When treated with an aqueous solution of tannic acid, it is considered that the protective film formed by the reaction of tannic acid with a metal material prevents the intrusion of corrosive substances and thus improves corrosion resistance. However, in this coating, it is difficult to cope with the recent high quality of the product (corrosion resistance, paint adhesion).

As a method of using coatings other than chromate coatings, they are disclosed in Japanese Patent Laid-Open Nos. 53-121034, 57-44751, and 1-177380.

The technique disclosed in Japanese Patent Laid-Open No. 53-121034 is a method of coating an aqueous solution containing water dispersible silica, an alkyd resin, and a trialkoxysilane compound on a metal surface and drying to form a film. However, in the film obtained by this method, it was not possible to obtain the desired corrosion resistance.

The technique disclosed in Japanese Patent Application Laid-Open No. 57-44751 is a water-soluble resin of a hydroxypyrone compound derivative, and the technique disclosed in Japanese Patent Laid-Open No. 1-177380 uses an aqueous solution of a hydroxystyrene compound or a water dispersible polymer, respectively. It was a method, which could not attain the corrosion resistance we aimed for.

In this way, it is a present situation that the coating which gives the outstanding corrosion resistance which can be used as a replacement of a chromate coating is not obtained by either method.

MEANS TO SOLVE THE PROBLEM This invention solves the problem of the said subject with the prior art, and the surface treating agent for metal materials which can form the film excellent in corrosion resistance and coating adhesiveness on the surface of a metal material (especially zinc-based galvanized steel sheet), and the surface treatment method using the same It is intended to provide.

The present inventors earnestly studied to solve the problems of the prior art, and as a result, the surface of the metal material was prepared by using a compound having two or more specific functional groups and a water-based chemical agent having a specific acid or compound in one molecule. The present inventors have newly discovered that a film having excellent corrosion resistance and paint adhesion can be formed by treatment, and have completed the present invention.

That is, the surface treatment agent for metal materials excellent in corrosion resistance of the present invention is a compound having two or more functional groups represented by the following formula (I) in one molecule as (A) component, and an organic acid, phosphoric acid and It contains at least one compound selected from the group consisting of complex fluorides, and the molecular weight (average molecular weight / number of functional groups) per one of the said functional groups in (a) component exists in the range of 100-30000 It is done.

In the above formula, R ¹ , R ² , and R ³ each independently represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms.

Furthermore, it is preferable that the processing agent of this invention contains resin which has at least 1 sort (s) of functional group chosen from the group which consists of a tertiary amino group or a quaternary amino group in frame | skeleton as (poly) component.

It is preferable that solid content weight ratio (A) / (C) of the said (A) component and (C) component exists in the range of 1 / 9-9 / 1.

The treatment agent of the present invention further comprises fluorine compounds, organic acid salts and phosphates of at least one metal selected from the group consisting of cobalt, tungsten, vanadium, magnesium, aluminum, manganese, titanium, trivalent chromium and molybdenum as (d) components. It is preferable to contain 0.01-100 weight% of at least 1 sort (s) of compound chosen from the group which consists of (a) with respect to 100 weight% of (a) component.

The treatment agent of the present invention is at least one member selected from C═O group, C═C group, C≡C group, C═N group, C≡N group and N═N group in one molecule as (e) component. It is preferable to contain 0.1-100 weight% of compounds which have at least 1 sort (s) of functional group chosen from the group which consists of a unsaturated group of an unsaturated group, NN group, and S atom with respect to 100 weight% of (A) component.

And the surface treatment method of the metal material of this invention apply | coats the above-mentioned surface treating agent for metal materials to the surface of a metal material, and immediately dries and forms the film of 0.1-3.0 g / m <^2> as a film amount on the said surface. It features.

Hereinafter, the content of the present invention will be described in detail.

(A) component and (B) component are important components of the surface treating agent of this invention. The surface treating agent of this invention uses the compound which has two or more functional groups represented by following formula (I) in 1 molecule as (A) component.

In the above formula, R ¹ , R ² , and R ³ each independently represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms.

