JP4879793B2 - High corrosion resistance surface-treated steel sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chromium-free surface treated steel sheet capable of obtaining excellent corrosion resistance. <P>SOLUTION: A surface treatment film by a composition comprising: a water base epoxy resin-dispersed liquid obtained by adding an active hydrogen-containing hydrazine derivative or the like to a specific polyalkylene glycol modified epoxy resin; a silane coupling agent; and phosphoric acid or hexafluorometal acid is formed on the surface of a galvanized steel sheet or the like. An upper layer film by a composition obtained by blending a specific cross linking agent into a resin obtained by modifying a specific epoxy resin with a soft component and further bringing the same into reaction with a hydrazine derivative is formed on the upper layer thereof. By the composite action between the surface treatment film in the upper layer and the upper layer film, particularly excellent worked part corrosion resistance can be obtained. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a surface-treated steel sheet that is most suitable for use in automobiles, home appliances, and building materials, and particularly relates to an environment-adaptive surface-treated steel sheet that does not contain chromium at all during the production of the surface-treated steel sheet and in the surface-treated film.

  Conventionally, steel sheets for home appliances, steel sheets for building materials, and steel sheets for automobiles have been used for the purpose of improving corrosion resistance (white rust resistance, red rust resistance) on the surface of galvanized steel sheets or aluminum galvanized steel sheets. Steel plates subjected to chromate treatment with a treatment liquid containing chromic acid or a salt thereof as a main component are widely used. This chromate treatment is an economical treatment method that has excellent corrosion resistance and can be performed relatively easily.

  Chromate treatment uses hexavalent chromium, a pollution-controlling substance, but this hexavalent chromium is treated in a closed system in the treatment process, completely reduced and recovered, and not released into nature. Since the elution of chromium from the chromate film can be made almost zero by the sealing action of the organic film, the environment and the human body are not substantially contaminated by hexavalent chromium. However, due to recent global environmental problems, there is a growing trend to voluntarily reduce the use of heavy metals including hexavalent chromium. In addition, in order not to pollute the environment when the shredder dust of discarded products is dumped, there has been a movement to minimize or reduce the amount of heavy metals contained in the product.

For this reason, in order to prevent the occurrence of white rust in galvanized steel sheets, many treatment techniques that do not rely on chromate treatment, so-called chromium-free techniques, have been proposed. For example, there is a method of forming a thin film by a method such as immersion, coating, or electrolytic treatment using an inorganic compound, an organic compound, an organic polymer material, or a solution combining these.
Among them, the following treatment methods other than chromate treatment and zinc phosphate treatment have been proposed, for example.
(1) Surface treatment method in which treatment is performed with an aqueous solution containing aluminum biphosphate and then heated at a temperature of 150 to 550 ° C. (for example, Patent Document 1)
(2) A method of treating with an aqueous solution containing tannic acid (for example, Patent Document 2)
(3) Treatment method using sodium nitrite, sodium borate, imidazole, aromatic carboxylic acid, surfactant, or a combination of these

However, in the method (1), when a paint is applied on the formed film, the adhesion of the film is not sufficient, and the method (2) is insufficient in corrosion resistance. In addition, both methods (3) have a problem that the corrosion resistance is inferior when exposed to a hot and humid atmosphere.
On the other hand, in order to improve corrosion resistance, a surface treatment composition using a hydrazine derivative has been developed. For example, Patent Documents 3 and 4 propose a method of treating with such a surface treatment composition. However, even if a high molecular weight epoxy resin is used in the surface treatment composition in this method, a sufficiently satisfactory coating film performance cannot be obtained when severe processing is applied to the steel sheet.

Japanese Patent Publication No.53-28857 JP-A-51-71233 JP 2001-49450 A JP 2003-34713 A

  Accordingly, an object of the present invention is to provide a surface-treated steel sheet that solves the problems of the prior art as described above and can obtain a high level flat plate and corrosion resistance after processing without applying treatment with chromium or phosphate. It is in.

In order to solve the above-mentioned problems, the present inventors have conducted the following investigation on the principle of corrosion inhibition for inhibiting corrosion of the plated steel sheet.
The corrosion of the zinc-based plated steel sheet on which the surface treatment film is formed proceeds in the following process.
(1) Corrosion factors (oxygen, water, chlorine ions, etc.) infiltrate into the surface treatment film and diffuse to the plating film / surface treatment film interface.
(2) At the plating film / surface treatment film interface, zinc is dissolved by the following oxidation-reduction reaction.
Cathode reaction: 2H ₂ O + O ₂ + 4e ⁻ → 4OH ⁻
Anode reaction: 2Zn → 2Zn ²⁺ + 4e ⁻

Therefore, to improve the corrosion resistance of the galvanized steel sheet, it is essential to suppress the progress of both reactions (1) and (2).
(A) Advanced barrier layer that acts as a diffusion barrier for corrosion factors (mainly acts to suppress the cathode reaction)
(B) Reaction layer with plating metal that inactivates the plating film surface layer (mainly acts to suppress the anode reaction)
It is most effective to have a film configuration that has a self-repairing action when a defect occurs in the reaction layer.

  As a result of the study, such a film configuration is not a two-layer film formed by separately coating a barrier layer forming component and a reaction layer forming component as in the prior art, but a single layer formed by a single coating. Realizing in the film, specifically, forming the barrier layer (a) above the film and the reaction layer (b) above the film, more preferably self-repair action in the film. It has been found that the effect of improving the corrosion resistance can be obtained by synergistic effects by precipitating the substance to be generated. When such a single-layer coating is defined as a pseudo-two-layer coating, the barrier layer and the reaction layer constituting the pseudo-two-layer coating are between the two-layer coating formed by the conventional double coating. There is no clear interface. On the contrary, it is considered that a high degree of corrosion resistance improvement effect that cannot be obtained by the conventional single layer coating can be exhibited by making the both compositions in a gradient composition.

The pseudo two-layer film as described above is prepared by reacting a water-dispersible liquid of a resin obtained by reacting a specific modified epoxy resin with a hydrazine derivative having active hydrogen, and a silane coupling agent and a specific acid component (phosphoric acid). , Hexafluorometal acid, etc.) is applied to the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet and dried.
A silane coupling agent is known to have an effect of improving the adhesion between an inorganic compound and an organic compound so far, and can improve the adhesion between a plating metal and a water-dispersible resin. When the above-mentioned specific surface treatment composition is used for the known effects of such a silane coupling agent, the acid component contained in the surface treatment composition activates the plating film surface by etching, It is considered that extremely excellent adhesion between the plating metal and the film-forming resin can be obtained by chemically bonding the silane coupling agent with both the activated plating metal and the film-forming resin. That is, by adding a silane coupling agent and a specific acid component to the surface treatment composition, the adhesion between the plating metal and the film-forming resin is markedly greater than when the silane coupling agent is added alone. As a result, it is considered that the progress of corrosion of the plated metal is effectively suppressed and particularly excellent corrosion resistance can be obtained.

  Although the mechanism by which the pseudo two-layer film having the above-described film structure is formed is not necessarily clear, the reaction between the acid component in the surface treatment composition and the surface of the plating film may be involved in the film formation. On the other hand, the following actions involving a silane coupling agent are also conceivable. That is, since the silane coupling agent hydrolyzed in an aqueous solution has a silanol group (Si-OH), the hydrogen bonding adsorption action of the silane coupling agent on the surface of the plating metal activated by the acid component The silane coupling agent is concentrated on the surface of the plated metal, and then dried to cause a dehydration condensation reaction to form a strong chemical bond, whereby the reaction layer (b) above (ie, the plating film) at the bottom of the film A barrier layer of (a) above (that is, a high-level barrier acting as a diffusion barrier for corrosion factors) is formed by a water-dispersible resin concentrated on the top of the film, while a reaction layer with a plating metal that inactivates the surface layer is formed. There is also a possibility of a mechanism that a layer) is formed. In addition, there is a possibility that the above-described action occurs in a composite manner. In addition, in the film formation process as described above, it is considered that a reaction product (compound) between a dissolved plating metal such as zinc and an acid component is deposited in the film.

  The anti-corrosion mechanism of such a pseudo-bilayer coating is not necessarily clear, but the individual anti-corrosion mechanism is a high-density organic layer by adding a hydrazine derivative to a specific modified epoxy resin as the barrier layer of (a) above. A molecular film is formed, which suppresses the permeation of corrosion factors (oxygen, water, chlorine ions, etc.) and effectively suppresses the cathodic reaction that causes corrosion, and also prevents the plating metal ions eluted by the corrosion reaction. The free hydrazine derivative in the film traps to form a stable insoluble chelate compound layer, and the reaction layer in (b) above effectively inactivates the surface of the plating film and causes an anodic reaction that causes corrosion. In addition, the deposited compound deposited in the film dissolves in a corrosive environment to produce acid components (such as phosphate ions). A self-repairing action that captures metal ions such as zinc ions eluted from the plating film (bonds with metal ions to form an insoluble compound) is obtained, and plating with a silane coupling agent activated by an acid component It is possible to form a dense film with high adhesion by binding firmly to the metal surface, suppressing dissolution of the plating metal, and also bonding with the film-forming resin. It is considered that extremely excellent corrosion resistance (white rust resistance) can be obtained.

  Further, by adding a water-soluble phosphate or a non-chromium rust preventive additive to the surface treatment composition, further excellent corrosion resistance can be obtained. In the same way as above, the poorly soluble film exhibits a barrier against corrosion factors, and the phosphate component captures the eluted plating metal ions, forming an insoluble compound with the plating metal ions. It is possible to do. Further, since the non-chromium rust preventive additive forms a protective film at the starting point of corrosion, further excellent anticorrosive performance can be obtained. In practice, these combined effects provide very good anticorrosion performance.

  The above is the anticorrosion mechanism of the surface treatment film obtained by the specific treatment composition, but according to the results of the study by the present inventors, an organic film was simply formed on such a surface treatment film or an upper layer thereof. In the two-layer coating structure, it was found that, particularly when subjected to severe processing such as a wrinkle presser bead in an automobile press die, the processed portion was greatly damaged and its corrosion resistance was considerably inferior. Furthermore, it has been found that the damaged part of the film is damaged by the alkaline degreasing performed to remove the oil after the processing, and the corrosion resistance is further deteriorated. Therefore, as a result of studying the coating composition that is highly satisfactory in the corrosion resistance of the processed part when subjected to such severe processing and further subjected to alkaline degreasing, a specific epoxy as a second layer coating is formed on the above-mentioned surface treatment coating. A coating composition in which a specific crosslinking agent is blended with a resin obtained by modifying a resin with a soft component and reacting with a hydrazine derivative having active hydrogen, and if necessary, a non-chromium rust preventive additive It was found that by forming a film by the above, a high degree of anticorrosion effect can be obtained even in the portion subjected to the above severe processing and alkali degreasing. That is, the present invention has been found that by combining the specific surface treatment film (lower film) and the specific upper film, particularly high corrosion resistance of the processed part can be obtained by their combined action.

