NZ776609A - Corrosion-resistant coating composition and method for producing corrosion-resistant coating film - Google Patents

Abstract

The present invention is directed to provide a corrosion-resistant coating composition that is capable of forming a coating film with superior moisture resistance and a superior corrosion-resistant property for a long period, particularly over a long period even under acidic environmental conditions, further with superior storage stability. The corrosion-resistant coating composition of the present invention comprises a coating film-forming resin (A), a crosslinking agent (B), and a magnesium hydroxide (C), wherein the oil absorption of the magnesium hydroxide (C) is 70 g/100 g or less and wherein the BET specific surface area is 4.0 m2/g or less. , further with superior storage stability. The corrosion-resistant coating composition of the present invention comprises a coating film-forming resin (A), a crosslinking agent (B), and a magnesium hydroxide (C), wherein the oil absorption of the magnesium hydroxide (C) is 70 g/100 g or less and wherein the BET specific surface area is 4.0 m2/g or less.

Description

DESCRIPTION TITLE OF INVENTION: CORROSION-RESISTANT G COMPOSITION AND METHOD FOR PRODUCING CORROSION-RESISTANT COATING FILM TECHNICAL FIELD The present invention relates to a corrosion— resistant coating composition and a method for producing a ion-resistant coating film using the coating composition.

BACKGROUND ART Coated steel plates prepared by coating substrates such as cold—rolled steel plates and plated steel plates are called ated metal, and they are used for various applications such as outdoor units of air conditioners, exterior parts of home ic appliances for water heaters, and exterior building materials such as roofs and walls. For example, a coated steel plate comprising a galvanized steel plate is usually coated with a corrosion— resistant coating material on the surface thereof in order to improve the corrosion—resistant property to t rusting.

Conventionally, chromium—containing coating als have been a commonly used corrosion—resistant coating materials and they are known to suppress the rusting by forming chromiumicontaining coating films. r, the use of chromium is becoming to be restricted due to the concern for its potential adverse environmental impact.

Hence proposed are g compositions containing vanadium nds as ion-resistant agents other than chromium compounds.

JP—A—2008—222834 (Patent Literature 1) discloses a coating composition sing (A) a hydroxy group- containing coating film—forming resin, (B) a crosslinking agent, and (C) a corrosion—resistant pigment mixture, wherein the corrosion—resistant pigment mixture (C) is composed of (l) at least one vanadium compound selected from vanadium pentoxide, calcium vanadate and ammonium nadate, (2) a metal silicate, and (3) a oric acid—based calcium salt.

JP—A-2009—227748 (Patent Literature 2) discloses a corrosion—resistant coating composition comprising (A) at least one hydroxy group-containing film- forming resin selected from specific acrylic resins and specific polyester resins, (B) a bisphenol—type epoxy resin, (C) a curing agent, (D) at least one adhesion—imparting resin selected from epoxy resins having a secondary or tertiary amino group, acrylic resins having a secondary or tertiary amino group, and resole—type phenol resins, and (E) a corrosion—resistant pigment. Further, it is disclosed that the corrosion-resistant t (E) comprises (1) at least one um compound selected from um pentoxide, calcium vanadate and ammonium metavanadate, (2) at least one silicon—containing compound selected from metal silicates and silica fine particles, and (3) a phosphoric acid—based metal salt.

ONS LIST PATENT LITERATURE Patent Literature 1: JP—A—2008—222834 Patent Literature 2: JP—A—2009—227748 SUMMARY OF INVENTION TECHNICAL PROBLEMS Recently, durability of coated steel plates under various environmental conditions is further required recently.

For example, a enon is recognized where coated steel plates are corroded by “acid rain.” “Acid rain” is caused by dissolution of acid rain precursors such as sulfur dioxide (802) and nitrogen oxides (NOX) into rain, snow, fog, and the like, and it exhibits er acidity than usual. In addition, acid rain precursors may migrate hundreds to nds of kilometers across national borders from when they are released to when they fall as acid rain.

The corrosion damages of coated steel plates are hence expected to increase over wide areas in the future.

Furthermore, when acid rain precursors exist in a dew condensation and humid environment, sulfides and/or nitrides contained in the acid rain precursors are exposed to a humid state, and these substances may advance the corrosion reaction on the coated steel plates.

However, the coating films formed from the coating compositions in Patent Literature 1 and 2 exhibits insufficient corrosion-resistant properties. For example, the ion-resistant properties are insufficient for ation to outdoor use, and there is a room for improvement in the coating films of Patent ture 1 and 2. Moreover, there is also a room for improvement in corrosion-resistant property under acidic environmental conditions.

Thus, a coating composition is required that has a corrosion—resistant ty under acidic nmental conditions and a lity of forming a coating film having a corrosion—resistant property for a longer period.

Further, coated articles or coating films may be d to a high humidity environment when they are used outdoors, and therefore a coating composition is required that is capable of forming a coating film with superior moisture resistance.

The present invention is directed to provide a corrosion-resistant coating composition that is capable of forming a coating film with superior moisture ance and a superior corrosion-resistant property for a long period, particularly over a long period even under acidic environmental conditions, further with superior storage stability. In the following, a corrosion—resistant coating ition may be referred to as a “coating composition”.

SOLUTIONS TO PROBLEMS The present disclosure provides the following [1] to A corrosion—resistant coating composition comprising a g film-forming resin (A), a crosslinking agent (B), and a magnesium hydroxide (C), wherein the magnesium hydroxide has an oil absorption of 70 g/100 g or less, and a BET specific e area of 4.0 mZ/g or less.

The corrosion—resistant coating composition according to [1], wherein the magnesium hydroxide (C) is a compound having a conductivity of 250 uS/cm or less in an aqueous solution prepared by adding 1 g of the ium hydroxide (C) to 100 g of purified water.

The corrosion—resistant coating composition according to [1] or [2], wherein the magnesium hydroxide (C) exhibits a pH of 8 or more and 12 or less in an aqueous solution prepared by adding 1 g of the magnesium hydroxide (C) to 100 g of purified water, and n an average particle diameter the magnesium hydroxide (C) is 0.5 pm or more and 20 um or less.

The corrosion-resistant coating composition according to any one of [1] to [3], n the coating film—forming resin (A) comprises at least one selected from the group ting of epoxy resin, polyester resin, acrylic resin, urethane resin, and modified products thereof.

The corrosion—resistant coating composition according to any one of [l] to [4], wherein the g film—forming resin (A) comprises at least one selected from the group consisting of ne resin and a modified product thereof, and wherein a glass transition temperature of the urethane resin is —50°C or higher and 70°C or lower.

The corrosion—resistant coating composition according to any one of [1] to [5], wherein the coating film—forming resin (A) comprises at least one ed from the group consisting of urethane resin and a modified product thereof, and wherein the urethane resin comprises at least one selected from the group consisting of ester—based urethane resin, ether-based urethane resin, and carbonate—based urethane resin.

The corrosion—resistant coating ition according to any one of [1] to [6], wherein a number—average molecular weight of the coating film-forming resin (A) is 1,000 or more and 40,000 or less.

The corrosion—resistant coating composition according to any one of [1] to [7], n the g film—forming resin (A) comprises at least one selected from the group consisting of ester—based urethane resin, epoxy resin, polyester resin, and modified products thereof.

The corrosion—resistant coating composition according to [8], wherein the solid acid value of at least one of the ester-based urethane resin, the epoxy resin, and the polyester resin is 30 g or less.

The ion—resistant coating composition according to any one of [l] to [9], wherein an amount of the magnesium hydroxide (C) is in the range of 1 part by mass or more and 150 parts by mass or less relative to 100 parts by mass of a total of a solid content of the coating film— g resin (A) and a solid content of the crosslinking agent (B).

A method for producing a corrosion—resistant g film, comprising: a coating step of applying the corrosion—resistant coating composition according to any one of [l] to [10] to an article to be coated, and a step of curing the corrosion—resistant coating composition at a temperature of 150°C or higher and 270°C or lower.

ADVANTAGEOUS EFFECTS OF ION The present invention provides a corrosion—resistant coating composition that is capable of forming a coating film with superior moisture resistance and a superior corrosion—resistant property for a long period, particularly even under acidic environmental conditions over a long period, further with superior storage stability.

BRIEF DESCRIPTION OF DRAWINGS is a schematic view showing an outline of a cross n of a coated steel plate specimen used in a corrosion resistance test. is a schematic view showing a crosscut part and a 4T folded part ed in a coated steel plate specimen used for a corrosion resistance test.

DESCRIPTION OF EMBODIMENTS The process leading to the present invention is described below.

Chromium compounds are used to impart a corrosion- resistant property to g films. For example, a coating composition containing a chromium-based compound is well capable of suppressing the rusting satisfactorily on an article to be coated. Meanwhile, in the technical field of corrosion-resistant coating itions, load ion to human body and environment is also required, and reduction or nce of chromium compounds is supposed to be necessary in corrosion-resistant coating compositions in the future.

For e, vanadium compounds such as metal salts of vanadic acid are used for reducing chromium—based compounds. As a means for improving the corrosion- resistant property of a corrosion—resistant coating ition comprising a vanadium compound, an increase of the vanadium compound amount is reported to be effective in the coating composition. r, since vanadium compounds, particularly vanadates, are highly water-soluble, coating films tend to absorb moisture when the coating compositions contain a large amount of vanadium compounds. It tends to result in a problem that moisture resistance of the g film decreases, which may induce rs on the coating film particularly in an acidic environment. Such blisters on a coating film may cause a decrease in corrosion—resistant property and a decrease in moisture resistance of the coating filmd Accordingly, it may become difficult to form a coating film with moisture resistance and a long—term corrosion-resistant property when a coating composition contains a large amount of a um compound.

Incidentally, in the conventional evaluation of corrosion—resistant ty, the test time is short, and only a shaped portion (a flat surface of an article to be ) has been used as an evaluation site.

However, coated articles with various shapes are manufactured recently. The protective effect of the coating film may be insufficient, for example, on a processed part, an edge face, a crosscut part, and the like in such coated articles with various shapes, and corrosion of the coated articles may occur from such parts.

A coating composition is therefore required that exhibits a superior corrosion—resistant ty for a long period even, for example, on a processed part, an edge face, and a ut part and that further exhibits a corrosion— resistant property for an ultra-long period.

The present inventors ntly d and accomplished the present invention.

The corrosion—resistant coating composition of the present disclosure comprises a coating film—forming resin (A), a crosslinking agent (B), and a magnesium hydroxide wherein the oil absorption of the magnesium hydroxide (C) is 70 g/100 g or less and wherein the BET specific surface area is 4.0 HF/g or less.

By using the corrosion—resistant coating composition of the present disclosure, a coating film is formed with superior moisture resistance and or corrosion— resistant property over a long . In particular, even under acidic environmental conditions, a coating film is formed with a superior corrosion-resistant property for a long period. The ion-resistant coating composition of the present disclosure is therefore capable of suppressing rusting that may occur due to “acid rain” for example. In addition, the ion—resistant g composition of the present disclosure has superior storage stability. In the following, the coating film formed from the coating composition of the present sure may be referred to as the coating film of the present invention.

The reason why the coating film of the present invention has the mentioned corrosion—resistant property is considered as follows.

In order to suppress corrosion of a coated article (for example, steel plate), the coating film is required to continuously supply an active agent for corrosion suppression (corrosion-suppressing agent) to the part where corrosion occurs on the coated article. In the present invention, the active agent derived from the magnesium hydroxide (C) functions as a corrosion—suppressing agent.

Since the magnesium hydroxide (C) has a relatively small BET specific surface area, a reaction on its surface is unlikely to occur. As a result, when the coating composition of the present disclosure is used, the magnesium hydroxide (C) is unlikely to elute from a coating film, and the magnesium hydroxide (C) is present in the g film for a long period. A corrosion-suppressing agent is hence supposed to be ed for a long period from a coating film to an article to be coated as a result when the coating composition of the present disclosure is used. Further, the above-mentioned oil absorption of the magnesium hydroxide (C) is also considered to afford stable supply of the corrosion—suppressing agent from the coating .film to the article to be coated for a long period. Thus, the use of the g composition of the present disclosure contributes to the prevention of corrosion of an article to be coated over a long period. Furthermore, the mentioned BET ic e area and oil absorption is supposed to afford suppression of a significant increase in the elution amount of the magnesium hydroxide (C) even in an acidic environment, and corrosion is suppressed for a long period even under acidic conditions as a result. Further, the inclusion of the magnesium ide (C) in the coating composition of the present disclosure affords a superior corrosion—resistant property for the coated article for a long period not only on a flat surface of an e to be coated but also on its processed part, edge face, and crosscut part. It thus affords a superior corrosion—resistant property for article to be coated with s shapes.

In addition, the coating film of the present invention has superior moisture resistance and water resistance, and rs are unlikely to occur in the coating film. As a result, the coating film of the present invention has a superior corrosion resistance even when used in an acidic environment. The coating film of the present ion exhibits superior moisture resistance even when the coated article is exposed to a high temperature and high humidity environment in such a case of outdoor use for example. It should not be interpreted only in a specific theory, the reason why the above s are obtained is however ered as follows. Assuming a case where a coating film contains moisture or ty, an acid rain precursor is supposed to be absorbed by these moisture or humidity, and the corrosion of the coated article easily progresses as a . The magnesium hydroxide (C) is however supposed to have low reactivity with water due to the above—mentioned BET specific surface area and oil absorption, and the coating film of the t invention has superior moisture resistance and water resistance as a result. The absorption of an acid rain sor into the coating film is supposed to be suppressed in a coating film of the present invention due to its superior moisture ance and water resistance, and the corrosion of the coated article is suppressed. The superiority in re resistance and water resistance of the coating film of the present invention suppresses blister in the coating film as well and further suppresses a decrease in corrosion— resistant property due to the blisters. Further, the magnesium hydroxide (C) ts superior dispersibility in the coating composition and contributes to the improvement in the storage stability of the coating composition as a result. sium hydroxide (C)] The magnesium hydroxide (C) has an oil absorption of 70 g/lOOg or less and a BET specific surface area of 4.0 nfl/g or less.

It should not be interpreted only in a specific theory, it is however considered that the oil absorption of the magnesium hydroxide (C) in the above range affords uous and stable supply of a corrosion—suppressing agent to a part of an article where corrosion may occur, which affords a formation of a coating film with superior corrosion resistance. In this disclosure, the oil absorption can be measured in accordance with the ion of JIS K 5101.

The oil absorption of the magnesium hydroxide (C) may be, for example, 65 g/100 g or less.

In one embodiment, the oil absorption of the magnesium hydroxide (C) may be 20 g/100 g or more, for example, 25 g/100 g or more.

In one embodiment, the oil absorption of the magnesium ide (C) is 20 g/100 g or more and 70 g/lOO g or less, for example, 25 g/100 g or more and 65 g/100 g or less.

In the present disclosure, the oil absorption of the magnesium hydroxide (C) may be appropriately ed within the above range.

The BET specific surface area of the magnesium hydroxide (C) is preferably 3.5 m?/g or less, and more preferably 3.0 Hfi/g or less.

Such a BET specific surface area allows the coating composition of the present disclosure to form a coating film with a superior corrosion-resistant property for a longer period. More specifically, the coating composition of the present disclosure forms a coating film with a ion—resistant property for a long period, and a g film capable of suppressing or significantly reducing corrosion in an acidic nment for a long In the present disclosure, BET specific surface area can be measured using an tic specific surface area analyzer GEMINI VII 23900 (manufactured by Shimadzu Corporation) for example.

In one embodiment, BET specific surface area of the magnesium hydroxide (C) may be 0.1 Hfl/g'or more, for example 0.2 Hfl/g or more, and may be 0.3 Hfl/g or more.

In one embodiment, the BET specific surface area of the magnesium hydroxide (C) is 0.1 m?/g or more and 2.0 m2/g or less, for example, 0.3 Hfi/g or more and 1.5 Hfi/g or less. [0031} In the t disclosure, the BET specific surface area of the magnesium hydroxide (C) may be appropriately combined within the above range.

In one embodiment, magnesium metal ion of an aqueous solution prepared by adding 1 g of the magnesium hydroxide (C) to 100 g of an artificial acidic seawater solution is 70 ppm or less.

It should not be interpreted only in a specific theory, however, the coating composition of the t disclosure supplies a corrosion—suppressing agent to an article to be coated ((for example, a steel plate) and the corrosion of the article is suppressed by comprising the magnesium ide (C) that ies these conditions.

The deterioration of the moisture resistance of a coating film is also suppressed or greatly reduced, and further, the blistering in a coating film is suppressed or greatly reduced. For example, by satisfying the above conditions, blistering of the coating film is ssed in a high temperature and high humidity environment and delamination n the coating film and the coated article is suppressed for a long period. Further, ring of the coating film in a processed part, an edge face, and a crosscut part is suppressed or greatly reduced.

In the present disclosure, the exhibition of a corrosion-resistant property in a high temperature environment refers to an tion of a superior corrosion—resistant ty even under a condition where the atmospheric temperature is high (for example, 40°C or higher) and at a high temperature of about 80°C.

In one embodiment, the magnesium hydroxide (C) comprises a magnesium hydroxide in such an amount that s a magnesium metal ion concentration of 69 ppm or less, for example, 66 ppm or less or 65 ppm or less, in an aqueous solution prepared by adding 1 g of the magnesium hydroxide (C) to 100 g of an artificial acidic seawater In one embodiment, the magnesium hydroxide (C) affords a magnesium metal ion concentration of 10 ppm or more, for e 20ppm or more in an aqueous solution prepared by adding 1 g of the magnesium hydroxide (C) of the present disclosure to 100 g of an artificial acidic seawater solution.

In the present sure, the magnesium metal ion concentration in an aqueous solution prepared by adding 1 g of the magnesium hydroxide (C) to 100 g of an artificial acidic seawater solution can be measured based on the JIS G 0594:2019 cyclic corrosion test method. For e, an aqueous solution based on an acidic aqueous salt solution used in Method B specified in the JIS G 0594:2019 cyclic ion test method can be used as an artificial acidic seawater solution.

In one embodiment, the measurement of magnesium metal ion can be performed as follows for example.

An artificial acidic seawater is prepared by adjusting pH to 2.5 by using a mixture of nitric acid and sulfuric acid specified in Section 4.1.1 of JIS G 0594:2019.

For example, the MARINE ART Series (manufactured by Tomita Pharmaceutical Co., Ltd.) may be used as a reagent.

Next, 100 g of artificial acidic seawater and 1 g of the magnesium hydroxide (C) are added to a vessel and a stirrer chip is added, and the mixture is stirred at room temperature (23°C) for 4 hours.

Then, after leaving it at room temperature for 24 hours, the supernatant is collected with a e equipped with a syringe filter, and the magnesium metal ion concentration is ied by measuring the element concentration using an ICP on spectrometer (ICPS—7510, manufactured by Shimadzu ation) for example.

Specifically, the value obtained by subtracting a blank from the element concentration (magnesium metal ion concentration) contained in the above supernatant may be used as a ium metal ion concentration in an aqueous solution prepared by adding 1 g of the magnesium ide (C) to 100 g of an artificial acidic seawater solution.

Here, the blank is a value obtained by measuring the element concentration (magnesium metal ion concentration) of the artificial acidic seawater in the same manner as for the supernatant.

In one embodiment, the magnesium ide (C) is a compound that affords a conductivity of 250 uS/cm or less, for example, 210 uS/cm or less, in an s solution prepared by adding 1 g of the magnesium hydroxide (C) to 100 g of purified water. Further, the magnesium hydroxide (C) may be a compound having a conductivity of 205 uS/cm or less, and may be, for example, a compound having a conductivity of less than 201 uS/cm.

In one embodiment, the magnesium hydroxide (C) may be a nd that affords a conductivity of 10 uS/cm or more, for example, 20 pS/cm or more, or 50 uS/cm or more, in an aqueous solution prepared by adding 1 g of the magnesium hydroxide (C) to 100 g of purified water. [0039} In another embodiment, the magnesium hydroxide (C) is a compound that affords a conductivity of 250 uS/cm or less in an aqueous solution prepared by adding 1 g of the magnesium hydroxide (C) to 100 g of purified water. For example, the magnesium hydroxide (C) is, for example, a compound having a conductivity of 210 pS/cm or less, and may be a compound having a conductivity of 205 uS/cm or less, and may be a nd having a tivity of less than 201 uS/cmu These conditions allows the corrosion— suppressing agent from the magnesium hydroxide (C) to be supplied further effectively and stably to a steel plate for a longer time without depletion, and it suppresses corrosion. Further, the deterioration of the re resistance of a g film is suppressed or greatly reduced, and the blisters in the coating film is also suppressed or greatly reduced. Moreover, corrosion— resistant coating composition of the present disclosure suppresses or greatly reduces ring in a processed part, an edge face, and a crosscut part.

In one embodiment, the magnesium ide (C) may be a compound that affords a conductivity of 10 uS/cm or more, for example 20 uS/cm or more, or 50 uS/cm or more, in an aqueous solution prepared by adding 1 g of the magnesium hydroxide (C) to 100 g of purified water.

In the present disclosure, the conductivity can be measured as follows. Ion—exchanged water (100 g) and 1 g of the magnesium hydroxide (C) are mixed, a stirrer chip is added, and the mixture is stirred at room temperature (23°C) for 4 hours. Then, the conductivity can be measured using an electrical conductivity meter (CM—42X, manufactured by DKK—TOA Corporation) for example.

In one embodiment, the magnesium hydroxide (C) is a compound that affords a conductivity of 250 uS/cm or less in an aqueous on prepared by adding 1 g of the magnesium hydroxide (C) to 100 g of purified water. ion in an acidic environment is suppressed for a longer period since the magnesium hydroxide (C) has the magnesium metal ion tration and the conductivity as described above. Further, in addition to the suppression of ion in an acidic environment, blistering and nation of a coating film is suppressed for a long period in a high ature and high humidity environment.

In the present disclosure, such a combination of magnesium metal ion concentration and conductivity can be appropriately selected within the ranges described in the present disclosure.

In one embodiment, the magnesium hydroxide (C) is a compound that affords a pH of 8 or more and 13 or less, for example 9 or more and 13 or less, or 10 or more and 13 or less, in an aqueous solution prepared by adding 1 g of the magnesium hydroxide (C) to 100 g of purified water. In another embodiment, the pH is 8 or more and 12 or less. By satisfying such conditions, se in the corrosion rate of the coated article is suppressed more ively, and a 'coating film with or corrosion resistance can be In the present disclosure, the pH value can be measured by a known method. For example, 100 g of ion— exchanged water and 1 g of the magnesium hydroxide (C) are mixed, a stirrer chip is added, and the mixture is stirred at room temperature (23°C) for 4 hours. Then, the pH can be ed by using a pH meter (benchtop pH meter F—74, manufactured by HORIBA, Ltd.) for example.

In one embodiment, the average particle diameter of the magnesium hydroxide (C) is 0.5 um or more and 20 um or less, for example, 1 um or more and 15 pm or less, and 1 um or more and 10 um or less. In the case where the average particle diameter is excessively small, the number of reaction points increases on the surface of the magnesium hydroxide (C) and corrosion of a coated article may not be sufficiently suppressed. In the case where the average particle diameter is excessively large, the coating film may have defects.

In the present disclosure, the average particle diameter can be measured using a laser diffraction type particle diameter distribution analyzer SALD—2300 actured by Shimadzu Corporation) for example. [0045} In one ment, the magnesium hydroxide (C) is comprised in an amount of 1 part by mass or more and 150 parts by mass or less, for example, 10 parts by mass or more and 140 parts by mass or less, relative to 100 parts by mass of the total of the solid content of the coating ‘film—forming resin (A) and the solid t of the crosslinking agent (B). The magnesium hydroxide (C) content in the above range allows the coating composition of the present disclosure to form a coating film with a superior corrosion—resistant property for a long period and further superior moisture resistance.

The ium hydroxide (C) functions as a corrosion- resistant t in the coating ition of the present disclosure. In one embodiment, the magnesium hydroxide (C) is a corrosion-resistant pigment. [0047} In one embodiment, the g composition of the t disclosure may comprise other metal compounds as long as the effects of the magnesium hydroxide (C) are not impaired.

[Coating film—forming resin (A)] The coating film—forming resin (A) in the corrosion— resistant coating composition of the present disclosure is not particularly limited as long as it comprises a functional group capable of reacting with the crosslinking agent (B) and it has a coating film—forming y.

Examples of the coating film—forming resin (A) include epoxy resin and modified products thereof (acrylic modified epoxy resins, and the like.); polyester resin and modified products thereof (urethane—modified polyester resins, epoxy-modified polyester resins, silicone—modified polyester resins, and the like); acrylic resin and ed products thereof one—modified acrylic resins, and the like); urethane resin and modified products thereof (ester- based urethane resins, based urethane , carbonate—based urethane resins, epoxy—based urethane , and the like); phenol resin and modified products thereof (acrylic-modified phenolic resins, epoxy-modified phenolic resins, and the like); phenoxy resin; alkyd resin and ed products thereof (urethane-modified alkyd resins, acrylic-modified alkyd resins, and the like); and such resins as fluororesin. These resins may be used singly, or two or more of them may be used in ation.

In one embodiment, the g film-forming resin (A) ses at least one selected from the group consisting of epoxy resin, polyester resin, acrylic resin, urethane resin, and modified products thereof.

In one embodiment, the coating film—forming resin (A) comprises at least one ed from the group consisting of ester-based urethane resins, epoxy resin, polyester resin, and modified products thereof.

'In one embodiment, in View of the folding processability of a resulting coating film or the balance among the moisture resistance, the corrosion resistance, and the weather resistance of a resulting coating film, the coating film—forming resin (A) comprises at least one selected from the group consisting of epoxy resin, polyester resin, urethane resin, and ed products thereof.

In one embodiment, the coating film-forming resin (A) comprises at least one selected from the group consisting of urethane resin and modified products thereof.

The number—average molecular weight of the coating film—forming resin (A) may be 1,000 or more and 40,000 or less. The number-average molecular weight within such a range allows the coating composition of the present disclosure to form a coating film with superior corrosion ance, and further to form a coating film that is superior in adhesion to an article to be coated and to a topcoating composition (topcoating material).

(Epoxy resin) The number-average molecular weight (Mn) of the epoxy resin, for example, a hydroxy group-containing epoxy resin, which is a ed product of an epoxy resin, is preferably 1,400 or more and 20,000 or less, more preferably 2,000 or more and 10,000 or less, and ularly able 2,000 or more and 4,000 or less.

Unless otherwise specified in the present disclosure, a simple term “epoxy resin” refers to an epoxy resin that comprises at least one ed from the group consisting of epoxy resin and modified ts of epoxy resin.

In the present disclosure, the number—average molecular weight (Mn) is a polystyrene—equivalent value determined by gel permeation chromatography (GPC).

The number—average molecular weight mentioned above allows the inking reaction between the epoxy resin and the crosslinking agent (B) described later to proceed sufficiently, and a coating film with high moisture resistance and superior corrosion resistance is formed. It should not be interpreted only in a specific theory, however, the number—average molecular weight mentioned above affords appropriate elution of magnesium hydroxide (C) comprised in a g film, and a coating film is formed with superior corrosion resistance even in an acidic environment. Further, the ink density of the coating film is suppressed from becoming excessively high, and a coating film is formed with a sufficient elongation rate.

For example, a coatings film is formed with a sufficient folding processability. Further, the corrosion—resistant coating composition of the present disclosure has an appropriate viscosity, and exhibits or handleability such as g material manufacturability and g workability.

The glass transition temperature (Tg) of the epoxy resin may be 120°C or lower, and may be 115°C or lower.

For example, the glass transition temperature (Tg) of the epoxy resin may be 110°C or lower. In one embodiment, the glass transition temperature (Tg) of the epoxy resin is 50°C or higher and may be 55°C or higher. For example, the glass transition temperature (Tg) of the epoxy resin may be in the range of 50°C or higher and 120°C or lower.

In the present disclosure, the glass transition temperature (Tg) can be measured using a thermal analyzer TMA7100 (manufactured by Hitachi High—Tech Science Corporation) for example.