It is preferable that the molecular weight (average molecular weight / number of functional groups) per said functional group exists in the range of 100-30000, and, as for this compound, More preferably, it is the range of 120-10000. When the molecular weight per functional group is less than 100, the synthesis of the compound is difficult. On the other hand, when the molecular weight exceeds 30000, the adhesion to the surface of the metal material, which is characteristic of the functional group, is not preferable. Moreover, it does not specifically limit as a skeleton of the said compound, It is preferable to have bond, such as an ester bond, an ether bond, an acid amide bond, a urethane bond, a urea bond, a vinyl bond.

The method for producing the compound is not particularly limited, but the method of obtaining the compound by the reaction of the compound having two or more functional groups with hydrogen and chlorosilane, the method of obtaining by the reaction of two or more silane coupling agents, the silane coupling agent The method obtained by reaction with the compound which has a functional group which can react with the organic functional group of the method, the method obtained by reaction with the vinyl compound copolymerizable with the silane coupling agent which has a vinyl group, etc. are mentioned.

Furthermore, in the case of a compound having only one functional group in one molecule, adhesion to the surface of the metal material is lowered, which is not preferable.

(B) component used for the surface treating agent of this invention is at least 1 sort (s) of compound chosen from the group which consists of organic acid, phosphoric acid, and complex fluoride. Organic acid is acid having a relatively low acidity in the acid, and thus corrosion resistance is improved because only an extremely thin oxide film on the plating surface is removed without strongly etching the galvanized steel sheet. On the other hand, other acids such as sulfuric acid, hydrochloric acid and nitric acid are not preferable because the etching force against zinc-based plating is too strong and corrosion resistance is lowered. Examples of the organic acid herein include formic acid, acetic acid, butyric acid, oxalic acid, succinic acid, lactic acid, L-ascorbic acid, tartaric acid, citric acid, DL-malic acid, malonic acid, maleic acid, and phthalic acid.

Phosphoric acid is very slightly on the zinc-based plated surface, but it forms a zinc phosphate chemical coating and thus improves corrosion resistance. As phosphoric acid herein, metaphosphoric acid, pyrophosphoric acid, orthophosphoric acid, triphosphate, tetraphosphoric acid, and ammonium salts, aluminum salts, magnesium salts, and the like can be used. In addition to the etching effect by fluorine, the complex fluoride has improved corrosion resistance due to the chelate action of the metal used for the complex fluoride. As a complex fluoride here, a zirconium fluoride acid, a titanium fluoride acid, a silico fluoride acid, these ammonium salts, a hydrofluoric acid, etc. are mentioned.

Moreover, as the compounding quantity of these compounds in the chemical | medical agent, it is 0.01-300 weight% with respect to 100 weight% of solid content of (A) component, Preferably it is 0.05-200 weight%, In the case of phosphoric acid, 0.01-200 weight%, Preferably it is 0.1-100 weight%, and in the case of a complex fluoride, it is 0.01-100 weight%, Preferably it is the range of 0.02-50 weight%. If it is less than these ranges, the compounding effect of (b) component is insufficient, and if it exceeds the range, the effect is saturated, so it is not economical.

In this invention, corrosion resistance can further be improved by further mix | blending resin which has at least 1 sort (s) chosen from the group which consists of a tertiary amino group or a quaternary amino group in a skeleton as (C) component. Although it does not specifically limit as a kind of resin, The acrylic resin, epoxy resin, urethane resin, ester resin, etc. which can be used universally are preferable. The method for introducing a tertiary amino group or quaternary amino group is not particularly limited, but a method of using a compound having an amino group in the resin synthesis step or a compound having a nitro or nitrile group in the resin synthesis step reduces the functional group. And a method of directly replacing hydrogen bonded to carbon with an amino group, and any method can be applied.

As a compounding quantity of (a) component, it is 1/9-9/1, Preferably it is 2/8-8/2 as solid content weight ratio (a) / (c) of (a) component and (c) component. If the range of (A) / (C) is less than 1/9, the compounding effect of the (A) component is insufficient, and corrosion resistance decreases, which is not preferable. On the other hand, when it exceeds 9/1, since the compounding effect of (C) component is lacking, it is not economical.

