TW200902650A - Coating composition and coated metal sheet by use of the same - Google Patents

Abstract

A coating composition containing containing (A) a hydroxyl group-containing coating film-forming resin, (B) a crosslinking agent, and an anticorrosion pigment mixture, the corrosion pigment mixture (C) being an anticorrosion pigment mixture (C-1) consisting of a combination of (1) at least one vanadium compound selected from vanadium pentoxide, calcium vanadate and ammonium metavanadate, (2) a metal silicate and (3) a phosphate-based calcium salt, or an anticorrosion pigment mixture (C-2) consisting of a combination of the vanadium compound (1), (4) a calcium compound and (5) at least one phosphate-based metal salt selected from a phosphate metal salt, hydrogen phosphate metal salt and tripolyphosphate metal salt, a metal in respective metal salts being zinc, aluminium or magnesium; and a coated metal sheet by use of the coating composition.

Description

200902650 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a non-chromium-based paint composition excellent in corrosion resistance and a coated metal plate using the same, and more particularly, to improve coating A coating composition effective in corrosion resistance of a flat portion of a metal plate and corrosion resistance of a processed portion or an end portion, and a coated metal plate using the same. [Prior Art] Conventionally, pre-coated metal sheets such as precoated steel sheets coated by wire coating treatment are widely used as building materials for roofs, walls, sun visors, garages, etc. of buildings. Home-related products such as home appliances, switchboards, frozen display boxes, steel furniture, and kitchen appliances. When such a house-related product is produced from the precoated metal sheet, the precoated steel sheet is usually cut and pressed and joined. However, most of these residential related products have a metal exposed portion of the cut surface or a cracked portion which is processed by press working. When the metal exposed portion or the cracked portion is compared with other portions, the corrosion resistance is liable to lower. Generally, in order to improve the corrosion resistance, it is necessary to carry the chromium-based anticorrosive pigment in the undercoat film of the precoated steel sheet. . However, the "systemic anti-embroidery pigment" is formed by containing hexavalent chromium having excellent rust resistance, and the hexavalent chromium has problems in terms of human health and environmental protection. Until now, most of the non-chromium-based rust-preventing pigments use commercially available zinc phosphate, tripolyphosphate, zinc molybdate, etc., and various proposals have been made to combine non-chromium pigment primers. For example, 'in the patent document i, it is described in the composition of the epoxy resin and the phenol resin as a mixture of anti-rust pigments, calcium citrate 200902650 and phosphorus vanadate, or combined calcium carbonate and calcium citrate and aluminum phosphate. A coating of anti-rust pigment with phosphorus vanadate. Further, Patent Document 2 discloses a coating material in which a combination of a magnesium phosphite, a manganese oxide, a vanadium oxide fired product, or a calcium phosphate and vanadium oxide fired product as a rust preventive pigment is blended in the polyester. However, the coating film formed of the coating materials described in Patent Documents 1 and 2 is inferior in corrosion resistance as compared with the coating material using the chromium-based pigment, and in particular, the corrosion resistance of the processed portion and the end surface portion is insufficient. Moreover, most of the resistance to corrosion or acid resistance is not good. In addition, when a large amount of anti-rust pigment is used, most of the water resistance is not good. When the pre-coated metal sheet is manufactured, the effect of replacing the chromium-based anti-rust pigment cannot be achieved. Further, Patent Document 3 describes a coating composition which contains an oil absorption amount of 30 to 200 ml/100 g and a pore volume in a vehicle liquid component composed of an organic resin containing a hydroxyl group or an epoxy group and a curing agent. It is a coating of 0.05 to 1.2 ml/g of cerium oxide microparticles, and the glass transition temperature of the cured coating film formed by the coating is in the range of 40 to 125 t. However, the coating film formed by the coating material described in Patent Document 3 has considerable resistance to rot, but is also inferior in corrosion resistance and chemical resistance when compared with a coating using a chromium-based pigment. 'In particular, the corrosion resistance of the end face is insufficient. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-199078 (Patent Document 3) Japanese Laid-Open Patent Publication No. 2000-129163 The object of the invention is to provide a non-chromium coating composition of the 200902650 film which is excellent in corrosion resistance to a general portion of a coated metal sheet or the like, and excellent in corrosion resistance of a processed portion or an end portion, and a coated metal using the same board. Therefore, the inventors of the present invention have found that the specific vanadium compound as a rust preventive pigment, a specific ruthenium, is blended in a hydroxyl group-containing coating film-forming resin system in order to solve the above-mentioned problems. A coating composition of an acid-containing material and a calcium phosphate salt, or a coating composition of a specific vanadium compound, a calcium compound, and a specific phosphate-based metal salt, which are doped in a certain amount, can form not only corrosion resistance of a flat portion but also a coated metal plate The present invention has been completed by a coating film having excellent corrosion resistance in a processed portion or an end surface. In other words, the present invention provides a coating composition characterized by a coating composition containing (A) a hydroxyl group-containing coating film-forming resin, (B) a crosslinking agent, and (C) a rust-preventive pigment mixture, the rust-preventing pigment The mixture (C) is formed by combining (i) a vanadium compound of at least one of vanadium pentoxide, calcium vanadate and ammonium methylvanadate, (2) a metal citrate and (3) a calcium phosphate salt. Embroidery pigment mixture (C-1) ' or combination (1) at least one of the vanadium compound, (4) a compound, and (5) a metal salt of scaly acid, a metal salt of hydrogen phosphate, and a metal salt of a metal tripolyphosphate, and The metal of each metal salt is an anti-recording pigment mixture (C-2) formed of a phosphate metal salt of Zn, A1 and Mg to a total solid content of 100 parts by mass of the resin (A) and the crosslinking agent (B). The amount of each of the rust preventive pigment mixture (c) is 10 to 150 parts by mass, and the amount of the vanadium compound (1) in the rust preventive pigment mixture (d) is 3 to 50 parts by mass, and the metal ruthenium The amount of the acid salt (2) is 3 to 5 parts by mass, and the amount of the calcium phosphate salt (3) is 3 to 5 parts by mass; the antirust pigment is mixed. In (C_2), the amount of the vanadium compound (1) is 3 to 50 parts by mass, and the amount of the calcium compound (4) is 3 to 50 parts by mass, and the amount of the metal phosphate (5) is 3 to 3 50 parts by mass; and a coated metal plate using the coating composition. [Effects of the Invention] The coating composition of the present invention is a coating composition which is free from chromium-based rust-preventive pigments and is environmentally-friendly, and the coating composition of the present invention can exhibit corrosion resistance in forming a flat portion. It is excellent in the coating effect of the processed part or the end surface which is excellent in the effect of the coating metal plate which is not easily achieved by the non-chromium-based rust-proof paint. The coated metal sheet forming the cured coating film is excellent in corrosion resistance of the flat portion, the processed portion, or the end surface portion, and has a conventionally used chromic acid such as strontium chromate or the like. The coating of the salt-based rust-preventing pigment is based on the corrosion resistance of the coated metal sheet forming the cured coating film. A coated metal sheet formed by forming a cured coating film and forming a surface coating film on the cured coating film based on the coating composition of the present invention is excellent in corrosion resistance of a flat portion, a processed portion or an end portion. When a metal plate formed of a coated object is coated with a galvanized steel sheet or an aluminum-zinc alloy, the coating composition of the present invention can be used to obtain excellent corrosion resistance in the flat portion, the end surface portion, and the processed portion. Sex. [Best Mode for Carrying Out the Invention] The coating composition of the present invention is a coating composition containing the following hydroxyl group-containing coating film-forming resin (A), crosslinking agent (B), and rust-preventive pigment mixture (C) 200902650 The coating film-forming resin containing a hydroxyl group in the coating composition of the present invention may be a hydroxyl group-containing resin having a coating film forming ability which can be generally used in the field of coating, and is not particularly limited, and is typically, for example, a hydroxyl group-containing polyester resin or a ring. One or more mixed resins of an oxygen resin, an acrylic resin, a fluorine resin, and a chlorinated vinyl resin. The film-forming resin may suitably use at least one organic resin selected from the group consisting of a hydroxyl group-containing polyester resin and an epoxy resin. The above hydroxyl group-containing polyester resin comprises an oil-free polyester resin, an oil-modified alkyd resin, and a modified product of the resins, which include, for example, a urethane-modified polyester resin, a urethane A modified alkyd resin, an epoxy-modified polyester resin, an acrylic modified polyester resin, or the like. The above hydroxyl group-containing polyester resin has a number average molecular weight of 1,500 to 3 5,000, preferably 2,000 to 2,500, and a glass transition temperature (Tg point) of 10 to 10 ° C. Preferably, it is 20 to 80 ° C, and the hydroxyl group is preferably 2 to 100 mgKOH/g, preferably 5 to 80 mgKOH/g. In the present invention, the "number average molecular weight" of the resin is determined by a gel permeation chromatography method ("HLC8120GPC", manufactured by Tosoh Corporation, "HLC8120GPC"), and the standard polystyrene is used. The molecular weight of ethylene is determined by the benchmark. The pipe column uses four "TSKgel G-4000HXL", "TSKgel G- 3 0 00HXL", "TSKgel G - 2 5 0 0 Η XL", "TSK ge 1 G2000HXL" (all are Tosoh Corporation) System, trade name), mobile phase: tetrahydrofuran, measuring temperature: 40 ° C, flow rate: Ice / min, detector: RI conditions are carried out. Further, in the present specification, the glass transition temperature (Tg) of the resin is by means of differential thermal analysis (DSC). 200902650 The above oil-free polyester resin is an esterified product of a polybasic acid component and a polyol component. The polybasic acid component is mainly used in one or more selected from, for example, phthalic anhydride, isophthalic acid, p-nonanoic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic acid, fumaric acid, adipic acid, sebacic acid, maleic anhydride. The dibasic acid and the lower alkyl ester of the acid, depending on the desired one, may be used as a monobasic acid such as benzoic acid, crotonic acid or p-tert-butylbenzoic acid, trimellitic anhydride, methylcyclohexene A trivalent or higher polybasic acid such as a carboxylic acid or a pyromellitic anhydride. The polyol component is mainly used, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl alcohol, 3-methylpentanediol, 1,4-hexanediol, 1,6-hexane. A diol such as an alcohol may be a trivalent or higher polyhydric alcohol such as glycerin, trimethylolethane or trimethylolpropane 'pentaerythritol, as needed. These polyols may be used singly or in combination of two or more. The esterification or transesterification of the two components can be carried out by a method known per se. The acid component is preferably isodecanoic acid, p-citric acid, and a lower alkyl ester of such acids. The alkyd resin may be an acid fatty acid such as coconut oil fatty acid, soybean oil fatty acid or castor oil fatty acid in addition to the acid component and the alcohol component of the above oil-free polyester resin. , sunflower oil fatty acid, tall oil fatty acid, dehydrated castor oil fatty acid, tung oil fatty acid. The oil of the alkyd resin has a length of 30% or less, particularly preferably about 5 to 20%. a urethane-modified polyester resin, for example, the above-mentioned oil-free polyester resin or a low molecular weight oil-free polyester resin obtained by reacting an acid component and an alcohol component used in the production of the above oil-free polyester resin, and The polyisocyanate compound is reacted in a manner known per se. Further, the amino group-10-200902650 formate modified alkyd resin contains a low molecular weight alkyd resin obtained by reacting the above alkyd resin or each component used in the production of the above alkyd resin, and a polyisocyanate compound. The method known per se is carried out by the responder. a urethane-modified polyester resin and a polyisocyanate compound used in the manufacture of a urethane-modified alkyd resin, such as hexamethylene diisocyanate, isophorone diisocyanate, benzodimethyl di Isocyanate, tolyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), 2,4,6-triisocyanate toluene, and the like. The above-mentioned urethane-modified resin is generally used in an amount of 30% by weight or less based on the amount of the polyisocyanate compound forming the urethane resin relative to the urethane-modified resin. The degree of modification achieved is preferred. The epoxy group-modified polyester resin can be, for example, a polyester resin produced from the respective components used in the production of the above polyester resin, a reaction product of a carboxyl group of the resin and an epoxy group-containing resin, or a polyester. A reaction product in which a hydroxyl group in a resin and a hydroxyl group in an epoxy resin are bonded via a polyisocyanate compound, and a reaction of addition, condensation, grafting, or the like of a polyester resin and an epoxy resin. The degree of modification of the epoxy-modified polyester resin is generally 0.1 to 30% by weight based on the epoxy group-modified polyester resin. The acrylic modified polyester resin may, for example, be a polyester resin produced from the respective components used in the production of the above polyester resin, and the residue or hydroxyl group of the resin may contain a group reactive with such a group (for example, a reaction product of an acrylic resin of a carboxyl group, a trans group or an epoxy group, or a graft polymerization of a polyester resin with a (meth)acrylic acid or a (meth) acrylate or the like using a peroxide-based polymerization initiator 200902650 The reaction product formed. The degree of modification of the acrylic modified polyester resin is generally preferably from 1 to 50% by weight based on the amount of the acrylic modified polyester resin. Among the above-mentioned polyester resins, an oil-free polyester resin or an epoxy-modified polyester resin is preferable in terms of balance between workability and corrosion resistance. A preferred epoxy resin for forming a resin containing the hydroxyl group-containing coating film, for example, a bisphenol type epoxy resin or a novolac type epoxy resin; and an epoxy group or a hydroxyl group in the epoxy resin reacts with various modifiers Modified epoxy resin. When the modified epoxy resin is produced, the modification period of the modifier is not particularly limited, and may be modified in the middle of the process of manufacturing the epoxy resin, or may be modified in the final stage of manufacturing the epoxy resin. Sex. The bisphenol type epoxy resin is condensed to a resin having a high molecular weight in the presence of a catalyst such as an alkali catalyst, such as epichlorohydrin and bisphenol, to give epichlorohydrin and bisphenol. It is required to carry out condensation in the presence of a catalyst such as a base catalyst to form a low molecular weight epoxy resin, and to obtain a resin obtained by polyaddition reaction of the low molecular weight epoxy resin and bisphenol. The above bisphenols, such as 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, isobutane, bis(4-hydroxy-tributyl) -Phenyl)-2,2-propane, p-(4-hydroxyphenyl)phenol, oxobis(4-hydroxyphenyl), sulfonylbis(4-hydroxyphenyl), 4,4' - Dihydroxybenzophenone, bis(2-hydroxynaphthyl)methane or the like, among which bisphenol A and bisphenol F are preferably used. The above bisphenols may be used alone or in combination of two or more. 200902650 Bisphenol type epoxy resin commercial products, such as Japan Epoxy Tree Picton (transliteration) 828, with 812, with 815, with 820, with 834, with 1 004, with 1〇〇7, with 1 〇〇9, same as 1010; Asahi Chiba Laruyton AER6099; and Mitsui Chemicals (shares) Yeboyin) R-3 09 and so on. Further, 'the preferred aldehyde varnish type epoxy resin as a resin containing a hydroxyl group-containing coating film, such as a phenol novolac resin, a cresol novolak type epoxy resin, and a phenol oxirane having a large amount in the molecule. A modified epoxy resin such as a type of epoxy resin or the like, and the above-mentioned modified epoxy resin is a bisphenol type epoxy resin novolak type epoxy resin, and an oxyester resin such as a dry oil fatty acid; and an acrylic acid or a methyl group. An epoxy acrylate resin which reacts with a polymerization monomer component such as acrylic acid; a urethane-modified epoxy resin which reacts with an organic compound; an epoxy resin, a novolac type epoxy resin or the like The epoxy group in the modification is reacted with an amine compound to introduce an amine group or an amine-modified epoxy resin or the like formed. Crosslinking agent (B) The crosslinking agent (B) is a resin which forms a hardened coating film with the above-mentioned hydroxyl group-containing coating film, and forms a resin (A) by heating or the like. The reaction may be carried out to be hardened, and an amine-based resin, a phenol resin, and an isocyanate compound may be preferably used. These crosslinking agents can be used in combination of one type.脂 之 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 The ammonium salt is intended to carry out (A) with the above-mentioned, non-segmented poly or two kinds of the above-mentioned amine-based resin of 200902650, for example, by making melamine, urea, benzoguanamine, acetyl decylamine, steroid decylamine And a methylolated amine-based resin obtained by reacting an amine component such as spiramide or dicyanamide with an aldehyde. The aldehyde used in the above reaction is, for example, formaldehyde, paraformaldehyde, acetaldehyde or benzaldehyde. The above-mentioned methylolated amine-based resin can also be used as an amine-based resin by etherification with a suitable alcohol. The alcohol used in etherification, such as methanol, ethanol, n-propanol, isopropanol, n-butyl Alcohol, isobutanol, 2-ethylbutanol, 2-ethylhexanol, etc. The phenol resin which can be used as the above-mentioned crosslinking agent is crosslinked with the above-mentioned hydroxyl group-containing coating film-forming resin (A). In the reaction, the phenol component and the formaldehyde are heated in the presence of a reaction catalyst. a resol-type phenol resin formed by introducing a methylol group into a methylol group, a part or all of a hydroxyl group of the obtained methylolated phenol resin, and alkyl etherification with an alcohol. When starting to produce a novolac type phenol resin, it is used as a starting point. As the phenol component of the raw material, a bifunctional phenol compound, a trifunctional phenol compound, a tetrafunctional or higher phenol compound, or the like can be used. The phenol compound is, for example, fluorenyl-cresol, P-cresol or P-third. As a bifunctional phenol compound, phenol, P-ethylphenol, 2,3-xylenol, 2,5-xylenol, etc., with phenol carbonate, m-cresol, m-ethylphenol 3,5- A bisphenol A, a bisphenol F, etc. are used as a tetrafunctional phenol compound, and a bisphenol A, a bisphenol F, etc. are used as a tetrafunctional phenol compound. In order to improve abrasion resistance, it is a trifunctional or more. The phenol compound, in particular, stone carbonate and/or m-cresol is preferable. These phenol compounds may be used singly or in combination of two or more kinds. 200902650 Formaldehydes used in the production of phenol resins, for example, formaldehyde, paraformaldehyde Or trioxane, etc. 'may be 1 or 2 The alcohol used in the alkylation of a part of the methylol group of the methylolated phenol resin is preferably a monohydric alcohol having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. A preferred monohydric alcohol is, for example, methanol, ethanol, n-propanol, n-butanol, isobutanol, etc. The reactivity of the phenol resin with the hydroxyl group-containing coating film-forming resin (A), etc., per nuclear benzene The core has an average of 0.5 or more alkoxymethyl groups, preferably 0.6 to 3.0. It is also possible to use a polyisocyanate compound which is not blocked in the block polyisocyanate compound as the above crosslinking agent, for example, An aliphatic diisocyanate of hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; a cyclic aliphatic diisocyanate such as hydrogenated dimethyl diisocyanate or isophorone diisocyanate: such as tolyl Diisocyanate, benzodimethyl diisocyanate or 4,4'-diphenylmethane diisocyanate, organic diisocyanate of the original MDI aromatic diisocyanate itself, or each of the organic diisocyanate and polyol, low molecular weight Polyester Butter or other water adducts, as described above, or of each of the organic diisocyanate cyclic polymer between ester, and an isocyanate-biuret, and the like. The blocked polyisocyanate compound is one in which the free isocyanate group in the above polyisocyanate compound is blocked by a blocking agent. The blocking agent is, for example, a phenol type such as phenol, cresol or xylenol; ε-caprolactam; a decylamine such as δ-valeroguanamine or γ-butylide; methanol, ethanol, An alcohol system of n-, iso- or tert-butanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, -15-200902650 diethylene glycol monoethyl ether, propylene glycol monomethyl ether, benzyl alcohol, etc.; , acetaminophen, acetamidine, methyl ethyl ketone oxime, diethyl hydrazino monohydrazine, benzophenone oxime 'cyclohexane hydrazine, etc.; dimethyl malonate, malonic acid diethyl A blocking agent such as an ester, an ethyl acetoxyacetate or an active methylene group such as etidylacetone is preferred. By mixing the above polyisocyanate compound and the above-mentioned blocking agent, the free isocyanate group in the above polyisocyanate compound can be easily blocked. The mixing ratio of the hydroxyl group-containing coating film-forming resin (A) and the crosslinking agent (B) is based on 100 parts by mass of the total solid content of the components (A) and (B), and a hydroxyl group-containing coating film is formed. The resin (A) is 5 to 95 parts by weight, preferably 60 to 95 parts by mass, and the crosslinking agent (B) is in the range of 5 to 45 parts by mass, preferably 5 to 40 parts by mass. Corresponding to corrosion resistance, boiling water resistance, workability, hardenability, and the like. In order to improve the hardenability of the coating composition of the present invention, a hardening catalyst may be blended as needed. The crosslinking agent (B) is an amine-based resin, particularly a mixed etherified melamine resin containing a low molecular weight formic acid or methyl ether and butyl ether, and is hardened by using an amine neutralizing agent of a sulfonic acid compound or a sulfonic acid compound. Catalyst is suitable. Typical examples of the sulfonic acid compound are, for example, P-toluenesulfonic acid, dodecylbenzenesulfonic acid, dimercaptoπ-propionic acid, monomethylnaphthalenesulfonic acid and the like. The amine in the amine neutralizer of the acid-expanding compound may be a primary amine, a secondary amine, or a tertiary amine. Among these, in terms of the stability of the coating, the effect of promoting the reaction, the physical properties of the obtained coating film, and the like, the amine neutralization of the hydrazine-methyl ester extended acid and/or the amine neutralization of dodecanebenzenesulfonic acid Things are appropriate. When the parent reagent (Β) is a phenol resin, an amine neutralizer using the above sulfonic acid compound or sulfonic acid 200902650 acid compound is used as a curing catalyst. When the crosslinking agent (B) is a blocked polyisocyanate compound, it is preferred to use a curing catalyst which promotes dissociation of a blocking agent of a blocked polyisocyanate compound of a crosslinking agent, and a preferred curing catalyst such as tin octylate. Dibutyltin bis(tin-2-ethylhexanoate), dioctyl bis(tin-2-ethylhexanoate), tin dioctyl diacetate, dibutyltin dilaurate, dibutyltin oxide, dioctane An organic metal catalyst such as tin oxide or lead 2-ethylhexanoate. When the crosslinking agent (B) is a combination of two or more kinds of crosslinking agents, each crosslinking agent can be used in combination with an effective curing catalyst. Antirust pigment mixture (C) In the coating composition of the present invention, the antirust pigment mixture (c) is formed by the following (1) vanadium compound, (2) metal niobate and (3) phosphate calcium salt. An anti-embroidery pigment mixture (C-1), or a combination of (1) a vanadium compound, (4) a calcium compound, and (5) a metal oxide of a rust preventive pigment (c_2).

