TWI411653B - Anti-corrosive coating composition - Google Patents

Abstract

The invention provides an anticorrosive coating composition, comprisng (A) flexible organic modified bisphenol epoxy resin, prepared from 5 to 15 weight% of flexible organic part and 50 to 55 weight% of bisphenol epoxy resins by reacting, (B)solidifying agent and (C)anticorrosive paint, wherein the flexible organic part is selected from C4 to C36 fatty polybasic acid, acrylic resin with the glass transition temperature of -20 to 50 DEG C and polyester resin with the glass transition temperature of -20 to 50 DEG C, the anticorrosive paint(C) is preferably non-chromium anticorrosive paint mixture containing vanadium compound and silicon-containing compound such as metal silicates, phosphates and the like.

Description

Anti-corrosion coating composition

The present invention relates to a coating composition having excellent corrosion resistance and a coated metal sheet obtained by using the coating composition, and more particularly to a coating composition for corrosion resistance, which is not only effective for improving the coated metal sheet The corrosion resistance of the flat portion produced can also improve the corrosion resistance of the manufactured portion and the edge surface, even if it is a chromium-free coating composition; the present invention also relates to a coated metal sheet obtained by using the coating composition.

Co-coated metal sheets coated by coil coating (such as pre-coated steel sheets) have been widely used in the field of residential related products, such as building materials for building structures, such as roofs, walls, shutters, garages, etc.; various household appliances ; inlaid board; freezer, steel furniture; kitchen utensils, etc.

Residential related articles are typically prepared from pre-coated metal sheets, for example, by the methods described below, which include cutting pre-coated steel sheets, followed by fabrication, such as compression molding and joining. Therefore, the house related articles usually have a metal exposed portion such as a cutting surface and a crack forming portion due to press molding. The corrosion resistance of the metal exposed portion and the crack-forming portion may be lowered as compared with other portions. In order to improve corrosion resistance, a primer coated film on a precoated steel sheet generally contains a chromium-based anticorrosive pigment.

However, the chromium-based anticorrosive pigment may contain or produce hexavalent chromium having excellent corrosion resistance, but it must be controlled for use from the viewpoint of human health and environmental protection.

Various chromium-free anticorrosive pigments such as zinc phosphate, aluminum tripolyphosphate, zinc molybdate, and the like are commercially available, and various primers containing a combination of a chromium-free pigment have been proposed. For example, Patent Reference 1 discloses a coating composition which is an anticorrosive pigment composition composed of a combination of calcium silicate and phosphorus vanadate, or a calcium carbonate, calcium silicate, aluminum phosphate, and phosphorus vanadate. The anticorrosive pigment composition composed of the combination is added to a carrier component composed of an epoxy resin and a phenol resin. Further, Patent Reference 2 discloses a coating composition which is an anticorrosive pigment composition composed of a combination of a magnesium dibasic magnesium phosphate and a calcined product of manganese oxide and vanadium oxide, or a calcination of calcium phosphate and vanadium oxide. The anticorrosive pigment composition composed of the product is obtained by adding it to a polyester resin. However, the coated film formed by the coating composition disclosed in Patent References 1 and 2 exhibits poor corrosion resistance, particularly in the production portion and the edge portion as compared with the coating composition prepared using the chromium-based pigment. Part of the corrosion resistance is unsatisfactory, and when a large amount of anti-corrosive pigment mixture is used, it often exhibits poor chemical resistance such as alkali resistance and acid resistance and poor water resistance. Therefore, the anti-corrosive pigment mixture disclosed in Patent References 1 and 2 is not sufficient to replace the chromium-based anticorrosive pigment when preparing the precoated metal sheet.

Patent Reference 3 discloses a coating composition prepared by adding cerium oxide microparticles having an oil absorption of 30 to 200 ml/100 g and a pore volume of 0.05 to 1.2 ml/g, and forming a glass transition. A hard coat film having a temperature in the range of 40 to 125 °C. However, the coating film formed by the coating composition disclosed in Patent Reference 3 exhibits some corrosion resistance, but exhibits poor corrosion resistance and poor performance as compared with the coating composition prepared using the chromium-based pigment. Chemical resistance, particularly in the edge portion, is not satisfactory.

Patent Reference 1: Japanese Licensed Publication No. 61001/99.

Patent Reference 2: Japanese Licensed Publication No. 199078/00.

Patent Reference 3: Japanese Licensed Open No. 129163/00.

One of the objects of the present invention is to provide a coating composition which, when applied to a coated metal sheet, can form a coating film which, in addition to other non-manufactured portions, can also exhibit excellent properties in the manufactured portion and the edge portion. Corrosion resistance, even a chromium-free coating composition; the object of the present invention also includes providing a coated metal sheet using the coating composition.

In order to solve the above problems faced by the prior art, the inventors conducted intensive research and found a coating composition containing a bisphenol epoxy resin and an acrylic resin modified with an aliphatic polybasic acid, a hardener, and an anti-corrosion agent. The corrosion pigment, when it is used for the coated metal sheet, can form a coating film having excellent corrosion resistance in the production portion and the edge portion, in addition to the coating film having excellent corrosion resistance in other non-manufactured flat portions.

That is, the present invention relates to:

"1. A corrosion-resistant coating composition comprising (A) a flexible organic-based modified bisphenol epoxy resin, which is 5 to 50% by weight of a flexible organic unit and 95 to 50% by weight a bisphenol epoxy resin obtained by reacting (B) a hardener and (C) a corrosion-resistant pigment, at least one selected from the group consisting of aliphatic polybasic acids having 4 to 36 carbon atoms, having -20 A group consisting of an acrylic resin having a glass transition temperature of 50 ° C and a polyester resin having a glass transition temperature of -20 to 50 ° C.

2. The corrosion-resistant coating composition according to item 1, wherein the resin (A) is a bisphenol epoxy resin which is an aliphatic polybasic acid having 4 to 36 carbon atoms and has a glass transition of -20 to 50 ° C The temperature of the acrylic resin is modified.

3. The corrosion-resistant coating composition according to item 1, wherein the aliphatic polybasic acid having 4 to 36 carbon atoms is a dimer acid.

4. The corrosion-resistant coating composition according to item 1. The hardener (B) is at least one crosslinking agent selected from the group consisting of an amine based resin, a phenol resin and an optional blocking polyisocyanate compound.

5. The corrosion-resistant coating composition of item 1, wherein the corrosion-resistant pigment (C) is a chromium-free anticorrosive pigment.

6. The corrosion-resistant coating composition of item 5. wherein the corrosion-resistant pigment comprises (1) at least one vanadium compound selected from the group consisting of vanadium pentoxide, calcium vanadate and ammonium metavanadate, and (2) at least one A cerium-containing compound selected from the group consisting of metal citrate and cerium oxide microparticles, and (3) a phosphate metal salt.

7. The corrosion-resistant coating composition according to Item 1, wherein the corrosion-resistant coating composition further comprises at least one epoxy resin selected from the group consisting of a secondary or tertiary amine group, and an acrylic acid having a secondary or tertiary amine group. Resin and resole phenolic resin.

8. A coated metal sheet having a hard coat film formed of the coating composition of item 1 on one or both sides of the surface of the metal sheet, the metal surface being subjected to a metal treatment method selected .

9. A coated metal sheet having a multilayer coating film comprising a hard coat film formed from a coating composition of item 1 on one or both sides of a surface of the metal sheet, the metal surface being applied A metal treatment method is selected, and a topcoat coating film formed on at least one side of the hardened coated film. ”

Specific embodiments of the invention may include:

"A. The corrosion-resistant coating composition of item 6, wherein the cerium-containing compound (2) is a metal cerate, and the metal is selected from the group consisting of calcium, magnesium and zinc.

B. The corrosion-resistant coating composition according to item 6, wherein the corrosion-resistant pigment (C) comprises (1) at least one vanadium compound selected from the group consisting of vanadium pentoxide, calcium vanadate and ammonium metavanadate, (2) At least one antimony-containing compound selected from the group consisting of metal citrate and cerium oxide microparticles, (3) a phosphate metal salt; and the vanadium compound (1) is a cerium-containing compound in the range of 3 to 50 parts by weight ( 2) is in the range of 3 to 50 parts by weight and the phosphate metal salt (3) is in the range of 3 to 50 parts by weight, and the compound (1), the compound (2) and the salt (3) The total amount is in the range of 10 to 150 parts by weight, based on the total solid content per 100 parts by weight of the resin (A) and the hardener (B), respectively.

C. The corrosion-resistant coating composition of item 1, wherein the coating composition further comprises at least one pigment component selected from the group consisting of titanium dioxide pigments and filler pigments.

D. The corrosion-resistant coating composition of item 1, the coating composition further comprising at least one selected from the group consisting of an ultraviolet absorber and an ultraviolet stabilizer. ”

Invention effect:

The present invention provides such a special effect that even a chromium-free anticorrosive pigment, when the coating composition of the present invention is used for a coated metal sheet, can form a coating film having excellent corrosion resistance in other non-manufactured flat portions. In addition, a coating film having excellent corrosion resistance can be formed in the production portion and the edge portion, although it is difficult to provide a chromium-free corrosion-resistant coating composition in this technical field.

