CN101397474B - Coating composition and paint metal plate using the composition - Google Patents

Abstract

The present invention provides a coating composition which comprises the following components: (A) a film forming resin comprising hydroxyl, (B) a cross linker and (C) a rust-preventive pigment compound. The invention is characterized in that the rust-preventive pigment compound (C) is a rust-preventive pigment compound (C1) which is combined by the following components: (1) at least one vanadium compound selected from vanadium pentoxide, calcium vanadate and ammonium metavanadate, (2) a metal silicate, and (3) a calcium phosphate; or the rust-preventive pigment compound (C) is a rust-preventive pigment compound (C2) which is combined by the following components: (1) the vanadium compound, (4) a calcium compound and (5) at least one metal salt selected from metal phosphate, metal hydrogen phosphate and metal triphosphate, wherein the metal of the metal salt is Zn, Al or Mg. The invention also provides a coated metal plate which uses the coating composition.

Description

The lacquer metal sheet of coating composition and use said composition

Technical field

The present invention relates to the non-chromium class coating composition of excellent corrosion resistance and the lacquer metal sheet of use said composition, more particularly, relate to the erosion resistance that not only effectively improves at lacquer position, metal sheet plane, and effectively improve the coating composition and the lacquer metal sheet that uses said composition of the erosion resistance of working position and end face area.

Background technology

Always, be widely used as the dwelling house dependent merchandises such as material of construction, various families electrical article, switching motherboard, refrigerated display case, steel furniture and kitchen appliance such as roof, wall, window shutter, garage of buildings by the prefinished metal plates such as pre-coated steel plate of coverings with paint such as coil coating.

When using prefinished metal plate to make these dwelling house dependent merchandises, general by cutting pre-coated steel plate, extrusion molding, and be bonded.Therefore, in these dwelling house dependent merchandises, the most of existence as the metal exposed position in cross section or the crack that forms because of extrusion processing generates the position.Above-mentioned metal exposed position or crack generate the position and compare with other parts, because erosion resistance reduces easily, therefore in order to improve erosion resistance, generally wrap the containing chronium rust-stabilising pigment in the primer coating film of pre-coated steel plate.

Yet chromium class rust-stabilising pigment contains 6 valency chromium of rust-preventing characteristic excellence, or produces this 6 valency chromium, and to the healthy aspect of human body, the viewpoint of environment protection, this 6 valency chromium is problematic.

So far, as the rust-stabilising pigment of non-chromium class, a large amount of appearance is zinc phosphate, aluminium triphosphate, zinc molybdate etc. on the market, and the priming paint as the non-chromium class pigment of combination has proposed a variety of.For example, in patent documentation 1, put down in writing following coating: in the carrier components of Resins, epoxy and resol, mix the combination of Calucium Silicate powder and vanadic acid phosphorus, or the rust-stabilising pigment of lime carbonate, Calucium Silicate powder, aluminum phosphate and the combination of vanadic acid phosphorus is as rust-stabilising pigment.In addition, patent documentation 2 has been put down in writing following coating: cooperate the combination of phosphorous acid magnesium and manganese oxide vanadium oxide sinter in polyester, or the sinter of calcium phosphate and vanadium oxide is as rust-stabilising pigment.Yet what patent documentation 1 and 2 was put down in writing compares the erosion resistance deficiency of corrosion-resistant, especially working position and end face area by filming of forming of coating with the coating that uses chromium class pigment.In addition, much be that chemical resistances such as alkali resistance or acid resistance are poor.And, if use antirust pigment in a large number, be mostly poor water resistance, in prefinished metal plate is made, can not reach the degree that replaces chromium class rust-stabilising pigment.

In addition, in patent documentation 3, put down in writing in the carrier components of forming by the organic resin and the solidifying agent of hydroxyl or epoxy group(ing), contain oil number 30～200ml/100g, the pore solvent is the coating of the silicon dioxide microparticle of 0.05～1.2ml/g, and is 40～125 ℃ of coating compositions in the scope by the second-order transition temperature of the formed cured coating film of this coating.But, though patent documentation 3 put down in writing shown certain erosion resistance by filming of forming of coating, compare with the coating that uses chromium class pigment, remain erosion resistance and chemical resistance is poor, especially the erosion resistance of end face area is not enough.

Patent documentation 1: the spy opens flat 11-61001 communique

Patent documentation 2: the spy opens the 2000-199078 communique

Patent documentation 3: the spy opens the 2000-129163 communique

Summary of the invention

The problem that invention will solve

The object of the present invention is to provide: non-chromium class coating composition and use the lacquer metal sheet of said composition, wherein this coating composition can be formation such as lacquer metal sheet also the filming of excellence of erosion resistance of the excellent corrosion resistance at conventional position but also working position or end face area not only.

For solving the means of problem

Therefore, the inventor etc. have solved the problems referred to above always fully, through the result who repeatedly furthers investigate, found in the film-forming resin class of hydroxyl, as rust-stabilising pigment, by the specific vanadium compound of quantitative cooperation, the specific coating composition that contains silicic acid thing and specific calcium phosphate salt, or quantitatively cooperate the coating composition of specific vanadium compound, calcium cpd and specific phosphoric acid metalloid salt, can form the not only excellent corrosion resistance at position, plane, and the filming of the excellent corrosion resistance of the working position of lacquer metal sheet etc. and end face area.

That is: the invention provides coating composition, this coating composition contains the film-forming resin of (A) hydroxyl, (B) linking agent and (C) rust-stabilising pigment mixture, it is characterized in that: this rust-stabilising pigment mixture (C) is (1) vanadium pentoxide, at least a vanadium compound of vanadic acid calcium and ammonium meta-vanadate, (2) the rust-stabilising pigment mixture (C-1) that constitutes of metal silicate and (3) phosphoric acid class calcium salt, or this vanadium compound (1), (4) calcium cpd and (5) phosphate metal salt, phosphoric acid hydrogen metal-salt and tripolyphosphate metal-salt at least a, and the metal of this each metal-salt is Zn, the rust-stabilising pigment mixture (C-2) that the phosphoric acid metalloid salt of Al or Mg combines, total solids component 100 mass parts with respect to this resin (A) and this linking agent (B), the amount of this rust-stabilising pigment mixture (C) is respectively 10～150 mass parts, and in this rust-stabilising pigment mixture (C-1), the amount of this vanadium compound (1) is 3～50 mass parts, the amount of metal silicate (2) is 3～50 mass parts, and the amount of this phosphoric acid class calcium salt (3) is 3～50 mass parts, in this rust-stabilising pigment mixture (C-2), the amount of this vanadium compound (1) is 3～50 mass parts, the amount of this calcium cpd (4) is 3～50 mass parts, and the amount of this phosphoric acid metalloid salt (5) is 3～50 mass parts; And the lacquer metal sheet that this coating composition of use is provided.

The invention effect

Coating composition of the present invention is the rust-stabilising pigment of not containing chronium, the coating composition favourable to environmental health, by coating composition of the present invention, performance can form the excellent corrosion resistance at position, plane not only and also at non-chromium class rust proof paint so far for to the working position of unapproachable lacquer metal sheet etc. or the also excellent effect of filming of erosion resistance of end face area.

Form the excellent corrosion resistance of the lacquer metal sheet of cured coating film by coating composition of the present invention in position, plane, working position or end face area, compare with the lacquer metal sheet that is formed with cured coating film based on the coating that uses chromate rust-stabilising pigment always such as strontium yellow, have identical or higher erosion resistance.

Form cured coating film by coating composition of the present invention, on this cured coating film, form the lacquer metal sheet that finish paint is filmed, the excellent corrosion resistance of its position, plane, working position or end face area.When using zinc steel plating plate, aluminum-zinc alloy steel plating plate,,, and also can both obtain excellent erosion resistance at end face area, working position not only at the position, plane by covering with paint, lacquer, colour wash, etc. coating composition of the present invention as the metal sheet of coated article.

Embodiment

Coating composition of the present invention is the coating composition of the film-forming resin (A), linking agent (B) and the rust-stabilising pigment mixture (C) that contain following hydroxyl.

The film-forming resin of hydroxyl (A)

Film-forming resin as the hydroxyl in the coating composition of the present invention, can use the normally used hydroxy-containing resin of paint field without restriction with film forming properties, as typical example, can enumerate one or more hybrid resin such as the vibrin that contains hydroxyl, Resins, epoxy, acrylic resin, fluorine resin, vinyl chloride resin.As film-forming resin, wherein, suitable use is selected from the vibrin of hydroxyl and at least a organic resin of Resins, epoxy.

Vibrin as above-mentioned hydroxyl, the modifier that comprises oil-free polyester resin, oil-modified alkyd resin and these resins, for example urethane modified polyester resin, urethane modified alkyd resin, epoxy modified polyester resin, acrylic acid modified polyester resin etc.The number-average molecular weight of the vibrin of above-mentioned hydroxyl is 1500～35000, and is preferred 2000～25000, and second-order transition temperature (Tg point) is 10～100 ℃, preferred 20 ℃～80 ℃, and hydroxyl value is 2～100mgKOH/g, preferred 5～80mgKOH/g.

In this manual, " number-average molecular weight " of resin is meant the color atlas of measuring by according to gel permeation chromatograph (Tosoh (strain) company make, " HLC8120GPC "), is the value that benchmark calculates with the molecular weight of polystyrene standard.Said determination carries out under the following conditions: pillar uses " TSK gel G-4000HXL ", " TSK gel G-3000HXL ", " TSK gel G-2500HXL ", " TSK gel G-2000HXL " (each all is the manufacturing of Tosoh (strain) company, trade(brand)name) 4, moving phase: tetrahydrofuran (THF), mensuration temperature: 40 ℃, flow velocity: 1mL/ branch, detector: RI.In addition, in this manual, the second-order transition temperature of resin (Tg) is the temperature that draws according to differential thermal analysis (DSC).