In the present invention, as the component (d), moreover, a group consisting of fluorides, organic acid salts and phosphates of at least one metal selected from the group consisting of cobalt, tungsten, vanadium, magnesium, aluminum, manganese, titanium, trivalent chromium and molybdenum By blending at least one compound selected from the group, the corrosion resistance can be further improved.

It is considered that these metals form poorly soluble salts with a compound selected from the group consisting of organic acids, phosphoric acid and complex fluorides as components (b) and control corrosion potential of zinc-based plating in a corrosive environment, thereby improving corrosion resistance.

As these compounding quantities, it is 0.01-100 weight% with respect to 100 weight% of solid content of (a) component, Preferably it is the range of 0.05-50 weight%. If the amount of the component (d) is less than 0.01% by weight, the effect of improving corrosion resistance is insufficient. On the other hand, if the content of the component (d) is more than 100% by weight, the effect is saturated.

In the present invention, at least one member selected from the group consisting of C═O group, C═C group, C≡C group, C═N group, C≡N group, and N═N group in one molecule. Corrosion resistance can be improved further by mix | blending the compound which has at least 1 sort (s) of functional group chosen from the group which consists of a functional group which has a unsaturated group, an NN group, or S element of. The compound having these functional groups is not particularly limited, but C = O-containing compounds such as aldehydes such as formaldehyde and acetaldehyde, ketones such as acetone and methyl ethyl ketone, benzene and derivatives thereof, naphthalene and derivatives thereof, and acrylic acid C-C group-containing compounds such as methacrylic acid and derivatives thereof, alkyl carboxylic acid esters, alkylaldehydes, C≡C-group-containing compounds such as acetylene alcohols and acetylene derivatives, azine, triazine, osazone dyes, triphenylmethane dyes NN such as C = N group-containing compounds such as knidine, pyrimidine, pyrazole, imidazole, pyridinium and quinolinium compounds, C≡N group-containing compounds such as ethylene cyanhydrin, hydrazine compounds and derivatives thereof N-N group-containing compounds such as group-containing compounds and azo dyes, and S element-containing compounds such as sulfonic acids, sulfonates, sulfamides, thioureas and cyclic thioureas, and the like. Can be mentioned.

When these compounds are blended, it is considered that the corrosion resistance is improved because the compound is adsorbed on the surface of the zinc-based galvanized steel to mitigate the corrosion potential of the zinc-based plating. As a compounding quantity of (e) component, it is 0.1-100 weight% with respect to 100 weight% of solid content of (a) component, Preferably it is the range of 0.5-50 weight%. When the amount of the component (e) is less than 0.1% by weight, the effect of improving the corrosion resistance is insufficient. On the other hand, when the amount of the component is greater than 100% by weight, the coating adhesion is lowered, which is not economical.

In addition, the surface treatment agent of the present invention is a surfactant or a thickener called a wettability improver for obtaining a uniform coating on the painted surface, a conductive improver for improving weldability, a coloring pigment for improving the designability, and for improving film formability. A film forming preparation etc. can also be added.

Examples of the material to which the surface treatment agent of the present invention is applied include zinc-based galvanized steel such as cold rolled steel and hot rolled pickled steel, such as galvanized steel, hot dip galvanized steel, galvanized steel and aluminum-containing galvanized steel. An aluminum sheet, such as a zinc nickel plated steel sheet, a zinc cobalt plated steel sheet, and a deposited zinc plated steel sheet, is preferable.                     

After applying the surface treating agent of the present invention to the surface of the metal material by a method such as a roll coater method, an immersion method, an electrostatic coating method, or the like, the hot air is brought to a temperature range of 60 to 250 ° C, preferably 80 to 220 ° C. Or it is preferable to dry by induction heating and to form the film of the range of 0.1-3.0 g / m <^2> as a film amount.

If the attained plate temperature is less than 60 ° C., the performance of the obtained film is insufficient, which is not preferable. On the other hand, if the plate temperature exceeds 250 ° C., thermal degradation of the film occurs, which is not preferable. In the case where the coating amount is less than 0.1 g / m ^2, the performance of the obtained film is insufficient, which is not preferable. When the coating amount is more than 3.0 g / m ² , the coating performance is saturated, so it is not economical.