Vanadium compound (U vanadium compound (1) is a vanadium compound of at least one vanadium pentoxide, calcium vanadate and ammonium methylvanadate. Vanadium pentoxide, calcium vanadate and ammonium methylvanadate are pentavalent vanadium ions. Excellent in water dissolution, by reacting a pentavalent vanadium ion released from a vanadium compound (丨) with a raw material metal and reacting with ions from other antirust pigment mixtures' Metal citrate (2) The metal sulphate (2) is a salt formed by cerium oxide and a metal oxide, and may be any of a raw acid salt, a polysilicate, or the like. Fresh acid, aluminum citrate, aluminum citrate, aluminum hydride, calcium aluminum citrate, 200902650 sodium aluminum citrate, aluminum bismuth citrate, sodium citrate, calcium citrate, calcium citrate, citric acid Calcium sodium, zirconium silicate, magnesium bismuth citrate, magnesium metasilicate, magnesium magnesium silicate, manganese ruthenate, bismuth citrate, olivine, garnet, vermiculite, heteropolar ore, blue cone, column Star-leaf stone, beryl, diopside, ash stone, red garnet, tremolite, hard calcareous stone, talc, fisheye, amine Acid salt, borosilicate, sodium phosphite, feldspar, zeolite, etc. In the metal citrate (2), it is preferred to use calcium orthosilicate, calcium metasilicate. Phosphate calcium phosphate (3, The phosphate-based salt (3) is a phosphate containing a metal element, such as calcium phosphate, calcium ammonium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium fluoride phosphate, etc. calcium phosphate salt (3) The released phosphate ions and calcium ions can effectively improve the corrosion resistance. Paper formation, compound (4) Calcium compound (4) For example, calcium compounds other than calcium vanadate or phosphate, such as calcium oxide, calcium hydroxide , raw calcium citrate, calcium metasilicate, calcium carbonate, calcium sulfate, calcium nitrate, calcium sulfide, calcium chloride, calcium fluoride, calcium bromide, calcium nitride, calcium acetate, calcium azide, cyania Calcium amination, calcium amination, calcium imide, calcium telluride, etc. Among them, calcium carbonate, calcium oxide and calcium metasilicate are preferred in terms of proper water solubility and corrosion resistance, especially Calcium metasilicate is preferred in terms of corrosion resistance. Phosphoric acid metal salt (5) Phosphoric acid metal salt (5) is at least one phosphorus a metal salt, a metal hydrogen phosphate salt, and a metal phosphate triphosphate, and the metal of the metal is a phosphate metal salt of Ζη, Α1 or Mg. 200902650 The above-mentioned phosphate metal salt, such as zinc phosphate, aluminum phosphate, magnesium phosphate, Zinc hydrogen phosphate, aluminum hydrogen phosphate, magnesium hydrogen phosphate, magnesium ammonium phosphate, aluminum dihydrogen sulphate, etc. Zn, A1 or Mg metal ions and phosphate ions released from the phosphate metal salt (5) are effective. In the coating composition of the present invention, the rust preventive pigment mixture (c-1) is used for 100 parts by mass of the total solid content of the above resin (A) and the crosslinking agent (B). The vanadium compound (1), the metal citrate (2), and the strontium phosphate strontium salt (3) are in the range of 10 to 150 parts by mass in terms of corrosion resistance. Preferably, it is 15 to 90 parts by mass. The amount of the vanadium compound U): 3 to 50 parts by mass, preferably 5 to 30 parts by mass, and the amount of the metal ruthenate (2): 3 to 50 parts by mass, preferably 5 to 3 parts by mass, The amount of the calcium phosphate salt (3) is from 3 to 50 parts by mass, preferably from 5 to 30 parts by mass. In the coating composition of the present invention, the rust-preventing pigment mixture (C-2) is a vanadium compound (1) for 100 parts by mass of the total solid content of the above resin (A) and the crosslinking agent (B). The calcium compound (4) and the phosphate metal salt (5) are in the following ranges, and the amount of the rust preventive pigment mixture (C) is from 10 to 150 parts by mass, preferably from 15 to 90, in terms of corrosion resistance. Parts by mass. The amount of the vanadium compound (1): 3 to 50 parts by mass, preferably 5 to 30 parts by mass, and the amount of the calcium compound (4): 3 to 50 parts by mass, preferably 5 to 30 parts by mass, The amount of the phosphate metal salt (5) is 3 to 50 parts by mass, preferably 5 to 30 parts by mass. In the coating composition of the present invention, by combining the quantitative components -19-200902650 (1), (2) and (3) as a rust preventive pigment mixture (c"), or combining the quantitative components (1) (4) and (5) as a mixture of anti-rust pigments (c _ 2 ), the effect of improving the resistance to hunger can be obtained. In the anti-rust pigment mixture (c _丨), in terms of corrosion resistance, it is preferable to combine vanadium pentoxide, metafluoric acid, and phosphoric acid. In addition, a vanadium compound (1) and a metal niobate constituting the anti-recording pigment mixture (C _ i) which are blended with 100 parts by mass of the total solid content of the above-mentioned resin (A) and the crosslinking agent (B) 2) The mixture of the mass parts in the respective amounts of the calcium phosphate salt (3) is added to 1 part by mass, 2 5 t: 5% by mass aqueous sodium chloride solution, and stirred for 6 hours. And the pH of the filtrate filtered by the supernatant liquid which is allowed to stand under the pressure of 2 5 X: for 48 hours is 3 to 10, preferably 5 to 9, and the vanadium compound (1), metal citrate (2) The phosphoric acid-based calcium salt (3) is preferred because of the solubility of water and the reactivity of the solution of the rust preventive pigment with the metal plate, and is more preferably in the range of corrosion resistance. In other words, the filtrate of the above pH 测定 is measured, and any of the sodium chloride aqueous solution having a concentration of 5% by mass and a concentration of 5 mass% at 25 ° C may be added to the vanadium compound (1) in an amount of from 3 to 50 parts by mass. The amount, the metal citrate (2) is any amount of 3 to 5 parts by mass, and the phosphate-based calcium salt (3) is any amount in the range of 3 to 50 parts by mass, and the filtrate of the dissolved solution is dissolved. Further, the vanadium compound (1) and the calcium compound (4) constituting the rust preventive pigment mixture (C-2) blended with 100 parts by mass of the total solid content of the above resin (A) and the crosslinking agent (B) The mixture of the mass parts in the respective amounts of the phosphate metal salt (5) was added to 100,000 parts by mass of a 5 mass% aqueous solution of sodium chloride at 25 ° C, and stirred for 6 hours, and allowed to stand at 25 The pH of the filtrate which was filtered for 48 hours at a temperature of ° C for a period of time was 3 to -20 - 200902650 10, preferably 5 to 9 ', for the vanadium compound (1), the calcium compound (4) and the phosphate system. The metal salt (5) is preferably in a range of reactivity with respect to the solubility of the water and the reactivity of the solution of the rust preventive pigment and the metal plate. In other words, 'the above-mentioned ρ Η値 filtrate is measured, and the vanadium compound (1) may be added in an amount of 3 to 50 parts by mass for 1 part by mass of the 5 5% by mass aqueous sodium chloride solution of 2 5 C. Any amount, the calcium compound (4) is any amount of 3 to 5 parts by mass, and the phosphate metal salt (5) is any amount of the dissolved solution in the range of 3 to 50 parts by mass. In the coating composition of the present invention, in addition to the above-mentioned hydroxyl group-containing coating film-forming resin (Α), a crosslinking agent (Β), an anti-rust pigment mixture (C), and a hardening catalyst which is mixed as required 'Coloring pigments, extender pigments, UV absorbers, UV stabilizers, organic solvents, and additives to prevent precipitants, defoamers, coating conditioners, etc., which can be blended in the coating range as needed. The coloring pigment is an organic coloring pigment such as an organic red pigment such as quinoline blue, quinoline green, azo or salivation; titanium white, titanium yellow, iron oxide red, carbon black, various calcined pigments, and the like. For inorganic coloring pigments, it is preferred to use white color. The above-mentioned extender pigments such as talc, clay, mica, alumina, calcium carbonate, barium sulfate and the like. The above ultraviolet absorber, for example, 2 _(2-hydroxy-3,s_di-p-tripentylphenyl)-2H-benzotriazole, isooctyl_3_(3_(2:9-benzotriazole) Keb 5_ second butyl_4_hydroxyphenylpropionate, 2-[2-hydroxy-3,5-bis(1d-dimethylphenyl)phenyl]-2H-benzotriazole, 2 ·[2_Hydroxy-3.dimethylbenzyl]5-(1,1,3,3-tetramethylbutyl)phenyl]_211-benzotriazole, methyl_3_[3_ 200902650 Tributyl 5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate/polyethylene glycol 300 condensate and other benzotriazole derivatives; 2-[ 4-(2-hydroxy-3-dodecyloxypropyl)oxy]-2.hydroxyphenyl-4,6-bis(2,4-dimethylphenyl)_1,3,5-triazole Equivalent three-trap derivative; ethane diamine-N-(2-ethoxyphenyl)-N'-(2-ethylphenyl)-(ethylenediamine), ethanediamine An oxalic acid aniline derivative such as -N-(2-ethoxyphenyl)-N'-(4-isododecylphenyl)-(ethylenediamine), etc. The above-mentioned ultraviolet stabilizer, for example, blocked Amine compounds, hindered phenol compounds; CHIMASORB944, TINUVIN144, TINUVIN292, TINUVIN7 7 0, IR GANOX1010, IRGANOX1〇98 (all of the above-mentioned products are products of Chiba Special Chemicals Co., Ltd.), etc. By blending a UV absorber or an ultraviolet stabilizer in the coating, light from the surface of the coating film can be suppressed. Deterioration, even when the coating is used as a primer, since the deterioration of the surface of the primer caused by the light reaching the surface of the primer coating film by the surface coating film can be suppressed, the deterioration of the surface of the primer coating film can be prevented. The resulting interlayer peeling of the primer coating film and the surface coating film can maintain excellent corrosion resistance. The above organic solvent which can be blended in the coating composition of the present invention can be visualized for improving the coating property of the composition of the present invention. It is required to be blended, and a hydrocarbon-containing coating film-forming resin (A) and a crosslinking agent (B) may be dissolved and dispersed, and specifically, for example, toluene, xylene, or a hydrocarbon having a boiling point petroleum hydrocarbon may be used. a ketone solvent such as a solvent, methyl ethyl ketone, methyl isobutyl hydrazine, cyclohexanone or isophorone, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether Acetate Ester solvent - methanol, ethanol 'isopropanol, butyl-22-200902650 alcohol-based solvent such as alcohol, ethylene glycol monoacetic acid, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc. In addition, these may be used alone or in combination of two or more. The coating composition of the present invention has a glass transition temperature of the cured coating film obtained from the composition of the present invention in terms of corrosion resistance, acid resistance, processability, and the like of the coating film. 4 0 to 1 1 5 ° C, preferably 5 0 to 1 0 5 ° C is suitable. The glass transition temperature of the coating film is based on DINAMIC VISCOELASTOMETER MODEL VIBRON (Dynamic Viscoelasticity Tester Type VIBRON) DDV-IIEA type (Toyo Buruton Co., Ltd., automatic dynamic viscoelasticity measuring machine), with a frequency of 10 10 Hz. The change in tan5 of the temperature dispersion measurement determines the maximum temperature of the crucible. When the coating composition of the present invention is applied to a coating film formed on a metal plate, and the rust-preventive pigment mixture (C-1) is used as the rust-preventing pigment mixture (C), excellent corrosion resistance is exhibited. The reason for the present invention is that the metal ions generated by dissolving a raw material metal such as chloride ions in a corrosive environment and the pentavalent vanadium ions (VOT or V043·vanadate ions) are not directly subjected to a redox reaction. The precipitated salt is formed, and the trivalent vanadium ion and the raw material metal ion formed by the redox reaction of the pentavalent vanadium ion and the raw material metal can efficiently form a precipitating salt or a compound with the phthalic acid ion, and are effectively coated on the exposed surface of the raw material. Further, the phosphoric acid ions eluted at the same time are adjusted to a suitable pH range at the portion where the etching proceeds and the periphery thereof (particularly, when the pentoxide ion and the raw material metal are subjected to a redox reaction). Further, by using the components (1), (2), and (3) constituting the rust preventive pigment mixture (C-1), the acid resistance of each of the components (1), (2), and (3) can be effectively eliminated. Sex or alkali resistance and water resistance weak -23 - 200902650 points. Further, since calcium ions have a function of suppressing dissolution of a raw material metal solution having a pH of more than 1 Torr and dissolving the raw material metal in a strong alkaline atmosphere, excellent chemical resistance and water resistance can be simultaneously achieved. Based on the anti-rust pigment mixture (C-1), the synergistic effect can be greatly exerted, so that excellent corrosion resistance can be achieved. When the coating composition of the present invention is applied to a metal plate to form a coating film, when the rust-preventive pigment mixture (C-2) is used as the rust-preventing pigment mixture (C), it has excellent corrosion resistance. The reason for this is that the present inventors consider a metal ion generated by dissolving a raw material metal such as chloride ion in a corrosive environment, or a zinc ion or an aluminum ion eluted from a rust inhibitor mixture, and a pentavalent vanadium ion ( The vanadium acid ion of ν〇Γ or vo43· does not directly form a precipitating salt via a redox reaction, or the calcium ion or other metal ion dissolved from the rust inhibitor mixture has an effect of suppressing the anodic dissolution reaction of the raw material metal, so that 5 The trivalent vanadium ion and the calcium ion formed by the oxidation reaction of the vanadium ion and the raw material metal can form a precipitate with the phosphate ion, and are effectively coated on the exposed surface of the raw material, particularly on the galvanized steel sheet. By forming a different kind of metal battery with zinc ions or vanadate ions, the charge body as a corrosion current migrates to the exposed portion of the iron, reacts and forms a salt to suppress the anodic polarization of the iron portion, and the potential difference between the different kinds of metals Small effect, in addition, calcium ions and other metal ions do not inhibit the formation of zinc hydroxide near the anode site under coating corrosion Water to form the reaction effect of the zinc oxide so. Further, by using the components (1), (4), and (5) ' constituting the rust preventive pigment mixture (C-2), the acid resistance of each of the components (1), (4), and (5) can be effectively eliminated. Sexual or alkali resistance and water resistance weakness. In addition, since the calcium ion has a function of melting the raw material metal solution of Ρ Η値 greater than 1 且 and dissolving in the strong raw material metal, it is possible to simultaneously achieve excellent water resistance. Based on the rust preventive pigment mixture (C _ 2 ), the synergistic effect can be used, so that excellent corrosion resistance can be achieved. Coating Metal Sheet The coating composition of the present invention can be obtained by hardening a metal sheet to obtain a coated metal sheet. The coated metal plates are, for example, hot-dip steel plates, electric galvanized steel sheets, iron-zinc alloys (galvanyl steel sheets), and aluminum-zinc alloy plated steel sheets (the alloys are plated with galvalium steel sheets). The alloy contains approximately galvan, or a nickel-zinc alloy plated steel plate, an aluminum plate, a steel plate, a plated steel plate, or a tin plated steel plate. The surface may also be treated. The chemical conversion treatment is, for example, a phosphate treatment such as a zinc phosphate treatment, a composite oxide film treatment, a phosphate treatment, or the like. The composition of the present invention can be applied to the above metal plate by a roll flow coating method, a spray method, a brush coating method, or a dipping method. The hardness of the coating film obtained from the composition of the present invention is particularly limited, and is usually 2 to 1 Ο μηη, preferably 3 Å. For the hardening treatment of the coating film, the type of the resin to be used may be subjected to continuous firing by a coating method such as a coil coating method, and the maximum temperature is 160 to 25 CTC, preferably 180 to 230 ° C. 5 to 6 0 seconds. When baking is carried out in batch mode, it is also calcined at 1 to 200 ° C for 10 to 30 minutes. In addition, in the alkaline atmosphere, the chemical properties and the resistance are greatly applied, and the cold-rolled steel sheet and the I-steel sheet are electroplated (the metal sheet or phosphoric acid containing a rare or non-bonded steel such as 55% aluminum and 5% aluminum is electroplated). The thickness of the conventional iron film such as iron chromium treatment, chromium coating method, curtain, etc., is not set to 66 μm, and is appropriately set, often under the condition of raw materials to be used. - 200902650 When a segmented polyisocyanate is used as the crosslinking agent (B), or in the case where a bisphenol type epoxy resin is used as the resin (A) and an amine compound is used as the crosslinking agent (B), the coating film is used. In the case where the crosslinking reaction does not need to be combined with heating in the formation process, it can be hardened by a normal method and dried at room temperature. The coated metal sheet of the present invention can be formed on the metal sheet which has been subjected to chemical conversion treatment. The coating composition of the invention is provided with a coating film which is supplied to the coated metal sheet of the coating film formed by the coating composition of the invention, and a coating film may be provided on the coating film. The film thickness of the surface coating film is usually 8~ 30μπι, preferably 10~25μπι The surface coating material for forming the above surface coating film is, for example, a conventional polyester resin system, an alkyd resin system, a cerium modified polyester resin system, a sand modified acrylic acid resin system, a fluorine resin resin or the like which is used for a precoated steel sheet. In the case of the surface coating material, a coated steel sheet which is particularly excellent in workability can be obtained by using a polyester-based surface layer coating for high processing. The coated metal sheet of the present invention can have a coating film excellent in corrosion resistance. The metal plate formed by the object to be coated 'when galvanized steel plate or aluminum-zinc alloy plated steel plate' can improve the corrosion resistance of the flat portion, and it is resistant to the cut end face and the formed portion until now. Corrosion is not sufficient, but by coating the coating composition of the present invention, excellent corrosion resistance can be obtained at the end surface portion and the processed portion. Further, a coating film can be provided on both sides of the object to be coated by the coating composition of the present invention. The above surface coating film may be formed on the coating film of the coating composition of the present invention as needed. The coating composition of the present invention is formed on both sides, and the formation of the surface can be formed on the back surface. Pigment, in terms of environmental hygiene, has a corrosion-resistant and excellent corrosion-resistant metal sheet. The coated metal sheet of the present invention can be provided on both sides of the surface of the metal sheet which can be chemically treated by the above-mentioned prevention The coating film provided on the rust coating composition may be used as it is, for the purpose of improving the appearance and durability, and a surface coating film may be provided on one or both sides of the rust-preventive coating film. When the film is coated, the surface coating material is coated on one side of the hardened rust-proof coating film and the rust-proof coating film on the other side can be hardened when the surface layer is coated, and the coated substrate can be applied after the surface layer coating. The material is heated and the coating film is hardened. When the surface coating film is provided on both sides, a metal material having a hardened rust-proof coating film on both sides of the surface is usually used, and a surface coating material is applied on one surface of the rust-preventing coating film. After hardening, apply a surface coating on the surface of the other surface of the rust-proof coating film and harden it, and apply a surface coating on both sides of the surface of the rust-proof coating film of the metal substrate to make both sides of the surface hard at the same time. Any one of the methods to make the cured topcoat. The film thickness of the surface coating film is usually 8 to 30 μm, preferably 10 to 25 μm. [Embodiment] Hereinafter, the present invention will be more specifically described by way of Production Examples and Examples. However, the invention is not limited by the following examples. Moreover, in the following, "parts" and "%" are based on quality. [Examples] Production Example 1 Production of Solvent Novolac Phenolic Resin Crosslinking Solution 100 parts of bisphenol A, 178 parts of 37% aqueous formaldehyde solution and 1 part of sodium hydroxide were blended in a reaction vessel at 60 ° C After the reaction was carried out for 3 hours, the mixture was dehydrated under reduced pressure for 5 hours. Then, 1 〇 0 parts of n-butyl -27 - 200902650 alcohol and 3 parts of phosphoric acid were added, and the reaction was carried out at 1 1 Torr to 1 2 ° C for 2 hours. After completion of the reaction, the resulting solution was filtered, and the resulting sodium phosphate was filtered to obtain a resol-type phenol resin cross-linking agent solution B 1 having a solid content of about 50%. The obtained resin had a number average molecular weight of 880, an average number of methylol groups per one equivalent of the benzene nucleus of 0.4 and an average number of alkoxymethyl groups of 1.0. Production Example 2 Production of the back surface coating was carried out by dissolving 80 parts of yipikton (transliteration) #1 009 (made by Nippon Epoxy Co., Ltd., bisphenol A type epoxy resin, hydroxyl group-containing resin) in 1 20 parts of a mixed solvent. 1 [cyclohexanone / ethylene glycol monobutyl ether / solubansone (transliteration) 150 (made by Jesso oil company, high boiling point aromatic hydrocarbon solvent) = 3/1/1 (mass ratio)] In 200 parts of epoxy resin solution, 40 parts of titanium dioxide, 40 parts of cerium oxide and an appropriate amount of mixed solvent 2 [Sorbanban 150 (manufactured by Jesso Petroleum Co., Ltd., high boiling point aromatic hydrocarbon solvent) / cyclohexanone = 1] /1 (mass ratio)] is mixed, and the pigment is dispersed until the particles (particle diameter of the pigment coarse particles) are 20 μm or less. Next, 26.7 parts (20 parts by weight of solid content) of Des Mojiro (transliteration) BL-3 17 5 (manufactured by Bayer Lui Company, methyl group) was added to the dispersion. Ethyl ketoxime-blocked HDI isocyanate-type polyisocyanate compound solution, solid content of about 75%), and 2 parts of Taken Nylon TK-1 (made by Takeda Pharmaceutical Co., Ltd., organotin-based block dissociation catalyst, The solid content was about 10%), and the mixture was uniformly mixed. Then, the above mixed solvent 2 was added to adjust the viscosity to about 80 seconds (Ford Cup #4/2 5 ° C) to obtain a coating for the back surface. Production Example 1 of the rust-preventing paint composition In the case of 85 parts of the yuppieton #1009 (made by Nippon Epoxy Co., Ltd., bisphenol-28-200902650 type A epoxy resin, hydroxyl group-containing resin) was dissolved in 丨3 5 220 parts of a mixed solvent 丨 [cyclohexanone / ethylene glycol monobutyl ether / solubansol 150 (manufactured by Jesmos Petroleum Co., Ltd., high-boiling aromatic hydrocarbon solvent) = 3/1/1 (mass ratio)] In the oxygen resin solution, make 5 parts of vanadium pentoxide, 3 parts of calcium citrate, 3 parts of calcium phosphate, 2 parts of titanium dioxide, 20 parts of cerium oxide and a proper amount of mixed solvent 2 [Soruban 丨 5 〇 (Jeso Oil company, high-boiling aromatic hydrocarbon solvent) /cyclohexanone = 1 / 1 (mass ratio)] Mixing "The pigment is dispersed until the particles (particle diameter of the pigment coarse particles) are 2 μm or less. Next, '20 parts (solid content: 15 parts) of Des Mojilu BL-3175 (HDI isocyanate, which is made of methyl ethyl ketone oxime, manufactured by Baye Lunil Amino Acid Co., Ltd.) is added to the dispersion. Type polyisocyanate compound solution, solid content of about 75%), 2 parts of Takenidon ΤΚ-1 (made by Takeda Pharmaceutical Co., Ltd., organotin blocker dissociation catalyst, solid content about 丨〇%) After mixing the sentences, the above mixed solvent 2 was added, and the viscosity was adjusted to about 8 sec (Ford Cup #4/25t) to prepare a rust-preventive coating composition. Examples 2 to 2 1. Comparative Examples 1 to 8 In Example 1, except that the hydroxyl group-containing resin, the crosslinking agent, the rust preventive pigment, and other pigments used were as shown in Table 1 below, the same as in Example 1. Each rust preventive coating composition was prepared. The amounts of the hydroxyl group-containing resin, the crosslinking agent and the pigment component of Table 1 are expressed by the mass of the solid component. However, in Example 14, 'there is no blending of Kennyton TK-1, and in the examples i 7 and 18, each blended with 1 part of Necchia (transliteration) 5225 (American Qiguyin Ruston Lilu ( Subsequent to the company, a solution of the amine neutralized solution of dodecylbenzenesulfonic acid) replaced 2 parts of TKNTON TK-1. In Table 1, in the resin component (the total solid content of the hydroxyl group-containing resin and the crosslinking agent is -29 - 200902650, the mass of the component is 100 parts by mass), the total amount of each rust preventive pigment is described as being added to 150 ° of 100,000 parts by mass. C. The pH of the filtrate (pH of the rust preventive pigment solution) which was stirred for 6 hours in a 5 mass% sodium chloride aqueous solution and allowed to stand at 25 ° C for 48 hours. For example, the pH of the rust preventive pigment solution of Example 1 is 5 parts by mass of vanadium pentoxide and 3 parts by mass of citric acid in 100 parts by mass of an aqueous solution of sodium chloride having a concentration of 5 mass% at 25 ° C. Calcium and 3 parts by mass of calcium phosphate, the pH of the filtrate which was filtered by the supernatant liquid which was dissolved under the above conditions. Example 22 Into 85 parts of yuppieton #1〇〇9 (made by Nippon Epoxy Co., Ltd., bisphenol A type epoxy resin, hydroxyl group-containing resin) was dissolved in 丨35 parts of mixed solvent 环[cyclohexanone] /ethylene glycol monobutyl ether / solubanban 150 (manufactured by Jesso Petroleum Co., Ltd., high boiling point aromatic hydrocarbon solvent) = 3/1/1 (mass ratio)] 22 of 5 epoxy resin solutions, 5 Parts of vanadium pentoxide, 3 parts of calcium citrate, 3 parts of calcium phosphate, 2 parts of titanium dioxide '20 parts of cerium oxide and a suitable amount of mixed solvent 2 [Sorubanso 150 (manufactured by Jesso Petroleum Corporation, high boiling point aromatic hydrocarbon system) Solvent) / cyclohexanone = 1 / 1 (mass ratio)] Mixing 'The pigment was dispersed until the particles (particle diameter of the pigment coarse particles) were 20 μm. Next, 20 parts (15 parts of solid content) of Des Mojiru bl-3175 (manufactured by Sustained Bayeride) and blocked with methyl ethyl ketone oxime were added to the dispersion. HDI isocyanate type polyisocyanate compound solution 'solid content about 75%), 2 parts of Taken Nitton (transliteration HKd (Wu fl @ &&& system, organotin block dissociation catalyst, solid content about 1 〇 %) uniformly mixed, and then the above mixed solvent 2 was added to adjust the viscosity to about 80 seconds (Ford Cup #4/2 5〇C) to obtain a rust preventive paint composition. -30 - 200902650 Examples 23 to 44, Comparative Examples 9 to 16 and Reference Examples 1 and 2 In Example 22, except that the hydroxyl group-containing resin, the crosslinked rust preventive pigment, and other pigments used were as shown in Table 1 below, the same as in Example 22 Each of the rust-preventive paint compositions was prepared. Reference Examples 1 and 2 are conventional rust-preventive paint compositions containing a sulphate-based rust preventive pigment. Table 1 shows the amount of the hydroxyl group-containing resin 'crosslinking agent and pigment component, All are represented by the mass of the solid component. However, in Examples 33, 34 and 39, the Takenyton TK-1 was not blended, and In 42 and 43, 1 part of Necchia 5225 (manufactured by Qiqiyin Ruston Lilu Co., Ltd., an amine neutralizing solution of dodecylbenzenesulfonic acid) was substituted for 2 parts of TAKKENTON TK · 1 .