The present invention has been made on the basis of the above-described findings, and has the following gist.
[1] A surface treatment composition containing the following components (a) to (c) and further containing the following component (d) as necessary is applied to the surface of a zinc-based plated steel plate or an aluminum-based plated steel plate, A surface treatment film having a film thickness of 0.01 to 1.0 μm formed by heating and drying at 30 to 200 ° C. (final plate temperature) ,
(A) a polyalkylene glycol-modified epoxy resin (A) obtained by reacting a polyalkylene glycol having a number average molecular weight of 400 to 20,000, a bisphenol type epoxy resin, an active hydrogen-containing compound and a polyisocyanate compound, and the polyalkylene glycol-modified A resin obtained by reacting an epoxy group-containing resin (B) other than the epoxy resin (A) with an active hydrogen-containing compound comprising a hydrazine derivative (C) in which some or all of the compounds have active hydrogen is used in water. Dispersed aqueous epoxy resin dispersion (b) Silane coupling agent: 1 to 300 parts by mass with respect to 100 parts by mass of the solid content of the aqueous epoxy resin dispersion (a) (c) Phosphoric acid and / or hexafluoro Metal acid: 0 with respect to 100 parts by mass of the solid content of the aqueous epoxy resin dispersion (a) 1 to 80 parts by weight
(D) Water-soluble phosphate: 0.1 to 60 parts by mass with respect to 100 parts by mass of the solid content of the aqueous epoxy resin dispersion (a), and the following components (D) and (E) are contained in the upper layer thereof. The coating thickness formed by applying the coating composition for the upper layer coating and drying has an upper layer coating of 0.3 to 2.0 μm ,
(D) A bisphenol A type epoxy resin (d1) having an epoxy equivalent of 750 to 5000 and a number average molecular weight of 1500 to 10,000 has a compound (d2) having two or more carboxyl groups in one molecule and active hydrogen. Resin solution obtained by reacting hydrazine derivative (d3) (E) Curing agent having functional group that reacts with hydroxyl group
In the component (a) contained in the surface treatment composition, the hydrazine derivative (C) having active hydrogen is at least one selected from mercaptotriazole and aminotriazole, and the coating composition for an upper film contains In the component (D), the hydrazine derivative (d3) having active hydrogen is at least one selected from mercaptotriazole and aminotriazole.

[2] In the surface-treated steel sheet according to [1], the component (D) contained in the upper layer coating composition is [number of moles of bisphenol A type epoxy resin (d1)] / [carboxyl group in one molecule]. A highly corrosion-resistant surface-treated steel sheet, wherein the ratio of the number of moles of the compound (d2) having two or more] is 1.1 to 5.
[3] In the surface-treated steel sheet according to [1] or [2], in the component (D) contained in the coating composition for an upper film, the compound (d2) having two or more carboxyl groups in one molecule is a fat A highly corrosion-resistant surface-treated steel sheet characterized by being a group dicarboxylic acid .

[4] In the surface-treated steel sheet according to any one of the above [1] to [3] , the coating composition for the upper film further comprises a non-chromium rust preventive additive, a resin solid of component (D) and component (E) A highly corrosion-resistant surface-treated steel sheet containing 0.1 to 50 parts by mass of solids with respect to 100 parts by mass in total.
[5] In the surface-treated steel sheet according to [4], the coating composition for the upper layer film contains at least one selected from the following (f1) to (f5) as a non-chromium rust preventive additive. High corrosion resistance surface-treated steel sheet.
(F1) silicon oxide (f2) calcium compound (f3) sparingly soluble phosphate compound (f4) molybdate compound (f5) one or more selected from triazoles, thiols, thiadiazoles, thiazoles, thiurams , Organic compounds containing S atoms

[6] In the surface-treated steel sheet according to any one of the above [1] to [5] , the coating composition for an upper layer film comprises a curing agent of component (E) and a solid content of 100 parts by mass of the resin solution of component (D). 1-60 mass parts with respect to the high corrosion-resistant surface-treated steel plate characterized by the above-mentioned.
[7] In the surface-treated steel sheet according to any one of [1] to [6 ] above, the curing agent of component (E) contained in the coating composition for upper layer coating has an average of 4 or more isocyanate groups in one molecule. A highly corrosion-resistant surface-treated steel sheet, which is a polyisocyanate compound.
[8] The surface-treated steel sheet according to [7] , wherein the polyisocyanate compound is obtained by blocking at least a part of isocyanate groups of the polyisocyanate compound with a blocking agent.
[9] In the surface-treated steel sheet according to any one of [1] to [8] , the upper layer coating composition further includes a solid lubricant and a total of 100 resin solids of component (D) and component (E). A highly corrosion-resistant surface-treated steel sheet containing 1 to 30 parts by mass of solids with respect to parts by mass.

  The surface-treated steel sheet of the present invention has a very excellent flat plate and post-processing corrosion resistance despite the fact that it does not contain chromium in the film, and also has excellent weldability and paintability. For this reason, the surface-treated steel sheet of the present invention is particularly useful for automobile applications.

The details of the present invention and the reasons for limitation will be described below.
Examples of the zinc-based plated steel sheet used as the base of the surface-treated steel sheet of the present invention include a galvanized steel sheet, a Zn-Ni alloy-plated steel sheet, a Zn-Fe alloy-plated steel sheet (electroplated steel sheet, galvannealed steel sheet), Zn-Cr. Alloy-plated steel sheet, Zn-Mn alloy-plated steel sheet, Zn-Co alloy-plated steel sheet, Zn-Co-Cr alloy-plated steel sheet, Zn-Cr-Ni alloy-plated steel sheet, Zn-Cr-Fe alloy-plated steel sheet, Zn-Al alloy plating Steel plate (for example, Zn-5% Al alloy-plated steel plate, Zn-55% Al alloy-plated steel plate), Zn-Mg alloy-plated steel plate, Zn-Al-Mg alloy-plated steel plate (for example, Zn-6% Al-3% Mg) Alloy-plated steel sheets, Zn-11% Al-3% Mg alloy-plated steel sheets), and metal oxides, polymers, etc. are dispersed in the plating film of these plated steel sheets Zinc-based composite-plated steel sheet (for example, Zn-SiO ₂ dispersion plating steel plate) was the like can be used.

In addition, among the above-described plating, a multi-layer plated steel sheet in which two or more layers of the same type or different types are plated can also be used.
Moreover, as an aluminum system plated steel plate used as the base of the surface treatment steel plate of this invention, an aluminum plating steel plate, an Al-Si alloy plating steel plate, etc. can be used.
Moreover, as a plated steel plate, the steel plate surface may be previously plated with lightness such as Ni, and various plating as described above may be performed thereon.
As a plating method, any feasible method among an electrolytic method (electrolysis in an aqueous solution or electrolysis in a non-aqueous solvent), a melting method, and a gas phase method can be adopted.
Furthermore, in order to prevent blackening of the plating, about 1 to 2000 ppm of one or more trace elements of Ni, Co, Fe are deposited in the plating film, or one of Ni, Co, Fe is deposited on the surface of the plating film. These elements may be deposited by performing a surface conditioning treatment with an alkaline aqueous solution or an acidic aqueous solution containing the above.

Next, the surface treatment film formed as the first layer film and the surface treatment composition for forming this film on the surface of the zinc-based plated steel sheet or the aluminum-based plated steel sheet will be described.
In the surface-treated steel sheet of the present invention, the surface-treated film formed on the surface of the zinc-based plated steel sheet or the aluminum-based plated steel sheet is applied with a surface treatment composition containing the following components (a) to (c) and dried. It is the surface treatment film formed by this. This surface treatment film does not contain chromium (except for chromium as an inevitable impurity).
(A) a polyalkylene glycol-modified epoxy resin (A) obtained by reacting a polyalkylene glycol having a number average molecular weight of 400 to 20,000, a bisphenol type epoxy resin, an active hydrogen-containing compound and a polyisocyanate compound, and the polyalkylene glycol-modified A resin obtained by reacting an epoxy group-containing resin (B) other than the epoxy resin (A) with an active hydrogen-containing compound comprising a hydrazine derivative (C) in which some or all of the compounds have active hydrogen is used in water. Dispersed aqueous epoxy resin dispersion (b) Silane coupling agent: 1 to 300 parts by mass with respect to 100 parts by mass of the solid content of the aqueous epoxy resin dispersion (a) (c) Phosphoric acid and / or hexafluoro Metal acid: 0 with respect to 100 parts by mass of the solid content of the aqueous epoxy resin dispersion (a) 1 to 80 parts by weight

The surface treatment composition for forming the surface treatment film needs to be a water-solvent type in order to generate the compound layer and the precipitated compound as described above. Therefore, a water-dispersible resin is used as the organic resin. It is done.
First, the aqueous epoxy resin dispersion that is the component (a) will be described.
In this aqueous epoxy resin dispersion, a specific polyalkylene glycol-modified epoxy resin (A), an epoxy group-containing resin (B) other than the polyalkylene glycol-modified epoxy resin (A), and a part or all of the compounds are active. An active hydrogen-containing compound comprising a hydrazine derivative (C) having hydrogen (that is, a hydrazine derivative (C) having active hydrogen and, if necessary, an active hydrogen-containing compound (i) other than the hydrazine derivative (C)); The resin obtained by reacting is dispersed in water.

The polyalkylene glycol-modified epoxy resin (A) is obtained by reacting a polyalkylene glycol having a number average molecular weight of 400 to 20000, a bisphenol type epoxy resin, an active hydrogen-containing compound, and a polyisocyanate compound. .
As the polyalkylene glycol, for example, polyethylene glycol, polypropylene glycol, polybutylene glycol and the like can be used, and among them, polyethylene glycol is particularly preferable. The number average molecular weight of the polyalkylene glycol is suitably in the range of 400 to 20000, preferably 500 to 10,000, from the viewpoint of water dispersibility and storage properties of the resulting resin.
The bisphenol-type epoxy resin is a bisphenol compound having at least one epoxy group in one molecule, and in particular, a bisphenol diester obtained by a condensation reaction between a bisphenol compound and an epihalohydrin (for example, epichlorohydrin). Glycidyl ether is preferable because a film excellent in flexibility and corrosion resistance can be easily obtained.

Typical examples of bisphenol compounds that can be used for the preparation of bisphenol-type epoxy resins include bis (4-hydroxyphenyl) -2,2-propane, bis (4-hydroxyphenyl) -1,1-ethane, and bis. (4-hydroxyphenyl) -methane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) -1,1-isobutane, bis (4-hydroxy-3-t- Butylphenyl) -2,2-propane and the like. Of the epoxy resins prepared using such bisphenol-based compounds, bisphenol A type epoxy resins are particularly suitable in that a film excellent in flexibility and corrosion resistance can be obtained.
Further, the bisphenol type epoxy resin generally has a number average molecular weight of about 310 to 10,000, particularly preferably about 320 to 2,000, from the viewpoint of production stability during production of the polyalkylene glycol-modified epoxy resin. The epoxy equivalent is preferably in the range of about 155 to 5000, particularly desirably about 160 to 1000.