And it is preferable that solid content concentration of the surface treating agent of this invention exists in 1 to 50% of range. If the solid content concentration is less than 1%, since the surface treatment agent is water-based, the time until drying becomes long is not preferable. On the other hand, when solid content concentration exceeds 50%, since discomforts, such as a fall of the dispersion stability of a chemical | medical agent and a viscosity increase, are unpreferable.

EXAMPLE

Hereinafter, the present invention will be described in detail with reference to Examples of the present invention together with Comparative Examples. Moreover, the scope of the present invention is not limited by these Examples. Below, the test piece used for the Example and the comparative example, the degreasing treatment, and the coating method of the surface treating agent for metal materials are demonstrated.

1. Construction of Test Specimen                     

(1-1) Disclosure

The commercially available materials shown below were used as test materials.

전기 아연도금 강판 (EG)

Electro Galvanized Steel Sheet (EG)

Plate thickness = 0.8 mm, coating weight = 20/20 (g / m ² )

5% 알루미늄 함유 용융아연도금 강판 (GF)

Hot-dip galvanized steel sheet containing 5% aluminum (GF)

Plate thickness = 0.8 mm, coating weight = 90/90 (g / m ² )

아연니켈 합금 도금 강판 (Zn/Ni)

Zinc Nickel Alloy Plated Steel Sheet (Zn / Ni)

Plate thickness = 0.8 mm, coating weight = 20/20 (g / m ² )

용융아연도금 강판 (GI)

Hot Dip Galvanized Steel Sheet (GI)

Plate thickness = 0.8 mm, coating weight = 90/90 (g / m ² )

용융 55% 아연합금 도금 강판 (GL)

Hot-Dip 55% Zinc Alloy Plated Steel Plate (GL)

Plate thickness = 0.8 mm, coating weight = 90/90 (g / m ² )

합금화 (Zn-Fe) 용융 아연도금 강판 (GA)

Alloyed (Zn-Fe) Hot Dip Galvanized Steel Sheet (GA)

Plate thickness = 0.8 mm, coating weight = 60/60 (g / m ² )

A-1100계 알루미늄판 (AL)

A-1100 series aluminum plate (AL)

         Plate thickness = 0.8 mm

(1-2) Degreasing treatment                     

The test material was sprayed for 2 minutes at a concentration of 20 g / L and a temperature of 60 ° C using Fine Cleaner 4336 (trademark: manufactured by Nippon Parkarizing Co., Ltd.), which is a silicate-based alkali degreasing agent. After washing with water, it was dried immediately.

(1-3) Application of Surface Treatment Agent for Metal Materials

Surfactants or thickeners called wettability enhancers for obtaining a uniform coating on the coated surface as described above, conductivity enhancers for improving weldability, coloring pigments for improving designability, film preparation for improving film formability, and the like. The added surface treatment agent for metal materials of the present invention was applied by a bar coater and dried at an ambient temperature of 300 ° C.

2. Paint plate performance test

(2-1) flat part corrosion resistance

The salt spray test according to JIS-Z-2371 was carried out for 120 hours, and the white rust occurrence condition was observed.

<Evaluation Criteria>

◎ = less than 3% of rust

= 녹발생이 전면적의 3% 이상 10% 미만

= Rust generation is more than 3% and less than 10%

= 녹발생이 전면적의 10% 이상 30% 미만

= Rust generation is more than 10% and less than 30%

× = more than 30% of rust occurrence

(2-2) Machining Part Corrosion Resistance

After the Eriksen test (7 mm extrusion) according to JIS-Z-2247, the salt spray test according to JIS-Z-2371 was carried out for 72 hours to observe the white rust occurrence.

