Title of Invention

"COATING COMPOSITION AND COATED METAL SHEET BY USE THE SAME"

Abstract A coating composition 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-l) consisting of a. combination of (D 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 EI phosphate metal i-alt, 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.
Full Text SPECIFICATION
Title: Coating Composition and Coated Metal Sheet by Use of the Same Field of the Invention;
The present invention relates to a chrome-free coating composition showing excellent corrosion resistance and a coated metal sheet by use of the coating composition, more particularly to a coating composition effective on improving corrosion resistance of not only non-fabricated flat portion but also fabricated portion and edge face and a coated metal sheet by use of the coating composition. Background of the Art:
A precoated metal sheet such as a precoated steel sheet coated by coil coating has widely been used in the art as housing-related goods, for example, building materials such as roofs, walls, shutters, garage and the like for an architectural structure, various kinds of household appliances, panel boards, refrigerator showcase, steel furniture, kitchen fitments, etc.
The housing-related goods are usually prepared from the precoated metal sheet, for example, by a process which comprises cutting a precoated steel sheet, followed by subjecting to fabrication such as press molding and joining. Consequently, the housing-related goods often have a metal-exposed portion as a cut surface and a crack-developed portion due to press molding. Corrosion resistance of the metal-exposed portion and the crack-developed portion may be
reduced compared with other portions. For the purpose of improving corrosion resistance, a primer coating film on the precoated steel sheet generally contains a chrome-based anticorrosion pigment.
However, the chrome-based anticorrosion pigment may contain or produce a hexavalent chrome showing excellent corrosion resistance, resulting in providing problems from the standpoints of health of human body and environmental protection.
Various kinds of chrome-free anticorrosion pigments such as zinc phosphate, aluminum tripolyphosphate, zinc molybdate and the like have been commercially available, and various kinds of primers containing combinations of chrome-free pigments have been proposed. For example, Patent Reference 1 discloses a coating composition prepared by adding an anticorrosion pigment mixture consisting of a combination of calciuin silicate and phosphorus vanadate, or an anticorrosion pigment mixture consisting of a combination of calcium carbonate, calcium silicate, aluminum phosphate and phosphorus vanadate to a vehicle component consisting of epoxy resin and phenol resin. Further, Patent. Reference 2 discloses a coating composition prepared by adding an anticorrosion pigment mixture consisting of a combination of dibasic magnesium phosphate and a calcined product of manganese oxide"vanadium oxide, or consisting of a calcined product of calcium phosphate and vanadium oxide to a polyester resin. However, a coating film formed from the
coating compositions disclosed in Patent References 1 and 2 shows poor corrosion resistance, particularly unsatisfactory corrosion resistance in the fabricated portion and edge face portion compared with a coating composition prepared by use of a chrome based pigment, and further often shows poor chemical resistance such as alkali resistance and acid resistance and poor water resistance when a large amount of the anticorrosion pigment mixture is used. Accordingly, the anticorrosion pigment mixture disclosed in Patent References 1 and 2 is unsatisfactory to be replaced for the chrome based anticorrosion pigment in the preparation of the precoated metal sheet.
Patent Reference 3 discloses a coating composition prepared by adding a silica fine particle having an oil absorption of 30 to 200 ml/100 g and a pore volume of 0.05 to 1.2 ml/g and forming a cured coating film having a glass transition temperature in the range of 40 to 125'C, However, a coating film formed from the coating composition disclosed in Patent Reference 3 shows some corrosion resistance, but shows poor corrosion resistance and poor chemical resistance, particularly unsatisfactory corrosion resistance in the edge face portion compared with a coating composition prepared by use of a chrome based pigment.
Patent Reference 1: Japanese Patent Application Laid-Open No. 61001/99.
Patent Reference 2; Japanese Patent Application Laid-Open No. 199078/00,
Patent Reference 3: Japanese Patent Application Laid-Open No.
129163/00.
Summary of the Invention:
it is an object of the present invention to provide a chrome-free coating composition capable of forming a coating film showing excellent corrosion resistance in a fabricated portion and an edge face portion in addition to other non-fabricated portions when used in a coated metal sheet, and a coated metal sheet by use of the coating composition.
The present inventors made intensive studies for the purpose of solving.the above-mentioned problems in the prior art to find out that a coating composition prepared by adding an anticorrosion pigment mixture consisting of a specified vanadium compound, a specified silicon-containing compound and a phosphate-based calcium salt in a predetermined amount respectively, or an anticorrosion pigment mixture consisting of a specified vanadium compound, calcium compound and specified phosphate based metal salt in a predetermined amount respectively, to a hydroxyl group containing coating film-forming resin respectively can form a coating film showing excellent corrosion resistance in a fabricated portion and an edge face portion in addition to other non-fabricated flat portion when used in a coated metal sheet, resulting in accomplishing the present invention.
That is, the present invention provides a coating composition containing (A) a hydroxyl group-containing coating film-forming resin, (B) a crosslinking agent, and (C)
an anticorrosion pigment mixture, the corrosion pigment mixture (C) being an anticorrosion pigment mixture (C-l) consisting of a combination of (l) 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, the anticorrosion pigment mixture (C) being in the range of 10 to 150 parts by weight, the vanadium compound (1) being in the range of 3 to 50 parts by weight, the metal silicate (2) being in the range of 3 to 50 parts by weight and the phosphate-based calcium salt (3) being in the range of 3 to 50 parts by weight in the anticorrosion pigment mixture (C-l) respectively, the vanadium compound (1) being in the range of 3 to 50 parts by weight, the calcium compound (4) being in the range of 3 to 50 parts by weight and the phosphate-based rnetal salt (5) being in the range of 3 to 50 parts by weight in the anticorrosion pigment mixture (C-2) respectively, per 100 parts by weight of a total solid content of the resin (A) and the crosslinking agent (B) respectively; and a coated metal sheet by use of the coating composition.
The coating composition of the present invention
provides such particular effects that the coating composition of the present invention does not contain a chrome-based anticorrosion pigment and is advantageous from the standpoints of environment and health, and that the coating composition of the present invention can form a coating film showing excellent corrosion resistance in a fabricated portion and an edge face portion in addition to other non-fabricated flat portion when used in the coated metal sheet, being difficult to provide for a chrome-free anticorrosive coating composition.
A coated metal sheet coated with a cured coating film formed from the coating composition of the present invention shows excellent corrosion resistance in non-fabricated flat portion, fabricated portion and edge face portion, and shows such corrosion resistance as to be the same or improved compared with a coated metal sheet coated with a cured coating film formed from a coating composition by use of a chromate based anticorrosion pigment.
A coated metal sheet prepared by being coated with a, cured coating film formed from the coating composition of the present invention, followed by being coated with a topcoating film formed onto the cured coating film shows excellent corrosion resistance in non-fabricated flat portion, fabricated portion and edge face portion. Coating of the coating composition of the present invention onto a metal sheet as a coating substrate, such as a galvanized steel sheet, or an aluminum-zinc alloy plated steel sheet makes it
possible to obtain excellent corrosion resistance in the edge face portion and fabricated portion in addition to non-fabricated flat portion. Preferred Embodiments of the Invention:
The coating composition of the present invention contains a hydroxyl group containing coating film-forming resin (A), a crosslinking agent (B) and an anticorrosion pigment mixture (C). Hydroxyl Group Containing Coating Film-Forming Resin (A)
The hydroxyl group-containing film-forming resin (A) in the coating composition of the present invention may include any hydroxyl group containing resin having film-forming properties and usually used in the field of the coating composition without particular limitations, and typically may include, for example, at least one hydroxyl group-containing resin selected from polyester resin, epoxy resin, acrylic resin, fluorocarbon resin, vinyl chloride resin and the like, preferably at least one organic resin selected from hydroxyl group containing polyester resin and hydroxyl group containing epoxy resin.
The hydroxyl group-containing polyester resin as the preferable organic resin may include an oil-free .polyester resin, oil-modified alkyd resin, modified products thereof, for example, urethane-modified polyester resin, urethane-modified alkyd resin, epoxy-modified polyester resin and acrylic-modified polyester resin, and the like. The hydroxyl group-containing polyester resin may preferably have a number
average molecular weight in the range of 1,500 to 35,000, preferably 2,000 to 25,000, a glass transition temperature (Tg) in the range of 10 to 100'C, preferably 20 to 80°C, and a hydroxyl value in the range of 2 to 100 mg KOH/g, preferably 5 to 80 mg KOH/g.
In the present specification, the number average molecular weight of the resin is a value calculated on the basis of molecular weight of a standard polystyrene from chromatogram measured by use of a gel permeation chromatograph (HLC8120GPC, trade name marketed by Tosoh Corporation). The above measurement was carried out under the following conditions, that is, 4 columns: TSK gel G-4000 HXL, TSK gel G-3000 HXL, TSK gel G-2500 HXL and TSK gel G-2000 HXL (Trade names marketed by Tosoh Corporation, respectively); mobile phase: tetrahydrofuran; measuring temperature: 40°C, flow rate: 1 ml/min, sensor: RI. In the present specification, the glass transition temperature (Tg) of the resin is determined by the differential scanning calorimeter (DSC).
The oil-free polyester resin consists of an esterified product between a polybasic acid component and a polyhydric alcohol component. The polybasic acid component may include, as the major component, for example, at least one dibasic acid selected from phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic acid, fumaric acid, adipic acid, sebacic acid arid maleic anhydride, and lower
alkyl esterified products thereof, and in addition to the above acids, may optionally include monobasic acid such as benzoic acid, crotonic acid, p-t-butyl benzoic acid and the like, trivalent or higher polybasic acid such as trimellitic anhydride, methylcyclohexene tricarboxylic acid, pyromelitic anhydride and the like, and the like. The polyhydric alcohol may include, as the major component, for example, dihydric alcohol such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butane diol, neopentyl glycol, 3-methylpentane diol, 1,4-hexane diol, 1,6-hexane diol and the like, and, in addition to the above acid, may optionally include trihydric or higher polyhydric alcohol such as glycerine, trimethylol ethane, trimethylol propane, pentaerythritol and the like. These polyhydric alcohols may be used alone or in combination, Esterification or ester exchange reaction between both components may be carried out by a process known per se. The acid component may particularly include isophthalic acid, terephthalic acid, and lower alkyl esterified products thereof.
The alkyd resin may be prepared by reacting an oil fatty acid in addition to the acid component and alcohol component in the above oil-free polyester resin according to a process known per se. The oil fatty acid may include, for example, coconut oil fatty acid, soybean oil fatty acid, linseed oil fatty acid, sun-flower oil fatty acid, tall oil fatty acid, dehydrated castor oil fatty acid, tung oil fatty acid and the like. The alkyd resin preferably has an oil
length in the range of 30% or less, particularly 5 to 20%.
The urethane-modifled polyester resin may include ones prepared by reacting a polyisocyanate compound with the above oil-free polyester resin or with a low molecular weight oil-free polyester resin obtained by reacting the acid component and alcohol component used in the preparation of the above oil-free polyester resin, according to a process known per se. The urethane-modified alkyd resin may include ones prepared by reacting a polyisocyanate compound with the above alkyd resin or with a low molecular weight alkyd resin obtained by reacting respective components used in the preparation of the above alkyd resin according to a process known per se. The polyisocyanate compound used in the preparation of the urethane-modified polyester resin and urethane-modified alkyd resin may include hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 2,4,6-triisocyanatotoluene and the like. The urethane-modified resin may preferably include ones having such a degree of modification that an amount of polyisocyanate compound forming the urethane-modified resin is in the range of 30% by weight or less based on the urethane-modified resin.
The epoxy-modified polyester resin may include reaction products by reactions such as addition, condensation and grafting between polyester resin and epoxy resin, for example, a reaction product of carboxyl group of a polyester resin
prepared from respective components used in the preparation of the above polyester resin with an epoxy group^containiiig resin; a reaction product obtained by bonding hydroxyl group in the polyester resin to hydroxyl group in the epoxy resin through the polyisocyanate compound. A degree of modification in the epoxy-modifled polyester resin is preferably such that an amount of the epoxy resin is in the range of 0.1 to 30% by weight based on the epoxy-modifled polyester resin.
The acrylic-modified polyester resin may include a reaction product between a polyester resin prepared from respective components used in the preparation of the above polyester resin and an acrylic resin containing a group reactable with carboxyl group or hydroxyl group in the polyester resin prepared as above, for example, carboxyl group, hydroxyl group or epoxy group; and a reaction product prepared by grafting (rneth) acrylic acid, (meth) acrylate and the like to polyester resin by use of a peroxide polymerization initiator. A degree of modification in the acrylic-modified polyester resin is preferably such that an amount of the acrylic resin is in the range of 0.1 to 50% by weight based on the acrylic-modified polyester resin.
Of the above polyester resins, the oil-free polyester resin and epoxy-modified polyester resin are preferable from the standpoints of fabrication properties and corrosion resistance.
The epoxy resin preferable as the hydroxyl group
containing coating film-forming resin may include bisphenol type epoxy resin, novolak type epoxy resin; and modified epoxy resins prepared by reacting various kinds of modifiers with epoxy group or hydroxyl group in the above epoxy resins. In the preparation of the modified epoxy resin, modification by use of the modifier may be carried out at any stage in, the preparation of epoxy resin and at a final stage in the preparation of epoxy resin without particular limitations.
The bisphenol type epoxy resin may include, for example, a resin prepared by subjecting epichlorohydrin and biaphenol optionally in the presence of a catalyst such as an alkali catalyst to condensation reaction so as to have a high molecular weight; and a resin obtained by subjecting epichlorohydrin and bisphenol optionally in the presence of a catalyst such as an alkali catalyst to condensation reaction to form a low molecular weight epoxy resin, followed by subjecting the low molecular weight epoxy resin and bisphenol to polyaddition reaction.
The bisphenol may preferably include bis (4-
hydroxyphenyl)methane [bisphenol F], 1,1-bis(4-hydroxyphenyl ethane, 2,2-bis (4-hydroxyphenyl)propane [bisphenol A], 2,2-bis(4-hydroxyphenyl)butane [bisphenol B], bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-hydroxy-tert-butylphenyl) -2 ,2-propane , p- (4-hydroxyphenyl') phenol, oxybis(4-hydroxyphenyl), sulfonyibis(4-hydroxyphenyl), 4,4'-dihydroxybenzophenone, bis(2-hydroxynaphthyl)methane and the like. Of these, bisphenol A and bisphenol F are preferably
used. The above bisphenols are used alone or in combination.
Examples of commercially available bisphenol type epoxy resin may include Epikote 828, 812, 815, 820, 834, 1001, 1004, 1007, 1009, 1010 (Trade names, all marketed by Japan Epoxy Resins Co, Ltd.); Araldite AER 6099 (Trade name, marketed by Asahi-Ciba Ltd.); Epomik R-309 (Trade name, marketed by Mitsui Chemicals), and the like.
Examples of novolak type epoxy resin usable as the epoxy resiri may include various kinds of novolak type epoxy resins such as phenol novolak type epoxy resin, cresol novolak type epoxy resiri, phenol glyoxalic type epoxy resin and the like.
The modified epoxy resin may include an epoxy ester resin obtained by reacting, for example, a drying oil fatty acid; an epoxy acrylate resin obtained by reacting a polymerizable unsaturated monomer component; and urethane-modified epoxy resin obtained by reacting an isocyanate compound with the bisphenol type epoxy resin or the novolak type epoxy resin respectively; an amine-modified epoxy resin obtained by reacting an amine compound with the epoxy group in the bisphenol type epoxy resin, the novolak type epoxy resin or the above modified epoxy resins so as to introduce amino group or quaternary ammonium salt. Crosslinking Agent (B)
The crosslinking agent (B) is reacted with the hydroxyl group containing coating film-forming resin (A) to form a cured coating film, and may include ones capable of curing by
reacting with the hydroxyl group containing coating film-forming resin (A), for example, by heating without particular limitations. Of these, an amino resin and an optionally blocked polyisocyanate compound are preferable. These crosslinking agents may be used alone or in combination.
The amino resin may include a methylol amino resin obtained by reaction of aldehyde with an amino component such as melamine, urea, benzoguanamine, acetoguanamine, stearoguanamine, spiroguanamine, dicyandiamide and the like. The aldehyde used in the above reaction may include formaldehyde, paraformaldehyde, acetoaldehyde, benzaldehyde and the like. The amino resin may also include ones obtained by etherifying the methylol amino resin with a suitable alcohol. Examples of the alcohol used in the etherification may include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-ethyl butanol, 2-ethyl hexanol and the like.
The phenol resin used as the crosslinking agent is reacted arid crosslinked with the hydroxyl group containing coating film-forming resin (A), and may include, for example, a resol phenol xeain prepared by heating and subjecting a phenol component and formaldehydes to condensation reaction in the presence of a reaction catalyst to introduce a methylol group, followed by alkyl etherifying at least part of the methylol group in the resulting methylol phenol resin with alcohol.
The phenol component used as a starting material in the
preparation of the resol phenol resin may include a bifunctional phenol compound, trifunctional phenol compound and tetra or higher functional phenol compound.
The phenol compound may include, for example, bifunctional phenol compounds such as o-cresol, p-cresol, p-tert-butyl phenol, p-ethyl phenol, 2,3-xylenol, 2,5-xylenol and the like, trifunctional phenol compounds such as phenol, m-cresol, m-ethyl phenol, 3,5-xylenol, m-methoxyphenol and the like, tetra-functional phenol compounds such as bisphenol A, bisphenol F and the like, and the like. Of these, trifunctional or higher phenol compounds, particularly phenol and/or m-cresol are preferable for the purpose of improving scratch resistance. These phenol compounds are used alone or in combination.
The formaldehydes used in the preparation of the phenol resin may include formaldehyde, paraformaldehyde, trioxane, etc., and may be used alone or in combination.
The alcohol used in partly alkyl etherifying the methylol group in the methylol phenol resin may preferably include monohydric alcohol having 1 to 8, preferably 1 to 4 carbon atoms, particularly methanol, ethanol, n-propanol, n-butanol, isobutanol, etc.
The phenol resin preferably include ones having 0.5 or more, preferably 0.6 to 3.0 on an average of alkoxymethyl group per one benzene ring from the standpoints of reactivity with the hydroxyl group containing coating film-forming resin (A) .
A non-blocked polyisocyanate compound in the optionally blocked polyisocyanate compound used in the crosslinking agent may include organic diisocyanate per se, for example, aliphatic diisocyanates such as hexamethylene diisocyanate/ trimethyIhexamethylene diisocyanate and the like; alicyclic diisocyanates such as hydrogenated xylylene diisocyanate, isophorone diisocyanate and the like; and aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, crude MDI, and the like; adducts of these organic diisocyanates with polyhydric alcohol, low molecular weight polyester resin, water and the like; cyclic polymers between above organic diisocyanates; isocyanate«biuret, and the like.
The blacked polyisocyanate compound usable as the crosslinking agent is a compound prepared by blocking a free isocyanate group in the polyisocyanate compound with a blocking agent. The blocking agent used in blocking isocyanato group may include, for example, phenols such as phenol, cresol, xylenol and the like; lactams such as e-caprolactam, 8-valerolactam, y-butylolactam, and the like; alcohols such as methanol, ethanol, n-, i- or t-butyl alcohol, ethylene glycol monomethylether, ethylene glycol monobutylether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, benzyl alcohol and the like; oximes such as forrnamidoxime, acetoaldoxime, acetoxime, methyl ethyl ketoxime, diacetylmonoxime, benzophenone oxime, cyclohexanone oxime and the like; and active methylene based ones such as
dimethyl maionate, diethyl malonate, ethyl acetoacetate, acetyl acetone, and the like. Mixing of the polyisocyanate compound with the blocking agent makes it possible to easily block the free isocyanato group in the polyisocyanate compound.
A mixing amount of the hydroxyl group-containing coating film-forming resin (A) and the curing agent (B) is such that the hydroxyl group containing coating film-forming resin (A) is in the range of 55 to 95 parts by weight, preferably 60 to 95 parts by weight, and the crosslinking agent (B) is in the range of 5 to 45 parts by weight, preferably 5 to 40 parts by weight per 100 parts by weight of the total solid content of the components (A) and (B) from the standpoints of corrosion resistance, boiling water resistance, fabrication properties, curing properties, etc.
The curing catalyst may optionally be used for the purpose of promoting a curing reaction of the coating composition and may arbitrarily be selected and used depending on kinds of the curing agent to be used.
In the case where the crosslinking agent (B) is amino resin, particularly methyl etherified or methyl ether-butyl ether mixed etherified melamine resin, the curing catalyst preferably includes a sulfonic acid compound and an amine-neutrified product of the sulfonic acid compound. Typical examples of the sulfonic acid compound may include p-toluene sulfonic acid, dodecylbenzene sulfonic acid, dinonylnaphthalene sulfonic acid, dinonylnaphthalene
disulfonic acid and the like. An amine used in the amine-neutralized product of the sulfonic acid compound may include a primary arnine, secondary amine and tertiary amine. Of these, the amine-neutralized product of p-toluene sulfonic acid and/or amine-neutralized product of dodecylbenzene sulfonic acid are preferable from the standpoints of stability and reaction-promoting effect of the coating composition, resulting coating film properties and the like.
In the case where the crosslinking agent (B) is a phenol resin, the curing catalyst may include the sulfonic acid compound and the amine-neutralized product of the sulfonic acid compound.
In the case where the crosslinking agent (B) is the blocked polyisocyanate compound, a curing catalyst promoting dissociation of a blocking agent of the blocked polyisocyanate compound as the crosslinking agent is preferable. Examples of preferable curing catalysts may include organometal catalysts such as tin octylate, dibutyltin di(2-ethylhexanoate), dioctyltin di(2-ethylhexanoate), dioctyltin diacetate, dioctyltin dilaurate, dibutyltin oxide, dioctyltin oxide, lead 2-ethylhexanoate and the like, and the like.
In the case where the crosslinking agent (B) is a combination of two or more crosslinking agents, the curing catalyst may include a combination of respective curing catalysts effective on respective crosslinking agents. Anticorrosion Pigment Mixture (Cj_
The anticorrosion pigment mixture (C) in the coating composition of the present invention is an anticorrosion pigment mixture (C-l) consisting of (1) a vanadium compound, (2) a metal silicate and (3) a phosphate-based calcium salt, or an anticorrosion pigment mixture (C-2) consisting of (1) the vanadium compound, (4) a calcium compound and (5) a phosphate-based metal salt. Vanadium Compound (1)
The vanadium compound (1) may include at least one vanadium compound selected from vanadium pentoxide, calcium vanadate and ammonium metavanadate. The vanadium pentoxide, calcium vanadate and ammonium metavanadate show excellent eluation properties in water of a pentavalent vanadium ion, and the pentavalent vanadium ion emitted from the vanadium compound (1) is effective on improvement in corrosion resistance due to a reaction with a substrate metal, or a reaction with ions emitted from other anticorrosion pigment mixture. Metal Silicate (2)
The metal silicate (2) is a salt consisting of silicon dioxide and a metal oxide, and may include orthosilicate, polysilicate, etc. The silicate may include, for example, zinc silicate, aluminum silicate, aluminum orthosilicate, aluminum hydrated silicate, aluminum calcium silicate, aluminum sodium silicate, aluminum beryllium silicate, sodium silicate, calcium orthosilicate, calcium metasilicate, calcium sodium silicate, zirconium silicate, magnesium
orthosilicate, magnesium metasilicate, magnesium calcium silicate, manganese silicate, barium silicate, chrysolite, garnet, thortvitite, hemimorphite, benitoite, neptunite, beryl, cliopside, wallastonite, rhodonite, tremolite, xonotilite, talc, apophyllite, aluminosilicate, borosilicate, beryllosilicate, feldspar, zeolite, etc.
The metal silicate (2) may preferably include calcium orthosilicate and calcium metasilicate. Phosphate-Based__Calcium Salt (3)
The phosphate-based calcium salt (3) is a phosphate containing calcium as a metal element, and may include, for example, calcium phosphate, calcium ammonium phosphate, calcium secondary phosphate, calcium dihydrogen phosphate, calcium fluorochloride phosphate, etc. The phosphate ion and calcium ion emitted from the phosphate-based calcium salt (3) are effective on improving corrosion resistance. Calcium Compound (4)
The calcium compound (4) is, for example, a calcium compound other than calcium vanadate and phosphate compound, and may include, for example, calcium oxide, calcium hydroxide, calcium orthosilicate, calcium metasilicate, calcium carbonate, calcium sulfate, calcium nitrate, calcium sulfide, calcium chloride, calcium fluoride, calcium bromide, calcium nitride, calcium acetate, calcium azide, calcium cyanamide, calcium amide, calcium imide, calcium silicon, etc, Of these, calcium carbonate, calcium oxide and calcium metaailicate are preferable from the standpoints of a
suitable water solubility and corrosion resistance, and calcium metasilicate is particularly preferable from the standpoint of corrosion resistance. Phosphate-Based Metal Salt (5)
The phosphate-based metal salt (5) may include at least one selected from a phosphate metal salt, hydrogen phosphate metal salt and tripolyphosphate metal salt, and is such that a metal in respective metal salts is zinc, aluminium or magnesium.
The phosphate-based metal salt may include, for example, zinc phosphate, aluminum phosphate, magnesium phosphate, zinc hydrogen phosphate, aluminum hydrogen phosphate, magnesium hydrogen phosphate, magnesium ammonium phosphate, aluminum dihydrogen tripolyphosphate, and the like.
A metal ion such as zinc ion, aluminum ion or magnesium ion, and phosphate ion respectively emitted from the phosphate-based metal salt (5) are effective on improving corrosion resistance.
In the coating composition of the present invention, from the standpoint of corrosion resistance, the anticorrosion pigment mixture (O-l) preferably contains the vanadium compound (1), the metal silicate (2) and the phosphate-based calcium salt (3) in an amount in the following ranges respectively, and the anticorrosion pigment mixture (C) is preferably contained in an amount in the range of 10 to 150 parts by weight, preferably 15 to 90 parts by weight per 100 parts by weight of a total solid content of
the resin (A) and the crosslinking agent (B) respectively.
The vanadium compound: 3 to 50 parts by weight, preferably 5 to 30 parts by weight, the metal silicate (2): 3 to 50 parts by weight, preferably 5 to 30 parts by weight, and the phosphate-based calcium salt (3): 3 to 50 parts by weight, preferably 5 to 30 parts by weight.
In the coating composition of the present invention, from the standpoint of corrosion resistance, the anticorrosion pigment mixture (C-2) preferably contains the vanadium compound (1), the calcium compound (4) and the phosphate-based metal salt (5) in an amount in the following ranges respectively, and the anticorrosion pigment mixture (C) is preferably contained in an amount in the range of 10 to 150 parts by weight, preferably 15 to 90 parts by weight per 100 parts by weight of a total solid content of the resin (A) and the crosslinking agent (B) respectively.
The vanadium compound (1); 3 to 50 parts by weight, preferably 5 to 30 parts by weight, the calcium compound (4): 3 to 50 parts by weight, preferably 5 to 30 parts by weight, the phosphate-based metal salt (5): 3 to 50 parts by weight, preferably 5 to 30 parts by weight.
In the coating composition of the present invention, a combination of the components (1), (2) and (3) as the anticorrosion pigment mixture (C-l) in respective specified amounts, or a combination of the components (1), (4) and (5) as the anticorrosion pigment mixture (C-2) in respective specified amounts can synergistically improve corrosion
resistance. Of these, a combination of vanadium pentoxide, calcium metasilicate and calcium phosphate is particularly preferable from the standpoint of corrosion resistance as the anticorrosion pigment mixture (C-l).
It is desirable from the standpoints of water solubility of the vanadium compound (1), the metal silicate
(2) and the phosphate-based calcium salt (3), reactivity
between an anticorrosion pigment-dissolved solution and a
metal sheet, and corrosion resistance that a filtrate
prepared by adding a mixture of the vanadium compound (1) ,
the metal silicate (2) and the phosphate-based calcium salt
(3) constituting the anticorrosion pigment mixture (C-l)
within the range of parts by weight per 100 parts by weight
of the total solid content of the resin (A) and the
crosslinking agent (B) as described below respectively to
10000 parts by weight of a 5 wt% aqueous sodium chloride
solution at 25'C, followed by stirring for 6 hours, leaving
at rest for 48 hours at 25°C, and filtering a resulting
supernatant liquid, has a pH in the range of 3 to 10,
preferably 5 to 9,
That is, the filtrate subjected to the pH measurement is a filtrate prepared by adding a mixture of the vanadium compound (1) in an amount of in the range of 3 to 50 parts by weight, the metal silicate (2) in an amount of in the range of 3 to 50 parts by weight, and the phosphate-based calcium salt (3) in an amount in the range of 3 to 50 parts by weight per 100 parts by weight of the total solid content of the
resin (A) and the crosslinking agent (B) respectively to 10000 parts by weight of a 5 wt% aqueous sodium chloride solution at 25°C, followed by dissolving, and filtering the resulting solution.
It is desirable from the standpoints of water solubility of the vanadium compound (1), the calcium compound
(4) and the phosphate-based metal salt (5), reactivity
between an anticorrosion pigment-dissolved solution and a
metal sheet, and corrosion resistance that a filtrate
prepared by adding a mixture of the vanadium compound (1),
the calcium compound (4) and the phosphate-based metal salt
(5) constituting the anticorrosion pigment mixture (C-2)
within the range of parts by weight per 100 parts by weight
of the total solid content of the resin (A) and the
crosslinking agent (B) as claimed in claim 1 respectively to
10000 parts by weight of a 5 wt% aqueous sodium chloride
solution at 25°C, followed by stirring for 6 hours, leaving
at rest for 48 hours at 25°C, and filtering a resulting
supernatant liquid, has a pH in the range of 3 to 10,
preferably 5 - 9.
That is, the filtrate subjected to the pH measurement is a filtrate prepared by adding a mixture of the vanadium compound (1) in an amount of in the range of 3 to 50 parts by weight, the calcium compound (4) in an amount of in the range of 3 to 50 parts by weight, and the phosphate-based metal salt (5) in an amount in the range of 3 to 50 parts by weight per 100 parts by weight of the total solid content of the
resin (A) and the crossiinking agent (B) respectively to 10000 parts by weight of a 5 wt% aqueous sodium chloride solution at 25°C, followed by dissolving, and filtering the resulting solution.
The coating composition of the present invention may optionally contain a color pigment, extender pigment, ultraviolet light absorber, ultraviolet stabilizer, organic solvent; additives such as anti-settling agent, anti-fearning agent, coating surface controlling agent and the like as known for use in the field of the coating composition in addition to the hydroxyl group-containing film-forming resin (A), the curing agent (B), the anticorrosion pigment mixture (C) and the optionally used curing catalyst.
The color pigment may include, for example, organic color pigments such as cyanine blue, cyanine green, organic red pigments such as azo pigment and guinacridone pigment and the like; inorganic color pigment titanium white, titanium yellow, red iron oxide, carbon black, various kinds of calcined pigments, of these titanium white is preferable.
The extender pigment may include, for example, talc, clay, mica, alumina, calcium carbonate, barium sulfate, and the like.
The ultraviolet light absorber may include, for example, benzotriazole derivatives such as 2-(2-hydroxy-3,5-di-t-amylphenyl)-2H-benzotriazole, isooctyl-3-(3-(2H-benzotriazole-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate, 2-[2-hydroxy-3,5-di(1,1-dimethylbenzine)phenyl]-2H-
benzotriazole, 2-[2-hydroxy-3-dimethylbenzyl-5-(1,1,3,3-tetramethylbutyl)phenyl]-2H~benzotriazole, a condensation product of methyl-3-[3-t-butyl-5-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate with polyethylene glycol 300, and the like; triazine derivatives such as 2-[4-(2-hydroxy-3-dodecyloxypropyl)-oxy]-2-hydroxyphenyl-4,6-bis(2,4-dimethylphenyl)-1,3,5-1, 3,5-triazine and the like; oxalic anilide derivatives such as ethanediamide-N-(2-ethoxyphenyl)-N'- (2-ethylphenyl)-(oxalic amide) , ethanediamide-N-(2-ethoxyphenyl)-N1-(4-isododecylphenyl)-(oxalic amide) and the like.
The ultraviolet stabilizer may include, for example, a hindered amine-based compound, a hindered phenol based compound; CHIMASORB 944, TINUVIN 144, TINUVIN 292, TINUVIN 770, IRGANOX 1010, IRGANOX 1098 (Trade names, marketed by Ciba Specialty Chemicals K.K. respectively), and the like.
Addition of the ultraviolet light absorber and the ultraviolet stabilizer to the coating composition makes it possible to control degradation of the coating film surface by light, and, when the coating composition used as a primer coating composition, to control degradation of the primer coating film surface by the light reached the primer coating film surface through a topcoating film, resulting in preventing intercoat peeling between the primer coating film and the topcoating film due to degradation of the primer coating film surface, and in keeping excellent corrosion resistance.
The organic solvent used in the coating composition of the present invention may include ones optionally added for the purpose of improving coating properties of the coating composition of the present invention, ones capable of dissolving or dispersing the hydroxyl group-containing film-forming resin (A) and the crosslinking agent (B), and specifically, for example, hydrocarbon solvent such as toluene, xylene, high boiling point petroleum based hydrocarbon and the like, ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone and the like, ester solvent such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and the like; alcohol solvent such as methanol, ethanol, isopropanol, butanol and the like; ether alcohol solvent such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether and the like, and the like. These solvents may be used alone or in combination.
The coating composition of the present invention is such that a glass transition temperature of a cured coating film obtained from the composition of the present invention is preferably in the range of 40 to 115°C, preferably 50 to 105°C, from the standpoints of corrosion resistance,, acid resistance, fabrication properties and the like. In the present invention, the glass transition temperature of the coating film is a maximum temperature determined from a tan 8 change due to a temperature dispersion measurement at a
frequency of 110 Hz by use of Dinamic Viscoelastomer Model Vibron DDV-II EA Type (Automatic Viscoelasticity Measuring Instrument, marketed by TOYO BALDWIN Co., Ltd.).
In the case where the anticorrosion pigment mixture (C-1) is used as the anticorrosion pigment mixture (C), the coating film formed by coating the coating composition of the present invention onto a metal sheet shows excellent corrosion resistance. This is because a direct formation of a precipitated salt in place of a redox reaction between a metal ion formed by dissolution of a substrate metal due to chloride ion or the like under corrosion environment and pentavalent vanadium ion, i.e., vanadate ion such as V03~ or V043~, and an effective formation of a precipitated salt or compound due to a combination of silicate ion with trivalent vanadium ion formed by redox reaction of pentavanadium ion with the substrate metal ion and the substrate metal ion, results in that exposed surface of a substrate may effectively coated, and further because a corrosion-proceeding portion and surrounding portion may be controlled at a pH range suitable for taking place a redox reaction between pentavalent vanadium ion and the substrate metal due to phosphate ion eluted simultaneously. In addition, a combined use of the components (1), (2) and (3) constituting the anticorrosion pigment mixture (C-l) makes it possible to effectively conquer respective poor properties in acid resistance, alkali resistance and water resistance of respective components (1), (2) and (3). Further, calcium ion
has a function to control dissolution of the substrate metal under such a strong alkali atmosphere of a pH higher than 10 that the substrate metal may easily be dissolved, resulting in providing excellent properties in chemical resistance and water resistance. These synergistic functions due to the anticorrosion pigment mixture (C-l) accomplish excellent corrosion resistance,
In the case where the anticorrosion pigment mixture (C-2) is used as the anticorrosion pigment mixture (C), the coating film formed by coating the coating composition of the present invention onto a metal sheet shows excellent corrosion resistance. This is because a direct formation of a precipitated salt in place of a redox reaction between a metal ion formed by dissolution of a substrate metal due to chloride ion or the like under corrosive environment, or the zinc ion or aluminum ion elated from the anticorrosion pigment mixture and pentavalent vanadium ion, i.e., vanadate ion such as VO3~ or VO43~, a function of calcium ion or other metal ion dissolved from the anticorrosion pigment mixture to control an anode dissolution reaction of the substrate metal, or formation of a precipitate due to a combination of phosphate ion with trivalent vanadium ion formed by redox reaction of pentavalent ion with substrate metal and calcium ion results in that a substrate-exposed surface may effectively coated, also because, particularly on the galvanized steel sheet, zinc ion and vanadate ion, in addition to calcium ion migrate to an iron-exposed portion as
a charged body of a corrosion current due to formation of a different kind metal cell, react and form a salt, resulting in providing such effects as to control cathode polarization of an iron portion and to function so as to reduce potential difference between different kind metals, and further because calcium ion and other metal provide such effect as to control a reaction to dehydrolize zinc hydroxide formed around the cathode portion on corrosion under the coating film to form zinc oxide. In addition, a combined use of the components (1), (4) and (5) constituting the anticorrosion pigment mixture (C-2) makes it possible to effectively conquer respective poor properties in acid resistance, alkali resistance and water resistance of respective components (1), (4) and (5) . Further, calcium ion has a function to control dissolution of the substrate metal under such a. strong alkali atmosphere of a pH higher than 10 that the substrate metal may easily dissolved, resulting in providing excellent properties in chemical resistance and water resistance. These synergistic functions due to the anticorrosion pigment mixture (C-2) accomplish excellent corrosion resistance. Coated Metal Sheet
The coated metal sheet of the present invention has a coating film formed by coating the coating composition of the present invention onto a metal sheet as a substrate, followed by curing.
The metal sheet as the substrate may include cold-rolled steel sheet, hot dipped galvanized sheet,
electroplated galvanized sheet, iron-zinc alloy plated steel sheet (galvanneal steel sheet), aluminum-zinc alloy plated steel sheet ("galvalurne steel sheet" containing about 55% of aluminum in the alloy, "galfan" containing about 5% of aluminum in the alloy, etc.), nickel-zinc alloy plated steel sheet, stainless steel sheet, aluminum sheet, copper sheet, copper plated steel sheet, tin plated steel sheet, etc. These metal sheet may optionally be subjected to conventional metal surface treating process, for example, the phosphating process such as zinc phosphate-treating process, iron phosphate-treating process and the like, composite oxide film-treating process, chrome phosphate-treating process, chromating process, etc.
The coating composition of the present invention may be coated onto the metal sheet by the conventional coating method such as roll coating method, curtain flow coating method, spray coating method, brushing method, dip coating method and the like. A film thickness of the coating film formed from the composition of the present invention may not particularly be limited, but is usually in the range of 2 to 10 µm, preferably 3 to 6 µm. Drying of the coating film may be carried out under suitable conditions depending on kind of the resin to be used, but in the case where a coating film formed by the coil coating method is continuously heat cured, the heat curing may be carried out, usually at a substrate maximum temperature of 160 to 250"C, preferably 180 to 230°C for 15 to 60 seconds. Heat curing in the batch-wise process
may be carried out, usually at a surrounding temperature of 80 to 200 °C for 10 to 30 minutes.
In the case where heating is unnecessary in the crosslinking reaction on forming a coating film, for example, in the case where a non-blocked polyisocyanate compound 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), drying may be carried out at room temperature to be cured according to the conventional process.
The coated metal sheet of the present invention may include ones having the coating film only formed from the coating composition of the present invention on an optionally surface treated metal sheet, but may also include ones having a topcoating film on the above coating film. The topcoating film has a film thickness in the range of 8 to 30 µm, preferably 10 to 25 µm.
A topcoating composition forming the topcoating film may include conventionally available ones for use in the precoat metal sheet, for example, polyester resin based, alkyd resin based, silicone-modified polyester resin based, silicone-modified acrylic resin based, fluorocarbon resin based topcoating compositions. In the case where fabrication properties are of a great importance, use of a topcoating composition having good fabrication properties such as a polyester resin based topcoating composition for use in high fabrication makes it possible to obtain a coated metal plate
having particularly good fabrication properties. The coated metal sheet having the above topcoatirig film in the present invention shows good film performances in corrosion resistance.
In the case where the galvanized steel sheet and aluminum-zinc alloy plated steel sheet, corrosion resistance in a non-fabricated flat portion has been improved to some extent, but corrosion resistance in a cut edge surface portion and fabricated portion have been unsatisfactory in the art. In contrast, coating of the coating composition of the present invention makes it possible to obtain excellent corrosion resistance in edge surface portion and fabricated portion.
A coating film from the coating composition of the present invention may be formed on a double-side of the substrate, and optionally the topcoating film may be formed on the coating film from the coating composition of the present invention. Forming the coating film from the coating composition of the present invention on the double-side including the back side of the substrate makes it possible to obtain a coated metal sheet free of a chrome-based ariticorrosion pigment and advantageous from the standpoints of environmental protection and health and showing excellent corrosion resistance.
The coated metal sheet of the present invention is such that a coating film from the coating composition of the present invention may be formed the double-side of the metal
sheet subjected to the optional surface chemical treatment to be used as it is, but for the purpose of improving appearance and durability, a topcoating film may be formed on at least one side of the coating film.
In the case where the topcoating film is formed on one side, a topcoat coating composition may be coated on one side-cured aiiticorrosive coating film, while another side anticorrosive coating film being optionally cured, followed by heating and curing. In the case where the topcoating film is formed on the double-side, the topcoating film may be cured by a method of coating the topcoat coating composition on one side of double-side cured anticorrosive coating film-having metal sheet and curing, followed by coating the topcoat coating composition on another cured anticorrosive coating film and curing, or a method of coating the topcoat coating composition on double-side of double-side cured anticorrosive coating film-having metal sheet, followed by curing the double-side simultaneously. A film thickness of the topcoat coating film may preferably in the range of 8 to 30 µm, preferably 10 to 25 µm. Example
The present invention is explained more specifically by reference to the following Preparation Examples and Examples. The present invention should not be limited to the following Examples. Hereinafter, "part" and "%" is represented by "part by weight" and "% by weight" respectively. Preparation Example 1
Preparation of resol phenol resin crosslinking agent, solution:
A reactor was charged with 100 parts of bisphenol A, 178 parts of 37% aqueous formaldehyde solution and one part of sodium hydroxide, followed by reacting for 3 hours at 60"C, dehydrating at 50'C for one hour under vacuum, adding 100 parts of n-butanol and 3 parts of phosphoric acid, reacting at 110 to 120°C for 2 hours, filtering the resulting solution, filtering off the resulting sodium phosphate to obtain resol phenol resin crosslinking agent solution Bl having a solid content of about 50%. The resin obtained as above had a number average molecular weight of 880, rnethylol group of 0.4 on an average and alkoxymethyl group of 1.0 on an average per one benzene ring, respectively. Preparation Example 2 Preparation of back side-used coating composition:
A mixture of 200 parts of an epoxy resin solution prepared by dissolving 80 parts of Epikote #1009 (trade name, marketed by Japan Epoxy Resins Co., Ltd., bisphenol A type epoxy resin, hydroxyl group-containing resin) in 120 parts of a mixed solvent 1 [cyclohexanone/ethylene glycol monobutyl ether/Solvesso 150 (trade name, marketed by Esso Standard Oil Co., Ltd., high boiling point aromatic hydrocarbon based solvent) = 3/1/1 by weight ratio] with 40 parts of titanium white, 40 parts'of baryta and a predetermined amount of a mixed solvent 2 [Solvesso 150 (trade name, marketed by Esso Standard Oil Co., Ltd., high boiling point aromatic
hydrocarbon based solvent)/cyclohexanone - 1/1 by weight ratio] was subjected to pigment dispersion so that a grain, i.e., particle size of pigment coarse particle may be reduced to 20 um or less, followed by adding 26.7 parts (20 parts as solid content) of Desmodur BL-3175 (trade name/ marketed by Sumika Bayel Urethane Co., Ltd., methyl ethyl ketoxime-blocked HDI isccyanurate type polyisocyanate compound solution, solid content about 75%) and 2 parts of Takenate TK-1 (trade name, marketed by Takeda Pharmaceutical Company Limited, organotin based blocking agent-dissociation catalyst, solid content about 10%), uniformly mixing, adding the mixed solvent 2 and controlling viscosity at about 80 sec. (Ford Cup #4/25°C) to obtain a back side-used coating composition. Preparation of Anticorrosive Coating Composition: Example 1
A mixture of 220 parts of an epoxy resin solution prepared by dissolving 85 parts of Epikote #1009 (trade name, marketed by Japan Epoxy Resins Co., Ltd., bisphenol A type epoxy resin, hydroxyl group containing resin) in 135 parts of a mixed solvent 1 (cyclohexanone/ethylene glycol monobutyl ether/Sorvesso 150 (trade name, marketed by Esso Standard Oil Co., Ltd-, high boiling point aromatic hydrocarbon based solvent) - 3/1/1 by weight ratio] with 5 parts of vanadium pentoxide, 3 parts of calcium metasilicate, 3 parts of calcium phosphate, 20 parts of titanium white, 20 parts of baryta and a predetermined amount of a mixed solvent 2 [Solvesso 150 (trade name, marketed by Esso Standard Oil Co.,
Ltd., high boiling point aromatic hydrocarbon based solvent)/cyclohexanone = 1/1 by weight ratio] was subjected to pigment dispersion so that a grain, i.e., particle size of pigment coarse particle may be reduced to 20 urn or less, followed by adding 20 parts (15 parts by solid content) of Desmodur BL-3175 (trade name, marketed by Sumika Bayel Urethane Co., Ltd., methyl ethyl ketoxime-blocked HDI isocyanurate type polyisocyanate compound solution, solid content about 75%, and 2 parts of Takenate TK-1 (trade name, marketed by Takeda Pharmaceutical Company Limited, organotin based blocking agent-dissociation catalyst, solid content about 10%), uniformly mixing, adding the mixed solvent 2 and controlling viscosity at about 80 sec. (Ford Cup #4/25GC) to obtain an anticorrosive coating composition. Examples 2-21, Comparative Examples 1-8:
Example 1 was duplicated except that respective hydroxyl group-containing resins, crosslinking agents, anticorrosion pigments and other pigments as shown in Table 1 were used. In Table 1, amounts of respective hydroxyl group-containing resin, crosslinking agents and pigment components are represented by weight of solid content. Provided with, Example 14 does not contain Takenate TK-1 (trade name as above defined), and Examples 17 and 18 contain one part of Nacure 5225 (trade name, marketed by US King Industries Ltd., amine-neutralized solution of dodecylbenzene sulfonic acid) in place of 2 parts of Takenate TK-1 respectively.
The pH of a filtrate, pH of an anticorrosion pigment-
dissolved liquid, prepared by adding a total amount of respective anticorrosion pigments per 100 parts by weight of the total solid content of the hydroxyl group-containing resin and the crosslinking agent as the resin components to 10000 parts by weight of 5 wt% aqueous sodium chloride solution at 25°C, followed by stirring for 6 hours, leaving at rest for 48 hours at 25°C, and filtering the resulting supernatant liquid is represented in Table 1. For example, the pH of the anticorrosion pigment-dissolved liquid in Example 1 is a pH of a filtrate prepared by adding 5 parts by weight of vanadium pentoxide, 3 parts by weight of calcium metasilicate and 3 parts by weight of calcium phosphate to 10000 parts by weight of 5 wt% aqueous sodium chloride solution at 25DC, followed by dissolving under the above-mentioned conditions, and filtering the resulting supernatant liquid. Example 22
A mixture of 220 parts of an epoxy resin solution prepared by dissolving 85 parts of Epikote #1009 (trade name, marketed by Japan Epoxy Resins Co., Ltd., bisphenol A type epoxy resin, hydroxyl group containing resin) in 135 parts of a mixed solvent 1 [cyclohexanone/ethylene glycol monobutyl ether/Solvesso 150 (trade name, marketed by Esso Standard Oil Co., Ltd., high boiling point aromatic hydrocarbon based solvent) = 3/1/1 by weight ratio] with 5 parts of vanadium pentoxide, 3 parts of calcium metasilicate, 3 parts of aluminum phosphate, 20 parts of titanium white, 20 parts of
baryta and a predetermined amount of a mixed solvent 2 [Solvesso 150 (trade name, marketed by Esso Standard Oil Co., Ltd., high boiling point aromatic hydrocarbon based solvent)/cyclohexanone = 1/1 by weight ratio] was subjected to pigment dispersion so that a grain, i.e., particle size of pigment coarse particle may be reduced to 20 um or less, followed by adding 20 parts (15 parts by solid content) of Desmodur BL-3175 (trade name, marketed by Sumika Bayel Urethane Co., Ltd., methyl ethyl ketoxime-blocked HDI isocyanurate type polyisocyanate compound solution, solid content about 75%, and 2 parts of Takenate TK-1 (trade name, marketed by Takeda Pharmaceutical Company Limited, organotin-based blocking agent-dissociation catalyst, solid content about 10%), uniformly mixing, adding the mixed solvent 2 and controlling viscosity at about 80 sec. (Ford Cup #4/25°C) to obtain an anticorrosive coating composition. Examples 23-44, Comparative Examples 9-16 and Reference Examples 1 and 2:
Example 22 was duplicated except that respective hydroxyl group-containing resins, crosslinking agents, anticorrosion pigments and other pigments as shown in Table 1 were used. Reference Examples 1 and 2 represent examples of anticorrosive coating compositions containing chromate-based anticorrosion pigments in the prior art. In Table 1, amounts of respective hydroxyl group-containing resin, crosslinking agents and pigment components are represented by weight of solid content. Provided with, Examples 33, 34 and 39 do not
contain Takenate TK-1 (trade name as above defined), and Examples 42 and 43 contain one part of Nacure 5225 (trade name, marketed by US King Industries Ltd., amine-neutralized solution of dodecylbenzene sulfonic acid) in place of 2 parts
of Takenate TK-1 respectively.
Table 1 (1) (Table Removed)
Table L (2) (Table Removed)
Table 1 (3) (Table Removed)

Table 1 (4)
in Table lf (Note 1) to (Note 6) are explained as
follows,
(Note 1) Epokey 837: trade name, marketed by Mitsui
Chemicals, Inc., urethane-modifled epoxy resin, hydroxyl group-containing resin, primary hydroxyl value about 35, acid value about 0 (zero).
(Note 2) Vylon 296: trade name, marketed by Toyobo Co., Ltd., epoxy-modified polyester resin, hydroxyl group-containing resin, hydroxyl value 7, acid value 6.
(Note 3) Arakyd 7018: trade name, marketed by Arakawa Chemical Industries, Ltd. , polyester resin, hydroxyl group-containing resin, hydroxyl value about 10, acid value 3 or less.
(Note 4) Sumidur N3300: trade name, marketed by Sumika Bayel Urethane Co., Ltd., isocyanurate type polyisocyanate compound, solid content 100%.
(Note 5) Cymel 303: trade name, marketed by Nihon Cytec industries inc., methyl etherified melamine resin.
(Note 6) Sandvor 3058: trade name, marketed by Clariant Japan KK, hindered amine-based ultraviolet stabilizer.
Preparation of Coating Test Panel
Respective anticorrosive coating compositions obtained
in Examples 1-21, Comparative Examples 1-8 and Reference
Examples 1 and 2, and topcoating composition were coated on
respective substrates and cured according to the following
coating specifications 1-3 to obtain respective coating test
panels.
Coating Specification 1:
The back side-used coating composition obtained in Preparation Example 2 was coated onto a galvalume steel sheet subjected to a metal surface treating process, with sheet thickness of 0,35 ram, aluminum-zinc alloy plated steel sheet, aluminum content in the alloy about 55%, plated alloy amount of 150 g/m2, GL steel sheet as referred in Table 2, to be a dry film thickness of 8 um by use of a bar coater, followed by curing at a maximum temperature of substrate of 180°C for 30 seconds to form a back side coating film, coating respective anticorrosive coating compositions obtained in the above-mentioned Examples onto a steel sheet on an opposite side to the back side with the back side coating film of the steel sheet to be a dry film thickness of 5 um by use of .a bar coater, followed by curing at a maximum temperature of substrate of 220"C for 40 seconds to obtain respective primer coating films, cooling, and coating KP Color 1580B40 (trade name, marketed by Kansai Paint Co., Ltd., polyester based topcoating composition, blue, glass transition temperature of cured coating film about 70°C) onto respective primer coating films to be a dry film thickness of about 15 um by use of a bar coater, and curing at a maximum temperature of substrate of 220°C for 40 seconds to obtain respective coating test panels. Coating Specification 2:
The back side-used coating composition obtained in Preparation Example 2 was coated onto a hot-dipped galvanized
steel sheet subjected to a metal surface treating process, with sheet thickness of 0.35 mm, plated zinc amount of 250 g/m2, Gl steel sheet as referred in Table 2, to be a dry film thickness of 8 µm by use of a bar coater, followed by curing at a maximum temperature of substrate of 180 °C for 30 seconds to form a back side coating film, coating respective ahticorrosive coating compositions obtained in the above-mentioned Examples onto a steel sheet on an opposite side to the back side with the back side coating film of the steel sheet to be a dry film thickness of 5 pm by use of a bar coater, followed by curing at a maximum temperature of substrate of 220°C for 40 seconds to obtain respective primer coating films, cooling, and coating KP Color 1580B40 (trade name, marketed by Kansai Paint Co., Ltd., polyester based topcoating composition, blue, glass transition temperature of cured coating film about 70°C) onto respective primer coating films to be a dry film thickness of about 15 µm by use of a bar coater, and curing at a maximum temperature of substrate of 220°C for 40 seconds to obtain respective coating test panels. Coating Specification 3:
The back side-used coating composition obtained in Preparation Example 2 was coated onto a cold-rolled steel sheet subjected to zinc phosphate-treating process, with sheet thickness of 0.8 mm, SPC steel sheet as referred in Table 2, to be a dry film thickness of 8 um by use of a bar coater, followed by curing at a maximum temperature of
substrate of 180°C for 30 seconds to form a back side coating film, coating respective anticorrosive coating compositions obtained in the above-mentioned Examples onto a steel sheet on an opposite side to the back side with the back side coating film of the steel sheet to be a dry film thickness of 20 jam by use of a bar coater, followed by curing at a maximum temperature of substrate of 180°C for 30 minutes to obtain respective coating test panels.
Respective anticorrosive coating compositions obtained in Examples 22-45, Comparative Examples 9-16 and Reference Examples 1 and 2, and topcoating composition were coated on respective substrates and cured according to the coating specifications 1-3 and the following coating specification 4 to obtain respective coating test panels. Coating Specification 4:
The anticorrosive coating composition obtained in Example 3 was coated onto a galvalume steel sheet subjected to a metal surface treating process, with sheet thickness of 0.35 mm, aluminum-zinc alloy plated steel sheet, aluminum content in the alloy about 55%, plated alloy amount of 150 g/m2, GL steel sheet as referred in Table 2, to be a dry film thickness of 8 urn by use of a bar coater, followed by curing at a maximum temperature of substrate of 180"C for 30 seconds to form a back side coating film, coating respective anticorrosive coating compositions obtained in the above-mentioned Examples onto a steel sheet on an opposite side to the back side with the back side coating film of the Steel
sheet to be a dry film thickness of 5 µm by use of a bar coater, followed by curing at a maximum temperature of substrate of 220°C for 40 seconds to obtain respective primer coating films, cooling, and coating KP Color 1580B40 (trade name, marketed by Kansai Paint Co., Ltd., polyester based topcoating composition, blue, glass transition temperature of cured coating film about 70°C) onto respective primer coating films to be a dry film thickness of about 15 urn by use of a bar coater, and curing at a maximum temperature of substrate of 220°C for 40 seconds to obtain respective coating test panels, Example 45
The coating test panel was prepared according to the following coating specification 5. Coating Specification 5:
The back side-used coating composition obtained in Example 1 was coated onto a galvanium steel sheet subjected to a metal surface treating process, with sheet thickness of 0.35 mm, aluminum-zinc alloy plated steel sheet, aluminum content in the alloy about 55%, plated alloy amount of 150 g/m2, GL steel sheet as referred in Table 2, to be a dry film thickness of 8 µm by use of a bar coater, followed by curing at a maximum temperature of substrate of 180°C for 30 seconds to form a back side coating film, coating the anticorrosive coating composition obtained in Example 1 onto a steel sheet on an opposite side to the back side with the back side coating film of the steel sheet to be a dry film thickness of
5 µm by use of a bar coater, followed by curing at a maximum temperature of substrate of 220°C for 40 seconds to obtain a primer coating film, cooling, and coating KP Color 1580B40 (trade name, marketed by Kansai Paint Co., Ltd., polyester based topcoating composition, blue, glass transition temperature of cured coating film about 70°C) onto the primer coating film to be a dry film thickness of about 15 um by use of a bar coater, and curing at a maximum temperature of substrate of 220"C for 40 seconds to obtain a coating test panel.
Examples 46-69, Comparative Examples 17-33, and Reference Examples 3-6:
Example 45 was duplicated except that anticorrosive coating compositions coated on the surface and back-side were as shown in Table 3 to obtain respective coating test panels. Example 70
The coating test panel was prepared according to following coating specification 6. Coating Specification 6:
The anticorrosive coating composition obtained in Example 1 was coated onto a hot-dipped galvanized steel sheet subjected to a zinc phosphate-treating process, with steel thickness of 0.35 mm, plated zinc amount of 250 g/m2, GI
steel sheet as referred in Table 3, to be a dry film
thickness of 8 um by use of a bar coater, followed by curing
at a maximum temperature of substrate of 180"C for 30 seconds to form a back side coating film, coating the anticorrosive
coating composition obtained in Example 1 onto a steel sheet on an opposite side to the back side with the back side coating film of the steel sheet to be a dry film thickness of 5 ym by use of a bar coater, followed by curing at a maximum temperature of substrate of 220 "C for 40 seconds to obtain a primer coating film, cooling, and coating KP Color 1580B40 (trade name, marketed by Kansai Paint Co., Ltd., polyester based topcoating composition, blue, glass transition temperature of cured coating film about 70°C) onto the primer coating film to be a dry film thickness of about 15 urn by use of a bar coater, and curing at a maximum temperature of substrate of 220'C for 40 seconds to obtain a coating test panel.
Examples 71-94, Comparative Examples 34-50 and Reference Examples 7-10:
Example 70 was duplicated except that respective anticorrosive coating compositions used in the surface and back side were as shown in the following Table 4 to obtain respective coating test panels. Coating Film Performance Test
Respective coating test panels obtained in Examples 1-94, Comparative Examples 1-50 and Reference Examples 1-10 were subjected to the coating film performance test according to the following test methods. Test results are shown in Tables 2-4. Test Methods Boiling Water Resistance; Respective coating test panels cut
to a size of 5 cm x 10 cm are dipped into a boiling water at about 100°C for 2 hours, followed by taking up to evaluate appearance of a coating film formed on the surface of the coating panel, and separately are subjected to the cross cut-tape method for evaluation. The cross cut-tape method is as defined in accordance with JIS K-5400 8.5.2 (1990) . That is, an adhesive cellophane tape is adhered onto the surface of suspective coating test panels with a cut interval of 1 mm, and 100 squares, followed by strongly separating the tape to evaluate the coating film with squares as follows. ⓪: No abnormalities such as development of blisters and
whitening on the coating film, remaining squares 100. O: No abnormalities such as development of blisters and
whitening on the coating film, remaining squares 91-99. ∆: slight development of blisters and whitening on the
coating film, remaining squares 91-99, or No
abnormalities such as development of blisters and
whitening on the coating film, but remaining squares 71-
90. X: considerable or remarkable development of blisters on the
coating film, or remaining squares 70 or less. Alkaline Resistance:
A back side and cut surface of respective coating test panels cut to a size of 5 cm x 10 cm were sealed with an anticorrosive coating composition and a cross cut reaching the substrate was formed at the center on the side of the surface of the coating panel. The resulting coating panel
was dipped in a 5% aqueous sodium hydroxide solution at 25°C for 48 hours, followed by taking up, washing and drying at room temperature to evaluate coating film appearance on the side of the surface of the coating film, and further an adhesive cellophane tape was adhered onto the cross cut portion, followed by strongly separating the tape to evaluate a separated width (one side) from the cross cut portion in the resulting coating film. ⓪: No blisters developed, tape-separated width from the cut
portion, 1.5 mm or less. O: No blisters developed, tape-separated width from the cut
portion, more than 1.5 mm but 3 mm or less.
∆: Slight development of blisters, tape-separated width from the cut portion 3 mm or less, or no blisters developed, cut tape separated width from the cut portion, more than 3 mm, X; Blisters developed, and tape-separated width from the cut
portion, more than 3 mm. Acid Resistance:
A back side and cut surface of respective coating test panels cut to a size of 5 cm * 10 cm were sealed with an anticorrosive coating composition and a cross cut reaching the substrate was formed at the center on the side of the surface of the coating panel. The resulting coating panel was dipped in a 5% aqueous sulfuric acid solution at 20"C for 48 hours, followed by taking up, washing and drying at room temperature to evaluate coating film appearance on the side
of the surface of the coating film, and further an adhesive cellophane tape was adhered onto the cross cut portion, followed by strongly separating the tape to evaluate a separated width (one side) from the cross cut portion in the resulting coating film. ⓪: No blisters developed, tape-separated width from the cut
portion, 1,5 mm or less. O: No blisters developed, tape-separated width from the cut
portion, more than 1.5 mm but 3 mm or less. ∆: Slight development of blisters, tape-separated width from
the cut portion, 3 mm or less, or no blisters developed,
cut tape separated width from the cut portion, more than
3 mm. X; Blisters developed, and tape-separated width from the cut
portion, more than 3 mm,
Anti-Scratch Property: At room temperature of 20°C, by use of a coin-scratch hardness tester (marketed by Jido-ka Giken Kogyo K.K.), an edge of a ten yen copper coin was kept at an angle of 45° on a coating film on the side of the surface of the respective coating test panels, followed by pulling the ten yen copper coin at a speed of 10 nun/sec., about 30 mm, while pressing under a load of 3 kg, forming mars on the coating film, and evaluating a degree of the mar as follows. ⓪: Substrate metal is not exposed in the mar portion. O; Substrate metal is slightly exposed in the mar portion. ∆: Substrate metal is considerably exposed in the mar
portion.
X: Almost no coating film remains and the substrate metal is clearly exposed in the'mar portion.
GL steel sheet and GI steel sheet were subjected to the following cyclic corrosion test (CCT) and SPC steel sheet was subjected to the following salt spray test as the corrosion resistance test.
Cyclic Corrosion Test (1) : Examples 1-44, Comparative Examples 1-16 and Reference Examples 1-2 were subjected to the following tests in accordance with JIS K-5621 (1990) . A cross cut reaching the substrate with an included angle 3D* and a line width of 0.5 mm was formed by use of a back of a cutter knife at the center on the side of the surface of respective coating test panels cut to a size of 6 cm x 12 cm so that a burr in an edge portion of a long side of respective coating test panels faces the side of the surface on the right side to the coating film on the side of the surface, and faces the back side on the light side to the coating film on the side of the surface, followed by sealing an upper end edge portion of the coating panel with an anticorrosive coating composition, and subjecting a coating panel prepared by subjecting the upper end portion to 4T folding fabrication, that is, a fabrication comprising folding the coating panel with the side of the surface of the coating panel outside, putting 4 sheets having the same thickness as the coating panel inside the folded, coating panel and folding the resulting coating panel at an angle of 180° by use of a vise, to a cyclic corrosion test comprising
300 cycles of 1800 hours in total by cycling one cycle consisting of the following successive steps: 5% salt spray test at 30'C for 0.5 hour, a test in a moisture resistance tester under RH 95% or higher at 30*C for 1.5 hours, drying at 50 °C for 2 hours, and drying at 30°C for 2 hours. The resulting coating panel was subjected to evaluation of conditions in an edge portion, cross cut portion and 4T folding-fabricated portion respectively.
4T fabricated portion: Evaluation was made on a total length of a rust portion in the 4T fabricated portion. ⓪: No rust developed.
O: White rust developed, but less than 20 mm. ∆; White rust 20 mm or more, but less than 40 mm. X; White rust in 40 mm or more, or red rust developed. Edge portion: An average value of an edge creep width of both left and right long sides was determined to evaluate as follows.
⓪: Less than 5 mm.
O: 5 mm or more, but less than 10 mm. ∆: 10 nun or more, but less than 20 nun. X; 20 nun or more.
Cross cut portion: Corrosion conditions in the cross cut portion were evaluated based on a degree of a white rust-developed length in a substrate metal exposed portion with a cut width of 0.5 mm, and an average value of a left and right blister width of both sides in the cut portion as follows. ⓪: Degree of white rust-developed length in the substrate
rnetal exposed portion is less than 50%, and the blister
width is less than 3 mm. O: Degree of white rust-developed length is 50% or more, and
the blister width is less than 3 mm, or degree of white
rust-developed length is less than 50%, and the blister
width is 3 mm or more, but less than 5 mm. ∆: Degree of white rust-developed length is 50% or more, and
the blister width is 5 mm or more, but less than 10 mm. X; Degree of white rust-developed width is 50% or more, and
the blister width is 10 mm or more.
Cyclic Corrosion Test (2): Examples 45,94, Comparative Examples 17-50 and Reference Examples 3-10 were subjected to the following tests. A cross cut reaching the substrate with an included angle 30° and a line width of 0.5 mm was formed by use of a cutter knife at the center on the side of the surface of respective coating test panels cut to a size of 6 cm x 12 cm so that a burr in an edge portion of a long side of respective coating test panels faces the side of the surface on the right side to the coating film on the side of the surface, and faces the back side on the light side to the coating film on the side of the surface, followed by sealing an upper end edge portion of the coating panel with an anticorrosive coating composition, and subjecting the upper end portion to 4T folding fabrication, that is, a fabrication comprising folding the coating panel with the side of the surface of the coating panel outside, putting 4 sheets having the same thickness as the coating panel inside the folded
coating panel, and folding the resulting coating panel at an angle of 180° by use of a vise.
Regarding to the coating test panel for coating specification 5, the resulting coating panel was subjected to a cyclic corrosion test, in accordance with JIS-H8502.8.1, comprising 150 cycles of 1200 hours in total by cycling one cycle consisting of the following successive steps: 5% salt spray test at 35°C for 2 hours, drying at 60 °C for 4 hours, and a moisture resistance test in a moisture resistance tester under RH 95% or higher at 50"C for 2 hours. The resulting coating panel was subjected to evaluation of conditions in an edge portion, cross cut portion and 4T folding-fabricated portion respectively.
Regarding to the coating test panel for coating specification 6, the resulting coating panel was subjected to the same cyclic corrosion test as the coating test panel in the coating specification 1, except that 150 cycles of 1200 hours in total is changed to 100 cycles of 800 hours in total. The resulting coating panel was subjected to evaluation of conditions in the edge portion, cross cut portion and 4T folding-fabricated portion respectively.
4T fabricated portion: Evaluation was made on a total length of a rust portion in the 4T fabricated portion. ⓪: No rust developed.
O: White rust developed, but less than 20 mm. ∆: White rust 20 mm or more, but less than 40 mm. X; White rust in 40 mm or more, or red rust developed.
Edge portion: An average value of an edge creep width of both left and right long sides was determined to evaluate as follows. ⓪: Less than 5 mm.
O: 5 mm or more, but less than. 10 mm. ∆: 10 mm or more, but less than 20 mm. X: 20 mm or more.
Cross cut portion: Corrosion conditions in the cross cut portion were evaluated based on a degree of a white rust-developed length in a substrate metal exposed portion with a cut width of 0.5 mm, and an average value of a left and right blister width of both sides in the cut portion as follows. ⓪: Degree of white rust-developed length in the substrate
metal exposed portion is less than 50%, and the blister
width is less than 3 mm, O: Degree of white rust-developed length is 50% or more, and
the blister width is less than 3 mm, or degree of white
rust-developed length is less than 50%, and the blister
width is 3 mm or more, but less than 5 mm. ∆: Degree of white rust-developed length is 50% or more, and
the blister width is 5 mm or more, but less than 10 mm. X; Degree of white rust-developed width is 50% or more, and
the blister width is 10 mm or more. Salt Water Spray Test:
A back side and cut surface of respective coating test panels of coated SPC steel sheet, cut to a size of 5 cm * 10 cm were sealed with an anticorrosive coating composition,
followed by forming a cross cut reaching the substrate at the center of the surface of the coating panel, and subjecting the resulting coating panel to salt spray test (JIS Z-2371) by use of 5% aqueous sodium chloride solution at 35"C for 500 hours, and evaluating red rust development conditions on the coating surface of the resulting coating panel, and separately adhering a cellophane adhesive tape onto the cross cut portion, followed by strongly peeling the tape to evaluate a tape-peeled width from the cut portion on the resulting coating film as follows.
⓪: No red rust developed or slightly developed, and a tape-peeled width from the cut portion is less than 5 mm. O: Red rust considerably developed, and a tape-peeled width from the cut portion is less than 5 mm, or no red rust developed or slightly developed, but the tape-peeled width from the cut portion is 5 mm or more, but less than 10 mm.
∆: Red rust developed throughout the cut portion and the tape-peeled width from the cut portion is 5 mm or more, but less than 10 mm, or red rust developed not wholly but considerably, and the tape-peeled width from the cut portion is 10 mm or more. X: Red rust developed throughout the cut portion, and the
tape-peeled width from the cut portion is .10 mm or more. Weather-Resistant Salt Spray Test:
A coating test panel cut to a size of 5 cm x 10 cm was subjected to 500 hour irradiation by use of a xenon weather
meter under a repeating cycle condition of wetting for 18 minutes followed by drying for 102 minutes in accordance with method A in tests for long term durability, accelerated weather resistance by xenon lamp method as defined in JIS K-5600 7.7, followed by sealing the back side and cut surface with an anticorrosive coating composition, forming a cross cut reaching the substrate at the center of the surface of the coating panel, subjecting the resulting coating panel to a salt spray test (JIS Z-2371) for 500 hours, and evaluating the appearance in the flat portion as follows. ⓪: A blister-rust-developed width from the cut portion is 3
mm or less on an average across the cut, and further no
abnormalities. O: The talisterrust-developed width from the cut portion is
more than 3 mm, and 5 mm or less, no abnormalities in
flat portion and others, or some blisters developed in
the flat portion, but the blister-rust-developed width
from the cut portion is 3 mm or less. ∆: The blister•rust-developed width from the cut portion is
more than 3 mm, but 5 mm or less, and some blisters
developed in the flat portion. X: The blister •rust-developed width from the cut portion is
more than 5 mm, or blister remarkably developed.
Table 2 (I) (Table Removed)
Table 2 (2) (Table Removed)
Table 2 (3) (Table Removed)
Table 2 (4) (Table Removed)
Table 3 (1) (Table Removed)
Table 3 (2) (Table Removed)
Table 3 (3) (Table Removed)
In Tabler *2 represents Preparation Example 2.

Table 4 (1) (Table Removed)
Table 4 (2) (Table Removed)
Table 4 (3) (Table Removed)
In Table, *2 represents Preparation Example 2.


We claim:
1. A coating composition comprising:
(A) a hydroxyl group-containing coating film-forming resin, in the range of 55 to 95 parts by weight, selected from hydroxyl group-containing polyester resin, hydroxyl group-containing epoxy resin, hydroxyl group-containing acrylic resin, hydroxyl group-containing fluorocarbon resin and hydroxyl group-containing vinyl chloride resin;
(B) a crosslinking agent, in the range of 5 to 45 parts by weight, selected from amino resin and optionally blocked polyisocyanate compound, and;
(C) anticorrosion pigment mixture, said anticorrosion pigment mixture (C) being:
an anticorrosion pigment mixture (C-l) consisting of a combination of:
• at least one vanadium compound (1) selected from vanadium pentoxide, calcium vanadate and ammonium metavanadate, in the range of 3 to 50 parts by weight,
• a metal silicate (2), in the range of 3 to 50 parts by weight; and
• a phosphate-based calcium salt (3), in the range of 3 to 50 parts by weight,
or
an anticorrosion pigment mixture (C-2) consisting of a combination of:
• at least one vanadium compound (1) selected from vanadium pentoxide, calcium vanadate and ammonium metavanadate, in the range of 3 to 50 parts by weight,
• a calcium compound (4), in the range of 3 to 50 parts by weight; and
• at least one phosphate-based metal salt (5) 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, in the range of 3 to 50 parts by weight,
the anticorrosion pigment mixture (C) being in the range of 10 to 150 parts by weight, per 100 parts by weight of a total solid content of the resin (A) and the crosslinking agent (B) respectively.
2. A coating composition as claimed in claim 1, wherein the hydroxyl group-containing, coating film-forming resin (A) is a hydroxyl group-containing film forming resin selected from a hydroxyl group-containing epoxy resin and hydroxyl group-containing polyester resin.
3. A coating composition as claimed, in claim 1 or 2, wherein the crosslinking agent (B) is a crosslinking agent selected from an amino resin, a phenol resin and optionally-blocked polyisocyanate compound.
4. A coating composition as claimed in claim 1, wherein the phosphate-based calcium salt (3) constituting the anticorrosion pigment mixture (C-1) is a phosphate-based calcium salt selected from calcium phosphate, calcium secondary phosphate, calcium dihydrogenphosphate and calcium tripolyphosphate.
5. A coating composition as claimed in claim 1, wherein the calcium compound (4) constituting the anticorrosion pigment mixture (C-2) is a calcium compound selected from calcium metasilicate, calcium oxide and calcium carbonate.
6. A coating composition as claimed in claim 1, wherein the coating composition optionally contains a pigment component selected from an anticorrosive pigment other than the anticorrosion pigment mixture (C), titanium dioxide pigment and an extender pigment in addition to the anticorrosion pigment mixture (C).
7. A coating composition as claimed in claim 1, wherein the coating composition optionally contains an ultraviolet light absorber and/or an ultraviolet stabilizer.
8. A coating composition as claimed in claim 1, wherein the coating composition is such that a filtrate prepared by adding a mixture of the vanadium compound (1), the metal silicate (2) and the phosphate-based calcium salt (3) constituting the anticorrosion pigment mixture (C-l) within the range of parts by weight per 100 parts by weight of the total solid content of the resin (A) and the crosslinking agent (B) as claimed in claim 1 respectively to 10000 parts by weight of a 5 wt% aqueous sodium chloride solution at 25°C, followed by stirring for 6 hours, leaving at rest for 48 hours at 25°C, and filtering a resulting supernatant liquid; having a pH in the range of 3 to 10.
9. A coating composition as claimed in claim 1, wherein the coating composition is
sucha that a filtrate prepared by adding a mixture of the vanadium compound (1), the
calcium compound (4) and the phosphate-based metal salt (5) constituting the
anticorrosion pigment mixture (C-2) within the range of parts by weight per 100 parts
by weight of the total solid content of the resin (A) and the crosslinking agent (B) as
claimed in claim 1 respectively to 10000 parts by weight of a 5 wt% aqueous sodium
chloride solution at 25 °C, followed by stirring for 6 hours, leaving at rest for 48 hours
at 25°C, and filtering a resulting supernatant liquid; having a pH in the range of 3 to
10.
10. A coated metal sheet having at least one coating film consisting of a cured coating film formed from the coating composition as claimed in claim 1 on the surface(s) of a metal sheet subjected to an optional metal surface treating process, and a topcoating film formed on the cured coating film.