  The active hydrogen-containing compound is used for blocking isocyanate groups in the polyalkylene glycol-modified epoxy resin (A). Typical examples thereof include monohydric alcohols such as methanol, ethanol and diethylene glycol monobutyl ether; monovalent carboxylic acids such as acetic acid and propionic acid; monovalent thiols such as ethyl mercaptan. Other blocking agents (active hydrogen-containing compounds) include secondary amines such as diethylamine; one secondary amino group or hydroxyl group such as diethylenetriamine and monoethanolamine and one or more primary groups. A compound in which a primary amino group of an amine compound containing an amino group is modified to aldimine, ketimine, oxazoline or imidazoline by heating reaction with a ketone, aldehyde or carboxylic acid at a temperature of, for example, 100 to 230 ° C .; methyl ethyl ketoxime And oximes such as phenol; phenols such as phenol and nonylphenol; These compounds generally have a number average molecular weight in the range of 30 to 2000, particularly preferably 30 to 200.

  The polyisocyanate compound is a compound having 2 or more, preferably 2 or 3 isocyanate groups in one molecule, and those generally used for the production of polyurethane resins can be used in the same manner. Such polyisocyanate compounds include aliphatic, alicyclic and aromatic polyisocyanate compounds. Representative examples include aliphatic polyisocyanate compounds such as hexamethylene diisocyanate (HMDI), HMDI biuret compound, HMDI isocyanurate compound; isophorone diisocyanate (IPDI), IPDI biuret compound, IPDI isocyanurate compound, Examples thereof include alicyclic polyisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated 4,4′-diphenylmethane diisocyanate; aromatic polyisocyanate compounds such as tolylene diisocyanate and xylylene diisocyanate.

In general, the blending ratio of each component during the production of the polyalkylene glycol-modified epoxy resin (A) is suitably in the following range.
That is, the equivalent ratio of the hydroxyl group of the polyalkylene glycol to the isocyanate group of the polyisocyanate compound is 1 / 1.2 to 1/10, preferably 1 / 1.5 to 1/5, particularly preferably 1 / 1.5 to A value of 1/3 is appropriate. The equivalent ratio of the hydroxyl group of the active hydrogen-containing compound to the isocyanate group of the polyisocyanate compound is 1/2 to 1/100, preferably 1/3 to 1/50, particularly preferably 1/3 to 1/20. Is appropriate. The equivalent ratio of the total amount of hydroxyl groups of the polyalkylene glycol, the bisphenol type epoxy resin and the active hydrogen-containing compound to the isocyanate group of the polyisocyanate compound is 1 / 1.5 or less, preferably 1 / 0.1 to 1/1. .5, particularly preferably 1 / 0.1 to 1 / 1.1.

The reaction of the polyalkylene glycol, the bisphenol type epoxy resin, the active hydrogen-containing compound and the polyisocyanate compound can be performed by a known method.
The polyalkylene glycol-modified epoxy resin (A) obtained above, an epoxy group-containing resin (B) other than the polyalkylene glycol-modified epoxy resin (A), and a hydrazine derivative in which some or all of the compounds have active hydrogen By reacting with the active hydrogen-containing compound comprising (C), an epoxy resin that can be easily dispersed in water and has good adhesion to the material can be obtained.

As the epoxy group-containing resin (B) other than the polyalkylene glycol-modified epoxy resin (A), a glycidyl group is introduced by reacting polyphenols such as bisphenol A, bisphenol F, and novolac type phenol with an epihalohydrin such as epichlorohydrin. Or an aromatic epoxy resin obtained by further reacting this glycidyl group-introduced reaction product with a polyphenol to increase the molecular weight; and further, an aliphatic epoxy resin, an alicyclic epoxy resin, etc. One kind can be used alone, or two or more kinds can be mixed and used. These epoxy resins preferably have a number average molecular weight of 1500 or more, particularly when film formation at low temperatures is required.
Examples of the epoxy group-containing resin (B) include resins obtained by reacting various modifiers with epoxy groups or hydroxyl groups in the epoxy group-containing resin. For example, epoxy ester resins obtained by reacting a dry oil fatty acid. An epoxy acrylate resin modified with a polymerizable unsaturated monomer component containing acrylic acid or methacrylic acid; a urethane-modified epoxy resin reacted with an isocyanate compound;

Further, as the epoxy group-containing resin (B), an unsaturated monomer having an epoxy group and a polymerizable unsaturated monomer component essentially comprising an acrylic ester or a methacrylic ester are used as a solution polymerization method, emulsion polymerization method or suspension polymerization method. An acrylic copolymer resin copolymerized with an epoxy group-containing monomer synthesized by a method such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl ( Acrylic or methacrylic acid such as (meth) acrylate, n-, iso- or tert-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate C1-C24 Alkyl ester; acrylic acid, methacrylic acid, styrene, vinyl toluene, acrylamide, acrylonitrile, N-methylol (meth) acrylamide, C1-4 alkyl etherified product of N-methylol (meth) acrylamide; N, N-diethylaminoethyl methacrylate, etc. Can be mentioned. Moreover, as an unsaturated monomer which has an epoxy group, if it has an epoxy group and a polymerizable unsaturated group, such as glycidyl methacrylate, glycidyl acrylate, and 3,4 epoxy cyclohexyl-1-methyl (meth) acrylate, It is not limited.
The acrylic copolymer resin may be a resin modified with a polyester resin, an epoxy resin, a phenol resin, or the like.

上記化学構造式中、ｑは０〜５０の整数、好ましくは１〜４０の整数、特に好ましくは２〜２０の整数である。
このようなビスフェノールＡ型エポキシ樹脂は、当業界において広く知られた製造法により得ることができる。 Particularly preferred as the epoxy group-containing resin (B) is a resin represented by the following chemical structural formula, which is a reaction product of bisphenol A and epihalohydrin, and is particularly suitable because of its excellent corrosion resistance.

In said chemical structural formula, q is an integer of 0-50, Preferably it is an integer of 1-40, Most preferably, it is an integer of 2-20.
Such a bisphenol A type epoxy resin can be obtained by a production method widely known in the art.

Examples of the active hydrogen-containing compound that reacts with the epoxy group of the epoxy group-containing resin (B) include the following.
・ Hydrazine derivatives with active hydrogen ・ Primary or secondary amine compounds with active hydrogen ・ Organic acids such as ammonia and carboxylic acids ・ Hydrogen halides such as hydrogen chloride ・ Alcohols, thiols ・ Active hydrogen Quaternary chlorinating agent which is a mixture of hydrazine derivative or tertiary amine and acid which does not have, when adjusting the aqueous epoxy resin dispersion, one or more of these can be used, but excellent corrosion resistance In order to obtain, at least a part (preferably all) of the active hydrogen-containing compound needs to be a hydrazine derivative having active hydrogen. That is, among these, the hydrazine derivative (C) having active hydrogen is an essential component, and an active hydrogen-containing compound (A) other than the hydrazine derivative (C) is used as necessary.

The following can be mentioned as a typical example of the amine compound which has the said activated hydrogen.
(1) a primary amino group of an amine compound containing one secondary amino group and one or more primary amino groups, such as diethylenetriamine, hydroxyethylaminoethylamine, ethylaminoethylamine, methylaminopropylamine, etc .; A compound modified with aldimine, ketimine, oxazoline or imidazoline by heating reaction with aldehyde or carboxylic acid at a temperature of about 100 to 230 ° C., for example;
(2) Secondary monoamines such as diethylamine, diethanolamine, di-n- or -iso-propanolamine, N-methylethanolamine, N-ethylethanolamine;

(3) a secondary amine-containing compound obtained by adding a monoalkanolamine such as monoethanolamine and a dialkyl (meth) acrylamide by a Michael addition reaction;
(4) A compound obtained by modifying a primary amine group of alkanolamine such as monoethanolamine, neopentanolamine, 2-aminopropanol, 3-aminopropanol, 2-hydroxy-2 '(aminopropoxy) ethyl ether to ketimine;

  The quaternary chlorinating agent that can be used as a part of the active hydrogen-containing compound can react with an epoxy group because a hydrazine derivative or a tertiary amine that does not have an active hydrogen is not reactive with an epoxy group by itself. Therefore, it is a mixture with an acid. The quaternary chlorinating agent reacts with an epoxy group in the presence of water as necessary to form a quaternary salt with the epoxy group-containing resin. The acid used to obtain the quaternary chlorinating agent may be any of organic acids such as acetic acid and lactic acid, and inorganic acids such as hydrochloric acid. Examples of the hydrazine derivative having no active hydrogen used for obtaining a quaternary chlorinating agent include 3,6-dichloropyridazine, and examples of the tertiary amine include dimethylethanolamine, triethylamine, Examples include trimethylamine, triisopropylamine, and methyldiethanolamine.

It is a hydrazine derivative having active hydrogen that exhibits the most useful and excellent corrosion resistance performance among the active hydrogen-containing compounds.
Specific examples of the hydrazine derivative having active hydrogen include the following.
(A) Carbohydrazide, propionic acid hydrazide, salicylic acid hydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanoic acid dihydrazide, isophthalic acid dihydrazide, thiocarbohydrazide, 4,4'-oxybisbenzenesulfonylhydrazide, benzophenone hydrazone, aminopolyacrylamide Hydrazide compounds such as;
(B) pyrazole compounds such as pyrazole, 3,5-dimethylpyrazole, 3-methyl-5-pyrazolone, 3-amino-5-methylpyrazole;

(C) 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 5-amino -3-mercapto-1,2,4-triazole, 2,3-dihydro-3-oxo-1,2,4-triazole, 1H-benzotriazole, 1-hydroxybenzotriazole (monohydrate), 6- Triazole compounds such as methyl-8-hydroxytriazolopyridazine, 6-phenyl-8-hydroxytriazolopyridazine, 5-hydroxy-7-methyl-1,3,8-triazaindolizine;

(D) tetrazole compounds such as 5-phenyl-1,2,3,4-tetrazole and 5-mercapto-1-phenyl-1,2,3,4-tetrazole;
(E) thiadiazole compounds such as 5-amino-2-mercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole;
(F) maleic hydrazide, 6-methyl-3-pyridazone, 4,5-dichloro-3-pyridazone, 4,5-dibromo-3-pyridazone, 6-methyl-4,5-dihydro-3-pyridazone, etc. Pyridazine compounds;
Among these, pyrazole compounds and triazole compounds having a 5-membered or 6-membered ring structure and having a nitrogen atom in the ring structure are particularly suitable.
These hydrazine derivatives can be used individually by 1 type or in mixture of 2 or more types.

  A polyalkylene glycol-modified epoxy resin (A) as described above, an epoxy group-containing resin (B) other than the polyalkylene glycol-modified epoxy resin (A), and a hydrazine derivative in which some or all of the compounds have active hydrogen. By reacting the active hydrogen-containing compound comprising (C) with a temperature of preferably 10 to 300 ° C., more preferably 50 to 150 ° C. for about 1 to 8 hours, and dispersing the resulting resin in water, The aqueous epoxy resin dispersion described above can be obtained.

  The above reaction may be performed by adding an organic solvent, and the type of the organic solvent to be used is not particularly limited. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, dibutyl ketone, cyclohexanone; ethanol, butanol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether , Propylene glycol, propylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and other alcohols and ethers containing hydroxyl groups; ethyl acetate, butyl acetate, ethylene glycol monobutyl ether acetate and other esters; toluene, xylene Aromatic hydrocarbons, etc. Indicates possible, it is possible to use one or more of these. Of these, ketone-based or ether-based solvents are particularly preferable from the viewpoints of solubility with an epoxy resin, film formation, and the like.