<Evaluation Criteria>

◎ = less than 10% of rust occurrence

= 녹발생이 전면적의 10% 이상 20% 미만

= Rust generation is more than 10% and less than 20%

= 녹발생이 전면적의 20% 이상 30% 미만

= Rust generation is more than 20% and less than 30%

× = more than 30% of rust occurrence

(2-3) Top coat paint adhesion

Melamine alkyd paint (Amirak # 1000, Trademark: Japan Paint Co., Ltd.) was applied so that the film thickness after baking was 25 µm, and baked at 125 ° C. for 20 minutes for the first test (after standing for 24 hours. ) And the secondary test (after 2 hours of boiling water immersion and 24 hours of standing). In the evaluation method, 100 checkerboards were made at intervals of 1 mm with an NT cutter, and the checkerboard part was extruded 7 mm with an Eriksen tester, followed by peeling of cellophane tape, and evaluated as a peeling condition of the coating film.

<Evaluation Criteria>

◎ = 0 peeling film

= 도막박리 개수 1개

= 1 peeling film

= 도막박리 개수 2 ∼ 10개

= 2 ~ 10 peeling of film

× = 11 to 100 peeling of film

3. Surface treatment agent for metal materials

<Processing liquid A>                     

(A) To 100% by weight of a compound obtained by reacting 1 mole of hexamethylenediamine and 2 moles of γ-glycidoxypropyltrimethoxysilane in ethanol, (B) 5% by weight of dihydrogen ammonium phosphate is added and the solid content concentration Dilute with deionized water to 5%. And (A) the number of functional groups in the component is two and the functional group equivalent is about 294.

<Processing Solution B>

(A) To 1 mole of # 828 type bisphenol A type epoxy resin and 2 moles of γ-aminopropyltriethoxysilane in N-methyl-2-pyrrolidone, to 100% by weight of the compound (B) Oxalic acid 5 Weight percent was added and diluted with deionized water to a solid concentration of 5%. And (A) component has 2 functional groups and its functional group equivalent is about 411.

<Processing liquid C>

(A) To 100% by weight of a compound obtained by emulsion polymerization of 1 mol of acrylic acid, 5 mol of butyl acrylate, 5 mol of methyl methacrylate, and 3 mol of γ-methacryloxypropyltriethoxysilane in deionized water (B) Silico 10% by weight of ammonium fluoride was added and diluted with deionized water to a solids concentration of 5%. And (A) component has 3 functional groups and its functional group equivalent is about 694.

<Processing liquid D>

20 weight of the compound obtained by carrying out emulsion polymerization of (C) 1 mol of acrylic acid, 5 mol of methyl methacrylate, 3 mol of 2-hydroxyethyl methacrylate, and 2 mol of dimethylaminoethyl methacrylate in the treated solution A in deionized water. % Was combined and diluted with deionized water to 5% solids concentration. The number of functional groups of component (A) is two, the functional group equivalent is about 294, and the solid content weight ratio (A) / (C) of component (A) and component (C) is 5/1.

<Processing liquid E>

After treating 1 mol of the # 828 type epoxy resin and 2 mol of dimethylethanolamine again to the treatment solution B, 100% by weight of a compound adjusted to pH 4.5 by adding acetic acid was added, and the concentration was removed so that the solid concentration was 5%. Dilute with deionized water. The number of functional groups of component (A) is two, the functional group equivalent is about 411, and the solid content weight ratio (A) / (C) of component (A) and component (C) is 1/1.

<Processing liquid F>

To the treatment liquid C, (a) water-based urethane resin having tertiary and quaternary amino groups (Adecarbonitata HUX-670, registered trademark: manufactured by Nippon Denshi Kogyo Co., Ltd.) was added. Dilution with deionized water to 5% solids concentration. The number of functional groups of component (A) is three, the functional group equivalent is about 694, and the solid content weight ratio (A) / (C) of component (A) and component (C) is 1/5.

<Treatment liquid G>

To Treatment A, again 10% by weight of (A) magnesium acetate [(CH ₃ COO) ₂ Mg] was added, and the mixture was diluted with deionized water so as to have a solid content concentration of 5%. And the functional group equivalent of (a) component is about 294, and the compounding quantity of (d) component with respect to (a) component is 10 weight%.

<Processing liquid H>

20% by weight of (D) ammonium metavanadate (NH ₄ VO ₃ ) was further added to the treatment solution B, and the mixture was diluted with deionized water so as to have a solid concentration of 5%. And the number of functional groups of (a) component is two, the functional group equivalent is about 411, and the compounding quantity of (d) component with respect to (a) component is 20 weight%.