The coated metal sheet coated with the hard coat film formed by the coating composition of the present invention exhibits excellent corrosion resistance in the non-manufactured flat portion, the manufactured portion, and the edge portion, and is resistant to corrosion by using chromate. The hardened coated film formed by the coating composition of the pigment (e.g., strontium chromate) has the same or better corrosion resistance.

The coated metal sheet is coated with the hard coat film formed by the coating composition of the present invention, and then coated with a top coat film formed on the hard coat film, which is manufactured in a non-manufactured flat portion. Both the portion and the edge portion exhibit excellent corrosion resistance. Coating the coating composition of the present invention on a metal sheet as a coated substrate, in addition to obtaining excellent corrosion resistance in other non-manufactured flat portions, excellent corrosion resistance can be obtained in the production portion and the edge portion, and such The metal sheet may be, for example, a galvanized steel sheet or a galvanized steel sheet such as an aluminum-zinc alloy steel sheet.

Preferred embodiments of the invention:

The coating composition of the present invention comprises a flexible organic element-modified bisphenol epoxy resin (A), a hardener (B), and a corrosion-resistant pigment mixture (C).

Flexible organic element modified bisphenol epoxy resin (A)

The flexible organic element-modified bisphenol epoxy resin (A) (hereinafter may be referred to as a modified resin (A)) in the coating composition of the present invention is a flexible organic element and a bisphenol ring. The resin obtained by the reaction of the oxyresin.

The flexible organic element is an organic element having a functional group reactive with a bisphenol epoxy resin and capable of plasticizing a bisphenol epoxy resin, at least one selected from the group consisting of fat having 4 to 36 carbon atoms. A polybasic acid, an acrylic resin having a glass transition temperature of -20 to 50 ° C, and a polyester resin having a glass transition temperature of -20 to 50 ° C.

The polyester resin may include an oil-free polyester resin, an oil-modified polyester resin, and a modified polyester resin such as a tamper-modified polyester resin, a urethane-modified polyester resin, or the like.

Such an aliphatic polybasic acid having 4 to 36 carbon atoms may include a saturated or unsaturated alicyclic polybasic acid having 4 to 36 carbon atoms, preferably 8 to 36 carbon atoms, for example, an alicyclic two a carboxylic acid such as hexahydroisodecanoic acid, hexahydropyridinic acid, hexahydrofurfuric acid, methyl hexahydrophthalic acid, methylhexahydropyridinic acid, Δ1-tetrahydrofurfuric acid, Δ2-tetrahydrofurfuric acid, Δ3-tetrahydrofurfuric acid, Δ4-tetrahydrofurfuric acid, Δ1-tetrahydrofurfuric acid, Δ1-tetrahydroisodecanoic acid, Δ2-tetrahydroisodecanoic acid, Δ3-tetrahydroisodecanoic acid, Δ4-tetrahydroiso Citrate, Δ1-tetrahydropyridinic acid, Δ2-tetrahydropyridinic acid, methyltetrahydrofurfuric acid, endo-tetrahydrofurfuric acid, methyl endamethylenetetrahydrofurfuric acid, hexachlorone tetra Hydroquinone or the like, and its anhydride; aliphatic dicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, sebacic acid, dodecanedioic acid, dodecanedicarboxylic acid, bisphenol Acid, pimelic acid, maleic acid, fumaric acid, itaconic acid, tridecanedioic acid, citraconic acid, chloro-maleic acid, dimer acid, etc., and anhydride thereof; A higher or higher aliphatic polybasic acid, such as hexahydrotrimellitic acid; lower carbon number Esters, such as methyl esters of these acids, ethyl esters and the like.

The acrylic resin used as the flexible organic unit in the preparation of the modified resin (A) may include an acrylic resin having a reactive group reactive with a bisphenol epoxy resin. Such an acrylic resin may include a modified acrylic resin such as a urethane modified acrylic resin. Such reactive groups may include carboxyl groups, amine groups, hydroxyl groups, and the like. Among them, a carboxyl group-containing acrylic resin is preferred.

The carboxyl group-containing acrylic resin may include a resin obtained by copolymerizing a carboxyl group-containing polymerizable unsaturated monomer with another polymerizable unsaturated monomer, which is subjected to a known method such as a solution polymerization method, a suspension polymerization method, The overall polymerization method or the like is preferably a solution polymerization method from the viewpoint of easiness of controlling the polymerization conditions. Other polymerizable unsaturated monomers may include (meth) acrylates. The amount of (meth) acrylate to be used is preferably in the range of 30 to 98% by weight based on the total amount of the monomers constituting the modified resin (A).

The carboxyl group-containing polymerizable unsaturated monomer may include, for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and the like.

Other polymerizable unsaturated monomers may include, for example, hydroxyl group-containing polymerizable unsaturated monomers such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)acrylic acid 4 - hydroxybutyl ester, (meth)acrylic acid tetrahydrofuran ester, ε-caprolactone modified (meth)acrylic acid tetrahydrofuran ester, ε-caprolactone modified (meth)acrylic acid hydroxyethyl ester, polyethylene glycol one ( Methyl) acrylate, polypropylene glycol mono(meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate, (meth)acrylic acid monohydroxyethyl phthalate or the like; alkyl (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (methyl) N-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octadecyl (meth)acrylate, (meth)acrylic acid Tridecyl ester, etc.; cycloalkyl (meth)acrylate, such as cyclohexyl (meth)acrylate; benzyl (meth)acrylate; phenyl (meth)acrylate; dialkylamine (meth)acrylate Alkyl esters such as (meth)acrylic acid Dimethylamine ethyl ester, diethylaminoethyl (meth)acrylate, etc.; an epoxy group-containing polymerizable unsaturated monomer such as glycidyl (meth)acrylate, methyl (meth)acrylate Glycidyl ester, allyl epoxidized ether, etc.; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyl toluene, etc.; acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate , acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, diacetone acrylamide, propylene fluorenyl porphyrin, N-vinyl-2 Pyrrolidone, γ-propyleneoxypropyltrimethoxysilane, γ-methylpropoxypropyltrimethoxysilane, vinyl chloride, propylene, ethylene, C ¹ -C ²⁰ -α-olefin, and the like. These can be used alone or in combination.

In the present patent application, "(meth)acrylate" means "acrylate or methacrylate".

From the viewpoint of compatibility and reactivity of the acrylic resin with the bisphenol epoxy resin, when the acrylic resin is synthesized by a solution polymerization method, it has a number average molecular weight of from 2,000 to 40,000, particularly Between 300 and 30,000.

In the present patent application, the number average molecular weight of the resin is determined by gel permeation chromatography (HLC8120GPC, trade name sold by Tosoh Corporation) and calculated based on the molecular weight of standard polystyrene. The value. The above measurements were carried out under the following conditions, that is, 4 columns: TSK gel G-4000HXL, TSK gel G-3000HXL, TSK gel G-2500HXL, and TSK gel G-2000HXL (sold by Tosoh Corporation) Product name); mobile phase: tetrahydrofuran; measuring temperature: 40 ° C, flow rate: 1 ml / min, sensor: RI.

From the viewpoint of reactivity and adhesion properties of the acrylic resin and the bisphenol epoxy resin, the acid value of the acrylic resin is 3 to 50 mg KOH/g, particularly 5 to 40 mg KOH/g; and the hardening ability of the coated film From the viewpoint of water resistance, the acrylic resin has a hydroxyl value of from 10 to 300 mgKOH/g, particularly from 30 to 250 mgKOH/g; and from the viewpoint of the balance between the properties of production and the hardness of the obtained coated film, The glass transition temperature (Tg) is -20 ° C to 50 ° C, preferably -20 ° C to 40 ° C. In the present patent application, the glass transition temperature (Tg) of the resin is determined by differential scanning calorimetry (DSC).

The polyester resin used as the flexible organic unit in the preparation of the modified resin (A) may include a polyester resin having a reactive group reactive with a bisphenol epoxy resin. Such a polyester resin may include an oil-free polyester resin, an oil-modified polyester resin, a tamper-modified polyester resin, and a urethane-modified polyester resin. Such reactive groups may include, for example, a carboxyl group, an amine group, a hydroxyl group, and the like. Among them, a carboxyl group-containing polyester resin is preferred.

Among these polyester resins, the oil-free polyester resin is prepared in accordance with a known method, such as a direct esterification method, an esterification exchange method, a ring opening method, and the like. Examples of the direct esterification method may include a method of performing a polycondensation reaction of a polybasic acid and a polyhydric alcohol. The polybasic acid as a main component may include, for example, at least one selected from the group consisting of phthalic anhydride, isophthalic acid, citric acid, succinic acid, adipic acid, fumaric acid, maleic anhydride, and tetra a dibasic acid of hydroquinone anhydride and hexahydrophthalic anhydride; a trivalent or higher polybasic acid such as trimellitic anhydride, methylcyclohexene tricarboxylic acid, pyromellitic anhydride, etc., and in addition to the above acid, A monobasic acid such as benzoic acid, crotonic acid, p-tert-butylbenzoic acid or the like may be optionally included. The polyol as a main component may include, for example, a glycol such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, and 1,4-hexanediol. 1,6-hexanediol, etc., and optionally in addition to the above alcohols, may include a trihydric or higher polyhydric alcohol such as glycerol, trimethylolethane, trimethylolpropane, pentaerythritol. Wait.