When the glass transition ature (Tg) of the epoxy resin is within the above range, the moisture bility of a coating film is not excessively high, the moisture resistance is sufficient, and the ion resistance is also good.

The acid value of the epoxy resin (including modified products thereof) may be 0 mg KOH/g or more and 30 mg KOH/g or less.

In the present disclosure, the acid value means the solid acid value and can be ed in accordance with the provisions of JIS K 0070.

The epoxy resin may be a hydroxy group—containing epoxy resin (including a modified hydroxy group-containing epoxy resin).

Examples of the epoxy resin include a resin prepared by condensing epichlorohydrin and bisphenol to a high molecular weight ally in the presence of a catalyst such as an alkaline catalyst; bisphenol type epoxy resins such as bisphenol A type and bisphenol F type; and novolak type epoxy .

Examples of the ed products of epoxy resin include modified epoxy resins such as acrylic-modified epoxy resins, urethane—modified epoxy resins, and amine— modified epoxy resins. For example, taking an acrylic— modified epoxy resin as an e, it can be prepared by reacting the bisphenol type epoxy resin or the novolak type epoxy resin with a polymerizable unsaturated monomer component containing acrylic acid, rylic acid, or the like.

Taking a urethane—modified epoxy resin as an example, it can be prepared by reacting the bisphenol type epoxy resin or the novolak type epoxy resin with a polyisocyanate compound.

Examples of the epoxy resin include jERlOO4, jERlOO7, 1255HX30 (bisphenol A skeleton) and YX8lOOBH3O manufactured by Mitsubishi Chemical Corporation. ster resin) The number—average molecular weight (Mn) of the polyester resin, for e, a hydroxy group—containing polyester reSin, which is a modified product of a polyester resin, is ably 1,400 to 40,000, more preferably 2,000 to 40,000, and particularly preferably 2,000 to 30,000.

Unless otherwise specified in the present sure, a simple term “polyester resin” refers to a polyester resin that comprises at least one ed from the group consisting of polyester resin and modified products of polyester resin.

The number—average molecular weight mentioned above allows the crosslinking reaction between the polyester resin and the crosslinking agent (B) to proceed sufficiently, and a coating film with high re resistance is formed. Further, superior corrosion resistance is ensured. It should not be interpreted only in a specific , however, the number—average molecular weight mentioned above allows the elution of magnesium hydroxide (C) comprised in a coating film to occur appropriately for example, and a coating film with superior corrosion resistance even under acidic environmental conditions is formed. Further, the crosslink density of the coating film is suppressed from becoming excessively high, and a coating film is formed with a sufficient elongation rate. For example, a coating film is formed with a sufficient folding processability. Further, the corrosion—resistant coating composition of the present disclosure has an appropriate viscosity, and exhibits superior handleability such as g material manufacturability and coating workability.

The glass transition ature (Tg) of the polyester resin is preferably —35°C or higher and 110°C or lower, for example, —30°C or higher and 80°C or lower, and may be —30°C or higher and 60°C or lower.

When the glass tion temperature (Tg) of the polyester resin is within the above range, the moisture permeability of a coating film is not excessively high, the moisture resistance of the coating film is sufficient, and the corrosion ance is also good.

The acid value of the polyester resin (including modified ts thereof) is, for example, 30 mg KOH/g or less, specifically, 0.1 mg KOH/g or more and 30 mg KOH/g or less, may be 0.1 mg KOH/g or more and 30 mg KOH/g or less, and may be 0.3 mg KOH/g or more and 30 mg KOH/g or less.

The acid value in such a range affords improvements in hydrolysis resistance and a formation of a coating film with moisture resistance. Further, superior corrosion resistance is ensured.

The-polyester resin can be obtained by polycondensation of a polyhydric alcohol and a polybasic acid.

Specific examples of the polyhydric alcohol e ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene , neopentyl glycol, 1,2—butanediol, tanediol, 2,3- butandiol or 1,4—butanediol, 1,5—pentanediol, 1,6— hexanediol, hydrogenated bisphenol A, hydroxyalkylated bisphenol A, l,4—cyclohexanedimethanol, 2,2—dimethyl-3— ypropyl—Z,2—dimethyl-3—hydroxypropionate N), N,N—bis—(2—hydroxyethyl)dimethylhydantoin, polycaprolactone polyol, in, sorbitol, annitol, trimethylolethane, trimethylolpropane, trimethylolbutane, hexanetriol, pentaerythritol, dipentaerythritol, and tris— (hydroxyethyl)isocyanate. The polyhydric alcohols may be used singly, or two or more of them may be used in combination.

Specific examples of the polybasic acid e phthalic acid, phthalic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, methyltetraphthalic acid, methyltetrahydrophthalic anhydride, hymic anhydride, trimellitic acid, trimellitic anhydride, llitic acid, pyromellitic anhydride, isophthalic acid, terephthalic acid, maleic acid, maleic anhydride, c acid, itaconic acid, adipic acid, azelaic acid, c acid, succinic acid, ic anhydride, lactic acid, dodecenylsuccinic acid, dodecenylsuccinic anhydride, cyclohexane—l,4—dicarboxylic acid, and endic anhydride. The polybasic acids may be used singly, or two or more of them may be used in combination.

Examples of the modified products of polyester resin include modified polyester resins such as ne—modified polyester resins, epoxy—modified polyester resins, acrylic- ed polyester resins, and silicone-modified polyester resins.

The urethane-modified polyester resin is a resin having polyester as its main chain that is urethane- modified by modifying the ends thereof with isocyanate.

The silicone—modified polyester resin can be prepared by reacting a polyester resin with an organic silicone (for example, an organic silicone having a -SiOCH3 group and/or a —SiOH group as a functional group and having a number- average molecular weight of about 300 to about 1,000). The amount of the c silicone used is usually about 5 to about 50 parts by mass relative to 100 parts by mass of the polyester resin.

The urethane-modified ter resin can be prepared by reacting the polyester resin with a polyisocyanate compound.

Examples of a polyester resin and a modified polyester resin having a hydroxy group include BECKOLITE 46-118, BECKOLITE M50, BECKOLITE M52, and BECKOLITE M—6402-50 manufactured by DIC Corporation, VYLON 220, VYLON UR3500, VYLON UR5537, VYLON UR8300, and VYLON UR4410 manufactured by Toyobo Co., Ltd.

(Acrylic resin) The number—average molecular weight (Mn) of the acrylic resin and modified products thereof is ably 1,400 to 40,000, more ably 2,000 to , and particularly preferably 2,000 to 30,000.

Unless otherwise specified in the present disclosure, the simple term “acrylic resin” means that the resin comprises at least one selected from the group consisting of acrylic resin and modified products of acrylic resin.

The number—average molecular weight mentioned above allows the crosslinking reaction between the acrylic resin and the crosslinking agent (B) to proceed sufficiently and a coating film with high re resistance is formed.

Further, superior corrosion resistance is ensured. It should not be reted only in a specific theory, however, the number-average lar weight mentioned above allows the elution of magnesium hydroxide (C) comprised in a coating film to occur appropriately for example, and a coating film is formed with superior corrosion ance even under acidic conditions. Further, the crosslink y of the coating film is suppressed from becoming ively high, and a coating film is formed with a sufficient elongation rate. For example, a coating film is formed with a sufficient folding processability. Further, the corrosion—resistant coating composition of the present disclosure_has an appropriate viscosity, and exhibits superior handleability such as g al manufacturability and coating workability.

The glass transition temperature (Tg) of the acrylic resin is preferably —35°C or higher and 110°C or lower, for example, —30°C or higher and 80°C or lower, and may be - °C or higher and 60°C or lower.

When the glass transition temperature (Tg) of the acrylic resin is within the above range, the moisture‘ permeability of a coating film is not ively high, the re resistance of the coating film is sufficient, and the corrosion resistance is also good.

The acid value of the acrylic resin (including modified products f) is 0.1 mg KOH/g or more and 30 mg KOH/g or less, for example 0.1 mg KOH/g or more and 30 mg KOH/g or less, and may be 0.3 mg KOH/g or more and 30 mg KOH/g or less.

When the acid value is in such a range, for example, hydrolysis resistance is improved and also a coating film is formed with moisture resistance. Further, superior corrosion resistance is d.

Examples of the acrylic resin include acrylic resins made up of one, or two or more of monomers ed from (meth)acrylic monomers having a hydroxy group, such as hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and N—methylolacrylamide, and lactone s thereof; (meth)acrylic acid; (meth)acrylic acid , such as alkyl (meth)acrylate; and (meth)acrylonitrile. The acrylic resin may contain, in addition to the constitutional units derived from the above-mentioned monomers, constitutional units d from other monomers (for example, carboxyl group-containing ethylenic monomers such as ic acid, itaconic acid, fumaric acid, and maleic acid, and vinyl- based monomers such as styrene). In the present disclosure, (meth)acrylic acid represents acrylic acid or methacrylic acid.

Examples of the modified products of acrylic resin include modified acrylic resins such as silicone-modified acrylic resins. For example, taking a ne—modified acrylic resin as an example, this can be prepared by reacting an acrylic resin with such an c silicone that was described above. The amount of the organic silicone is usually about 5 to about 50 parts by mass relative to 100 parts by mass of the acrylic resin.

(Urethane resin) In one embodiment, the number-average molecular weight (Mn) of the urethane resin and the modified urethane resin is 1,000 or more and 30,000 or less, for example, 2,000 or more and 28,000 or less, and may be 2,500 or more and 25,000 or less. In one embodiment, the number-average molecular weight (Mn) of the urethane resin and the modified urethane resin is 6,000 or more and 15,000 or less.

Unless otherwise specified in the t disclosure, a simple term “urethane resin” means that the urethane resin comprises at least one selected from the group consisting of urethane resin and modified products of ne resin.

The number-average molecular weight mentioned above allows the crosslinking reaction between the urethane resin and the inking agent (B) to proceed sufficiently and a coating film with high moisture resistance is formed.

Further, or corrosion ance is ensured. For example, it should not be interpreted only in a ic theory, however, the number—average molecular weight mentioned above allows the elution of magnesium hydroxide (C) comprised in a coating film to occur appropriately, and a g film is formed with superior corrosion resistance even under acidic conditions. Further, the crosslink density of the coating film is suppressed from becoming excessively high, and a coating film is formed with a sufficient elongation rate. For example, a coating film is formed with a sufficient folding processability. Further, the corrosion—resistant coating composition of the present disclosure has an riate viscosity, and exhibits superior handleability such as coating al manufacturability and coating workability.

In one embodiment, the glass transition temperature (Tg) of the urethane resin is -30°C or higher and 80°C or lower, for example -30°C or higher and 60°C or lower, and may be —30°C or higher and 50°C or lower. In another embodiment, the glass transition temperature (Tg) of the urethane resin is -50°C or higher and 70°C or lower.

When the glass transition temperature (Tg) of the urethane resin is within the above range, the moisture permeability of a coating film is not excessively high, the moisture resistance of the coating film is sufficient, and the corrosion resistance is also good.

The acid value of the urethane resin (including modified products f) is 0.1 mg KOH/g or more and 30 mg KOH/g or less, for example 0.1 mg KOH/g or more and 30 mg KOH/g or less, and may be 0.3 mg KOH/g or more and 30 mg KOH/g or less.

When the acid value is in such a range, for example, hydrolysis resistance is improved and also a coating film is formed with moisture resistance. Further, or ion resistance is ensured.

In one embodiment, the urethane group concentration (mass%) in the urethane resin in the t disclosure is 2% by mass or more and 20% by mass or less, for example 5% by mass or more and 17% by mass or less.

When the urethane group concentration in the resin of the urethane resin is within such a range, superior moisture resistance and corrosion resistance is ensured in a formed coating film.

Examples of the urethane resin e those obtained by reacting a polyol compound with a polyisocyanate compound and then r chain—extending with a chain extender.

The polyol compound is not particularly limited as long as it is a compound containing two or more hydroxy groups per molecule, and examples thereof include ethylene glycol, propylene , diethylene glycol, 1,6—hexanediol, tyl glycol, triethylene glycol, glycerin, trimethylolethane, trimethylolpropane, polycarbonate s, polyester polyols, polyether polyols such as bisphenol hydroxypropyl ether, teramide polyols, acrylic polyols, polyurethane polyols, or mixtures thereof.

The polyisocyanate compound is not particularly limited as long as it is a compound containing two or more isocyanate groups per molecule, and examples thereof include aliphatic isocyanates such as hexamethylene diisocyanate (HDI), alicyclic diisocyanates such as isophorone diisocyanate , ic diisocyanates such as tolylene diisocyanate (TDI), aromatic aliphatic diisocyanates such as diphenylmethane diisocyanate (MDI), or mixtures thereof.

The chain extender is not ularly limited as long as it is a compound containing one or more active hydrogen atoms in the molecule, and water or an amine compound can be applied. Examples of the amine nd include aliphatic polyamines such as nediamine, propylenediamine, thylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, and tetraethylenepentamine, aromatic polyamines such as tolylenediamine, xylylenediamine, and diaminodiphenylmethane, alicyclic polyamines such as diaminocyclohexylmethane, piperazine, 2,5- dimethylpiperazine, and isophoronediamine, hydrazines such as hydrazine, succinic dihydrazide, adipic dihydrazide, and phthalic dihydrazide, and alkanolamines such as hydroxyethyldiethylenetriamine, 2—[(2— thyl)amino]ethanol, and 3-aminopropanediol.

In one embodiment, the urethane resin comprises at least one selected from the group consisting of ester—based urethane resins, ether-based urethane resins, and carbonate-based ne resins.

In one embodiment, the urethane resin is an ester— based urethane resin.

In the present disclosure, the ester—based urethane resin refers to a resin having both urethane groups and ester groups in the main chain. Further, a resin is called an based urethane resin when the number of urethane groups is larger than the number of ester groups by 5% or more based on a comparison between the number of urethane groups and the number of ester groups in the main chain of the resin.

In one embodiment, the urethane resin can be prepared by polycondensation of a copolymerized polyester resin having hydroxy groups with a polyisocyanate compound. In one embodiment, the hydroxy group-containing polyester resin can be ed by ndensing an acid component such as a polycarboxylic acid and/or an acid anhydride with a polyhydric alcohol.

In one embodiment, the urethane resin is an ether— based urethane resin. In the present disclosure, the based urethane resin refers to a resin having both urethane groups and ether groups in the main chain.

Further, a resin is called an ether based ne resin when the number of urethane groups is larger than the number of ether groups by 5% or more based on a comparison between the number of urethane groups and the number of ester groups in the main chain-of the resin.

In one embodiment, the urethane resin is a carbonate- based ne resin. In the present disclosure, the carbonate-based ne resin refers to a resin having both urethane groups and carbonate groups in the main chain.

Further, a resin is called a carbonate—based urethane resin when the number of urethane groups is larger than the number of carbonate groups by 5% or more based on a comparison between the number of urethane groups and the number of carbonate groups in the main chain of the resin.

In one embodiment, the acid value of the ester—based urethane resin, the ether—based urethane resin, and the carbonate—based urethane resin is 0.1 mg KOH/g or more and 50 mg KOH/g or less, for example, 0.1 mg KOH/g or more and 40 mg KOH/g or less, and may be 0.3 mg KOH/g or more and 40 mg KOH/g or less. When the acid value is in such a range, for example, hydrolysis resistance is improved and also a coating is formed with having moisture resistance. Further, superior corrosion resistance is ensured.

Examples of the polycarboxylic acid that forms the copolymerized polyester resin having hydroxy groups include aliphatic polycarboxylic acids such as oxalic acid, succinic acid, adipic acid, and azelaic acid, ic polycarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'—diphenyldicarboxylic acid, and litic acid, and examples of the polyol ent include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butadiol, 1,4—butadiol, 1,5—bentandiol, 1,6— hexanediol, neopentyl glycol, trimethylolpropane, trimethylolethane, and pentaerythritol.

The copolymerized polyester of the present disclosure is preferably one in which the equivalent ratio of the carbonyl groups in the polycarboxylic acid and the hydroxy groups of the polyol component is in the range of 1.0/1.001 to 0 and the hydroxy groups are excessively d, and it can be prepared by a usual sterification method or a direct esterification reaction. A particularly preferable equivalent ratio is in the range of l.O/l.01 to 1.0/1.5.

The acid anhydride that may be comprised in the acid component is not particularly limited and examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, trimellitic ide, pyromellitic dianhydride, maleic anhydride, succinic anhydride, and dodecenylsuccinic anhydride.

In the preparation of the hydroxy group—containing polyester resin, other reaction components may be used in addition to the acid component and the polyol component.

Examples of the other on components e monocarboxylic acids, hydroxycarboxylic acids, lactones, drying oils, semi—drying oils, and fatty acids thereof.

More specific es include monoepoxide compounds such as Cardura E (manufactured by Shell Chemicals) and lactones.

The lactones can be ring-opened and added to polyesters of polycarboxylic acids and polyhydric alcohols to form graft chains and examples thereof include B—propiolactone, ylpropiolactone, butyllactone, y—valerolactone, s- caprolactone, y—caprolactone, ylolactone, crotolactone, o—valerolactone, and 6—caprolactone. Of these, e-caprolactone is the most preferable.

The ester—based urethane resin can be prepared by reacting a hydroxy group-containing polyester resin with an tic yanate compound, for example, by a conventionally known method.

In the coating composition of the present disclosure, a thermoplastic resin may also be used in addition to the Coating film-forming resin (A).

Examples of the thermoplastic resin include chlorinated olefin-based resins such as chlorinated hylene and chlorinated polypropylene; homopolymers or copolymers comprising vinyl chloride, vinyl acetate, Vinylidene chloride, and the like as monomer components; cellulose-based ; acetal resins; alkyd resins; chlorinated rubber—based resins; modified polypropylene resins (acid ide—modified polypropylene resins, and the like); and fluororesins (for e, vinylidene fluoride resin, vinyl fluoride resin, copolymers of fluorinated olefin and vinyl ether, and copolymers of fluorinated olefin and vinyl ester).

As the thermoplastic resin, only one may be used alone, or two or more may be used in combination. By using the thermoplastic resin in ation, further superior coating film properties such as coating film strength and elongation are obtained.

[Crosslinking agent (B)] The crosslinking agent (B) reacts with the coating film—forming resin (A) to form a cured coating film.

Examples of the crosslinking agent (B) include polyisocyanate compounds; blocked polyisocyanate compounds in which nate groups of polyisocyanate compounds are blocked with active hydrogen-containing compounds (sometimes referred to as “81”); amino resins; and phenol Of these, the inking agent (B) preferably ses one or more selected from blocked polyisocyanate compounds and amino resins.

Such a crosslinking agent (B) affords coating films with a superior corrosion-resistant property for a long period and further a superior moisture resistance.

The polyisocyanate compound and the polyisocyanate compound that constitutes the blocked polyisocyanate compound are not particularly limited, and conventionally known ones may be used. Specific examples include 1,4- tetramethylene diisocyanate, 1,6—hexamethylene diisocyanate, odecamethylene diisocyanate, cyclohexane-l,3— or 1,4- yanate, l-isocyanato—3—isocyanatomethyl-3,5,5— trimethylcyclohexane (also known as isophorone diisocyanate; IPDI), dicyclohexylmethane—4,4'-diisocyanate (also known as hydrogenated MDI), 2- or 4- isocyanatocyclohexyl—Z'—isocyanatocyclohexylmethane, 1,3— or l,4—bis—(isocyanatomethyl)-cyclohexane, bis-(4- isocyanato—3—methylcyclohexyl)methane, 1,3- or 1,4— d,d,d‘,d'—tetramethylxylylene diisocyanate, 2,4— or 2,6— diisocyanatotoluene, 2,2'—, 2,4'— or 4,4'— diisocyanatodiphenylmethane (MDI), 1,5-naphthalene diocyanate, p- or m—phenylene diocyanate, xylene diisocyanate, and diphenyl-4,4'—diisocyanate. Further, as the polyisocyanate compound, a ed polymer of each diisocyanate (isocyanurate type), an nate/biuret body (biuret type), or an adduct type may be used.

The polyisocyanate compound may be used singly, or two or more may be used in combination. The isocyanurate— type polyisocyanate compound is one of those preferably used in the present ion.

As the ocyanate compound, for example, it is preferable to use an aromatic polyisocyanate compound containing one or more aromatic functional groups in the molecule. By using the aromatic polyisocyanate compound, the moisture resistance of a coating film is improved and the strength of a coating film is also improved. Examples of a able aromatic polyisocyanate compound include 2,4- or 2,6-diisocyanatotoluene (TDI), 2,2'—, 2,4'—or 4,4'— diisocyanatodiphenylmethane (MDI), xylene yanate (XDI), and alene diisocyanate (NDI).

The isocyanate group content of the polyisocyanate compound that forms the blocked polyisocyanate compound as measured in accordance with JIS K 7301-1995 is usually 3 to %, preferably 5 to 15% in the solid content of the polyisocyanate nd. When the isocyanate group content is within the above range, the curability of a coating film is further improved. In addition, an excessively high ink y is suppressed in a resulting coating film, and superior corrosion resistance is obtained.

The active hydrogen—containing compound (blocking agent) to be used for the blocked ocyanate compound is not particularly limited, and es thereof include compounds having an -OH group (alcohols, phenols, and the like), an =N-OH group (oximes, and the like), an =N—H group (amines, amides, imides, lactams, and the like), or a -CH2— group e methylene group), and azoles. Specific examples include phenol, cresol, xylenol, e-caprolactam, o- valerolactam, y-butyrolactam, methanol, ethanol, n—, i-, or t—butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, benzyl alcohol, ide oxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monoxime, benzophenone oxime, cyclohexane oxime, dimethyl malonate, ethyl acetoacetate, acetyl e, and pyrazole. The active hydrogen— ning compounds may be used singly, or two or more of them may be used in combination.

The thermal dissociation temperature of the blocked polyisocyanate compound depends on the types of the polyisocyanate compound and the active hydrogen—containing compound constituting the blocked polyisocyanate compound, the ce or absence of a catalyst, and the amount thereof. In the present sure, a blocked polyisocyanate compound having a thermal dissociation temperature (in a catalyst—free condition) of 120 to 180°C is preferably used. By using a blocked polyisocyanate compound having a dissociation temperature within this range, the ity of the coating material is improved, r the compound is or in crosslinking reactivity with the coating film-forming resin (A), and therefore a coating film with superior moisture resistance is obtained.

Examples of the blocked polyisocyanate compound having a dissociation temperature of 120 to 180°C include Desmodur BL3175 manufactured by Sumika Covestro ne Co., Ltd. and Coronate 2554 manufactured by Tosoh Corporation.

In the t sure, the blocked polyisocyanate compound may be referred to as (BI).

Examples of the amino resin include melamine resin and urea resin, and among them, melamine resin is preferably used.

“Melamine resin” generally refers to a thermosetting resin synthesized from melamine and aldehyde, and has three reactive functional groups —NXD@ in one triazine nucleus molecule. Examples of the ne resin include the following four types: a complete alkyl type containing -N- (CH20R)2 [R is an alkyl group, the same applies hereinafter] as a reactive functional group; a methylol group type containing -N—(CH20R)(CH20H) as a reactive functional group; an imino group type containing —N— KHhOR)(H) as a reactive functional group; a methylol/imino group type containing -N-(CH20R)(CH20H) and 20R)(H) or containing -N-(CH20H)(H) as reactive functional .

In the present disclosure, among the above—mentioned melamine resins, preferably used are melamine resins having one or more methylol groups or imino groups on average in one le, namely, methylol group-type, imino group—type, or methylol/imino group-type melamine resins or mixtures thereof.

Examples of the melamine resin include MYCOAT 715 as the trade name manufactured by Allnex Japan Inc.

Amino resins such as melamine resin exhibit or crosslinking reactivity with the coating film—forming resin (A) even in the absence of catalyst and afford coating films with superior moisture resistance.

In the present disclosure, the melamine resin may be referred to as (MF).

The amount of the inking agent (B) of the present disclosure is ably 1 part by mass or more and 150 parts by mass or less, for example 2 parts by mass or more and 150 parts by mass or less, in terms of solid t relative to 100 parts by mass of the solid content of the coating film—forming resin (A). The crosslinking agent (B) content under such conditions affords a coating film with a superior corrosion—resistant property for a long period and further superior moisture resistance.

In one embodiment, the amount of the crosslinking agent (B) is 5 parts by mass or more and 95 parts by mass or less in terms of solid content relative to 100 parts by mass of the solid content of the coating film—forming resin (A). The crosslinking agent (B) content under such conditions allows the crosslinking reaction between the g film-forming resin (A) and the crosslinking agent (B) to proceed more satisfactorily, and a g film with better moisture resistance and corrosion resistance is formed. Further, the magnesium hydroxide (C) comprised in a coating film is stably eluted for a long period, and a coating film with r superior corrosion resistance is obtained.

[Extender pigment] The coating composition of the present disclosure may further comprise at least one extender pigment selected from the group consisting of calcium carbonate, barium sulfate, clay, talc, mica and silica.

The extender pigment affords further improvement in the strength of a g film, and surface ess generation on the surface of a coating film to be formed from the coating composition according to the t invention, without impairing the al properties of the coating film. The adhesion to a topcoating film is thereby further improved. Moreover, the moisture resistance is improved. [0101} In one embodiment, the amount of the extender pigment is 1 part by mass or more and 40 parts by mass or less, for example 10 parts by mass or more and 30 parts by mass or less relative to 100 parts by mass of the total solid content of the coating film—forming resin (A) and the crosslinking agent (B). The amount of the extender pigment within such a range allows the moisture resistance of a coating film to e. Further, the re permeability of the coating film is suppressed from being excessively high. For example, water is suppressed from penetrating the coating film excessively and the moisture resistance of the coating film is ed.

[Coupling agent] The g composition of the present sure may further comprise at least one coupling agent selected from the group consisting of silane-based ng agents, titanium-based coupling agents and zirconium-based coupling agents.

The addition of the coupling agent the adhesion between the base material (article to be coated) and a coating film formed from the coating composition of the present disclosure to be further improved, and the moisture resistance of the coating film is further improved.

The coupling agent is not particularly limited, and conventionally known ones may be used. Specific examples of preferably used ng agents include silane—based coupling agents such as Z—6011 and Z-604O manufactured by Dow Toray Co., Ltd.; titanium—based coupling agents such as ORGATIX TC—40l and ORGATIX TC-750 manufactured by Matsumoto Fine Chemical Co., Ltd.; and zirconium-based coupling agents such as ORGATIX ZC—580 and ORGATIX ZC—7OO ctured by Matsumoto Fine Chemical Co., Ltd. Of these, silane-based ng agents are preferably used.

The amount of the coupling agent may be 0.1 part by mass or more and 20 parts by mass or less, for example may be 0.5 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the total solid content of the coating film-forming resin (A) and the crosslinking agent (B).

The amount of the ng agent within such a range affords an improvement in the moisture resistance of a coating film and also a sufficient maintenance of the storage stability of the coating composition.

[Curing catalyst] When a blocked polyisocyanate compound and/or a polyisocyanate compound is used as the crosslinking agent (B), the g composition of the t disclosure may further comprise a curing catalyst. es of the curing catalyst include tin catalysts, amine catalysts, and lead catalysts, and among them, organotin compounds are preferably used.

As the organotin compound, for example, dibutyltin dilaurate (DBTL), dibutyltin oxide, and tetra—n—butyl-l,3— diacetoxystannoxane_can be used.

The amount of the curing catalyst may be 0.1 part by lmass or more and 10 parts by mass or less, for example may be 0.1 part by mass or more and 1.0 part by mass or less relative to 100 parts by mass of the total solid content of the coating film—forming resin (A) and the crosslinking agent (B). The amount of the curing st within such a range affords sufficient maintenance of the storage stability of the coating composition for example.

Also when an amino resin is used as the crosslinking agent (B), the coating composition of the present disclosure may comprise a curing catalyst. es of the curing catalyst in this case include acid catalysts such as carboxylic acid and sulfonic acid, and among them, dodecylbenzenesulfonic acid and paratoluenesulfonic acid are preferably used.