<Processing liquid I>

To the treatment solution C, (a) 30% by weight of aluminum phosphate (AlPO ₃ ) was further blended and diluted with deionized water so as to have a solid concentration of 5%. And the number of functional groups of (a) component is three, the functional group equivalent is about 694, and the compounding quantity of (d) component with respect to (a) component is 30 weight%.

<Processing liquid J>

To Treatment A, 10 wt% of (but) 2-butyne-1,4-diol (HOCH ₂ C≡CCH ₂ OH) was further blended and diluted with deionized water to a solid content concentration of 5%. And the number of functional groups of (a) component is two, the functional group equivalent is about 294, and the compounding quantity of (e) component with respect to (a) component is 10 weight%.

Treatment liquid K

To Treatment Liquid B, 10% by weight of (e) thiourea (H ₂ NCSNH ₂ ) was further blended and diluted with deionized water so as to have a solid content concentration of 5%. And the number of functional groups of (a) component is two, the functional group equivalent is about 411, and the compounding quantity of (e) component with respect to (a) component is 10 weight%.

<Processing liquid L>

20% by weight of (D) magnesium acetate [(CH ₃ COO) ₂ Mg] was further added to the treatment solution D, and the mixture was diluted with deionized water so as to have a solid content concentration of 5%. (A) The number of functional groups of the component (2), the functional group equivalent of about 294, the solids weight ratio (a) / (c) of the component (a) and (c) is 5/1, (a) ) The compounding amount of the component is 20% by weight.

<Treatment liquid M>

To treatment solution E, 20% by weight of ammonium metavanadate (NH ₄ VO ₃ ) and 30% by weight of aluminum phosphate (AlPO ₃ ) were further blended and diluted with deionized water to a solid content concentration of 5%. And (a) the number of functional groups in the component is two, the functional group equivalent is about 411, and the solids weight ratio (a) / (c) of the component (a) and (c) is 1/1, and (a) ) The compounding quantity of the component is 40 weight%.

<Processing liquid N>

To the treatment solution F, again, 20% by weight of (a) magnesium acetate [(CH ₃ COO) ₂ Mg] and 10% by weight of (thio) thiourea (H ₂ NCSNH ₂ ) were added to deionized water so as to have a solid concentration of 5%. Diluted as. (A) The number of functional groups of component (a) is 3, the functional group equivalent is about 694, and the solid content ratio (a) / (c) of component (a) and (c) is 1/5, (a) The compounding quantity of the component) is 20 weight%, and the compounding quantity of the (e) component with respect to (a) component is 10 weight%.

<Processing liquid O>

(A) To 100% by weight of a compound obtained by reacting 1 mole of hexamethylenediamine and 2 moles of γ-glycidoxypropyltrimethoxysilane in ethanol (B) 5% by weight of dihydrogen ammonium phosphate and ammonium silicofluoride 10 Weight percent was added and diluted with deionized water to 5% solids concentration. And (A) the number of functional groups in the component is two and the functional group equivalent is about 294.

<Processing liquid P>

(A) To 100% by weight of bis (trimethoxysilylpropyl) amine (manufactured by Nippon Unicar Co., Ltd., product name A-1170), (B) 5% by weight of dihydrogen ammonium phosphate and 10% by weight of ammonium silicofluoride (C) water-based urethane resins having tertiary and quaternary amino groups (registered trademark: Adecarbonitata HUX-760, registered trademark: manufactured by Japan Denim Chemical Co., Ltd.) The mixture was diluted with deionized water so as to have a solid concentration of 5%. The number of functional groups of component (A) is two, the functional group equivalent is about 171, and the solid content weight ratio (A) / (C) of component (A) and component (C) is 1/2.