-31- 200902650 Table 1(1) Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Hydroxyl-containing resin (component A) Yappicton #1009 85 85 85 85 85 85 85 85 85 85 85 85 85 85 Yeboc 837 (Note 1) 90 Bailong 296 (Note 2) Alachiton 7018 (Note 3) Hardener (B component) Diss Geely BL3175 15 15 15 15 15 15 15 15 15 15 15 15 10 Smijilu N3300 (Note 4) 15 Soluble phenolic phenol resin solution B-1 15 obtained in Production Example 1 Semeru 303 (Note 5) Antirust pigment (C-1 component) 5 Vanadium oxide 5 10 30 30 50 30 30 30 30 10 50 50 30 30 30 Calcium vanadate ammonium vanadate calcium citrate 3 10 30 30 50 30 50 10 50 30 30 30 Magnesium citrate 20 Aluminum citrate 20 20 Calcium phosphate 3 10 30 30 50 30 50 50 10 30 30 30 Calcium hydrogen phosphate 30 30 Calcium triphosphate 30 Other pigment Titanium white 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Cerium oxide 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 S Andvor3058(/£ 6) 3 3 Anti-rust pigment c-1 total 11 30 90 90 150 80 80 80 90 110 110 110 90 90 90 Anti-rust pigment solution pH値6,6 8.0 8.1 8.1 8.1 7.3 7.0 7, 0 8.1 9.6 5.2 8.4 8,1 8.1 8.1 200902650 Table 1 (2) Example Comparative Example Reference Example 16 17 18 19 20 21 1 2 3 4 5 6 7 8 1 2 Hydroxyl-containing resin (component A) Yappicton #1009 85 85 85 85 85 85 85 85 85 85 85 85 Yeboc 837 (Note 1) Bailong 296 (Note 2) 85 Alacington 7018 (Note 3) 80 80 Hardener (B component) Diss魔吉鲁BL3175 15 15 15 15 15 15 15 15 15 15 15 15 15 15 Smijilu N3300 (Note 4) Resolvent novolac type phenol resin solution obtained in Production Example 1 B-1 5 5 Semelu 303 (Note 5) 15 15 anti-rust pigment (component C-1) 5 vanadium oxide 30 20 20 50 1 60 100 30 30 0 30 30 ammonium vanadate 20 calcium vanadate 30 calcium citrate 30 20 20 30 30 10 1 60 30 100 30 30 0 30 magnesium niobate Calcium acid 30 20 20 30 30 10 60 30 30 100 30 30 0 Calcium hydrogen phosphate triphosphate calcium strontium chromate 50 90 Other pigment titanium white 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Sandvor 3058 (Note 6) 3 Anti-rust pigment C-1 total 90 60 60 80 90 70 3 180 160 160 160 60 60 60 50 90 Anti-rust pigment solution pH 値 8.1 8.1 8.1 9.0 10.3 3.1 8.0 8.2 4.4 9.1 8.0 11.2 4.3 8.1 7.7 7.7 200902650 Table 1 (3) Example 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 Hydroxyl-containing resin (component A)耶皮克顿#1009 85 85 85 85 85 85 85 85 85 85 85 85 85 85 85 Yeboc 837 (Note 1) Bailong 296 (Note 2) Alacington 7018 (Note 3) Hardener ( Component B) Diss Magic Gillow BL3175 15 15 15 15 15 15 15 15 15 15 15 15 15 Smijilu N3300 (Note 4) 15 The soluble aldehyde type phenol resin solution obtained in Production Example 1 B-1 15 15 stopper Meru 303 ( 5) Anti-rust pigment (component C-2) 5 vanadium oxide 5 10 30 30 50 30 30 30 30 30 10 50 50 ammonium vanadate 30 calcium vanadate 30 30 calcium citrate 3 10 30 30 50 30 30 30 10 30 30 50 10 50 Calcium carbonate 20 Calcium oxide 20 Aluminum phosphate 3 10 30 30 50 30 30 50 30 30 50 50 10 Zinc phosphate 30 Magnesium phosphate 30 Tripoly ortho-catecholate 30 Other pigment Titanium white 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 钡 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Sandvor 3058 (Note 6) 3 3 Anti-rust pigment C-2 total 11 30 90 90 150 80 80 90 90 90 70 90 90 110 110 110 pH of anti-rust pigment solution 値 6.6 8.1 8.1 8.1 7.7 8.3 7.9 8.0 8.1 7.4 10.3 10.3 9.4 5.0 8.4 -34 - 200902650 Table 1 (4) Example comparison example Reference example 38 39 40 41 42 43 44 9 10 11 12 13 14 15 16 1 2 Hydroxyl-containing resin (component A) Yappicton #1009 85 85 85 85 85 85 85 85 85 85 85 85 85 Yeboc 837 (Note 1) 85 Baylong 296 (Note 2) 85 Alacington 7018 (Note 3) 80 80 Hardener (B component) Diss Magic Gyro BL3175 15 15 15 15 15 15 15 15 15 15 15 15 15 Smijilu N3300 (Note 4) 15 Resole type phenol resin solution obtained in Production Example 1 B-1 15 5 5 Semelu 303 (Note 5) 15 15 Antirust pigment (component C-2) 5 Vanadium oxide 30 30 30 30 30 30 50 1 60 100 30 30 30 30 Calcium ammonium vanadate vanadate calcium citrate 30 30 30 30 30 30 10 1 60 30 100 30 30 30 Calcium carbonate calcium oxide aluminum phosphate 30 30 30 30 30 30 10 60 30 30 100 30 30 Zinc phosphate magnesium phosphate triphosphate calcium strontium chromate 50 90 other pigment titanium white 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 yttrium oxide 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Sandvor3058('Ji 6) 3 Anti-rust pigment C-2 total 90 90 90 90 90 90 70 3 180 160 160 160 60 60 60 50 90 pH of anti-rust pigment solution 値 8.1 8.1 8.1 8.1 8.1 3.4 8.0 8.1 4.4 9.1 7.8 10.9 4.5 8.0 7.7 7.7 In Table 1 above, the notes in the table have the following meanings. . (Note 1) Jebucci 8 3 7: manufactured by Mitsui Chemicals Co., Ltd., trade name, urethane-modified epoxy resin, hydroxyl-containing resin, valence of a primary hydroxyl group of about 35, and an acid value of about 0. -35 - 200902650 (Note 2) Bailong 296: manufactured by Toyobo Co., Ltd., trade name, epoxy-modified polyester resin, hydroxyl-containing resin, hydroxyl group 7, acid value 6. (Note 3) Alacchiton 7018: Arakawa Chemical Co., Ltd., trade name, polyester resin, hydroxyl-containing resin, hydroxyl group price of about 1 〇, acid value of 3 or less. (Note 4) Smijilu (transliteration) N3 3 00: Sustained by yyylidene urethane (meth), isocyanate type polyisocyanate compound, solid content 10 0 ° ° (Note 5) Semel (transliteration) ) 3 0 3 : Made in Japan, Saigu Valley, Russell Lilu (transliteration) (share) company, trade name, methyl etherified melamine resin. (Note 6) SandV〇r3〇58: Gula Rinton (transliteration) company, brand name, hindered amine UV stabilizer. Each of the rust-preventive paint compositions and the surface coatings obtained in the above-mentioned Examples 1 to 2 and Comparative Examples 1 to 8 was used as a test-coated plate, and each of the raw materials was coated by the following coating treatment and fired. A coating plate for each test was obtained. Coating treatment 1: In the case of a zinc-aluminum-plated steel sheet (a thickness of 0.35 mm, an aluminum-zinc alloy plated steel sheet, an alloy containing about 55 % aluminum, and an alloy plating unit weight of 150 g/m 2 , Table 2) In the middle of the "GL steel plate", the back surface coating material obtained in the above Production Example 2 was coated with a bar coater at a dry film thickness of 8 // m and the raw material reached a maximum temperature of 180 k t: The firing was performed for 30 seconds to form a back coating film. On the side of the steel sheet opposite to the back coating film of the coating sheet on which the back coating film was formed, the respective rust-preventive coating compositions obtained in the above respective examples were coated with a bar at a dry film thickness of 5 // m. The device was coated, and -36 - 200902650 raw materials reached a maximum temperature of 2 2 ° ° C for 40 seconds, each forming a main coating film. After cooling, the enamel color of the main coating film is 1 580 Β 4 0 (manufactured by Kansai Paint Co., Ltd., trade name, polyester-based surface coating, blue, hardened coating film, glass transition temperature of about 7 (TC) The coating was applied by a bar coater and a dry film thickness of about 1 5 // m, and the raw materials were brought to a maximum temperature of 220 ° C for firing for 40 seconds to prepare test plates for each test. 2: The back surface obtained in the above Production Example 2 was applied to a hot-dip galvanized steel sheet having a chemical conversion treatment (thickness: 0.35 mm, gold plating unit area weight: 250 g/m2, and "GI steel sheet" in Table 2) Coating with a coating at a dry film thickness of 8 // m with a bar coater, and baking the raw material to a maximum temperature of 18 for 30 seconds to form a back coating film. On the steel sheet surface on the opposite side of the back coating film of the coated sheet, each of the rust-preventive coating compositions obtained in the above respective examples was coated with a bar coater at a dry film thickness of 5 #m, and the raw material reached the highest. The main coating film is formed by firing at a temperature of 220 ° C for 40 seconds. After cooling, the main coating is performed here. *1KP color 1580B40 (made by Kansai Paint Co., Ltd., trade name, polyester surface coating, blue, hard coating film glass transfer temperature of about 70 ° C), with a bar coater, dry film thickness of about 1 5 #m was applied, and the raw materials reached a maximum temperature of 2 2 ° C for 40 hours to prepare a test plate for each test. Coating treatment 3: In the implementation of the treatment with zinc phthalate The back surface coating material obtained in the above Production Example 2 was coated with a bar coater at a dry film thickness of 8/zm on a cold-rolled steel sheet (plate thickness: 8 mm, indicated by "SPC steel sheet" in Table 2), and The raw material -37 - 200902650 was baked at a maximum temperature of 180 ° C for 30 seconds to form a back coating film. On the opposite side of the steel sheet on the back coating film of the coated sheet on which the back coating film was formed. The rust-preventive coating composition obtained in each of the above examples was coated with a bar coater at a dry film thickness of 20/zm, and the raw material reached a maximum temperature of 18 (for 30 minutes at TC). Each of the test coated sheets was prepared. Each of the rust preventives obtained in the above Examples 22 to 44, Comparative Examples 9 to 16 and Reference Examples 1 and 2 was used. The coating composition and the surface coating material were coated and fired by the coating treatments i to 3 and the coating treatment 4 described below to prepare coating sheets for each test. Coating treatment 4: plating having a chemical conversion treatment was carried out. Aluminium-zinc-bismuth steel plate (plate thickness 〇.35mm, Ming-Xi alloy plated steel plate, alloy containing about 55% aluminum, alloy plating unit area weight 150g/m2, Table 2 is indicated by "GL steel plate") The rust-preventive coating composition obtained in Example 3 was coated with a bar coater at a dry film thickness of 8 // m, and the raw material was baked at a maximum temperature of 180 ° C for 30 seconds to form a back coating film. . On the side of the steel sheet opposite to the back coating film of the coating sheet on which the back coating film was formed, each of the rust-preventive coating compositions obtained in the above respective examples was coated with a bar at a dry film thickness of 5 // m. The device was coated, and the raw materials were allowed to reach a maximum temperature of 2 2 ° C for firing for 40 seconds to form a main coating film. After cooling, the KP color 1580B40 (made by Kansai Paint Co., Ltd., trade name, polyester-based surface coating, blue, hardened coating film, glass transition temperature of about 70 ° C) was applied to the main coating film. The applicator and the dried film were coated at a thickness of about 15 μm, and the raw materials were brought to a maximum temperature of 220 ° C for 40 seconds to prepare test plates for each test. -38 - 200902650 Example 45 Coating and baking treatment were carried out on the raw material by the coating treatment 5 described below to obtain a test coated sheet. Coating treatment 5: In the case of a zinc-aluminum-plated steel sheet having a chemical conversion treatment (plate thickness 0.35 mm, ingot-zinc alloy plated steel, alloy containing about 55 % aluminum, alloy plating unit weight: 150 g/m 2 , Table 2 The back surface coating material obtained in the above Example 1 was coated with a bar coater at a dry film thickness of 8 // m on a "GL steel plate", and the raw material reached a maximum temperature of 180 ° C. The firing was performed for 30 seconds to form a back coating film. On the steel sheet surface opposite to the back surface coating film of the coating sheet on which the back coating film was formed, each of the rust-preventive coating compositions obtained in the above respective examples was dried at a film thickness of 5 #m, and a bar coater was used. The coating was applied, and the raw materials were allowed to stand at a maximum temperature of 220 ° C for 40 seconds to form a main coating film. After cooling, the KP color of the main coating film is 1 5 8 0 B 4 0 (manufactured by Kansai Paint Co., Ltd., trade name, polyester-based surface coating, blue, hardened film, glass transition temperature of about 70). °C) The coating was applied by a bar coater and a dry film thickness of about 15/zm, and the raw materials were brought to a maximum temperature of 220 ° C for 40 seconds to prepare test plates for each test. Example 4 6 to 6 9. Comparative Example 1 7 to 3 3 and Reference Examples 3 to 6 In the above-mentioned Example 4, 'except for the anticorrosive coating composition used for the front and back surfaces, as shown in Table 3 below, The same operation as in Example 4 was carried out to prepare each test coated sheet. Example 7 0 A coating plate for testing was prepared by the following coating treatment 6. -39 - 200902650 Coating Treatment 6:

