# Patent

## Title
Zinc-based metal coated steel sheet

## Abstract

A surface treatment liquid contains a resin emulsion that contains a cationic urethane resin emulsion and/or a nonionic acrylic resin emulsion, a tetraalkoxysilane, at least one silane coupling agent (c) that contains at least one reactive functional group selected from active hydrogen-containing amino group, an epoxy group, a mercapto group, and a methacryloxy group, a chelating agent (d), a vanadic acid compound (e), a titanium compound (f), and water in a specific ratio. The surface treatment liquid has a pH of 3 to 6. The surface treatment liquid is applied to a surface of a zinc-based metal coated steel sheet and dried by heating to form a first layer. Next, a surface treatment liquid containing an organic resin is applied to a surface of the first layer and dried by heating to form a second layer.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is the U.S. National Phase application of PCT International Application No. PCT/JP2011/072909, filed Sep. 28, 2011, and claims priority to Japanese Patent Application No. 2010-220050, filed Sep. 29, 2010, the disclosures of both being incorporated herein by reference in their entireties for all purposes.
FIELD OF THE INVENTION
The present invention relates to an environmentally friendly, surface-treated zinc-based metal coated steel sheet for use in, for example, automobiles, household electric appliances, and building materials, the zinc-based metal coated steel sheet being subjected to surface treatment to form a surface treatment film free from a pollution control substance, such as hexavalent chromium. In particular, the present invention relates to a zinc-based metal coated steel sheet having excellent electromagnetic wave shielding properties and corrosion resistance and suitably used for, for example, electric and electronic equipment, which is required to prevent electromagnetic interference (EMI).
BACKGROUND OF THE INVENTION
With the recent digitization of household electrical appliances and increase in the speed of CPUs, importance has been attached to problems with electromagnetic interference that adversely affects peripheral equipment and the human body. To address the problems, in our country, the “Voluntary Control Council for Interference by Information Technology Equipment (VCCI)” has been established. In these days, to comply with the standards of VCCI, there is a strong tendency to exercise voluntary restraint on the problems with electromagnetic interference. As an example of countermeasures against electromagnetic noise generated from electronic substrates in electric and electronic equipment, there is a technique for shielding electromagnetic waves by surrounding electronic substrates and so forth with a shield box composed of a metal (conductive) material.
For the shield box, the conductive material constituting the shield box reflects electromagnetic waves to shield electromagnetic waves. A higher conductivity of the material constituting the shield box results in higher reflectance to electromagnetic waves, improving electromagnetic wave shielding properties. So, in order to ensure the electromagnetic wave shielding properties, it is important that a metal plate constituting the shield box should have high conductivity.
The shield box is produced by forming a metal sheet and thus has discontinuities (joints and junctions). The discontinuities are likely to cause the leakage or penetration of electromagnetic waves. For the shield box, thus, a conductive gasket is usually interposed in the discontinuities to prevent the leakage and penetration of electromagnetic waves.
Here, to further ensure the shielding properties of the shield box, it is necessary to form a structure in such a manner that a desired current can be passed through the entire shield box. However, the contact pressure is usually low at a contact portion between the metal body and the gasket. So, the electrical conductivity (hereinafter, referred to simply as “conductivity”) between the metal body and the gasket is low. The amount of current passing through the contact portion tends to be reduced. Thus, in addition to ensuring the conductivity of the metal plate constituting the shield box, ensuring the conductivity between the metal plate and the gasket is important to achieve higher performance of the shield box.
Nowadays, electric and electronic equipment is used in all environments. A material constituting the shield box is required to have excellent corrosion resistance even under a severe usage environment. Chromate treatment is known as a typical method for improving the corrosion resistance (resistance to white rust and red rust) of a zinc-based metal coated steel sheet. Traditionally, zinc-based metal coated steel sheets subjected to chromate treatment with a treatment liquid mainly containing chromic acid, dichromic acid, or salts thereof have been widely used as steel sheets for household electrical appliances, steel sheets for building materials, and steel sheets for automobiles.
As described above, the metal body (steel sheet) constituting the shield box is required to have high conductivity and conductivity between metal body and the gasket. Here, although a film formed on a surface of the steel sheet by chromate treatment has lower conductivity than the base steel sheet, the film formed by chromate treatment provides rust preventive performance even at a small thickness. So, in the case of a surface-treated steel sheet subjected to chromate treatment, minimizing the thickness of the film having inferior conductivity provides conductivity comparable to a steel sheet (without being subjected to surface treatment). It is thus possible to ensure sufficient conductivity between the steel sheet and the gasket, thereby striking a good balance between rust preventive performance and electromagnetic wave shielding properties. However, recent global environmental issues require a pollution-free surface-treated steel sheet, i.e., a chromium-free treatment steel sheet, without using chromate treatment.
Many techniques about chromium-free treatment steel sheet have been reported. Examples of the techniques that have been reported include a technique of using a passivation effect of molybdic acid and tungstic acid, which belong to the IVA group the same as chromic acid; a technique of using metal salts of transition metals, such as Ti, Zr, V, Mn, Ni, and Co, and rare-earth elements, such as La and Ce; a technique based on polyhydric phenol carboxylic acid, such as tannic acid, and a chelating agent, such as a compound containing S or N; a technique of forming a polysiloxane film with a silane coupling agent; and combinations of these techniques.
Specific examples are as follows:
(1) a technique for forming a film from a treatment liquid containing a covering agent prepared by reaction of an organic resin, such as a polyvinylphenol derivative, an acid component, and an epoxy compound, a silane coupling agent, a vanadium compound, and so forth (for example, PTLs 1, 2, 3, and 4);

(2) a technique for forming a film containing a water-based resin, a thiocarbonyl group, a vanadic acid compound, and phosphoric acid (for example, PTL 5);

(3) a technique for forming a film from a treatment liquid containing a metal compound, such as Ti, a fluoride, an inorganic acid, such as phosphate compound, and an organic acid (PTLs 6, 7, 8, 9, 10, 11, and 12);

(4) a technique in which a composite film composed of rare-earth elements, such as Ce, La, and Y, and Ti and Zr elements is formed and in which in the film, an oxide layer is thickened on the coated layer side, and a hydroxide layer is thickened on the surface side (PTL 13), and a technique for forming a composite film of Ce and Si oxide (PTL 14);

(5) a technique for forming an organic composite coating including an oxide-containing phosphoric acid and/or phosphate compound film serving as a lower layer and a resin film serving as an upper layer (for example, PTLs 15 and 16); and

(6) a technique for forming a composite film including a specific inhibitor component and a silica/zirconium compound (for example, PTL 17).

The films formed by these techniques aim to inhibit the occurrence of white rust by combined addition of the organic components or inorganic components. For example, in each of the techniques of items (1) and (2), the corrosion resistance is ensured by mainly adding the organic resin. For such film composition containing the organic resin, however, the organic resin is insulative. So, the steel sheet including the film does not have sufficient conductivity and thus is not suitable as a material for the shield box.
In each of the techniques of items (3) and (4), the inorganic film free from an organic component is reported. The composite film composed of the metal oxide and metal hydroxide is required to have an increased thickness in order to provide sufficient corrosion resistance. Furthermore, a surface of the zinc coated steel sheet is covered with a nonconductive film (insulative film) composed of, for example, zinc phosphate. So, it is disadvantageous to provide satisfactory conductivity, and it is thus difficult to strike a balance between the corrosion resistance and the conductivity.
In the technique of item (5), attention is focused on the dependence of the conductivity of a surface of the surface-treated steel sheet on the thickness of the insulating film covering the surface. The technique aims to provide satisfactory conductivity by reducing the thickness of the insulating film. However, a smaller thickness results in a reduction in the corrosion resistance of the steel sheet. It is thus difficult to provide a surface-treated steel sheet having excellent corrosion resistance and conductivity.
In the technique of item (6), the use of the passivation effect of the vanadic acid compound and a sparingly soluble metal salt due to the phosphate compound, which serve as the inhibitor components, and the formation of the composite film, serving as a skeletal film, composed of the zirconium compound, fine particle silica, and the silane coupling agent provide excellent corrosion resistance. However, in the case where conduction is required under severe conditions where contact is established at a very low load, it is necessary to reduce the thickness of the film, thus causing difficulty in striking a balance between the corrosion resistance and the conductivity.
As described above, for the chromium-free treatment steel sheets reported so far, in order to ensure corrosion resistance comparable to that of a traditional chromate film, it is necessary to increase the thickness of a highly insulative film. For the chromium-free treatment steel sheets, it is thus difficult to ensure conductivity. The steel sheets do not sufficiently satisfy the properties required for a steel sheet constituting the shield box. As described above, in order to further ensure the shielding properties of the shield box, the conductivity between the metal body (steel sheet) and the gasket at a low contact pressure needs to be sufficiently ensured. However, in the foregoing techniques, the conductivity is not considered.
PATENT LITERATURE


    PTL 1: Japanese Unexamined Patent Application Publication No. 2003-13252
    PTL 2: Japanese Unexamined Patent Application Publication No. 2001-181860
    PTL 3: Japanese Unexamined Patent Application Publication No. 2004-263252
    PTL 4: Japanese Unexamined Patent Application Publication No. 2003-155452
    PTL 5: Japanese Patent No. 3549455
    PTL 6: Japanese Patent No. 3302677
    PTL 7: Japanese Unexamined Patent Application Publication No. 2002-105658
    PTL 8: Japanese Unexamined Patent Application Publication No. 2004-183015
    PTL 9: Japanese Unexamined Patent Application Publication No. 2003-171778
    PTL 10: Japanese Unexamined Patent Application Publication No. 2001-271175
    PTL 11: Japanese Unexamined Patent Application Publication No. 2006-213958
    PTL 12: Japanese Unexamined Patent Application Publication No. 2005-48199
    PTL 13: Japanese Unexamined Patent Application Publication No. 2001-234358
    PTL 14: Japanese Patent No. 3596665
    PTL 15: Japanese Unexamined Patent Application Publication No. 2002-53980
    PTL 16: Japanese Unexamined Patent Application Publication No. 2002-53979
    PTL 17: Japanese Unexamined Patent Application Publication No. 2008-169470


SUMMARY OF THE INVENTION
The present invention provides a zinc-based metal coated steel sheet including a surface treatment film free from a pollution control substance, such as hexavalent chromium, the steel sheet having excellent conductivity even under severe conditions where the steel sheet is in contact with, for example, a gasket at a low contact pressure without reducing corrosion resistance.
To overcome the foregoing problems, the inventors have conducted intensive studies and have found the following: A surface treatment liquid (A) is applied to a surface of a zinc-based metal coated layer and dried by heating to form a first layer composed of a composite oxide film, the surface treatment liquid (A) containing a resin emulsion that contains a cationic urethane resin emulsion and/or a nonionic acrylic resin emulsion, the cationic urethane resin emulsion containing at least one cationic functional group selected from primary to tertiary amino groups and quaternary ammonium salt groups, a tetraalkoxysilane, at least one silane coupling agent that contains at least one reactive functional group selected from active hydrogen-containing amino groups, an epoxy group, a mercapto group, and a methacryloxy group, a chelating agent, a vanadic acid compound, a titanium compound, and water in a specific ratio. A surface treatment liquid (B) containing an organic resin is applied to a surface of the first layer and dried by heating to form a second layer, thereby overcoming the foregoing problem.
The foregoing findings have led to the completion of the present invention. The outline of exemplary embodiments of the present invention is described below.
(1) A zinc-based metal coated steel sheet includes a surface film arranged on a surface of a zinc-based metal coated layer, the surface film having a two-layer structure including a first layer and a second layer,
in which the first layer is formed by applying a surface treatment liquid (A) for a zinc-based metal coated steel sheet to the surface of the zinc-based metal coated layer and performing drying by heating, the surface treatment liquid (A) containing a resin emulsion (a) that contains a cationic urethane resin emulsion (a-1) and/or a nonionic acrylic resin emulsion (a-2), the cationic urethane resin emulsion (a-1) containing at least one cationic functional group selected from primary to tertiary amino groups and quaternary ammonium salt groups, a tetraalkoxysilane (b), at least one silane coupling agent (c) that contains at least one reactive functional group selected from active hydrogen-containing amino groups, an epoxy group, a mercapto group, and a methacryloxy group, a chelating agent (d), a vanadic acid compound (e), a titanium compound (f), and water, the surface treatment liquid (A) having a pH of 3 to 6 and being adjusted so as to satisfy requirements (I) to (V) described below, in which the second layer is formed by applying a surface treatment liquid (B) that contains an organic resin (g) to a surface of the first layer and performing drying by heating, and in which the total thickness of the first layer and the second layer is in the range of 0.1 to 3.0 μm per side:
(I) the proportion of the solid (aS) of the resin emulsion (a) is in the range of 11% to 45% by mass with respect to the total solid of the treatment liquid;
(II) the ratio by mass of the solid of the silane coupling agent (c) to the solid of the resin emulsion (a), i.e., (cS/aS), is in the range of 1.51 to 5.35;
(III) the ratio by mass of the solid of the tetraalkoxysilane (b) to the solid of the chelating agent (d), i.e., (bS/dS), is in the range of 0.15 to 1.49;
(IV) the ratio of the mass (eV) of the vanadic acid compound (e) in terms of V to the mass of the solid (dS) of the chelating agent (d), i.e., (eV/dS), is in the range of 0.03 to 0.23; and
(V) the ratio of the mass (fT) of the titanium compound (f) in terms of Ti to the mass of the solid (dS) of the chelating agent (d), i.e., (fT/dS), is in the range of 0.02 to 0.19.
(2) In the zinc-based metal coated steel sheet described in item (1), the organic resin (g) in the surface treatment liquid (B) contains an organic resin (g-1) that contains an OH group and/or a COOH group.
(3) In the zinc-based metal coated steel sheet described in item (1), the organic resin (g) in the surface treatment liquid (B) contains a hydrazine-modified organic resin (g-2) formed by reaction with an active hydrogen-containing compound (i) composed of a hydrazine derivative (h) in which some or all of compounds contain active hydrogen.

(4) In the zinc-based metal coated steel sheet described in any one of items (1) to (3), the surface treatment liquid (B) further contains a rust preventive additive (j).

(5) In the zinc-based metal coated steel sheet described in item (4), the rust preventive additive (j) contains (k) and/or (l) described below, the proportion of the rust preventive additive (k) is in the range of 1 to 100 parts by mass in terms of the solid content with respect to the total amount of 100 parts by mass of the organic resin (g) in the surface treatment liquid (B):

(k) Ca ion-exchanged silica; and

(l) silicon oxide.

(6) In the zinc-based metal coated steel sheet described in any one of items (1) to (5), the surface treatment liquid (B) further contains a lubricant (m).

According to the present invention, it is possible to provide a zinc-based metal coated steel sheet having excellent properties, such as corrosion resistance and adhesion, and having excellent conductivity even under severe conditions where the steel sheet is in contact with, for example, a gasket at a low contact pressure, in particular, without reducing corrosion resistance.


DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION
The present invention according to exemplary embodiments will be specifically described below.
<Zinc-Based Metal Plated Steel Sheet>
Examples of a zinc-based metal coated steel sheet according to the present invention include, but are not particularly limited to, a hot-dip galvanized steel sheet (GI), a hot-dip galvannealed steel sheet (GA) produced by alloying the galvanized steel sheet, a hot-dip 5 mass % Al—Zn alloy coated steel sheet (GF), a hot-dip Zn-55 mass % Al—Zn alloy steel sheet (GL), an electrogalvanized steel sheet (EG), and a Ni—Zn (11 mass % Ni—Zn) alloy electroplated steel sheet.
<First Coating Film>
In embodiments of the present invention, a surface treatment liquid (A) is applied to a surface of a zinc-based metal coated layer of a zinc-based metal coated steel sheet and dried by heating to form a first layer. The first layer formed from the surface treatment liquid (A) is composed of a composite oxide and has satisfactory heat resistance, weldability, and adhesion and excellent conductivity. So, in the present invention, the first layer plays an important role in providing a zinc-based metal coated steel sheet having excellent conductivity even under severe conditions where the steel sheet is in contact with, for example, a gasket at a low contact pressure, in particular, without reducing corrosion resistance.
(Surface Treatment Liquid (A))
The surface treatment liquid (A) for a zinc-based metal coated steel sheet used in the present invention preferably contains a resin emulsion (a) composed of a cationic urethane resin emulsion (a-1) and/or a nonionic acrylic resin emulsion (a-2), a tetraalkoxysilane (b), a silane coupling agent (c), a chelating agent (d), a vanadic acid compound (e), a titanium compound (f), and water.
The formation of a surface treatment film on a surface of a zinc-based metal coated steel sheet by the use of the surface treatment liquid containing the cationic urethane resin emulsion (a-1) and/or nonionic acrylic resin emulsion (a-2) provides the zinc-based metal coated steel sheet having excellent properties, such as corrosion resistance, adhesion of the formed film, and corrosion resistance after alkaline degreasing, and having excellent formability, which is a characteristic of a resin film-coated steel sheet.
With respect to a cationic urethane resin contained in the cationic urethane resin emulsion (a-1), a polyol, a isocyanate component, which are monomer components of the resin, and a polymerization method are not particularly limited as long as the cationic urethane resin contains at least one cationic functional group selected from primary to tertiary amino groups and quaternary ammonium salt groups. Examples of the cationic functional group include an amino group, a methylamino group, an ethylamino group, a dimethylamino group, a diethylamino group, a trimethylamino group, and a triethylamino group. However, the cationic functional group is not limited as long as it is a primary, secondary, or tertiary amino group, or a quaternary ammonium salt group and the performance of the present invention is not impaired.
The type of nonionic acrylic resin emulsion (a-2) is not particularly limited. Examples of the nonionic acrylic resin emulsion (a-2) that may be used include acrylic resins emulsified with nonionic emulsifiers, for example, aqueous emulsions each prepared by emulsion polymerization of a vinyl monomer, such as acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, and styrene, in water in the presence of a nonionic surfactant (emulsifier) having a structure of polyethylene oxide or polypropylene oxide.
The proportion of the solid (aS) of the resin emulsion (a) containing the cationic urethane resin emulsion (a-1) and/or nonionic acrylic resin emulsion (a-2) is in the range of 11% to 45% by mass and preferably 15% to 30% by mass with respect to the total solid of the treatment liquid. A proportion of the solid of the resin emulsion (a) of less than 11% by mass does not result in a zinc-based metal coated steel sheet having excellent adhesion. A proportion exceeding 45% by mass results in a reduction in corrosion resistance.
The surface treatment liquid (A) contains the tetraalkoxysilane (b) together with the resin emulsion (a). The formation of a surface treatment film on a zinc-based metal coated steel sheet by the use of the surface treatment liquid containing the tetraalkoxysilane (b) provides the zinc-based metal coated steel sheet having excellent properties, such as corrosion resistance, adhesion of the formed film, and corrosion resistance after alkaline degreasing, and having excellent heat resistance and weldability, which are characteristics of an inorganic film. Although the reason these excellent properties are obtained is not clear, it is speculated that these excellent properties are attributed to the fact that the use of the tetraalkoxysilane (b) in combination with the resin emulsion (a) results in the formation of a film having a three-dimensional cross-linked structure composed of the tetraalkoxysilane (b) and the cationic urethane resin and/or the nonionic acrylic resin.
Examples of the tetraalkoxysilane (b) include, but are not particularly limited to, tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane. One or more thereof may be used. Among these, tetraethoxysilane and tetramethoxysilane are preferred from the viewpoint of providing better corrosion resistance of a zinc-based metal coated steel sheet.
The surface treatment liquid (A) contains at least one silane coupling agent (c) containing at least one reactive functional group selected from an active hydrogen-containing amino group, an epoxy group, a mercapto group, and a methacryloxy group, together with the resin emulsion (a) and the tetraalkoxysilane (b). The formation of a surface treatment film on a zinc-based metal coated steel sheet by the use of the surface treatment liquid containing the silane coupling agent (c) provides the zinc-based metal coated steel sheet having excellent properties, such as corrosion resistance and corrosion resistance after alkaline degreasing. In particular, the surface treatment film having excellent adhesion and scratch resistance is formed on a surface of the zinc-based metal coated layer.
The type of at least one silane coupling agent (c) containing at least one reactive functional group selected from an active hydrogen-containing amino group, an epoxy group, a mercapto group, and a methacryloxy group is not particularly limited. For example, trialkoxysilanes each having three alkoxy groups and at least one reactive functional group selected from an active hydrogen-containing amino group, an epoxy group, a mercapto group, and a methacryloxy group are preferred. At least one of these trialkoxysilanes is preferably used. Specific examples of trialkoxysilanes that may be used include, but are not particularly limited to, N-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4epoxycyclohexyl)ethyltriethoxysilane, vinyltriethoxysilane, and 3-mercaptopropyltrimethoxysilane.
The proportion of at least one silane coupling agent (c) selected from an active hydrogen-containing amino group, an epoxy group, a mercapto group, and a methacryloxy group is in the range of 1.51 to 5.35 and preferably 2.0 to 5.0 in terms of the ratio by mass of the solid of the silane coupling agent (c) to the solid of the resin emulsion (a), i.e., (cS/aS). A ratio by mass of less than 1.51 does not result in a zinc-based metal coated steel sheet having excellent corrosion resistance. A ratio by mass exceeding 5.35 results in a reduction in the adhesion of the film.
For the purpose of ensuring the shelf stability (storage stability) of the surface treatment liquid, the surface treatment liquid contains the chelating agent (d). It is speculated that the reason desired shelf stability can be ensured is that the chelating agent (d) has the effect of suppressing the polymerization of the tetraalkoxysilane (b) in the surface treatment liquid. It is speculated that owing to the effect, the quality of the surface treatment liquid at the time of preparation is maintained without alteration even if the surface treatment liquid is stored for an extended period of time after preparation. The chelating agent (d) is needed to stably dissolve the vanadic acid compound (e) and the titanium compound (f), which are described below, in the surface treatment liquid. Furthermore, the chelating agent (d) is less likely to etch a surface of a zinc-based metal coated layer and does not form a nonconductive film composed of, for example, zinc phosphate, as compared with inorganic acids, such as nitric acid, phosphoric acid, sulfuric acid, and hydrofluoric acid. It is thus speculated that a zinc-based metal coated steel sheet including a film formed by the use of the surface treatment liquid containing the chelating agent (d) has better conductivity.
Examples of the chelating agent (d) include, but are not particularly limited to, hydroxycarboxylic acids, such as acetic acid, tartaric acid, and malic acid, monocarboxylic acids, polycarboxylic acids, such as dicarboxylic acids, e.g., oxalic acid, malonic acid, succinic acid, citric acid, and adipic acid, and tricarboxylic acids, aminocarboxylic acids, such as glycine, phosphonic acid, and phosphonate. One or more of these chelating agents may be used. In particular, a compound containing a carboxy group or a phosphonate group in its one molecule is preferred in view of the shelf stability (storage stability) of the surface treatment liquid and the corrosion resistance and conductivity of the zinc-based metal coated steel sheet.
The proportion of the chelating agent (d) is in the range of 0.15 to 1.49 and preferably 0.17 to 1.30 in terms of the ratio by mass of the solid of the tetraalkoxysilane (b) to the solid of the chelating agent (d), i.e., (bS/dS). In each of the cases where a ratio by mass of less than 0.15 and where a ratio by mass of more than 1.49, a zinc-based metal coated steel sheet having excellent corrosion resistance is not provided.
The surface treatment liquid (A) for a zinc-based metal coated steel sheet used in the present invention preferably contains the vanadic acid compound (e). The vanadic acid compound (e) is uniformly dispersed in a film formed on a surface of a zinc-based metal coated steel sheet in a state such that the compound dissolves easily in water, and provides what is called an inhibitor effect at the time of corrosion of zinc. Examples of the vanadic acid compound (e) include ammonium metavanadate, sodium metavanadate, and vanadium acetylacetonate. One or more of them may be used.
The proportion of the vanadic acid compound (e) is in the range of 0.03 to 0.23 and preferably 0.04 to 0.20 when expressed in the ratio of the mass (eV) of the vanadic acid compound (e) in terms of V to the mass of the solid (dS) of the chelating agent (d), i.e., (eV/dS). A ratio by mass of less than 0.03 does not result in a zinc-based metal coated steel sheet having excellent corrosion resistance. A ratio by mass exceeding 0.23 makes it difficult to dissolve the vanadic acid compound (e) in the surface treatment liquid.
The surface treatment liquid (A) contains the titanium compound (f). In a film formed on a surface of a zinc-based metal coated steel sheet, the titanium compound (f) is effective in imparting excellent corrosion resistance to the zinc-based metal coated steel sheet (in particular, a processed portion). Examples of the titanium compound (f) include titanyl sulfate, titanyl nitrate, titanium nitrate, titanyl chloride, titanium chloride, titania sols, titanium oxide, potassium titanate oxalate, fluorotitanic acid, ammonium fluorotitanate, titanium lactate, titanium tetraisopropoxide, titanium acetylacetonate, and diisopropyltitanium bis(acetylacetonate). Further examples thereof include metatitanic acid prepared by thermal hydrolysis of an aqueous solution of titanyl sulfate, orthotitanic acid prepared by alkali neutralization of an aqueous solution of titanyl sulfate, and salts thereof.
The proportion of the titanium compound (f) is in the range of 0.02 to 0.19 and preferably 0.03 to 0.15 when expressed in the ratio of the mass (fT) of the titanium compound (f) in terms of Ti to the mass of the solid (dS) of the chelating agent (d), i.e., (fT/dS). A ratio by mass of less than 0.02 does not result in a zinc-based metal coated steel sheet having excellent corrosion resistance. A ratio by mass exceeding 0.19 makes it difficult to dissolve the titanium compound (f) in the surface treatment liquid.
The surface treatment liquid (A) for a steel sheet is required to have a pH of 3 to 6 and preferably 4 to 5. A pH of the surface treatment liquid of less than 3 results in a reduction in the shelf stability (storage stability) of the surface treatment liquid and causes significant etching of zinc, thereby reducing the corrosion resistance and conductivity of a zinc-based metal coated steel sheet. A pH exceeding 6 results in a reduction in the adhesion of a film formed on a surface of a zinc-based metal coated steel sheet. In the present invention, in the case of using an alkali to adjust the pH, ammonium, amine, an amine derivative, or amino polycarboxylic acid is preferred. In the case of using an acid, one selected from chelating agents (d) described above is preferred. In particular, in the case where the pH is adjusted with an inorganic acid, for example, nitric acid, phosphoric acid, sulfuric acid, or hydrofluoric acid, the amount of the acid added is, at most, less than 4% by mass with respect to the total solid of the surface treatment liquid because of a reduction in the conductivity of a zinc-based metal coated steel sheet.
Note that, for example, a surfactant, called a wettability improver, used to form a uniform film on a surface to be coated, a thickener, a conductive material used to improve conductivity, a color pigment used to improve design, and a solvent used for improving film formability, may be appropriately added to the surface treatment liquid (A), as needed.
The surface treatment liquid (A) is prepared by mixing the foregoing components in, for example, deionized water or distilled water. The solid content of the surface treatment liquid may be appropriately selected. Furthermore, a water-soluble solvent, for example, alcohol, ketone, or cellosolve, a surfactant, an antifoaming agent, a leveling agent, antibacterial and antifungal agents, and a coloring agent may be added to the surface treatment liquid, as needed. The addition thereof improves drying properties of the surface treatment liquid, the appearance of a coating, workability, shelf stability (storage stability), and design. However, it is important to add the additives to the extent that the quality obtained in the present invention is not impaired. The amount added is, at most, less than 5% by mass with respect to the total solid of the surface treatment liquid.
(Formation of First Layer)
As described above, in the present invention, the predetermined surface treatment liquid (A) is preferably applied to a surface of a zinc-based metal coated layer of a zinc-based metal coated steel sheet and dried by heating to form the first layer. Examples of a method for applying the surface treatment liquid (A) to the zinc-based metal coated steel sheet include a roll coating method, a bar coating method, an immersion method, and a spray coating method. An optimum method is selected, depending on, for example, the shape of a zinc-based metal coated steel sheet to be treated. More specifically, for example, if a zinc-based metal coated steel sheet to be treated has a sheet shape, the surface treatment liquid is applied by a roll coating method or a bar coating method or is sprayed on a zinc-based metal coated steel sheet, and then the coating weight is adjusted with squeeze rolls or by blowing a gas thereto at high pressure. If a zinc-based metal coated steel sheet is formed into a formed article, for example, a method is selected in which the article is immersed in the surface treatment liquid and withdrawn therefrom, and in some cases, an excess of the surface treatment liquid is blown off with compressed air to adjust the coating weight.
Before applying the surface treatment liquid (A) to a zinc-based metal coated steel sheet, the zinc-based metal coated steel sheet may be subjected to a pretreatment to remove oil and dirt on a surface of a coated layer of the zinc-based metal coated steel sheet, as needed. Zinc-based metal coated steel sheets are often coated with rust preventive oil to prevent the formation of rust. Even if they are coated with rust preventive oil, oil, dirt, and so forth attached during processing are present. These applied oil, oil, and dirt inhibit the wettability of the surface of the zinc coated layer and create difficulties in forming the uniform first layer. So, the foregoing pretreatment is performed to clean the surface of the zinc-based metal coated layer, the clean surface being likely to be uniformly wetted. In the case where there is no oil or dirt on the surface of the zinc-based metal coated steel sheet and where the surface is uniformly wetted with the surface treatment liquid (A), a pretreatment step is not particularly required. Examples of a method for performing the pretreatment include, but are not particularly limited to, hot-water washing, solvent cleaning, and alkaline cleaning.
A heating temperature (maximum sheet temperature) when the surface treatment liquid (A) applied on a surface of a zinc-based metal coated layer is dried by heating is usually in the range of 60° C. to 200° C. and preferably 80° C. to 180° C. A heating temperature of 60° C. or higher does not cause a problem, such as a reduction in the corrosion resistance of the zinc-based metal coated steel sheet, because water serving as a main solvent is not left in the film. A heating temperature of 200° C. or lower does not cause the problem because the occurrence of cracking of the film is suppressed.
An appropriately optimized heating time is selected, depending on, for example, the type of zinc-based metal coated steel sheet used. The heating time is preferably in the range of 0.1 to 60 seconds and more preferably 1 to 30 seconds in view of, for example, productivity.
The first layer is preferably formed so as to have a thickness of 0.01 to 1.0 μm after drying by heating. At a thickness of 0.01 μm or more, there is no concern about lack of corrosion resistance. A thickness of 1.0 μm or less does not lead to a reduction in the conductivity of the zinc-based metal coated steel sheet. Note that the thickness is more preferably in the range of 0.05 to 0.5 μm.
The resulting first layer has excellent heat resistance, weldability, and adhesion. In the present invention, the formation of the first layer on a surface of a zinc coated layer of a zinc-based metal coated steel sheet provides a zinc-based metal coated steel sheet having desired conductivity without reducing corrosion resistance. Although the reason for this is not clear, it is speculated that the properties are attributed to the following effects.
In the present invention, the resin emulsion (a) containing the cationic urethane resin emulsion (a-1) and/or the nonionic acrylic resin emulsion (a-2), the tetraalkoxysilane (b), and the silane coupling agent (c) in the components of the first layer constitute the preferred skeleton of the film formed on a surface of a zinc-based metal coated layer of a zinc-based metal coated steel sheet. When a film containing the resin emulsion (a) that contains emulsion (a-1) and/or the nonionic acrylic resin emulsion (a-2) is once dried, the film does not dissolve in water again and serves as a barrier, thus providing the zinc-based metal coated steel sheet having excellent properties, such as corrosion resistance, adhesion of the film, and corrosion resistance after alkaline degreasing, and having excellent formability, which is a characteristic of a resin film.
It is speculated that the dense film is formed because the incorporation of the tetraalkoxysilane (b) causes a silanol group derived from the alkoxy group of the tetraalkoxysilane (b) and the cationic urethane resin and/or nonionic acrylic resin emulsion (a-2) to be three-dimensionally cross-linked. It is also speculated that the incorporation of the silane coupling agent (c) causes a cross-linking reaction with a silanol group of the tetraalkoxysilane (b), thereby increasing the bonding strength of the film.
Among the components in the first layer, the vanadic acid compound (e) and the titanium compound (f) are uniformly dispersed in the film in states such that these compounds dissolve easily in water, and provide what is called an inhibitor effect at the time of corrosion of zinc. That is, it is speculated that the vanadic acid compound (e) and the titanium compound (f) are partially ionized under a corrosive environment and passivated to inhibit the corrosion of zinc itself. In particular, it is speculated that even in the case where a zinc-based metal coated steel sheet is formed into a desired shape and where defects occur in the film at a processed portion, the titanium compound (f) is preferentially eluted in the defective portion of the film to inhibit the corrosion of zinc.
It is speculated that among the components in the first layer, the chelating agent (d) has the effects of suppressing the polymerization of the tetraalkoxysilane (b) in the surface treatment layer and stably dissolving the vanadic acid compound (e) and the titanium compound (f) in the surface treatment liquid (A). Furthermore, it is speculated that in the case where the film is formed by heating and drying, a carboxy group or phosphonate group of the chelating agent (d) serves as a cross-linking agent that is cross-linked with the skeletal components of the film to form the dense film skeleton without forming an insulating film (nonconductive film), such as zinc phosphate, thus contributing to improvement in conductivity.
That is, the first layer according to the present invention has high corrosion resistance despite the small thickness of the film composed of the cationic urethane resin emulsion and/or nonionic acrylic resin emulsion, tetraalkoxysilane, and the silane coupling agent. Furthermore, it is speculated that the incorporation of the corrosion inhibitors, i.e., the chelating agent, the vanadic acid compound, and the titanium compound, in the film makes it possible to maintain excellent conductivity even when the steel sheet is in contact with, for example, a gasket at a low pressure.
<Second Layer>
The first layer imparts satisfactory corrosion resistance to a zinc-based metal coated steel sheet. However, the first layer is a complex oxide film (inorganic film); hence, in the case where countermeasures are taken against the corrosion of a zinc-based metal coated steel sheet, the effect of the first layer is inferior to an organic resin film. In some applications, it is assumed that it is difficult to satisfy required corrosion resistance. So, in the present invention, a surface treatment liquid (B) is preferably applied to a surface of the first layer and dried by heating to form a second layer. The second layer resulting from surface treatment liquid (B) is an organic resin layer. In the present invention, the second layer plays a role in protecting the first layer and reinforcing the corrosion resistance (chemical resistance, galling resistance, fingerprint resistance, design, and so forth) of the zinc-based metal coated steel sheet.
The steel sheet is formed so as to have a thickness such that the conductivity of the zinc-based metal coated steel sheet is not impaired. Therefore, the present invention provides a practical zinc-based metal coated steel sheet which has a good balance between conductivity and corrosion resistance and which is usable as a material for, for example, a shield box.
(Surface Treatment Liquid (B))
The surface treatment liquid (B) contains an organic resin (g) as a main component. Any organic resins may be used as an organic resin (g). Examples thereof include, but are not limited to, epoxy resins, modified epoxy resins, urethane resins, alkyd resins, acrylic resins, ethylene resins (polyolefin resins), polyester resins, polybutadiene resins, amino resins, phenolic resins, fluorocarbon resins, and silicon resins. The proportion of the organic resin (g) in the surface treatment liquid (B) is in the range of about 50% to 90% by mass in terms of the solid content. In this range, the role of the second layer can be achieved.
As described above, an organic resin film is more effective in imparting corrosion resistance to a zinc-based metal coated steel sheet than a complex oxide film (inorganic film). So, in the present invention, despite the type of organic resin (g) contained in the surface treatment liquid (B), the second layer is formed in order to protect the first layer and reinforce the corrosion resistance of a zinc-based metal coated steel sheet.
Here, when an organic resin (g-1) containing an OH group and/or a COOH group or a hydrazine-modified organic resin (g-2) described below is used as the organic resin (g) contained in the surface treatment liquid (B), it is possible to further improve the film.
(Organic Resin (g-1) Containing OH Group and/or COOH Group)
In the present invention, the use of the surface treatment liquid (B) that contains the organic resin (g-1) containing an OH group and/or a COOH group results in a zinc-based metal coated steel sheet having excellent adhesion between the first layer and the second layer and having better corrosion resistance.
Examples of the organic resin (g-1) containing an OH group and/or a COOH group include (g-11) an epoxy resin, (g-12) a modified epoxy resin, (g-13) a polyhydroxy polyether resin, (g-14) a urethane resin, (g-15) an alkyd resin, (g-16) an acrylic resin, (g-17) am ethylene copolymer, (g-18) acrylic silicon resin, and (g-19) a fluorocarbon resin copolymer, which are described below.
(g-11) Epoxy Resin
Examples of the epoxy resin that may be used include an epoxy resin in which, for example, bisphenol A, bisphenol F, or novolac is formed into a glycidyl ether; an epoxy resin in which bisphenol A is subjected to addition of propylene oxide, ethylene oxide, or polyalkylene glycol to form a glycidyl ether; aliphatic epoxy resins, alicyclic epoxy resins; and polyether-based epoxy resins. In the case where the surface treatment liquid (B) containing the epoxy resin is dried by heating to form the second layer, in particular, when the film is needed to be formed in a low-temperatures range, an epoxy resin having a number-average molecular weight of 1500 or more is preferred. These epoxy resins described above may be used separately or in combination as a mixture of different types.
(g-12) Modified Epoxy Resin
Examples of the modified epoxy resin include resins prepared by allowing epoxy groups or hydroxy groups in the epoxy resins described above to react with various modifiers. Specific examples thereof include epoxy ester resins prepared by allowing epoxy groups or hydroxy groups described above to react with carboxy groups in drying oil fatty acids; epoxy acrylate resins prepared by allowing epoxy groups or hydroxy groups described above to react with acrylic acid or methacrylic acid; urethane-modified epoxy resins prepared by allowing epoxy groups or hydroxy groups described above to react with isocyanate compounds; and amine-added urethane-modified epoxy resins prepared by addition of alkanolamines to urethane-modified epoxy resins resulting from the reaction of epoxy resins with isocyanate compounds.
(g-13) Polyhydroxy Polyether Resin
The polyhydroxy polyether resin is a polymer prepared by polycondensation of a mononuclear or binuclear dihydric phenol, or a mixture of mononuclear and binuclear dihydric phenols with a substantially equimolar amount of epihalohydrin in the presence of an alkaline catalyst. Typical examples of the mononuclear dihydric phenol include resorcin, hydroquinone, and catechol. A typical example of the binuclear phenol is bisphenol A. These may be used separately or in combination or two or more.
(g-14) Urethane Resin
Examples of the urethane resin include oil-modified polyurethane resins, alkyd polyurethane resins, polyester urethane resins, polyether urethane resins, and polycarbonate polyurethane resins.
(g-15) Alkyd Resin
Examples of the alkyd resin include oil-modified alkyd resins, rosin-modified alkyd resins, phenol-modified alkyd resins, styrene-alkyd resins, silicon-modified alkyd resins, oil-free alkyd resins, and high-molecular-weight oil-free alkyd resins.
(g-16) Acrylic Resin
Examples of the acrylic resin include polyacrylic acid and copolymers thereof, polyacrylate and copolymers thereof, polymethacrylic acid and copolymers thereof, polymethacrylate and copolymers thereof, urethane-acrylic acid copolymers (or urethane-modified acrylic resins), and styrene-acrylic acid copolymers. Furthermore, resins prepared by modification of these resins with, for example, other alkyd resins, epoxy resins, and phenolic resins may be used.
(g-17) Ethylene Copolymer
Examples of the ethylene copolymer include ethylene copolymers, such as ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, and carboxy-modified polyolefin resins, ethylene-unsaturated carboxylic acid copolymers, ethylene ionomers.
(g-18) Acrylic Silicon Resin
An example of the acrylic silicon resin is a resin which contains an acrylic copolymer, serving as a main component, having a hydrolyzable alkoxysilyl group in its side chain or at its end, and a curing agent. The use of such an acrylic silicon resin should provide excellent weatherability.
(g-19) Fluorocarbon Resin Copolymer
Examples of the fluorocarbon resin copolymer include fluoroolefin copolymers. An example of fluoroolefin copolymers is a copolymer prepared by copolymerization of a fluorocarbon monomer (fluoroolefin) with, for example, alkyl vinyl ether, cycloalkyl vinyl ether, carboxylic acid-modified vinyl ester, hydroxyalkyl allyl ether, or tetrafluoropropyl vinyl ether, which serve as a monomer. The use of the fluorocarbon resin copolymer should provide excellent weatherability and hydrophobicity.
As the organic resin (g-1) of the present invention, thermosetting resins are preferred. Among these resins, thermosetting epoxy resins and modified epoxy resins having excellent barrier properties against corrosive factor, such as oxygen, are optimal. In the case where the second layer is formed by the use of the surface treatment liquid (B) containing the organic resin (g-1), it is possible to provide a zinc-based metal coated steel sheet having desired corrosion resistance even at a small thickness of the film. So, it is particularly advantageous when importance is attached to the conductivity and spot weldability of a zinc-based metal coated steel sheet to suppress the coating weight of the film to a low level.
From the viewpoint of corrosion resistance, formability, and paintability, among the organic resins (g-1) described above, (g-11) the epoxy resin, (g-12) a modified epoxy resin, and (g-17) an ethylene copolymer are preferred. In particular, thermosetting epoxy resins and modified epoxy resins having excellent barrier properties against corrosive factor, such as oxygen, are particularly preferred. Examples of these thermosetting resins include thermosetting epoxy resins, thermosetting modified epoxy resins, acrylic copolymer resins copolymerized with epoxy group-containing monomers, epoxy group-containing polybutadiene resins, epoxy group-containing polyurethane resins, and adducts and condensates of these resin. These epoxy group-containing resins may be used separately or in combination as a mixture of two or more.
In addition to (g-11) to (g-19), for example, a polybutadiene resin, a phenolic resin, a polyamine resin, or polyphenylene resin may be used as the organic resin (g) of the present invention. Furthermore, a mixture of two or more or an addition polymer of these resins described above may be used.
A core-shell water-dispersible resin in which the core and the shell of each particle of the resin are composed of different resin components or resin components having different glass transition temperatures may be used in order to reduce the heat-drying temperature of the resin.
A water-dispersible resin having self-crosslinking properties, for example, containing alkoxysilane groups may be used. In this case, it is possible to use interparticle cross-linking by means of the formation of silanol groups by the hydrolysis of alkoxysilane and a dehydration condensation reaction of the silanol groups between resin particles during the drying of the resin by heating.
Furthermore, organic composite silicate in which an organic resin is combined with silica using a silane coupling agent is preferred as the organic resin (g) of the present invention.
As described above, for the purpose of improving the corrosion resistance and formability of the second layer, in particular, a thermosetting resin is preferably used as the organic resin (g-1). In this case, an amino resin, e.g., a urea resin (for example, butylated urea resin), a melamine resin (butylated melamine resin), a butylated urea-melamine resin, or a benzoguanamine resin, and a curing agent, e.g., a blocked isocyanate, an oxazoline compound, or a phenolic resin, may be incorporated in the organic resin (g-1).
The formation of the second layer from surface treatment liquid (B) containing the organic resin (g-1) described above results in improvement in adhesion between the first layer and the second layer, thereby providing a zinc-based metal coated steel sheet having better corrosion resistance. Although the reason the effects are provided is not clear, it is speculated that the organic resin (g-1) containing an OH group and/or a COOH group (preferably a thermosetting resin and more preferably an epoxy resin and/or a modified epoxy resin) is reacted with a curing agent (cross-linking agent) to form a dense barrier film having the excellent ability to inhibit permeation of a corrosive factor, such as oxygen. It is also speculated that the barrier film contributes significantly to improvement in adhesion between the first layer and the second layer because an OH group or a COOH group in its molecule is tightly bonded to an alkoxysilane or an epoxy group-containing compound in the first layer.
(Hydrazine-Modified Organic Resin (G-2))
In the present invention, the use of the surface treatment liquid (B) containing the hydrazine-modified organic resin (g-2) prepared by reaction with an active hydrogen-containing compound (i) composed of a hydrazine derivative (h) in which some or all of compounds contain active hydrogen makes it possible to provide a zinc-based metal coated steel sheet having significantly satisfactory corrosion resistance while a reduction in conductivity is minimized.
The hydrazine-modified organic resin (g-2) is formed by the reaction of a predetermined organic resin (C) and the active hydrogen-containing compound (i) composed of the hydrazine derivative (h) in which some or all of compounds contain active hydrogen. Any resin may be used as the organic resin (C) without particular limitation as long as it can react with the active hydrogen-containing compound (i) composed of the hydrazine derivative (h) to establish a bond between the organic resin and the active hydrogen-containing compound (i) by addition or condensation reaction and as long as it appropriately forms a film. Examples of the organic resin (C) include epoxy resins, modified epoxy resins, polyurethane resins, polyester resins, alkyd resins, acrylic copolymer resins, polybutadiene resins, phenolic resins, and adducts and condensates of these resins. These resins may be used separately or in combination as a mixture of two or more.
As the organic resin (C), an epoxy group-containing resin (C1) that contains an epoxy group in the resin is particularly preferred in view of, for example, reactivity, ease of reaction, and corrosion resistance. Examples of the epoxy group-containing resin (C1) include an epoxy resin (C1-1), a modified epoxy resin (C1-2), an acrylic copolymer resin (C1-3) prepared by, for example, copolymerization with an epoxy group-containing monomer, epoxy group-containing polybutadiene resins, epoxy group-containing polyurethane resins, and adducts and condensates of these resins. These epoxy group-containing resins may be used separately or in combination as a mixture or two or more.
Among these resins serving as the epoxy group-containing resin (C1), the epoxy resin (C1-1) and the modified epoxy resin (C1-2) are particularly preferred in view of adhesion to a surface of the first layer (composite oxide film) and corrosion resistance. Among these resins, thermosetting epoxy resins and modified epoxy resins, which have excellent barrier properties against a corrosive factor, such as oxygen, are optimal. The second layer is formed by use of the surface treatment liquid (B) containing the hydrazine-modified organic resin (g-2) prepared by reaction of the epoxy group-containing resin (C1) described above and the active hydrogen-containing compound (i) composed of the hydrazine derivative (h) in which some or all of compounds contain active hydrogen, thereby providing a zinc-based metal coated steel sheet having significantly satisfactory corrosion resistance even at a small thickness of the film. So, it is particularly advantageous when importance is attached to the conductivity and spot weldability of a zinc-based metal coated steel sheet to suppress the coating weight of the film to a low level.
Examples of the epoxy resin (C1-1) include aromatic epoxy resins prepared by reaction of polyphenol, such as bisphenol A, bisphenol F, and novolac phenols, with epihalohydrin, such as epichlorohydrin, to introduce glycidyl groups, or reaction of the resulting glycidyl group-containing products with polyphenols to increase the molecular weight; aliphatic epoxy resins; and alicyclic epoxy resins. These resins may be used separately or in combination as a mixture of two or more. In the case where the surface treatment liquid (B) containing the hydrazine-modified organic resin (g-2) prepared by reaction of the epoxy resin (C1-1) and the active hydrogen-containing compound (i) composed of the hydrazine derivative (h) in which some or all of compounds contain active hydrogen, is dried by heating to form the second layer, in particular, when the film needs to be formed at a low temperature, the epoxy resin (C1-1) having a number-average molecular weight of 1500 or more is preferred.
A resin having a chemical structure represented by formula (1) and being prepared by a reaction product of bisphenol A and epihalohydrin is particularly preferred as the epoxy resin (C1-1) described above. The epoxy resin is particularly preferred because of its excellent corrosion resistance.