<Comparative Treatment Q>

(A) 50 moles of acrylic acid, 100 moles of butyl acrylate, 100 moles of methyl methacrylate, 100 moles of 2-hydroxyethyl methacrylate, and 1 mole of γ-methacryloxypropyltriethoxysilane are emulsified in deionized water. To 100% by weight of the obtained compound (average molecular weight of about 40000), 10% by weight of (B) ammonium silicate fluoride was added and diluted to a solid content concentration of 5%. And the number of functional groups of (A) component in this process liquid is one, and the functional group equivalent is about 40000, and is outside the range of the functional group equivalent of (A) component of this invention.

<Comparative Treatment Liquid R>

(A) 1% by weight of sulfuric acid is added to 100% by weight of a compound obtained by reacting 1 mol of hexamethylenediamine and 2 mol of γ-glycidoxypropyltrimethoxysilane in ethanol, and then deionized water to obtain a solid content of 5%. Diluted. The number of functional groups of the (A) component in this treatment liquid is two and the functional group equivalent is about 294. The compound corresponding to the component (B) is not blended in this treatment liquid.

<Comparative Treatment Liquid S>

(A) To 100% by weight of γ-mercaptopropyltrimethoxysilane (manufactured by Nihon Chemical Co., Ltd., product name KBM803), (5) 5% by weight of phosphoric acid is added and the weight is removed so that the solid content is 5%. Dilute with deionized water. The component (A) has one functional group in one molecule, which is outside the scope of the present invention.

<Comparative Treatment Fluid T>

Chromate 3360H (registered trademark: manufactured by Nippon Parkarizing Co., Ltd.), a chromate-treated chemical agent for galvanized steel sheets, was used by appropriately diluting it.

<Comparative Treatment Fluid U>

Chromate 3383 (registered trademark: manufactured by Nippon Parkarizing Co., Ltd.), a chromate-treated chemical agent for galvanized steel sheets, was used by appropriately diluting it.

4. Test result

Table 1 of [Level] shows a list of test levels of the surface treatment agent for metal materials, and Table 2 of [Results] shows a list of performance test results of the surface treatment agent for metal materials. Examples and comparative examples are described. .

No. of Table 2 1 to 25 are coated by coating the surface treatment agent for metal materials (Nos. 1 to 25 in Examples of Table 1) of the present invention to a zinc-based galvanized steel sheet and drying them to form a coating film. Each of the performances of coating adhesiveness is good. On the other hand, the comparative example No. of Table 1 different from this invention. No. 2 in Table 2 using the treatment agents 1-5. In 27-31, planar part corrosion resistance, a process part corrosion resistance, and top coat coating adhesiveness are all bad.

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[Table 1] List of test levels of surface treatment agent for metal materials

No. Material Treatment solution Reach plate temperature Coating amount, g / ㎡       Example One EG A 100 ℃ 1.0 2 EG B 100 ℃ 1.0 3 EG C 100 ℃ 1.0 4 EG D 100 ℃ 1.0 5 EG E 100 ℃ 1.0 6 EG F 100 ℃ 1.0 7 EG G 100 ℃ 1.0 8 EG H 100 ℃ 1.0 9 EG I 100 ℃ 1.0 10 EG J 100 ℃ 1.0 11 EG K 100 ℃ 1.0 12 EG L 100 ℃ 1.0 13 EG M 100 ℃ 1.0 14 EG N 100 ℃ 1.0 15 EG O 100 ℃ 1.0 16 EG P 100 ℃ 1.0 17 EG A  80 ℃ 1.0 18 EG B 220 ℃ 1.0 19 EG C 100 ℃ 0.3 20 EG D 100 ℃ 3.0 21 GF E 100 ℃ 1.0 22 GI E 100 ℃ 1.0 23 GA E 100 ℃ 1.0 24 GL E 100 ℃ 1.0 25 Zn-Ni E 100 ℃ 1.0 26 AL E 100 ℃ 1.0   Comparative Example One EG Q 100 ℃ 1.0 2 EG R 100 ℃ 1.0 3 EG Q 150 ℃ 3.0 4 EG R 150 ℃ 3.0 5 EG S 100 ℃ 1.0 6 GI T  60 ℃ Cr = 15mg / ㎡ 7 EG U 100 ℃ Cr = 40mg / ㎡

Table 2 List of paint plate performance test results for surface treatment agents for metal materials