Above-mentioned oil-free polyester resin is the carboxylate of polyprotonic acid composition and polyhydroxy reactant.As the polyprotonic acid composition, main use for example is selected from more than one diprotic acid and these sour low alkyl group esterification things such as anhydrous phthalic acid, m-phthalic acid, terephthalic acid, the anhydrous phthalic acid of tetrahydro-, the anhydrous phthalic acid of hexahydro-, succsinic acid, fumaric acid, adipic acid, sebacic acid, Maleic Acid, Anhydrous, as required, can and use phenylformic acid, Ba Dousuan, right-monoprotic acid such as p t butylbenzoic acid, the polyprotonic acid that 3 valencys such as anhydrous trimellitic acid, tetrahydrotoluene tricarboxylic acid, anhydrous pyromellitic acid are above etc.As polyol component, mainly use for example ethylene glycol, glycol ether, propylene glycol, 1,4-butyleneglycol, neopentyl glycol, 3-methyl pentanediol, 1,4-hexylene glycol, 1, dibasic alcohol such as 6-hexylene glycol, in addition, as required, can and use the above polyvalent alcohol of 3 valencys such as glycerol, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane.These polyvalent alcohols can use separately, or mix two or more uses.The esterification of two components or transesterification reaction can be undertaken by known method itself.As acid constituents, preferred especially m-phthalic acid, terephthalic acid and these sour low alkyl group esterification things.

Synolac can also make by known method and fatty acid oil reaction except the acid constituents and alkoxide component of above-mentioned oil-free polyester resin.As fatty acid oil, can enumerate for example coco-nut oil fatty acid, soya fatty acid, linseed oil fatty acid, Thistle oil lipid acid, ready denier oil acid, dehydrated castor oil fatty acid, tung oil lipid acid etc.The oil length of Synolac is below 30%, preferred especially about 5～20%.

As the urethane modified polyester resin, can enumerate: the low-molecular-weight oil-free polyester resin of acid constituents that above-mentioned oil-free polyester resin or make uses when the preparation of above-mentioned oil-free polyester resin and alkoxide component reaction gained and polyisocyanate compound react the resin for preparing by himself known method.In addition, the urethane modified alkyd resin comprises above-mentioned Synolac or makes the low-molecular-weight Synolac of each the component reaction gained that uses and resin that polyisocyanate compound prepares by himself known method reaction when above-mentioned alkyd resin production.Spendable polyisocyanate compound during as preparation urethane modified polyester resin and urethane modified alkyd resin, can enumerate hexamethylene diisocyanate, isophorone diisocyanate, xylylene vulcabond, toluylene group diisocyanate, 4,4 '-diphenylmethanediisocyanate, 4,4 '-methylene radical two (cyclohexyl isocyanate), 2,4,6-three isocyanic acid toluene etc.It is the resin of the modification degree of the amount below the 30 weight % with respect to urethane modified resin that above-mentioned urethane modified resin can preferably use the amount of the polyisocyanate compound that forms urethane modified resin usually.

As epoxy modified polyester resin, can enumerate: use the vibrin that is prepared from by each component that is used for above-mentioned vibrin preparation, the carboxyl of this resin and contain the resultant of reaction of the resin of epoxy group(ing), or the resultant of reaction that the reactions such as the addition of passing through vibrin and Resins, epoxy, condensation, grafting of the hydroxyl in the vibrin and the resultant of the hydroxyl bonding in the Resins, epoxy etc. are generated.Modification degree in the described epoxy modified polyester resin is usually with respect to epoxy modified polyester resin, and the amount of Resins, epoxy is the amount of 0.1～30 weight %.

As acrylic acid modified polyester resin, can enumerate: the vibrin that is prepared from by each component that is used for the preparation of above-mentioned vibrin, the carboxyl of this resin or hydroxyl and these groups have the resultant of reaction that reactive group for example contains the acrylic resin of carboxyl, hydroxyl or epoxy group(ing), or use the peroxide polymerization starter, to the resultant of reaction of vibrin graft polymerization (methyl) vinylformic acid or (methyl) acrylate.Modification degree in the acrylic acid modified polyester resin that relates to is preferably usually with respect to acrylic acid modified polyester resin, and the amount of acrylic resin is the amount of 0.1～50 weight %.

In above-described vibrin, from processibility, erosion resistance isoequilibrium viewpoint, preferred oil-free polyester resin, epoxy modified polyester resin wherein.

As the preferred epoxy of the film-forming resin of aforementioned hydroxyl, can enumerate bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin; The modified epoxy that epoxy group(ing) in these Resins, epoxy or hydroxyl obtain by various properties-correcting agent reactions.In the preparation of modified epoxy, the modification time by this properties-correcting agent has no particular limits, and can carry out modification in the stage midway of Resins, epoxy preparation, also can carry out modification in the terminal stage of Resins, epoxy preparation.

Above-mentioned bisphenol-type epoxy resin can be for example as required in the presence of catalyzer such as alkaline catalysts, makes epoxy chloropropane and bis-phenol be condensed into the high-molecular weight resin; Or as required in the presence of catalyzer such as alkaline catalysts, condensation forms low-molecular-weight Resins, epoxy, carries out any of resin that polyaddition reaction obtains by making this low-molecular-weight epoxy resin and bis-phenol.

As above-mentioned bis-phenol; can enumerate two (4-hydroxy phenyl) methane " Bisphenol F ", 1; 1-two (4-hydroxy phenyl) ethane, 2; 2-two (4-hydroxy phenyl) propane " dihydroxyphenyl propane ", 2; 2-two (4-hydroxy phenyl) butane " bisphenol b ", two (4-hydroxy phenyl)-1; 1-Trimethylmethane, two (4-hydroxyl-tertiary butyl-phenyl)-2; 2-propane, right-(4-hydroxy phenyl) phenol, oxygen two (4-hydroxy phenyl), alkylsulfonyl two (4-hydroxy phenyl), 4; 4 '-dihydroxy benzophenone, two (2 hydroxy naphthalene base) methane etc., wherein preferably use dihydroxyphenyl propane, Bisphenol F.Above-mentioned bisphenols can use one or more mixture.

As the commodity of bisphenol-type epoxy resin, for example, can enumerate the Epikote828,812,815,820,834,1001,1004,1007,1009,1010 of japan epoxy resin company; The Araldite AER6099 of rising sun Chiba corporate system; And the Epomik R-309 of Mitsui Chemicals (strain) system etc.

In addition, film-forming resin as hydroxyl, the aforementioned phenolic resin varnish type epoxy resin of preferred epoxy can exemplify the various phenolic resin varnish type epoxy resins such as phenol oxalic dialdehyde type Resins, epoxy that for example phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, intramolecularly have many epoxy group(ing).

As aforementioned modified epoxy, can enumerate: in aforementioned bisphenol-type epoxy resin or above-mentioned phenolic resin varnish type epoxy resin, for example make the epoxy ester resin of drying oil fatty acid reaction; Make the Epocryl of the polymerizability unsaturated monomer composition reaction that contains acrylic or methacrylic acid etc.; Make the urethane modified epoxy of isocyanate compound reaction; Epoxy group(ing) in above-mentioned bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin or above-mentioned various modified epoxy and amine compound reaction import the amine-modified epoxy resin of amino or quaternary ammonium salt etc.

Linking agent (B)

Linking agent (B) is and the reaction of the film-forming resin (A) of aforementioned hydroxyl, form the material of cured coating film, as long as can be by film-forming resin (A) reaction with aforementioned hydroxyl such as heating, and make its solidified linking agent, just have no particular limits this use, wherein, preferred aminoresin, resol and polyisocyanate compound that can block.These linking agents can use a kind of or make up two or more uses.

As above-mentioned aminoresin, can enumerate methylolation aminoresin by amino groups such as trimeric cyanamide, urea, benzo guanamine, ethanoyl guanamine, sterol guanamine, volution guanamine, diamines hydrazine and aldehyde reaction gained.As the employed aldehyde of above-mentioned reaction, can enumerate formaldehyde, Paraformaldehyde 96, acetaldehyde, phenyl aldehyde etc.In addition, make above-mentioned methylolation aminoresin etherificate products therefrom can be used as aminoresin by suitable alcohol.As the example of the alcohol that uses in the etherificate, can enumerate methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, 2-ethyl butanol, 2-Ethylhexyl Alcohol etc.

Can be as the resol of above-mentioned linking agent, be resin with film-forming resin (A) crosslinking reaction of above-mentioned hydroxyl.Can enumerate: in the presence of catalysts, to phenol component and aldehydes heating, carry out condensation reaction, import methylol, part or all of the methylol of the methylolation resol of the gained first rank phenolic varnish type resol that the alkyl etherificate forms in alcohol.

In the preparation of first rank phenolic varnish type resol,, can use the above phenolic compound of 2 functionality phenolic compound, 3 functionality phenolic compound, 4 functionality etc. as the above-mentioned phenol component of starting raw material.

As above-mentioned phenolic compound, for example as 2 functionality phenolic compound, can enumerate adjacent methoxycresol, to methoxycresol, p-tert-butylphenol, right-ethylphenol, 2,3-xylenol, 2,5-xylenol etc. are as 3 functionality phenolic compound, can enumerate phenylic acid, a methoxycresol, m-ethylphenol, 3, the 5-xylenol ,-methoxyphenol etc., as 4 functionality oxybenzene compounds, can enumerate dihydroxyphenyl propane, Bisphenol F etc.Wherein,, preferably use the above oxybenzene compound of 3 functionality, especially preferably use a phenylic acid and/or a methoxycresol in order to improve the scratch resistance trace.These oxybenzene compounds can use a kind of or mix two or more more than.

The aldehydes that uses when preparing as resol can be enumerated formaldehyde, Paraformaldehyde 96, trioxa cyclohexane etc., can use a kind of or mixes two or more uses.

Employed alcohol during as the methylol part alkyl etherificate that makes methylolated resol can use 1～8 of carbonatoms, preferred 1～4 monohydroxy-alcohol.As preferred monohydroxy-alcohol, can enumerate methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, isopropylcarbinol etc.