An activity comprising a polyalkylene glycol-modified epoxy resin (A), an epoxy group-containing resin (B) other than the polyalkylene glycol-modified epoxy resin (A), and a hydrazine derivative (C) in which some or all of the compounds have active hydrogen. The compounding ratio with the hydrogen-containing compound is such that the equivalent ratio of the active hydrogen group in the hydrazine derivative (C) to the epoxy group in the polyalkylene glycol-modified epoxy resin (A) and the epoxy group-containing resin (B) is 0.01 to 10. From the viewpoints of corrosion resistance, water dispersibility of the resin, and the like, it is appropriate that the thickness is preferably 0.1 to 8, more preferably 0.2 to 4.
Further, a part of the hydrazine derivative (C) having active hydrogen can be replaced with the active hydrogen-containing compound (i), but the amount to be replaced (that is, active hydrogen in the active hydrogen-containing compound including the hydrazine derivative (C)) It is appropriate from the viewpoint of corrosion resistance and adhesion that the ratio of the compound (a) is 90 mol% or less, preferably 70 mol% or less, more preferably 10 to 60 mol%.

  Moreover, in order to form a dense barrier film, it is desirable to mix a curing agent in the resin composition and heat cure the film. The curing method for forming a film with the resin composition was selected from (1) a curing method using a urethanization reaction between an isocyanate and a hydroxyl group in a base resin, and (2) melamine, urea, and benzoguanamine. Etherification reaction between an alkyl etherified amino resin obtained by reacting one or more methylol compounds obtained by reacting formaldehyde with one or more monovalent alcohols having 1 to 5 carbon atoms and a hydroxyl group in the base resin. However, it is particularly preferable to use a urethanization reaction between an isocyanate and a hydroxyl group in the base resin as a main reaction.

  The polyisocyanate compound as a curing agent that can be used in the curing method (1) is an aliphatic, alicyclic (including heterocyclic) or aromatic isocyanate compound having at least two isocyanate groups in one molecule. Or a compound obtained by partially reacting these compounds with a polyhydric alcohol. Examples of such polyisocyanate compounds include the following.

(A) m- or p-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, o- or p-xylylene diisocyanate, hexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate (B) above (A) Or a mixture thereof and a polyhydric alcohol (dihydric alcohols such as ethylene glycol and propylene glycol; trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric alcohols such as pentaerythritol; sorbitol, dipentaerythritol, etc. A compound obtained by reaction with a hexavalent alcohol, etc., in which at least two isocyanates remain in one molecule. These polyisocyanate compounds are used singly or in combination of two or more. it can.

Moreover, as a protective agent (blocking agent) of a polyisocyanate compound, for example,
(I) aliphatic monoalcohols such as methanol, ethanol, propanol, butanol, octyl alcohol;
(Ii) ethylene glycol and / or diethylene glycol monoethers, for example, monoethers such as methyl, ethyl, propyl (n-, iso), butyl (n-, iso, sec);
(Iii) aromatic alcohols such as phenol and cresol;
(Iv) oximes such as acetooxime and methyl ethyl ketone oxime;
A polyisocyanate compound that is stably protected at least at room temperature can be obtained by reacting one or more of these with the polyisocyanate compound.

  Thus, the polyisocyanate compound (a2) to be blended as a curing agent preferably has a blending ratio with the aqueous epoxy resin dispersion (a) (the above component (a)) of (a) / (a2) = 95/5. It is appropriate that 55/45 (mass ratio of nonvolatile content), more preferably (a) / (a2) = 90/10 to 65/35. The polyisocyanate compound has water absorbency, and if it is blended exceeding the blending ratio of (a) / (a2) = 55/45, the adhesion of the surface treatment film is deteriorated. Furthermore, an unreacted polyisocyanate compound moves into the upper layer coating film by electrodeposition coating or the like, causing inhibition of curing of the upper layer coating film or poor adhesion. From such a viewpoint, the upper limit of the blending ratio of the polyisocyanate compound (a2) is preferably (a) / (a2) = 55/45.

The water-dispersible resin is sufficiently crosslinked by the addition of the crosslinking agent (curing agent) as described above, but it is desirable to use a known curing accelerating catalyst in order to further increase the low-temperature crosslinking property. Examples of the curing accelerating catalyst include N-ethylmorpholine, dibutyltin dilaurate, cobalt naphthenate, stannous chloride, zinc naphthenate, and bismuth nitrate.
In addition, for the purpose of slightly improving physical properties such as adhesion, a known resin such as acrylic, alkyd, or polyester can be mixed and used together with the epoxy group-containing resin (B).

To water-disperse a reaction product of an active hydrogen-containing compound comprising a polyalkylene glycol-modified epoxy resin (A), an epoxy group-containing resin (B) and a hydrazine derivative (C) in which some or all of the compounds have active hydrogen. For example, the following method can be adopted.
(1) A tertiary amine which is a neutralizing agent by reacting an epoxy group of an epoxy group-containing resin (ie, resin (A) or (B)) with a dibasic acid or secondary amine which is an active hydrogen-containing compound. , Neutralization with acetic acid or phosphoric acid, water dispersion (2) Using a modified epoxy resin obtained by reacting an epoxy resin with a terminal hydroxyl group-containing polyalkylene oxide such as polyethylene glycol or polypropylene glycol with an isocyanate, Method to disperse in water (3) Method using both (1) and (2) above

  In the surface treatment composition, in addition to the specific water-dispersible resin described above, other water-dispersible resins and / or water-soluble resins include, for example, acrylic resins, urethane resins, polyester resins, epoxy resins, You may mix | blend 1 type (s) or 2 or more types, such as ethylene-type resin, alkyd-type resin, a phenol resin, and an olefin resin, by about 15 mass% by the ratio in the total resin solid content.

Next, the silane coupling agent which is the said component (b) is demonstrated.
Examples of the silane coupling agent include vinyl methoxy silane, vinyl ethoxy silane, vinyl trichloro silane, vinyl trimethoxy silane, vinyl triethoxy silane, β- (3,4 epoxy cyclohexyl) ethyl trimethoxy silane, and γ-glycid. Xylpropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ -Aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-me Tacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, γ -Acryloxypropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, γ-isocyanatopropyl Triethoxysilane, γ-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N- (vinylbenzylamine) -β-aminoethyl-γ-aminopropyltri Etc. can be mentioned Tokishishiran, these one may be used alone or in combination of two or more.

In the present invention, the reason described above is considered to improve the white rust resistance by including a silane coupling agent together with a specific acid component in the surface treatment composition.
Among the silane coupling agents, a silane coupling agent having an amino group as a reactive functional group is particularly preferable from the viewpoint of having a functional group highly reactive with the water-dispersible resin of the component (a). . Examples of such silane coupling agents include N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ. -Aminopropyltrimexysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc., specifically, “KBM-903” and “KBE-903” manufactured by Shin-Etsu Chemical Co., Ltd. , “KBM-603”, “KBE-602”, “KBE-603” (all are trade names), and the like.

  The compounding quantity of a silane coupling agent is 1-300 mass parts with respect to 100 mass parts of solid content of the aqueous | water-based epoxy resin dispersion which is the said component (a), Preferably it is 5-100 mass parts, More preferably, it is 15-50. The mass part is appropriate. If the amount of the silane coupling agent is less than 1 part by mass, the corrosion resistance is inferior. On the other hand, if it exceeds 300 parts by mass, a sufficient film cannot be formed, so that the effect of improving the adhesion and barrier properties with the water-dispersible resin can be exhibited. Therefore, the corrosion resistance is reduced.

Next, phosphoric acid and / or hexafluorometal acid, which is the component (c), acts on an inactive plating metal surface to activate the plating metal surface. The phosphoric acid and hexafluorometal acid may be used alone or in combination.
The type of hexafluorometal acid is not particularly limited, but in particular hexafluorometal containing one or more elements selected from Ti, Si, Zr such as fluorinated titanate, fluorinated zirconate, and fluoric acid. Acids are preferred, and one or more of these can be used.

  The total amount of phosphoric acid and / or hexafluorometal acid is 0.1 to 80 parts by mass, preferably 1 to 100 parts by mass of the solid content of the aqueous epoxy resin dispersion as component (a). 60 mass parts, more preferably 5-50 mass parts is suitable. When the blending amount of phosphoric acid and / or hexafluorometal acid is less than 0.1 parts by mass, the corrosion resistance is inferior. On the other hand, when it exceeds 80 parts by mass, the soluble component of the film increases, so that the corrosion resistance is lowered.

A water-soluble phosphate can be added to the surface treatment composition as necessary for the purpose of improving the corrosion resistance. As the water-soluble phosphate, for example, one or more metal salts such as orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid, and metaphosphoric acid can be used. Moreover, you may add 1 or more types of the salt (for example, phytic acid, phytate, phosphonic acid, phosphonate, and these metal salts) of organic phosphoric acid. Of these, the primary phosphate is preferable from the viewpoint of the stability of the surface treatment composition.
There is no particular limitation on the form of phosphate present in the film, and it may be crystalline or non-crystalline. There are no particular restrictions on the ionicity and solubility of the phosphate in the film. The reason why the corrosion resistance is improved by adding the water-soluble phosphate is considered that the water-soluble phosphate forms a dense hardly soluble compound at the time of film formation.

  As described above, the silane coupling agent chemically bonds with both the activated plating metal and the film-forming resin, thereby providing excellent adhesion and corrosion resistance between the plating metal and the film-forming resin. There are unavoidably inactive portions on the metal surface, and such an inactive site hardly causes the above-mentioned chemical bond and cannot sufficiently exhibit the rust prevention effect. The water-soluble phosphate forms a dense hardly soluble compound at the time of film formation on such a plated film portion. That is, as the plating film is dissolved by the phosphate ions of the water-soluble phosphate, the pH increases at the plating film / surface treatment composition interface, resulting in the formation of a precipitate film of the water-soluble phosphate, which is corrosion resistant. It contributes to the improvement.

From the viewpoint of obtaining particularly excellent corrosion resistance, Al, Mn, Ni, and Mg are particularly desirable as the cationic species of the water-soluble phosphate, and the water-soluble phosphorus containing one or more elements selected from these is preferred. It is preferable to use an acid salt. Examples of such water-soluble phosphates include primary aluminum phosphate, primary manganese phosphate, primary nickel phosphate, primary magnesium phosphate, and among these, primary aluminum phosphate is particularly preferable. Is most preferred. In addition, the ratio of the cation component to the P ₂ O ₅ component is preferably 40% to 100%, based on the case of a saturated primary phosphate, when this is taken as 100%. Therefore, in the case of a divalent metal primary phosphate (for example, Mg (H ₂ PO ₄ ) ₂ ), the molar ratio of cation (for example, Mg) / P ₂ O ₅ is 0.4 to 1.0, 3 The molar ratio of cation (for example, Al) / P ₂ O ₅ in the case of a monovalent metal monophosphate (for example, Al (H ₂ PO ₄ ) ₃ ) is preferably 0.27 to 0.67. If the ratio of the cation component to the P ₂ O ₅ component is less than 40%, the soluble solubility of the film is impaired by the soluble phosphoric acid and the corrosion resistance is lowered. On the other hand, if it exceeds 100%, the stability of the processing solution is significantly lost. This is not preferable.