The content of the curing catalyst is, for example, 0.1 parts by mass or more and 10 parts by mass or less, and may be 0.1 parts by mass or more and 1.0 part by mass or less relative to 100 parts by mass of the total solid content of the coating film—forming resin (A) and the crosslinking agent (B). The amount of the curing catalyst within such a range affords ient maintenance of the storage stability of the coating composition for example.

[Other additives] The coating composition of the t disclosure may comprise additives other than those mentioned above, as Examples of such other additives include corrosion— resistant pigments other than the magnesium hydroxide (C); extender pigments other than the above-described extender pigment; coloring agents such as coloring pigments and dyes; luster pigments; solvents; ultraviolet ers (benzophenone—based ultraviolet ers); antioxidants (phenolic—based, sulfide-based, or hindered amine-based antioxidants, and the like); plasticizers; surface conditioning agents one, organic polymers, and the like); sagging inhibitors; viscosity control agents; lubricants such as wax; pigment dispersants; pigment wetting agents; leveling ; color separation inhibitors; suspending agents; defoaming agents; antiseptic agents; antifreezing agents; emulsifiers; antifungal agents; antibacterial agents; and stabilizers.

These additives may be used singly, or two or more of them may be used in combination.

Examples of the corrosion-resistant t other than magnesium hydroxide (C) include romium corrosion-resistant pigments. The non-chromium ion— resistant pigments may be used as long as the effects by the present disclosure are not impaired.

Examples of the non—chromium corrosion—resistant pigments include molybdate pigments (zinc molybdate, strontium molybdate, and the like), phosphomolybdate ts (aluminum phosphomolybdate pigments, and the like), calcium silica—based pigments, ate-based corrosion— resistant pigments, silicate—based corrosion-resistant pigments, vanadate—based corrosion—resistant pigments, hydroxides or oxides of Group 2 elements such as m hydroxide and magnesium oxide.

These may be used singly, or two or more of them may be used in combination. The coating composition of the present disclosure exhibits sufficiently high ion resistance since it comprises a prescribed ium hydroxide (C), and it may further comprise a corrosion— resistant pigment other than the magnesium hydroxide (C) such as those mentioned above as necessary.

As other pigments other than the extender pigment, alumina, bentonite and the like may be added as long as the moisture resistance, the corrosion-resistant property, the folding processability, and the like of a ing coating film are not impaired. These may be used singly, or two or more of them may be used in combination. [0111} Examples of the coloring pigments include coloring inorganic pigments such as titanium dioxide, carbon black, graphite, iron oxide, and coal'dust; coloring organic pigments such as phthalocyanine blue, phthalocyanine green, quinacridone, perylene, anthrapyrimidine, carbazole Violet, anthrapyridine, azo orange, flavanthrone yellow, oline yellow, azo yellow, indanthrone blue, dibromanzathrone red, perylene red, azo red, and anthraquinone red; aluminum powder, alumina powder, bronze powder, copper , tin , zinc powder, iron ide, and atomized titanium. These may be used , or two or more of them may be used in combination.

Examples of the luster pigments include foil pigments such as aluminum foil, bronze foil, tin foil, gold foil, silver foil, titanium metal foil, stainless steel foil, alloy foil of nickel, copper and the like, and foil-like phthalocyanine blue. These may be used singly, or two or more of them may be used in combination.

Examples of the t include water; glycol—based organic solvents such as ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate; alcohol-based organic solvents such as methanol, ethanol, and isopropyl ' alcohol; ether—based c solvents such as e and tetrahydrofuran; ester—based c solvents such as 3— ybutyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; ketone—based c ts such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, and isophorone; N—methyl—Z—pyrrolidone, toluene, e, iso-pentane, hexane, iso—hexane, and cyclohexane, solvent naphtha, mineral spirits, Solvesso 100, and Solvesso 150 (Solvesso are both aromatic hydrocarbon— based solvents manufactured by Shell Chemicals). These may be used , or two or more of them may be used in combination.

The coating composition of the present disclosure may be either a water—borne coating material or an organic solvent—borne g material.

The coating ition of the present disclosure may be applied as an undercoating material, which is also called a primer. Further, it may be used as a topcoating material to be oyerlaid on an undercoating material.

Moreover, it may be used as an intermediate coating material to form an intermediate layer between an undercoating material and a topcoating material.

In another embodiment, the coating composition of the present disclosure may be used as a coating composition not only for forming a multi-layer coating film but also for g a single-layer coating film.

The coating composition of the present sure exhibits superior corrosion resistance and moisture ance when it is used at any part of a multi-layer coating film. The undercoating material, the topcoating material and the intermediate coating material other than the coating composition of the present disclosure may be those conventionally known. Examples of the undercoating material include conventionally known non-chromium corrosion—resistant coating materials, and es of the topcoating material and the intermediate g al include ter resin—based coating materials and fluororesin-based coating materials.

The coating composition of the present disclosure is preferably used as an undercoating material. When the g composition of the present disclosure is used as an undercoating material, it exhibits particularly superior adhesion on a contact surface with a coating film formed of a topcoating material or an intermediate g material that is in direct contact with the undercoating material.

[Method for preparing coating composition] The method for preparing the coating composition of the present disclosure is not particularly limited. The coating composition of the present disclosure can be prepared, for example, by mixing a coating film—forming resin (A), a crosslinking agent (B) and a magnesium hydroxide (C), in addition, a thermoplastic resin, an er pigment, a coupling agent, a curing catalyst and other additives, which are optionally used, by using a mixer such as a roller mill, a ball mill, a bead mill, a pebble mill, a sand grind mill, a pot mill, a paint shaker, and a disper.

In another embodiment, the coating composition of the present disclosure may be a two-component type g material composed of a base component sing a coating orming resin (A) and a magnesium ide (C) and a crosslinking agent component comprising a crosslinking agent (B). [01211 [Article to be coated] The article is not particularly limited, on which a coating film of the corrosion-resistant coating composition of the present disclosure is formed, as long as it is required to have corrosion resistance. Examples thereof comprise steel plate that serves as a substrate for pre- coated metal (coated steel plate), and the like.

Examples of the steel plate include galvanized steel plate, cold—rolled steel plate, stainless steel plate, and um plate.

Examples of galvanized steel plates include zinc— containing plated steel plates that utilize sacrificial protection of zinc, specifically, hot-dip galvanized steel , electrogalvanized steel plates, alloyed hot—dip galvanized steel plates, aluminum—zinc plated steel plates, and nickel—zinc plated steel plates, magnesium—aluminum— zinc plated steel plates, and magnesium-aluminum—silica— zinc plated steel plates.

The steel plate is preferably one surface-treated with a chemical conversion treatment agent before g.

The surface ent may be carried out by a conventionally known method, and examples thereof include chromate treatment and non-chromate treatment such as zinc phosphate treatment. While the e ent may be appropriately selected depending on the steel plate to be used, a treatment free of heavy metals is preferable.

[Method for manufacturing corrosion—resistant coating film] In a certain embodiment, the present disclosure provides a method for producing a corrosion—resistant coating film, comprising a coating step of applying the coating composition of the present invention to an article to be coated, and a step of curing the coating composition at a temperature of 150°C or higher and 270°C or lower.

As a means for applying the coating composition of the present disclosure to an article to be coated, conventionally known means such as a roll coater, an airless spray, an electrostatic spray, and a curtain flow coater can be employed.

The coating film of the present invention can be formed by applying a coating composition to an e such as a steel plate to be coated and then ming a baking treatment of heating the article. The baking temperature (the maximum temperature reached by an article such as a steel plate to be coated) is, for e, 150°C or higher and 270°C or lower. By curing the coating composition of the present disclosure at such a temperature, a coating film is formed with sufficient strength. By virtue of a coating film with ient strength to be formed, a superior corrosion-resistant property is exhibited for a longer period, and further a coating film with superior moisture resistance is formed.

The baking time (curing time) is, for example, 10 to 200 seconds. For example, in the case of forming a multi— layer coating film ting of two layers, namely, an undercoating film and a topcoating film, le methods comprise applying an undercoating composition, ed by baking treatment, then applying a topcoating composition, and then baking the topcoating film, and another possible method comprises applying an undercoating composition, followed by applying a topcoating composition wet—on—wet t baking the undercoating composition, and then baking both of the compositions simultaneously.

The film thickness (dry film thickness) of the coating film of the present invention is usually 1 to 30 um, and for example, in the case of a topcoating film, it is ably 10 to 30 pm.

[About corrosion resistance] The coating film formed from the coating composition of the present disclosure shows superior results in both “immersion—drying cycle test using acidic salt water, 15 cycles” and “CCHC test, 2,000 hours”, for example. When superior results are shown in these tests, both a long—term stable corrosion—resistant property and moisture ance are achieved.

In the “immersion-drying cycle test using acidic salt water”, the measurement can be performed based on the method sed in Japanese Patent No. 5857156. It is considered, for example, that a g film having both a ion—resistant property under acidic environmental conditions and a long-term stable corrosion—resistant property are obtained when they exhibit superior test results.

The “CCHC test, 2,000 hours” is an evaluation test relating to blistering of a coated film in which evaluation is performed by ng a coating film for 2,000 hours to a high temperature and high humidity environment that is called CCHC (Cleveland Condensing Humidity Cabinet: ASTM D- 2247—87—Type A2). r, it is considered that the coating film of the present disclosure can be evaluated to maintain its or moisture resistance for a long period even if the coating film is exposed to a harsher environment since the test time is 2,000 hours.

The coating composition of the present disclosure shows superior results in such a plurality of tests and forms a coating film having both a long-term stable corrosion—resistant ty and moisture resistance.

In addition, it achieves both a superior corrosion- resistant ty and superior moisture resistance also in a processed part, an edge face, a crosscut part, and the like.

Further, the rusting is suppressed that may be caused by acid rain or the like.

In the present disclosure, the corrosion—resistant property under acidic nmental conditions can be evaluated based on a test using “acidic salt water”.

Further, in the present disclosure, a coating film having a superior corrosion—resistant property under acidic environmental conditions is obtained, and for example, it exhibits a superior corrosion-resistant ty against acid rain.

EXAMPLES The present invention will be described more specifically with reference to the following es, and the present invention is not limited to the examples. In the examples, “parts” and “%” are on a mass basis unless otherwise indicated.

[Magnesium hydroxide] The ions and characteristic values about the magnesium hydroxides (C1) to (C7) used in Examples and Comparative Examples are shown in Tables 1A to 1B.

[Table 1A} Magnesium Magnesium m“ hymnde. . (C) hydroxide (c1) hydroxide (c2) Raw material MAGSEEDS DS Commercial product name EP—l EP-3 BET specific surface area Oil absorption Conductivity (us/cm) of aqueous solution ed by adding 1 g of (C) to 100 g of purified water pH of aqueous solution prepared by adding 1 g of (C) to 100 g of ed water [Table 1B] eeeeeee eeeeee eeeeee eeeee h . oxide (C3) h droxide (C4) - oxide (C5) h . oxide (C6) h droxide (C7) Raw material MAGSEED Kyowa Suimag MAGSEEDS MPGSEEDS MA$EEDS Cannercial oroduct name X—6 WEI—4 S—6 EP—lA Manufacturer Konoshma Kyowa Chanical Kanoshima Konoshima Konoshima Chemical Co., Industry Co., Chaucal Oo. , metrical Co.., Chanical Co., Ltd. Ltd. Ltd. Ltd Ltd. (mZ/-) Oil absorption 77 43 (./1o..) eeeeeeeeeeeeeeeee ( I ) Conductivity (HS/on) of 114 aqueous solution ed by adding 1 g of (C') to 100 of - ified water pH of aqueous solution prepared by adding 1 g of (C') to 100 g of purified water [Preparation of g film-forming resin (Al) (ester- based urethane resin 1)] In a reaction vessel equipped with a thermometer, a reflux condenser and a stirrer, 55 parts by mass of adipic 'acid, 6.1 parts by mass of ic anhydride, 27 parts by mass of neopentyl glycol and 26.1 parts by mass of propylene glycol were mixed and the temperature was gradually raised up to 230°C in a en stream. .An esterification reaction was carried out for about 10 hours until the acid value became l or less (dehydrated amount: 14.2 parts by mass) while the water generated was distilled off. Then, the temperature of the reaction vessel was lowered to 50°C, and then 135 parts by mass of cyclohexanone and 35 parts by mass of 4,4'—diphenylmethane diisocyanate were mixed and held at 80°C for 8 hours to react, and thus an ester—based urethane resin 1 (solid concentration: 50% by mass) was obtained. g film—forming resins (A2) to (A8) (ester-based urethane resins 2 to 8, respectively) were prepared in the same manner as above except that the r types and amounts were changed as shown in Tables 2A and 2B. The monomer composition and characteristic values such as molecular weight of each resin are shown in Tables 2A and [Table 2A] Coating film- COating film— Coating film- Coating film- fonning resin fomung resin fomu'ng resin fonning resin (Al) (A2) (A3) (A4) Ester—based Ester—based Ester-based Ester-based urethanle resin urethane resin urethan3e resin urethane resin Neopentyl glycol Propylene glycol 26.1 Dehydration amt too 0 too 0 too 0 too 0 Cyclohexanone Trimellitic anhydride Number—average lar weight( 9, 000 9, 000 9, 000 9,000 solid acid value an KOH/g) —_== [Table ZB] Coating film- Coating film- Coating film— forming )resin fonning resin ng resin g film—fomung resin (A6) (A?) (A8) Ester—based Ester—based Ester—based Ester—based thaneresin urethane resin urethan7e resin urethane resin _5_5. 0 Dehydration mum Subtotal 100.0 100.0 100 0 100.0 Number-average molecular weight( 1, 000 3,000 19,000 23,000 cttvatut (mg tow Glass ttattttton tatteratute <°c> [Preparation of coating film-forming resin (A9) (ether- based urethane resin 1)] In a reaction vessel equipped with a thermometer, a reflux condenser and a stirrer, 100 parts by mass of 0 (polytetramethylene glycol ctured by Mitsubishi Chemical Corporation), 135 parts by mass of cyclohexanone and 35 parts by mass of 4,4'—diphenylmethane diisocyanate were mixed and held at 80°C for 8 hours to react, and thus an ether—based urethane resin 1 (solid tration: 50% by mass) was obtained. ration of coating film—forming resin (A10) (carbonate—based urethane resin 1)] In a reaction vessel equipped with a thermometer, a reflux condenser and a stirrer, 100 parts by mass of DURANOL T5650E (polycarbonate diol manufactured by Asahi Kasei ation), 135 parts by mass of cyclohexanone and parts by mass of 4,4'—diphenylmethane diisocyanate were mixed and held at 80°C for 8 hours to react, and thus a carbonate—based urethane resin 1 (solid concentration: 50% by mass) was obtained.