Resol from the aspects such as reactivity worth of the film-forming resin (A) of hydroxyl, be fit to use each benzene nucleus on average to contain alkoxy methyl more than 0.5, preferably contain 0.6～3.0.

Do not have the polyisocyanate compound of blockization in the polyisocyanate compound as the optional blockization that can be used as above-mentioned linking agent, for example can enumerate: aliphatics such as hexamethylene diisocyanate or trimethyl hexamethylene diisocyanate two cyanates; Annular aliphatic diisocyanates such as the xylylene vulcabond of hydrogenation or isophorone diisocyanate; Toluylene group diisocyanate, xylylene vulcabond or 4,4 '-organic two cyanates itself such as aromatic diisocyanate class such as '-diphenylmethane diisocyanate, thick MDI, or the affixture of these organic two cyanates and polyvalent alcohol, low molecular weight polyester resin or water etc., mutual cyclized polymer between perhaps above-mentioned each organic diisocyanate, or the isocyanic ester biuret etc.

The blocked polyisocyanate compound is by encapsulant, makes the compound of the non-isocyanate base blockization of above-mentioned polyisocyanate compound.As above-mentioned encapsulant, for example can use phenols such as phenol, cresols, xylenol; Lactams such as 'epsilon '-hexanolactam, δ-Valerolactim, butyrolactam; Methyl alcohol, ethanol, just-, alcohols such as exclusive OR uncle-butanols, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, phenylcarbinol; Oximes such as formyl amidoxime, ethylidenehydroxylamine, acetoxime, methyl ethyl ketoxime, biacetyl monoxime, diphenylketoxime, hexanaphthene oxime; Encapsulants such as dimethyl malonate, diethyl malonate, methyl aceto acetate, Acetyl Acetone isoreactivity methylene base class.By mixing above-mentioned polyisocyanate compound and above-mentioned encapsulant, can easily make the non-isocyanato sealing of above-mentioned polyisocyanate compound.

The blending ratio of film-forming resin of aforementioned hydroxyl (A) and above-mentioned linking agent (B) is from aspects such as erosion resistance, resistance to boiling water, processibility, solidified nature, with respect to (A) and (B) total solids component 100 weight parts of component, the film-forming resin of hydroxyl (A) is 5～95 weight parts, preferred 60～95 weight parts, linking agent (B) is 5～45 weight parts, preferred 5～40 weight parts.

In order to improve the solidified nature of coating composition of the present invention, as required can mixing cured catalyzer.Linking agent (B) is aminoresin, particularly during the low-molecular-weight complex etherified melamine resin that contains methyl-etherified or methyl ether and butyl ether, the amine neutralized reaction product that can preferably use sulfoacid compound or sulfoacid compound is as curing catalysts.As the representation example of sulfoacid compound, can enumerate right-toluenesulphonic acids, Witco 1298 Soft Acid, dinonylnaphthalene sulfonic acid, dinonylnaphthalene disulfonic acid etc.As the amine in the amine neutralized reaction product of sulfoacid compound, can be any one of primary amine, secondary amine, tertiary amine.Among these, viewpoints such as rerum natura, the amine neutralized reaction product of preferably right-toluenesulphonic acids and/or the amine neutralized reaction product of Witco 1298 Soft Acid of filming from the stability of coating, reaction facilitation effect, gained.

When linking agent (B) was resol, the amine neutralized reaction product of preferably using above-mentioned sulfoacid compound or sulfoacid compound was as curing catalysts.

When linking agent (B) is the closure polyisocyanate compound, preferably as the curing catalysts of the encapsulant depolymerization of the promotion blocked polyisocyanate compound of linking agent.As preferred curing catalysts, can enumerate for example organo-metallic catalysts such as stannous octoate, dibutyl tin two (2-ethylhexyl), dioctyl tin two (2-ethylhexyl), dioctyl tin diacetate esters, dibutyl tin dilaurate ester, dibutyl tin oxide, dioctyltin oxide, 2 ethyl hexanoic acid lead etc.

When linking agent (B) is the combination of two or more linking agent, can be used in combination the effective curing catalysts of each linking agent.

Rust-stabilising pigment mixture (C)

In coating composition of the present invention, rust-stabilising pigment mixture (C) is to contain the rust-stabilising pigment mixture (C-1) that following (1) vanadium compound, (2) metal silicate and (3) phosphoric acid class calcium salt form, or contains the rust-stabilising pigment mixture (C-2) that (1) vanadium compound, (4) calcium cpd and (5) phosphoric acid metalloid salt form.

Vanadium compound (1)

Vanadium compound (1) is at least a vanadium compound of vanadium pentoxide, vanadic acid calcium and ammonium meta-vanadate.The pentavalent vanadium ion of vanadium pentoxide, vanadic acid calcium and ammonium meta-vanadate is to the stripping property excellence of water, pentavalent vanadium ion that from vanadium compound (1), discharges and feed metal reaction, or by with ionic reaction from other rust-stabilising pigment mixtures, can improve erosion resistance with imitating.

Metal silicate (2)

Metal silicate (2) is the salt that is formed by silicon-dioxide and metal oxide, can be ortho-silicate, polysilicate etc. any one.As silicate, can enumerate for example zinc silicate, pure aluminium silicate, orthosilicic acid aluminium, hydrated aluminium silicate, Aluminum calcium silicate, lagoriolite, pure aluminium silicate beryllium, water glass, calcium orthosilicate, calcium metasilicate, Calucium Silicate powder sodium, zirconium silicate, magnesium orthosilicate, metasilicic acid magnesium, calcium magnesium silicate, manganous silicate, barium silicate, peridotites, garnet, thortveitite, lapis calaminaris, benitoite, carlosite, beryl, diopside, wollastonite, rock ruby, the tremolite, xonotlite, talcum, apophyllite, aluminosilicate, borosilicate, beryllium silicate, feldspar, zeolite etc.

As metal silicate (2), wherein preferred calcium orthosilicate, calcium metasilicate.

Phosphoric acid class calcium salt (3)

Phosphoric acid class calcium salt (3) is to contain the phosphoric acid salt of calcium as metallic element, can enumerate for example calcium phosphate, ammonium calcium phosphate, calcium monohydrogenphosphate, monocalcium phosphate, phosphoric acid chlorination Calcium Fluoride (Fluorspan) etc.Can improve the phosphate anion of release from phosphoric acid class calcium salt (3) and the erosion resistance of calcium ion effectively.

Calcium cpd (4)

As calcium cpd (4), for example be the calcium cpd beyond vanadic acid calcium or the phosphate cpd, for example can enumerate calcium oxide, calcium hydroxide, calcium orthosilicate, calcium metasilicate, lime carbonate, calcium sulfate, nitrocalcite, sulfurated lime, calcium chloride, Calcium Fluoride (Fluorspan), Calcium Bromide, CaCl2, lime acetate, azide calcium, calcium cyanamide, amination calcium, imino-calcium, calcium silicide etc.Wherein,, preferably have the lime carbonate, calcium oxide, calcium metasilicate of suitable water-soluble etc., preferred especially calcium metasilicate from the erosion resistance aspect.

Phosphoric acid metalloid salt (5)

Phosphoric acid metalloid salt (5) is at least a of phosphate metal salt, phosphoric acid hydrogen metal-salt and tripolyphosphate metal-salt, and the metal of each metal-salt is the phosphoric acid metalloid salt of Zn, Al and Mg.

As above-mentioned phosphoric acid metalloid salt, can enumerate for example zinc phosphate, aluminum phosphate, trimagnesium phosphate, phosphoric acid hydrogen zinc, phosphoric acid hydrogen aluminium, secondary magnesium phosphate, ammonium magnesium phosphate, aluminium dihydrogen tripolyphosphate etc.

Zn, Al that discharges from phosphoric acid metalloid salt (5) and metal ion, the phosphate anion of Mg have improved erosion resistance effectively.

In coating composition of the present invention, total solids component 100 mass parts with respect to aforementioned resin (A) and this linking agent (B), rust-stabilising pigment mixture (C-1) is from corrosion resistant viewpoint, described above-mentioned vanadium compound (1), metal silicate (2) and phosphoric acid class calcium salt (3) are in the following ranges, and the amount of rust-stabilising pigment mixture (C) is 10～150 mass parts, is preferably 15～90 mass parts.

Vanadium compound (1): 3～50 mass parts, preferred 5～30 mass parts,

Metal silicate (2): 3～50 mass parts, preferred 5～30 mass parts,

Phosphoric acid class calcium salt (3): 3～50 mass parts, preferred 5～30 mass parts.

In coating composition of the present invention, total solids component 100 mass parts with respect to aforementioned resin (A) and this linking agent (B), rust-stabilising pigment mixture (C-2) is from corrosion resistant viewpoint, preferred above-mentioned vanadium compound (1), calcium cpd (4) and phosphoric acid metalloid salt (5) are in the following ranges, and the amount of rust-stabilising pigment mixture (C) is 10～150 mass parts, is preferably 15～90 mass parts.

Vanadium compound (1): 3～50 mass parts, preferred 5～30 mass parts,

Calcium cpd (4): 3～50 mass parts, preferred 5～30 mass parts,

Phosphoric acid metalloid salt (3): 3～50 mass parts, preferred 5～30 mass parts.

In coating composition of the present invention, as rust-stabilising pigment mixture (C-1), be with quantitative blending ingredients (1), (2) and (3), perhaps as rust-stabilising pigment mixture (C-2), be by with quantitative blending ingredients (1), (4) and (5), can significantly improve erosion resistance.As rust-stabilising pigment mixture (C-1), from the viewpoint of erosion resistance, the combination of wherein preferred vanadium pentoxide, calcium metasilicate, calcium phosphate.