  The amount of the water-soluble phosphate is 0.1 to 60 parts by mass in terms of the solid content with respect to 100 parts by mass of the solid content of the aqueous epoxy resin dispersion (a) as the component (a), preferably Is suitably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass. If the blending amount of the water-soluble phosphate is less than 0.1 parts by mass, the effect of improving the corrosion resistance is not sufficient. On the other hand, if it exceeds 60 parts by mass, the soluble component of the film increases, so the corrosion resistance decreases, which is not preferable. .

A non-chromium rust preventive additive can be blended with the surface treatment composition as needed for the purpose of improving corrosion resistance. Particularly excellent anticorrosion performance (self-repairing property) can be obtained by blending such a non-chromium rust preventive additive into the surface treatment composition.
In particular, it is preferable to use one or more selected from the following (f1) to (f5) as the non-chromium anticorrosive additive.
(F1) silicon oxide (f2) calcium compound (f3) sparingly soluble phosphate compound (f4) molybdate compound (f5) one or more selected from triazoles, thiols, thiadiazoles, thiazoles, thiurams The organic compound containing an S atom The details and anticorrosion mechanisms of the non-chromium rust preventive additives (f1) to (f5) are as follows.

First, as the component (f1), colloidal silica or dry silica, which is fine particle silica, can be used. From the viewpoint of corrosion resistance, calcium ion-exchanged silica in which calcium is bound to the surface is used. Is desirable.
As colloidal silica, for example, SNOWTEX O, 20, 30, 40, C, S (all trade names) manufactured by Nissan Chemical Co., Ltd. can be used, and as fumed silica, Nippon Aerosil ( AEROSIL made by
R971, R812, R811, R974, R202, R805, 130, 200, 300, 300CF (all are trade names) can be used. As calcium ion exchange silica, WRGrace & Co. SHIELDEX C303, SHIELDEX AC3, SHIELDEX AC5 (all are trade names) manufactured by SHIELDEX, SHIELDEX manufactured by Fuji Silysia Chemical Co., Ltd.
SY710 (both are trade names) can be used. These silicas contribute to the production of dense and stable zinc corrosion products in a corrosive environment, and the corrosion products are formed densely on the plating surface, thereby suppressing the promotion of corrosion.

In addition, the above components (f2) and (f3) exhibit particularly excellent anticorrosion performance (self-repairing property) due to precipitation.
The calcium compound as the component (e2) may be any of calcium oxide, calcium hydroxide, and calcium salt, and one or more of these can be used. In addition, there are no particular restrictions on the type of calcium salt. In addition to simple salts containing only calcium as a cation such as calcium silicate, calcium carbonate, and calcium phosphate, calcium and calcium such as calcium phosphate / zinc, calcium phosphate / magnesium, etc. Double salts containing other cations may be used. The components (f2) is baser calcium than zinc and aluminum as the plating metal in a corrosive environment is preferentially dissolved, this OH produced by the cathode reaction ^- sequestering defective portion as a product of dense and poorly soluble And suppress the corrosion reaction. Moreover, when it mix | blends with the above silicas, a calcium ion adsorb | sucks to the surface and neutralizes a surface charge electrically and aggregates. As a result, a dense and sparingly soluble protective film is formed to block the corrosion and suppress the corrosion reaction.

  Moreover, as a poorly soluble phosphoric acid compound which is said (f3), a poorly soluble phosphate can be used. This sparingly soluble phosphate includes all types of salts such as simple salts and double salts. Moreover, there is no limitation in the metal cation which comprises it, and any metal cation, such as poorly soluble zinc phosphate, magnesium phosphate, calcium phosphate, aluminum phosphate, may be sufficient. Further, there is no limitation on the skeleton or the degree of condensation of phosphate ions, and any of normal salt, dihydrogen salt, monohydrogen salt or phosphite may be used. In addition, orthophosphate may be polyphosphate other than orthophosphate. Includes all condensed phosphates such as salts. This hardly soluble phosphorus compound is a metal plating zinc or aluminum eluted by corrosion, and forms a dense and hardly soluble protective film by complexing reaction with phosphate ions dissociated by hydrolysis, thereby blocking the origin of corrosion. Inhibits corrosion reactions.

  As the molybdate compound (f4), for example, molybdate can be used. The molybdate is not limited in its skeleton and degree of condensation, and examples thereof include orthomolybdate, paramolybdate, and metamolybdate. Moreover, all salts, such as a single salt and a double salt, are included, and a phosphomolybdate etc. are mentioned as a double salt. Molybdate compounds exhibit self-repairing properties due to the passivating effect. That is, by forming a dense oxide on the plating film surface together with dissolved oxygen in a corrosive environment, the corrosion starting point is blocked and the corrosion reaction is suppressed.

  Examples of the organic compound (f5) include the following. That is, as triazoles, 1,2,4-triazole, 3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 5-amino-3-mercapto-1,2 1,4-triazole, 1H-benzotriazole, etc., and as thiols, 1,3,5-triazine-2,4,6-trithiol, 2-mercaptobenzimidazole, etc., and as thiadiazoles, 5- Amino-2-mercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole and the like, and as thiazoles, 2-N, N-diethylthiobenzothiazole, 2-mercapto Examples include benzothiazoles, and examples of thiurams include tetraethylthiuram disulfide. It is. These organic compounds exhibit self-repairing properties due to the adsorption effect. That is, zinc and aluminum eluted by corrosion are adsorbed on polar groups containing sulfur contained in these organic compounds to form an inert film, thereby blocking the corrosion starting point and suppressing the corrosion reaction.

The blending amount of the non-chromium rust preventive additive is preferably 0.1 to 50 parts by mass, more preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the solid content of the aqueous epoxy resin dispersion as the component (a). The amount is preferably 0.5 to 30 parts by mass. If the blending amount of the non-chromium rust preventive additive is less than 0.1 parts by mass, the effect of improving the corrosion resistance after alkali degreasing cannot be sufficiently obtained. On the other hand, if it exceeds 50 parts by mass, the paintability and workability deteriorate. In addition to this, the corrosion resistance tends to decrease.
Two or more rust preventive additives (f1) to (f5) may be added in combination. In this case, since the inherent anticorrosive action is combined, higher corrosion resistance can be obtained. In particular, calcium ion-exchanged silica is used as the component (f1) and one or more of the components (f3), (f4), and (f5), particularly preferably the components (f3) to (f5). When all are added in combination, particularly excellent corrosion resistance is obtained.

  Further, in the surface treatment film (and surface treatment composition), other oxide fine particles (for example, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, antimony oxide, etc.), phosphomolybdate as corrosion inhibitors. One or more kinds of organic inhibitors (for example, hydrazine and its derivatives, thiol compounds, thiocarbamates, etc.) can be added.

Further, if necessary, in the surface treatment film (and surface treatment composition), as an additive, an organic coloring pigment (for example, condensed polycyclic organic pigment, phthalocyanine organic pigment, etc.), a coloring dye (for example, water-soluble) Azo metal dyes), inorganic pigments (eg, titanium oxide), conductive pigments (eg, metal powders such as zinc, aluminum, nickel, iron phosphide, antimony-doped tin oxide, etc.), coupling agents (eg, 1 type, or 2 or more types, such as a titanium coupling agent etc.) and a melamine cyanuric acid adduct.
The surface treatment film formed by the surface treatment composition containing the above components has a dry film thickness of 0.01 to 1.0 μm, preferably 0.1 to 0.8 μm. When the dry film thickness is less than 0.01 μm, the corrosion resistance is insufficient. On the other hand, when the dry film thickness exceeds 1.0 μm, the conductivity and workability are lowered.

Next, an upper layer film (organic film) formed as a second layer film on the surface treatment film and a coating composition for forming this film will be described.
This upper film is a film having a film thickness of 0.3 to 2.0 μm formed by applying and drying an upper film coating composition containing the following components (D) and (E). This upper layer film also does not contain chromium (except for chromium as an inevitable impurity).
(D) A bisphenol A type epoxy resin (d1) having an epoxy equivalent of 750 to 5000 and a number average molecular weight of 1500 to 10,000 has a compound (d2) having two or more carboxyl groups in one molecule and active hydrogen. Resin solution obtained by reacting hydrazine derivative (d3) (E) Curing agent having functional group that reacts with hydroxyl group

上記化学構造式中、ｑは０〜５０の整数、好ましくは１〜４０の整数、特に好ましくは２〜２０の整数である。 First, the resin solution (epoxy resin solution) which is the said component (D) is demonstrated.
As the bisphenol A type epoxy resin (d1), those having a number average molecular weight of 1500 to 10,000, preferably 2000 to 8000, and an epoxy equivalent of 750 to 5000, preferably 1000 to 4000 are used. When the number average molecular weight is less than 1500 or the epoxy equivalent is less than 750, the curing reaction rate is lowered and the film hardness is insufficient. On the other hand, if the number average molecular weight exceeds 10,000 or the epoxy equivalent exceeds 5000, the coating liquid becomes highly viscous and handling becomes difficult. In addition, when the coating solution concentration is lowered with respect to such increase in the viscosity of the coating solution, it becomes difficult to ensure the target film thickness, and the practicality is lowered.
From the viewpoint of the corrosion resistance of the coating film obtained, a bisphenol type epoxy resin represented by the following chemical structural formula, which is a reaction product of bisphenol A and epihalohydrin, is used as the bisphenol A type epoxy resin (d1). preferable.

In said chemical structural formula, q is an integer of 0-50, Preferably it is an integer of 1-40, Most preferably, it is an integer of 2-20.

  Examples of such commercially available bisphenol A type epoxy resin (d1) include jER1004 (epoxy equivalent of about 950, number average molecular weight of about 1600), jER1007 (epoxy equivalent of about 2250, number average molecular weight) manufactured by Japan Epoxy Resin Co., Ltd. About 2900), jER1009 (epoxy equivalent of about 3250, number average molecular weight of about 3750), jER1010 (epoxy equivalent of about 4000, number average molecular weight of about 5500), Araldite AER6099 (epoxy equivalent of about 3500, number average molecular weight of about 3800) manufactured by Asahi Ciba ), And Epoxy R-309 (epoxy equivalent of about 3500, number average molecular weight of about 3800) manufactured by Mitsui Chemicals, Inc. (all are trade names).

The structure of the compound (d2) having two or more carboxyl groups in one molecule is not particularly limited. For example, a polybasic acid compound, especially an aliphatic dicarboxylic acid (d21), or a polybasic acid compound A polycondensate (d22) having two carboxyl groups at the terminal obtained by a polycondensation reaction with a polyhydric alcohol can be particularly preferably applied.
Polybasic acid compounds include adipic acid, sebacic acid, suberic acid, succinic acid, glutaric acid, maleic acid, chloromaleic acid, fumaric acid, dodecanic acid, pimelic acid, azelaic acid, itaconic acid, ditraconic acid, etc. Examples thereof include 4 to 10 aliphatic dicarboxylic acids, derivatives of aliphatic dicarboxylic acids having 4 to 10 carbon atoms, dimer acid and hydrogenated dimer, phthalic acid, and terephthalic acid. Of these, straight-chain dibasic acids having 4 or more carbon atoms, such as adipic acid, sebacic acid, and dodecanoic acid, are particularly preferred from the viewpoint of press workability.