Documents:

918-DEL-2008-Abstract-(27-02-2012).pdf

918-del-2008-abstract.pdf

918-DEL-2008-Claims-(27-02-2012).pdf

918-del-2008-claims.pdf

918-DEL-2008-Correspondence Others-(27-02-2012).pdf

918-del-2008-correspondence-others.pdf

918-del-2008-description (complete).pdf

918-DEL-2008-Form-1-(27-02-2012).pdf

918-del-2008-form-1.pdf

918-del-2008-form-18.pdf

918-DEL-2008-Form-2-(27-02-2012).pdf

918-del-2008-form-2.pdf

918-DEL-2008-Form-3-(27-02-2012).pdf

918-del-2008-form-3.pdf

918-del-2008-form-5.pdf

918-DEL-2008-Petition-137-(27-02-2012).pdf


Patent Number 255295
Indian Patent Application Number 918/DEL/2008
PG Journal Number 07/2013
Publication Date 15-Feb-2013
Grant Date 11-Feb-2013
Date of Filing 10-Mar-2008
Name of Patentee KANSAI PAINT CO.LTD
Applicant Address 33-1, KANZAKI-CHO, AMAGASAKI-SHI, HYOGO-KEN 661-0964 JAPAN
Inventors:
# Inventor's Name Inventor's Address
1 MATSUDA HIDEKI KANSAI PAINT CO. LTD 17-1, HIGASHIYAWATA 4-CHOME, HIRATSUKE-SHI, KANAGAWA-KEN,2540016 JAPAN.
2 SAKAMOTO AKIHISA KANSAI PAINT CO. LTD 17-1, HIGASHIYAWATA 4-CHOME, HIRATSUKE-SHI, KANAGAWA-KEN,2540016 JAPAN.
3 HORIKE NAOKI KANSAI PAINT CO. LTD 17-1, HIGASHIYAWATA 4-CHOME, HIRATSUKE-SHI, KANAGAWA-KEN,2540016 JAPAN.
4 MASUDA HIDEKI KANSAI PAINT CO. LTD 17-1, HIGASHIYAWATA 4-CHOME, HIRATSUKE-SHI, KANAGAWA-KEN,2540016 JAPAN.
PCT International Classification Number C09D183/04
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 07/062,051 2007-03-12 Japan
2 07/062,052 2007-03-12 Japan
3 07/110,696 2007-04-19 Japan