In addition, to constitute the vanadium compound (1) of rust-stabilising pigment mixture (C-1), the mixture of mass parts adds in 25 ℃ sodium chloride aqueous solution 10000 mass parts of 5 quality % concentration in metal silicate (2) and each weight range of phosphoric acid class calcium salt (3), stirred 6 hours, under 25 ℃, left standstill 48 hours, filtering supernatant, the pH of filtrate is 3～10, be preferably 5～9, wherein rust-stabilising pigment mixture (C-1) is the total solids component 100 mass parts blended of relative aforementioned resin (A) and linking agent (B), from vanadium compound (1), metal silicate (2) and phosphoric acid class calcium salt (3) solvability and the lysate of rust-stabilising pigment and the reactive view of metal sheet in water is preferred, consider from the viewpoint of erosion resistance, be preferably placed at this scope.

Promptly, the filtrate of said determination pH, be sodium chloride aqueous solution 10000 mass parts of 5 quality % concentration with respect to 25 ℃, the vanadium compound (1) of any amount in the scope of interpolation 3～50 mass parts, the metal silicate (2) of any amount in 3～50 mass parts scopes, and 3～50 phosphoric acid class calcium salts (3) of any amount in the mass parts scope, be dissolved into the filtrate of lysate.

In addition, to constitute the vanadium compound (1) of rust-stabilising pigment mixture (C-2), the mixture of mass parts adds in 25 ℃ sodium chloride aqueous solution 10000 mass parts of 5 quality % concentration in calcium cpd (4) and each weight range of phosphoric acid metalloid salt (5), stirred 6 hours, under 25 ℃, left standstill 48 hours, filtering supernatant, the pH of filtrate is 3～10, be preferably 5～9, wherein rust-stabilising pigment mixture (C-2) is the total solids component 100 mass parts blended of relative aforementioned resin (A) and linking agent (B), from vanadium compound (1), calcium cpd (4) and phosphoric acid metalloid salt (5) solubleness and the lysate of rust-stabilising pigment and the reactive view of metal sheet in water is preferred, consider from the viewpoint of erosion resistance, preferably be in this scope.

Promptly, the filtrate of said determination pH, be sodium chloride aqueous solution 10000 mass parts of 5 quality % concentration with respect to 25 ℃, the vanadium compound (1) of any amount in the scope of interpolation 3～50 mass parts, the calcium cpd (4) of any amount in 3～50 mass parts scopes, and 3～50 phosphoric acid class calcium salts (5) of any amount in the mass parts scope, be dissolved into the filtrate of lysate.

In coating composition of the present invention, except the film-forming resin (A) of aforementioned hydroxyl, linking agent (B), rust-stabilising pigment mixture (C) and as required the blended curing catalysts, operable tinting pigment, filler pigment, UV light absorber, ultra-violet stabilizer, organic solvent in the compo field as required; Antisettling agent, defoamer, the face that is coated with are adjusted the additive of agent etc. etc.

As above-mentioned tinting pigment, for example be that cyanines indigo plant, cyanines are green, the organic coloring pigment of organic red such as azo class and quinoline a word used for translation ketone etc.; Inorganic coloring pigment such as titanium white, titanium trioxide, ferric oxide, carbon black, various sintering pigment wherein can preferably use titanium white.

As above-mentioned filler pigment, can use for example talcum, clay, mica, aluminum oxide, lime carbonate, barium sulfate etc.

As above-mentioned UV light absorber, for example can enumerate and 2-(2-hydroxyl-3,5-two-tert-pentyl phenyl)-the 2H-benzotriazole, iso-octyl-3-(3-(2H-benzotriazole-2-yl)-5-tertiary butyl-4-hydroxy Phenpropionate, 2-[2-hydroxyl-3,5-two (1, the 1-dimethyl benzyl) phenyl]-the 2H-benzotriazole, 2-[2-hydroxyl-3-dimethyl benzyl-5-(1,1,3, the 3-tetramethyl butyl) phenyl]-the 2H-benzotriazole, methyl-3-[3-the tertiary butyl-5-(2H-benzotriazole-2-yl)-4-hydroxy phenyl] the benzotriazole analog derivative of condenses etc. of propionic ester/Liquid Macrogol; 2-[4-(2-hydroxyl-3-dodecane oxygen propyl group) oxygen]-2-hydroxy phenyl-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3, three azines derivatives of 5-three azines etc.; The oxalic acid anilid of second two hydrazines-N-(2-ethoxyl phenenyl)-N '-(2-ethylphenyl)-(oxamide), second two hydrazines-N-(2-ethoxyl phenenyl)-N '-(4-Permethyl 99A. base phenyl)-(oxamide) etc.

As above-mentioned ultra-violet stabilizer, can enumerate for example hindered amine compound, hindered phenol compound; CHIMASORB944, TINUVIN144, TINUVIN292, TINUVIN770, IRGANOX1010, IRGANOX1098 (more than, the goods of these trade(brand)names all are the commodity of the special chemical company of Chiba.) etc.

By in coating, mixing UV light absorber or ultra-violet stabilizer, can suppress the deterioration that this film coated surface produces because of light, use this coating to make the deterioration on the priming paint surface that light that priming paint also can suppress to arrive because of filming by the top film coated surface of priming paint produces, therefore can prevent primer coating film that the deterioration because of the primer coating film surface produces and the top splitting between filming, keep excellent erosion resistance.

Can be mixed in aforementioned organic solvent in the coating composition of the present invention and be covering with paint in order to improve the present composition etc. and blended as required, can use the film-forming resin (A) that can dissolve or disperse hydroxyl and the solvent of linking agent (B), particularly, can enumerate for example toluene, dimethylbenzene, the varsol of high point petroleum class hydrocarbon etc., methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, the ketones solvent of isophorone etc., ethyl acetate, butylacetate, ethylene glycol monoethyl ether acetate, esters solvents such as diethylene glycol monoethyl ether acetate esters, methyl alcohol, ethanol, Virahol, alcoholic solvents such as butanols, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ether alcohol kind solvents such as diethylene glycol monobutyl ether etc., these can use or mix two or more uses separately.

From the viewpoints such as erosion resistance, acid resistance and processibility of filming, coating composition of the present invention is 40～115 ℃ by the second-order transition temperature of the cured coating film of present composition gained preferably, preferred 50～105 ℃.The second-order transition temperature of filming is to use DINAMIC VISCOELASTOMETER MODEL VIBRONDDV-IIEA type (Japan BALDWIN company make, automatic dynamic determination of viscoelasticity machine), the temperature of the maximum value of trying to achieve by the variation of the tan δ that measures according to the temperature dispersion among the frequency 110Hz.

Coating composition of the present invention is covered with paint, lacquer, colour wash, etc. on metal sheet, and filming when using rust-stabilising pigment mixture (C-1) as rust-stabilising pigment mixture (C) of formation shown excellent erosion resistance.The inventor etc. think that its reason is: because the chloride ion etc. under the corrosive environment, and metal ion and 5 valency vanadium ion (VO that the dissolving by material metal generates ₃ ^-Or VO ₄ ^3-The vanadic acid radical ion) not through redox reaction direct generation precipitation threshold salt just, 3 valency vanadium ions and material metal ion that redox reaction by 5 valency vanadium ions and material metal generates, owing to generate precipitable salt or compound effectively with silicate ion, covering material exposes face effectively, in addition, phosphate anion by the while stripping, the position is carried out in corrosion and periphery is adjusted to suitable pH scope, is particularly suitable for carrying out the redox reaction of 5 valency vanadium ions and material metal.In addition, with the component (1), (2) and (3) that constitute rust-stabilising pigment mixture (C-1), acid resistance or alkali resistance and water-proof weakness that component (1), (2) and (3) have respectively can have been eliminated by also effectively.In addition, therefore calcium ion can realize excellent chemical-resistant and water tolerance simultaneously owing to have the dissolving that suppresses to surpass the material metal under the easy dissolved highly basic of the material metal atmosphere of pH10.This thinks to play a role greatly based on the synergy of the effect of these rust-stabilising pigment mixtures (C-1), thereby reaches excellent erosion resistance.

Coating composition of the present invention is covered with paint, lacquer, colour wash, etc. on metal sheet, what form films when using rust-stabilising pigment mixture (C-2) as rust-stabilising pigment mixture (C), shown excellent erosion resistance, the inventor etc. think that its reason is: because corrosive environment chloride ion down etc., and the metal ion that the dissolving by material metal generates or pass through the rust-preventive agent mixture and dissolved zine ion or aluminum ion and 5 valency vanadium ion (VO ₃ ^-Or VO ₄ ^3-The vanadic acid radical ion) not through redox reaction direct generation precipitation threshold salt just, in addition, the effect that has the anode dissolution reaction that suppresses material metal by rust-preventive agent mixture dissolved calcium ion or other metal ions, 3 valency vanadium ion and the calcium ions that redox reaction by 5 valency vanadium ions and material metal generates, generate throw out with phosphate anion, covering material exposes face effectively, in addition especially on galvanized steel plate, calcium ion not only, zine ion or vanadic acid radical ion are also transferred to the iron extending part owing to forming the dissimilar metal battery as the charged object of corrosion current, because reaction generates salt, and suppressed the cathodic polarization of iron part, has the effect that reduces the potential difference between dissimilar metal, in addition, think that it does not suppress in calcium ion and the corrosion of other metal ions under filming, near the zinc hydroxide that generates the negative electrode position forms the effect of the reaction of zinc oxide owing to dewater.In addition, by and with the aforementioned component (1), (4) and (5) that constitute rust-stabilising pigment mixture (C-2), can eliminate acid resistance or alkali resistance and water-proof weakness that aforementioned component (1), (4) and (5) have respectively effectively.In addition, therefore calcium ion can realize excellent chemical-resistant and water tolerance simultaneously owing to have the dissolving that suppresses to surpass the material metal under the easy dissolved highly basic of the material metal atmosphere of pH10.This thinks to play a role greatly based on the synergy of the effect of these rust-stabilising pigment mixtures (C-2), thereby reaches excellent erosion resistance.

The lacquer metal sheet

Solidify on metal sheet by coating composition of the present invention is covered with paint, lacquer, colour wash, etc., can obtain coating with lacquer metal sheet.As the metal sheet of being covered with paint, lacquer, colour wash, etc., can enumerate metal sheets such as cold-rolled steel sheet, hot-dip galvanized steel sheet, electrogalvanizing steel plate, iron-zinc alloy steel plating plate (steel plate galvanized), aluminum-zinc alloy steel plating plate (contain in the alloy in " galvalume steel plate ", the alloy of 55% aluminium of having an appointment and contain 5% aluminium of having an appointment " galfan " etc.), nickel-zinc alloy steel plating plate, stainless-steel sheet, aluminium sheet, copper coin, Copper Plated Steel, tin plate, these metal sheet surfaces also can form processing.Handle as being shaped, for example, can enumerate phosphatizing, complex oxide film processing, Plessy's green processing, chromate treating etc. such as zinc phosphate processing or tertiary iron phosphate processing.

The present composition can pass through known method such as rolling method, curtain film stream decorations method, spray method, spread coating, pickling process and cover with paint, lacquer, colour wash, etc. on above-mentioned metal sheet.The curing thickness of filming by present composition gained is not particularly limited, and uses in the scope of 2～10 μ m, preferred 3～6 μ m usually.The curing of filming is suitably set according to the kind of using resin etc., and is common when baking is by the filming of covering with paint such as spiral coating process continuously, and reaching top temperature at material is to toast 15～60 seconds under 160～250 ℃, preferred 180～230 ℃ condition.During the formula of criticizing baking, can be by toasting 10～30 minutes down at 80～200 ℃.In addition, use when not have the polyisocyanates that seals as linking agent (B), or use bisphenol-type epoxy resin as resin (A), use amine compound when not needing the combination of special heating in this crosslinking reaction in the forming process of filming of linking agent (B), can under Air drying, make its curing according to well-established law.

Lacquer metal sheet of the present invention can chosen wantonly on the metal sheet that carries out the chemical transformation processing, setting is by filming that the invention described above coating composition forms, the coating composition according to the present invention can be provided and form the lacquer metal sheet of filming and itself use, in addition, can on this is filmed finish paint be set films.The thickness that finish paint is filmed is generally 8～30 μ m, preferred 10～25 μ m.

As the finish paint coating that forms the finish paint coating that above-mentioned finish paint is filmed, for example can enumerate the known polyester resin used as pre-coated steel plate, Synolac class, silicon modified polyesters resene, fluorine-silicon modified acrylic resene, fluorine type resin etc.When paying attention to processibility especially, highly process the polyester finish paint coating of usefulness, can obtain the excellent especially lacquer steel plate of processibility by using.Lacquer metal sheet of the present invention can show the film performance of excellent corrosion resistance.

When using steel plate galvanized, aluminum-zinc alloy steel plating plate when forming the metal sheet of coated thing, can improve the erosion resistance at position, plane by certain degree, on the other hand, so far in the working position of the end face area of cutting off, forming process, erosion resistance is not enough, but,, can obtain excellent erosion resistance at end face area, working position by covering with paint, lacquer, colour wash, etc. coating composition of the present invention.

In addition, on the two sides of coated thing, the coating composition according to the present invention also can be set and filming of forming, and as required, can coating composition of the present invention is formed film on, form above-mentioned finish paint and film.By on the two sides, forming coating composition of the present invention, promptly also form overleaf, can obtain the lacquer metal sheet of containing chronium rust-stabilising pigment not, and excellent corrosion resistance favourable to environmental health.

Lacquer metal sheet of the present invention is on the two sides at the surface of choosing the metal sheet that carries out the chemical transformation processing wantonly, the back side, can be provided with by filming that aforementioned anticorrosive coating composition forms, can directly be used, in order to improve aesthetic property, weather resistance etc., can also on the one or both sides of this anti-rust coating, finish paint be set and film.

When one side is provided with finish paint and films, can on the solidified anti-rust coating face of one side, be coated with finishing paint coating, the anti-rust coating of another side can not be cured carrying out this finish paint when covering with paint, lacquer, colour wash, etc., and after finish paint was covered with paint, lacquer, colour wash, etc., the base material heating to covering with paint, lacquer, colour wash, etc. made curing of coating.When on the two sides finish paint being set and filming, usually, the metallic substance that has the anti-rust coating that has solidified by the two sides of using surface, the back side, on the anti-rust coating face of this single face, after being coated with finishing paint coating it being solidified, on another anti-rust coating face, be coated with finishing paint coating again, make its solidified method, with on the two sides at the surface of the anti-rust coating face of metal base, the back side, be coated with finishing paint coating, then, make arbitrary method of the two sides while solidified method at surface, the back side simultaneously, make the finish paint curing of coating.The thickness that finish paint is filmed is generally 8～30 μ m, preferred 10～25 μ m.

Embodiment

Below, set forth the present invention in further detail by preparation example, embodiment.The present invention is not defined as following embodiment.In addition, below, " part " and " % " all is based on quality standard.

The preparation of preparation example 1 first rank phenolic varnish type phenolic resin crosslinking agent solvent

In reaction vessel, mix 100 parts of dihydroxyphenyl propanes, 178 part of 37% formalin and 1 part of sodium hydroxide, reacted 3 hours down at 60 ℃, then, under reduced pressure, dewatered 1 hour at 50 ℃.Then, add 100 parts of propyl carbinols and 3 parts of phosphoric acid, reacted 2 hours at 110～120 ℃.After reaction finishes, filter the solution of gained, the sodium phosphate elimination with generating obtains solids component and is about 50% first rank bisphenol type phenolic resin crosslinking agent solution B 1.The number-average molecular weight of the resin of gained is 880, and having average methylol number to be 0.4 in each benzene nucleus is 1.0 with average alkoxy methyl number.

The preparation of coating of preparation example 2 back sides

In 200 parts of epoxy resin solutions, mix 40 parts of titanium whites, 40 parts of barium oxide and mixed solvent 2[Solvesso 150 (Esso oil company preparation, the high boiling point aromatic hydrocarbon solvent)/pimelinketone=1/1 (mass ratio) appropriate amount], wherein this Resins, epoxy is in 120 parts of mixed solvent 1[pimelinketone/ethylene glycol monobutyl ether/Solvesso 150 (Esso oil company preparation, the high boiling point aromatic hydrocarbon solvent)=3/1/1 (mass ratio)] 80 parts of Epikote#1009 of middle dissolving (japan epoxy resin company preparation, bisphenol A type epoxy resin, hydroxy-containing resin), up to particle diameter (particle diameter of pigment coarse particle) is below 20 microns, carries out colo(u)rant dispersion.Then, in this dispersion thing, add 26.7 parts of (the solid state component amount is 20 parts) Desmodur BL-3175 (firmly changing the preparation of Bayel Urethane company, HDI isocyanuric acid ester type polyisocyanic acid esterification compound solution, solid state component about 75% by the methyl ethyl ketone oxime sealing), 2 parts of Takenate TK-1 (preparation of military field drug company, organic tin encapsulant dissociation catalyst, solid state component about 10%), uniform mixing, and add above-mentioned mixed solvent 2, adjust about 80 seconds of viscosity (Ford Cup#4/25 ℃), obtain back side coating.

The preparation of anticorrosive coating composition

Embodiment 1

In 220 parts of epoxy resin solutions, mix 5 parts of vanadium pentoxides, 3 parts of calcium metasilicates, 3 parts of calcium phosphate, 20 parts of titanium whites, 20 parts of barium oxide and an amount of mixed solvent 2[Solvesso 150 (Esso oil company preparation, the high boiling point aromatic hydrocarbon solvent)/pimelinketone=1/1 (mass ratio)], wherein this Resins, epoxy is in 135 parts of mixed solvent 1[pimelinketone/ethylene glycol monobutyl ether/Solvesso 150 (Esso oil company preparation, the high boiling point aromatic hydrocarbon solvent)=3/1/1 (mass ratio)] 85 parts of Epikote#1009 of middle dissolving (japan epoxy resin company preparation, bisphenol A type epoxy resin, hydroxy-containing resin), up to particle diameter (particle diameter of pigment coarse particle) is below 20 microns, carries out colo(u)rant dispersion.Then, in this dispersion thing, add 20 parts of (the solid state component amount is 15 parts) Desmodur BL-3175 (firmly changing the preparation of Bayel Urethane company, HDI isocyanuric acid ester type polyisocyanate compound solution, solid state component about 75% by the methyl ethyl ketone oxime sealing), 2 parts of Takenate TK-1 (preparation of military field drug company, organic tin encapsulant dissociation catalyst, solid state component about 10%), uniform mixing, and add above-mentioned mixed solvent 2, adjust about 80 seconds of viscosity (FordCup#4/25 ℃), obtain anticorrosive coating composition.

Embodiment 2～21, comparative example 1～8

In embodiment 1, except the hydroxy-containing resin that uses, linking agent, rust-stabilising pigment, other pigment are shown in following table 1, react in the same manner with embodiment 1, obtain each rust-stabilising pigment mixture.The amount of the hydroxy-containing resin in the table 1, linking agent and pigment composition is represented according to the solids component quality respectively.Wherein, in embodiment 14, do not mix Takenate TK-1, in addition, in embodiment 17 and 18, mix 1 part of Nacure 5225 (the amine neutralization solution of the preparation of U.S. King Industries company, Witco 1298 Soft Acid) respectively and replace 2 parts Takenate TK-1.

Table 1 has also been put down in writing: in sodium chloride aqueous solution 10000 mass parts of 25 ℃ 5 quality % concentration, add the summation of each rust-stabilising pigment of relative resinous principle (total solids constituent mass 100 mass parts of hydroxy-containing resin and linking agent), stirred 6 hours, under 25 ℃, put only 48 hours, and filtered the pH (pH of rust-stabilising pigment lysate) of the filtrate of supernatant liquor.For example, the pH of the rust-stabilising pigment lysate of embodiment 1 is meant in sodium chloride aqueous solution 10000 mass parts of 25 ℃ 5 quality % concentration, add 5 mass parts vanadium pentoxides, 3 mass parts calcium metasilicates and 3 mass parts calcium phosphate, make its dissolving under these conditions, filtered the pH of the supernatant liquor of gained.

Embodiment 22

In 225 parts of epoxy resin solutions, mix 5 parts of vanadium pentoxides, 3 parts of calcium metasilicates, 3 parts of aluminum phosphates, 20 parts of titanium whites, 20 parts of barium oxide and an amount of mixed solvent 2[Solvesso 150 (Esso oil company preparation, the high boiling point aromatic hydrocarbon solvent)/pimelinketone=1/1 (mass ratio)], wherein this Resins, epoxy is in 135 parts of mixed solvent 1[pimelinketone/ethylene glycol monobutyl ether/Solvesso 150 (Esso oil company preparation, the high boiling point aromatic hydrocarbon solvent)=3/1/1 (mass ratio)] 85 parts of Epikote#1009 of middle dissolving (japan epoxy resin company preparation, bisphenol A type epoxy resin, hydroxy-containing resin), up to particle diameter (particle diameter of pigment coarse particle) is below 20 microns, carries out colo(u)rant dispersion.Then, in this dispersion thing, add 20 parts of (the solid state component amount is 15 parts) Desmodur BL-3175 (firmly changing the preparation of Bayel Urethane company, HDI isocyanuric acid ester type polyisocyanate compound solution, solid state component about 75% by the methyl ethyl ketone oxime sealing), 2 parts of Takenate TK-1 (preparation of military field drug company, organic tin encapsulant dissociation catalyst, solid state component about 10%), uniform mixing, and add above-mentioned mixed solvent 2, adjust about 80 seconds of viscosity (FordCup#4/25 ℃), obtain anticorrosive coating composition.

Embodiment 23～44, comparative example 9～16 and reference example 1 and 2

In embodiment 22, except the hydroxy-containing resin that uses, linking agent, rust-stabilising pigment, other pigment are shown in following table 1, react in the same manner with embodiment 22, obtain each rust-stabilising pigment mixture.Reference example 1 and 2 is anticorrosive coating compositions that contain the chromate rust-stabilising pigment in the past.The amount of the hydroxy-containing resin in the table 1, linking agent and pigment composition is represented according to the solids component quality respectively.Wherein, in embodiment 33,34 and 39, do not mix Takenate TK-1, in addition, in embodiment 42 and 43, mix 1 part of Nacure5225 (the amine neutralization solution of the preparation of U.S. King Industries company, Witco 1298 Soft Acid) respectively and replace 2 parts Takenate TK-1.

Table 1 (1)

Table 2

Table 1 (2)

Table 3

Table 1 (3)

Table 4

Table 1 (4)

In above-mentioned table 1, (notes) in the table have following implication respectively.

(annotate 1) Epokey 837: the preparation of Mitsui Chemicals (strain) company, trade(brand)name, urethane modified epoxy, hydroxy-containing resin, monovalence hydroxyl value are about 35, acid number is about 0,

(annotate 2) Vylon 296: the preparation of Japan weaving (strain) company, trade(brand)name, epoxy modified polyester resin, hydroxy-containing resin, hydroxyl value are 7, acid number is 6.

(annotate 3) Arakyd 7018: the preparation of waste river chemistry (strain) company, trade(brand)name, vibrin, hydroxy-containing resin, hydroxyl value are about 10, acid number is below 3.

(annotating 4) Sumidur N3300: firmly change the preparation of Bayel Urethane (strain) company, isocyanuric acid ester type polyisocyanate compound, solid state component 100%.

(annotating 5) Cymel 303: the preparation of Japanese Cytec Industries (strain) company, trade(brand)name, methyl-etherified melamine resin.

(annotating 6) Sandvor3058:Clariant company preparation, trade(brand)name, hindered amines ultra-violet stabilizer.

The test making that is coated with plaque

Use each anticorrosive coating composition and the finish paint coating of the foregoing description 1～21, comparative example 1～8 gained,, cover with paint, lacquer, colour wash, etc. on each material, toast, obtain each test with being coated with plaque according to following covering with paint explanation.

Cover with paint, lacquer, colour wash, etc. explanation 1:

(containing have an appointment 55% aluminium, alloy plating weight per unit area in thickness of slab 0.35mm, aluminum-zinc alloy steel plating plate, the alloy is 150g/m carrying out the galvalume steel plate that chemical transformation handled ², in the table 2 with " GL steel plate " expression) on, by rod be coated with the back side that method covers with paint, lacquer, colour wash, etc. aforementioned preparation example 2 gained with coating so that dry film thickness 8 μ m, arriving top temperature with material is 180 ℃ of bakings 30 seconds, forms the back side and films.With form the back side that is coated with plaque of filming at this back side and film on the steel plate face of reverse side, be coated with method by rod and cover with paint, lacquer, colour wash, etc. each anticorrosive coating composition of above-mentioned each routine gained so that dry film thickness is 5 μ m, arriving top temperature with material is 220 ℃ of bakings 40 seconds, forms each primer coating film.After the cooling, on these primer coating films, be coated with method by rod and cover with paint, lacquer, colour wash, etc. KP Color1580B40 (second-order transition temperature of Northwest paint company preparation, trade(brand)name, polyester finish paint coating, blueness, cured coating film is about 70 ℃), so that dry film thickness is about 15 μ m, arriving top temperature with material is 220 ℃ of bakings 40 seconds, obtains each test with being coated with plaque.

Cover with paint, lacquer, colour wash, etc. explanation 2:

(thickness of slab 0.35mm, zinc-plated weight per unit area are 250g/m to hot-dip galvanized steel sheet after carrying out the chemical transformation processing ², in the table 2 with " GI steel plate " expression) on, by rod be coated with the back side that method covers with paint, lacquer, colour wash, etc. aforementioned preparation example 2 gained with coating so that dry film thickness 8 μ m, arriving top temperature with material is 180 ℃ of bakings 30 seconds, forms the back side and films.With form the back side that is coated with plaque of filming at this back side and film on the steel plate face of reverse side, be coated with method by rod and cover with paint, lacquer, colour wash, etc. each anticorrosive coating composition of above-mentioned each routine gained so that dry film thickness is 5 μ m, arriving top temperature with material is 220 ℃ of bakings 40 seconds, forms each priming paint and is coated with plaque.After the cooling, be coated with on the plaque at these priming paint, be coated with method by rod and cover with paint, lacquer, colour wash, etc. KP Color 1580B40 (second-order transition temperature of Northwest paint company preparation, trade(brand)name, polyester finish paint coating, blueness, cured coating film is about 70 ℃), so that dry film thickness is about 15 μ m, arriving top temperature with material is 220 ℃ of bakings 40 seconds, obtains each test with being coated with plaque.

Cover with paint, lacquer, colour wash, etc. explanation 3:

On the cold-rolled steel sheet (representing with " SPC steel plate " in thickness of slab 0.8mm, the table 2) that carries out after the zinc phosphate chemical transformation is handled, be coated with method by rod and cover with paint, lacquer, colour wash, etc. the back side usefulness coating of aforementioned preparation example 2 gained so that dry film thickness 8 μ m, arriving top temperature with material is 180 ℃ of bakings 30 seconds, forms the back side and films.With form the back side that is coated with plaque of filming at this back side and film on the steel plate face of reverse side, be coated with method by rod and cover with paint, lacquer, colour wash, etc. each anticorrosive coating composition of above-mentioned each routine gained so that dry film thickness is 20 μ m, arriving top temperature with material is 180 ℃ of bakings 30 seconds, forms each test with being coated with plaque.

Use each anticorrosive coating composition and the finish paint coating of the foregoing description 22～44, comparative example 9～16 and reference example 1 and 2 gained, cover with paint, lacquer, colour wash, etc. on each material, toast, obtain each test with being coated with plaque by aforementioned covering with paint explanation 1～3 and following covering with paint explanation 4.

Cover with paint, lacquer, colour wash, etc. explanation 4:

(containing have an appointment 55% aluminium, alloy plating weight per unit area in thickness of slab 0.35mm, aluminum-zinc alloy steel plating plate, the alloy is 150g/m carrying out the galvalume steel plate that chemical transformation handled ², in the table 2 with " GL steel plate " expression) on, be coated with that method is covered with paint, lacquer, colour wash, etc. embodiment 3 gained anticorrosive coating compositions so that dry film thickness 8 μ m by rod, arriving top temperature with material is 180 ℃ of bakings 30 seconds, forms the back side and films.With form the back side that is coated with plaque of filming at this back side and film on the steel plate face of reverse side, be coated with method by rod and cover with paint, lacquer, colour wash, etc. each anticorrosive coating composition of above-mentioned each routine gained so that dry film thickness is 5 μ m, arriving top temperature with material is 220 ℃ of bakings 40 seconds, forms each primer coating film.After the cooling, on these primer coating films, be coated with method by rod and cover with paint, lacquer, colour wash, etc. KP Color 1580B40 (second-order transition temperature of Northwest paint company preparation, trade(brand)name, polyester finish paint coating, blueness, cured coating film is about 70 ℃), so that dry film thickness is about 15 μ m, arriving top temperature with material is 220 ℃ of bakings 40 seconds, obtains each test with being coated with plaque.

Embodiment 45

Cover with paint, lacquer, colour wash, etc. on each material by following covering with paint explanation 5, toast, obtain test with being coated with plaque.

Cover with paint, lacquer, colour wash, etc. explanation 5

(containing have an appointment 55% aluminium, alloy plating weight per unit area in thickness of slab 0.35mm, aluminum-zinc alloy steel plating plate, the alloy is 150g/m carrying out the galvalume steel plate that chemical transformation handled ², in the table 2 with " GL steel plate " expression) on, be coated with anticorrosive coating composition that method covers with paint, lacquer, colour wash, etc. previous embodiment 1 gained so that dry film thickness 8 μ m by rod, arriving top temperature with material is 180 ℃ of bakings 30 seconds, forms the back side and films.With form the back side that is coated with plaque of filming at this back side and film on the surface steel sheet face of reverse side, be coated with method by rod and cover with paint, lacquer, colour wash, etc. the anticorrosive coating composition of embodiment 1 gained so that dry film thickness is 5 μ m, arriving top temperature with material is 220 ℃ of bakings 40 seconds, forms primer coating film.After the cooling, on these primer coating films, be coated with method by rod and cover with paint, lacquer, colour wash, etc. KPColor 1580B40 (second-order transition temperature of Northwest paint company preparation, trade(brand)name, polyester finish paint coating, blueness, cured coating film is about 70 ℃), so that dry film thickness is about 15 μ m, arriving top temperature with material is 220 ℃ of bakings 40 seconds, obtains test with being coated with plaque.