The hot-dip galvanized steel sheet having a zinc phosphate chemical conversion treatment (thickness: 0.35 mm, zinc plating unit area weight: 250 g/m2, and "GI steel plate" in Table 3) was used to prevent the above-mentioned Example 1 The rust coating composition was applied as a dry film thickness of 8 // m with a bar coater, and the raw material was allowed to reach a maximum temperature of 18 ° C for 30 seconds to form a back coating film. On the side of the steel sheet opposite to the back coating film of the coating sheet on which the back coating film was formed, each of the rust-preventive coating compositions obtained in Example 1 was coated with a bar at a dry film thickness of 5 // m. The coating was applied, and the raw materials were brought to a maximum temperature of 22 (40 seconds after firing at TC) to form a main coating film. After cooling, KP color 1580B40 was made on the main coating film (manufactured by Kansai Paint Co., Ltd. Trade name, polyester surface coating, blue, hard coating film glass transfer temperature of about 70 ° C) coated with a bar coater, dry film thickness of about 15 / zm, so that the raw material reaches the maximum temperature Each of the test coated sheets was prepared by firing at 220 ° C for 40 seconds. Example 7 1 to 9 4, Comparative Example 3 4 to 5 0 and Reference Examples 7 to 1 0 In the above Example 70, The rust-preventing paint composition used for the front and back surfaces was subjected to the same operation as in Example 70 except that the rust-preventive paint composition used in the surface and the back surface was subjected to the same operation to obtain a test-coated plate for each test. Each of the test coated sheets obtained in 1 to 94 and Comparative Examples 1 to 50 and Reference Examples 1 to 10 was coated by the following test method. Performance test. The test results are shown in Tables 2 to 4 below. Test Method - 40 - 200902650 Resistance to boiling water: immerse each test plate cut to a size of 5 cm χ 10 cm at about 1 °C After boiling in boiling water for 2 hours, take out and evaluate the appearance of the coating film on the surface side. Perform the evaluation of the checkerboard tape adhesion test. The checkerboard tape adhesion test system is JI SK - 5 4 0 0 8 . 5 . 2 (1 9 9 0) Using the tape method as a reference, the gap between the cuts was 1 mm, and 10 checkerboards were made, and the adhesive tape was adhered to the surface to observe the number of checkers remaining on the coated surface after the intense peeling. There are no abnormalities such as debris and whitening. The number of remaining checkerboards is 100. There are no abnormalities such as debris and whitening on the coating film. The number of remaining checkerboards is 91~99. △: On the coating film There are abnormal cases of fragmentation, whitening, etc., the number of remaining checkerboards is 91~99, or there is no abnormality such as fragmentation, whitening, etc. on the coating film. However, the number of remaining chessboards is 7 1~9 0 X: Produces a fairly significant fragmentation on the film , or the residual checkerboard number is 70 or less alkali resistance: the back surface and the cut surface of each test coated board which are cut into 5cm x 10cm size are sealed with anti-rust paint, and placed in the central part of the surface side of the coated board After reaching the cross-cut surface of the texture, the coated plate was immersed for 2 hours in a 5% aqueous solution of sodium hydroxide, and then taken out and washed to evaluate the surface side of the coated plate which was dried at room temperature. The appearance of the coating film was adhered to the cross-cut portion by an adhesive tape, and the peeling width (single side) of the coating film from the cut portion after the intense peeling was evaluated. -41 - 200902650 ◎: There is no chipping. The tape peeling width from the cutting part is 1 · 5 mm or less. 〇: There is no chipping. The tape peeling width from the cutting part is larger than 1.5 mm and 3 mm or less. △: There is a slight fragmentation. In this case, the tape peeling width from the cutting portion is 3 mm or less, or no chipping occurs, but the tape peeling width from the cutting portion is larger than 3 mm. X: Fragmentation occurs, and the tape peeling width from the cutting portion is larger than 3 mm. : The back surface and the cut surface of each test coated sheet which were cut to a size of 5 cm X 10 cm were sealed with an anti-rust paint, and placed on the cross-cut surface of the texture on the center side of the surface side of the coated sheet. After the coated plate was immersed in a 5% aqueous sodium hydroxide solution at 20 ° C for 48 hours, it was taken out and washed, and the appearance of the coating film on the surface side of the coated plate dried at room temperature was evaluated, and in the cross-cut portion. Adhesive tape is adhered to 'evaluate' the peeling width (single side) of the coating film from the cutting portion after intense peeling. ◎: There is no chipping, and the tape peeling width from the cutting portion is 1. 5 m in or less. 没有: No chipping occurs. The tape peeling width from the cutting portion is larger than l_5 mm and 3 mm or less. △ There is a slight fragmentation, and the self-cutting portion The tape peeling width is less than 3 mm' or there is no chipping, but the tape peeling width from the cutting portion is greater than 3 mm X: There is a fragmentation situation, and the tape peeling width from the cutting portion is greater than -42-200902650. At room temperature of 20 ° C, a coil abrasion test (manufactured by Automation Technology Co., Ltd.) was used, and the edge of the 10 round copper coins was maintained at an angle of 45 degrees on the coated surface of the surface of each test coated sheet. The load was attached and the 1 〇 round copper coin was stretched by about 30 mm at a speed of 10 mm / sec. The degree of scratching when the surface was scratched was evaluated on the basis of the following criteria. ◎: There is no metal raw material in the scratched part: There is a slight metal raw material in the scratched part △: There is a significant metal raw material in the scratched part. X: There is almost no coating film in the scratched part, and it is completely corrosion resistance test of the metal raw material. The GL steel plate and the GI steel plate were subjected to the following composite cyclic corrosion test (CCT test), and the coated plate of the SPC steel plate was subjected to the following salt spray test. Composite cycle corrosion test (1): Examples 1 to 44, Comparative Examples 1 to 16, and Reference Examples 1 to 2 were carried out as follows. Take JIS K-5621 (1990) as the standard. The burrs of the long side edge portions of the test coated sheets were directed toward the surface side coating film surface, the right side toward the surface side, and the left side toward the back side, and the center portion of the surface side of each of the test coated sheets having a small force of 6 cm X 1 2 cm was reached. The cross section of the texture with a narrow angle of 30 degrees and a line width of 0.5 mm is cut by the back of the cutter. {The upper edge portion of the enamel coating is sealed with anti-rust paint, and the upper end portion is bent at the upper end portion (13⁄4 β 4Τ) Applying the outer side of the surface of the coated plate to the outside, and bending the four plates of the same thickness as the coated plate on the inner side of the coated plate, and the coated plate is subjected to a 180-degree bending process with a vise. 3 (rc · 5V. saline spray ο" hour) one (3 〇 it rH95% or more humidity tester tested 1 · 5 hours) one (5 (dry under rc for 2 hours) _ (3 ( Rc 200902650 Drying for 2 hours) 300 cycles (total 1800 hours) test for 1 cycle. The state of the edge portion, the cross-cut portion, and the 4 T bending portion of the coated plate after the test was evaluated. (4T Machining Department) ) Evaluate the total length of the rusted portion of the 4T processing section ◎: There is no rust. 〇: The white rust is less than 20mm. △: The white rust is more than 40mm. X: The white rust is more than 4mm. or there is red rust. The average 値 of the effective edge width of the long side of the left and right sides of the coated plate is evaluated by the following criteria: ◎: less than 5 mm 〇: 5 mm or more, less than l〇mm △ : 10 mm or more, lower 20mm X: 20mm or more (cross-cutting part) makes the corrosion condition of the cross-cut part, the ratio of white rust on the exposed part of the gold-plated part of the cutting width of 〇5mm, and the width of the left and right pieces of the cut part (both sides) And the average enthalpy is evaluated on the basis of the following criteria: ◎: the ratio of white rust on the exposed portion of the gold plating is less than 50% and the shard width is less than 3 mm 〇: the ratio of white rust on the exposed part of the gold plating is more than 50% and The width of the fragments is less than 3 mm, or the proportion of white rust on the exposed portion of the gold plating is less than 50% and the width of the fragments is more than 3 mm and less than 5 mm. △: The ratio of white rust on the exposed part of the gold plating is more than 50% and the width of the fragments is 5mm or more, less than 10mm -44 - 200902650 X : The ratio of the white rust on the gold exposed portion was 50% or more and the fragment width was 10 mm or more. The composite cycle corrosion test (2): Examples 45 to 94, Comparative Examples 17 to 50, and Reference Examples 3 to 10 were carried out as follows. The burrs on the long side edge portions of the test coated sheets were applied to the surface side coating film surface, the right side toward the surface side, and the left side toward the back side, and cut into the center of the surface side of each test coated sheet having a size of 6 cm X 1 2 cm. The cross-cut portion of the narrow angle of 30 degrees and the line width 〇·5 that reaches the texture is cut by the back of the cutter, so that the end edge portion of the coating is sealed with anti-rust paint, and the upper end portion is provided with 4 T bending. The portion is formed by bending the outer surface side of the coated sheet, sandwiching four sheets of the same thickness as the coated sheet on the inner side, and subjecting the coated sheet to a 180-degree bending process with a vise. The test coated plate for the coating treatment 5 was sprayed at 5% (5 °C for 5 hours with a salt water for 2 hours) on JIS-H8502.8. 1 (150 ° C, RH9 5 % or more moisture resistance tester is subjected to moisture resistance test for 2 hours) for 1 cycle '150 cycles (total 1 2 0 0 hours) test. The state of the edge portion, the cross-cut portion, and the 4T curved portion of the coated sheet after the test was evaluated. Regarding the test coating plate for the coating treatment 6, in the cycle test of the test coated plate in the above coating treatment i, the number of cycles was changed from 150 cycles (total 12,000 hours) to 100 times. The same test was carried out except for the cycle (total of 80 hours). After the test, the state of the edge portion of the coated sheet, the cross-cut portion, and the 4T bent portion was evaluated. (4T processing unit) The total length of the rusted portion of the 4T processing portion is evaluated. 200902650 ◎: No rusting situation: White rust is less than 20mm △: White rust is more than 20 mm, less than 4 〇mm X: White rust is more than 4 〇mm or red In the case of rust generation (edge portion), the average 値 of the effective edge width of the long sides of the left and right sides of the coated plate was determined, and evaluated by the following criteria. ◎: less than 5 mm 〇: 5 mm or more, less than 10 mm △ : 10 mm or more, less than 20 mm X : 20 mm or more (cross-cutting part), the uranium state of the cross-cut portion, by the cutting degree of 〇.5nim The ratio of the amount of gold on the exposed part of the gold deposit and the average width of the width of the fragments (the sum of the sides) of the cut portion are evaluated on the basis of the following criteria. ◎: The proportion of the white gold exposed portion is less than 5 〇% and the shard width is less than 3 mm 〇: the ratio of white rust on the exposed part of the gold plating is more than 50% and the fragment width is less than 3 mm, or the gold plating is exposed. The ratio of white rust is less than 5 〇% and the width of the shard is 3mm or more and less than 5mm. △: the ratio of white rust on the exposed portion of gold is more than 5%, and the width of the shard is more than 5mm, less than l〇mm x: gold plating The exposed portion has a white rust ratio of 50% or more and a fragment width of 10 mm or more. Salt spray test: cuts into 5 cm X 1 〇cm size for each test coating -46-200902650 Mounting plate (SPC steel plate coating plate) The back surface and the cut surface are sealed with an anti-rust paint, and placed on the cross-cut surface of the texture on the central portion of the surface side of the coated sheet. The coated plate was subjected to a salt spray test (JIS Z-2 3 7 1 ) at 5 5 ° C for 5 hours, and the red rust generation state of the coated surface after the test was evaluated, and in the cross-cut portion. The adhesive tape was adhered to each other to evaluate the peeling width (single side) of the coating film from the cut portion after the intense peeling. ◎: No red rust is generated or slightly, the tape peeling width from the cutting portion is less than 5 mm 〇: There is a considerable red rust situation, and the tape peeling width from the cutting portion is less than 5 mm, or no red rust is generated or Slightly, the tape peeling width from the cutting portion is 5 mm or more and less than 10 mm. △: The red rust is generated in the entire cutting portion, but the tape peeling width from the cutting portion is 5 mm or more and less than 10 mm, or There is no red rust in the entire cutting part, but the tape peeling width from the cutting part is 1 〇mm or more. X: The whole part of the cutting part is red rust, and the tape peeling width from the cutting part is 10 mm or more. The test coated sheet of the coating treatment 1 which is cut into a size of 5 cm X 1 〇cm is based on the A method of the long-term durability-promoting weather resistance (xenon lamp method) test of the coating film specified in JIS K 5 600 7.7. The irradiation was continued for 500 hours with a helium gas analyzer under repeated cycling conditions of (wetting for 18 minutes - drying for 12 minutes). Then, the back surface and the cut surface are sealed with an anti-rust paint, and placed on the cross-cut surface of the surface of the surface of the coated sheet to the texture. Regarding the coated plate, a salt spray test was carried out -47 - 200902650 (JIS Z-2 3 7 1) After 50 hours, the flat portion was evaluated by the following criteria. ◎: The chips are cut from the cutting part. The average width of the rust is less than 3 mm, and there are no other abnormalities. 切割: The cutting piece is cut from the cutting part. The rust is generated to have a width of more than 3 mm and less than 5 mm, and there is no other part on the plane. An abnormal situation occurs, or there is a slight amount of debris on the flat surface, but the cutting piece is cut from the cutting part _ The width of the rust is 3 mm or less △: The cutting piece is cut from the cutting part. The rust is generated to have a width of more than 3 mm and less than 5 mm. There is a slight abnormality in the plane part. X: The cutting part is cut from the cutting part. The rust produces a width greater than 5 mm, and there is significant debris on the flat part.