The monomer compositions and characteristic values such as molecular weight of the coating film—forming resins (A9) and (A10) are shown in Table 2C.

[Table 2C] Coating filnr g filnr mresin forming resin m9) @lm Eflnrflxwed 1 . Cmibmfiedxwed too 0— DURANOL T5650E _ 100.0 Cyclohexanone Trimellitic anhydride NUIIIber—average molecular weight( 9, 000 9,000 satin atia vain in town .— Giana tannitinn taneaatnaa <°c> [Coating film—forming resins (A11) to (A13)] In addition to the above, the details of the g film—forming resins (A) used in Examples and Comparative Examples are as follows.

— Coating film—forming resin (A11) (epoxy resin 1); E1255HX30 (manufactured by ishi Chemical ation, hydroxy group-containing epoxy resin), number—average molecular weight: 10,000, solid acid value: 1.0 mg KOH/g, glass transition temperature: 85°C, solid tration: % by mass — Coating film-forming resin (A12) (polyester resin 1); BECKOLITE M-6902—50 (manufactured by DIC Corporation), number—average molecular weight: 12,000, solid acid value: 7.5 mg KOH/g, glass transition temperature: 26°C, solid concentration: 50% by mass — Coating film—forming resin (A13) (acrylic resin 1); ACRYDIC A452 (manufactured by DIC Corporation), number— average molecular weight: , solid acid value: 2.7 mg KOH/g, glass transition ature: 70°C, solid concentration: 40% by mass [Crosslinking agents (B1), (B2)] The details of the crosslinking agent (B) are as follows.

— Crosslinking agent (B1) (polyisocyanate nd 1); Desmodur BL3575 (manufactured by Sumika Covestro ne Co., Ltd., blocked polyisocyanate), blocked body of hexamethylene diisocyanate (HDI) (isocyanurate type, blocking agent: dimethylpyrazole), isocyanate group t: 10.5% by mass, solid concentration: 75% by mass — Crosslinking agent (B2) (amino resin); MYCOAT 715 (made by Allnex Japan Inc., imino group—type melamine resin), solid concentration: 80% by mass Details of other components are as follows.

- Solvent 1; cyclohexanone (manufactured by Shoei Chemical Co., Ltd.) — Solvent 2; Solvesso 150 (manufactured by Shell Chemicals) - Curing catalyst; TVS KS—1260 (manufactured by Kyodo al Co., Ltd., dibutyltin dilaurate), non-volatile content: 100% by mass — Aluminum hydroxide; Higilite H32 (manufactured by Showa Denko K.K.), oil absorption: 20 g/100 g, BET specific surface area: 2.0 Hfi/g — Calcium vanadate; LF BOUSEI CRF—318 (manufactured by Kikuchi Color & Chemicals Corporation) — Tricalcium phosphate; Tricalcium phosphate (manufactured by Taihei Chemical Industrial Co., Ltd.) - sed phosphate; K—WHITE # 82 (manufactured by TAYCA Corporation, aluminum dihydrogen tripolyphosphate) - Magnesium oxide; magnesium oxide S (manufactured by Ube Material Industries, Ltd.) (Example 1) Mixed were 142.9 parts by mass of the coating film— forming resin (A1), 45.0 parts by mass of exanone, 45.0 parts by mass of Solvesso 150 and 60 parts by mass of the magnesium hydroxide (C1), and the mixture was dispersed with a sand mill (dispersion medium: glass beads) until the m particle diameter of pigment coarse particles reached 10 pm or less, and thus, sion composition 1 was prepared. To the obtained dispersion composition 1, 38.1 parts by mass of the crosslinking agent (Bl) (Desmodur BL-35?5) and 0.5 parts by mass of K81260 (manufactured by Kyodo Chemical Co., Ltd.) as a curing catalyst were added, and the mixture was uniformly mixed with a disper, and thus, coating composition 1 was prepared. Details of the composition of Example 1 are shown in Table 3A.

(Examples 2 to 31, ative Examples 1 to 10) The coating compositions were prepared in the same manner as in e 1 except that the types and amounts of each components were changed as shown in Tables 3A to 3H and Tables 4A to 4C.

[Table 3A] oat'. film-fo- ' - resin 1 2 3 4 mm mmhydroxide(cu —m-mmm hydrOXide . , (C) Magne51mn hydroxide (C2) Coating film—forming resin (Al) Ester-based urethane resin 1 142.9 142.9 Coating film—forming resin (A2) based urethane resin 2 Coating orming resin (A3) Ester—based urethane resin 3 g film—forming resin (A4) Ester—based urethane resin 4 Coating film—forming resin A5) Ester—based urethane resin 5 142.9 g film—forming resin A6) Ester—based urethane resin 6 142 . 9 fihn—fongingCoatin Coating film—forming resin (A7) Ester—based urethane resin 7 resm (A) Coating film—forming resin (A8) Ester—based ne resin 8 Coating film—forming resin EAA9) Ether—based urethane resin 1 Carbonate—based urethane Coating film—forming resin ( resin 1 IilllCoating film—fonning resin (A11 Epoxy resin 1 Coating film—forming resin (A12 V Polyester resin 1 Coating film-forming resin (A13) Acrylic resin 1 E 45.0 45.0 45.0 45.0 Solvent Solvesso 150 45 . 0 45. 0 45.0 45. 0 agent0» ——---- ——---—— ——--- [Table 3B] . coat' . filrn-fonnin- resin 5 6 7 8 $3511: im hydronde (61> —mmmm-enmm (c. mesmheome (c2) —---- Coating film—forming resin (A1) Ester—based urethane resin 1 Coating fihn-fontu'ng resin (A2) Ester—based urethane resin 2 142.9 Coating fihn—fonning resin (A3) Ester~based ne resin 3 142.9 Coating onning resin (A4) Ester~based urethane resin 4 Coating orming resin (A5) Ester—based urethane resin 5 Coating film—forming resin (A6) Ester—based urethane resin 6 fim_fol:lfijlgCoat' Coating film-forming resin A7) Ester-based urethane resin 7 142.9 resin (A) Coating film—fonning resin A8) Ester—based urethane resin 8 142.9 Coating film—forming resin A9) r~based urethane resin 1 Carbonate-based urethane Coating film—forming resin ( Coating film-forming resin (All) Epoxy resin 1 Coating film—forming resin (A12) Polyester resin 1 Coating film-forming resin (A13) lic resin 1 Cyclohexanone 45.0 45.0 45.0 45.0 Solvent Solvesso 150 45.0 45.0 45.0 45.0 Crossljnking Crosslinking agent (B1) 38.1 38.1 331 33,1 agent (B) Crosslinking agent (B2) _- ——----— _---—— [Table 3C] Details °f ooatin- film-fo- ' - resin 9 10 11 12 mm mm hydroxide <c1> —mnmmm hYd?oxide Wmmeme, «22> _---- Coating film—forming resin (A1) Ester—based urethane resin 1 - 194.2 188.7 105.3 Coating film—forming resin (A2) Ester—based urethane resin 2 Coating film—forming resin (A3) Ester—based urethane resin 3 Coating film—forming resin (A4) Ester—based urethane resin 4 142.9 Coating fihn—forming resin (A5 Ester—based urethane resin 5 Coating film—fanning resin (A6 Ester—based urethane resin 6 Coating . . . . oming Coating film-forming resrn (A7) Ester—based urethane resm 7. resin (A) g film—fonning resin (A8) Ester—based urethane resin 8 - g film-forming resin (A9) Ether—based urethane resin 1 - Coating film—forming resin - 45.0 45.0 ——-45.0 45.0 45.0 9 7.5 63.2 agent<3)——- catalyst—_- 0.5 0.5 0.5 ——_348.6 346.7 319.0 [Table 3D] —eeeecoat'. onnin- resin 13 14 15 16 Magnesm——mmmmm “is“——-—-- Coating fihn—forming resin (A2) Ester—based urethane resin 2 Coating film-forming resin (A3) Ester—based ne resin 3 Coating film—fonning resin (A4) Ester—based urethane resin 4 Coating film—forming resin (A5) Ester—based urethane resin 5 Coating film—forming resin (A6) Ester-based urethane resin 6 film-foamingCoatin Coating film—forming resin (A7) Ester—based urethane resin 7 resin (A) Coating film—forming resin (A8) Ester—based urethane resin 8 g film—forming resin A9) Ether—based urethane resin 1 142 . 9 Carbonate—based urethane Coating film—forming resin (E resin 1 Coating film—fonning resin (A11) Epoxy resin 1 238. 1 Coating filin—foming resin (A12) Polyester resin 1 142.9 g film—forming resin (A13) Acrylic resin 1 Cyclohexanone 45.0 10.0 45.0 Solvent Solvesso 150 45 . 0 62 . 9 10. 0 45 . 0 agent ei ng agent on —---- seine non —--— ——-—-- [0149 1 [Table 3B] Details of Encarrple lib-(ample Exanple coating film-fomin- resin 17 18 19 20 Magnesimu Magiesiun ide (on —mmmmmm hydroxide , , Magnesqu hydrox1de (C2) Coating mnng resin (A1) —--—- CCatinC nning resin (n2) —- Coating rinnfomnng resin (e3) —- Coating fihnfoming resin (A4) _- coating rihnfoming resin (A5) —- g rimming resin (is) —- Coating Coating fiintfoming resin (A7) —- film—forming resin (A) Coating film—forming resin (A8) Ester—based urethane resin 8 Coating film—fonruing resin (A9) Ether-based urethane resin 1 - Coating film—forming resin (A10) wresmonite‘based ”reu’ane 142.9 Coating film-forming resin (All) -- Coating film-fonm'ng resin (A12) -- Coating finefoming resin (A13)—--178 6 deheenone —- 45-0 45.0 Solvent Solveeso 150 —- 45-0 45.0 Crossiimong Croeslirieing agent(Bl) —- agent (B) ixflcing agent (B2) —-- 35.7 w 03 Catalyst KS-1260 — ——-328. 6 347 . 8 [Table 3F] Details of e Example coatin- film-forming resin 21 22 23 24 Magnesium Magnesmn hydroxide (cl) —mmmmmmmm hydroxide (C) Magnesium hydroxide (C2) Coating film—forming resin (Al) Ester—based urethane resin 1 188 .7 105.3 Coating film-foming resin (A2) Ester-based urethane resin 2 Coating film-forming resin (A3) Ester-based ne resin 3 Coating orming resin (A4) based urethane resin 4 Coating fihn—forming resin (A5) Ester-based urethane resin 5 Coating film. Coating film—fuming resin (A6) Ester—based urethane resin 6 forming resin Coating film—forming resin (A7) Ester—based urethane resin 7 (A) g film-forming resin (A8) Ester-based urethane resin 8 Coating film—forming resin (A9) based urethane resin 1 Coating film—forming resin (A10) Carbonate-based urethane resin 1 Coating film-feming resin (A11) Epoxy resin 1 Coating fihn-foming resin (A12) Polyester resin 1 142 . 9 Coating film—forming resin (A13) rylic resin 1 Cyclohexanone 45 . 0 45.0 45.0 62.9 Solvesso 150 45.0 45.0 45.0 62.9 Crosslinking Crosslinking agent (B1) agent (B) Crosslinking agent (B2) 7'1 59 .2 68 . 2 5. \J _——--- ——---- [Table 3G] _Detafls°fcoatin-filn‘r-fo- ' . resin 25 26 27 28 Meereeeeu_—mmmm —---- ——-—-- ——--—- ceeere rrrr-rerrrre reerr err _- Coating film—forming resin (A) Ooating film—foming resin (A9) Ether—based urethane resin 1 142.9 —:::::n:medW 142.9 —rrexyresin 1 r reer-e r —reryrre rerrr 178.6 45.0 45.0 30.0 5.0 Solvent 45.0 45.0 30.0 5.0 eraser-merg— 38.1 Catalyst ---- _—--- [Table 3H] ooat' . film-fonnin- resin 29 30 31 “891165411“——--- hydride——-—- Coating film-foaming resin (A1) Ester—based urethane resin 1 142.9 Coating fihn—foming resin (A2) Ester—based urethane resin 2 Coating film—forming resin (A3) Ester—based urethane resin 3 Coating orming resin (A4) Ester—based urethane resin 4 Coating film—forming resin (A5) Ester—based urethane resin 5 Coating film-forming resin (A6) Ester-based urethane resin 6 o:l:m]?ingCoat' Coating fihn~fonnjng resin (A7) Ester—based urethane resin 7 resin (A) Coating film—forming resin (A8) Ester—based urethane resin 8 Coating film—fomung resin (A9) Ether—based urethane resin 1 Carbonate—based ne Coating orming resin (A10) resin 1 Coating film—fornu'ng resin (A11) Epoxy resin 1 Coating orming resin (A12) Polyester resin 1 Coating film—forming resin (A13) lic resin 1 Cyclohexanone U1 . C) 80. o Solvent Solvesso 150 U1 . 0 80 o Crosslinking Crosslinkjng agent (B1) 38.1 38.1 agent 03) inking agent (32) - Catalyst KS-1260 0 5 0.5 [Table 4A] Comparative Ccmparative Carparative (Imperative Ebemple 1 Example 2 Example 3 Example 4 Maeesiunhydrome (c3) ”— Magnesia——— #30:; uhydmxme (c7) —— other mmwaroxme —— materials Calcium te —— Calciun phosphate hydroxide —— Condensed phosphate — Magnesim oxide —_ Coating film—forming resin (A1) 142 9 142.9 142.9 142.9 Ester—based urethane resin 1 sesame 45.0 Solvent salvesso :50 “0551mm Crosslinking agent (131) 33 1 3s 1 39.1 38 1 agent catalyst Ks-neo O . 5 0 U1 0 U1 !331.5 331.5 331.5 331.5 [Table 4B] Ebtaxrple 7 Example 8 MfifififiUMfifififimfiflllllIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII ————_ ——_—— Magnesium——_—— hydroxide (03m C' —m——— and Almnimm hydroxide —m_— materials———m— calcium phosphate hydroxide ———m Comm phasphate ———— _———— Coating film-forming resin (Al) 142.9 142.9 142.9 142.9 Ester—hased ure ] resin 1 Solvent ' solvesso 15o —xs-1zeo _T—Btai‘——331-s————3313 331-3 [Table 4C] —-—-ExaIrple9 Example 10 Exalrple 1 Magnesm——— 11ch3=,°’;33:§_—— other materials——— Coating fihn—forming resin (Al) 142. 9 142. 9 Ester-based ne resin 1 45-0 45-0 Solvent 45-0 45-0 agent catalyst Ks—mo 331-3 3313 [Method of preparing coated plate for evaluation] A 0.4 mm thick aluminum-zinc plated steel plate was alkali-degreased, and then subjected to non-chromium chemical sion ent by applying a phosphoric acid treatment agent, SURFCOAT EC2310 (manufactured by Nippon Paint Surf Chemicals Co., Ltd.) to the front and back surfaces of the steel plate, followed by drying.

Next, the g composition 1 obtained above was applied to the back surface of the obtained d steel plate such that the dry coating film was 7 pm in the thickness, and baked at a maximum temperature of 180°C for seconds, and thus a back coating film was formed.

Meanwhile, one of the coating compositions of Examples 1 to 31 and Comparative Examples 1 to 10 was applied to the front surface of the treated steel plate such that the dry coating film was 5 pm in the thickness, and baked at a maximum temperature of 200°C for 30 seconds, and thus a front undercoating film was formed. Furthermore, Nippe Supercoat 3OOHQ actured by Nippon Paint Industrial Coatings Co., Ltd.; polyester—based topcoat paint) was d as a topcoating material on the above front undercoating film such that the dry coating film was um in the thickness, and baked at a maximum temperature of 210°C for 40 seconds to form a front topcoating film, and thus a coated steel plate for evaluation was ed.

(Reference Example 1) NRC300 (manufactured by Nippon Paint Surf Chemicals Co., Ltd.), which is a chromate—based treatment agent, was applied to the front and back surfaces of a steel plate instead of the phosphoric acid treatment agent (SURFCOAT EC23lO) used in the method of the preparation of the coated sheet for evaluation, to perform chromate ent, followed by drying. Nippe Supercoat 667 Primer (manufactured by Nippon Paint Industrial Coatings Co., Ltd.; ium chromate—based undercoating material) was applied to the front and back surfaces of the obtained treated steel plate such that the dry coating film was 3 um in the thickness, and baked at a maximum temperature of 200°C for 30 s, and thus a front and back undercoating films were formed. Furthermore, Nippe Supercoat 3OOHQ (manufactured by Nippon Paint Industrial Coatings Co., Ltd.; polyester—based topcoat paint) was applied as a topcoating material such that the dry coating film was 10 pm in thickness, and baked at a maximum temperature of 210°C for 40 seconds, and thus a coated steel plate for evaluation was obtained. The conditions are shown in Table 4C.

The evaluation results of the coating itions and the coated steel plates for tion prepared in Examples, Comparative Examples and nce Example are shown in Tables 5A to 5H and 6A to 6C.

[Table 5A] _——-— Magnesium hydroxide (C) Coating fihn—formjng Type Esteugrhlebased based Ester—based Ester-based resm (A) thaneresin urethanle resin urethan: resin urethane resin Crosslnndng agent (B) Part(s) by mass (solid content) of crosslirfldng agent (B) relative to 100 parts by mass of coating 40 anning resin (A) Part(5) by mass (50nd content) Of magneSim u... hydroxide (C) ve to 100 parts by mass in total of g film—forming resin (A) and crosslinking agent (B) —_——_ ————— _'———_ EZ§§°51°D ”gist“ ——_—_. . ————— ——_—— ———_— Immersion—drying cycle test using acidic salt water [ 0 l 6 O ] [Table SB] ————_ Coating film-foaming Ester-based Ester-based Ester-based Esterbased resin (A) thaneresin urethane resin urethan2e resin urethan: resin _issll'ldongagent(1903—) Part(s ) by mass (solid content) of inking agent (B) relative to 100 parts by mass of coating 40 film—forming resin (A) Part (5) by mass (solid content) of magnesium hydroxide (C) relative to 100 parts by mass in total of coating film—fomu'ng resin (A) and crosslinking agent (B) Storage stability test ——_— Boning water resistance test ——_— re resistance test (CCHC test) 4T folded part Corrosion resistance test Crosscut part Acid resistance test —_—_ Immersion—dang cycle 4T folded part test using acidic salt water crosseue pare [Table 5C] ————— Coating fiilntfonning Ester-based Ester-based Type Ester-based Ester-based resm (A) urethane resin urethane resin ne resin urethanle resin Crossiinidng agent (B) Part (5 by mass (solid content) of crosslinking agent (B) relative to 100 parts by mass of coating 3 film—forming resin (A) Part(s) by mass (solid t) of- magnesium hydroxide (C) relative to 100 parts by mass in total of coating film—forming resin (A) and crosslinldng agent (B) —_——— —_——— ———_— ————— ion resistance test_— ———_— _———— —_——— sion—drying cycle ————— test using acidic salt ———n- water —.-——— [ O l 62 ] [Table 5D] ——_—— Coatin film-fonnjn _ resin 1 Part(s) by mass (solid content) of crosslinldng agent (B) relative to 100 parts by mass of coating 120 40 film—forming resin (A) Part (5) by mass (solid content) of magnesium hydroxide (C) relative to 100 parts by mass in total of coating film—forming resin (A) and crosslinking agent (B) 5 ———_— ———_— ———_— corrosion resistancetest—__—_ ————— ————_ ————— Msimsssm cycle —_———- tsst using acidic salt ———‘ water ————n [Table 5E] ———_— (A10) (A13) Coating film-forming Carbonate— T F5 , . Ester-based Ester-based resin (A) based urethane Acrylli resm ne resin urethane resin resin 1 1 1 Crosslinking agent (B) Part (5) by mass (solid content) of crosslinking agent (B) relative to 100 parts by mass of coating 40 3 film—forming resin (A) Part (5) by mass (solid content) of magnesium hydroxide (C) ve to 100 parts by mass in total of coating film—fanning resin (A) and crosslinking agent (B) H. corrosion resistance test immersion—(mg cycle ————- test using acidic seii _—n_.- We ——--n [Table 51?} _iirarrrnle 21 sle 22 ample 23 Magnesium hydroxide (C) (c1) (c1) (c1) Coating film-forming based based TYPE Ester-based 1 1 1 Crossli'mong agent (B) (132) (B2) Part(s) by mass (solid content) of crosslinking agent (B) relative to 100 parts by mass of coating 120 film—fomu’ng resin (A) Part(s) by mass (solid content) of magnesium hydroxide (C) relative to 100 parts by mass in total of coating fiJJn—fomung resin (A) and crosslinldng agent (B) storage senoiiiiy rest g water resistance test Moisture resistance test (mac test) 4T folded part Corrosion resistance test Crosscut part Alkali resistance test Acid resistance test Immersion—drying cycle 4T fOldEd part test using acidic salt Edge part water Crosscut part [Table 5G] ————— (A10) (A13) Coating film-fanning Euler-based T1155 Carbonate- . . based IGSi—U (A) : urethane resin based ne 311:1: resin urethane resin 1 resin 1 1 Crosslinking agent (B) Part(s) by Kass (solid content) of crosslinking agent (B) relative to 100 parts by mass of coating film—fanning resin (A) Part(s) by mass (solid content) of magnesium u.- hydroxide (C) relative to 100 parts by mass in total of coating film—forming resin (A) and crosslinking agent (B) Corrosion ance test Immersion—drying cycle ———-—— test usmg acidic salt ———-— water _—-.-— [ O l 6 6] [Table 5H] —mm29mile so mile 31 Magnesium hydroxide (C) (C1) (C1) (C1) Coating film-forming based Ester-based Type Ester-based resm (A) urethane resin urethane resin ne resin 1 1 1 Crosslinking agent (B) Part(s) by mass (solid content) of crosslinking agent (B) relative to 100 parts by mass of coating film—fonning resin (A) Part(s) by mass (solid content) of magnesium hydroxide (C) relative to 100 parts by mass in 3 140 160 total of coating orming resin (A) and crosslinking agent (B) storage stability test Boiling water resistance test Moisture resistance test (CCHC test) 1 4T folded part C°rr°5i°n ream” part— “ Edge Alkali resistance test Immersion—drying cycle 4T f°ld3d part test using acidic salt Edge part n voter crosscut par: .- [Table 6A] Conparative Carparative Ocmparative Comparative Ebrample 1 marble 2Eb§m1ple 3 Example 4 Magma“ hydeide (C') and ”her materials Magnesiun ium Magnesium Magnesium hydroxide (c3) hydroxide (c4) hydroxide (c5) h—ydroxide(C6) _———Al> Coating onnjng based Ester—based Ester—based Ester—based resin (A) urethane resin urethane resin urethane resin ne resin _rosslinkmgagent(B) Part (5) by mass of inking agent (13) relative to 100 parts by mass of coating film—fonning resin Part(s) by mass of (C‘) or other materials relative to 100 parts by mass in total of coating film-forming resin (A) and crosslinking agent (B) Corrosion resistance test using acidic salt [Table 6B] Comparative Canparative ative Comparative Example 5 Example 6 Ebcalrple 7 Example 8 Calciun um Calcium Magnesium hydroxide (C' ) and other materials Magnesiun hydroxide (C7) hydroxide vanadate Eggphatd:on Coating film-fonning Ester—based Ester—based Ester—based Ester—based resin (A) urethaneeresin urethane resin urethane resin urethane resin __Crosslmang B) (B1) Part(s) by mass of crosslinking agent (B) relative to 100 parts by mass of coating film—fouling resin Part (5) by mass of (C') or other materials relative to 100 parts by mass in total of coating film—forming resin (A) and crosslinking agent( e stability test — Boiling water resistance test .15- Moisture resistance test (CCHC test) m- 4T folded part — Corrosion resistance test Edge part .- ‘- Crosscut part — u Alkali resistance test m- — Acid resistance test n — Immersion—drying cycle 4T folded part .- ah n test using acidic salt Edge part — 0» — water Crosscut part — (A) _ [Table 6C] ative Carparative Reference Ebrample 9 Ebcample 10 Brample 1 . . Condensed Magnesum hydroxide (C‘) and other materials. ium phos 1 te Coating orming Type Ester—based Ester-based resm (A) urethane resin urethane resin 1 1 WEE crosslmkm; agent. . Supercoat (B) 667 Prim Part(s) by mass of inking agent (B) relative to 100 parts by mass of g film—forming resin (A) Part (5) by mass of (C‘) or other materials relative to 100 parts by mass in total of coating film—forming resin (A) and crosslinking agent (B) ——3 3 3 flflHMMEEEEEfififlfiflllllllllllllllllIIIEJIII w m Moisture resistance test (CG-1C test) 10 10 Corrosion ance test—- 5 —-§_10 Innersion—dryjng cycle—“ test using acidic salt water [Evaluation item] (Procedure for measuring the solubility of magnesium hydroxide in artificial acidic seawater) As an acidic solution comprising sulfate radicals, the acidic aqueous salt solution used in Method B specified in JIS G 0594:2019 cyclic corrosion test method was used as a reference.

MARINE ART SF—l (manufactured by Tomita Pharmaceutical Co., Ltd.) was used as artificial seawater, and it was adjusted to pH = 2.5 with a mixed solution of nitric acid and sulfuric acid as specified in JIS G 0594, 4.1.1, Item c), and artificial acidic seawater was obtained.

Next, 100 g of artificial acidic seawater and l g of a pigment (magnesium hydroxide) were added to a narrow- mouthed bottle made of polyethylene and a r chip was added, and the mixture was stirred at room temperature for 4 hours.

Then, after leaving it at room temperature for 24 hours, the supernatant was collected with a syringe equipped with a syringe filter, and the element concentration was measured with an ICP emission spectrometer ICPS—751O actured by Shimadzu ation). Element concentration of the artificial acidic seawater was also measured in the same manner. The value obtained by subtracting the magnesium metal ion concentration contained in the artificial acidic seawater from the magnesium metal ion concentration ned in the atant is defined as the ium metal ion concentration in an s solution prepared by adding 1 g of a magnesium hydroxide to 100 g of an artificial acidic seawater solution.

(Procedure for measuring conductivity in purified water) 100 g of ion—exchanged water and 1 g of a pigment (magnesium hydroxide) were added to a narrow—mouthed bottle made of polyethylene, then a stirrer chip was added, and the mixture was stirred at room temperature for 4 hours.

Then, the conductivity was ed using an electrical conductivity meter CM—42X (manufactured by DKK—TOA Corporation). ge ity test) The coating composition obtained above was allowed to stand at 50°C for 4 weeks. The state of the g composition after standing was visually observed and the storage stability was evaluated according to the following criteria.

: The coating composition is uniform without stirring. 4: Although some sediment was ted, the coating composition easily becomes uniform by stirring with a spatula. 3: Although some sediment was generated, the coating composition becomes uniform by stirring with a spatula. 2: Although sediment was generated, the coating composition becomes uniform by stirring with a disper. l: Sediment was generated, and the coating composition does not become uniform even if it is stirred with a disper.

[Evaluation items of coating film] 1) g water resistance test The coated steel plate obtained above was cut into 5 cm x 10 cm, and the obtained specimen was immersed in boiling water at about 100°C for 2 hours and then pulled up.

Then, the appearance of the coating film on its front side was evaluated ing to ASTM D714—56 (flat part blistering evaluation).