Embodiment 46～69, comparative example 17～33 and reference example 3～6

In the foregoing description 45, the anticorrosive coating composition that uses except surface and the back side as described later shown in the table 3, carry out 45 identical operations with embodiment, obtain each and test with being coated with plaque.

Embodiment 70

Make test with being coated with plaque by following covering with paint explanation 6.

Cover with paint, lacquer, colour wash, etc. explanation 6

(thickness of slab 0.35mm, zinc plating weight per unit area are 250g/m carrying out fused zinc steel plating plate that the zinc phosphate chemical transformation handled ², in the table 3 with " GI steel plate " expression) on, be coated with anticorrosive coating composition that method covers with paint, lacquer, colour wash, etc. previous embodiment 1 gained so that dry film thickness 8 μ m by rod, arriving top temperature with material is 180 ℃ of bakings 30 seconds, forms the back side and films.With form the back side that is coated with plaque of filming at this back side and film on the surface steel sheet face of reverse side, anticorrosive coating composition to the dry film thickness that is coated with method covering with paint the foregoing description 1 gained by rod is 5 μ m, arriving top temperature with material is 220 ℃ of bakings 40 seconds, forms each priming paint and is coated with plaque.After the cooling, be coated with on the plaque at these priming paint, be coated with method by rod and cover with paint, lacquer, colour wash, etc. KP Color 1580B40 (second-order transition temperature of Northwest paint company preparation, trade(brand)name, polyester finish paint coating, blueness, cured coating film is about 70 ℃), so that dry film thickness is about 15 μ m, arriving top temperature with material is 220 ℃ of bakings 40 seconds, obtains test with being coated with plaque.

Embodiment 71～94, comparative example 34～50 and reference example 7～10

In the foregoing description 70, the anticorrosive coating composition that uses except surface and the back side as described later shown in the table 4, carry out 70 identical operations with embodiment, obtain each and test with being coated with plaque.

The film performance test

To respectively testing of the foregoing description 1～94 and comparative example 1～50 and reference example 1～10 gained, carry out the film performance test according to following test method with being coated with plaque.Test-results is as described later shown in table 2～4.

Test method

Resistance to boiling water: each test that will cut into 5cm * 10cm size is placed in about 100 ℃ boiling water dipping 2 hours with being coated with plaque, then, mentions, and to estimate the appearance of film of face side, simultaneously, carries out grid band bond test and estimates.Grid band bond test is according to JIS K-5400 8.5.2 (1990) grid band method, and the crack interbody spacer of crackle is 1mm, makes 100 grids, and the glassine paper self adhesive tape is adhered in its surface, studies the grid number residual on the face that is coated with after acutely peeling.

◎: do not produce projection on filming, turn white etc. unusually, residual grid number is 100

Zero: do not produce projection on filming, turn white etc. unusually, residual grid number is 91～99

△: find a little to film to go up to produce projection or turn white and wait unusually, residual grid number is 91～99, or does not produce projection on finding to film, turns white etc. unusually, residual grid number be 71～90,

*: obviously finding films goes up the generation projection, or residual grid number is below 70.

Alkali resistance: use rust proof paint that each test that cuts into 5cm * 10cm size is sealed with covering with paint, lacquer, colour wash, etc. backboard face and cross section, extend to the intersection otch of substrate at the face side central part that is coated with plaque.This is coated with plaque is placed in the 5% about 20 ℃ aqueous sodium hydroxide solution dipping 48 hours, then, take out washing, to estimate the appearance of film that exsiccant at room temperature is coated with the face side of plaque, simultaneously, adhere to the glassine paper self adhesive tape on the notch intersecting, the width (side) of peeling off that the notch of filming after acutely peel is peeled off is estimated.

◎: do not have projection to produce, it is below the 1.5mm that the band of peeling off from notch is peeled off width,

Zero: do not have projection to produce, peel off width above 1.5mm, below the 3mm from the band that notch is peeled off,

△: find that a little projection produces, do not have to find that peeling off width from the band that notch is peeled off surpasses below the 3mm, or do not find to produce projection to surpass 3mm but peel off width from the band that notch is peeled off,

*: find that projection produces, and peel off width above 3mm from the band that notch is peeled off.

Acid resistance: use rust proof paint that each test that cuts into 5cm * 10cm size is sealed with covering with paint, lacquer, colour wash, etc. backboard face and cross section, extend to the intersection otch of substrate at the face side central part that is coated with plaque.This is coated with plaque is placed in the 5% about 20 ℃ aqueous sulfuric acid dipping 48 hours, then, take out washing, to estimate the appearance of film that exsiccant at room temperature is coated with the face side of plaque, simultaneously, to adhere to the glassine paper self adhesive tape on the intersection notch, the width (side) of peeling off that the notch of filming after acutely peeling is peeled off is estimated.

◎: do not have projection to produce, it is below the 1.5mm that the band of peeling off from notch is peeled off width,

Zero: do not have projection to produce, peel off width above 1.5mm, below the 3mm from the band that notch is peeled off,

△: find that a little projection produces, do not have to find that peeling off width from the band that notch is peeled off is below the 3mm, or do not find to produce projection to surpass 3mm but peel off width from the band that notch is peeled off,

*: find that projection produces, and peel off width above 3mm from the band that notch is peeled off.

Scratch resistance trace: in 20 ℃ room temperature, use coin scratch test device (the automatization skill is ground industrial and made), each test being coated with on the face with the face side that is coated with plaque, the edge that keeps 10 yen of copper coins with the angle of 45 degree, apply the load extruding of 3kg, simultaneously by with 10mm/ 10 yen of about 30mm of copper coin of speed tractive of second, be coated with scuffing degree when scuffing is arranged on the face according to following benchmark evaluation.

◎: scratching the substrate of partly not seeing metal,

Zero: scratching the substrate of partly seeing metal a little,

△: scratching the substrate of partly seeing the metal of considerable part,

*: almost do not have residual filming in the scuffing part, obviously see the substrate of metal.

As corrosion resistance test, the plaque that is coated with of GL steel plate and GI steel plate is carried out following compound cycle corrosion test (CCT test), the plaque that is coated with to the SPC steel plate carries out following salt spray testing.

Compound cycle corrosion test (1): embodiment 1～44, comparative example 1～16, reference example 1～2 are carried out test as described below.According to JIS K-5621 (1990) standard.Cutting into each test face side central part that is coated with plaque of 6cm * 12cm size, the angle that the center of use cutting blade partly extends to substrate is 30 degree, live width is the intersection otch of 0.5mm, make each test with the burr of the edge part on the long limit that is coated with plaque along the face side coated surface on the right side towards face side, in the left side towards rear side, use rust proof paint to seal to being coated with plaque upper end-face edge position, for being set in the upper end, 4T Bending Processing position (will be coated with the surface lateral outside bending of plaque, in this inboard, narrow go into 4 with the plate that is coated with the plaque same thickness, be coated with the Bending Processing that plaque carries out 180 degree by vice to above-mentioned) be coated with plaque, with (at 30 ℃, with 5% salt solution spraying 0.5 hour)-(at 30 ℃, test is 1.5 hours in the humidity test device more than RH95%)-(at 50 ℃, dry 2 hours)-(at 30 ℃, dry 2 hours) as once circulation, carry out 300 circulations (amounting to 1800 hours) test.State to the edge that is coated with plaque after this test, intersection cutting part, 4T Bending Processing position is estimated.

(4T working position) estimates the total length of the rusty part in the 4T working position.

◎: do not find to get rusty,

Zero: find white rust, but not enough 20mm,

△: white rust more than 20mm and not enough 40mm,

*: find that white rust is more than 40mm or produce red rust.

(edge) obtain be coated with plaque about the edge on long limit spread the mean value of width, estimate according to following benchmark.

◎: not enough 5mm,

Zero: the above and not enough 10mm of 5mm,

Above and the not enough 20mm of △: 10mm,

*: more than the 20mm.

(intersection cutting part) according to expose to the open air in the position at the wide metal of the otch of 0.5mm the length ratio that produces white rust and cutting part about the mean value of projection wide (both sides and), estimate intersecting the etch state of cutting part by following benchmark.

◎: metal exposes length ratio less than 50% and the not enough 3mm of spout width that white rust produces in the position to the open air,

Zero: metal exposes length ratio that white rust in the position produces to the open air 50% or more and the not enough 3mm of spout width, or metal expose to the open air the length ratio less than 50% of white rust generation in the position and spout width more than 3mm, not enough 5mm,

△: metal expose to the open air length ratio that white rust in the position produces more than 50% and spout width be more than the 5mm, not enough 10mm,

*: metal expose to the open air length ratio that white rust in the position produces more than 50% and spout width be more than the 10mm.

Compound cycle corrosion test (2): embodiment 45～94, comparative example 17～50, reference example 3～10 are carried out test as described below.Each test face side central part that is coated with plaque in the cut-out that cuts into 6cm * 12cm size, the angle that the back of use cutting blade extends to substrate is 30 degree, live width is the intersection otch of 0.5mm, make each test with the burr of the edge part on the long limit that is coated with plaque along the face side coated surface on the right side towards face side, in the left side towards rear side, use rust proof paint to seal to being coated with plaque upper end-face edge position, for being set in the upper end, 4T Bending Processing position (will be coated with the surface lateral outside bending of plaque, in this inboard, hold under the arm into 4 with the plate that is coated with the plaque same thickness, be coated with the Bending Processing that plaque carries out 180 degree by vice to above-mentioned) be coated with plaque.