-48 - 200902650 Table 2 (1) Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Coating processing 1 (GL steel sheet) Boiling water resistance ◎ ◎ ◎ ◎ 〇〇 ◎ ◎ ◎ ◎ ◎ 〇 ◎ 〇 ◎ Alkali resistance ◎ ◎ 〇〇〇〇〇〇〇 ◎ 〇〇 ◎ 〇〇 Acid resistance ◎ ◎ 〇〇〇〇〇〇〇〇 ◎ 〇〇〇〇 〇〇〇〇 〇〇〇〇 〇〇〇〇 〇〇〇〇〇 〇〇〇〇〇 〇〇〇 ◎ ◎ CCT test 4T processing section 〇〇 ◎ ◎ ◎ 〇〇〇〇〇 ◎ ◎ 〇〇 ◎ Edge part 〇〇 ◎ ◎ ◎ 〇〇〇〇〇 ◎ ◎ ◎ 〇 ◎ Cross cutting section 〇〇〇〇 ◎ 〇〇〇〇〇〇〇〇◎ 〇 weathering salt spray test 〇〇〇 ◎ 〇〇〇 〇〇〇〇〇〇〇 〇〇〇〇〇〇〇 coating processing 2 (GI steel plate) boiling resistance water ◎ ◎ ◎ ◎ 〇〇 ◎ ◎ ◎ ◎ ◎ 〇 ◎ 〇 ◎ alkaline resistance 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 acid resistance ◎ 〇〇〇〇〇〇〇〇〇〇〇〇〇〇 scratch resistance 〇〇〇〇 ◎ 〇〇 〇〇〇〇〇 ◎ ◎ CCT test 4T processing section 〇〇〇〇 ◎ 〇〇〇〇〇〇〇〇〇 ◎ edge section 〇〇〇〇 ◎ 〇〇〇〇〇〇〇〇〇〇 cross cutting section 〇〇〇 〇〇〇〇〇〇〇〇〇〇〇〇Coating process 3 (SPC steel plate) Boiling water resistance ◎ ◎ ◎ ◎ 〇〇 ◎ ◎ ◎ ◎ ◎ 〇 ◎ 〇 ◎ Alkali resistance ◎ ◎ ◎ ◎ 〇〇〇〇〇 〇 ◎ 〇〇 ◎ 〇 acid resistant 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 scratch resistance 〇〇〇〇〇〇〇〇〇〇〇〇〇 ◎ ◎ salt spray test 〇〇〇〇 ◎ 〇 〇〇〇〇〇〇〇〇〇200902650 Table 2(2)