A method for producing such a bisphenol A-type epoxy resin is widely known in the art. In the chemical structure, q represents 0 to 50, preferably 1 to 40, and more preferably 2 to 20.
Examples of the modified epoxy resin (C1-2) described above include resins prepared by prepared by allowing epoxy groups or hydroxy groups in the epoxy resin (C1-1) described above to react with various modifiers. Specific examples thereof include epoxy ester resins prepared by reaction with drying oil fatty acids; epoxy acrylate resins prepared by modification with polymerizable unsaturated monomer components containing, for example, acrylic acid or methacrylic acid; and urethane-modified epoxy resins prepared by reaction with isocyanate compounds.
An example of the acrylic copolymer resin (C1-3) prepared by copolymerization with the epoxy group-containing monomer is a resin prepared by, for example, aqueous polymerization, emulsion polymerization, or suspension polymerization of an epoxy group-containing unsaturated monomer and a polymerizable unsaturated monomer component essentially containing acrylate or methacrylate.
Examples of the polymerizable unsaturated monomer component include C1 to C24 alkyl esters of acrylic acid and methacrylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-, iso-, and tert-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, and lauryl (meth)acrylate; C1 to C4 alkyl ether compounds of acrylic acid, methacrylic acid, styrene, vinyltoluene, acrylamide, acrylonitrile, N-methylol(meth)acrylamide; and N,N-diethylaminoethyl methacrylate.
Any monomer containing an epoxy group and a polymerizable unsaturated group, for example, glycidyl methacrylate, glycidyl acrylate, or 3,4-epoxycyclohexylmethyl (meth)acrylate may be used as the epoxy group-containing unsaturated monomer without particular limitation.
Furthermore, the acrylic copolymer resin (C1-3) prepared by copolymerization with the epoxy group-containing monomer may be a resin modified with, for example, a polyester resin, an epoxy resin, or a phenolic resin.
The organic resin (C) may be soluble in an organic solvent, dispersible in an organic solvent, soluble in water, or dispersible in water.
The hydrazine-modified organic resin (g-2) of the present invention aims to incorporate the hydrazine derivative (h) into the molecule of the organic resin (C) described above. So, at least part (preferably, the whole) of the active hydrogen-containing compound (i) needs to be the hydrazine derivative (h) containing active hydrogen.
In the case where the organic resin (C) is the epoxy group-containing resin (C1), the following compounds may be exemplified as the active hydrogen-containing compound (i) that reacts with the epoxy group. One or two or more of these compounds may be used. Also in this case, at least part (preferably, the whole) of the active hydrogen-containing compound (i) needs to be the hydrazine derivative (h) containing active hydrogen.

    
    
        a hydrazine derivative (i1) containing active hydrogen
        a primary or secondary amine compound (i2) containing active hydrogen
        ammonia and organic acid (i3), such as carboxylic acid
        hydrogen halide (i4), such as hydrogen chloride
        alcohol and thiol (i5)
        an active hydrogen-free hydrazine derivative, and a quaternary chlorinating agent (i6) that is a mixture of a tertiary amine and an acid
    
    


Examples of the hydrazine derivative (h) containing active hydrogen include:
(1) hydrazide compounds, such as carbohydrazide, propionic acid hydrazide, salicylic acid hydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, isophthalic acid dihydrazide, thiocarbohydrazide, 4,4′-oxybisbenzenesulfonylhydrazide, benzophenonehydrazone, and N-aminopolyacrylamide;

(2) pyrazole compounds, such as pyrazole, 3,5-dimethylpyrazole, 3-methyl-5-pyrazolone, and 3-amino-5-methylpyrazole;

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

(4) tetrazole compounds, such as 5-phenyl-1,2,3,4-tetrazol and 5-mercapto-1-phenyl-1,2,3,4-tetrazol;

(5) thiadiazole compounds, such as 2-amino-5-mercapto-1,3,4-thiadiazole and 2,5-dimercapto-1,3,4-thiadiazole; and

(6) pyridazine compounds, such as maleic acid hydrazide, 6-methyl-3-pyridazone, 4,5-dichloro-3-pyridazone, 4,5-dibromo-3-pyridazone, and 6-methyl-4,5-dihydro-3-pyridazone.

Among these compounds, pyrazole compounds and triazole compounds each having a five- or six-membered ring structure and containing a nitrogen atom in its ring structure are particularly preferred.
These hydrazine derivatives (h) may be used separately or in combination as a mixture of two or more.
Typical examples of the active hydrogen-containing amine compound (i2) that may be used as part of the active hydrogen-containing compound (i) include:
(1) compounds of aldimine, ketimine, oxazoline, or imidazoline prepared by reaction of a primary amino group of an amine compound containing one secondary amino group and one or more primary amino groups, for example, diethylenetriamine, hydroxyethylaminoethylamine, ethylaminoethylamine, or methylaminopropylamine, with ketone, aldehyde, or carboxylic acid at, for example, about 100° C. to about 230° C.;

(2) secondary monoamines, such as diethylamine, diethanolamine, di-n- or di-1-propanolamine, N-methylethanolamine, and N-ethylethanolamine;

(3) secondary amine-containing compounds prepared by Michael addition reaction of monoalkanolamine, such as monoethanolamine, and dialkyl(meth)acrylamide; and

(4) compounds prepared by modifying a primary amino group of alkanolamine, for example, monoethanolamine, neopentanolamine, 2-aminopropanol, 3-aminopropanol, or 2-hydroxy-2′(aminopropoxy)ethyl ether into ketimine.

Examples of the organic acid (i3) that may be used as part of the active hydrogen-containing compound (i) include formic acid, acetic acid, propionic acid, butyric acid, caproic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linolenic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, benzoic acid, phthalic acid, gallic acid, terephthalic acid, isophthalic acid, salicylic acid, lactic acid, citric acid, maleic acid, and adipic acid.
Examples of the hydrogen halide (i4) that may be used as part of the active hydrogen-containing compound (i) include hydrogen fluoride, hydrogen bromide, and hydrogen iodide.
Examples of the alcohol and thiol (i5) that may be used as part of the active hydrogen-containing compound (i) include methanol, ethanol, propanol, propan-2-ol, butanol, phenylmethanol, propane-1,2-diol, ethanethiol, butane-2,3-dithiol, and 3-mercapto-2-butanol.
The quaternary chlorinating agent (i6) that may be used as part of the active hydrogen-containing compound (i) is composed of a mixture of an acid and an active hydrogen-free hydrazine derivative or a tertiary amine in order to permit the active hydrogen-free hydrazine derivative or the tertiary amine, which does not have reactivity to an epoxy group, to react with an epoxy group. The quaternary chlorinating agent reacts with an epoxy group in the presence of water to form an epoxy group-containing organic resin and a quaternary salt, as needed. As the acid used to prepare the quaternary chlorinating agent, any of acids, such as organic acids, e.g., acetic acid and lactic acid, and inorganic acids, e.g., hydrochloric acid, may be used. An example of the active hydrogen-free hydrazine derivative used to prepare the quaternary chlorinating agent is 3,6-dichloropyridazine. Examples of the tertiary amine include dimethylethanolamine, triethylamine, trimethylamine, triisopropylamine, and methyldiethanolamine.
The hydrazine-modified organic resin (g-2) prepared by reaction of the organic resin (C) and the active hydrogen-containing compound (i) composed of the hydrazine derivative (h) in which some or all of compounds contain active hydrogen is formed by reaction of the organic resin (C) and the active hydrogen-containing compound (i) at 10° C. to 300° C. and preferably 50° C. to 150° C. for about 1 to about 8 hours. The reaction may be performed after addition of an organic solvent. The type of organic solvent used is not particularly limited. Examples thereof include ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, dibutyl ketone, and cyclohexanone; alcohols and ethers containing hydroxy groups, such as ethanol, butanol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monohexyl ether, propylene glycol, propylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoethyl ether, and diethylene glycol mono-n-butyl ether; esters, such as ethyl acetate, butyl acetate, and ethylene glycol mono-n-butyl ether acetate; and aromatic hydrocarbons, such as toluene and xylene. One or two or more of these compounds may be used. Among these compounds, a ketone or ether solvent is particularly preferred in view of solubility in an epoxy resin and film formability.
The proportion of the active hydrogen-containing compound (i) composed of the hydrazine derivative (h) in which some or all of compounds contain active hydrogen is in the range of 0.5 to 20 parts by mass and particularly preferably 1.0 to 10 parts by mass with respect to 100 parts by mass of the organic resin (C) in terms of the solid content. In the case where the organic resin (C) is the epoxy group-containing resin (C1), with respect to the mixing ratio of the epoxy group-containing resin (C1) to the active hydrogen-containing compound (i), the ratio of the number of active hydrogen groups of the active hydrogen-containing compound (i) to the number of epoxy groups of the epoxy group-containing resin (C1), i.e., [number of active hydrogen groups/number of epoxy groups], is appropriately set in the range of 0.01 to 10, more preferably 0.1 to 8, and still more preferably 0.2 to 4 in view of corrosion resistance.
The proportion of the hydrazine derivative (h) containing in the active hydrogen-containing compound (i) is preferably in the range of 10% to 100% by mole, more preferably 30% to 100% by mole, and still more preferably 40% to 100% by mole. A proportion of the hydrazine derivative (h) containing active hydrogen of less than 10% by mole fails to impart sufficient anticorrosive properties to the second layer (organic resin film). So, the resulting rust-inhibiting effect is not much different from that in the case where a simple mixture of a film-forming organic resin and a hydrazine derivative is used.
The possible anticorrosion mechanism of the second layer (organic resin film) described above is as follows.
That is, the hydrazine derivative (h) containing active hydrogen is added to the organic resin (C), so that a hydrazine derivative is incorporated into a molecule of the organic resin (C).
(1) The dense organic resin film (second layer) is formed and provides the effect of blocking corrosive factors, such as oxygen and chlorine ions.
(2) The hydrazine derivative (h) is tightly bonded to a surface of the first layer to form a passivation layer.
(3) The free hydrazine derivative group (h) in the second layer traps zinc ions eluted by a corrosion reaction to form a stable insoluble chelate compound layer, thereby inhibiting the formation of an ion-conducting layer at the interface between the first layer and the zinc coated layer to inhibit the progress of corrosion.

It is believed that the progress of corrosion is effectively inhibited by the foregoing advantageous effects, thereby providing excellent corrosion resistance.