Here, ASTM D7l4—56 evaluates the size (mean diameter) and y of each r in comparison with a standard judgment photograph and indicates a grade symbol. The size is classified in four grades in the order of 8 (diameter: about 1 mm), 6 (diameter: about 2 mm), 4 (diameter: about 3 mm) and 2 (diameter: about 5 mm), and the density is classified in five grades in the ing order of F, FM, M, MD and D, and when there is no blister, this is evaluated as 10. A score of 8 FM or higher was evaluated as good.

Coated steel plate specimens were evaluated after immersed in boiling water at about 100°C for 2 hours by performing a grid tape adhesion test (grid adhesion test).

In the grid tape on test was performed according to JIS K 5400 8.5.2 (1990) grid tape method, and the gap between cuts was set to 1 mm, 100 grids were made, and cellophane adhesive tape was adhered to the surface of the grid. Then, the tape was peeled off rapidly, and the number of grids remaining on the coated surface was examined. 2) Moisture resistance test (CCHC test) A coated steel plate was cut into 5 cm x 10 cm, and the resulting specimen was left to stand for 500 hours under the condition of 50°C X 98 RH% with purified water.

Then the blistering of a flat part was evaluated according to ASTM D7l4—56 in the same manner as in the boiling water resistance test. A score of 8 FM or higher was evaluated as good. In this test, a large wet tester (manufactured by Suga Test ments Co., Ltd.) was used. 3) Corrosion resistance test A coated steel plate was cut to a size of 5 cm X 15 cm. The cutting was performed alternately from the front surface and the back surface, and the specimens were ed such that the cross section of each specimen had both an upper burr (cut from the back surface) and a lower burr (cut from the front surface).

Next, a crosscut having a narrow angle of 30 degrees and a cut width of 0.5 mm was formed with a y knife at the center of the front side such that the crosscut reached the substrate. The upper edge part of the coated steel plate was sealed with a corrosion—resistant coating material, and a 4T folded part was formed at the lower end, from which four plates were to be removed after processing.

The 4T g processing refers to a process in which a coated plate is folded with the front surface thereof outside, then four plates with the same thickness as the coated plate are interjected inside, and the coated plate is folded 180 degrees with a vise. After processing, four of the plates were removed and the ing coated plate was provided for the test.

A schematic view of the coated steel plate specimen obtained as described above is shown in is a diagram schematically showing a cross section 20 of an upper burr and a cross section 30 of a lower burr in the ed coated steel plate specimen 10.

Further, the coated steel plate specimen 10 has a coating film front surface 11 and a coating film back surface 12.

B) is a schematic view showing a crosscut part 40 and a 4T folded part 50 provided in a coated steel plate specimen 10 used for a corrosion resistance test. Further, the coated steel plate specimen 10 has an upper burr 21 and a lower burr 31.

Each of the ed coated steel plate specimens was subjected to a combined cyclic corrosion test (CCT) in accordance with JIS K 5600—7—9A JASO M609. Taking ing 5% saline at 35°C for 2 hours)-(drying at 60°C for 4 hours)—(allowing to stand in a moisture resistance tester at 50°C and RH 95% or more for 2 hours) as one cycle, a 120—cycle test (960 hours in total) was carried out. The state of the edge part, the crosscut part and the 4T folded part of the coated steel plate specimen after this test was evaluated based on the following evaluation method and evaluation criteria. In each case, a score of 4 or higher was evaluated as good.

Equipment used: ed cyclic tester CYP—9O (manufactured by Suga Test Instruments Co., Ltd.) (Corrosion resistance test: 4T folded part) The total length of a rusted part in a 4T folded part was measured and evaluated according to the following : No generation of rust is observed. 4: White rust is observed, and it has a total length of less than 10 mm. 3: White rust has a total length of 10 mm or more and less than 25 mm. 2: White rust has a total length of 25 mm or more and less than 40 mm. 1: White rust has a total length of 40 mm or more, or generation of red rust is observed.

(Corrosion ance test: edge part) The average value of the edge creep width (blister width) of the left and right long sides (that is, the long side having the upper burr and the long side having the lower burr) of a coated steel plate specimen was calculated and evaluated according to the following criteria.

: Blister width is less than 5 mm. 4: Blister width is 5 mm or more and less than 10 mm. 3: Blister width is 10 mm or more and less than 15 mm. 2: r width is 15 mm or more and less than 20 mm. 1: Blister width is 20 mm or more.

(Corrosion resistance test: crosscut part) The corrosion state of a cross-cut part was evaluated ing to the following criteria based on the ratio of the length of white rust generated in an exposed portion of a substrate with a cut width of 0.5 mm and the average value of the widths (the sum of both sides) of the left and right blisters of the crosscut part.

: The length ratio of the white rust generated in the substrate—exposed portion is less than 25% and the blister width is less than 3 mm. 4: The length ratio of the white rust generated in the substrate-exposed portion is 25% or more and less than 50% and the blister width is less than 3 mm. 3: The length ratio of the white rust generated in the substrate—exposed n is 50% or more and the blister width is less than 3 mm. 2: The length ratio of the white rust generated in the substrate—exposed portion is 50% or more and the blister width is 3 mm or more and less than 5 mm. 1: The length ratio of the white rust generated in the substrate-exposed portion is 50% or more and the blister width is 5 mm or more. 4) Alkali resistance test Each coated steel plate was cut into 5 cm x 10 cm, and each specimen was immersed in a 5% aqueous sodium hydroxide solution at 23°C for 48 hours, taken out, washed with water, and dried at room temperature. The resulting coated steel plate en was evaluated as to blister on a flat portion in ance with ASTM D714—56 in the same manner as in the boiling water resistance test. A score of 8 PM or higher was evaluated as good.

) Acid resistance test Each coated steel plate was cut into 5 cm x 10 cm, and the obtained specimen was immersed in a 5% s sulfuric acid solution at 23°C for 48 hours, taken out and washed, and dried at room temperature. The resulting coated steel plate specimen was evaluated for blister on a flat portion in accordance with ASTM D714—56 in the same manner as in the boiling water resistance test. A score of 8 FM or higher was ted as good. 6) Immersion—drying cycle test using acidic salt water ration of test plates) Each of the coated steel plates obtained above was cut into 5 cm x 10 cm, and a 4T folded part was provided in the lower end of the obtained specimen in the same manner as in the corrosion resistance test.

(Preparation of acidic salt water) As an acidic solution comprising sulfate radicals, the acidic aqueous salt solution used in Method B specified in JIS G 0594 cyclic ion test method was used as a reference. Specifically, using MARINE ART SF-l (manufactured by Tomita Pharmaceutical Co., Ltd.) having a composition similar to that of the artificial seawater specified in JIS G 0594, it was adjusted to pH = 2.5 with a mixed solution of nitric acid and sulfuric acid specified in 4.2.2, and acidic salt water was obtained.

(Test conditions) Each of the obtained coated steel plate specimens was subjected to a lS—cycle test (360 hours in total) under a 230 C ion with 6 hours of immersion —+ 18 hours of drying as one cycle. The state of the edge part, the crosscut part and the 4T folded part of the coated steel plate specimen after the test was evaluated based on the following evaluation method and evaluation criteria. In each case, a score of 4 or higher was evaluated as good.

(Test using acidic salt water: 4T folded part) The total length of a rusted part in a 4T folded part was measured and evaluated according to the following criteria.

: No generation of rust is ed. 4: White rust is observed, and it has a total length of less than 10 mm. 3: White rust has a total length of 10 mm or more and less than 25 mm. 2: White rust has a total length of 25 mm or more and less than 40 mm. 1: White rust has a total length of 40 mm or more, or generation of red rust is observed.

(Test using acidic salt water: edge part) The average value of the edge creep width er width) of the left and right long sides (that is, the long side having the upper burr and the long side having the lower burr) of a coated steel plate en was calculated and evaluated according to the following criteria. : r width is less than 5 mm. 4: Blister width is 5 mm or more and less than 10 mm. 3: Blister width is 10 mm or more and less than 15 mm. 2: Blister width is 15 mm or more and less than 20 mm. 1: Blister width is 20 mm or more.

(Test using acidic salt water: crosscut part) The corrosion state of a cross—cut part was evaluated according to the following criteria based on the ratio of the length of white rust generated in an exposed portion of a substrate with a cut width of 0.5 mm and the average value of the widths (the sum of both sides) of the left and right blisters of the crosscut part.

: The length ratio of the white rust generated in the substrate—exposed portion is less than 25% and the blister width is less than 3 mm. 4: The length ratio of the white rust generated in the substrate-exposed portion is 25% or more and less than 50% and the blister width is less than 3 mm. 3: The length ratio of the white rust generated in the substrate-exposed portion is 50% or more and the blister width is less than 3 mm. 2: The length ratio of the white rust ted in the ate—exposed portion is 50% or more and the blister width is 3 mm or more and less than 5 mm. 1: The length ratio of the white rust generated in the substrate—exposed portion is 50% or more and the blister width is 5 mm or more. ing to the results of Examples, the ion— resistant coating composition of the present invention had superior storage stability and formed a coating film with a superior corrosion—resistant property and superior moisture resistance over a long period. Moreover, it formed a coating film with a superior corrosion—resistant property for a long period even under acidic environmental conditions. Thus, for example, the rust generation that may be caused by “acid rain” or the like can be inhibited.

In addition, the deterioration of the moisture resistance of a coating film is suppressed or greatly reduced, and the blistering in a coating film is also suppressed. Further, in the Examples, the protective effects by a coating film were sufficiently elicited even at an edge part, a crosscut part, and the like. Further, in the Examples, the same level of corrosion-resistant property was observed as the corrosion—resistant test result obtained using the coating composition ning chromium of Reference Example 1, and the storage ity of the coating compositions was evaluated better than that of Reference Example 1.

In Comparative Examples 1 to 5, the BET specific surface area and the e constant of the magnesium ide are outside the ranges of those of the magnesium hydroxide (C) according to the present ion. For this, the formed coating films were not able to exhibit sufficient corrosion—resistant property and moisture resistance. ative Examples 6 to 10 do not n magnesium hydroxide (C). For this, the results were not good in any of the storage stability of the coating composition, the corrosion—resistant property and the moisture resistance of the formed coating film.

For example, in Comparative Example 7, calcium vanadate is used instead of the magnesium hydroxide (C).

The storage stability of the coating composition of Comparative Example 7 was not good, and the durability of the coating film was not good at the edge part and the ut part when acidic salt water was used. It is considered to be because calcium vanadate is highly water— soluble, so that it reacts with water in the coating composition, resulting in an effect on storage ity, and when a coating film is formed, it easily elutes from the coating film and it becomes difficult to provide corrosion—suppressing agents for a long period.

Further, for example, in Comparative Example 10, magnesium oxide is used instead of the magnesium hydroxide (C). The storage stability of the coating ition of Comparative Example 10 was not good. It is considered to be because magnesium oxide is inferior in dispersibility in the g composition compared with the magnesium hydroxide (C).

INDUSTRIAL APPLICABILITY The corrosion—resistant coating composition of the present invention can t a superior corrosion- ant property for a long period and can form a g film that exhibits superior moisture resistance.

Further, according to the method for producing a coating film according to the present invention, a superior corrosion-resistant property is elicited for a long period and a coating film with superior re resistance can be formed.

REFERENCE SIGNS LIST Coated steel plate specimen 11 Front surface of coating film 12 Back surface of coating film Cross section of upper burr 21 Upper burr Cross section of lower burr 31 Lower burr 4O Crosscut part 50 4T folded part

Claims (11)

1. A corrosion-resistant coating composition comprising a coating film—forming resin (A), a crosslinking agent (B), and a magnesium hydroxide (C), wherein the magnesium ide has an oil absorption of 70 g/100 g or less, and a BET specific surface area of 4.0 mZ/g or less.

2. The corrosion-resistant g composition ing to claim 1, wherein the magnesium hydroxide (C) is a compound having a conductivity of 250 uS/cm or less in an aqueous solution prepared by adding 1 g of the magnesium hydroxide (C) to 100 g of purified water.

3. The corrosion—resistant coating composition according to claim 1 or 2, wherein the magnesium hydroxide (C) exhibits a pH of 8 or more and 12 or less in an aqueous solution prepared by adding 1 g of the magnesium hydroxide (C) to 100 g of purified water, and wherein an average particle diameter of the magnesium ide (C) is 0.5 pm or more and 20 pm or less.

4. The corrosion—resistant coating composition according to any one of claims 1 to 3, wherein the g film- forming resin (A) comprises at least one selected from the group consisting of epoxy resin, polyester resin, c resin, urethane resin, and modified products thereof.

5. The corrosion-resistant coating composition according to any one of claims 1 to 4, n the coating film-forming resin (A) comprises at least one selected from the group consisting of urethane resin and a modified product thereof, and wherein a glass transition temperature of the urethane resin is -50°C or higher and 70°C or lower.

6. The corrosion—resistant coating composition according to any one of claims 1 to 5, wherein the coating film-forming resin (A) comprises at least one selected from the group consisting of urethane resin and a modified product thereof, and n the urethane resin comprises at least one selected from the group consisting of ester—based urethane resin, ether—based urethane resin, and carbonate—based urethane resin.

7. The ion—resistant coating composition according to any one of claims 1 to 6, n a -average molecular weight of the coating film—forming resin (A) is 1,000 or more and 40,000 or less.

8. The corrosion—resistant coating composition according to any one of claims 1 to 7, wherein the coating film— forming resin (A) ses at least one selected from the group consisting of ester—based urethane resin, epoxy resin, polyester resin, and modified products thereof.

9. The corrosion—resistant coating composition according to claim 8, wherein at least one of the ester—based urethane resin, the epoxy resin, and the ter resin has a solid acid value of 30 mg KOH/g or less.

10. The ion—resistant coating composition according to any one of claims 1 to 9, wherein an amount of the magnesium hydroxide (C) is in the range of 1 part by mass or more and 150 parts by mass or less relative to 100 parts by mass of a total of a solid content of the coating film— forming resin (A) and a solid content of the crosslinking agent (B).

11. A method for producing a corrosion—resistant coating film, comprising: a coating step of applying the corrosion—resistant coating composition according to any one of claims 1 to 10 to an article to be coated, and a step of curing the corrosion—resistant coating ition at a temperature of 150°C or higher and 270°C or lower.