-50 - 200902650 Table 2 (3) Example 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 Coating Process 1 (GL steel plate) Resistance to boiling water ◎ ◎ ◎ ◎ 〇〇〇〇〇 ◎ 〇〇 〇〇〇〇 Alkali resistance ◎ ◎ ◎ ◎ 〇〇 ◎ ◎ 〇 ◎ 〇〇〇 ◎ 〇〇 acid resistance ◎ ◎ 〇〇〇〇〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇〇〇〇〇〇 〇〇〇〇 〇 〇 〇〇〇〇〇 ◎ ◎ 〇〇〇CCT test 4T processing department 〇〇 ◎ ◎ ◎ ◎ ◎ 〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 edge part 〇〇〇〇 ◎ 〇 ◎ 〇〇〇〇〇〇〇〇〇 cross Cutting section 〇〇〇〇 ◎ 〇 ◎ 〇〇〇〇〇〇〇〇〇 weather resistant salt spray test 〇〇〇 ◎ 〇〇〇〇〇〇〇〇 ◎ 〇〇〇 coating processing 2 (GI steel plate) resistance to boiling water ◎ ◎ ◎ ◎ 〇〇〇〇〇 ◎ 〇〇〇〇〇〇 alkali resistance 〇〇〇〇〇〇〇 〇 〇 ◎ 〇〇〇〇〇〇 acid resistance ◎ ◎ 〇〇〇〇〇〇〇〇〇〇〇 〇〇〇 〇〇〇 〇〇〇 〇〇〇〇 〇〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇〇〇 CCT test 4T processing section 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 edge part 〇〇〇〇 ◎ 〇〇〇〇〇〇〇〇〇〇〇 Cross cutting section 〇〇〇〇 ◎ 〇 〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇 coating processing 3 (SPC steel plate) Resistance to boiling water ◎ ◎ ◎ ◎ 〇〇〇〇〇 ◎ 〇〇〇 ◎ ◎ 〇 alkali resistance ◎ ◎ ◎ ◎ 〇〇 ◎ ◎ 〇 ◎ 〇〇〇〇 ◎ 〇 acid resistant 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 scratch resistance 〇〇〇 〇〇〇〇〇〇〇〇〇〇〇〇〇Salt spray test 〇〇〇〇 ◎ 〇 〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇 coating processing 4 (GL steel plate, back: Example 24 coating) Resistance to boiling water ◎ ◎ ◎ ◎ 〇〇〇〇〇 ◎ 〇〇〇〇〇〇 〇〇〇〇〇〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇〇 acid resistance ◎ ◎ 〇〇〇 〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇〇 〇〇〇〇〇〇〇〇〇〇 ◎ ◎ 〇〇〇 CCT test 4T processing department 〇〇 ◎ ◎ ◎ ◎ ◎ 〇〇 ◎ 〇〇〇〇〇〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 026 39 40 41 42 43 44 9 10 11 12 13 14 15 16 1 2 Coating process 1 (GL steel boiling resistance ◎ ◎ ◎ 〇〇〇〇 ◎ X Δ 〇〇 ◎ ◎ 〇〇 Δ Alkali resistance ◎ 〇〇〇 〇〇〇 ◎ Δ X 〇〇〇〇〇〇 Δ Acid resistance ◎ ◎ 〇〇〇〇〇 ◎ Δ 〇 Δ 〇〇 ◎ 〇〇〇 擦 儒 〇 〇 ◎ ◎ ◎ 〇 Δ ◎ 〇〇〇〇 Δ 〇〇 ◎ CCT test 4T processing section 〇〇 ◎ 〇〇〇 X 〇〇 Δ Δ X Δ Δ 〇 ◎ edge part 〇〇 ◎ ◎ ◎ ◎ 〇 X 〇〇 Δ Δ XX Δ ◎ ◎ Cross cutting part 〇 ◎ 〇〇 ◎ ◎ 〇Δ 〇〇Δ 〇X Δ 〇〇◎ Weather-resistant salt spray test 〇〇〇〇〇◎ 〇X 〇〇Δ 〇XX 〇〇〇Coating process 2 (GI steel plate) Boiling water resistance ◎ ◎ ◎ 〇〇〇〇◎ X Δ 〇〇 ◎ ◎ 〇〇 Δ Alkali resistance 〇〇〇〇〇〇〇〇 XX Δ Δ 〇〇〇〇 Δ Acid resistance ◎ ◎ 〇〇〇〇〇〇 Δ 〇 Δ 〇〇 ◎ 〇〇〇 〇〇〇 〇〇〇 〇 ◎ 〇〇 ◎ ◎ 〇 Δ ◎ 〇〇〇〇 Δ 〇〇 ◎ CCT test 4T processing part 〇〇〇〇〇〇〇 X 〇〇 Δ Δ X Δ Δ ◎ ◎ Edge part 〇 ◎ ◎ ◎ ◎ ◎ 〇 X 〇〇 Δ Δ XX Δ 〇 ◎ Cross cutting section 〇 〇〇 ◎ ◎ 〇 Δ 〇〇 Δ 〇 X Δ 〇〇〇 coating processing 3 (SPC steel® boiling water resistance ◎ 〇 ◎ 〇〇〇〇 ◎ X Δ 〇〇 ◎ ◎ 〇〇Δ alkali resistance 〇 〇〇 ◎ ◎ 〇 Δ Δ X 〇〇〇 Δ 〇〇 Δ acid resistance X Δ X 〇〇〇〇〇〇 scratch resistance 〇 ◎ ◎ 〇 ◎ ◎ 〇△ 〇〇〇 〇〇Δ 〇〇〇Salt spray test 〇〇〇〇〇〇〇X 〇〇Δ XX Δ Δ 〇〇Coating process 4 (GL steel plate, back: Example 24 coating) Boiling water resistance ◎ ◎ ◎ 〇〇〇〇 ◎ X Δ 〇〇 ◎ ◎ 〇〇 Δ Alkali resistance ◎ 〇〇〇〇〇〇 ◎ X 〇〇〇〇〇〇 Δ Acid resistance ◎ ◎ 〇〇〇〇〇 ◎ Δ 〇 Δ 〇〇 ◎ 〇〇〇 耐擦 ◎ 〇〇〇〇 〇〇〇 〇〇〇 CCT test 4T processing unit 〇〇 ◎ ◎ 〇〇〇 X 〇〇 Δ Δ X Δ Δ 〇 ◎ edge portion ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ 〇〇〇 Δ Δ ◎ ◎ Cross cutting section 〇 ◎ ◎ ◎ 〇 Δ 〇〇 Δ 〇 X Δ 〇〇 ◎ 200902650 Table 3 (1) Example 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 Surface anti-corrosive coating composition 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Back anti-rust coating) Shake composition 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Coating processing 5 (GL steel plate) Boiling water resistance ◎ ◎ ◎ ◎ 〇〇 ◎ ◎ ◎ ◎ ◎ 〇 ◎ 〇 ◎ Alkali resistance ◎ ◎ 〇〇〇〇〇〇〇 ◎ 〇〇 ◎ 〇〇 Acid resistance ◎ ◎ 〇〇〇〇〇〇〇〇 ◎ 〇〇〇〇 〇〇〇〇 〇〇〇〇 〇〇〇〇 〇 〇 〇〇〇〇〇〇〇 ◎ ◎ CCT test 4T processing part 〇〇 ◎ ◎ ◎ 〇〇〇〇〇 ◎ ◎ 〇〇 ◎ edge part 〇〇 ◎ ◎ ◎ ◎ 〇〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Cross cutting section 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 耐 耐 耐 盐水 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 200902650 Table 3 (2) Real Ji Comparative Example 60 61 62 63 64 65 66 67 68 69 17 18 19 20 21 Surface anti-corrosive coating composition 16 Π 18 19 20 21 1 2 4 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Back rust-proof coating composition 16 17 18 19 20 21 3 3 3 3 *2 *2 *2 *2 *2 Coating processing 5 (GL steel ί® boiling resistance 〇〇〇〇〇〇 ◎ ◎ ◎ 〇 ◎ X Δ 〇〇 alkali resistance 〇〇〇 〇〇〇◎ ◎ 〇〇◎ Δ X 〇〇耐Acid 〇〇〇〇〇〇 ◎ ◎ 〇〇 Δ Δ 〇 Δ 〇 〇 〇 Δ ◎ 〇〇〇 CCT test 4T processing section ◎ 〇〇〇〇〇〇〇 ◎ ◎ X 〇〇 Δ Δ edge portion ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Δ 〇 cross cutting unit ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ X 〇 ◎ Δ ◎ weathering salt spray test ◎ ◎ ◎ 〇〇〇〇 〇 ◎ ◎ X 〇 Δ Δ 〇 Table, * 2 shows manufacturing example 2