The carboxyl group-containing polyester resin can be produced according to a known method, which comprises reacting a polybasic acid and a polyhydric alcohol in the case where the acid group is excessive with respect to the hydroxyl group, or is, for example, trimellitic anhydride and decanoic anhydride. The polybasic acid of the class is subjected to a post addition reaction with a hydroxyl group of the hydroxyl group-containing polyester resin.

The oil-free polyester resin can also be produced by a polycondensation reaction caused by transesterification between a lower alkyl ester of a polybasic acid and a polyol. Further, such an oil-free polyester resin can also be produced by ring-opening polymerization of a lactone such as δ-valerolactone and ε-caprolactone.

This oil-modified polyester resin of a polyester resin is prepared by reacting an oil-free polyester resin with an oil fatty acid. Such oil fatty acids may include, for example, coconut oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, safflower oil fatty acid, pine oil fatty acid, anhydrous castor oil fatty acid, tung oil fatty acid, and the like. The reaction between the polyester resin and the fatty acid can be carried out in accordance with a known method, and its oil length is usually 30% or less.

The polyester resin has a weight average molecular weight in the range of from 1,000 to 30,000, particularly from 2,000 to 20,000, from the viewpoints of compatibility and reactivity of the polyester resin with the bisphenol epoxy resin. The polyester resin has an acid value of from 3 to 100 mgKOH/g, particularly from 5 to 70 mgKOH/g, from the viewpoints of reactivity and adhesion properties of the polyester resin and the bisphenol epoxy resin. The glass transition temperature (Tg) is from -20 ° C to 50 ° C, preferably from -20 ° C to 40 ° C from the viewpoint of the balance between the properties of the production and the hardness of the resulting coated film.

The bisphenol type epoxy resin used in the preparation of the modified resin (A) may include, for example, a resin in which epichlorohydrin and bisphenol are selectively present in the presence of a catalyst such as an alkali metal catalyst. The condensation reaction is carried out to have a high molecular weight; and a resin which selectively condenses epichlorohydrin and bisphenol in the presence of a catalyst such as an alkali metal catalyst to form a low molecular weight epoxy The resin is then subjected to addition polymerization of a low molecular weight epoxy resin and bisphenol.

The bisphenol epoxy resin has a number average molecular weight in the range of 350 to 5,000, particularly 400 to 4,000, and an epoxy group content of 0.5 to 15.4 mmol/g, preferably 0.8 to 10 m. Moor / gram.

Such bisphenols may preferably include bis(4-hydroxyphenyl)methane [bisphenol F], 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl). Propane [bisphenol A], 2,2-bis(4-hydroxyphenyl)butane [bisphenol B], bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-hydroxyl) Tributylphenyl)-2,2-propane, p-(4-hydroxyphenyl)phenol, bis(4-hydroxyphenyl)oxy, sulfonylbis(4-hydroxyphenyl), 4,4'- Dihydroxydiphenyl ketone, bis(2-hydroxynaphthyl)methane, and the like. Among them, bisphenol A and bisphenol F are preferably used. The above bisphenols may be used singly or in combination.

Examples of commercially available bisphenol type epoxy resins may include jER 828, 812, 815, 820, 834, 1001, 1004, 1007, 1009, 1010, 4004P, 4007P, 4210 (trade names, all of which are made of Japanese epoxy resin) Company sales); Araldite AER 6099 (trade name, sold by Asahi-Ciba); Epomik R-309 (trade name, sold by Mitsui Chemicals Co., Ltd.).

The method of obtaining the modified resin (A) by reacting the flexible organic element with the bisphenol epoxy resin is not particularly limited. For example, if two flexible organic motifs are used, the above method can include a method of simultaneously reacting two flexible organic motifs with a bisphenol epoxy resin; and a flexible organic motif and a bisphenol ring. The method in which the oxy resin is reacted and then reacted with the remaining flexible organic unit.

The above reaction is preferably carried out, for example, at a temperature of from 100 to 150 ° C for 1 to 5 hours in a solvent capable of simultaneously dissolving the two reactants, optionally in the presence of a reaction catalyst.

The reaction catalyst may include, for example, a quaternary salt catalyst such as tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium chloride, tetrabutylphosphonium bromide, triphenylbenzylhydrazine chloride, etc.; Classes such as triethylamine, tributylamine, and the like.

In the above reaction, if the reactive group of the flexible organic unit is a carboxyl group, the equivalent ratio of (epoxy group in the bisphenol epoxy resin) / (carboxy group in the flexible organic unit) is 10/1. In the range of 1/1, it is preferably 5/1 to 2/1. If an acrylic resin having a reactive group is reacted with an epoxy group different from a carboxyl group in the synthesis reaction of the modified resin (A), the "carboxy group in the flexible organic unit" is replaced by the above formula. In addition to the "reactive group reactive with a carboxyl group-free epoxy group", the equivalent ratio of the respective reactive groups is still in the range of the above formula.

In the preparation of the modified resin (A), the mixing ratio of the flexible organic group to the bisphenol epoxy resin is such that the flexible organic group is in the range of 5 to 50% by weight, preferably 10 to 40% by weight. And the bisphenol epoxy resin is in the range of 50 to 95% by weight, preferably 60 to 90% by weight, based on the total weight of the two reactants, respectively.

If a combination of an aliphatic polybasic acid and a flexible resin composed of an acrylic resin and/or a polyester resin is used as the flexible organic group in the preparation of the modified resin (A), a modified resin is prepared ( The mixing ratio of the aliphatic polybasic acid, the flexible resin and the bisphenol epoxy resin of A) is: the aliphatic polybasic acid is in the range of 1 to 30 parts by weight, preferably 3 to 20 parts by weight, and the flexible resin It is in the range of 1 to 49 parts by weight, preferably 7 to 37 parts by weight, and the bisphenol epoxy resin is in the range of 50 to 95 parts by weight, preferably 60 to 90 parts by weight. They are each based on 100 parts by weight of the total weight of the respective reactants.

If the epoxy group remains after the reaction between the flexible organic element and the bisphenol epoxy resin is completed, in order to block the residual epoxy group, the modified resin (A) and, for example, benzoic acid and salicylate may be used. A blocking agent such as an acid or a secondary amine compound is reacted. In this case, it is possible to react with the blocking agent during the reaction between the flexible organic element and the bisphenol epoxy resin.

The modified resin (A) has a flexible element in the molecular structure, and thus can participate in the development of stress relaxation, the manufacture of the production part, and the improvement of the adhesion property in the crosslinked coated film, and the high corrosion resistance of the resulting coated film. which performed.

Hardener (B)

The hardener (B) is reacted with the modified resin (A) to form a hardened coating film, and may include a substance which can be hardened by reacting with the modified resin (A) (for example, by heating without particular limitation) . Among them, an amine-based resin, a phenol resin, and an optional blocking polyisocyanate compound are preferred. These hardeners may be used singly or in combination.

The amine-based resin may include a methylolamine group obtained by reacting an aldehyde with an amine component such as melamine, urea, benzoguanamine, acetamide, stearylamine, spiramide, dicyandiamide or the like. Resin. The aldehyde used in the above reaction may include formaldehyde, trioxane, acetaldehyde, benzaldehyde or the like. The amine-based resin may also include an amine-based resin obtained by etherifying a methylolamine-based resin with a suitable alcohol. Examples of the alcohol used in the etherification reaction may include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-ethylbutanol, 2-ethylhexanol, and the like.

The phenol resin used as a hardener is reacted and crosslinked with the modified resin (A), and may include, for example, a resol resin which is heated and the phenol component and formaldehyde are present in the reaction catalyst. In the case where a condensation reaction is carried out to introduce a methylol group, and then at least a part of the methylol group of the obtained methylol phenol resin is subjected to alkyl etherification reaction with an alcohol.

The phenol component used as a starting material in the preparation of the resol resin may include a bifunctional phenol compound, a trifunctional phenol compound, and a tetra- or higher-functional phenol compound.

Such a phenolic compound may include, for example, a bifunctional phenol compound such as o-cresol, p-cresol, p-tert-butylphenol, p-acetol, 2,3-indophenol, 2,5-fluorene. a phenol or the like; a trifunctional phenol compound such as phenol, m-cresol, m-ethylphenol, 3,5-nonanol, m-methoxyphenol, etc.; a tetrafunctional phenol compound such as bisphenol A, bisphenol F, etc. . For the purpose of improving scratch resistance, among them, a trifunctional or higher phenol compound is preferred, particularly phenol and/or m-cresol. These phenol compounds may be used singly or in combination.

Formaldehydes which can be used to prepare phenol resins may include formaldehyde, trioxane, and tris Alkanes and the like, and they may be used singly or in combination.

The alcohol used in the partial alkyl etherification of the methylol group in the methylol phenol resin is preferably a monohydric alcohol having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. In particular, methanol, ethanol, n-propanol, n-butanol, isobutanol and the like.

From the viewpoint of reactivity with the modified resin (A), the phenol resin has an average number of alkoxymethyl groups per benzene ring of 0.5 or more, preferably 0.6 to 3.0.

The non-blocking polyisocyanate compound used in the blocking polyisocyanate compound for use in the hardener may include an organic diisocyanate such as an aliphatic diisocyanate such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate or the like; An alicyclic diisocyanate such as hydrogenated didecyl diisocyanate, isophorone diisocyanate or the like; and an aromatic diisocyanate such as toluene diisocyanate, decyl diisocyanate, 4,4'-diphenylmethane diisocyanate, Crude MDI or the like; an adduct of these organic diisocyanates with a polyhydric alcohol, a low molecular weight polyester resin, water or the like; a cyclic polymer between the above organic diisocyanates; an isocyanate biuret or the like.

The blocked polyisocyanate compound which can be used as a crosslinking agent is a compound obtained by blocking a free isocyanate group in the polyisocyanate compound by a blocking agent. The blocking agent for blocking the isocyanate group may include, for example, phenols such as phenol, cresol, indophenol; indoleamine such as ε-caprolactam, δ-valeroside, γ- Butanolamine, etc.; alcohols such as methanol, ethanol, n-, iso- or tert-butyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol mono Ether, benzyl alcohol, etc.; anthraquinones such as formamide, acetaldoxime, acetone oxime, methyl ethyl ketone oxime, butanone oxime, diphenyl ketone oxime, cyclohexanone oxime, etc.; and active methylene Substances such as dimethyl malonate, diethyl malonate, ethyl acetate, acetone, and the like. By mixing the polyisocyanate compound with a blocking agent, the free isocyanate group in the polyisocyanate compound can be easily blocked.

The amount of the modified resin (A) and the hardener (B) should be such that the amount of the modified resin (A) is 55 to 95 parts by weight from the viewpoints of corrosion resistance, boiling water resistance, manufacturing properties, hardening properties, and the like. The range of the number is preferably 60 to 95 parts by weight, and the hardener (B) is in the range of 5 to 45 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight. The total solids content of ingredients (A) and (B) is based on the basis.

In order to promote the hardening reaction of the coating composition, a hardening catalyst may be selectively used, and may be arbitrarily selected, depending on the kind of the hardener to be used.

If the hardener (B) is an amine based resin, in particular an etherified melamine resin mixed with methyl etherified or methyl ether-butyl ether, the hardening catalyst is an amine neutralized product comprising a sulfonic acid compound and a sulfonic acid compound. It is better. Typical examples of the sulfonic acid compound may include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalene disulfonic acid, and the like. The amine used in the amine neutralizing product of the sulfonic acid compound may include a primary amine, a secondary amine, and a tertiary amine. From the viewpoints of stability of the coating composition, promotion of the reaction effect, properties of the obtained coating film, and the like, among them, an amine neutralized product of p-toluenesulfonic acid and/or an amine neutralized product of dodecylbenzenesulfonic acid is preferred. .

If the hardener (B) is a phenol resin, the hardening catalyst may include an amine neutralized product of a sulfonic acid compound and a sulfonic acid compound.

If the hardener (B) is a blocking polyisocyanate compound, it is preferred to have a hardening catalyst which promotes dissociation of the blocking agent of the polyisocyanate compound as a hardening agent. Examples of preferred hardening catalysts may include organometallic catalysts such as tin zincate, dibutyltin di(2-ethylhexanoate), dioctyltin di(2-ethylhexanoate), dioctyltin. Diacetate, dioctyltin dilaurate, dibutyltin oxide, dioctyl tin oxide, lead 2-ethylhexanoate, and the like.

If the hardener is a combination of two or more hardeners, the hardener can include a combination of individual hardeners that can be effective for each hardener.

Anti-corrosion pigment (C)

The anticorrosive pigment may include a chromium-based pigment and a chromium-free pigment, which must exhibit corrosion-resistant properties, and is preferably a chromium-free anticorrosive pigment from the viewpoint of human health and environmental protection.

The chromium-based anticorrosive pigment may include, for example, strontium chromate, zinc chromate, potassium zinc chromate, strontium chromate, chromic chromate, chromic phosphate, and the like.

The chromium-free anticorrosive pigment may include, for example, zinc phosphate, aluminum tripolyphosphate, zinc molybdate, calcium citrate, vanadium pentoxide, calcium vanadate, ammonium metavanadate, phosphorus vanadate, aluminum phosphate, calcium phosphate, A calcined product of magnesium hydrogen phosphate, calcium oxide and vanadium oxide, cerium oxide microparticles having an oil absorbance of 30 to 200 ml/100 g and a pore volume of 0.05 to 1.2 ml/g. These anti-corrosion pigments may be used singly or in combination.

Among the above chromium-free anticorrosive pigments, as described below, a combination of (1) a vanadium compound, (2) a ruthenium-containing compound, and (3) a phosphate-based metal salt is particularly suitable for use in the coating composition of the present invention. .

Vanadium compound (1)

The vanadium compound (1) may include at least one vanadium compound selected from the group consisting of vanadium pentoxide, calcium vanadate, and ammonium metavanadate. The vanadium pentoxide, calcium vanadate and ammonium metavanadate can exhibit excellent elutriation properties of pentavalent vanadium ions in water, and the pentavalent vanadium ion released from the vanadium compound (1) can effectively improve corrosion resistance. This is due to its reaction with the substrate metal or with the reaction of ions from other anti-corrosion pigment mixtures.

Compound compound (2)

The ruthenium-containing compound (2) is at least one ruthenium-containing compound selected from the group consisting of metal ruthenate and ruthenium dioxide particles.

The metal citrate is a salt composed of cerium oxide and a metal oxide, and may include a decanoic acid salt, a polyphthalic acid salt or the like. Such bismuth salts may include, for example, zinc phthalate, aluminum ruthenate, aluminum n-decanoate, aluminum hydrated aluminum citrate, calcium aluminum citrate, aluminum citrate, strontium aluminum citrate, sodium citrate, n-decanoic acid. Calcium, calcium metasilicate, sodium calcium citrate, zirconium silicate, magnesium orthosilicate, magnesium metasilicate, calcium magnesium citrate, manganese citrate, barium strontium silicate, olivine, garnet, vermiculite, Heterogeneous ore, blue cone, column, star, beryl, diopside, ash, rhodochro, tremolite, hard strontium, talc, fisheye, aluminosilicate, borosilicate, Citrate, feldspar, zeolite, etc.

The metal citrate (2) preferably comprises calcium orthosilicate and calcium metasilicate.

The cerium oxide microparticles may include any of the cerium oxide microparticles, and are not particularly limited, and, for example, cerium oxide microparticles which have not been surface-treated, cerium oxide microparticles which are surface-treated with an organic substance, calcium ion-exchanged cerium oxide microparticles, Organic solvent dispersible colloidal cerium oxide or the like.

The surface-treated ceria particles or the organic substance surface-treated ceria particles may include ceria particles having an average particle diameter of 0.5 to 15 μm, preferably 1 to 10 μm, and an organic solvent dispersible. Colloidal cerium oxide. Such cerium oxide microparticles preferably comprise cerium oxide microparticles having an oil absorbance of 30 to 350 ml / 100 g (more preferably 30 to 150 ml / 100 g). The trade name may include, for example, Sylysia 710, Sylysia 740, Sylysia 550, Aerosil R972 (trade name, sold by Fuji Sylysia Chemical Co., Ltd., respectively), MIZUKASIL (trade name, sold by Mizusawa Chemical Industry Co., Ltd.), Gasil 200DF (trade name, sold by Crosfield Chemicals), etc. Calcium ion-exchanged ceria particles are ceria particles obtained by ion exchange of calcium ions onto a fine porous ceria support. A trade name of calcium ion-exchanged ruthenium dioxide, for example, SHIELDEX (trademark) C303, SHIELDEX AC-3, SHIELDEX AC-5 (sold by W.R. Grace Co., Ltd., etc.). Calcium ions released by calcium ion exchange of ceria can participate in electrochemical action and various salt formation effects, and can effectively improve corrosion resistance. The cerium oxide fixed in the coated film can effectively control the peeling of the coated film in a corrosive environment. The organic solvent dispersible colloidal cerium oxide may be an organic cerium oxide sol, and is stably dispersed in an organic solvent such as an alcohol, a glycol, an ether or the like to have a particle diameter of about 5 to 120 Å. Rice cerium oxide particles. The trade name may include, for example, an OSCAL series (trade name, sold by Nisshin Touch Chemical Co., Ltd.), ORGANO SOL (trade name, sold by Nissan Chemical Industries Co., Ltd.), and the like. Among them, calcium ion exchange-cerium oxide particles are preferred.

The various metal silicates and cerium oxide particles as the cerium-containing compound (2) may be used singly or in combination.

Phosphate metal salt (3)

The phosphate metal salt (3) may include at least one phosphate metal salt selected from the group consisting of a metal phosphate, a metal hydrogen phosphate, and a metal phosphate, and the metal in each metal salt is calcium, zinc, aluminum. Or magnesium.

The phosphate metal salt may include, for example, calcium phosphate, calcium ammonium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, calcium chlorohydrate, zinc phosphate, aluminum phosphate, magnesium phosphate, zinc hydrogen phosphate, aluminum phosphate, magnesium phosphate. , aluminum hydrogen phosphate, magnesium hydrogen phosphate, magnesium ammonium phosphate, aluminum dihydrogen phosphate, and the like. From the viewpoint of corrosion resistance, calcium phosphate, calcium monohydrogen phosphate and calcium dihydrogen phosphate are preferred.

Phosphate ions and metal ions (such as calcium ions, zinc ions, aluminum ions, and magnesium ions) which are respectively released from the phosphate metal salt (3) can effectively improve corrosion resistance.

In the coating composition of the present invention, the anticorrosive pigment (C) contains (1) at least one vanadium compound selected from vanadium pentoxide, calcium vanadate and ammonium metavanadate, and (2) at least one ruthenium-containing compound. , which is selected from the group consisting of metal citrate and cerium oxide microparticles, (3) a phosphate metal salt; and the vanadium compound (1) is in the range of 3 to 50 parts by weight, and the cerium-containing compound (2) is In the range of 3 to 50 parts by weight and the phosphate metal salt (3) is in the range of 3 to 50 parts by weight, and the total amount of the compound (1), the compound (2) and the salt (3) is In the range of 10 to 150 parts by weight, preferably 15 to 90 parts by weight, based on the total solid content of the resin (A) and the hardener (B) per 100 parts by weight, respectively.

In the coating composition of the present invention, the anticorrosive pigment composition in which the compound (1), the compound (2) and the metal salt (3) are combined in each of the specified amounts can synergistically enhance the improvement of the corrosion resistance.

The coating composition of the present invention may optionally contain, in addition to the modified resin (A), the hardener (B), the anticorrosive pigment (C), and the selectively used hardening catalyst, a field known to be useful for coating compositions. Adhesives, color pigments, filler pigments, UV absorbers, UV stabilizers, organic solvents; additives, such as anti-settling agents, defoamers, coating surface control agents.

Such tackifiers may include epoxy resins containing secondary or tertiary amine groups and acrylic resins containing secondary or tertiary amine groups. As explained in the hardener (B), the resol resin can also be used as a tackifier.

The resin containing a secondary or tertiary amine group is a resin having an epoxy resin backbone and a secondary or tertiary amine group, and the epoxy resin backbone may include a bisphenol epoxy resin backbone, a phenolic epoxy backbone, and the like.

The epoxy resin containing a secondary or tertiary amine group can be obtained, for example, by adding an amine compound to an epoxy group such as a glycidyl group to introduce a secondary or tertiary amine group. From the viewpoint of the reactivity of the epoxy resin with the amine compound, the epoxy resin preferably has 200 to 1000 epoxy equivalents, and preferably includes a bisphenol epoxy resin and a novolac epoxy resin.

If a bisphenol epoxy resin is used, an epoxy resin having a secondary or tertiary amine group at the resin backbone or at the terminal group can be made of a bisphenol epoxy resin having 400 to 1000 epoxy equivalents with one or three The amine compound is obtained by reaction. If a phenolic epoxy resin is used, since a phenolic epoxy resin having 200 to 500 epoxy equivalents is usually used, and its reaction with the primary amine compound can cause gelation easily at the time of preparation, the novolac epoxy resin is more preferable. The reaction is carried out with a secondary amine compound such as N-methylethanolamine, diethanolamine or the like to obtain a novolac epoxy resin having a high secondary or tertiary amine group content.

The amino group-containing acrylic resin may include, for example, acrylic acid obtained by reacting an acrylic resin produced by copolymerization of an epoxy group-containing acrylic monomer such as glycidyl methacrylate with a primary or secondary liquid compound. a resin, and a acrylate or methacrylate monomer containing a tertiary amino group (such as N,N-dimethylaminoethyl (meth) acrylate and N,N-dimethylaminopropyl (methyl) An acrylic resin formed by copolymerization of acrylate).

Among the above-mentioned tackifiers (D), an epoxy resin is preferred from the viewpoint that the coating film requires toughness due to scratch resistance, but from the viewpoint of water resistance and chemical resistance, Acrylic resin is preferred. Two or more kinds of adhesives may be selectively used in combination.

The color pigments may include, for example, organic color pigments such as cyanine blue, cyanine green; organic red pigments such as azo pigments and quinacridone pigments; inorganic color pigments titanium white, titanium yellow, erythritol oxide, carbon black And various calcined pigments, of which titanium white is preferred.

The filler pigment may include, for example, talc, clay, mica, alumina, calcium carbonate, barium sulfate, and the like.

The ultraviolet absorber may include, for example, a benzotriazole derivative such as 2-(2-hydroxy-3,5-di-p-pentylphenyl)-2H-benzotriazole, isooctyl-3-( 3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate, 2-[2-hydroxy-3,5-di(1,1-di) Methyl petroleum ether) phenyl]-2H-benzotriazole, 2-[2-hydroxy-3-dimethylbenzyl-5-(1,1,3,3-tetramethylbutyl)phenyl -2H-benzotriazole, methyl-3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate and polyethylene a condensation product of alcohol 300, etc.; a triazine derivative such as 2-[4-(2-hydroxy-3-dodeoxypropyl)oxy]-2-hydroxyphenyl-4,6-bis (2,4) - dimethylphenyl)-1,3,5-1,3,5-triazine, etc.; aniline oxalic acid derivatives such as ethylenediamine-N-(2-ethoxyphenyl)-N'-( 2-ethylphenyl)-(oxalylamine), ethanediamine-N-(2-ethoxyphenyl)-N'-(4-isododecylphenyl)-(pezamide), etc. .

The UV stabilizer may include, for example, a hindered amine compound, a hindered phenol compound; CHIMASORB 944, TINUVIN 144, TINUVIN 292, TINUVIN 770, IRGANOX 1010, IRGANOX 1098 (trade names, respectively sold by Ciba Specialty Products Co., Ltd. ),and many more.

The addition of the ultraviolet absorber and the ultraviolet stabilizer to the coating composition allows it to control the surface degradation of the coated film, and when such a coating composition is used as a primer coating composition, it can be made The surface of the primer coating film can be controlled to be degraded by the light reaching the surface of the primer coating film through the topcoat, and the interlayer paint between the primer coating film and the topcoat film can be prevented from being peeled off due to surface degradation of the primer coating film, and can be maintained. Excellent corrosion resistance.

The organic solvent used for the coating composition of the present invention may include an organic solvent which is selectively added in order to improve the coating property of the coating composition of the present invention; a film-forming resin (A) capable of dissolving or dispersing a hydroxyl group and a crosslinking agent (B) An organic solvent, particularly, for example, a hydrocarbon solvent such as toluene, xylene, a hydrocarbon having a high boiling point petroleum, etc.; a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or the like Fosone and the like; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, etc.; alcohol solvents such as methanol, ethanol, isopropanol, Butanol or the like; an ether alcohol solvent such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether or the like. These solvents may be used singly or in combination.

The coating composition of the present invention may have a glass transition temperature of the cured coating film obtained from the composition of the present invention in the range of 40 to 115 ° C, preferably 50 to 50, from the viewpoints of corrosion resistance, acid resistance, manufacturing properties, and the like. 105 ° C. In the present invention, the glass transition temperature of the coated film is the maximum temperature measured by the temperature dispersion, and the dynamic viscoelasticity measuring instrument (automatic viscoelasticity measuring instrument) model Vibron DDV-II EA is used. , sold by TOYO BALDWIN Co., Ltd.) Measurements were carried out at a frequency of 110 Hz.

The coating composition of the present invention is coated on a metal sheet, and the resulting coated film can exhibit excellent corrosion resistance because the resin element in the coating composition of the present invention has excellent stress relaxation properties and can It is formed into a coated film which has an excellent balance between the elastic modulus and the tensile modulus.

Coated metal sheet

The coated metal sheet of the present invention has a coating film formed by coating the coating composition of the present invention on a metal sheet as a substrate and then hardening it.

The metal sheet used as the substrate may include cold rolled steel sheets, hot dip galvanized sheets, electrogalvanized sheets, iron-zinc alloy steel sheets (galvanized annealed steel sheets), and aluminized-zinc alloy steel sheets ("galvalume" Steel sheet", containing about 55% aluminum in the alloy, "galfan", containing about 5% aluminum in the alloy, etc.), nickel-zinc alloy steel sheet, stainless steel sheet, aluminum sheet, copper sheet, copper plated steel Sheet, tin plated steel sheet, etc. These metal sheets can be selectively subjected to conventional metal surface treatment methods, for example, phosphate treatment methods such as zinc phosphate treatment, iron phosphate treatment, composite oxide film treatment, chromium phosphate treatment, chromic acid Salt treatment methods, etc.

The coating composition of the present invention can be applied to a metal sheet by a conventional coating method such as a roll coating method, a curtain coating method, a spray coating method, a brush coating method, a dip coating method, or the like. The film thickness of the coating film formed from the coating composition of the present invention is not particularly limited, but is usually in the range of 2 to 10 μm, preferably 3 to 6 μm. The drying of the coated film can be carried out under appropriate conditions, but if the coated film formed by the coil coating method is continuously thermally cured, it can usually be carried out at a maximum substrate temperature of 160 to 250 ° C, preferably 180 to 230 ° C. Heat hardened for 15 to 60 seconds. In the batch method, heat hardening can usually be carried out at an ambient temperature of 80 to 200 ° C for 10 to 30 seconds.

If heating is not required in the crosslinking reaction for forming the coating film, for example, if it is used as the hardener (B) as a non-blocking polyisocyanate compound, drying can be carried out at room temperature under hardening according to a conventional method.

The coated metal sheet of the present invention may comprise a metal sheet which is formed of a coating film only on the surface-treated metal sheet selected from the coating composition of the present invention, and may also include a metal sheet having a top coat film on the above-mentioned coated film. The film thickness of the topcoat film is in the range of 8 to 30 μm, preferably 10 to 25 μm.

The topcoat composition forming the topcoat film may include a topcoat composition conventionally used for precoating a metal sheet, for example, a polyester resin type, an alkyd resin type, a tamper type polyester resin type, a tamper type acrylic resin A fluorocarbon resin topcoat composition. If the manufacturing properties are quite important, a coated metal sheet having particularly good manufacturing properties, such as a polyester resin topcoat composition, can be obtained using a topcoat composition having good manufacturing properties. The coated metal sheet having the above-mentioned topcoat film in the present invention exhibits a good film function in terms of corrosion resistance.

In this technical field, for galvanized steel sheets and aluminized-zinc alloy steel sheets, the corrosion resistance in the non-manufactured flat portion has been improved to some extent, but the corrosion resistance at the surface portion of the cutting edge and the manufacturing portion is improved. Sex is not satisfactory. Conversely, coating the coating composition of the present invention provides excellent corrosion resistance at the edge surface portion and the manufactured portion.

The coated film from the coating composition of the present invention may be simultaneously formed on both sides of the substrate, and the top coat film may be selectively formed on the coated film from the coating composition of the present invention. If a chromium-free anticorrosive pigment is used as the anticorrosive pigment in the coating composition of the present invention, the coated film formed from the coating composition of the present invention can obtain a coated metal sheet containing no chromium-based anticorrosive pigment, and also Conducive to environmental protection and health, and can show excellent corrosion resistance.

Example

The invention will be explained in more detail with reference to the following Preparation Examples and Examples. The invention should not be limited to the following examples. Hereinafter, "parts" and "%" mean "parts by weight" and "% by weight", respectively.

Synthesis Example 1 Preparation of Flexible Acrylic Resin AC1 Solution

In a reactor equipped with a stirrer, a condenser, a thermometer, a nitrogen inlet, and a drooling device, 65.0 parts of SWASOL 1000 (trade name, sold by Maruzen Petrochemical Company, a high-boiling aromatic petroleum solvent) was charged, followed by stirring. At the same time, the temperature in the reactor was raised to between 110 ° C, and a mixture of the following starting materials containing the monomers was added dropwise over a period of 3 hours while maintaining the temperature at 110 ° C.

Styrene 18.4 parts

Methyl methacrylate 31.2 parts

N-butyl acrylate 37.5 parts

2-hydroxyethyl acrylate 11.0 parts

Acrylic 1.9 parts

2,2'-azobisisobutyronitrile 1.7 parts

After complete dropwise addition, 0.5 part of 2,2'-azobisisobutyronitrile was added, followed by reaction at this temperature for 2 hours, and 35.0 parts of cyclohexanone was added to obtain a flexibility of 50% solids. Acrylic resin AC1 solution. The acrylic resin AC1 solution had an acid value of 15 mg KOH/g, a hydroxyl value of 53 mg KOH/g, a glass transition temperature of 5 ° C and a number average molecular weight of about 10,000.

Synthesis Example 2-10

The procedure of Preparation Example 1 was repeated except that the monomer compositions shown in the formulations in Table 1 were used to obtain flexible acrylic resins AC2 to AC10 having a solid content of 50%, respectively.

Synthesis Example 11

A mixture of the following starting materials was placed in a reactor equipped with a stirrer, a heater, a thermometer, a separator, and a distillate storage container, followed by heating.

Neopentyl glycol 105 parts

1,6-hexanediol 354 parts

Hexahydrophthalic anhydride 564 parts

Adipic acid 123 parts

After the heating was started, the stirring was started, the stirring was started while the condensate was discharged, and the temperature was raised to 240 ° C, and then the reaction was further carried out at this temperature, and after the water was stopped for 1.5 hours, 40 parts were charged. Xylene was used to promote the reaction, and further dehydrogenation condensation was carried out until the acid value became 52, which was allowed to cool, and 417 parts of cyclohexanone for dilution was added to obtain a polyester resin PE1 solution having a solid content of 70%. The number average molecular weight of the polyester resin PE1 was 2,100.

Synthesis Examples 12-15

The procedure of Example 11 was repeated except that the formulation shown in Table 1 was used to obtain flexible polyester resins PE2 to PE5. The formulations shown in Table 1 represent the weight.

Preparation Example 1 Preparation of modified bisphenol epoxy resin ME1 solution:

In a flask equipped with a stirrer, a condenser and a thermometer, 60 parts of cyclohexanone and 90 parts of jER 1007 (trade name, bisphenol A epoxy resin sold by Nippon Epoxy Co., Ltd., epoxy equivalent) were placed. 1800), followed by heating to 130 ° C and completely dissolving the epoxy resin to obtain an epoxy resin solution having a solid content of 60%. 150 parts of an epoxy resin solution having a solid content of 60%, 20 parts of a 50% flexible acrylic resin AC1 obtained by Synthesis Example 1 (10 parts by solid content), and 0.5 part of tetraethylammonium bromide The reaction was carried out at 130 ° C for 3 to 4 hours, and it was confirmed that the acid value of the resin was 1 or less, and a mixed solvent 1 [cyclohexanone / SWASOL 1000 (trade name, sold by Maruzen Petrochemical Co., Ltd., high-boiling aromatic petroleum solvent) was added. = 1/2 (weight ratio)] to obtain a resin solution ME1 having a solid content of 40%.

Preparation Examples 2-37 (Preparation Examples 29-37 are provided for comparison)

The procedure of Example 1 was repeated except that the formulation shown in Table 2 was used to obtain a modified bisphenol epoxy resin ME2-37 solution having a solid content of 40%, respectively. The formulations shown in Table 2 represent the weight. The dissolution of the epoxy resin was carried out in the same manner as in Production Example 1, except that the epoxy resin solution having a solid content of 60% was respectively obtained by using the kinds and amounts of epoxy resins as shown in Table 2, respectively. .

The polyester resin PE6 used in Preparation Examples 34 and 37 represents ER-8101 (trade name, sold by Unitika, polyester resin, acid value of about 62, glass transition temperature of about 64 ° C, number average molecular weight of about 2,000) .

The (Note 1) to (Note 5) shown in Table 2 are explained below.

(Note 1) jER 1007: Trade name, sold by Japan Epoxy Resin Co., Ltd., bisphenol A epoxy resin, epoxy equivalent of about 1800).

(Note 2) jER 4007P: Trade name, sold by Japan Epoxy Resin Co., Ltd., bisphenol F epoxy resin, epoxy equivalent of about 2270).

(Note 3) jER 1004: Trade name, sold by Japan Epoxy Resin Co., Ltd., bisphenol A epoxy resin, epoxy equivalent of about 925).

(Note 4) jER 4004P: trade name, sold by Japan Epoxy Resin Co., Ltd., bisphenol F epoxy resin, epoxy equivalent of about 880).

(Note 5) jER 1001: Trade name, sold by Japan Epoxy Resin Co., Ltd., epoxy equivalent of approximately 475).

Preparation Example 38 Preparation of Resole Phenolic Resin D1 Solution:

The reactor was charged with 100 parts of p-cresol, 178 parts of 37% aqueous formaldehyde solution and 1 part of sodium hydroxide, followed by reaction at 60 ° C for 3 hours, dehydration under vacuum at 50 ° C for one hour, and 100 parts were added. N-butanol and 3 parts of phosphoric acid were reacted at 110 to 120 ° C for 2 hours, and the resulting solution was filtered, and the obtained sodium phosphate was filtered off to obtain a resol-type phenol resin crosslinking agent solution D1 having a solid content of about 50%. The number of the resins obtained as above was an average molecular weight of 880, and each of the benzene rings had an average of 0.4 methylol groups and an average of 1.0 alkoxymethyl groups.

Preparation Example 39 Preparation of Resole Phenolic Resin D2 Solution:

The reactor was charged with 100 parts of carbolic acid, 178 parts of 37% aqueous formaldehyde solution and 1 part of sodium hydroxide, followed by reaction at 60 ° C for 3 hours, dehydration under vacuum at 50 ° C for one hour, and addition of 100 parts of n-butanol. And 3 parts of phosphoric acid, the reaction was carried out at 110 to 120 ° C for 2 hours, the resulting solution was filtered, and the obtained sodium phosphate was filtered off to obtain a resol phenol resin crosslinking agent solution D2 having a solid content of about 50%. The number of the resins obtained as above was an average molecular weight of 880, and each of the benzene rings had an average of 0.4 methylol groups and an average of 1.0 alkoxymethyl groups.

Preparation Example 40 Preparation of amine-containing epoxy resin D3 solution:

In a reactor equipped with a stirrer and a heating temperature control device, 65 parts by weight of a methoxybutyl acetate solvent and 35 parts by weight of jER 1002 (trade name, sold by Nippon Epoxy Co., Ltd., bisphenol A epoxy) were charged. Resin, epoxy equivalent 650) and 1.09 parts by weight of 2-aminoethanol, followed by reaction at 90 ° C for 2 hours under stirring in a nitrogen atmosphere, adding 1.89 parts by weight of diethanolamine, and reacting at 90 ° C It was diluted for 1 hour and diluted with a methoxybutyl acetate solvent to obtain an amine-containing epoxy resin D3 solution having a solid content of about 35%.