  Examples of the polyhydric alcohol used in the production of the polycondensate (d22) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, 1,4-butylene glycol, 1,6-hexanediol, and neopentyl. Examples include glycol, trimethylol ethane, trimethylol propane, glycerin, pentaerythritol and the like. In particular, linear dibasic acids such as adipic acid, sebacic acid and dodecanoic acid as polybasic acid compounds, and linear chains such as 1,4-butylene glycol and 1,6-hexanediol among polyhydric alcohols. Use of a polycondensate with glycol is preferred from the viewpoint of press workability.

Specific examples of the hydrazine derivative (d3) having active hydrogen include the following.
(1) Carbohydrazide, propionic acid hydrazide, salicylic acid hydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanoic acid dihydrazide, isophthalic acid dihydrazide, thiocarbohydrazide, 4,4'-oxybisbenzenesulfonylhydrazide, benzophenone hydrazone, aminopolyacrylamide Hydrazide compounds such as;

(2) pyrazole compounds such as pyrazole, 3,5-dimethylpyrazole, 3-methyl-5-pyrazolone, 3-amino-5-methylpyrazole;
(3) 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 5-amino -3-mercapto-1,2,4-triazole, 2,3-dihydro-3-oxo-1,2,4-triazole, 1H-benzotriazole, 1-hydroxybenzotriazole (monohydrate), 6- Triazole compounds such as methyl-8-hydroxytriazolopyridazine, 6-phenyl-8-hydroxytriazolopyridazine, 5-hydroxy-7-methyl-1,3,8-triazaindolizine;

(4) tetrazole compounds such as 5-phenyl-1,2,3,4-tetrazole and 5-mercapto-1-phenyl-1,2,3,4-tetrazole;
(5) thiadiazole compounds such as 5-amino-2-mercapto-1,3,4-thiadiazole and 2,5-dimercapto-1,3,4-thiadiazole;
(6) Maleic hydrazide, 6-methyl-3-pyridazone, 4,5-dichloro-3-pyridazone, 4,5-dibromo-3-pyridazone, 6-methyl-4,5-dihydro-3-pyridazone, etc. Pyridazine compounds;
Among these, pyrazole compounds and triazole compounds having a 5-membered or 6-membered ring structure and having a nitrogen atom in the ring structure are particularly suitable.
The hydrazine derivatives listed above can be used singly or in combination of two or more.
Further, mercaptotriazole and aminotriazole are particularly suitable because they are excellent in reactivity with epoxy groups and excellent in storage stability of paints.

Here, in the production of the epoxy resin solution as component (D), the compound (d2) having two or more carboxyl groups in one molecule is added to the bisphenol A type epoxy resin (d1) at 60 to 200 ° C., preferably 100 After obtaining the resin (I) reacted at a temperature of ˜160 ° C. to an acid value of 1 mgKOH / g or less, the hydrazine derivative (d3) having active hydrogen is heated to a temperature of 40 to 200 ° C., preferably 80 to 130 ° C. For about 1-8 hours.
The reaction ratio of the bisphenol A type epoxy resin (d1), the compound (d2) having two or more carboxyl groups in one molecule, and the hydrazine derivative (d3) having active hydrogen is based on the total number of moles. 35 to 90 mol%, preferably 40 to 70 mol% of bisphenol A type epoxy resin (d1), and 5 to 50 mol%, preferably 10 to 45, of compound (d2) having two or more carboxyl groups in one molecule. It is appropriate that the hydrazine derivative (d3) having mol% and active hydrogen is in the range of 5 to 45 mol%, preferably 8 to 40 mol%.

  In the production of the resin (I), in particular, [number of moles of bisphenol A type epoxy resin (d1)] / [number of moles of compound (d2) having two or more carboxyl groups in one molecule] = 1.1 To 5, preferably 1.2 to 3, and more preferably 1.25 to 2. By setting it as the said range, the terminal of resin (I) can be made into an epoxy group, the hydrazine derivative (d3) which has active hydrogen can be made to react there, and an improvement in corrosion resistance can be aimed at. In addition, the compound (d2) having two or more carboxyl groups in one molecule is a soft component compared to the epoxy resin, and by distributing such a soft component uniformly and appropriately in the epoxy resin, the corrosion resistance is improved. And workability can be achieved. In addition, when the number of moles of the bisphenol A type epoxy resin (d1) / the number of moles of the compound (d2) is out of the range of 1.1 to 5, the aliphatic hydrocarbon chain as a soft component is unevenly distributed, This is not preferable because the workability of the obtained film is impaired. Further, the resin (I) is polymerized to increase the varnish viscosity, which is not preferable from the viewpoint of handling work and production.

  The above reaction may be performed by adding an organic solvent, and the type of the organic solvent to be used is not particularly limited. For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, dibutyl ketone, cyclohexanone; ethanol, butanol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether , Propylene glycol, propylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and other alcohols and ethers containing hydroxyl groups; ethyl acetate, butyl acetate, ethylene glycol monobutyl ether acetate and other esters; toluene, xylene Aromatic hydrocarbons etc. Illustration can, it is possible to use one or more of these. Of these, ketone-based or ether-based solvents are particularly preferable from the viewpoints of solubility with an epoxy resin and film-forming properties.

Next, the curing agent having a functional group that reacts with a hydroxyl group, which is the component (E), will be described.
In order to form a dense barrier film, a curing agent having a functional group that reacts with a hydroxyl group is blended in the resin composition, and the film is heated and cured. The curing method for forming a film with the resin composition was selected from (1) a curing method using a urethanization reaction between isocyanate and a hydroxyl group in the base resin, and (2) melamine, urea and benzoguanamine. Etherification reaction between an alkyl etherified amino resin obtained by reacting one or more methylol compounds obtained by reacting formaldehyde with one or more monovalent alcohols having 1 to 5 carbon atoms and a hydroxyl group in the base resin. Among these, a curing method utilizing an urethane reaction between an isocyanate and a hydroxyl group in the base resin is preferable.

The polyisocyanate compound as a curing agent that can be used in the curing method (1) is an aliphatic, alicyclic (including heterocyclic) or aromatic isocyanate compound having at least two isocyanate groups in one molecule. Or a compound obtained by partially reacting these compounds with a polyhydric alcohol. Examples of such polyisocyanate compounds include the following.
(I) m- or p-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, o- or p-xylylene diisocyanate, hexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate (ii) above (i) Or a mixture thereof and a polyhydric alcohol (dihydric alcohols such as ethylene glycol and propylene glycol; trihydric alcohols such as glycerin and trimethylolpropane; tetrahydric alcohols such as pentaerythritol; sorbitol, dipentaerythritol, etc. A compound of at least two isocyanates in one molecule. These polyisocyanate compounds may be used alone or in combination of two or more. It can be.

Moreover, as a protective agent (blocking agent) of a polyisocyanate compound, for example,
(1) Aliphatic monoalcohols such as methanol, ethanol, propanol, butanol, octyl alcohol;
(2) ethylene glycol and / or diethylene glycol monoethers, for example, monoethers such as methyl, ethyl, propyl (n-, iso), butyl (n-, iso, sec);
(3) Aromatic alcohols such as phenol and cresol;
(4) oximes such as acetooxime and methyl ethyl ketone oxime;
A polyisocyanate compound that is stably protected at least at room temperature can be obtained by reacting one or more of these with the polyisocyanate compound.

  Among them, a polyisocyanate compound having 4 or more, particularly 6 to 10 isocyanate groups in one molecule can form a tough film with the base resin even when the reaction temperature is lowered, The corrosion resistance of the processed part when strict processing is performed can be particularly improved. Specific examples of commercially available products containing four or more isocyanate groups in one molecule include, for example, MF-B80M, MF-B60X, MF-K60X, ME20-B80S (all trade names) manufactured by Asahi Kasei Corporation. And so on.

The mixing ratio of the curing agent of component (E) is 1 to 60 parts by mass with respect to 100 parts by mass of the solid content of the resin solution of component (D). If the blending ratio of the curing agent is less than 1 part by mass, the alkaline degreasing property is lowered and the corrosion resistance after processing is deteriorated, which is not preferable. On the other hand, when the amount exceeds 60 parts by mass, the workability is reduced, and film damage due to the processing increases. In this case, the corrosion resistance after processing deteriorates, which is not preferable.
Moreover, when using the above polyisocyanate compound as a hardening | curing agent which is a component (E), (E) / (D in mass ratio of solid content with respect to the resin solution which is the said component (D). ) = 5/95 to 45/55, preferably (E) / (D) = 10/90 to 35/65. The polyisocyanate compound has water absorbency, and if it is blended in excess of (E) / (D) = 45/55, the unreacted polyisocyanate compound moves into the upper layer coating film by electrodeposition coating, etc. It will cause curing inhibition and poor adhesion.
The epoxy resin is sufficiently crosslinked by the addition of the crosslinking agent (curing agent) as described above, but it is desirable to use a known curing accelerating catalyst in order to further increase the low temperature crosslinking property. Examples of the curing accelerating catalyst include N-ethylmorpholine, dibutyltin dilaurate, cobalt naphthenate, stannous chloride, zinc naphthenate, and bismuth nitrate.

The upper layer coating (upper layer coating composition) may contain a non-chromium rust preventive additive as needed for the purpose of improving corrosion resistance. By including such a non-chromium-based anticorrosive additive in the upper layer film, more excellent anticorrosion performance can be obtained.
In particular, it is preferable to use one or more selected from the following (f1) to (f5) as the non-chromium anticorrosive additive.
(F1) silicon oxide (f2) calcium compound (f3) sparingly soluble phosphate compound (f4) molybdate compound (f5) one or more selected from triazoles, thiols, thiadiazoles, thiazoles, thiurams , Organic Compound Containing S Atom The details and anticorrosion mechanism of the non-chromium rust preventive additives (f1) to (f5) are as described above for the surface treatment film.

The blending amount of the non-chromium-based rust preventive additive is preferably 0.1 to 50 parts by mass with respect to a total of 100 parts by mass of the resin solids of component (D) and component (E), and more preferably Preferably it is 1.0-30 mass parts. If the blending amount of the non-chromium rust preventive additive is less than 0.1 parts by mass, the effect of improving the corrosion resistance after alkaline degreasing cannot be sufficiently obtained, while if it exceeds 50 parts by mass, the paintability, workability and weldability are increased. Is not preferable because the corrosion resistance is also lowered. Furthermore, it is preferably 1.0 to 20 parts by mass from the viewpoint of weldability.
Two or more rust preventive additives (f1) to (f5) may be added in combination. In this case, since the inherent anticorrosive action is combined, higher corrosion resistance can be obtained. In particular, calcium ion-exchanged silica is used as the component (f1) and one or more of the components (f3), (f4), and (f5), particularly preferably the components (f3) to (f5). When all are added in combination, particularly excellent corrosion resistance is obtained.

  In addition to the above rust preventive additive components, other oxide fine particles (for example, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, etc.) may be used as the corrosion inhibitor in the upper layer coating (upper layer coating composition). Antimony oxide, etc.), phosphomolybdate (eg, aluminum phosphomolybdate), organic phosphoric acid and its salts (eg, phytic acid, phytate, phosphonic acid, phosphonate, and metal salts thereof, alkali metals) 1 type, or 2 or more types, such as a salt, an alkaline-earth metal salt, etc.), an organic inhibitor (for example, a hydrazine derivative, a thiol compound, a dithiocarbamate etc.) can be added.