-54 - 200902650 Table 3 (3) Comparative Example Reference Example 22 23 24 25 26 27 28 29 30 31 32 3 4 5 6 Bibibi ratio is more than the reference parameter and the anti-rust coating is more resistant. More Comparative Test Cases Examples Examples Examples 8 6 2 2 3 4 5 6 7 8 1 2 1 2 Bibibi ratio ginseng back anti-rust coating Composition *2 *2 *2 More Comparative than 2 Ice 2 Test Cases Examples Examples 1 2 3 4 5 6 7 8 1 2 Boiling Water Resistance ◎ ◎ 〇 ◎ X Δ 〇〇 ◎ ◎ 〇〇 Δ 〇 Δ Alkali resistance 〇〇〇 Δ X 〇〇〇〇〇〇 Δ 〇 Δ Acid resistance 〇 ◎ ◎ Δ 〇 Δ 〇〇 ◎ 〇〇〇〇〇 〇〇〇〇〇 〇〇〇〇〇 〇 〇 〇Δ ◎ 〇〇〇〇Δ 〇〇◎ 〇◎ Coating processing 5 CCT 4T processing (GL steel plate) Test section X △ Δ X Δ 〇 Δ Δ X 〇 Δ 〇 ◎ 〇 ◎ Edge portion X Δ 〇 X ◎ ◎ 〇 ◎ X Δ ◎ ◎ ◎ ◎ ◎ Cross-cutting part X Δ Δ X 〇 ◎ Δ ◎ Δ 〇 Δ 〇 ◎ ◎ ◎ Weather-resistant salt spray test X Δ 〇 X 〇 Δ Δ Δ X Δ ◎ In the table, *2 shows the manufacturing example 2