For the test of covering with paint, lacquer, colour wash, etc. explanation 5 with being coated with plaque, according to JIS-H8502.8.1, with (at 35 ℃, with 5% salt solution spraying 2 hours)-(at 60 ℃, dry 4 hours)-(at 50 ℃, carried out humidity test 2 hours in the humidity test device more than RH95%) as once circulation, carry out 150 circulations (amounting to 1200 hours) test.State to the edge that is coated with plaque after this test, intersection cutting part, 4T Bending Processing position is estimated.

, be coated with in the round-robin test of plaque except using in the test of above-mentioned covering with paint explanation 1 with being coated with plaque for the test of covering with paint, lacquer, colour wash, etc. explanation 6, cycle number is transformed into 100 circulations (amounting to 800 hours) by 150 circulations (amounting to 1200 hours) and in addition, carries out same test.State to the edge that is coated with plaque after this test, intersection cutting part, 4T Bending Processing position is estimated.

(4T working position) estimates the total length of the rusty part in the 4T working position.

◎: do not find to get rusty,

Zero: find white rust, but not enough 20mm,

△: white rust more than 20mm and not enough 40mm,

*: white rust is more than 40mm or find to produce red rust.

(edge) calculate be coated with plaque about the edge on long limit spread the mean value of width, estimate according to following benchmark.

◎: not enough 5mm,

Zero: the above and not enough 10mm of 5mm,

Above and the not enough 20mm of △: 10mm,

*: more than the 20mm.

(intersection cutting part) according to expose to the open air in the position at the wide metal of the otch of 0.5mm the length ratio that produces white rust and cutting part about the mean value of projection wide (both sides and), estimate intersecting the etch state of cutting part by following benchmark.

◎: metal exposes length ratio less than 50% and the not enough 3mm of spout width that white rust produces in the position to the open air,

Zero: metal exposes length ratio that white rust in the position produces to the open air 50% or more and the not enough 3mm of spout width, or metal expose to the open air the length ratio less than 50% of white rust generation in the position and spout width more than 3mm, not enough 5mm,

△: metal expose to the open air length ratio that white rust in the position produces more than 50% and spout width be more than the 5mm, not enough 10mm,

*: metal expose to the open air length ratio that white rust in the position produces more than 50% and spout width be more than the 10mm.

Salt spray testing: use rust proof paint that each test that cuts into 5cm * 10cm size is sealed with the back side and the cut surface that are coated with plaque (the SPC steel plate is coated with plaque), be coated with the surface central authorities of plaque, extend to the intersection otch of substrate.Under 35 ℃, with 5% salt solution this is coated with the salt spray testing (JIS Z-2371) that plaque carries out 500 hours, the red rust of the face that is coated with after the evaluation test produces state, simultaneously, the glassine paper self adhesive tape is sticked to intersect on the cutting part, estimate the band of the cutting part in the filming after acutely peeling and peel off wide (side).

◎: do not have red rust generation or a small amount of red rust, peel off the not enough 5mm of width from the band of cutting part,

Zero: find that considerable part produces red rust and peels off the not enough 5mm of width from the band of cutting part, or do not have red rust to produce or a small amount of red rust, peel off from the band of cutting part that width is more than the 5mm, not enough 10mm,

△: whole cutting part all finds the generation of red rust, peel off from the band of cutting part that width is more than the 5mm, not enough 10mm, or be not to find that at whole cutting part red rust produces but the considerable part red rust arranged and peel off width from the band of cutting part is more than the 10mm

*: whole cutting part is all found the generation of red rust and peeled off width from the band of cutting part is more than the 10mm.

Weather-proof salt spray testing: to cutting into test 5cm * 10cm size, covering with paint explanation 1 with being coated with plaque, according to the long durability of filming of regulation among the JIS K 56007.7, the A method of promotion weathering resistance (Xenon Lamp method) test, under the cycling condition repeatedly of (moistening 18 minutes-dry 102 minutes), in xenon network metering device, carry out 500 hours Continuous irradiation.Then, the back side and cross section are sealed, extend to the intersection otch of substrate in the surperficial central authorities that are coated with plaque with rust proof paint.Be coated with plaque for this, the salt spray testing (JIS Z-2371) of carrying out 500 hours is waited, according to the outward appearance at position, following benchmark evaluation plane.

◎: stride across cutting part, below the average out to 3mm, do not find that other are unusual from the projection rust generation width of cutting part,

Zero: generating that width surpasses 3mm and be below the 5mm from the projection of cutting part rust, do not find that at the position, plane other are unusual, produce though perhaps find some projections at the position, plane, is below the 3mm from the projection rust generation width of cutting part.

△: generate that width surpasses 3mm and be below the 5mm from the projection of cutting part rust, find the several projections generation at the position, plane,

*: generate width above 5mm from the projection rust of cutting part, or find that at the position, plane tangible projection produces.

Table 5

Table 2 (1)

Table 6

Table 2 (2)

Table 7

Table 2 (3)

Table 8

Table 2 (4)

Table 9

Table 3 (1)

Table 10

Table 3 (2)

In the table, * 2 expression preparation examples 2.

Table 11

Table 3 (3)

In the table, * 2 expression preparation examples 2.

Table 12

Table 4 (1)

Table 13

Table 4 (2)

The table first, * 2 expression preparation examples 2.

Table 14

Table 4 (3)

In the table, * 2 expression preparation examples 2.

Claims (13)

1. coating composition, this coating composition contains the film-forming resin of hydroxyl, linking agent and rust-stabilising pigment mixture C, it is characterized in that: this rust-stabilising pigment mixture C is a vanadium pentoxide, at least a vanadium compound in vanadic acid calcium and the ammonium meta-vanadate, the rust-stabilising pigment mixture C-1 that metal silicate and phosphoric acid class calcium salt combine, or described vanadium compound, the rust-stabilising pigment mixture C-2 that calcium cpd and phosphoric acid metalloid salt combine, wherein said phosphoric acid metalloid salt is phosphate metal salt, at least a in phosphoric acid hydrogen metal-salt and the tripolyphosphate metal-salt, and the metal of this metal-salt is Zn, Al or Mg, described calcium cpd is the calcium cpd except that vanadic acid calcium or phosphate cpd, total solid state component 100 mass parts with respect to film-forming resin He this linking agent of this hydroxyl, the amount of this rust-stabilising pigment mixture C is respectively 10～150 mass parts, and in this rust-stabilising pigment mixture C-1

The amount of this vanadium compound is 3～50 mass parts,

The amount of metal silicate is 3～50 mass parts, and

The amount of this phosphoric acid class calcium salt is 3～50 mass parts,

In this rust-stabilising pigment mixture C-2,

The amount of this vanadium compound is 3～50 mass parts,

The amount of this calcium cpd is 3～50 mass parts, and

The amount of this phosphoric acid metalloid salt is 3～50 mass parts.

2. the described coating composition of claim 1, wherein the film-forming resin of hydroxyl is at least a in hydroxyl-containing epoxy resin and the hydroxyl group containing polyester resin.

3. claim 1 or 2 described coating compositions, wherein, linking agent is at least a linking agent that is selected from the polyisocyanate compound of aminoresin, resol and optional sealing.

4. the described coating composition of claim 1, wherein, the phosphoric acid class calcium salt that constitutes this rust-stabilising pigment mixture C-1 is at least a in calcium phosphate, calcium monohydrogenphosphate, monocalcium phosphate and the tripolyphosphate calcium.

5. the described coating composition of claim 1, wherein, the calcium cpd that constitutes this rust-stabilising pigment mixture C-2 is at least a in calcium metasilicate, calcium oxide and the lime carbonate.

6. the described coating composition of claim 1 wherein also contains at least a pigment component in TiO 2 pigment and the filler pigment.

7. the described coating composition of claim 1 wherein also contains at least a in UV light absorber and the ultra-violet stabilizer.

8. the described coating composition of claim 1, wherein, the mixture that constitutes mass parts in vanadium compound, metal silicate and each weight range of phosphoric acid class calcium salt of rust-stabilising pigment mixture C-1 added in 25 ℃ sodium chloride aqueous solution 10000 mass parts of 5 quality % concentration, stirred 6 hours, under 25 ℃, left standstill 48 hours, filtering supernatant, the pH of filtrate is 3～10, wherein rust-stabilising pigment mixture C-the 1st, the film-forming resin of this hydroxyl and the total solids component 100 mass parts blended of linking agent relatively.

9. the described coating composition of claim 1, wherein, the mixture that constitutes mass parts in vanadium compound, calcium cpd and this each weight range of phosphoric acid metalloid salt of rust-stabilising pigment mixture C-2 added in 25 ℃ sodium chloride aqueous solution 10000 mass parts of 5 quality % concentration, stirred 6 hours, under 25 ℃, left standstill 48 hours, filtering supernatant, the pH of filtrate is 3～10, wherein rust-stabilising pigment mixture C-the 2nd, the film-forming resin of this hydroxyl and the total solids component 100 mass parts blended of linking agent relatively.

10. lacquer metal sheet, this lacquer metal sheet are optional carrying out from the teeth outwards on the metal sheet that chemical transformation handles, and the cured coating film that forms coating composition according to claim 1 forms.

11. lacquer metal sheet, this lacquer metal sheet are to choose wantonly on the metal sheet that carries out the chemical transformation processing from the teeth outwards, have the cured coating film that forms coating composition according to claim 1, form the multilayer film that finish paint is filmed and formed on this cured coating film.

12. lacquer metal sheet, this lacquer metal sheet are to choose wantonly on the two sides of the metal sheet that carries out the chemical transformation processing from the teeth outwards, the cured coating film that forms coating composition according to claim 1 forms.

13. lacquer metal sheet, this lacquer metal sheet is to choose wantonly from the teeth outwards on the two sides of the metal sheet that carries out the chemical transformation processing, have the cured coating film that forms coating composition according to claim 1, on cured coating film at least simultaneously, form the multilayer film that finish paint is filmed and formed.