Preparation Example 41 Preparation of amine-containing epoxy resin D4 solution:

In a reactor equipped with a stirrer and a heating temperature control device, 65 parts by weight of methoxybutyl acetate solvent and 35 parts by weight of Araldite ECN 1299 (trade name, sold by Asahi Kasei Chemicals Co., Ltd., cresol novolac ring) were charged. Oxygen resin, epoxy equivalent 225) and 5.83 parts by weight of N-methylethanolamine, followed by reaction at 80 ° C for 2 hours under stirring in a nitrogen atmosphere, adding 1.89 parts by weight of diethanolamine at 90 ° C The reaction was carried out for 1 hour, and diluted with a methoxybutyl acetate solvent to obtain an amine-containing epoxy resin D4 solution having a solid content of about 35%.

Preparation Example 42 Preparation of Amino Acrylic Resin D5 Solution:

In a reactor equipped with a stirrer and a heating temperature control device, 40 parts of propylene glycol monomethyl ether was charged, followed by heating at 90 ° C under a nitrogen atmosphere, and 50 parts of styrene and 50 parts of methacrylic acid were added over a period of 3 hours. A mixed solution of glycidyl ester, 1 part of 2,2'-azobisisobutyronitrile and 10 parts of propylene glycol monomethyl ether was dropped into a reactor at 90 ° C, and 0.2 part of AIBN was added thereto, and the reaction was carried out at this temperature. Minutes, and 50 parts of propylene glycol monomethyl ether were added to obtain an acrylic resin solution having a solid content of 50%.

In a separate reactor equipped with a stirrer and a heating temperature control device, 200 parts of the previously obtained acrylic resin solution having a solid content of 50% was charged, followed by heating at 85 ° C with stirring for 30 minutes. A mixed solution of 26.4 parts of N-methylethanolamine and 53.6 parts of propylene glycol monomethyl ether was dropped into the reactor, the reaction was carried out at this temperature for 5 hours, and 36 parts of propylene glycol monomethyl ether was added to obtain a solid content of 40%. Acryl-containing acrylic resin D5 solution.

Preparation Example 43 Preparation of Amino Acrylic Resin D6 Solution:

In a reactor equipped with a stirrer and a heating temperature control device, 40 parts of propylene glycol monomethyl ether was charged, followed by heating at 90 ° C under a nitrogen atmosphere, and 50 parts of styrene and 30 parts of ethyl acrylate were added over a period of 3 hours. 20 parts of a mixture solution of N,N-dimethylamine ethyl acrylate, 1 part of 2,2'-azobisisobutyronitrile and 10 parts of propylene glycol monomethyl ether was dropped into a reactor at 90 ° C, and 0.2 was added. A portion of AIBN was reacted at this temperature for 30 minutes, 0.2 part of 2,2'-azobisisobutyronitrile was added, reacted for 3 hours, and 100 parts of propylene glycol monomethyl ether was added to obtain a solid content of 40%. Amino acrylic resin D6 solution.

Preparation Example 44 Preparation of the coating composition for the back side:

80 parts of jER 1009F (trade name, bisphenol A epoxy resin sold by Nippon Epoxy Co., Ltd., epoxy equivalent of about 2000) was dissolved in 120 parts of mixed solvent 2 [cyclohexanone / ethylene glycol monobutyl ether / Swasol 200 parts of epoxy resin solution prepared in 1500 (trade name, sold by Maruzen Petrochemical Company, high boiling point aromatic hydrocarbon solvent) = 3/1/1 (weight ratio)] and 40 parts of titanium white, 40 parts of helium oxygen a pigment mixture is dispersed in a mixture of a predetermined amount of a mixed solvent 3 [Swasol 1500 (trade name, sold by Maruzen Petrochemical Co., Ltd., high-boiling aromatic hydrocarbon solvent) / cyclohexanone = 1 / 1 (weight ratio)], so that The particle size, ie the particle size of the pigment coarse particles, can be reduced to 20 microns or less, followed by the addition of 26.7 parts of Desmodur BL-3175 (trade name, sold by Sumika Bayer Amino Acid Company, methyl ethyl ketone oxime - resistance) HDI isocyanurate type polyisocyanate compound solution, solid content of about 75%) and 2 parts Takenate TK-1 (trade name, sold by Takeda Pharmaceutical Co., Ltd., organotin blocker - dissociation catalyst, solid Content about 10%), stir evenly, add mixed solvent 3 and control viscosity 80 seconds (Ford cup # 4/25 ℃), to obtain a coating composition for the back surface.

Preparation of anti-corrosion coating composition: Example 1

200 parts (80 parts of solid content) modified bisphenol epoxy resin ME1 modified with flexible organic base in Preparation Example 1 and 20 parts of calcium metasilicate, 20 parts of calcium phosphate, 20 parts of titanium white 20 parts of a mixture of 10 parts of oxygen and a predetermined amount of mixed solvent 3 [Swasol 1500 (trade name, sold by Maruzen Petrochemical Company, high boiling point aromatic solvent) / cyclohexanone = 1 / 1 (weight ratio)] The pigment dispersion is carried out so that the particle size, that is, the particle size of the pigment coarse particles can be reduced to 20 μm or less, followed by the addition of 26.7 parts (20 parts by solid content) of Desmodur BL-3175 (trade name, by Sumika Bayer amine base) The company sells, methyl ethyl ketone oxime - blocking HDI isocyanurate type polyisocyanate compound solution, solid content of about 75%) and 2 parts Takenate TK-1 (trade name, sold by Takeda Pharmaceutical Co., Ltd., Organotin-based blocker-dissociation catalyst, solid content of about 10%), uniformly stirred, mixed solvent 3 was added and viscosity was controlled for about 80 seconds (Ford Cup No. 4 / 25 ° C) to obtain a corrosion-resistant coating composition.

Example 2-51 and Comparative Example 1-11

The procedure of Example 1 was repeated except that the modified bisphenol epoxy resin, hardener, tackifier, anti-corrosive pigment, other pigment, and the like were used in accordance with the formulation shown in Table 3 to obtain corrosion-resistant coating, respectively. Composition. In Table 3, the individual amounts of the modified bisphenol epoxy resin, hardener and pigment represent the solids content. In Examples 26-30, 2 parts of Takenate TK-1 was replaced with 1 part of Nacure 5225 (trade name, sold by King Industries, USA, amine neutralization solution of dodecylbenzenesulfonic acid). In Table 3, when a resol resin and other hardeners are used, the resol resin is used as a tackifier, and if no other hardener is used, the resol resin is used as a hardener.

In Table 3, (Note 6) and (Note 7) are explained below.

(Note 6) Cymel 303: trade name, sold by Nihon Cytec Industries, methyl etherified melamine resin.

(Note 7) Calcium ion exchange ruthenium dioxide: SHIELDEX (trademark) C303, marketed by W.R. Grace.

Preparation of coated test panels

Each of the anticorrosive coating composition and the topcoat composition obtained in Example 1-51, Comparative Example 1-11 was coated on an individual substrate, and hardened according to the following coating specification to obtain individual coating test panels. .

Coating specification:

The coating composition for the back surface obtained in Preparation Example 44 was coated on a galvalume steel sheet which had been subjected to a metal surface treatment method, and the thickness of the steel sheet was 0.35 mm, which was an aluminum-zinc alloy steel sheet and alloy. The aluminum content is about 55%, and the amount of alloy plating is 150 g/m2. In Table 2, it is called "GL steel sheet", which uses a coating rod to form a dry film thickness of 8 microns, and then The substrate was cured at a maximum temperature of 180 ° C for 30 seconds to form a back coating film; the anti-corrosion coating composition obtained in the above examples was individually coated on the other side of the back surface of the steel sheet having the steel back coating film, which was coated. The rod was used to form a dry film thickness of 5 μm, and then hardened at a maximum substrate temperature of 220 ° C for 40 seconds to obtain an individual primer coating film; cooled, and KP Color 1580B40 (trade name, sold by Kansai Paint Co., Ltd.) , a polyester-based topcoat composition, a blue, hard-coated film having a glass transition temperature of about 70 ° C) coated on an individual primer-coated film using a coating bar to form a dry film thickness of about 15 microns. And cured for 40 seconds at a maximum substrate temperature of 220 ℃, to obtain respective coating test panels.

Coating film function test

The individual coated test panels obtained by previously preparing the coated test panels were subjected to a coated film functional test in accordance with the following test methods. The test results are shown in Table 4.

testing method Manufacturing properties:

Each of the coated test sheets was cut into a size of 6 cm × 12 cm, and was subjected to 4T folding, that is, a manufacturing method including folding the coated sheet with the side of the outer surface of the coated sheet, wherein the inside of the coated sheet was placed Four sheets of the same thickness as the coated sheets were placed, and the obtained coated sheets were bent at an angle of 180° with a vise so that the length of the folded portions was 6 cm at room temperature of 20 ° C, and the folding at 4 T was separately evaluated in the following manner. The crack resistance and adhesion properties of the coated film of the manufactured portion. The evaluation of the adhesion property of the folded manufacturing portion was to adhere the cellophane tape to the folded manufacturing portion, and then the tape was strongly separated, and the degree of peeling of the coated film of the folded portion was observed.

◎: No film crack was formed in the production portion and no film peeling occurred.

○: There is a slight formation of film cracks and film peeling at the same time, or one of them is slightly formed.

△: Film cracks and film peeling were formed at the same time in the production portion, or one of them was clearly formed.

╳: There are quite a lot of film cracks and film peeling formed at the same time in the manufacturing part, or one of them is very obvious.