No. Level No. in Table 1 Corrosion resistance Top coat paint adhesion Flat part Machining department Primary Secondary One Example No. 1 ◎

◎ ◎ 2 Example No. 2 ◎

◎ ◎ 3 Example No. 3 ◎

◎ ◎ 4 Example No. 4 ◎ ◎ ◎ ◎ 5 Example No. 5 ◎ ◎ ◎ ◎ 6 Example No. 6 ◎ ◎ ◎ ◎ 7 Example No. 7 ◎ ◎ ◎ ◎ 8 Example No. 8 ◎ ◎ ◎ ◎ 9 Example No. 9 ◎ ◎ ◎ ◎ 10 Example No.10 ◎ ◎ ◎ ◎ 11 Example No. 11 ◎ ◎ ◎ ◎ 12 Example No.12 ◎ ◎ ◎ ◎ 13 Example No.13 ◎ ◎ ◎ ◎ 14 Example No.14 ◎ ◎ ◎ ◎ 15 Example No.15 ◎ ◎ ◎ ◎ 16 Example No. 16 ◎

◎ ◎ 17 Example No. 17 ◎

◎ ◎ 18 Example No. 18

◎ ◎ 19 Example No. 19 ◎ ◎ ◎ ◎ 20 Example No. 20 ◎ ◎ ◎ ◎ 21 Example No.21 ◎ ◎ ◎ ◎ 22 Example No. 22 ◎ ◎ ◎ ◎ 23 Example No. 23 ◎ ◎ ◎ ◎ 24 Example No. 24 ◎ ◎ ◎ ◎ 25 Example No.25 ◎ ◎ ◎ ◎ 26 Example No. 26 ◎ ◎ ◎ ◎ 27 Comparative Example No. 1 × ×

△ 28 Comparative Example No. 2 × ×

△ 29 Comparative Example No. 3 △ △ △ △ 30 Comparative Example No. 4 △ △ △ △ 31 Comparative Example No. 5 × × △ △ 32 Comparative Example No. 6 △ × × × 33 Comparative Example No. 7

◎ ◎ ×

As described above, by coating the surface treatment agent for metal materials of the present invention on the surface of the zinc-based galvanized steel sheet, a film having excellent flat surface corrosion resistance, processed portion corrosion resistance, and top coat paint adhesion is obtained.

Claims (6)

At least one compound selected from the group consisting of a compound having two or more functional groups represented by the following formula (I) in one molecule as the component (A) and an organic acid, phosphoric acid and a complex fluoride as the component (B). The compound which contains a compound, and has a molecular weight (average molecular weight / number of functional groups) per said functional group in (a) component in the range of 100-30,000, The surface treatment agent for metal materials excellent in corrosion resistance.

In the above formula, R ¹ , R ² , and R ³ each independently represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. The surface treatment agent for metal material with excellent corrosion resistance according to claim 1, further comprising a resin having at least one functional group selected from the group consisting of tertiary amino groups and quaternary amino groups in the skeleton as (C) component. The surface treatment agent for metal materials according to claim 2, wherein the solid content weight ratio (A) / (C) of the component (A) and the component (C) is in the range of 1/9 to 9/1. The at least one metal according to any one of claims 1 to 3, further selected from the group consisting of cobalt, tungsten, vanadium, magnesium, aluminum, manganese, titanium, trivalent chromium and molybdenum as (d) a component. The surface treating agent for metal materials excellent in corrosion resistance which contains 0.01-100 weight% of at least 1 sort (s) of compound chosen from the group which consists of a fluorine compound, an organic acid salt, and a phosphate salt with respect to 100 weight% of (A) component. The C = O group, C = C group, C≡C group, C = N group, C≡N group and N = in any one of the molecules according to any one of claims 1 to 3 0.1 to 100% by weight of a compound having at least one unsaturated group selected from N or at least one functional group selected from the group consisting of NN and functional groups containing S atoms Surface treatment agent for metal materials excellent in corrosion resistance to contain. The surface treatment agent according to any one of claims 1 to 3 is applied to the surface of the metal material and immediately dried to form a coating film of 0.1 to 3.0 g / m ² as the coating amount on the surface. Surface treatment method.