In the upper layer coating (upper layer coating composition), if necessary, a solid lubricant can be blended for the purpose of improving the processability of the coating.
Examples of the solid lubricant applicable to the present invention include the following, and one or more of these can be used.
(1) Polyolefin wax, paraffin wax: For example, polyethylene wax, synthetic paraffin, natural paraffin, micro wax, chlorinated hydrocarbon, etc. (2) Fluororesin fine particles: For example, polyfluoroethylene resin (polytetrafluoroethylene resin, etc.) , Polyvinyl fluoride resin, polyvinylidene fluoride resin, etc.

  In addition, fatty acid amide compounds (eg, stearic acid amide, palmitic acid amide, methylene bis stearoamide, ethylene bis stearoamide, oleic acid amide, esylic acid amide, alkylene bis fatty acid amide), metal Soaps (eg, calcium stearate, lead stearate, calcium laurate, calcium palmitate, etc.), metal sulfides (eg, molybdenum disulfide, tungsten disulfide, etc.), graphite, graphite fluoride, boron nitride, polyalkylene glycol, You may use 1 type, or 2 or more types, such as an alkali metal sulfate.

Among the above solid lubricants, polyethylene wax and fluororesin fine particles (in particular, polytetrafluoroethylene resin fine particles) are preferable.
Examples of the polyethylene wax include, for example, Celestus 9615A, Celidust 3715, Seridust 3620, Seridust 3910 (all trade names) manufactured by Hoechst, Sunwax 131-P and Sunwax 161-P manufactured by Sanyo Chemical Co., Ltd. (Trade name), Chemipearl W-100, Chemipearl W-200, Chemipearl W-500, Chemipearl W-800, Chemipearl W-950 (all trade names) manufactured by Mitsui Chemicals, Inc. can be used.

Further, as fluororesin fine particles, tetrafluoroethylene fine particles are particularly suitable. For example, Lubron L-2 and Lubron L-5 (both trade names) manufactured by Daikin Industries, Ltd., Mitsui DuPont Co., Ltd. MP1100, MP1200 (all are trade names), Fullon Dispersion AD1, Fullon Dispersion AD2, Fullon L141J, Fullon L150J, and Fullon L155J (all are trade names) manufactured by Asahi IC Fluoropolymers Co., Ltd. are suitable. .
Among these, a particularly excellent lubricating effect can be expected by the combined use of polyolefin wax and tetrafluoroethylene fine particles.
The blending amount of the solid lubricant is preferably 1 to 30 parts by mass, more preferably 1 to 10 parts by mass in terms of the solid content with respect to a total of 100 parts by mass of the resin solids of component (D) and component (E). It is appropriate to make a part. If the blending amount of the solid lubricant is less than 1 part by mass, the lubricating effect is poor. On the other hand, if the blending amount exceeds 30 parts by mass, the paintability is lowered, which is not preferable.

For the upper layer film (coating composition for the upper layer film), an organic coloring pigment (for example, a condensed polycyclic organic pigment, a phthalocyanine organic pigment, etc.), a coloring dye (for example, an organic solvent) is further added as necessary. Soluble azo dyes, water-soluble azo metal dyes, etc.), inorganic pigments (eg titanium oxide, etc.), chelating agents (eg thiols, etc.), conductive pigments (eg, metal powders such as zinc, aluminum, nickel etc., phosphorus 1 type, or 2 or more types, such as an iron fluoride, an antimony dope-type tin oxide, a coupling agent (for example, a silane coupling agent, a titanium coupling agent, etc.), a melamine cyanuric acid adduct, etc. can be added.
The dry film thickness of the upper layer film is 0.3 to 2.0 μm, preferably 0.4 to 1.5 μm. When the film thickness of the upper layer film is less than 0.3 μm, the corrosion resistance is insufficient. On the other hand, when the film thickness exceeds 2.0 μm, the weldability and the electrodeposition coating property are deteriorated.
Further, from the viewpoint of weldability and electrodeposition coating properties, the total film thickness of the surface treatment film of the first layer and the upper film of the second layer is preferably 2.0 μm or less.

Next, the manufacturing method of the surface treatment steel plate of this invention is demonstrated.
In order to form the surface treatment film on the surface of a zinc-based plated steel sheet or an aluminum-based plated steel sheet, a surface treatment composition (treatment liquid) having the above-described composition is applied to the surface of the plated steel sheet so as to have the above-described dry film thickness. And heat-dried without washing with water.
As a method for forming the surface treatment composition on the surface of the plated steel sheet, any of a coating method, a dipping method, and a spray method may be used. As a coating treatment method, any method such as a roll coater (3-roll method, 2-roll method, etc.), a squeeze coater, or a die coater may be used. In addition, after the coating process or dipping process using a squeeze coater or the like, or the spray process, the coating amount can be adjusted, the appearance can be made uniform, and the film thickness can be made uniform by an air knife method or a roll drawing method.

After coating the surface treatment composition, drying is performed without washing with water. As the heating and drying means, a dryer, a hot air furnace, a high frequency induction heating furnace, an infrared furnace or the like can be used. Heat drying is preferably performed in the range of 30 to 150 ° C., preferably 40 to 140 ° C., at the ultimate plate temperature. If the heating and drying temperature is less than 30 ° C., a large amount of moisture remains in the film, resulting in insufficient corrosion resistance. Further, when the heating and drying temperature exceeds 150 ° C., not only is it uneconomical, but there is a possibility that defects occur in the film and the corrosion resistance is lowered. In general, when the heat drying temperature exceeds 150 ° C., it cannot be applied to the BH steel sheet.
An upper layer film (organic resin film) is formed as the second layer film on the upper layer of the surface treatment film formed as described above. The upper layer coating composition having the above-described composition is applied to the surface-treated coating surface so as to have the above-described dry film thickness, and dried by heating. Application | coating of a coating composition should just be performed according to the method used for formation of the surface treatment film mentioned above.

After application of the coating composition for the upper layer film, heating drying is usually performed without washing with water, but washing with water may be performed after application of the coating composition. For the heat drying treatment, a dryer, a hot air furnace, a high-frequency induction heating furnace, an infrared furnace, or the like can be used. Heat drying is preferably performed in the range of 30 to 150 ° C., preferably 40 to 140 ° C., at the ultimate plate temperature. If the heating and drying temperature is less than 30 ° C., a large amount of moisture remains in the film, resulting in insufficient corrosion resistance. Further, when the heating and drying temperature exceeds 150 ° C., not only is it uneconomical, but there is a possibility that defects occur in the film and the corrosion resistance is lowered. In general, when the heat drying temperature exceeds 150 ° C., it cannot be applied to the BH steel sheet.
In addition, the surface treatment film and the upper layer film described above may be formed on either one side or both sides of the plated steel sheet. As a combination of the film forms on the front and back surfaces of the plated steel sheet, for example, surface treatment film + upper layer film / no treatment, The surface treatment film + upper layer film / surface treatment film, surface treatment film + upper layer film / surface treatment film + upper layer film, and the like can be used.

  The surface-treatment composition for forming the first layer is a water-soluble or water-dispersible epoxy resin shown in Table 2 as a resin composition (those satisfying the conditions of the present invention are “aqueous epoxy resin dispersion (a ) "), And silane coupling agent (Table 3), phosphoric acid or hexafluorometal acid (Table 4), water-soluble phosphate (Table 5), non-chromium rust preventive additive (Table 6) was appropriately blended and prepared by stirring for a predetermined time using a paint disperser (sand grinder).

The water-soluble or water-dispersible epoxy resin shown in Table 2 was produced as follows.
-Production of polyalkylene glycol-modified epoxy resin <Production Example 1>
To a glass four-necked flask equipped with a thermometer, a stirrer, and a condenser tube, 1688 g of polyethylene glycol having a number average molecular weight of 4000 and 539 g of methyl ethyl ketone were added, and the mixture was stirred and mixed at 60 ° C. to be uniformly transparent. In addition, after reacting for 2 hours, 1121 g of jER834X90 (epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent 250), 66 g of diethylene glycol ethyl ether and 1.1 g of 1% dibutyltin dilaurate solution were added, and 2 Reacted for hours. Thereafter, the temperature was raised to 80 ° C. and reacted for 3 hours to confirm that the isocyanate value was 0.6 or less. Thereafter, the temperature was raised to 90 ° C., and methyl ethyl ketone was removed by distillation under reduced pressure until the solid content concentration reached 81.7%. After removal, 659 g of propylene glycol monomethyl ether and 270 g of deionized water were added and diluted to obtain a polyalkylene glycol-modified epoxy resin solution A1 having a solid concentration of 76%.

・ Production of aqueous epoxy resin dispersion <Production Example 2>
2029 g of EP1004 (epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent 1000) and 697 g of propylene glycol monobutyl ether were charged into a four-necked flask, heated to 110 ° C. and completely dissolved in 1 hour. After 1180 g of the polyalkylene glycol-modified epoxy resin solution A1 obtained in Production Example 1 and 311.7 g of 3-amino-1,2,4-triazole (molecular weight 84) were added to this product and reacted at 100 ° C. for 5 hours. Then, 719.6 g of propylene glycol monobutyl ether was added to obtain a resin solution D1.
257.6 g of the above resin solution D1 was mixed with 50 g of MF-K60X (isocyanate curing agent, manufactured by Asahi Kasei Kogyo Co., Ltd.) and 0.3 g of Scat24 (curing catalyst), and after stirring well, 692.1 g of water was added dropwise little by little. Mixing and stirring were performed to obtain an aqueous epoxy resin dispersion E1.

<Production Example 3> (Aqueous epoxy resin dispersion containing no hydrazine derivative)
2029 g of EP1004 (epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent 1000) and 697 g of propylene glycol monobutyl ether were charged into a four-necked flask, heated to 110 ° C. and completely dissolved in 1 hour. 1180 g of the polyalkylene glycol-modified epoxy resin solution A1 obtained in Production Example 1 and 527.0 g of propylene glycol monobutyl ether were added to this to obtain a resin solution D2.
To 257.6 g of the above resin solution D2, 50 g of MF-K60X (isocyanate curing agent, manufactured by Asahi Kasei Kogyo Co., Ltd.) and 0.3 g of Scat24 (curing catalyst) were mixed and stirred well, and then 692.1 g of water was dropped and mixed little by little. The mixture was stirred to obtain an aqueous epoxy resin dispersion E2.

  For the coating composition for the upper layer film (second layer), the epoxy resin solution shown in Table 7 (those satisfying the conditions of the present invention is the “resin solution (D)” used in the present invention), These were combined with a curing agent to give a resin composition shown in Table 8 (those satisfying the conditions of the present invention are “resin solution (D) + curing agent (E)” used in the present invention). To this resin composition, a non-chromium rust preventive additive (Table 6) and a solid lubricant (Table 9) are appropriately blended and stirred for a predetermined time using a paint disperser (sand grinder). Prepared.

The epoxy resin solution shown in Table 7 was produced as follows.
-Production of a compound having two or more carboxyl groups in one molecule [Production Example 1]
A reactor equipped with a thermometer, a stirrer, a heating device and a rectifying tower was charged with 2810 parts by mass of adipic acid (2 mol) and 1135 parts by mass of 1,6 hexanediol (1 mol), and the temperature was raised to 160 ° C. The temperature was gradually raised from 160 ° C. to 230 ° C. over 3 hours, and the reaction was continued at 230 ° C. for 30 minutes. The rectification column was replaced with a water separator, and 144 parts by mass of xylene was added to the contents. Xylene was also added to the separator, water and xylene were azeotroped to remove condensed water, the reaction was continued until the acid value reached 300 mgKOH / g, and then cooled, and then 256 parts by mass of cyclohexanone was added, Compound X having two or more carboxyl groups in one molecule having a solid content of 90% was obtained.
[Production Example 2]
In the production conditions of Production Example 1 above, “2810 parts by mass of adipic acid” is 3055 parts by mass (3 mol) of sebacic acid, 1135 parts by mass of “1,6 hexanediol” is 906 parts by mass of 1,4 butylene glycol (2 mols). ), And the solid content was adjusted with cyclohexanone to obtain Compound Y having two or more carboxyl groups in one molecule having a solid content of 90%.

Production of epoxy resin solution Epoxy resin solution No. satisfying the conditions of the present invention by the bisphenol A type epoxy resin (d1), compound (d2) and hydrazine derivative (d3) having active hydrogen in the types and blending ratios shown in Table 7 0.1 to 7 and epoxy resin solutions No. 8 to 11 as comparative examples were produced.
A reactor equipped with a thermometer, a stirrer and a heating device was charged with 1307 parts by weight of bisphenol A type epoxy resin “jER1009” and 571 parts by weight of cyclohexanone, heated to 140 ° C. and completely dissolved in 2 hours. Next, 25 parts by mass of dodecanedioic acid was charged and reacted at this temperature until the acid value was 1 mgKOH / g or less. This was cooled to 80 ° C., 539 parts by mass of cyclohexanone, 540 parts by mass of methyl isobutyl ketone, and 18 parts by mass of 3-amino-1,2,4-triazole were added and reacted for about 6 hours until the epoxy group disappeared. . Thereafter, 1095 parts by mass of cyclohexanone and 405 parts by mass of methyl isobutyl ketone were added to obtain an epoxy resin solution No. 1 having a solid content of 30%.
Epoxy resin solutions Nos. 2 to 11 were obtained in the same manner as described above except that the blending contents shown in Table 7 were used.

The plated steel sheet shown in Table 1, which is a plated steel sheet for home appliances, building materials, and automobile parts based on cold-rolled steel sheets, was used as a processing original sheet. In addition, the thing of predetermined | prescribed board thickness was employ | adopted for the board thickness of the steel plate according to the objective of evaluation. After the surface of this plated steel sheet was subjected to alkali degreasing treatment, washed with water and dried, the surface treatment composition for forming the first layer was applied with a roll coater and dried by heating at various temperatures. The film thickness of the film was adjusted by the solid content (heating residue) of the surface treatment composition or coating conditions (rolling force of the roll, rotation speed, etc.).
Next, the coating composition for the upper layer film (second layer) was applied by a roll coater and dried by heating at various temperatures. The film thickness of the film was adjusted by the solid content (heating residue) of the coating composition or application conditions (rolling force of roll, rotation speed, etc.).

Tables 10 to 21 show the results of evaluating the film composition and quality performance (corrosion resistance, post-processing corrosion resistance, weldability, electrodeposition coating property) of the obtained surface-treated steel sheet. The quality performance was evaluated as follows.
(1) Corrosion resistance About each sample, the following combined cycle test (CCT) was given, and it evaluated by the white rust generation | occurrence | production area rate and red rust generation | occurrence | production area rate after 69 cycles progress.
Salt spray (based on JIS Z 2371): 4 hours ↓
Dry (60 ° C): 2 hours ↓
Wet (50 ° C., 95% RH): 2 hours The evaluation criteria are as follows.
◎: White rust generation area ratio less than 10% ○ +: White rust generation area ratio of 10% or more, less than 20% ○: White rust generation area ratio of 20% or more, less than 30% ○-: White rust generation area ratio of 30% or more No red rust occurrence △: Red rust occurrence, red rust occurrence area ratio less than 10% ×: Red rust occurrence area ratio 10% or more

(2) Corrosion resistance after processing For each sample, deformation and sliding were added with a draw bead under the following conditions, and this sample was used at 45 ° C. for 2 minutes using “FC-4460” manufactured by Nihon Parkerizing Co., Ltd. After degreasing under the conditions, the CCT performed in the above “(1) Corrosion resistance” was performed, and the white rust generation area ratio and red rust generation area ratio after 39 cycles were evaluated.
Pressing load: 800kgf
Drawing speed: 1000mm / min
Bead shoulder R: Male side 2mmR, Female side 3mmR
Pushing depth: 7mm
Oil used: Preton R-352L
The evaluation criteria are as follows.
◎: White rust generation area ratio less than 10% ○ +: White rust generation area ratio of 10% or more, less than 20% ○: White rust generation area ratio of 20% or more, less than 30% ○-: White rust generation area ratio of 30% or more No red rust occurrence △: Red rust occurrence, red rust occurrence area ratio less than 10% ×: Red rust occurrence area ratio 10% or more

(3) Weldability With respect to each sample, a welding test with continuous spotting was performed under the conditions of using electrode: CF-type Cr—Cu electrode, applied pressure: 200 kgf, energizing time: 10 cycles / 50 Hz, welding current: 10 kA, and continuously hitting. The score was evaluated. The evaluation criteria are as follows.
◎: 2000 points or more ○: 1500 points or more, less than 2000 points ○ −: 1000 points or more, less than 1500 points Δ: 500 points or more, less than 1000 points ×: Less than 500 points

(4) Electrodeposition coating property Each sample was coated with a cationic electrodeposition paint (“GT-10” manufactured by Kansai Paint Co., Ltd.) to a film thickness of 30 μm, and then baked at 130 ° C. for 30 minutes. . The coated sample was immersed in boiling water for 2 hours, immediately cut in a grid pattern (10 × 10, 1 mm interval), attached and peeled with an adhesive tape, and the peeled area ratio of the coating film was measured. The evaluation criteria are as follows.
◎: No peeling ○: Peeling area rate less than 5% △: Peeling area rate of 5% or more and less than 20%

In addition, * 1 to * 9 described in Tables 10 to 21 indicate the following contents.
* 1: No. described in Table 1. (Plated steel plate)
* 2: No. in Table 2 (Water-soluble or water-dispersible epoxy resin)
* 3: No. described in Table 3 (Silane coupling agent)
* 4: No. in Table 4 (Phosphoric acid or hexafluorometal acid)
* 5: No. in Table 5 (Water-soluble phosphate)
* 6: No. in Table 6 (Non-chromium rust preventive additive)
* 7: part by mass * 8: No. in Table 8 (Resin composition)
* 9: No. in Table 9 (Solid lubricant)

Claims (9)

Zinc-plated steel sheet or the surface of an aluminum-based plated steel sheet, containing the following components (a) ~ (c), further coated with a surface treatment composition comprising the following component (d) optionally, 30 to 200 Form a surface treatment film with a film thickness of 0.01 to 1.0 μm formed by heating and drying at ℃ (attainment plate temperature) ,
(A) a polyalkylene glycol-modified epoxy resin (A) obtained by reacting a polyalkylene glycol having a number average molecular weight of 400 to 20,000, a bisphenol type epoxy resin, an active hydrogen-containing compound and a polyisocyanate compound, and the polyalkylene glycol-modified A resin obtained by reacting an epoxy group-containing resin (B) other than the epoxy resin (A) with an active hydrogen-containing compound comprising a hydrazine derivative (C) in which some or all of the compounds have active hydrogen is used in water. Dispersed aqueous epoxy resin dispersion (b) Silane coupling agent: 1 to 300 parts by mass with respect to 100 parts by mass of the solid content of the aqueous epoxy resin dispersion (a) (c) Phosphoric acid and / or hexafluoro Metal acid: 0 with respect to 100 parts by mass of the solid content of the aqueous epoxy resin dispersion (a) 1 to 80 parts by weight
(D) Water-soluble phosphate: 0.1 to 60 parts by mass with respect to 100 parts by mass of the solid content of the aqueous epoxy resin dispersion (a), and the following components (D) and (E) are contained in the upper layer thereof. The coating thickness formed by applying the coating composition for the upper layer coating and drying has an upper layer coating of 0.3 to 2.0 μm ,
(D) A bisphenol A type epoxy resin (d1) having an epoxy equivalent of 750 to 5000 and a number average molecular weight of 1500 to 10,000 has a compound (d2) having two or more carboxyl groups in one molecule and active hydrogen. Resin solution obtained by reacting hydrazine derivative (d3) (E) Curing agent having functional group that reacts with hydroxyl group
In the component (a) contained in the surface treatment composition, the hydrazine derivative (C) having active hydrogen is at least one selected from mercaptotriazole and aminotriazole, and the coating composition for an upper film contains In the component (D), the hydrazine derivative (d3) having active hydrogen is at least one selected from mercaptotriazole and aminotriazole.   Component (D) contained in the upper layer coating composition is [number of moles of bisphenol A type epoxy resin (d1)] / [number of moles of compound (d2) having two or more carboxyl groups in one molecule]. The high corrosion resistance surface-treated steel sheet according to claim 1, wherein the ratio is 1.1 to 5.   3. The component (D) contained in the coating composition for an upper film, wherein the compound (d2) having two or more carboxyl groups in one molecule is an aliphatic dicarboxylic acid. High corrosion resistance surface-treated steel sheet. The coating composition for the upper layer film further contains a non-chromium anticorrosive additive in a proportion of 0.1 to 50 mass in terms of solid content with respect to 100 mass parts in total of resin solid content of component (D) and component (E). The highly corrosion-resistant surface-treated steel sheet according to any one of claims 1 to 3 , wherein the highly corrosion-resistant surface-treated steel sheet is contained. The highly corrosion-resistant surface treatment according to claim 4 , wherein the coating composition for the upper layer film contains at least one selected from the following (f1) to (f5) as a non-chromium rust preventive additive. steel sheet.
(F1) silicon oxide (f2) calcium compound (f3) sparingly soluble phosphate compound (f4) molybdate compound (f5) one or more selected from triazoles, thiols, thiadiazoles, thiazoles, thiurams , Organic compounds containing S atoms Layer film for a coating composition, according to claim, characterized in that the curing agent component (E), containing 1 to 60 parts by mass relative to 100 parts by mass of the solid content of the resin solution component (D). 1 to 5 The highly corrosion-resistant surface-treated steel sheet according to any one of the above. Curing agent component (E) to the upper layer coating paint composition contains is according to any one of claims 1 to 6, characterized in that a polyisocyanate compound having an isocyanate group average of 4 or more in one molecule High corrosion resistance surface-treated steel sheet. 8. The highly corrosion-resistant surface-treated steel sheet according to claim 7 , wherein the polyisocyanate compound is obtained by blocking at least a part of isocyanate groups of the polyisocyanate compound with a blocking agent. The upper layer coating composition further comprises 1 to 30 parts by mass of a solid lubricant in a ratio of solids to 100 parts by mass in total of resin solids of components (D) and (E). The highly corrosion-resistant surface-treated steel sheet according to any one of claims 1 to 8 .