Boiling water resistance: Each coated test sheet was cut into a size of 5 cm × 10 cm, and immersed in boiling water of about 100 ° C for 5 hours, and then taken out and evaluated for the appearance of the coated film formed on the surface of the coated sheet, and A cross cut-tape method evaluation was performed separately. The Baige test method is defined in accordance with JIS K-5400 8.5.2 (1990). That is, the cellophane tape was adhered to the surface of each of the coated test sheets with a cutting interval of 1 mm and cut into 100 squares, and then the tape was strongly separated, and the coated film having a check was evaluated in the following manner.

◎: There was no abnormality on the coated film (such as foaming and whitening), and 100 squares were left.

○: There was no abnormality on the coated film (such as foaming and whitening), leaving 91-99 squares.

△: slight foaming or whitening was formed on the coated film, leaving 91-99 squares; or there was no abnormality on the coated film (such as foaming and whitening), but 71-90 squares were left.

╳: There is a significant or very pronounced formation of blistering and whitening on the coated film, or 70 or fewer squares are left.

Alkali resistance:

The back surface and the cutting surface of each of the coated test sheets cut to a size of 5 cm × 10 cm were sealed with a corrosion-resistant coating composition, and a cross-cut was formed at the center of the surface of the coated sheet, the slit of which may extend to the substrate. The obtained coated plate was immersed in a 5% sodium hydroxide aqueous solution at 25 ° C for 48 hours, then taken out, rinsed, and dried at room temperature to evaluate the appearance of the coated film on the surface of the coated film, and further to the cellophane The tape was adhered to the cross-cut portion, and then the tape was strongly separated to evaluate the width (one side) of the separation from the cross-cut portion in the obtained coated film.

◎: No foaming was formed, and the tape separation width from the slit portion was 1.5 mm or less.

○: No foaming was formed, and the tape separation width from the slit portion was larger than 1.5 mm, but equal to 3 mm or less.

△: There was slight formation of foaming, the tape separation width from the slit portion was more than 3 mm or less, or no foaming was formed, but the tape separation width from the slit portion was more than 3 mm.

╳: Foaming is formed, and the tape separation width from the slit portion is more than 3 mm.

Scratch resistance: The edge of a 10-yuan copper plate (Japanese yen) was placed on the coated film on the surface of each coated test plate at a 45° angle at room temperature of 20 ° C, followed by a load of 10 kg while pressing a load of 3 kg. The speed of /sec was dragged by a 10-yuan copper plate by about 30 mm, and damage was formed on the coated film, and the degree of damage was evaluated in the following manner.

◎: The substrate metal was not exposed in the damaged portion.

○: The substrate metal was slightly exposed in the damaged portion.

△: The substrate metal was clearly exposed in the damaged portion.

╳: There is almost no coating film remaining, and the substrate metal is clearly exposed in the damaged portion.

Cyclic Corrosion Test: The following tests were carried out in accordance with JASO M609-91 (Car Body Material Corrosion Test, 1991). A knife blade having a cutting blade was used to form a cross slit at the center of each of the coated test panel surfaces cut into a size of 6 cm × 12 cm, which slit was extended to the substrate, and the angle was 30° and the line width was 0.5 mm, so that each coating was performed. The burr of the long side edge portion of the test plate faces the surface on the right side of the coated film on the surface, and faces the back surface on the right side of the coated film on the surface, and then seals the end edge portion of the coated plate with the anti-corrosion composition, and The upper edge portion is manufactured by 4T folding, that is, a manufacturing method including folding the coated plate with the side of the outer surface of the coated plate, wherein 4 sheets of the same thickness as the coated plate are placed inside the folded coated plate, and the vise is utilized The resulting coated panels were bent at an angle of 180 and the resulting coated panels were subjected to a cyclic corrosion test comprising a total of 150 cycles of 1200 hours, each cycle comprising the following sequential steps: a 5% salt spray test at 35 °C. After 2 hours, it was dried at 60 ° C for 4 hours under conditions of a relative humidity of 95%, and wetted at 50 ° C for 2 hours under a condition of a relative humidity of 95%. The edge portion, the intersecting slit portion, and the 4T folded manufacturing portion of the obtained coated sheet were evaluated separately.

4T Manufacturing Section: Evaluated for the total length of the rusted portion of the 4T manufacturing section.

◎: No rust was formed.

○: White rust is formed, but less than 20 mm.

△: White rust is formed to be 20 mm or longer, but less than 40 mm.

╳: White rust is formed 40 mm or longer, or red rust is formed.

Cross-cut portion: The corrosion of the cross-cut portion and the bubble width at the left and right sides of the cut portion were evaluated based on the extent to which the white rust was extended in the exposed portion of the substrate metal having a cut width of 0.5 mm in the following manner. average value

◎: The degree of white rust extension in the exposed portion of the substrate metal is less than 50%, and the foaming width is less than 3 mm.

○: The degree of extension of white rust is 50% or more, and the foaming width is less than 3 mm, or the degree of white rust extension is less than 50%, and the foaming width is 3 mm or more, but less At 5 mm.

△: The degree of extension of white rust is 50% or more, and the foaming width is 5 mm or more, but less than 10 mm.

╳: The degree of extension of white rust is 50% or more, and the foaming width is 10 mm or more.

Edge portion: The average value of the edge creep width of the long side of the left side and the long side of the right side is simultaneously measured and evaluated in the following manner.

◎: Less than 5 mm.

○: 5 mm or longer, but less than 10 mm.

△: 10 mm or longer, but less than 20 mm.

╳: 20 mm or longer.

Weathering salt spray test:

The coated test panel cut into 5 cm x 10 cm was subjected to a 500-hour irradiation of a xenon arc lamp weathering tester in accordance with the method A for long-term durability test, and the important cycle conditions of wetting for 18 minutes followed by drying for 102 minutes. The process is performed under the xenon lamp method defined in JIS K-5600 7.7, and then the back surface and the cutting surface are sealed with a corrosion-resistant coating composition, and a cross-cut is formed at the center of the coating plate, and the slit can be extended to The substrate was subjected to a salt spray test (JIS Z-2371) for 500 hours, and the appearance of the flat portion was evaluated in accordance with the following criteria.

◎: On average, the blistering portion formed by extending from the slit portion across the slit portion has a width of 3 mm or less and has no other abnormality.

○: foaming from the slit portion is formed. The width of the rust is more than 3 mm, and 5 mm or less, there is no abnormality in the flat portion and other portions, or some foaming is formed in the flat portion, but from the slit Part of the foaming ‧ rust is 3 mm or less in width.

△: foaming was formed from the slit portion. The width of the rust was more than 3 mm, but 5 mm or less, and some foaming was formed in the flat portion.

╳: foaming is formed from the slit portion. The width of the rust is greater than 5 mm, or foaming is formed remarkably.

Claims (6)

A corrosion-resistant coating composition comprising: (A) a flexible organic element-modified bisphenol epoxy resin, which is 5 to 50% by mass of a flexible organic unit and 95 to 50% by mass of a double a phenol epoxy resin obtained by reacting; (B) a hardener which is at least one selected from the group consisting of an amine resin and a blockable polyisocyanate compound; (C) an anticorrosive pigment; and (D) a tackifier. a coating composition comprising at least one of an epoxy resin containing a secondary or tertiary amine group, an acrylic resin containing a secondary or tertiary amine group, and a resol resin; wherein the flexibility of the resin (A) The organic element is at least one of an aliphatic polybasic acid having 4 to 36 carbon atoms, an acrylic resin having a glass transition temperature of -20 to 50 ° C, and a polyester resin having a glass transition temperature of -20 to 50 ° C. The corrosion pigment (C) contains (1) a vanadium compound which is at least one of vanadium pentoxide, calcium vanadate and ammonium metavanadate, and (2) a ruthenium-containing compound which is a metal ruthenate and ruthenium dioxide. At least one of the fine particles, and (3) a phosphate metal salt, and based on 100 parts by mass of the total solid content of the resin (A) and the hardener (B), The resin (A) is 55 to 95 parts by mass, the curing agent (B) is 5 to 45 parts by mass, the vanadium compound (1) is 3 to 50 parts by mass, and the cerium-containing compound (2) is 3 to 50 parts by mass. The phosphate metal salt (3) is in the range of 3 to 50 parts by mass, and the total amount of the vanadium compound (1), the ruthenium-containing compound (2) and the phosphate metal salt (3) is 10 to 150. Within the range of parts by mass. The anti-corrosion coating composition of claim 1, wherein the resin (A) is a bisphenol epoxy resin, which is an aliphatic polybasic acid having 4 to 36 carbon atoms and has a glass transition of -20 to 50 ° C. Temperature acrylic resin Upgraded. The anticorrosive coating composition according to claim 1 or 2, wherein the aliphatic polybasic acid having 4 to 36 carbon atoms is a dimer acid. A corrosion-resistant coating composition according to claim 1 or 2, wherein the cerium-containing compound (2) contains calcium ion-exchanged cerium oxide. A coated metal sheet which is formed on one side or both sides of a metal sheet to form a hardened coating film based on the corrosion-resistant coating composition according to any one of claims 1 to 4, the metal The sheet can be treated with a metal finish on the surface. A coated metal sheet having a multi-layer coating film on one side or both sides of a metal sheet to form an anti-corrosion coating composition according to any one of claims 1 to 4. The hardened coating film may be subjected to a metal surface treatment on the surface, and a top coat coating film is formed on at least one side of the hard coat film.