In particular, in the case where the epoxy group-containing resin (C1) is used as the organic resin (C), the reaction of the epoxy group-containing resin (C1) and a curing agent (cross-linking agent) results in the formation of a dense barrier film. The barrier film has the excellent ability to inhibit permeation of a corrosive factor, such as oxygen. Furthermore, owing to a hydroxy group in its molecule, excellent bonding strength to the first layer is obtained, thereby providing quite excellent corrosion resistance (barrier properties). Moreover, in particular, the use of an active hydrogen-containing pyrazole compound and/or an active hydrogen-containing triazole compound as the hydrazine derivative (h) containing active hydrogen results in better corrosion resistance (barrier properties).
A method in which a mixture of a film-forming organic resin and a hydrazine derivative is used has been known in the related art. Like this related art, the simple mixing of the film-forming organic resin with the hydrazine derivative provides little improvement in corrosion-inhibiting effect. The reason for this is that in the related art, the hydrazine derivative is not incorporated in the molecule of the film-forming organic resin. It is speculated that although the hydrazine derivative that is not incorporated in the molecule of the film-forming organic resin forms a chelate compound together with a metal in the first layer, the chelate compound is not formed into a dense barrier layer because of its low molecular weight. In contrast, in the present invention, the incorporation of the hydrazine derivative into the molecule of the film-forming organic resin provides the quite excellent corrosion-inhibiting effect. Thus, even if the thickness of the second layer, which is an organic resin film, is reduced in order to ensure the conductivity of a zinc-based metal coated steel sheet, the second layer that is formed by use of the surface treatment liquid (B) containing the hydrazine-modified organic resin (g-2) makes it possible to impart desired corrosion resistance to the zinc-based metal coated steel sheet.
In the present invention, the surface treatment liquid (B) containing the organic resin (g) may further contain a rust preventive additive (j).
(Rust Preventive Additive (j))
As described above, the formation of the second layer using the surface treatment liquid (B) of the present invention provides a zinc-based metal coated steel sheet having significantly satisfactory corrosion resistance. In order to further inhibit the occurrence of rust and enhance the corrosion resistance of the zinc-based metal coated steel sheet, it is effective to add the rust preventive additive (j). The rust preventive additive (j) content of the surface treatment liquid (B) is preferably in the range of about 20% to about 30% by mass in terms of the solid content.
The type of rust preventive additive (j) is not particularly limited. Any of rust preventive additives, such as known rust preventives, sufficiently provides the foregoing effect. At least one of the following compounds (k) and (l), which are self-repairing materials, is particularly preferably used:
(k) Ca ion-exchanged silica; and
(l) silicon oxide.
The Ca ion-exchanged silica used as the component (k) is a porous silica gel powder containing calcium ions fixed to surfaces of particles of the powder. The Ca ion-exchanged silica releases Ca ions in a corrosive environment to form a precipitate film, thereby providing the rust preventive effect.
Any desired Ca ion-exchange silica may be used. The Ca ion-exchanged silica has an average particle size of 6 μm or less and more preferably 4 μm or less. For example, the Ca ion-exchanged silica having an average particle size of 2 to 4 μm may be preferably used. An average particle size of Ca ion-exchanged silica exceeding 6 μm can result in reductions in corrosion resistance and dispersion stability in the surface treatment liquid (B).
The Ca ion-exchanged silica preferably has a Ca concentration of 1% by mass or more and more preferably 2% to 8% by mass. A Ca concentration of less than 1% by mass can result in an insufficient rust preventive effect owing to the release of Ca. The surface area, pH, and oil absorption of the Ca ion-exchanged silica are not particularly limited.
Examples of the Ca ion-exchanged silica that may be used include SHIELDEX C303 (average particle size: 2.5 to 3.5 μm, Ca concentration: 3% by mass), SHIELDEX AC3 (average particle size: 2.3 to 3.1 μm, Ca concentration: 6% by mass), and SHIELDEX AC5 (average particle size: 3.8 to 5.2 μm, Ca concentration: 6% by mass) (trade names, manufactured by W. R. Grace & Co.); and SHIELDEX (average particle size: 3 mm, Ca concentration: 6% to 8% by mass) and SHIELDEX SY710 (average particle size: 2.2 to 2.5 μm, Ca concentration: 6.6% to 7.5% by mass) (trade names, manufactured by Fuji Silysia Chemical Ltd).
The silicon oxide used as the component (l) may be either colloidal silica or dry-process silica. In the case where a water-based film-forming resin is used as a base, Examples of the colloidal silica that may be used include Snowtex O, Snowtex N, Snowtex 20, Snowtex 30, Snowtex 40, Snowtex C, and Snowtex S (trade names, manufactured by Nissan Chemical Industries Ltd.); Cataloid S, Cataloid SI-350, Cataloid SI-40, Cataloid SA, and Cataloid SN (trade names, manufactured by Catalyst & Chemicals Co., Ltd.); and Aderite AT-20 to 50, Aderite AT-20N, Aderite AT-300, Aderite AT-330S, and Aderite AT20Q (trade names, manufactured by Asahi Denka Co. Ltd).
In the case where a solvent-based film-forming resin is used as a base, examples of the colloidal silica that may be used include Organosilica Sol MA-ST-MS, Organosilica Sol IPA-ST, Organosilica Sol EG-ST, Organosilica Sol IPA-ST-ZL, Organosilica Sol NPC-ST-30, Organosilica Sol DMAC-ST, Organosilica Sol MEK-ST-L, Organosilica Sol XBA-ST, and Organosilica Sol MIBK-ST (trade names, manufactured by Nissan Chemical Industries Ltd.); and OSCAL-1132, OSCAL-1232, OSCAL-1332, OSCAL-1432, OSCAL-1532, OSCAL-1632, and OSCAL-1722 (trade names, manufactured by Catalyst & Chemicals Co., Ltd).
In particular, an organic solvent-dispersible silica sol has excellent dispersibility and excellent corrosion resistance in comparison with fumed silica.
Examples of the fumed silica include that may be used include AEROSIL R812, AEROSIL R974, AEROSIL R202, AEROSIL R805, AEROSIL 130, AEROSIL 200, and AEROSIL 300 (trade names, manufactured by Nihon Aerosil Co., Ltd).
It is believed that fine-particle silica as described above contributes to the formation of a dense, stable corrosion product of zinc in a corrosive environment and that the formation of the dense corrosion product on a coated surface inhibits the acceleration of corrosion.
The fine-particle silica preferably has a particle size of 5 to 50 nm, more preferably 5 to 20 nm, and still more preferably 5 to 15 nm in view of corrosion resistance.
Even in the case where one or more of the following self-repairing materials are used as the rust preventive additive (j) in addition to the components (k) and (l), the same effect as that of the components (k) and (l) is provided:
(n) phosphate;
(o) molybdate; and
(p) one or more organic compounds selected from triazoles, thiols, thiadiazoles, thiazole, and thiurams.
The phosphate used as component (n) includes all types of salts including, for example, simple salts and double salts. Metal cations contained the salts are not limited. Any metal cation of, for example, zinc phosphate, magnesium phosphate, calcium phosphate, and aluminum phosphate, may be used. The skeleton and the degree of condensation of the phosphate ion are not limited. Any one of normal salts, dihydrogen salts, monohydrogen salts, and phosphite may be used. The normal salts include orthophosphates and all condensed phosphates, such as polyphosphates.
Furthermore, the combined addition of the phosphate serving as component (n) together with a calcium compound further improves the corrosion resistance. The calcium compound may be any one of calcium oxide, calcium hydroxide, and a calcium salt. One or two or more of these compounds may be used. Examples of the calcium salt that may be used include, but are not particularly limited to, normal salts, such as calcium silicate, calcium carbonate, and calcium phosphate, each containing only calcium as a cation; and double salts, such as calcium-zinc phosphate and calcium-magnesium phosphate, each containing calcium and a cation other than calcium.
The skeleton and the degree of condensation of the molybdate used as the component (o) are not limited. Examples of the molybdate include orthomolybdates, paramolybdates, and metamolybdates. The molybdate includes all salts, such as normal salts and double salts. Examples of the double salts include phosphomolybdates.
Examples of the organic compound used as the component (p) include triazoles, such as 1,2,4-triazole, 3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 5-amino-3-mercapto-1,2,4-triazole, and 1H-benzotriazole; thiols, such as 1,3,5-triazine-2,4,6-trithiol, and 2-mercaptobenzimidazole; thiadiazoles, such as 5-amino-2-mercapto-1,3,4-thiadiazole, and 2,5-dimercapto-1,3,4-thiadiazole; thiazoles, such as 2-N,N-diethylthiobenzothiazole and 2-mercaptobenzothiazole; and thiurams, such as tetraethylthiuram disulfide.
The total amount of the rust preventive additive (j) (the total amount of one or more of the self-repairing materials selected from the components (k), (l), and (n) to (p)) in the second layer is preferably in the range of 1 to 100 parts by mass (solid content), more preferably 5 to 80 parts by mass (solid content), and still more preferably 10 to 50 parts by mass (solid content) with respect to 100 parts by mass (solid content) of the organic resin in the surface treatment liquid (B). An amount of the rust preventive additive (j) added of less than 1 part by mass or more than 100 parts by mass can result in a reduction in corrosion resistance, which is not preferred.
In the present invention, the incorporation of appropriate amounts of the self-repairing materials (n) to (p) serving as the rust preventive additive (j) in the second layer provides quite excellent corrosion resistance (self-repairing effect). The possible anticorrosion mechanism of the second layer containing the rust preventive additive (j) is as follows.
In the case where the component (k), which is the rust preventive additive (j), is incorporated in the second layer, when cations, such as Na ions, enters the second layer in a corrosive environment, Ca ions on silica surfaces are released by an ion exchange function. Furthermore, OH ions are formed by cathodic reaction in a corrosive environment to increase the pH in the vicinity of an interface of the coated layer. So, the Ca ions released from the Ca ion-exchanged silica are precipitated in the form of Ca(OH)2 in the vicinity of the interface of the coated layer. The resulting dense, sparingly soluble product seals defects, thereby inhibiting a corrosion reaction. Moreover, it is believed that the eluted zinc ions are exchanged for the Ca ions and fixed to the silica surfaces.
The component (l) contributes to the formation of a dense, stable corrosion product of zinc in a corrosive environment. The corrosion product is densely formed on the surface of the coated layer, thereby inhibiting the acceleration of corrosion.
The component (n) is dissociated into phosphate ions by hydrolysis in a corrosive environment and is subjected to a complexation reaction with the eluted metal to form a protective film.
The component (o) provides the self-repairing properties on the basis of a passivation effect. That is, the component forms a dense oxide on the surface of the coated film together with dissolved oxygen in a corrosive environment, thereby sealing the origin of corrosion to inhibit a corrosion reaction.
The component (p) provides the self-repairing properties on the basis of an adsorption effect. That is, eluted zinc and aluminum due to corrosion are adsorbed to a nitrogen- or sulfur-containing polar group in the component (p) to form an inert film, thereby sealing the origin of corrosion to inhibit a corrosion reaction.
In the present invention, even if the components (k) and (l), or components (n) to (p) in addition thereto are incorporated in a general organic film, the rust preventive effect is provided to some extent. In the case where the self-repairing materials, i.e., the components (k) and (l), or components (n) to (p) in addition thereto, are incorporated in the second layer having excellent barrier properties and containing a specific organic resin (organic resin (g-1) containing an OH group and/or a COOH group, or the hydrazine-modified organic resin (g-2)), both effects (barrier effect and self-repairing effect) may be combined to provide the outstanding rust preventive effect.
In the case where a calcium compound is added in combination with the component (n), the calcium compound is eluted in a corrosive environment before the elution of a coating metal, and thus is subjected to a complexation reaction with phosphate ions to form a dense, sparingly soluble protective film without using the elution of the coating metal as a trigger, thereby inhibiting a corrosion reaction.
The combined addition of two or more of the components (k) and (l) or components (n) to (p) in addition thereto results in the combination of the corrosion-inhibiting effects of the components, thereby providing better corrosion resistance.
In addition to the rust preventive additives, the organic film may further contain one or two or more of other oxide fine particles, phosphomolybdates, organic phosphoric acids and salts thereof, and organic inhibitors, which serve as a corrosion inhibitors.
(Lubricant (m))
In the present invention, the surface treatment liquid (B) may further contain a lubricant (m) in order to improve the formability of the film, as needed. Examples of the lubricant (m) that may be used are described below. One or two or more of these compounds may be used.
(m1) Polyolefin wax and paraffin wax, e.g., polyethylene wax (m1-1), synthetic paraffin, natural paraffin, microcrystalline wax, and chlorinated hydrocarbons; (m2) fine particles of fluorocarbon resins, e.g., polyfluoroethylene resins (polytetrafluoroethylene resins), polyvinyl fluoride resins, and polyvinylidene fluoride resins.
Other examples thereof include fatty acid amide compounds (for example, stearic amide, stearamide, palmitamide, methylenebisstearamide, ethylenebisstearamide, oleamide, erucamide, and alkylenebisfatty acid amide); metallic soaps (for example, calcium stearate, lead stearate, calcium laurate, and calcium palmitate); metallic sulfides (for example, molybdenum disulfide and tungsten disulfide); graphite; graphite fluoride; boron nitride; polyalkylene glycol; and alkali metal sulfates. One or two or more of these compounds may be used.
Among these lubricants, the polyethylene wax (m1) and fluorocarbon resins fine particles (m2) (in particular, polytetrafluoroethylene resin fine particles) are particularly preferred.
Examples of the polyethylene wax (m1) include Ceridust 9615A, Ceridust 3715, Ceridust 3620, and Ceridust 3910 (trade names, manufactured by Clariant (Japan) K.K.); Sanwax 131-P and Sanwax 161-P (trade names, manufactured by Sanyo Chemical Industries, Ltd.; and Chemipearl W-100, Chemipearl W-200, Chemipearl W-500, Chemipearl W-800, and Chemipearl W-950 (trade names, manufactured by Mitsui Petrochemical Industries, Ltd).
As the fluorocarbon resin fine particles (m2), tetrafluoroethylene fine particles are most preferred. Preferred examples thereof include Lubron L-2 and Lubron L-5 (trade names, manufactured by Daikin Industries, Ltd.; MP1100 and MP1200 (trade names, manufactured by Mitsui-Dupont Co., Ltd.; and Fluon Dispersion AD1, Fluon Dispersion AD2, Fluon L141J, Fluon L150J, and Fluon L155J (trade names, manufactured by Asahi ICI Fluoropolymers Co., Ltd).
Among these compounds, combinations of the polyolefin wax and the tetrafluoroethylene fine particles should provide a quite excellent lubricating effect.
The amount of the lubricant (m) in the second layer is preferably in the range of 1 to 80 parts by mass (solid content) and more preferably 3 to 40 parts by mass (solid content) with respect to 100 parts by mass (solid content) of the organic resin in the surface treatment liquid (B). An amount of the lubricant (m) of 1 part by mass or more results in a sufficient lubricating effect. An amount of 80 parts by mass or less does not cause a reduction in paintability.
In the present invention, a curing agent may be added to the surface treatment liquid (B) in order to form the second layer serving as a dense barrier film. So, the second layer may be formed by thermal curing.
As a curing method for forming the second layer serving as a dense barrier film, the following methods are appropriate:
(1) a curing method that uses a urethane-forming reaction between an isocyanate and a hydroxy group of a base resin; and
(2) a curing method that uses an etherification reaction between an alkyl-etherified amino resin and a hydroxy group of a base resin (the alkyl-etherified amino resin is prepared by partially or entirely reacting a methylol compound, which is prepared by reaction of one or more compounds selected from melamine, urea, and benzoguanamine with formaldehyde, with a monohydric alcohol having 1 to 5 carbon atoms). It is particularly preferable to use the urethane-forming reaction between an isocyanate and a hydroxy group of a base resin as a main reaction.
In the present invention, the surface treatment liquid (B) may further contain one or two or more of organic color pigments (for example, fused polycyclic organic pigments and phthalocyanine organic pigments), color dyes (for example, organic solvent-soluble azo dyes and water-soluble azo metal dyes), inorganic pigments (for example, titanium oxide), chelating agents (for example, thiols), conductive pigments (for example, powders of metals, such as zinc, aluminum, and nickel, iron phosphide, and antimony-doped tin oxide), coupling agents (for example, silane coupling agents and titanium coupling agents), and melamine-cyanuric acid adducts, as needed.
(Another Organic Resin)
As described above, the use of the surface treatment liquid (B) which contains the organic resin (g-1) containing an OH group and/or a COOH group, or which contains the hydrazine-modified organic resin (g-2) results in a zinc-based metal coated steel sheet having excellent adhesion and conductivity. For example, when importance is attached to the formability of a zinc-based metal coated steel sheet, the surface treatment liquid (B) containing a water-soluble urethane-modified acrylic resin and/or a water-dispersible urethane-modified acrylic resin (q) serving as the organic resin (g), the curing agent (r), the silicon oxide (l), and the lubricant (m) in a specific ratio is preferably used.
The water-soluble urethane-modified acrylic resin (q) may be a water-soluble resin, a water-dispersible resin, or a mixture of these resins. A method for modifying an acrylic resin with urethane is not particularly limited. For the water-soluble or water-dispersible urethane-modified acrylic resin (q), the solid content by mass of a urethane component in the solid resin is preferably in the range of 10% to 50% by mass and more preferably 10% to 30% by mass.
Curing agent (r) is added in order to form sufficient cross-links in the film. The cross-links provide excellent corrosion resistance and solvent resistance. The type of curing agent is not particularly limited. A compound containing at least one functional group selected from an epoxy group, an oxazoline group, an isocyanate group, and an aziridinyl group, which are not hydrophilic groups, is particularly preferably used rather than, for example, amine, polyhydric alcohol, and polybasic acid containing amino groups, hydroxy groups, and carboxy groups, which are hydrophilic groups.
The silicon oxide (l) is added in order to improve corrosion resistance. The type of silicon oxide (l) is not particularly limited. One or more of, for example, colloidal silica and fumed silica described above may be used. In the present invention, the particle size and type of silica are not particularly limited.
The lubricant (m) serves as a lubricating component to improve scratch resistance. Examples of the lubricant (m) that may be used include, but are not particularly limited to, carnauba wax, rice wax, lanolin wax, montan wax, paraffin wax, microcrystalline wax, fatty ester wax, fatty acid amide wax and partially saponified products thereof, polyethylene wax, polyolefin wax, chlorinated hydrocarbons, fluorinated hydrocarbons, and ethylene-acrylic copolymer wax. One or two or more of these compounds may be used. The lubricant (m) preferably has an average particle size of 0.05 to 3.0 μm. The lubricant (m) preferably has a melting point of 50° C. to 160° C. The shape of the lubricant particles is preferably spherical in order to achieve a high degree of formability.
The proportion of the total mass of the solids of (q) and (r) is preferably in the range of 50% to 95% by mass and more preferably 55% to 75% by mass with respect to the total mass of the solids of the water-soluble urethane-modified acrylic resin and/or water-dispersible urethane-modified acrylic resin (q)+ the curing agent (r)+ the silicon oxide (l)+ the lubricant (m) (hereinafter, referred to as “(q)+(r)+(l)+(m)”).
The curing agent (r) is preferably added in such a manner that the ratio of the solid content by mass of curing agent (r) to the solid content by mass of the water-soluble urethane-modified acrylic resin and/or water-dispersible urethane-modified acrylic resin (q), i.e., (q)/(r), is in the range of 4 to 49.
The amount of the silicon oxide (l) added is preferably in the range of 3% to 40% by mass in terms of the solid content by mass with respect to (q)+(r)+(l)+(m).
The amount of the lubricant (m) added is preferably in the range of 2% to 20% by mass and more preferably 5% to 15% by mass in terms of the solid content by mass with respect to (q)+(r)+(l)+(m).
In the present invention, for example, a surfactant, called a wettability improver, used to form a uniform film on a surface to be coated, a thickener, a conductive material used to improve conductivity, a color pigment used to improve design, and a solvent used for improving film formability, may be appropriately added to the surface treatment liquid (B) used for the second layer, as needed.
(Formation of Second Layer)
As described above, in the present invention, the surface treatment liquid (B) is applied to a surface of the first layer and dried by heating to form the second layer.
Examples of a method for applying the surface treatment liquid (B) to the surface of the first layer include a roll coating method, a bar coating method, an immersion method, and a spray coating method. An optimum method is selected, depending on, for example, the shape of a zinc-based metal coated steel sheet to be treated. More specifically, for example, if a zinc-based metal coated steel sheet to be treated has a sheet shape, the surface treatment liquid is applied by a roll coating method or a bar coating method or is sprayed on a zinc-based metal coated steel sheet, and then the coating weight is adjusted with squeeze rolls or by blowing a gas thereto at high pressure. If a zinc-based metal coated steel sheet is formed into a formed article, for example, a method is selected in which the article is immersed in the surface treatment liquid and withdrawn therefrom, and in some cases, an excess of the surface treatment liquid is blown off with compressed air to adjust the coating weight.
After the application of the surface treatment liquid (B), drying is performed by heating without washing with water. However, a water-washing step may be performed after the application of the surface treatment liquid (B). A heating temperature (maximum sheet temperature) when the surface treatment liquid (B) is dried is usually in the range of 50° C. to 350° C. and more preferably 80° C. to 250° C. A heating temperature of 50° C. or higher does not cause a problem, such as a reduction in the corrosion resistance of the zinc-based metal coated steel sheet, because the solvent is not left in the second layer. A heating temperature of 350° C. or lower does not cause the problem because the occurrence of cracking of the second layer is suppressed. A heat-drying method is not particularly limited. The surface treatment liquid (B) may be dried by heating using, for example, hot air, an induction heater, infrared radiation, or near infrared radiation.
An appropriately optimized heating time is selected, depending on, for example, the type of zinc-based metal coated steel sheet used. The heating time is preferably in the range of 0.1 to 60 seconds and more preferably 1 to 30 seconds in view of, for example, productivity.
The thickness of the second layer is preferably 0.01 μm or more and less than 3 μm, and more preferably in the range of 0.1 to 2 μm after drying by heating. When the thickness after drying by heating is 0.01 μm or more, sufficient corrosion resistance and fingerprint resistance are provided. A thickness of less than 3 μm does not cause a reduction in conductivity.
In particular, the use of the hydrazine-modified organic resin (g-2) as the organic resin (g) for the second layer results in a uniform film having excellent corrosion resistance even at a small thickness. So, it is particularly advantageous when the conductivity is improved without reducing the corrosion resistance.
<Total Film Thickness>
The total thickness per side of the first layer (composite oxide film) and the second layer (organic resin film) located thereon is in the range of 0.1 to 3 μm and preferably 0.1 to 2 μm. A total thickness of less than 0.1 μm leads to insufficient corrosion resistance. A total thickness exceeding 3 μm leads to a reduction in conductivity.
To strike a balance between the corrosion resistance and the conductivity, preferably, the first layer (composite oxide film) has a thickness of 0.05 μm or more, and the second layer (organic resin film) has a thickness of 1.0 μm or less.
The present invention provides a steel sheet including the foregoing films located on one or both sides. Examples of the configuration of the steel sheet of the present invention include the following:
(1) one side: coated layer-first layer-second layer, one side: coated layer;
(2) one side: coated layer-first layer-second layer, one side: coated layer-known phosphate-treated film or the like;
(3) both sides: coated layer-first layer-second layer;
(4) one side: coated layer-first layer-second layer, one side: coated layer-first layer; and
(5) one side: coated layer-first layer-second layer, one side: coated layer-second layer.
With respect to the thicknesses of the first layer and the second layer, a thickness measurement method is not particularly limited as long as the thickness of each film can be surely measured by the method. For example, the section of the films processed by FIB is observed with a SEM. Representative elements present in the films are measured by, for example, EDX to determine the interface between the films, thereby calculating the thickness of each film. For example, thicknesses are measured at any three points per one field of view of the section observed with the SEM. The mean value of the thicknesses is defined as the thickness.
According to the present invention, it is possible to provide a zinc-based metal coated steel sheet having excellent corrosion resistance and adhesion and having excellent conductivity even under severe conditions where steel sheets are contacted at a low pressure, in particular, without reducing the corrosion resistance. The zinc-based metal coated steel sheet of the present invention may be used for various applications and suitably used as a material for use in various fields, such as architecture, electricity, and automobiles.
EXAMPLES
While advantageous effects of the present invention will be described by means of examples and comparative examples, these examples are merely examples to illustrate the present invention and are not limited to the present invention.
1. Method for Forming Test Sheet
(1) Test Sheet (Material)
Commercially available materials described below were used as test sheets.
(i) electrogalvanized steel sheet (EG): sheet thickness: 0.8 mm, weight per area: 20/20 (g/m2)
(ii) hot-dip galvanized steel sheet (GI): sheet thickness 0.8 mm, weight per area: 60/60 (g/m2)
(iii) hot-dip galvannealed steel sheet (GA): sheet thickness: 0.8 mm, weight per area: 40/40 (g/m2)
The “weight per area” indicates the weight per area of each steel sheet. For example, in the case of the electrogalvanized steel sheet, “20/20 (g/m2)” indicates that a coated layer having a weight of 20 g/m2 is arranged on each side of the steel sheet.
(2) Pretreatment (Washing)
Test pieces were produced by the following process. Surfaces of the test sheets were treated with Palclean N364S (manufactured by Nihon Parkerizing Co., Ltd.) to remove oil and dirt on the surfaces. The test sheets were then washed with tap water. After checking that the test sheets were completely wetted with water, pure water (deionized water) was poured onto the test sheets. The test sheets were dried in an atmosphere having a temperature of 100° C. in an oven and then used as the test pieces.
(3) Preparation of Surface Treatment Liquid (A)
Components were mixed in water so as to achieve compositions (ratio by mass) described in Tables 1-1 to 1-4 to prepare treatment liquids (A) for zinc-coated steel sheets. aS, bS, cS, dS, eV, and fT in Tables 1 represent the solid content of the resin emulsion (a), the solid content of the tetraalkoxysilane (b), the solid content of the silane coupling agent (c), the solid content of the chelating agent (d), the solid content of the vanadic acid compound (e) in terms of V, and the titanium compound (f) in terms of Ti, respectively.









TABLE 1-1









Surface treatment liquid (A)










Composition



























Com-








Com-
Com-
Com-
Com-
Com-
Com-
ponent
(cs)/(as)
(bs)/(ds)
(es)/(ds)
(fs)/(ds)



ponent
ponent
ponent
ponent
ponent
ponent
(as)
Ratio
Ratio
Ratio
Ratio



(a)
(b)
(c)
(d)
(e)
(f)
mass
by
by
by
by



















Test level
Type
Type
Type
Type
Type
Type
% (*3)
mass
mass
mass
mass
pH























Example
1
a1
b1
c1
d1
e1
f1
11
5.35
0.50
0.08
0.06
4.0


Example
2
a1
b1
c1
d1
e1
f2
11
5.35
0.50
0.08
0.06
4.0


Example
3
a1
b1
c1
d1
e1
f2
20
2.41
0.50
0.08
0.06
3.0


Example
4
a1
b1
c1
d1
e1
f2
20
2.41
0.50
0.08
0.06
4.0


Example
5
a1
b1
c1
d1
e1
f2
20
2.41
0.50
0.08
0.06
5.0


Example
6
a1
b1
c1
d1
e1
f2
20
2.41
0.50
0.08
0.06
6.0


Example
7
a1
b1
c2
d1
e1
f2
20
2.41
0.50
0.08
0.06
4.0


Example
8
a1
b1
c3
d1
e1
f2
20
2.41
0.50
0.08
0.06
4.0


Example
9
a1
b1
c1
d1
e1
f2
40
1.51
0.83
0.08
0.06
4.0


Example
10
a1
b2
c1
d1
e1
f2
40
1.51
0.83
0.08
0.06
4.0


Example
11
a1
b1
c1
d1
e2
f2
35
1.51
0.99
0.08
0.06
4.0


Example
12
a1
b1
c2
d1
e2
f2
30
1.51
1.49
0.08
0.06
4.0


Example
13
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
14
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
15
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
16
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
17
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
18
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
19
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
20
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
21
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
22
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
23
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
24
a1
b1
c2
d1
e2
f2
40
1.66
0.50
0.08
0.06
4.0


Example
25
a1
b1
c2
d1
e2
f2
20
3.02
0.50
0.08
0.06
4.0


Example
26
a1
b1
c1
d1
e1
f2
20
4.52
0.50
0.08
0.06
4.0


Example
27
a2
b1
c1
d1
e1
f2
20
4.52
0.50
0.08
0.06
4.0


Example
28
a2
b1
c1
d1
e1
f2
45
1.51
0.53
0.08
0.07
4.0


Example
29
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
30
a2
b1
c1
d1
e1
f2
30
1.51
0.25
0.04
0.03
4.0


Example
31
a2
b2
c1
d1
e1
f2
25
1.51
0.17
0.03
0.02
4.0


Example
32
a2
b2
c1
d1
e1
f2
45
1.51
0.50
0.10
0.06
4.0


Example
33
a2
b2
c1
d2
e1
f2
45
1.51
0.50
0.10
0.06
4.0


Example
34
a2
b2
c1
d2 + d3 (*2)
e1
f2
45
1.51
0.50
0.10
0.06
4.0


Example
35
a2
b2
c1
d1
e1
f2
40
1.51
0.50
0.15
0.06
4.0


Example
36
a2
b2
c3
d1
e1
f2
40
1.51
0.50
0.23
0.06
4.0


Example
37
a2
b2
c3
d1
e1
f1
45
1.51
0.50
0.08
0.09
4.0


Example
38
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
39
a2
b2
c3
d1
e2
f1
45
1.51
0.50
0.08
0.09
4.0


Example
40
a1
b1
c3
d2
e1
f1
45
1.51
0.50
0.08
0.13
4.0





(*1) The ratio (by mass) of c1 to c2 is 1:1.


(*2) The ratio (by mass) of d2 to d3 is 1:1.


(*3) The proportion (solid content) of the solid (as) of component (a) in surface treatment liquid (A)















TABLE 1-2









Surface treatment liquid (A)










Composition



























Com-








Com-
Com-
Com-
Com-
Com-
Com-
ponent
(cs)/(as)
(bs)/(ds)
(es)/(ds)
(fs)/(ds)



ponent
ponent
ponent
ponent
ponent
ponent
(as)
Ratio
Ratio
Ratio
Ratio



(a)
(b)
(c)
(d)
(e)
(f)
mass
by
by
by
by



















Test level
Type
Type
Type
Type
Type
Type
% (*3)
mass
mass
mass
mass
pH























Example
41
a1
b1
c3
d2
e1
f1
40
1.51
0.50
0.08
0.19
4.0


Example
42
a1
b1
c3
d2
e1
f1
40
1.51
0.50
0.08
0.06
4.0


Example
43
a1
b1
c3
d2
e1
f1
40
1.51
0.50
0.08
0.06
4.0


Example
44
a1
b1
c3
d2
e1
f1
40
1.51
0.50
0.08
0.06
4.0


Example
45
a1
b1
c3
d2
e1
f1
40
1.51
0.50
0.08
0.06
4.0


Example
46
a1
b1
c3
d2
e1
f1
40
1.51
0.50
0.08
0.06
4.0


Example
47
a1
b1
c3
d2
e1
f1
40
1.51
0.50
0.08
0.06
4.0


Example
48
a1
b1
c3
d2
e1
f1
40
1.51
0.50
0.08
0.06
4.0


Example
49
a1
b1
c3
d2
e1
f1
40
1.51
0.50
0.08
0.06
4.0


Example
50
a1
b1
c3
d2
e1
f1
40
1.51
0.50
0.08
0.06
4.0


Example
51
a1
b1
c3
d2
e1
f1
40
1.51
0.50
0.08
0.06
4.0


Example
52
a1
b1
c3
d2
e1
f1
40
1.51
0.50
0.08
0.06
4.0


Comparative
53
a1
b1
c1
d2
e1
f1
5
12.03
0.50
0.08
0.06
4.0


Example


Comparative
54
a1
b1
c1
d2
e1
f1
65
0.91
0.50
0.08
0.06
4.0


Example


Comparative
55
a1
b1
c1
d2
e1
f2
48
1.51
0.12
0.08
0.06
4.0


Example


Comparative
56
a2
b1
c1
d2
e1
f2
27
1.51
1.99
0.08
0.06
4.0


Example


Comparative
57
a2
b1
c1
d2
e1
f2
70
0.38
0.50
0.08
0.06
4.0


Example


Comparative
58
a2
b2
c3
d2
e1
f2
13
6.03
0.50
0.08
0.06
4.0


Example


Comparative
59
a2
b2
c3
d2
e2
f1
50
1.51
1.99
0.30
0.25
4.0


Example


Comparative
60
a2
b2
c3
d1
e2
f1
22
1.51
0.12
0.02
0.02
4.0


Example


Comparative
61
a1
b1
c2
d1
e1
f2
47
1.51
0.50
0.08
0.01
4.0


Example


Comparative
62
a1
b1
c2
d1
e1
f2
35
1.51
0.50
0.08
0.25
4.0


Example


Comparative
63
a1
b1
c2
d1
e1
f2
20
2.41
0.50
0.08
0.06
2.0


Example


Comparative
64
a1
b1
c2
d1
e1
f2
20
2.41
0.50
0.08
0.06
7.0


Example


Comparative
65
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example


Comparative
66
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example


Comparative
67
—
b1
c1
d2
e1
f2
0
—
0.50
0.08
0.06
4.0


Example


Comparative
68
a2
—
c3
d1
e2
f1
6
12.03
0.00
0.08
0.06
4.0


Example


Comparative
69
a1
b1
—
d1
e2
f2
14
0
0.50
0.08
0.06
4.0


Example


Comparative
70
a1
b1
c2
—
e2
f2
6
12.03
—
—
—
4.0


Example


Comparative
71
a1
b1
c2
d1
—
f2
5
12.03
0.50
0.00
0.06
4.0


Example


Comparative
72
a1
b1
c2
d1
e2
—
5
12.03
0.50
0.08
0.00
4.0


Example


Example
73
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
74
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
75
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
76
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
77
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
78
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
40


Example
79
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
80
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0





(*1) The ratio (by mass) of c1 to c2 is 1:1.


(*3) The proportion (solid content) of the solid (as) of component (a) in surface treatment liquid (A)















TABLE 1-3









Surface treatment liquid (A)










Composition



























Com-








Com-
Com-
Com-
Com-
Com-
Com-
ponent
(cs)/(as)
(bs)/(ds)
(es)/(ds)
(fs)/(ds)



ponent
ponent
ponent
ponent
ponent
ponent
(as)
Ratio
Ratio
Ratio
Ratio



(a)
(b)
(c)
(d)
(e)
(f)
mass
by
by
by
by



















Test level
Type
Type
Type
Type
Type
Type
% (*3)
mass
mass
mass
mass
pH























Example
81
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
82
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
83
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
84
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
85
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
86
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
87
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
88
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
89
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
90
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
91
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
92
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
93
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
94
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
95
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
96
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
97
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
98
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
99
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
100
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
101
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
102
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
103
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
104
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
105
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
106
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
107
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
108
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
109
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
110
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
111
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Comparative
112
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example


Comparative
113
—
—
—
—
—
—
—
—
—
—
—
—


Example


Comparative
114
—
—
—
—
—
—
—
—
—
—
—
—


Example


Comparative
115
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example


Comparative
116
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example


Example
117
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
118
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
119
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
120
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0





(*1) The ratio (by mass) of c1 to c2 is 1:1.


(*3) The proportion (solid content) of the solid (as) of component (a) in surface treatment liquid (A)















TABLE 1-4









Surface treatment liquid (A)










Composition



























Com-








Com-
Com-
Com-
Com-
Com-
Com-
ponent
(cs)/(as)
(bs)/(ds)
(es)/(ds)
(fs)/(ds)



ponent
ponent
ponent
ponent
ponent
ponent
(as)
Ratio
Ratio
Ratio
Ratio



(a)
(b)
(c)
(d)
(e)
(f)
mass
by
by
by
by



















Test level
Type
Type
Type
Type
Type
Type
% (*3)
mass
mass
mass
mass
pH























Example
121
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
122
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
123
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
124
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
125
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
126
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
127
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
128
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
129
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
130
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
131
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.6


Example
132
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
133
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
134
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
135
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
136
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
137
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
138
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
139
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
140
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
141
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
142
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
143
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
144
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
145
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
146
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
147
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
148
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
149
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
150
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
151
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
152
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example
153
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Comparative
154
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example


Comparative
155
a2
b2
c1 + c2 (*1)
d2
e2
f2
45
1.51
0.50
0.08
0.06
4.0


Example





(*1) The ratio (by mass) of c1 to c2 is 1:1.


(*3) The proportion (solid content) of the solid (as) of component (a) in surface treatment liquid (A)






Compounds in Tables 1-1 to 1-4 are described below.
<Resin Emulsion (a) Containing Cationic Urethane Resin Emulsion (a-1) and/or Nonionic Acrylic Resin Emulsion (a-2)>
a1: styrene-ethyl methacrylate-n-butyl acrylate-acrylic acid copolymer (nonionic acrylic resin emulsion (a-2))
a2: ADEKA BONTIGHTER HUX-670 (cationic urethane resin emulsion (a-1))
<Tetraalkoxysilane (b)>
b1: tetraethoxysilane
b2: tetramethoxysilane
<Silane Coupling Agent (c)>
c1: γ-glycidyltriethoxysilane
c2: 3-mercaptopropyltrimethoxysilane
c3: N-(2-aminoethyl)-3-aminopropyltrimethoxysilane
<Chelating Agent (d)>
d1: 1-hydroxymethane-1.1-diphosphonic acid
d2: acetic acid
d3: phosphoric acid
<Vanadic Acid Compound (e)>
e1: ammonium metavanadate
e2: vanadyl acetylacetonate (V: 19.2%)
<Titanium Compound (f)>
f1: ammonium fluorotitanate
f2: titanium acetylacetonate (Ti: 12.5%)
(4) Preparation of Surface Treatment Liquid (B)
The surface treatment liquids (B) appropriately containing additives, described in Tables 2-1 to 2-4, mixed with the organic resins (g1 to g7) described below were prepared. Concentrations of the organic resins (g), described in Tables 2-1 to 2-4, in the surface treatment liquid (B) were in the range of 4 to 10 g/l. The amounts of the components (k), (l), and (m) are expressed in terms of proportions in the base resin (g).









TABLE 2-1









Surface treatment liquid (B)










Organic resin












Concen-
Addi-
Mixing ratio



tration
tive
(ratio by mass)












Test level
Type
(*4)
Type
g:(k + l)
g:m
















Example
1
g6
10
—
—
—


Example
2
g6
10
—
—
—


Example
3
g6
10
—
—
—


Example
4
g6
10
—
—
—


Example
5
g6
10
—
—
—


Example
6
g6
10
—
—
—


Example
7
g6
10
—
—
—


Example
8
g6
10
—
—
—


Example
9
g6
10
—
—
—


Example
10
g6
10
—
—
—


Example
11
g6
10
—
—
—


Example
12
g6
10
—
—
—


Example
13
g6
10
—
—
—


Example
14
g6
10
—
—
—


Example
15
g6
10
—
—
—


Example
16
g6
10
—
—
—


Example
17
g6
8
k1 + l1 (*5)
100:30
—


Example
18
g6
8
l2
100:30
—


Example
19
g4
10
—
—
—


Example
20
g5
10
—
—
—


Example
21
g6
10
—
—
—


Example
22
g6
10
—
—
—


Example
23
g6
10
—
—
—


Example
24
g6
10
—
—
—


Example
25
g6
10
—
—
—


Example
26
g6
10
—
—
—


Example
27
g6
10
—
—
—


Example
28
g6
10
—
—
—


Example
29
g6
10
—
—
—


Example
30
g6
10
—
—
—


Example
31
g6
10
—
—
—


Example
32
g6
10
—
—
—


Example
33
g6
10
—
—
—


Example
34
g6
10
—
—
—


Example
35
g6
10
—
—
—


Example
36
g6
10
—
—
—


Example
37
g6
10
—
—
—


Example
38
g6
10
—
—
—


Example
39
g6
10
—
—
—


Example
40
g6
10
—
—
—





(*4) indicates the concentration (g/n) of base resin g in surface treatment liquid (B).


(*5) The mixing ratio (ratio by mass) of k1 to l1 is 1:1.


(*6) The mixing ratio (ratio by mass) of k1 to l1 to n1 is 1:1:0.1.


(*7) The mixing ratio (ratio by mass) of k1 to l1 to o1 is 1:1:0.1.


((*8) The mixing ratio (ratio by mass) of k1 to l1 to n1 to o1 is 1:1:0.1:0.1.















TABLE 2-2









Surface treatment liquid (B)










Organic resin












Concen-
Addi-
Mixing ratio



tration
tive
(ratio by mass)












Test level
Type
(*4)
Type
g:(k + l)
g:m
















Example
41
g6
10
—
—
—


Example
42
g6
10
—
—
—


Example
43
g6
10
—
—
—


Example
44
g6
10
—
—
—


Example
45
g6
10
—
—
—


Example
46
g6
8
k1 + l1 (*5)
100:30
—


Example
47
g6
8
l2
100:30
—


Example
48
g4
10
—
—
—


Example
49
g5
10
—
—
—


Example
50
g6
10
—
—
—


Example
51
g6
10
—
—
—


Example
52
g6
10
—
—
—


Comparative
53
g6
10
—
—
—


Example


Comparative
54
g6
10
—
—
—


Example


Comparative
55
g6
10
—
—
—


Example


Comparative
56
g6
10
—
—
—


Example


Comparative
57
g6
10
—
—
—


Example


Comparative
58
g6
10
—
—
—


Example


Comparative
59
—
—
—
—
—


Example


Comparative
60
g6
10
—
—
—


Example


Comparative
61
g6
10
—
—
—


Example


Comparative
62
—
—
—
—
—


Example


Comparative
63
g6
10
—
—
—


Example


Comparative
64
g6
10
—
—
—


Example


Comparative
65
g6
10
—
—
—


Example


Comparative
66
g6
10
—
—
—


Example


Comparative
67
g6
10
—
—
—


Example


Comparative
68
g6
10
—
—
—


Example


Comparative
69
g6
10
—
—
—


Example


Comparative
70
g6
10
—
—
—


Example


Comparative
71
g6
10
—
—
—


Example


Comparative
72
g6
10
—
—
—


Example


Example
73
g1
10
—
—
—


Example
74
g2
10
—
—
—


Example
75
g3
10
—
—
—


Example
76
g7
10
—
—
—


Example
77
g3
8
l2
100:30
—


Example
78
g3
8
k1 + l1 (*5)
100:30
—


Example
79
g3
8
k1 + l1 + n1 (*6)
100:30
—


Example
80
g3
8
k1 + l1 + o1 (*7)
100:30
—





(*4) indicates the concentration (g/n) of base resin g in surface treatment liquid (B).


(*5) The mixing ratio (ratio by mass) of k1 to l1 is 1:1.


(*6) The mixing ratio (ratio by mass) of k1 to l1 to n1 is 1:1:0.1.


(*7) The mixing ratio (ratio by mass) of k1 to l1 to o1 is 1:1:0.1.


((*8) The mixing ratio (ratio by mass) of k1 to l1 to n1 to o1 is 1:1:0.1:0.1.















TABLE 2-3









Surface treatment liquid (B)










Organic resin












Concen-
Addi-
Mixing ratio



tration
tive
(ratio by mass)












Test level
Type
(*4)
Type
g:(k + l)
g:m
















Example
81
g3
8
k1 + l1 +
100:30
—






n1 + o1 (*8)


Example
82
g3
10
m1
—
100:3


Example
83
g3
8
l2 + m1
100:30
100:3


Example
84
g3
8
k1 + l1 (*5) +
100:30
100:3






m1


Example
85
g3
8
l3
100:30
—


Example
86
g3
8
l3 + m1
100:30
100:3


Example
87
g3
10
—
—
—


Example
88
g3
10
—
—
—


Example
89
g3
10
—
—
—


Example
90
g3
10
—
—
—


Example
91
g3
10
—
—
—


Example
92
g3
10
—
—
—


Example
93
g3
10
—
—
—


Example
94
g3
10
—
—
—


Example
95
g3
10
—
—
—


Example
96
g3
10
—
—
—


Example
97
g3
10
—
—
—


Example
98
g3
10
—
—
—


Example
99
g3
10
—
—
—


Example
100
g3
10
—
—
—


Example
101
g3
10
—
—
—


Example
102
g3
10
—
—
—


Example
103
g3
10
—
—
—


Example
104
g3
10
—
—
—


Example
105
g3
10
—
—
—


Example
106
g4
10
—
—
—


Example
107
g4
10
—
—
—


Example
108
g4
10
—
—
—


Example
109
g4
10
—
—
—


Example
110
g4
10
—
—
—


Example
111
g4
10
—
—
—


Comparative
112
—
—
—
—
—


Example


Comparative
113
g3
10
—
—
—


Example


Comparative
114
g4
10
—
—
—


Example


Comparative
115
g3
10
—
—
—


Example


Comparative
116
g4
10
—
—
—


Example


Example
117
g6
10
l2
100:5 
—


Example
118
g6
9
l2
100:10
—


Example
119
g6
6
l2
100:70
—


Example
120
g6
5
l2
 100:100
—





(*4) indicates the concentration (g/n) of base resin g in surface treatment liquid (B).


(*5) The mixing ratio (ratio by mass) of k1 to l1 is 1:1.


(*6) The mixing ratio (ratio by mass) of k1 to l1 to n1 is 1:1:0.1.


(*7) The mixing ratio (ratio by mass) of k1 to l1 to o1 is 1:1:0.1.


((*8) The mixing ratio (ratio by mass) of k1 to l1 to n1 to o1 is 1:1:0.1:0.1.















TABLE 2-4









Surface treatment liquid (B)










Organic resin












Concen-
Addi-
Mixing ratio



tration
tive
(ratio by mass)












Test level
Type
(*4)
Type
g:(k + l)
g:m
















Example
121
g7
9
l2
100:10
—


Example
122
g7
8
l2
100:30
—


Example
123
g7
6
l2
100:70
—


Example
124
g6
8
k1
100:30
—


Example
125
g6
8
k1
100:30
—


Example
126
g6
9
k1 + l1 (*5)
100:10
—


Example
127
g6
8
k1 + l1 (*5)
100:30
—


Example
128
g6
6
k1 + l1 (*5)
100:70
—


Example
129
g7
9
k1 + l1 (*5)
100:10
—


Example
130
g7
8
k1 + l1 (*5)
100:30
—


Example
131
g7
6
k1 + l1 (*5)
100:70
—


Example
132
g6
10
l1
100:5 
—


Example
133
g7
10
l1
100:5 
—


Example
134
g6
8
l2
100:30
—


Example
135
g6
8
l2
100:30
—


Example
136
g6
8
l2
100:30
—


Example
137
g6
8
l2
100:30
—


Example
138
g6
8
l2
100:30
—


Example
139
g6
8
l2
100:30
—


Example
140
g6
8
l2
100:30
—


Example
141
g6
8
l2
100:30
—


Example
142
g6
8
l2
100:30
—


Example
143
g6
8
l2
100:30
—


Example
144
g6
8
l2
100:30
—


Example
145
g6
8
l2
100:30
—


Example
146
g6
8
l2
100:30
—


Example
147
g6
8
l2
100:30
—


Example
148
g6
8
l2
100:30
—


Example
149
g6
8
l2
100:30
—


Example
150
g6
8
l2
100:30
—


Example
151
g6
8
l2
100:30
—


Example
152
g6
8
l2
100:30
—


Example
153
g6
4
l2
 100:150
—


Comparative
154
—
0
l2
 0:30
—


Example


Comparative
155
—
0
k1 + l1 (*5)
 0:30
—


Example





(*4) indicates the concentration (g/n) of base resin g in surface treatment liquid (B).


(*5) The mixing ratio (ratio by mass) of k1 to l1 is 1:1.


(*6) The mixing ratio (ratio by mass) of k1 to l1 to n1 is 1:1:0.1.


(*7) The mixing ratio (ratio by mass) of k1 to l1 to o1 is 1:1:0.1.


((*8) The mixing ratio (ratio by mass) of k1 to l1 to n1 to o1 is 1:1:0.1:0.1.






Compounds in Tables 2-1 to 2-4 are described below.
<Organic Resin: Organic Resin that does not Contain OH Group and/or COOH Group>
g1: polyolefin resin (Model: HYTEC S-3121, manufactured by TOHO Chemical Industry Co., Ltd.)
g2: fluorocarbon resin (Model: Lumiflon LF552, manufactured by Asahi Glass Co., Ltd.)
<Organic Resin: Organic Resin (g-1) Containing OH Group and/or COOH Group>
g3: epoxy resin (Model: jER1009, manufactured by Japan Epoxy Resin Co., Ltd.)
g4: urethane resin (Model: Superflex E-2000, manufactured by Dai-Ichi Kogyo Seiyaku Co., Ltd.)
g5: alkyd resin (Model: PHTHALKYD W2343, manufactured by Hitachi Chemical Company, Ltd.)
<Organic Resin: Hydrazine-Modified Organic Resin (g-2)>
g6: [Synthesis Example 1]
EP828 (manufactured by Yuka Shell Epoxy K.K., epoxy equivalent: 187) (1870 parts by mass), bisphenol A (91 2 parts by mass), tetraethylammonium bromide (2 parts by mass), and methyl isobutyl ketone (300 parts by mass) were charged into a four-necked flask. The mixture was heated to 140° C. and reacted for 4 hours to give an epoxy resin having an epoxy equivalent of 1391 and a solid content of 90% by mass. Ethylene glycol mono-n-butyl ether (1500 parts by mass) was added thereto. The mixture was cooled to 100° C. Then 3,5-dimethylpyrazole (molecular weight: 96) (96 parts by mass) and dibutylamine (molecular weight: 129) (129 parts by mass) were added thereto. The mixture was reacted for 6 hours until the epoxy groups disappear. Methyl isobutyl ketone (205 parts by mass) was then added thereto with cooling, thereby yielding a pyrazole-modified epoxy resin having a solid content of 60% by mass. This resin is defined as an organic resin (g6). The organic resin (g6) is a reaction product of the organic resin (C) and the active hydrogen-containing compound (i) that contains the active hydrogen-containing hydrazine derivative (h) in an amount of 50 mol %.
g7: [Synthesis Example 2]
EP1007 (manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 2000) (4000 parts by mass) and ethylene glycol mono-butyl ether (2239 parts by mass) were charged into a four-necked flask. The mixture was heated to 120° C. to completely dissolve the epoxy resin in 1 hour. The solution was cooled to 100° C. Then 3-amino-1,2,4-triazole (molecular weight: 84) (168 parts by mass) was added thereto. The mixture was reacted for 6 hours until the epoxy groups disappear. Methyl isobutyl ketone (540 parts by mass) was then added thereto with cooling, thereby yielding a triazole-modified epoxy resin having a solid content of 60% by mass. This resin is defined as an organic resin (g7). The organic resin (g7) is a reaction product of the organic resin (C) and the active hydrogen-containing compound (i) that contains the active hydrogen-containing hydrazine derivative (h) in an amount of 100 mol %.
<Ca Ion-Exchanged Silica (k)>
k1: Ca ion-exchanged silica (Model: SHIELDEX C303, manufactured by W. R. Grace & Co.)
<Silicon oxide (l)>
l1: fumed silica (Model: AEROSIL 200, manufactured by Nihon Aerosil Co., Ltd.)
l2: organosilica sol (Model: Organosilica Sol MA-ST-MS, manufactured by Nissan Chemical Industries Ltd.)
l3: colloidal silica (Model: Snowtex 30, manufactured by Nissan Chemical Industries Ltd.)
<Lubricant (m)>
m1: polyethylene wax (Model: Ceridust 3620, manufactured by Clariant (Japan) K.K.)
<Phosphate (n)>
n1: zinc phosphate
<Molybdate (o)>
o1: aluminum molybdate
(5) Method for Producing Zinc-Based Metal Coated Steel Sheet
The surface treatment liquid (A) was applied to one surface of each of the test pieces by bar coating. The resulting test pieces were not washed with water. The test pieces were placed in an induction furnace and dried by heating at drying temperatures described in Tables 3-1 to 3-4, thereby forming films having thicknesses (μm) described in Tables 3-1 to 3-4. The surface treatment liquid (B) for the formation of the second layer was applied to a surface of each of the films. The test pieces were placed in the induction furnace and dried by heating at drying temperatures described in Tables 3-1 to 3-4, thereby forming films having thicknesses (μm) described in Tables 3-1 to 3-4. Thereby, zinc-based metal coated steel sheets according to examples and comparative examples were produced.
The heat-drying temperature was adjusted on the basis of induction heating power. Note that, the heat-drying temperature corresponds to the maximum temperature of the surface of the test piece.
A specific bar coating method is as follows.
Each of the surface treatment liquids was dropped on a corresponding one of the test pieces and applied with a bar coater (selected from rod Nos. 3 to 5). The thickness of each film was adjusted by selecting the rod number of the bar coater and the concentration of the surface treatment liquid so as to obtain the thicknesses described in Tables 3-1 to 3-4.











TABLE 3-1









Treatment method of surface
Treatment method of surface




treatment liquid (A)
treatment liquid (B)
















Test
Coating

Drying
Coating

Drying
Total film



sheet
method
Thickness
temperature
method
Thickness
temperature
thickness


Test level
Type
Type
μm
° C.
Type
μm
° C.
μm



















Example
1
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
2
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
3
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
4
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
5
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
6
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
7
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
8
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
9
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
10
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
11
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
12
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
13
(i)
Bar coating
0.01
140
Bar coating
0.5
140
0.51


Example
14
(i)
Bar coating
0.05
140
Bar coating
0.5
140
0.55


Example
15
(i)
Bar coating
0.1
140
Bar coating
0.5
140
0.6


Example
16
(i)
Bar coating
0.2
140
Bar coating
0.5
140
0.7


Example
17
(i)
Bar coating
0.2
140
Bar coating
0.5
140
0.7


Example
18
(i)
Bar coating
0.2
140
Bar coating
0.5
140
0.7


Example
19
(i)
Bar coating
0.2
140
Bar coating
0.5
140
0.7


Example
20
(i)
Bar coating
0.2
140
Bar coating
0.5
140
0.7


Example
21
(i)
Bar coating
0.3
140
Bar coating
0.5
140
0.8


Example
22
(i)
Bar coating
0.5
140
Bar coating
0.5
140
1.0


Example
23
(i)
Bar coating
0.8
140
Bar coating
0.5
140
1.3


Example
24
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
25
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
26
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
27
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
28
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
29
(ii)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
30
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
31
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
32
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
33
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
34
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
35
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
36
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
37
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
38
(iii)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
39
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
40
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65




















TABLE 3-2









Treatment method of surface
Treatment method of surface




treatment liquid (A)
treatment liquid (B)
















Test
Coating

Drying
Coating

Drying
Total film



sheet
method
Thickness
temperature
method
Thickness
temperature
thickness


Test level
Type
Type
μm
° C.
Type
μm
° C.
μm



















Example
41
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
42
(i)
Bar coating
0.01
140
Bar coating
0.5
140
0.51


Example
43
(i)
Bar coating
0.05
140
Bar coating
0.5
140
0.55


Example
44
(i)
Bar coating
0.1
140
Bar coating
0.5
140
0.6


Example
45
(i)
Bar coating
0.2
140
Bar coating
0.5
140
0.7


Example
46
(i)
Bar coating
0.2
140
Bar coating
0.5
140
0.7


Example
47
(i)
Bar coating
0.2
140
Bar coating
0.5
140
0.7


Example
48
(i)
Bar coating
0.2
140
Bar coating
0.5
140
0.7


Example
49
(i)
Bar coating
0.2
140
Bar coating
0.5
140
0.7


Example
50
(i)
Bar coating
0.3
140
Bar coating
0.5
140
0.8


Example
51
(i)
Bar coating
0.5
140
Bar coating
0.5
140
1.0


Example
52
(i)
Bar coating
0.8
140
Bar coating
0.5
140
1.3


Comparative
53
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example


Comparative
54
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example


Comparative
55
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example


Comparative
56
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example


Comparative
57
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example


Comparative
58
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example


Comparative
59
—
—
—
—
—
—
—
—


Example


Comparative
60
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example


Comparative
61
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example


Comparative
62
—
—
—
—
—
—
—
—


Example


Comparative
63
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example


Comparative
64
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example


Comparative
65
(i)
Bar coating
0.005
140
Bar coating
0.005
140
0.01


Example


Comparative
66
(i)
Bar coating
1.5
140
Bar coating
2.0
140
3.5


Example


Comparative
67
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example


Comparative
68
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example


Comparative
69
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example


Comparative
70
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example


Comparative
71
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example


Comparative
72
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example


Example
73
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
74
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
75
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
76
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
77
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
78
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
79
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
80
(i)
Bar coating
0.15
140
Bar coating
0.50
140
0.65




















TABLE 3-3









Treatment method of surface
Treatment method of surface




treatment liquid (A)
treatment liquid (B)
















Test
Coating

Drying
Coating

Drying
Total film



sheet
method
Thickness
temperature
method
Thickness
temperature
thickness


Test level
Type
Type
μm
° C.
Type
μm
° C.
μm



















Example
81
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
82
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
83
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
84
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
85
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
86
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
87
(i)
Bar coating
0.15
140
Bar coating
0.01
140
0.16


Example
88
(i)
Bar coating
0.15
140
Bar coating
0.05
140
0.2


Example
89
(i)
Bar coating
0.15
140
Bar coating
0.1
140
0.25


Example
90
(i)
Bar coating
0.15
140
Bar coating
0.3
140
0.45


Example
91
(i)
Bar coating
0.15
140
Bar coating
1.0
140
1.15


Example
92
(i)
Bar coating
0.15
140
Bar coating
2.0
140
2.15


Example
93
(i)
Bar coating
0.10
140
Bar coating
0.3
140
0.4


Example
94
(i)
Bar coating
0.10
140
Bar coating
1.0
140
1.1


Example
95
(i)
Bar coating
0.20
140
Bar coating
0.3
140
0.5


Example
96
(i)
Bar coating
0.20
140
Bar coating
1.0
140
1.20


Example
97
(i)
Bar coating
0.05
140
Bar coating
2.5
140
2.55


Example
98
(i)
Bar coating
0.50
140
Bar coating
0.01
140
0.51


Example
99
(i)
Bar coating
0.50
140
Bar coating
2.5
140
3.00


Example
100
(i)
Bar coating
0.01
140
Bar coating
0.01
140
0.02


Example
101
(i)
Bar coating
0.15
140
Bar coating
0.5
50
0.65


Example
102
(i)
Bar coating
0.15
140
Bar coating
0.5
100
0.65


Example
103
(i)
Bar coating
0.15
140
Bar coating
0.5
200
0.65


Example
104
(i)
Bar coating
0.15
140
Bar coating
0.5
250
0.65


Example
105
(i)
Bar coating
0.15
140
Bar coating
0.5
350
0.65


Example
106
(i)
Bar coating
0.15
140
Bar coating
0.3
140
0.45


Example
107
(i)
Bar coating
0.15
140
Bar coating
1.0
140
1.15


Example
108
(i)
Bar coating
0.10
140
Bar coating
0.3
140
0.4


Example
109
(i)
Bar coating
0.10
140
Bar coating
1.0
140
1.1


Example
110
(i)
Bar coating
0.20
140
Bar coating
0.3
140
0.5


Example
111
(i)
Bar coating
0.20
140
Bar coating
1.0
140
1.2


Comparative
112
(i)
Bar coating
0.15
140
—
0
—
0.15


Example


Comparative
113
(i)
—
0
—
Bar coating
0.5
140
0.5


Example


Comparative
114
(i)
—
0
—
Bar coating
0.5
140
0.5


Example


Comparative
115
(i)
Bar coating
0.15
140
Bar coating
3.0
140
3.15


Example


Comparative
116
(i)
Bar coating
0.15
140
Bar coating
3.0
140
3.15


Example


Example
117
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
118
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
119
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
120
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65




















TABLE 3-4









Treatment method of surface
Treatment method of surface




treatment liquid (A)
treatment liquid (B)
















Test
Coating

Drying
Coating

Drying
Total film



sheet
method
Thickness
temperature
method
Thickness
temperature
thickness


Test level
Type
Type
μm
° C.
Type
μm
° C.
μm



















Example
121
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
122
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
123
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
124
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
125
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
126
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
127
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
128
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
129
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
130
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
131
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
132
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
133
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example
134
(i)
Bar coating
0.15
140
Bar coating
0.01
140
0.16


Example
135
(i)
Bar coating
0.15
140
Bar coating
0.05
140
0.2


Example
136
(i)
Bar coating
0.15
140
Bar coating
0.1
140
0.25


Example
137
(i)
Bar coating
0.15
140
Bar coating
0.3
140
0.45


Example
138
(i)
Bar coating
0.15
140
Bar coating
1.0
140
1.15


Example
139
(i)
Bar coating
0.15
140
Bar coating
2.0
140
2.15


Example
140
(i)
Bar coating
0.10
140
Bar coating
0.3
140
0.40


Example
141
(i)
Bar coating
0.10
140
Bar coating
1.0
140
1.1


Example
142
(i)
Bar coating
0.20
140
Bar coating
0.3
140
0.5


Example
143
(i)
Bar coating
0.20
140
Bar coating
1.0
140
1.2


Example
144
(i)
Bar coating
0.05
140
Bar coating
2.5
140
2.55


Example
145
(i)
Bar coating
0.50
140
Bar coating
0.01
140
0.51


Example
146
(i)
Bar coating
0.50
140
Bar coating
2.5
140
3.0


Example
147
(i)
Bar coating
0.01
140
Bar coating
0.01
140
0.02


Example
148
(i)
Bar coating
0.15
140
Bar coating
0.5
50
0.65


Example
149
(i)
Bar coating
0.15
140
Bar coating
0.5
100
0.65


Example
150
(i)
Bar coating
0.15
140
Bar coating
0.5
200
0.65


Example
151
(i)
Bar coating
0.15
140
Bar coating
0.5
250
0.65


Example
152
(i)
Bar coating
0.15
140
Bar coating
0.5
350
0.65


Example
153
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Comparative
154
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example


Comparative
155
(i)
Bar coating
0.15
140
Bar coating
0.5
140
0.65


Example









(6) Evaluation Test Method

(6-1) Evaluation of Corrosion Resistance

Test pieces each measuring 70 by 150 mm were cut out from each test sheet on which the two films had been formed. The back surface and ends of each test piece were sealed with a vinyl tape. The test pieces were subjected to a salt-water spray test (SST) complying with JIS-Z-2371-2000. The corrosion resistance was evaluated on the basis of the time required to cause the area proportion of white rust to reach 5% during the salt-water spray test. Evaluation criteria are described below.
Evaluation Criteria
⊙: The length of time the area proportion of white rust reaches 5% is 240 hours or more.
◯: The length of time the area proportion of white rust reaches 5% is 192 hours or more and less than 240 hours.
◯−: The length of time the area proportion of white rust reaches 5% is 144 hours or more and less than 192 hours.
Δ: The length of time the area proportion of white rust reaches 5% is 72 hours or more and less than 144 hours.
x: The length of time the area proportion of white rust reaches 5% is less than 72 hours.
(6-2) Evaluation of Overcoatability (Adhesion)
A commercially available melamine alkyd paint was applied to test pieces each having the same size as described above in such a manner that the resulting coating films each had a thickness of 30 μm after baking at 140° C. for 30 minutes. The test pieces were immersed in boiling water for 2 hours. Cuts extending to base steel were made on a surface of each test piece with an NT cutter to form a grid pattern divided into 100 sections each measuring 1 mm by 1 mm. The test piece was pushed out by 5 mm with an Erichsen tester in such a manner that the cut portion faced outward. The Erichsen test was performed under the following conditions complying with JIS-Z-2247-2006 (symbol of the Erichsen value: IE): punch diameter: 20 mm, die diameter: 27 mm, and drawing width: 27 mm. After the Erichsen test, a tape peel test was performed to evaluate the overcoatability (adhesion) on the basis of the state of the coating film. Evaluation criteria are described below.
Evaluation Criteria
⊙: Peeled area is zero and less than 50.
◯: Peeled area is 5% or more and less than 10%.
Δ: Peeled area is 10% or more and less than 20%.
x: Peeled area is 20% or more.
(6-3) Evaluation of Conductivity
The surface resistance of each of the test pieces was measured using an ESP probe of Loresta GP (manufactured by Mitsubishi Chemical Analytech Co., Ltd). The surface resistance was measured while a load on the probe was increased in increments of 50 g. The conductivity was evaluated on the basis of the minimum load that allowed the surface resistance to be 10−4Ω or less.
⊙: The average load at 10 points is less than 400 g.
◯: The average load at 10 points is 400 g or more and less than 600 g.
◯−: The average load at 10 points is 600 g or more and less than 800 g.
Δ: The average load at 10 points is 800 g or more and less than 950 g.
x: The average load at 10 points is 950 g or more.
(6-4) Evaluation of Shelf Stability (Storage Stability)
Surface treatment liquids (A) having the compositions described in Tables 1-1 to 1-4 were stored in a constant temperature oven set at 40° C. for 30 days. The appearance of the surface treatment liquids was visually evaluated.
⊙: No change is observed.
◯: Extraordinarily minute amounts of precipitates are observed.
Δ: Minute amounts of precipitates are observed. Alternatively, the viscosity is slightly increased.
x: Large amounts of precipitates are observed. Alternatively, gelation occurs.
Evaluations described in items (6-1) to (6-4) were performed for the zinc-based metal coated steel sheets produced by use of the surface treatment liquids described in examples and comparative examples. The evaluation results are described in Tables 4-1 to 4-4.
Note that in Comparative Examples 59 and 62, the surface treatment liquids were unstable, thus failing to form a film. So, the evaluations were not performed.











TABLE 4-1






Corrosion


Shelf


Test level
resistance
Adhesion
Conductivity
stability




















Example
1
⊚
⊚
⊚
⊚


Example
2
⊚
⊚
⊚
⊚


Example
3
⊚
⊚
◯
⊚


Example
4
⊚
⊚
⊚
⊚


Example
5
⊚
⊚
⊚
⊚


Example
6
⊚
◯
⊚
⊚


Example
7
⊚
⊚
⊚
⊚


Example
8
⊚
⊚
⊚
⊚


Example
9
⊚
⊚
⊚
⊚


Example
10
⊚
⊚
⊚
⊚


Example
11
⊚
⊚
⊚
⊚


Example
12
◯
⊚
⊚
⊚


Example
13
◯
⊚
⊚
⊚


Example
14
⊚
⊚
⊚
⊚


Example
15
⊚
⊚
⊚
⊚


Example
16
⊚
⊚
⊚
⊚


Example
17
⊚
⊚
⊚
⊚


Example
18
⊚
⊚
⊚
⊚


Example
19
⊚
⊚
⊚
⊚


Example
20
⊚
⊚
⊚
⊚


Example
21
⊚
⊚
⊚
⊚


Example
22
⊚
⊚
◯
⊚


Example
23
⊚
⊚
 ◯−
⊚


Example
24
◯
⊚
⊚
⊚


Example
25
⊚
⊚
⊚
⊚


Example
26
⊚
⊚
⊚
⊚


Example
27
⊚
◯
⊚
⊚


Example
28
⊚
⊚
⊚
◯


Example
29
⊚
⊚
⊚
⊚


Example
30
⊚
⊚
⊚
⊚


Example
31
⊚
⊚
⊚
⊚


Example
32
◯
⊚
⊚
⊚


Example
33
⊚
⊚
⊚
⊚


Example
34
⊚
⊚
◯
⊚


Example
35
⊚
⊚
⊚
⊚


Example
36
⊚
⊚
⊚
◯


Example
37
⊚
⊚
⊚
⊚


Example
38
◯
⊚
⊚
⊚


Example
39
⊚
⊚
⊚
⊚


Example
40
⊚
⊚
⊚
⊚




















TABLE 4-2






Corrosion


Shelf


Test level
resistance
Adhesion
Conductivity
stability




















Example
41
⊚
⊚
⊚
◯


Example
42
◯
⊚
⊚
⊚


Example
43
⊚
⊚
⊚
⊚


Example
44
⊚
⊚
⊚
⊚


Example
45
⊚
⊚
⊚
⊚


Example
46
⊚
⊚
⊚
⊚


Example
47
⊚
⊚
⊚
⊚


Example
48
⊚
⊚
⊚
⊚


Example
49
⊚
⊚
⊚
⊚


Example
50
⊚
⊚
⊚
⊚


Example
51
⊚
⊚
◯
⊚


Example
52
⊚
⊚
 ◯−
⊚


Comparative
53
◯
X
◯
⊚


Example


Comparative
54
X
◯
Δ
Δ


Example


Comparative
55
X
◯
Δ
◯


Example


Comparative
56
X
◯
⊚
◯


Example


Comparative
57
X
◯
Δ
Δ


Example


Comparative
58
◯
X
Δ
Δ


Example


Comparative
59
—
—
—
—


Example


Comparative
60
X
◯
⊚
Δ


Example


Comparative
61
X
◯
⊚
Δ


Example


Comparative
62
—
—
—
—


Example


Comparative
63
◯
◯
X
X


Example


Comparative
64
◯
X
⊚
Δ


Example


Comparative
65
X
◯
⊚
⊚


Example


Comparative
66
⊚
◯
X
⊚


Example


Comparative
67
X
X
◯
⊚


Example


Comparative
68
X
X
X
⊚


Example


Comparative
69
X
X
X
⊚


Example


Comparative
70
X
X
X
X


Example


Comparative
71
X
X
X
⊚


Example


Comparative
72
X
X
X
⊚


Example


Example
73
 ◯−
◯
⊚
⊚


Example
74
 ◯−
◯
⊚
⊚


Example
75
◯
⊚
⊚
⊚


Example
76
⊚
⊚
⊚
⊚


Example
77
◯
⊚
⊚
⊚


Example
78
◯
⊚
⊚
⊚


Example
79
◯
⊚
⊚
⊚


Example
80
◯
⊚
⊚
⊚




















TABLE 4-3






Corrosion


Shelf


Test level
resistance
Adhesion
Conductivity
stability




















Example
81
◯
⊚
⊚
⊚


Example
82
◯
⊚
⊚
⊚


Example
83
◯
⊚
⊚
⊚


Example
84
◯
⊚
⊚
⊚


Example
85
◯
⊚
⊚
⊚


Example
86
◯
⊚
⊚
⊚


Example
87
 ◯−
⊚
⊚
⊚


Example
88
◯
⊚
⊚
⊚


Example
89
◯
⊚
⊚
⊚


Example
90
◯
⊚
⊚
⊚


Example
91
⊚
⊚
◯
⊚


Example
92
⊚
⊚
 ◯−
⊚


Example
93
◯
⊚
⊚
⊚


Example
94
⊚
⊚
⊚
⊚


Example
95
⊚
⊚
⊚
⊚


Example
96
⊚
⊚
◯
⊚


Example
97
⊚
⊚
◯
⊚


Example
98
⊚
⊚
⊚
⊚


Example
99
⊚
⊚
 ◯−
⊚


Example
100
Δ
⊚
⊚
⊚


Example
101
 ◯−
⊚
⊚
⊚


Example
102
◯
⊚
⊚
⊚


Example
103
◯
⊚
⊚
⊚


Example
104
◯
⊚
⊚
⊚


Example
105
 ◯−
⊚
⊚
⊚


Example
106
◯
⊚
⊚
⊚


Example
107
⊚
⊚
◯
⊚


Example
108
◯
⊚
⊚
⊚


Example
109
⊚
⊚
◯
⊚


Example
110
⊚
⊚
⊚
⊚


Example
111
⊚
◯
◯
⊚


Comparative
112
Δ
⊚
⊚
⊚


Example


Comparative
113
X
Δ
⊚
⊚


Example


Comparative
114
X
Δ
⊚
⊚


Example


Comparative
115
⊚
◯
X
⊚


Example


Comparative
116
⊚
◯
X
⊚


Example


Example
117
⊚
⊚
⊚
⊚


Example
118
⊚
⊚
⊚
⊚


Example
119
⊚
⊚
⊚
⊚


Example
120
◯
⊚
⊚
⊚




















TABLE 4-4






Corrosion


Shelf


Test level
resistance
Adhesion
Conductivity
stability




















Example
121
⊚
⊚
⊚
⊚


Example
122
⊚
⊚
⊚
⊚


Example
123
⊚
⊚
⊚
⊚


Example
124
⊚
⊚
⊚
⊚


Example
125
⊚
⊚
⊚
⊚


Example
126
⊚
⊚
⊚
⊚


Example
127
⊚
⊚
⊚
⊚


Example
128
⊚
⊚
◯
⊚


Example
129
⊚
⊚
⊚
⊚


Example
130
⊚
⊚
⊚
⊚


Example
131
⊚
⊚
◯
⊚


Example
132
⊚
⊚
⊚
⊚


Example
133
⊚
⊚
⊚
⊚


Example
134
◯
⊚
⊚
⊚


Example
135
◯
⊚
⊚
⊚


Example
136
◯
⊚
⊚
⊚


Example
137
⊚
⊚
⊚
⊚


Example
138
⊚
⊚
◯
⊚


Example
139
⊚
⊚
 ◯−
⊚


Example
140
◯
⊚
⊚
⊚


Example
141
⊚
⊚
⊚
⊚


Example
142
⊚
⊚
⊚
⊚


Example
143
⊚
⊚
◯
⊚


Example
144
⊚
⊚
◯
⊚


Example
145
⊚
⊚
⊚
⊚


Example
146
⊚
⊚
 ◯−
⊚


Example
147
 ◯−
⊚
⊚
⊚


Example
148
 ◯−
⊚
⊚
⊚


Example
149
◯
⊚
⊚
⊚


Example
150
⊚
⊚
⊚
⊚


Example
151
⊚
⊚
⊚
⊚


Example
152
◯
⊚
⊚
⊚


Example
153
 ◯−
Δ
 ◯−
⊚


Comparative
154
X
X
◯
⊚


Example


Comparative
155
X
X
Δ
⊚


Example









As described in Tables 4-1 to 4-4, each of the zinc-based metal coated steel sheets according to the present invention has excellent corrosion resistance, adhesion, and conductivity even if the steel sheet is in contact with, for example, a gasket at a low contact pressure. In contrast, in each of the comparative examples, in which any of the requirements is outside the appropriate range of the present invention, at least one of the corrosion resistance, adhesion, conductivity, and shelf stability was not sufficient.
It is possible to provide a zinc-based metal coated steel sheet including a film free from a pollution control substance, such as hexavalent chromium, the steel sheet having excellent properties, such as corrosion resistance and adhesion, and having excellent conductivity even under severe conditions where the steel sheet is in contact with, for example, a gasket at a low contact pressure, in particular, without reducing corrosion resistance. So, the zinc-based metal coated steel sheet of the present invention is significantly useful for components for use in, for example, automobiles, household electrical appliances, and OA equipment.

## Claims

1. A zinc-based metal coated steel sheet comprising:
a surface film arranged on a surface of a zinc-based metal coated layer, the surface film having a two-layer structure including a first layer and a second layer,
wherein the first layer is formed by applying a surface treatment liquid (A) for a zinc-based metal coated steel sheet to the surface of the zinc-based metal coated layer and performing drying by heating, the surface treatment liquid (A) containing a resin emulsion (a) that contains a cationic urethane resin emulsion (a-1) and/or a nonionic acrylic resin emulsion (a-2), the cationic urethane resin emulsion (a-1) containing at least one cationic functional group selected from primary to tertiary amino groups and quaternary ammonium salt groups, a tetraalkoxysilane (b), at least one silane coupling agent (c) that contains at least one reactive functional group selected from active hydrogen-containing amino groups, an epoxy group, a mercapto group, and a methacryloxy group, a chelating agent (d), a vanadic acid compound (e), a titanium compound (f), and water, the surface treatment liquid (A) having a pH of 3 to 6 and being adjusted so as to satisfy requirements (I) to (V) described below, wherein the second layer is formed by applying a surface treatment liquid (B) that contains an organic resin (g) to a surface of the first layer and performing drying by heating, and wherein the total thickness of the first layer and the second layer on a side of the steel sheet is in the range of 0.1 to 3.0 μm:
(I) the proportion of the solid (aS) of the resin emulsion (a) is in the range of 11% to 45% by mass with respect to the total solid of the treatment liquid;
(II) the ratio by mass of the solid of the silane coupling agent (c) to the solid of the resin emulsion (a), i.e., (cS/aS), is in the range of 1.51 to 5.35;
(III) the ratio by mass of the solid of the tetraalkoxysilane (b) to the solid of the chelating agent (d), i.e., (bS/dS), is in the range of 0.15 to 1.49;
(IV) the ratio of the mass (eV) of the vanadic acid compound (e) in terms of V to the mass of the solid (dS) of the chelating agent (d), i.e., (eV/dS), is in the range of 0.03 to 0.23; and
(V) the ratio of the mass (fT) of the titanium compound (f) in terms of Ti to the mass of the solid (dS) of the chelating agent (d), i.e., (fT/dS), is in the range of 0.02 to 0.19.

2. The zinc-based metal coated steel sheet according to claim 1, wherein the organic resin (g) in the surface treatment liquid (B) contains an organic resin (g-1) that contains an OH group and/or a COOH group.

3. The zinc-based metal coated steel sheet according to claim 1, wherein the organic resin (g) in the surface treatment liquid (B) contains a hydrazine-modified organic resin (g-2) formed by reaction with an active hydrogen-containing compound (i) composed of a hydrazine derivative (h) in which some or all of compounds contain active hydrogen.

4. The zinc-based metal coated steel sheet according to claim 1, wherein the surface treatment liquid (B) further contains a rust preventive additive (j).

5. The zinc-based metal coated steel sheet according to claim 4, wherein the rust preventive additive (j) contains (k) and/or (I) described below, and when rust preventive additive (k) is contained in (j), the proportion of the rust preventive additive (k) is in the range of 1 to 100 parts by mass in terms of the solid content with respect to the total amount of 100 parts by mass of the organic resin (g) in the surface treatment liquid (B):
(k) Ca ion-exchanged silica; and
(l) silicon oxide.

6. The zinc-based metal coated steel sheet according to claim 1, wherein the surface treatment liquid (B) further contains a lubricant (m).