-55 - 200902650 Table 4(1) 1 mm 70 71 72 73 74 75 76 ΊΊ 78 79 80 81 82 83 84 Surface anti-corrosive coating composition 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Back rust Coating composition 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Coating process 6 (GI reverse) Boiling water resistance ◎ ◎ ◎ ◎ 〇〇 ◎ ◎ ◎ ◎ ◎ 〇 ◎ 〇 ◎ Alkali resistance 〇〇〇〇〇〇〇〇〇〇〇〇〇acid resistance ◎ 〇〇〇〇〇〇〇〇〇〇〇〇〇〇 scratch resistance 〇〇〇〇 ◎ ◎ ◎ CCT test 4T processing part 〇〇〇〇 ◎ 〇〇〇〇〇〇〇〇〇 ◎ edge part 〇〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ Cross cutting section 〇〇 ◎ ◎ 〇〇 ◎ ◎ ◎ 〇〇〇 〇◎ 〇

-56 - 200902650 Table 4(2) Comparative Example 85 86 87 88 89 90 91 92 93 94 34 35 36 37 38 Bibibi ratio 16 17 18 19 20 21 4 More surface anti-corrosive coating composition 1 1 j Example 1 Example 2 Example 3 Example 4 Example 5 Back rust-proof coating composition 16 17 18 19 20 21 3 3 3 3 *2 *2 η *2 η Resistance to boiling water 〇〇〇〇〇〇 ◎ ◎ ◎ 〇 ◎ X Δ 〇〇 alkali resistance 〇〇〇〇〇〇〇〇〇〇 Δ X 〇〇 coating plus acid resistance 〇〇〇〇〇〇 〇〇〇 ◎ Δ 〇 X Completion 6 (GI: abrasion resistance 〇〇〇〇〇〇〇〇〇 Δ ◎ 〇〇〇 steel plate) CCT 4T processing part 〇〇〇〇〇〇〇〇〇 ◎ X 〇〇 Δ Δ test edge part ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ X ◎ ◎ Δ 〇 cross-cutting section 〇 ◎ 〇〇〇〇〇 ◎ ◎ X 〇〇 Δ Δ In the table, *2 shows the manufacturing example 2

-57 - 200902650 Table 4(2): 匕 Comparative Example Reference Example 39 40 41 42 43 44 45 46 47 48 49 7 8 9 10 Ratio, specific ratio of ginseng ginseng surface anti-rust coating composition More Comparative Examinations, Examples, Cases, Examples, Examples, Examples, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases, Cases Rust coating composition *2 *2 η is relatively better than *2 *2 test case 1 case 2 case 3 case 4 case 5 case 6 case 7 case 8 case 1 case 2 resistance to boiling water ◎ ◎ 〇 ◎ X Δ 〇〇 ◎ ◎ 〇〇 Δ 〇 Δ Alkali resistance 〇 〇 Δ Δ X 〇〇〇 Δ 〇〇 Δ Δ 涂 Ή π Acid resistance 〇 ◎ ◎ ◎ 〇 X 〇〇 ◎ Completion 6 (GI scratch resistance 〇Δ 〇 Δ ◎ 〇〇〇〇 Δ 〇〇 ◎ 〇 ◎ 4T machined steel plate) CCT part XXXX 〇〇 Δ 〇 XX Δ ◎ ◎ ◎ ◎ Test edge part Δ Δ Δ Δ ◎ ◎ ◎ 〇 〇 Δ 〇〇〇◎ ◎ X X Δ X cross-cut square ◎ Δ Δ X X Δ ◎ ◎ billion square section cutting table, * 2 are diagrams illustrating [Production Example 2] BRIEF DESCRIPTION te. J\S\ [Description of component symbols] ^FR- 〇 -58 -

Claims (1)

200902650 X. Patent application scope: 1 · A coating composition 'is a coating composition containing (A) a hydroxyl-containing coating film forming tree and a bismuth, (B) crosslinking agent and (c) rust preventing pigment mixture The anti-money pigment mixture (C) is a vanadium compound (2) at least one of vanadium pentoxide 'vanadate and ammonium methylvanadate, (2) metal citrate and (3) phosphate a rust preventive pigment mixture (c _ 丨) formed by a salt, or a combination of the vanadium compound 〇), (4) a calcium compound, and (5) a metal phosphate, a metal hydrogen phosphate, and a tripoly acid metal salt And the metal of each metal salt is a rust preventive pigment mixture (C·2) of Zn, A1 and Mg phosphate metal salts combined to 1 part by mass of the resin (a) and the crosslinking In the total solid content of the agent (b), the amount of each of the rust preventive pigment mixture (c) is from 10 to 150 parts by mass, and the rust preventive pigment mixture ((: υ, the amount of the vanadium compound (1)) 3 to 50 parts by mass, metal citrate (2) is 3 to 50 parts by mass, and the phosphate-based calcium salt (3) is 3 to 50 parts by weight. In the rust preventive pigment mixture (C-2), the amount of the vanadium compound (1) is 3 to 50 parts by mass, the amount of the calcium compound (4) is 3 to 50 parts by mass, and the phosphate metal is used. The amount of the salt (5) is 3 to 50 parts by mass. 2. The coating composition of the first aspect of the invention, wherein the hydroxyl group-containing coating film-forming resin (A) is a hydroxyl group-containing epoxy resin and a hydroxyl group. -59 - 200902650 3. The coating composition of claim 1 or 2, wherein the crosslinking agent (B) is at least one selected from the group consisting of an amine based resin, a phenol resin, and the like. A cross-linking agent of a blocked polyisocyanate compound. The coating composition of claim 1, wherein the phosphate-based calcium salt (3) constituting the rust-preventing pigment mixture (C-1) is At least one of calcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, and calcium tripolyphosphate. 5. A coating composition according to claim 1 wherein calcium constituting the rust preventive pigment mixture (C-2) The compound (4) is at least one of calcium methyl citrate, calcium oxide and calcium carbonate. 6. A coating composition according to claim 1 which additionally contains a pigment component of at least one of a rust preventive pigment, a titanium dioxide pigment and an extender pigment other than the rust preventive pigment mixture (C). The coating composition of the first aspect, which additionally contains at least one of an ultraviolet absorber and an ultraviolet stabilizer. 8 A coating composition according to claim 1, wherein the resin is used for 1 part by mass ( A) a vanadium compound (1) constituting the rust preventive pigment mixture (C-1), a metal citrate (2), and a calcium phosphate salt (a) which are blended with the total solid content of the crosslinking agent (B) 3) The mixture of the mass parts in each of the respective amounts is added to 100 parts by mass of a 5 mass% aqueous solution of sodium chloride at 25 ° C for 6 hours, and allowed to stand at 25 ° C. The pH of the filtrate filtered by the supernatant liquid of the hour is 3 to 10 0. 9. The coating composition of claim 1, wherein the rust-preventing pigment mixture is blended for 10 parts by mass of the total solid content of the resin (A) and the crosslinking agent (B) C-2) a mixture of a vanadium compound (1), a calcium compound-60 - 200902650 (4) and a mass part of the amount of the phosphate metal salt (5), added to 100 parts by mass, 25 The mixture was stirred for 6 hours in a 5 mass% aqueous solution of sodium chloride at °C for 6 hours, and the pH of the filtrate which was allowed to stand at 45 ° C for 48 hours was filtered to be 3 to 10. 10. A coated metal sheet characterized by forming a hardened coating film on a metal sheet which can be subjected to a chemical conversion treatment on the surface, based on a coating composition of the first application of the patent application. A coated metal plate characterized in that a metal plate which can be subjected to a chemical conversion treatment on a surface thereof has a hardened coating film formed on the basis of a coating composition according to claim 1 of the patent application, and in the hardened coating film A plurality of layer coating films formed by forming a surface coating film thereon. A coated metal sheet characterized in that both sides of a metal sheet which can be subjected to a chemical conversion treatment on the surface are formed by forming a hardened coating film based on a coating composition of the first application of the patent application. 13_ a coated metal plate characterized in that both sides of a metal plate which can be subjected to a chemical conversion treatment on the surface have a hardened coating film as a reference on the coating composition of the first application of the patent application, and at least one side A plurality of layer coating films formed by forming a surface coating film on the cured coating film. 200902650 VII. Designation of representative representatives: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: