CN101993644A - Anticorrosive paint composition - Google Patents

Abstract

A paint composition contains (A) hydroxyl-containing paint film forming resin, (B) cross linker, (C) anticorrosive pigment mixture, and (D) organic phosphate group- or phosphate group containing resin, the anticorrosive pigment mixture (C) is composed of a (1) vanadium compound and (2) ion exchange silicon oxide, per 100 parts by weight of a total solid content of the resin (A) and cross linker (B), respectively, the vanadium compound (1) is 3-50 parts by weight, ion exchange silicon oxide (2) is 3-50 parts by weight, and the organic phosphate group- or phosphate group containing resin (D) is 1-30 parts by weight.

Description

Anticorrosion coating composition

Technical field

The present invention relates to a kind of metallic sheet that does not contain chromium coating composition and this coating composition of use that demonstrates excellent erosion resistance, particularly, relate to a kind of following coating composition and the metallic sheet of this coating composition of use, described coating composition, even owing to the photodegradation in the outdoor environment and hydrolysis make film carry out deterioration after, also effectively improve the not only unprocessed planar section in the metallic sheet but also the erosion resistance of part of having processed and edge surface.

Background technology

The pre-coated steel plate that precoat metal plate for example applies by coiled material, be widely used in the prior art as the article relevant with dwelling house, described article for example, the material of construction that is used for building structure as roof, wall, window shutter, garage etc., various household electrical appliance, dashboard, refrigeration showcase, steel furniture, galley equipment etc.

The described article relevant with dwelling house are usually by precoat metal plate preparation, for example by comprising that cutting pre-coated steel plate, the technology that then stands to process as pressing mold and joint prepare.Therefore, the described article relevant with dwelling house often have metal exposed part and because the crackle generation part that pressing mold causes as the cutting surface.Described metal exposed part is compared with other parts and may be reduced with the erosion resistance that part takes place crackle.In order to improve erosion resistance, the bottom coating on pre-coated steel plate contains chromium class corrosion-inhibiting pigment usually.

Yet chromium class corrosion-inhibiting pigment may contain or produce the sexavalent chrome that demonstrates excellent erosion resistance, and from the viewpoint of HUMAN HEALTH and environment protection, the result causes problem.

Various chromium corrosion-inhibiting pigment such as zinc phosphate, aluminium triphosphate, zinc molybdates etc. of not containing, commercially available, and the various priming paint that contain the combination that does not contain chrome pigment have been proposed.For example, patent documentation 1 discloses by will perhaps being added into the carrier component that is made of Resins, epoxy and resol and the coating composition for preparing by the corrosion-inhibiting pigment mixture that constitutes of lime carbonate, Calucium Silicate powder, aluminum phosphate and vanadic acid phosphorus by the corrosion-inhibiting pigment mixture that constitutes of Calucium Silicate powder and vanadic acid phosphorus.And, patent documentation 2 disclose by will by the calcinate of secondary magnesium phosphate and manganese oxide vanadium oxide constitute or be added into the coating composition that vibrin prepares by the corrosion-inhibiting pigment mixture that the calcinate of calcium phosphate and vanadium oxide constitutes.Yet, the coating composition for preparing with using chromium class pigment of filming that disclosed coating composition forms in patent documentation 1 and 2 is compared, show the erosion resistance of going on business, particularly, especially not satisfied erosion resistance in the part of having processed and edge surface part, and further often demonstrate for example water tolerance of alkali resistance and acid resistance and the difference when a large amount of corrosion-inhibiting pigment mixture of use of poor chemical resistant properties.Therefore, disclosed corrosion-inhibiting pigment mixture can not replace chromium class corrosion-inhibiting pigment satisfactorily in the preparation of precoat metal plate in patent documentation 1 and 2.

Patent documentation 3 discloses the fine particles of silica by the void content that will have 30 to 200ml/100g oil number and 0.05 to 1.2ml/g, add in the carrier component that contains organic resin with hydroxyl or epoxy group(ing) and solidifying agent and the coating composition of preparation, and form cured coating film in 40-125 ℃ of scope of second-order transition temperature.Yet, though formed the filming of disclosed coating composition demonstrates some erosion resistances in patent documentation 3, but the coating composition for preparing with using chromium class pigment is compared, show the erosion resistance and the poor chemical resistant properties of going on business, in the gratifying especially inadequately erosion resistance of edge surface part.

And, patent documentation 4 discloses a kind of anticorrosion coating composition, said composition contains the formation resin of filming of (A) hydroxyl, (B) linking agent, (C) the corrosion-inhibiting pigment mixture that constitutes by specific vanadium compound, silica dioxide granule and phosphoric acid salt metal-salt, and demonstrate good anti-corrosion, described phosphoric acid salt metal-salt is selected from phosphoric acid salt calcium salt, phosphoric acid salt zinc salt, phosphoric acid salt eka-aluminum salt, phosphoric acid salt magnesium salts etc.

Yet, aforementioned coating composition face film since outdoor exposure and after the deterioration to the patience of corrosion reaction, be unsatisfactory aspect the corrosion resistant weather resistance, require further to improve erosion resistance.

Patent documentation 1: Japanese Patent Application Publication No.61001/99.

Patent documentation 2: Japanese Patent Application Publication No.199078/00.

Patent documentation 3: Japanese Patent Application Publication No.129163/00.

Patent documentation 4: Japanese Patent Application Publication No.222833/08.

Summary of the invention

The purpose of this invention is to provide a kind of metallic sheet that does not contain the chromium coating composition and use this coating composition, the described chromium coating composition that do not contain is when being used for metallic sheet, even owing to the photodegradation in the outdoor environment and hydrolysis make film carry out deterioration after, also can form except other unprocessed part, also partly demonstrating filming of excellent erosion resistance in part of having processed and edge surface.

In order to solve the aforementioned problems in the prior, the inventor in depth studies, found a kind of corrosion-inhibiting pigment mixture by constituting by specific vanadium compound and ion-exchange silicon-dioxide, and at least a resin in the resin of the resin of phosphoric acid ester group (phosphate group-containing) and phosphoric acid salt group (phosphate salt group-containing), join respectively that hydroxyl is filmed in the mixture that forms resin and linking agent and the coating composition of preparation with predetermined amount, when in outdoor environment, being used for metallic sheet, can form except also partly demonstrate filming of excellent erosion resistance in part of having processed and edge surface other unprocessed planar section, the result has finished the present invention.

Promptly, the invention provides a kind of coating composition, this coating composition contains (A) not formation resin of filming of phosphoric acid ester group, hydroxyl, (B) linking agent, (C) corrosion-inhibiting pigment mixture and (D) at least a resin [resin (D) that is called phosphoric acid ester group or phosphate group hereinafter] in the resin of the resin of phosphoric acid ester group and phosphoric acid salt group; Corrosion-inhibiting pigment mixture (C) is the corrosion-inhibiting pigment mixture that is constituted by following: (1) is selected from least a vanadium compound and (2) ion-exchange silicon-dioxide of Vanadium Pentoxide in FLAKES, vanadic acid calcium and ammonium meta-vanadate; The total solids level of resin of per 100 weight parts (A) and linking agent (B), respectively, vanadium compound (1) is the 3-50 weight part, ion-exchange silicon-dioxide (2) is the 3-50 weight part, the total amount of the resin of the resin of phosphoric acid ester group and phosphoric acid salt group is the 1-30 weight part in the resin of phosphoric acid ester group or phosphate group (D), and corrosion-inhibiting pigment mixture (C) is the 6-100 weight part.

The invention provides the metallic sheet with cured coating film, described cured coating film is formed on the surface of metal sheet by aforementioned coating composition, the metal surface treatment process that the surface of described metal sheet stands to choose wantonly.

The invention provides and have by the film metallic sheet of the multilayer film that constitutes of cured coating film and the face that on cured coating film, forms, described cured coating film is formed on the surface of metal sheet by aforementioned coating composition, the metal surface treatment process that the surface of described metal sheet stands to choose wantonly.

The invention provides metallic sheet with cured coating film, described cured coating film is gone up at two-sided (double-side) on two surfaces of metal sheet by aforementioned coating composition and is formed, and two surfaces of described metal sheet two-sided stood the metal surface treatment process chosen wantonly respectively.

The invention provides have by cured coating film and on the one side at least of two cured coating films the film metallic sheet of the multilayer film that constitutes of the face that forms, described cured coating film is formed on two surfaces of metal sheet two-sided by aforementioned coating composition, and two surfaces of described metal sheet top stands the metal surface treatment process chosen wantonly respectively.

The effect of invention

Coating composition of the present invention provides this special effect: coating composition of the present invention does not contain chromium class corrosion-inhibiting pigment and sees it is favourable from environment and healthy viewpoint, when coating composition of the present invention is used for metallic sheet, can be formed in except other unprocessed planar section and also partly demonstrate filming of excellent anticorrosive in part of having processed and edge surface, these do not contain the chromium anticorrosive coating composition and are difficult to provide, and the resin (D) of phosphoric acid ester group that is contained in the coating composition of the present invention or phosphate group plays the effect of strong tackify component, and in sour environment, has excellent thickening property, in time the improvement of erosion resistance in generating chamber's external environment with as the specific vanadium compound of corrosion-inhibiting pigment mixture and the combination of ion-exchange silicon-dioxide the time.

Promptly, the invention provides the metallic sheet of a kind of coating composition and this coating composition of use, this coating composition, except by the effect by the exposed surface of the effective coated substrate of corrosion-inhibiting pigment mixture (C) component of vanadium compound (1) and ion-exchange silicon-dioxide (2) formation, also the resin (D) by phosphoric acid ester group or phosphate group suppresses to corrode the effect of carrying out near the anode of part of filming and peeling off, and the conduct effect of tackify component by force in sour environment, even owing to the photodegradation in the outdoor environment and hydrolysis make film carry out deterioration after, also effectively improve the erosion resistance of not only unprocessed planar section in the metallic sheet but also the part of having processed and edge surface part.

Use the coated metallic sheet of the cured coating film that forms by coating composition of the present invention partly to demonstrate excellent erosion resistance at unprocessed planar section, the part of having processed and edge surface, and compare with the metallic sheet that is coated with by the formed cured coating film of coating composition that uses the chromate corrosion-inhibiting pigment, demonstrate identical or improved this erosion resistance.

By use by the formed cured coating film of coating composition of the present invention apply, then filming with the face on the described cured coating film of being formed on applies the metallic sheet for preparing, at unprocessed planar section, processing part and edge surface partly demonstrate excellent erosion resistance.Coating composition of the present invention is coated on the metal sheet such as steel plate galvanized or aluminium-zinc alloy coated steel sheet as coated substrate, make it possible to except unprocessed planar section also the edge surface part and the processing part obtain excellent erosion resistance.

Embodiment

Coating composition of the present invention comprises filming of hydroxyl and forms the resin (D) of resin (A), linking agent (B), corrosion-inhibiting pigment mixture (C) and phosphoric acid ester group or phosphate group.

Filming of hydroxyl forms resin (A)

Not comprised in the coating composition field by specific limited ground normally used and have a resin of any hydroxyl of film forming properties for the film-forming resin of hydroxyl (A) in the coating composition of the present invention, and typically can comprise, for example the resin that is selected from vibrin, Resins, epoxy, acrylic resin, fluorocarbon resin, vinyl chloride resin etc. of at least a hydroxyl.Be preferably selected from least a organic resin in the Resins, epoxy of the vibrin of hydroxyl and hydroxyl.

Vibrin as the hydroxyl of preferred organic resin can comprise oil-free polyester resin, oil-modified alkyd resin, their modified product, for example urethane-modified polyester, urethanated alkyd, epoxy modified polyester resin and acrylic acid modified polyester resin etc.The vibrin of hydroxyl can preferably have 1,500～35,000, preferred 2,000～25, second-order transition temperature (Tg) in the number-average molecular weight in 000 scope, 10～100 ℃, preferred 20 ℃～80 ℃ scopes and 2～100mg KOH/g, the interior hydroxyl value of preferred 5～80mg KOH/g scope.

In this manual, the number-average molecular weight of resin is based on the molecular weight of polystyrene standard, by using the value of calculating in the measured chromatogram of gel permeation chromatograph (HLC8120GPC, trade(brand)name, sold by Tosoh Corporation).Above-mentioned measurement is carried out under the following conditions, i.e. 4 posts: tsk gel G-4000HXL, tsk gel G-3000HXL, tsk gel G-2500HXL and tsk gel G-2000HXL (trade(brand)name, sold by Tosoh Corporation respectively); Moving phase: tetrahydrofuran (THF); Measure temperature: 40 ℃, flow velocity: 1ml/min, detector: RI.In this manual, the second-order transition temperature of resin (Tg) is definite by differential scanning calorimeter (DSC).

Oil-free polyester resin is made of the esterification products between polyprotonic acid component and the polyol component.The polyprotonic acid component can comprise, as main ingredient, for example be selected from least a diprotic acid of Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, succsinic acid, fumaric acid, hexanodioic acid, sebacic acid and maleic anhydride and their low alkyl group esterification product, and except that above-mentioned acid, can choose wantonly and comprise monoprotic acid for example phenylformic acid, Ba Dousuan, p-tert-butyl benzoic acid etc., ternary or higher polyprotonic acid be trimellitic anhydride, tetrahydrotoluene tricarboxylic acid, pyromellitic acid acid anhydride or the like for example.Polyvalent alcohol can comprise, as main ingredient, for example dibasic alcohol such as ethylene glycol, glycol ether, propylene glycol, 1,4-butyleneglycol, neopentyl glycol, 3-methyl pentanediol, 1,4-hexylene glycol, 1,6-hexylene glycols etc., and except that above-mentioned dibasic alcohol can be chosen wantonly and comprise trivalent alcohol or higher polyvalent alcohol for example glycerol, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane etc.These polyvalent alcohols may be used singly or in combin.Esterification between two components or transesterification reaction can be undertaken by known method itself.Acid constituents can preferably include m-phthalic acid, terephthalic acid and their low alkyl group esterification product especially.

Synolac can prepare by reacting with fatty acid oil according to known method itself except that the acid constituents and alkoxide component of above-mentioned oil-free polyester resin.Fatty acid oil can comprise for example coco-nut oil fatty acid, soya fatty acid, linseed oil lipid acid, sunflower oil lipid acid, ready denier oil acid, dehydrogenated castor oil lipid acid, tung oil lipid acid etc.Synolac preferably has below 30%, preferred especially 5～20% oil length.

Urethane-modified polyester can comprise by making polyisocyanate compound and above-mentioned oil-free polyester resin or reacting the lower molecular weight oil-free polyester resin that is obtained with acid constituents that makes use in above-mentioned oil-free polyester resin preparation and alkoxide component and react the resin for preparing by known method own.Urethanated alkyd can comprise by making polyisocyanate compound and above-mentioned Synolac or reacting the resin for preparing with make the low-molecular-weight Synolac that each component reaction obtained that uses in above-mentioned alkyd resin production by known method own.The polyisocyanic acid compound that uses in urethane-modified polyester and urethanated alkyd can comprise hexamethylene diisocyanate, isophorone diisocyanate, xylylene vulcabond, tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 4,4 '-methylene radical two (cyclohexyl isocyanate), 2,4,6-three isocyanide acyl toluene etc.It is the resin of the modification degree of the amount below the 30 weight % based on urethane-modified resin that urethane-modified resin can preferably include the amount with the polyisocyanate compound that forms urethane-modified resin.

Epoxy modified polyester resin can comprise: react the reaction product that generates by the addition between vibrin and Resins, epoxy, condensation, grafting etc., for example, the vibrin of each component preparation of in above-mentioned vibrin preparation, using, the carboxyl of this resin and the reaction product that contains the resin of epoxy group(ing); The reaction product that hydroxyl in the vibrin and the hydroxyl bonding in the Resins, epoxy is obtained by polyisocyanate compound.Modification degree in the described epoxy modified polyester resin, with respect to epoxy modified polyester resin, the amount of preferred epoxy is the amount of 0.1～30 weight %.

Acrylic acid modified polyester resin can comprise: by the vibrin of each the component preparation that is used for above-mentioned vibrin preparation, the carboxyl of this resin or hydroxyl and contain for example reaction product between the acrylic resin of carboxyl, hydroxyl or epoxy group(ing) of reactive group, with use peroxide polymerization starter, to the reaction product of vibrin graft polymerization (methyl) vinylformic acid or (methyl) acrylate etc.Modification degree in the acrylic acid modified polyester resin, with respect to acrylic acid modified polyester resin, the amount of preferred acrylic resins is 0.1～50 weight %.

In above-mentioned vibrin, from the viewpoint of processibility and erosion resistance, preferred oil-free polyester resin, epoxy modified polyester resin.

Form the preferred Resins, epoxy of resin as filming of hydroxyl, can comprise bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin; And modified epoxy by epoxy group(ing) in various properties-correcting agent and the above-mentioned Resins, epoxy or hydroxyl reaction are prepared.In the preparation of modified epoxy, can carry out in any stage of Resins, epoxy preparation with in the terminal stage of Resins, epoxy preparation by the modification of using properties-correcting agent, be not particularly limited.

Bisphenol-type epoxy resin for example can comprise, chooses wantonly in the presence of catalyzer such as alkaline catalysts, makes epoxy chloropropane and bis-phenol stand the resin that condensation reaction prepares to have high molecular; With choose wantonly in the presence of catalyzer such as alkaline catalysts, make epoxy chloropropane and bis-phenol stand condensation reaction to form lower molecular weight, then make this low-molecular-weight epoxy resin and bis-phenol carry out polyaddition reaction and the resin that obtains.

Bis-phenol can preferably include two (4-hydroxy phenyl) methane [Bisphenol F], 1, two (4-hydroxy phenyl) ethane, 2 of 1-, two (4-hydroxy phenyl) propane [dihydroxyphenyl propane], 2 of 2-, two (4-hydroxy phenyl) butane [bisphenol b] of 2-, two (4-hydroxy phenyl)-1,1-Trimethylmethane, two (4-hydroxyl-trimethylphenylmethane base)-2,2-propane, p-(4-hydroxy phenyl) phenol, oxygen two (4-hydroxy phenyl), sulphonyl two (4-hydroxy phenyl), 4,4 '-dihydroxy benaophenonel, two (2 hydroxy naphthalene base) methane etc.Wherein, preferably use dihydroxyphenyl propane and Bisphenol F.Above-mentioned bis-phenol may be used singly or in combin.

The example of commercially available bisphenol-type epoxy resin can comprise jER 828,812,815,820,834,1001,1004,1007,1009,1010 (trade(brand)name, all sold by Japan EpoxyResins Co.Ltd.); Araldite AER 6099 (trade(brand)name, by Asahi-CibaLtd. sell); Epomik R-309 (trade(brand)name, by Mitsui Chemicals sell) etc.

The example that can be used as the phenolic resin varnish type epoxy resin of Resins, epoxy can comprise various phenolic resin varnish type epoxy resins, for example phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, phenol glyoxalic type Resins, epoxy etc.

The example of modified epoxy can comprise: for example by making the epoxy ester resin of drying oil fatty acid reaction acquisition; By the Epocryl that polymerizability unsaturated monomer component reaction is obtained; Make isocyanate compound react the polyurethane modified epoxy resin that obtains with above-mentioned bisphenol-type epoxy resin or phenolic resin varnish type epoxy resin respectively by this; By making the reaction of epoxy group(ing) in above-mentioned bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin or the above-mentioned various modified epoxy and amine compound import the amine-modified epoxy resin that amino or quaternary ammonium salt obtain.

Linking agent (B)

Linking agent (B) forms resin (A) reaction with the formation cured coating film with filming of hydroxyl, and can comprise and can form for example solidified linking agent by heating of resin (A) reaction by filming of hydroxyl, and nothing is restriction especially.Wherein, preferred aminoresin and optional end capped polyisocyanate compound.These linking agents may be used singly or in combin.

Aminoresin can comprise by aldehyde and the amino group methylol aminoresin that obtains of reactions such as trimeric cyanamide, urea, benzoguanamine, acetoguanamine, sterol guanamines, volution guanamines, Dyhard RU 100 for example.Employed aldehyde can comprise formaldehyde, Paraformaldehyde 96, acetaldehyde, phenyl aldehyde etc. in the above-mentioned reaction.Aminoresin also can comprise the product that above-mentioned methylol aminoresin etherificate is obtained by with suitable alcohol.The example of the alcohol that uses in etherificate can comprise methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, 2-ethyl butanol, 2-Ethylhexyl Alcohol etc.

Form resin (A) reaction and crosslinked as the resol of linking agent and filming of hydroxyl, and for example can comprise by in the presence of catalysts to phenol component and aldehydes heating and make its stand condensation reaction with the importing methylol, follow with pure at least a portion of methylol in the resol resin that obtains carried out the resole (resolphenol resin) that the alkyl etherificate prepares.

In resole preparation, be used as the phenol component of parent material, can comprise phenolic compound that two functionality phenolic compound, three-functionality-degree phenolic compound, four functionality are above etc.

Phenolic compound can comprise, for example two functionality phenolic compound such as ortho-cresol, p-cresol, p-tert-butylphenol, p-ethyl phenol, 2,3-xylenol, 2,5-xylenol etc., three-functionality-degree phenolic compound such as phenylic acid, meta-cresol, m-ethylphenol, 3,5-xylenol, meta-methoxy phenol etc., four functionality oxybenzene compound such as dihydroxyphenyl propane, Bisphenol F etc.Wherein, in order to improve the scratch resistance trace, above phenolic compound, particularly phenylic acid and/or the m-cresol of preferred three-functionality-degree.These phenolic compound can be used alone or be used in combination.

The aldehydes that uses in the resol preparation can comprise formaldehyde, Paraformaldehyde 96, trioxane etc., and can be used alone or be used in combination.

Employed alcohol in the methylol groups alkyl etherificate in the methylolation resol, can preferably include have 1～8, the monohydroxy-alcohol of preferred 1～4 carbon atom, special particular methanol, ethanol, n-propyl alcohol, propyl carbinol, isopropylcarbinol etc.

From forming reactive viewpoint of resin (A) with filming of hydroxyl, resol preferably includes each phenyl ring on average to have more than 0.5, preferably contains 0.6～3.0 alkoxy methyl.

The optional end capped polyisocyanate compound that is used for linking agent does not have end capped polyisocyanate compound to comprise: organic two cyanates itself, for example aliphatics two cyanates such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate etc.; Alicyclic diisocyanate class such as hydrogenation of benzene dimethyl vulcabond, isophorone diisocyanate etc.; With aromatic diisocyanate class such as tolylene diisocyanate, xylylene vulcabond, 4,4 '-diphenylmethanediisocyanate, thick MDI etc.; The affixture of these organic two cyanates and polyvalent alcohol, low molecular weight polyester resin, water etc.; Cyclic polymer between the above-mentioned organic diisocyanate; Isocyanic ester biuret etc.

Blocked polyisocyanates compound as linking agent is the compound for preparing by the free isocyanate groups end-blocking that makes with end-capping reagent in the polyisocyanate compound.The end-capping reagent that uses in end-blocking isocyanide acyl group for example can comprise phenols such as phenol, cresols, xylenol etc.; Lactams such as 'epsilon '-hexanolactam, δ-Valerolactim, butyrolactam etc.; Alcohols such as methyl alcohol, ethanol, just-, exclusive OR uncle-butanols, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, phenylcarbinol etc.; Oximes such as formamidoxime, ethylidenehydroxylamine, acetoxime, methyl ethyl ketone oxime, Diacetylmonoxime, diphenylketoxime, cyclohexanone-oxime etc.; And active methylene group end-capping reagent such as dimethyl malonate, diethyl malonate, methyl aceto acetate, Acetyl Acetone etc.Make the mixing of polyisocyanate compound and end-capping reagent can be easily with the free isocyanide acyl group end-blocking of polyisocyanate compound.

From aspects such as erosion resistance, resistance to boiling water, processing characteristics, curing performances, the combined amount that the filming of hydroxyl forms resin (A) and linking agent (B) is to make the component (A) of per 100 weight parts and total solids component (B), the formation resin (A) of filming of hydroxyl is the scope of 55～95 weight parts, preferred 60～95 weight parts, and linking agent (B) is the scope of 5～45 weight parts, preferred 5～40 weight parts.

In order to promote the curing reaction of coating composition, curing catalysts can be randomly used, and curing catalysts can be at random selected and use, this depends on the kind of solidifying agent to be used.

At linking agent (B) is that curing catalysts preferably includes the amine neutralized reaction product of sulfoacid compound and sulfoacid compound under the situation of aminoresin, particularly methyl etherified or methyl ether-butyl ether complex etherified melamine resin.The exemplary of sulfoacid compound can comprise tosic acid, Witco 1298 Soft Acid, dinonylnaphthalene sulfonic acid, dinonylnaphthalene disulfonic acid etc.Employed amine can comprise primary amine, secondary amine, tertiary amine in the amine neutralized reaction product of sulfoacid compound.Wherein, from the viewpoint of the stability and the reaction facilitation effect of coating composition, the film performance that obtains etc., the amine neutralized reaction product of preferred tosic acid and/or the amine neutralized reaction product of Witco 1298 Soft Acid.

At linking agent (B) is under the situation of resol, and curing catalysts can comprise the amine neutralized reaction product of sulfoacid compound and sulfoacid compound.

At linking agent (B) is under the situation of blocked polyisocyanates compound, preferably the curing catalysts that will carry out depolymerization as the end-capping reagent of the blocked polyisocyanates compound of linking agent.The example of preferred curing catalysts can include organic metal catalyst for example stannous octoate, dibutyl tin two (2-ethylhexanoate), dioctyl tin two (2-ethylhexanoate), dioctyl tin diacetate esters, dibutyltin dilaurate, dibutyl tin oxide, dioctyltin oxide, 2 ethyl hexanoic acid lead etc.

At linking agent (B) is under the situation of two or more linking agent combination, and curing catalysts can comprise the effectively combination of each curing catalysts of each linking agent.

Corrosion-inhibiting pigment mixture (C)

Corrosion-inhibiting pigment mixture (C) in the coating composition of the present invention is the corrosion-inhibiting pigment mixture that is made of (1) vanadium compound and (2) ion-exchange silicon-dioxide.

Vanadium compound (1)

Vanadium compound (1) can comprise at least a vanadium compound that is selected from Vanadium Pentoxide in FLAKES, vanadic acid calcium and the ammonium meta-vanadate.Vanadium Pentoxide in FLAKES, vanadic acid calcium and ammonium meta-vanadate demonstrate excellent pentavalent vanadium ion dissolving out capability in water, and the pentavalent vanadium ion that discharges from vanadium compound (1) is effective to the improvement of erosion resistance owing to reacting with the reaction of substrate metal or with the ionic that discharges from other corrosion-inhibiting pigment mixture.

Ion-exchange silicon-dioxide (2)

Ion-exchange silicon-dioxide (2) is the silicon-dioxide fine particle by adopting ion-exchange that positively charged ion such as calcium ion are incorporated into carefully, obtain on the porous silica supports.Ion-exchange silicon-dioxide can comprise for example calcium ion-exchanged silicon-dioxide, magnesium ion exchange silicon-dioxide, cobalt ion exchange silicon-dioxide etc.

Ion-exchange silicon-dioxide (2) can preferably include have 0.5-15 μ m, the average particle size particle size of the scope of preferred 1-10 μ m, and the fine silica end of the oil number of the scope of 30-300ml/100g, preferred 30-150ml/100g.

In ion-exchange silicon-dioxide (2), preferred calcium ion-exchanged silicon-dioxide.Commercially available calcium ion-exchanged silicon-dioxide can comprise for example SHIELDEX (trade mark) C303, AC-3 and C-5, respectively by W.R.Grace ﹠amp; Co sells.

The positively charged ion that discharges from ion-exchange silicon-dioxide for example calcium ion has electrochemical action and salification, and acts on effectively improving erosion resistance.The silicon-dioxide that is fixed in filming acts on effectively to the antistripping of filming under corrosive atmosphere.

The resin of phosphoric acid ester group or phosphate group (D)

In the resin (D) of phosphoric acid ester group or phosphate group, the resin of phosphoric acid ester group can comprise phosphoric acid ester group [OPO (OH) (OR ¹)] resin, R wherein ¹Expression hydrogen atom, phenyl or have the alkyl of 1-20 carbon atom, hydrogen atom and have the alkyl of 1-20 carbon atom particularly, and can comprise with filming of hydroxyl forming resin (A) and the compatible resin of linking agent (B), for example the vibrin of the Resins, epoxy of the acrylic resin of phosphoric acid ester group, phosphoric acid ester group, phosphoric acid ester group etc.

The acrylic resin of phosphoric acid ester group can obtain by unsaturated monomer and other the polymerisable unsaturated monomer copolymerization with the phosphoric acid ester group.

The unsaturated monomer of phosphoric acid ester group for example can comprise (methyl) acryloyloxyalkyl phosphate ester acid, wherein alkyl has 2-20 carbon atom, phosphate ester acid is (2-acrylyl oxy-ethyl) phosphate ester acid, (2-methylacryoyloxyethyl) phosphate ester acid, (2-acryloyl-oxy propyl group) phosphate ester acid, (2-methacryloxypropyl) phosphate ester acid for example, 10-acryloyl-oxy decyl phosphate ester acid, 10-methacryloxypropyl decyl phosphate ester acid etc.; Ortho-phosphoric acid or phosphate ester acid with 1-20 carbon atom and the unsaturated monomer that contains epoxy group(ing) for example (methyl) glycidyl acrylate etc. wait mole affixture; Kayamer PM-2, Kayamer PM-21 (trade(brand)name, sell by Nippon Kayaku company respectively).The example of phosphate ester acid can comprise methyl phosphate ester acid, butyl phosphate ester acid, 2-ethylhexyl phosphate ester acid, isodecyl phosphate ester acid, dodecyl phosphate ester acid, isotridecyl phosphate ester acid, oleyl phosphate ester acid, phenyl phosphate ester acid etc.

Can comprise with the unsaturated monomer copolymerization of phosphoric acid ester group and other polymerisable unsaturated monomer of constituting the acrylic resin of phosphoric acid ester group, for example, the unsaturated monomer of hydroxyl such as 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 2-hydroxyl butyl (methyl) acrylate, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyethyl alkyl oxide etc.; Vinylformic acid, methacrylic acid; Vinyl aromatic compounds such as vinylbenzene, alpha-methyl styrene, Vinyl toluene, α-chloro-styrene etc.; Alkyl ester of acrylic or methacrylic acid (alkyl has 1-24 carbon atom) or cycloalkyl ester are as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) vinylformic acid (just, different, uncle) butyl ester, (methyl) Ethyl acrylate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid n-octyl, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) vinylformic acid stearyl, (methyl) isobornyl acrylate etc.; Vinyl-acetic ester, vinylchlorid, vinyl ether, vinyl cyanide, methacrylonitrile etc.

Above, " (methyl) acrylate " expression " acrylate or methacrylic ester ".

The acrylic resin of phosphoric acid ester group can also by phosphate compounds is added to contain epoxy group(ing) unsaturated monomer for example the copolymer resin of (methyl) glycidyl acrylate and above-mentioned other polymerisable unsaturated monomer obtain.The phosphate compounds that is used for addition can comprise, for example ortho-phosphoric acid, phosphate ester acid etc.Phosphate ester acid can comprise above illustrative phosphate ester acid.

The Resins, epoxy of phosphoric acid ester group can obtain by phosphate compounds is added to Resins, epoxy.The Resins, epoxy that is used for the addition of phosphate compounds can comprise, for example bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin, and the modified epoxy by epoxy group(ing) in various properties-correcting agent and the above-mentioned Resins, epoxy or hydroxyl reaction are obtained.The phosphate compounds that is used for addition can comprise as the illustrated compound of phosphate compounds of the copolymer resin that is used to add to the unsaturated monomer that contains epoxy group(ing) and other polymerizable unsaturated monomer, be explained in the acrylic resin of phosphoric acid ester group as mentioned.

The vibrin of phosphoric acid ester group can be for example by obtaining the hydroxyl reaction in phosphate compounds and the vibrin.

The phosphate compounds of question response can comprise as the illustrated compound of phosphate compounds in the explanation in the acrylic resin of phosphoric acid ester group.

In the resin (D) of phosphoric acid ester group or phosphate group, the resin of phosphoric acid salt group can obtain by the bound phosphate groups metallizing thing reaction formation phosphoric acid salt in the resin that makes the phosphoric acid ester group.

Can comprise for example calcium oxide, magnesium oxide, cobalt oxide, nickel oxide, zinc oxide, cerium oxide, lanthanum trioxide etc. with the metallic compound of bound phosphate groups reaction.

Bound phosphate groups or phosphate group in the resin of phosphoric acid ester group or phosphate group (D) play the effect that improves thickening property and erosion resistance effectively.

Viewpoint from erosion resistance, the total solids level of resin of per 100 weight parts (A) and linking agent (B), coating composition of the present invention preferably contains the vanadium compound (1) of 3-50, preferred 5-40 weight part scope respectively, the ion-exchange silicon-dioxide (2) of 3-50, preferred 3-30 weight part scope, the corrosion-inhibiting pigment mixture (C) of the phosphoric acid ester group of 1-30, preferred 1-20 weight part scope or the resin (D) of phosphate group and 6-100, preferred 10-60 weight part scope.

According to coating composition of the present invention, the vanadium compound (1) of the specified amount separately in the corrosion-inhibiting pigment mixture (C) and ion-exchange silicon-dioxide (2) make it possible to improve synergistically erosion resistance with the combination of the resin (D) of phosphoric acid ester group or phosphate group.

Water-soluble from vanadium compound (1) and ion-exchange silicon-dioxide (2), reactivity between corrosion-inhibiting pigment lysate and the metal sheet, and erosion resistance viewpoint, hope has 3-8 by the filtrate that is prepared as follows, the pH of preferred 5-8 scope: with the total solids level of the resin (A) of per 100 weight parts and linking agent (B) respectively the mixture of the vanadium compound (1) of the formation corrosion-inhibiting pigment mixture (C) in weight part scope as mentioned below and ion-exchange silicon-dioxide (2) join in the sodium chloride aqueous solution of 5 weight % under 25 ℃ of 10000 weight parts, then stirred 6 hours, under 25 ℃, left standstill 48 hours, and filter the supernatant liquor that obtains.

Promptly, stand filtrate that pH measures and be filtrate: at 25 ℃ of mixtures of ion-exchange silicon-dioxide (2) that are respectively the amount of the vanadium compound (1) of the amount of 3-50 weight part and 3-50 weight part down by total solids level with the resin (A) of per 100 weight parts and linking agent (B) by being prepared as follows, join in the sodium chloride aqueous solution of 10000 weight parts, 5 weight %, then dissolve, and filter the solution that is produced.

Except that the resin (D) and the optional curing catalysts that uses of film-forming resin (A), solidifying agent (B), corrosion-inhibiting pigment mixture (C), phosphoric acid ester group or the phosphate group of hydroxyl, coating composition of the present invention can be chosen wantonly and contain tinting pigment, pigment extender, UV light absorber, ultra-violet stabilizer, organic solvent; Additive for example antisettling agent, defoamer, be coated with the known additives that in the coating composition field, use such as face control agent.

Tinting pigment can comprise, for example, organic coloring pigment such as cyanines indigo plant, cyanines are green, organic red such as azo pigment and quinacridone pigment etc.; Inorganic coloring pigment such as titanium white, titan yellow, red iron oxide, carbon black, various calcination pigment, wherein preferred titanium white.

Pigment extender can comprise, for example talcum, clay, mica, aluminum oxide, lime carbonate, barium sulfate etc.

UV light absorber can comprise, for example, benzotriazole derivatives such as 2-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl)-the 2H-benzotriazole, iso-octyl-3-(3-(2H-benzotriazole-2-yl)-5-tert-butyl-hydroxy phenyl) propionic ester, 2-[2-hydroxyl-3,5-two (1,1-dimethyl benzyl (benzine)) phenyl]-the 2H-benzotriazole, 2-[2-hydroxyl-3-dimethyl benzene methyl-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] condensation product etc. of propionic ester and Liquid Macrogol; Pyrrolotriazine derivatives such as 2-[4-(2-hydroxyl-3-dodecyl oxygen propyl group)-oxygen]-2-hydroxy phenyl-4, and 6-two (2,4-3,5-dimethylphenyl-1,3,5-1,3,5-triazine etc.; Oxanilide derivative such as oxalamide-N-(2-phenelyl)-N '-(2-ethylphenyl)-(oxamide), oxalamide-N-(2-phenelyl)-N '-(4-Permethyl 99A. base phenyl)-(oxamide) etc.

Ultra-violet stabilizer can comprise, hindered amine compound for example, hindered phenol compound; CHIMASORB 944, and TINUVIN 144, and TINUVIN 292, and TINUVIN 770, and IRGANOX 1010, IRGANOX 1098 (trade(brand)name, sold by Ciba Specialty Chemicals K.K. respectively) etc.

In coating composition, add UV light absorber and ultra-violet stabilizer and make it possible to control the deterioration that causes by light of film coated surface, and when this coating composition is used as primer composition, can control the deterioration on the bottom coating surface that light caused that arrives the bottom coating surface by filming by face, prevention because the interlayer that is coated with that deterioration caused on bottom coating surface peels off, and keeps excellent erosion resistance between bottom coating and face are filmed.

The organic solvent that uses in coating composition of the present invention can comprise the optional solvent that is used to improve the coating property of coating composition of the present invention with adding, can dissolve or disperse the film-forming resin (A) of hydroxyl and the solvent of linking agent (B), and concrete example as, varsol such as toluene, dimethylbenzene, high point petroleum class hydrocarbon etc., ketones solvent such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, isophorone etc., esters solvent such as ethyl acetate, butylacetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetic ester etc., alcoholic solvent such as methyl alcohol, ethanol, Virahol, butanols etc., ether alcohol kind solvent such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether or the like.These solvents can be used alone or in combination.

From viewpoints such as erosion resistance, acid resistance and processing characteristicies, coating composition of the present invention makes the second-order transition temperature of the cured coating film that obtained by composition of the present invention be preferably 40～115 ℃, more preferably 50～105 ℃.In the present invention, the second-order transition temperature of filming is to use Dinamic Viscoelastomer ModelVibron DDV-II EA type (automatic dynamic determination of viscoelasticity machine, TOYO BALDWIN Co., Ltd makes), determine maximum temperature by the variation of the tan δ that measures in the temperature dispersion at frequency 110Hz place.

Demonstrate excellent erosion resistance by coating composition of the present invention being coated to filming of forming on the metal sheet.

Its first reason is: metal ion and 5 valency vanadium ions that the dissolving of the substrate metal that causes owing to the chloride ion under the corrosive environment forms (are vanadic acid radical ion such as VO ₃ ^-Or VO ₄ ^3-) between directly generate precipitation threshold salt without redox reaction, and ion-exchange silicon-dioxide in corrosive environment hydrolysis and the positively charged ion and the silicate ion of emitting combine with the 3 valency vanadium ions and the substrate metal ionic that redox reaction generated of 5 valency vanadium ions and substrate metal, effectively generate precipitable salt or compound, cause the exposed surface of base material effectively to obtain applying.

Second reason is: except because in the corrosive environment the caused effect of positively charged ion of emitting, also because the effect of its lip-deep slightly acidic functional group, ion-exchange silicon-dioxide plays the effect that the pH with the wetting environment approaching with being in slightly acidic value corrosive environment controls consumingly, promote the redox reaction between pentavalent vanadium ion and the substrate metal, and further this ion-exchange silica stationary in filming and for a long time to carrying out corrosive pH retentive control ability under the corrosive environment, and sacrifice property ground keeps hydrolysis takes place under the corrosive environment in stronger carrying out, and discharges silicate ion.

The 3rd reason is: under the situation of coated steel plates, may be although face is filmed owing to deterioration becomes hydrophilic, and various promotion corrosive materials may see through from the unprocessed planar section that face is filmed, but the resin of phosphoric acid ester group or phosphate group (D) plays a role as strong tackify component in sour environment and has a effect of filming and peeling off near the anode that suppresses the part that corrosion carries out, and in can be effectively and in the negative electrode oxygen the hydroxyl that reduction reaction produced and the pH that produces can be kept near neutrality.

The bound phosphate groups and the phosphate group of the resin of phosphoric acid ester group or phosphate group (D) can provide the effect that the pH of environment is remained on the slightly acidic value.

The combination of above-mentioned various effects can realize excellent erosion resistance.

Constitute the composition use of the resin (D) of the vanadium compound (1) of corrosion-inhibiting pigment mixture (C) and ion-exchange silicon-dioxide (2) and phosphoric acid ester group or phosphate group, make it possible to overcome effectively the performance of difference that vanadium compound (1), ion-exchange silicon-dioxide (2) and phosphorus contain each comfortable acid resistance of resin (D), alkali resistance and the water tolerance aspect of acid esters group or phosphate group.The synergy of each self-applying of the resin (D) of corrosion-inhibiting pigment mixture (C) and phosphoric acid ester group or phosphate group produces excellent erosion resistance.

Promptly, the invention provides the metallic sheet of a kind of coating composition and this coating composition of use, this coating composition, except the effect on the surface by the effective coated substrate exposure of corrosion-inhibiting pigment mixture (C) component that constitutes by vanadium compound (1) and ion-exchange silicon-dioxide (2), also the resin (D) by phosphoric acid ester group or phosphate group is suppressed at corrosion in the sour environment and carries out the effect of filming and peeling off near the part the anode, together with effect as strong tackify component, even owing to the photodegradation in the outdoor environment and hydrolysis make film carry out deterioration after, also effectively improve the erosion resistance of not only unprocessed planar section in the metallic sheet but also the part of having processed and edge surface part.

Metallic sheet

Metallic sheet of the present invention has by coating composition of the present invention being coated on the metal sheet as base material, then being cured filming of forming.

Described metal sheet as base material can comprise cold-rolled steel sheet, hot-dip galvanized steel sheet, electrogalvanizing steel plate, iron-zinc alloy coated steel sheet (zinc coating annealed sheet steel), aluminum-zinc alloy coated steel sheet (" the galvalume steel plate " that contains 55% aluminium of having an appointment in alloy, " the galvanized iron alloy annealed sheet steel " that in alloy, contains 5% aluminium of having an appointment, etc.), nickel-zinc alloy coated steel sheet, stainless steel plate, aluminium sheet, copper coin, Copper Plated Steel, tin plate etc.These metal sheets can be chosen wantonly and stand conventional metal surface treatment process, for example phosphatizing technology such as zinc phosphate treatment process, tertiary iron phosphate treatment process etc., combined oxidation membrane treatment process, chromium phosphatizing technology, chromate treating technology etc.

Coating composition of the present invention can be by routine cladding process for example rolling method, curtain formula flow coat method, spraying method, spread coating, dip coating etc. are coated on the metal sheet.The thickness of filming that is formed by composition of the present invention can have no particular limits, and still is generally 2-10 μ m, is preferably 3-6 μ m.Described drying of filming can be carried out under suitable condition, the type that depends on used resin, but under the situation of the thermofixation continuously of filming that will be formed by the coiled material cladding process, this thermofixation can be carried out 15-60 second usually under 160-250 ℃, preferred 180-230 ℃ of maximum base material temperature.Thermofixation in the batch process can be carried out under 80-200 ℃ envrionment temperature 10-30 minute usually.

Under the situation that does not need in the crosslinking reaction when formation is filmed to heat, for example, use not end capped polyisocyanate compound as the situation of solidifying agent (B) under or use bisphenol-type epoxy resin as resin (A) and use amine compound under the situation as linking agent (B), drying can at room temperature be carried out to be cured according to conventional methods.

Metallic sheet of the present invention can comprise the metallic sheet of filming that is only formed by coating composition of the present invention on the metal sheet that has had in optional surface treatment, has the metallic sheet that face is filmed on above-mentioned the filming but can also be included in.This face film have 8-30 μ m, the thickness of preferred 10-25 μ m.

The coating materials composition that formation face is filmed can comprise the conventional obtainable composition that is used for precoat metal plate, for example, polyester resin, Synolac class, silicon modified polyesters resene, organosilicon-modified acrylic resinoid class, fluorocarbon resin borne overcoating material composition.Under the very important situation of processing characteristics, use coating materials composition for example to be used for the highly vibrin borne overcoating material composition of processing, the metallic sheet that makes it possible to obtain to have special good processing properties with excellent machinability.Have the metallic sheet that above-mentioned face films among the present invention and on erosion resistance, demonstrate good film properties.

Under the situation of the steel plate of steel plate galvanized and aluminium-zinc alloy plating, improve in the erosion resistance of unprocessed planar section with certain limit, but in this area at the surface portion of cutting edge with the erosion resistance of processing part is still unsatisfactory.Be that the coating of coating composition of the present invention makes it possible to obtain excellent erosion resistance at the surface portion at edge and the part of having processed on the contrary.

Can be formed on base material two-sided by filming of forming of coating composition of the present invention, and optional face film can be formed on film by coating composition of the present invention is formed on.On the two sides that comprises the back side of base material, form and film, can obtain not the containing chronium corrosion-inhibiting pigment and see metallic sheet favourable and that demonstrate excellent erosion resistance from the viewpoint of environment protection and HUMAN HEALTH by coating composition of the present invention.

Embodiment

More specifically set forth the present invention with reference to following preparation example and embodiment.The present invention should not be subject to the following examples.Hereinafter, " part " and " % " represents " weight part " and " % weight " respectively.

Preparation example 1

The preparation of resole cross-linking agent solution:

In reaction vessel, pack into 100 parts of dihydroxyphenyl propanes, 178 part of 37% formalin and 1 part of sodium hydroxide, then reacted 3 hours down at 60 ℃, under vacuum, dewatered 1 hour at 50 ℃, add 100 parts of propyl carbinols and 3 parts of phosphoric acid, reacted 2 hours down at 110～120 ℃, the solution that filter to generate, the sodium phosphate that leaches generation is about 50% resole cross-linking agent solution B1 to obtain solids content.The resin that as above obtains has 880 number-average molecular weight, 0.4 methylol is on average arranged respectively in each phenyl ring and 1.0 alkoxy methyls are on average arranged.

Preparation example 2

The back side preparation of coating composition:

200 parts are passed through in 120 parts of mixed solvent 1[pimelinketone/ethylene glycol monobutyl ethers/Solvesso 150 (trade(brand)names, Esso Standard Oil Co., Ltd. sell, the high boiling point aromatic hydrocarbon solvent)=3/1/1/ weight ratio] in 80 parts of jER 1009 (trade(brand)names of dissolving, Japan Epoxy Resins Co.Ltd. sells, bisphenol A type epoxy resin, hydroxy-containing resin) and the preparation epoxy resin solution and 40 parts of titanium whites, the mixed solvent 2[Solvesso 150 (trade(brand)names of 40 parts of barium oxide and predetermined amount, Esso Standard Oil Co., Ltd. sell, the high boiling point aromatic hydrocarbon solvent)/pimelinketone=1/1, weight ratio] mixture stand colo(u)rant dispersion, so that particle diameter, it is the coarse grained particle size of pigment, can be reduced to below 20 microns, then add 26.7 parts of (counting 20 parts) Desmodur BL-3175 (trade(brand)names with solids constituent, Sumika Bayer Urethane Co., Ltd. sell, the end capped HDI isocyanuric acid ester of methyl ethyl ketone oxime type polyisocyanate compound solution, solids content about 75%) and 2 parts of TakenateTK-1 (trade(brand)names, Takeda Pharmaceutical Company Limited sells, organic tin end-capping reagent dissociation catalyst, solids content about 10%), uniform mixing, add mixed solvent 2 and with viscosity controller at about 80sec (Ford Cup#4/25 ℃), to obtain back side coating composition.

The preparation of the resin of phosphoric acid ester group or phosphate group:

Preparation example 3

The preparation of the acrylic resin 1 of phosphoric acid ester group

The 100 parts of butanols of in reaction vessel, packing into, then 0 part of vinylbenzene of Dropwise 5,35 parts of methacrylic acid 2-ethylhexyls, 15 parts of glycidyl methacrylate and 2.0 part 2 in 3 hours, 2 '-mixture of Diisopropyl azodicarboxylate, temperature of reactor is remained on 110 ℃ simultaneously.

Then, add 0.5 part 2,2 '-Diisopropyl azodicarboxylate, then reacted 2 hours down at 110 ℃, temperature of reactor is remained on 80 ℃, slowly add 12.2 parts 85% ortho-phosphoric acid and 10.4 parts of butanols and reacted 1 hour, the turbidity disappeared of the mixture that is produced in reactor is with acrylic resin 1 solution of the phosphoric acid ester group that obtains having 50% solids content.The acrylic resin 1 of phosphoric acid ester group has 54 resinous acid value (in phosphate-based mass contg 0.096 equivalent/100g resin) as solids constituent.

Preparation example 4

The preparation of the acrylic resin 2 of phosphoric acid ester group

The 100 parts of butanols of in reaction vessel, packing into, then 3 parts of vinylbenzene of Dropwise 5,40 parts of methacrylic acid 2-ethylhexyls, 7 parts of glycidyl methacrylate and 2.0 part 2 in 3 hours, 2 '-mixture of Diisopropyl azodicarboxylate, temperature of reactor is remained on 110 ℃ simultaneously.

Then, add 0.5 part 2,2 '-Diisopropyl azodicarboxylate, then reacted 2 hours down at 110 ℃, temperature of reactor is remained on 80 ℃, slowly add 5.7 parts 85% ortho-phosphoric acid and 4.9 parts of butanols and reacted 1 hour, the turbidity disappeared of the mixture that produces is with acrylic resin 2 solution of the phosphoric acid ester group that obtains having 50% solids content in reactor.The acrylic resin 2 of phosphoric acid ester group has 26 resinous acid value (in phosphate-based mass contg 0.047 equivalent/100g resin) as solids constituent.

Preparation example 5

The preparation of the acrylic resin 3 of phosphoric acid ester group

The 100 parts of butanols of in reaction vessel, packing into, then in 3 hours, drip 40 parts of vinylbenzene, 30 parts of methacrylic acid 2-ethylhexyls, 30 parts of glycidyl methacrylate and 2.0 part 2,2 '-mixture of Diisopropyl azodicarboxylate, temperature of reactor is remained on 110 ℃ simultaneously.

Then, add 0.5 part 2,2 '-Diisopropyl azodicarboxylate, then reacted 2 hours down at 110 ℃, temperature of reactor is remained on 80 ℃, slowly add 25 parts 85% ortho-phosphoric acid and 17 parts of butanols and reacted 1 hour, the turbidity disappeared of the mixture that produces in reactor is with acrylic resin 3 solution of the phosphoric acid ester group that obtains having 50% solids content.The acrylic resin 3 of phosphoric acid ester group has 98 resinous acid value (in phosphate-based mass contg 0.17 equivalent/100g resin) as solids constituent.

Preparation example 6

The preparation of the Resins, epoxy of phosphoric acid ester group

100 parts of pimelinketone and 100 parts of jER 1007 (trade(brand)name, JapanEpoxy Resins Co.Ltd. sale, bisphenol-type epoxy resin, hydroxy-containing resin) pack in reaction vessel, then stir and 70 ℃ down heating with this resin dissolves, 85% ortho-phosphoric acid that adds 5.76 parts, reacted 2 hours down at 70 ℃, and add 4 parts of pimelinketone to obtain the epoxy resin solution of 50% phosphoric acid salt group.The resin of phosphoric acid ester group has 28 resinous acid value (in phosphate-based mass contg 0.05 equivalent/100g resin) as solids constituent.

Preparation example 7

The preparation of the acrylic resin of phosphoric acid salt group

Acrylic resin 1 solution and 5 parts of calcium oxide that in mortar, pulverize of in blocky Glass Containers, adding 50% solids content that obtains in 100 parts of (counting 50 parts) preparation examples 3 with solids constituent, the glass beads of then packing into, with Skandex (trade(brand)name, by Mitsuwa-Tech Ltd. sell, agitator) disperse, up to this resin solution bleach, at room temperature leave standstill 48 hours, and remove glass beads to obtain the acrylic resin solution of phosphoric acid salt group.

The preparation of ion-exchange silicon-dioxide

Preparation example 8

The preparation of magnesium ion exchange silicon-dioxide

The Sylysia710 (trade(brand)name, by Fuji Silysia Chemical Ltd. sale, silicon-dioxide fine particle, the about 105ml/100g of oil number) that in 10000 weight parts, 5 weight % magnesium chloride brines, adds 10 weight parts, mixed 5 hours under then stirring, filter and remove solids constituent, this solids constituent of water thorough washing, and carry out drying to obtain magnesium ion exchange silicon-dioxide.

Preparation example 9

The preparation of cobalt ion exchange silicon-dioxide

The Sylysia710 (trade(brand)name, by Fuji Silysia Chemical Ltd. sale, silicon-dioxide fine particle, the about 105ml/100g of oil number) that in 10000 weight parts, 5 weight % cobalt chloride solutions, adds 10 weight parts, mixed 5 hours under then stirring, filter and remove solids constituent, this solids constituent of water thorough washing, and carry out drying to obtain cobalt ion exchange silicon-dioxide.

The preparation of anticorrosive coating composition

Embodiment 1

220 parts are passed through at 135 parts of mixed solvent 1[pimelinketone/ethylene glycol monobutyl ether/Solvesso 150 (trade(brand)name, Esso Standard Oil Co., Ltd. sell, the high boiling point aromatic hydrocarbon solvent)=3/1/1, weight ratio] in the epoxy resin solution of dissolving 85 parts of jER 1009 (trade(brand)name, Japan Epoxy Resins Co.Ltd. sale, bisphenol A type epoxy resin, hydroxy-containing resin) and preparation and 5 parts of Vanadium Pentoxide in FLAKESs, 3 parts of Shieldex AC-3 (trade(brand)name, W.R.Grace ﹠amp; Co. sell, calcium ion-exchanged silicon-dioxide), mixed solvent 2[Solvesso 150 (trade(brand)name, the EssoStandard Oil Co. of 20 parts of titanium whites, 20 parts of barium oxide and predetermined amount, Ltd. sell, the high boiling point aromatic hydrocarbon solvent)/pimelinketone=1/1, weight ratio)] mixture, stand colo(u)rant dispersion, make particle diameter, pigment coarse particle particle diameter, reduce to below 20 microns.Then, add 20 parts of (solid is divided into 15 parts) Desmodur BL-3175 (trade(brand)names, Sumika Bayer Urethane Co., Ltd. sell, the end capped HDI isocyanuric acid ester of methyl ethyl ketone oxime type polyisocyanate compound solution, solids content about 75%), acrylic resin 1 solution of the phosphoric acid ester group that obtains in 4 parts of (counting 2 parts) preparation examples 3 with solids constituent, 2 parts of Takenate TK-1 (trade(brand)names, Takeda PharmaceuticalCompany Limited sells, organic tin end-capping reagent dissociation catalyst, solids content about 10%), uniform mixing, add mixed solvent 2 and with viscosity controller at about 80sec (FordCup#4/25 ℃), to obtain anticorrosive coating composition.

Embodiment 2-20, comparative example 1-10, reference example 1-2:

Repeat embodiment 1, except using each hydroxy-containing resin, linking agent, corrosion-inhibiting pigment and other pigment shown in the table 1.Reference example 1 and 2 expressions contain the conventional anticorrosive coating composition of chromium class corrosion-inhibiting pigment.In table 1, the resin of each hydroxy-containing resin, linking agent, phosphoric acid ester group or phosphate group and the amount of pigment component are represented with solid weight content.Condition is, embodiment 15 does not contain and contains 1 part of Nacure 5225 (trade(brand)name, sold the amine neutralization solution of Witco 1298 Soft Acid by USKing Industries Ltd.) in Takenate TK-1 (trade(brand)name as hereinbefore defined) and embodiment 16 and 19 respectively and replace 2 parts Takenate TK-1.

Shown in the table 1 by in the 5 weight % sodium chloride aqueous solutions that will join 25 ℃ of 10000 weight parts as the total amount of each corrosion-inhibiting pigment (C) of the total solids level of the hydroxy-containing resin of per 100 weight parts of resin Composition and linking agent and strontium yellow, then stir 6 hours, under 25 ℃, leave standstill 48 hours, and filter pH, the pH of corrosion-inhibiting pigment lysate of the filtrate that the supernatant liquor that obtains prepares.For example, the pH of the corrosion-inhibiting pigment lysate among the embodiment 1 joins in 5 weight % sodium chloride aqueous solutions of 25 ℃ of 10000 weight parts, then dissolves under these conditions, and filters the pH of the filtrate that the supernatant liquor that obtains prepares by the Shieldex AC-3 with the Vanadium Pentoxide in FLAKES of 5 weight parts and 3 weight parts.

In the table 1, (annotating 1)-(annotating 7) is explained as follows.

(annotate 1) Epokey 837: trade(brand)name, Mitsui Chemicals, about 35, about 0 (zero) of acid number of Inc. sale, urethane-modified Resins, epoxy, hydroxy-containing resin, primary hydroxyl value.

(annotating 2) Vylon 296: trade(brand)name, Toyobo Co. sale, epoxy modified polyester resin, hydroxy-containing resin, hydroxyl value 7, acid number 6.

(annotating 3) Sumidur N3300: trade(brand)name, Sumika Bayer Urethane Co., Ltd. sale, isocyanuric acid ester type polyisocyanate compound, solids constituent 100%.

(annotating 4) Cymel 303: trade(brand)name, Nihon Cytec Industries Inc. sell, methyl etherified melamine resin.

(annotating 5) Shieldex C 303: trade(brand)name, W.R.Grace ﹠amp; Co. sell, calcium ion-exchanged silicon-dioxide.

(annotating 6) Aerosil 200: trade(brand)name, Nippon Aerosil Co., Ltd. sale, silicon-dioxide fine particle, the about 280ml/100g of oil number.

(annotating 7) Sandvor 3058: trade(brand)name, Clariant Japan KK sell, the hindered amines ultra-violet stabilizer.

The preparation of coated test panel

Each anticorrosive coating composition that will obtain in embodiment 1～20, comparative example 1～10 and reference example 1 and 2 and coating materials composition are coated on each base material according to following coating explanation 1-3 and solidify, to obtain each coated test panel.

Apply explanation 1:

The back side that will obtain in preparation example 2 with excellent coating machine is coated to the galvalume steel plate that stood metal surface treatment process with coating composition, and (the aluminium content in the alloy is about 55%, plating alloy amount 150g/m for thickness of slab 0.35mm, aluminium-zinc alloy coated steel sheet ²In table 2, be expressed as the GL steel plate) on, form the thick dry film of 8 μ m, then under 180 ℃ maximum base material temperature, solidify and filmed to form the back side in 30 seconds, on the steel plate face opposite that each anticorrosive coating composition that will obtain in the above-described embodiments with excellent coating machine is coated to this steel plate with having the back side of filming at the back side, form the thick dry film of 5 μ m, then under 220 ℃ maximum base material temperature, solidify 40 seconds to obtain each bottom coating, cooling and with excellent coating machine coating KP Color 1580B40 (trade(brand)name, by Kansai Paint Co., Ltd. sell, polyester coating materials composition, blue, about 70 ℃ of the second-order transition temperature of cured coating film) to each bottom coating, form the thick dry film of about 15 μ m, and under 220 ℃ maximum base material temperature, solidify 40 seconds to obtain each coated test panel.

Apply explanation 2:

The back side that will obtain in preparation example 2 with excellent coating machine is coated to hot-dip galvanized steel sheet (thickness of slab 0.35mm, the galvanized amount 250g/m that has stood metal surface treatment process with coating composition ²In table 2, be expressed as the GI steel plate) on, form the thick dry film of 8 μ m, then under 180 ℃ maximum base material temperature, solidify and filmed to form the back side in 30 seconds, on the steel plate face opposite that each anticorrosive coating composition that will obtain in the above-described embodiments with excellent coating machine is coated to this steel plate with having the back side of filming at the back side, form the thick dry film of 5 μ m, then under 220 ℃ maximum base material temperature, solidify 40 seconds to obtain each bottom coating, cooling and with excellent coating machine coating KPColor 1580B40 (trade(brand)name, by Kansai Paint Co., Ltd. sell, polyester coating materials composition, blue, about 70 ℃ of the second-order transition temperature of cured coating film) to each bottom coating, form the thick dry film of about 15 μ m, and under 220 ℃ maximum base material temperature, solidify 40 seconds to obtain each coated test panel.

Apply explanation 3:

The anticorrosive coating composition that will obtain in embodiment 3 with excellent coating machine is coated on the galvalume steel plate identical with applying explanation 1, form the thick dry film of 8 μ m, then under 180 ℃ maximum base material temperature, solidify and filmed to form the back side in 30 seconds, on the steel plate face opposite that each anticorrosive coating composition that will obtain in the above-described embodiments with excellent coating machine is coated to this steel plate with having the back side of filming at the back side, form the thick dry film of 5 μ m, then under 220 ℃ maximum base material temperature, solidify 40 seconds to obtain each bottom coating, cooling and with excellent coating machine coating KPColor 1580B40 (trade(brand)name, by Kansai Paint Co., Ltd. sell, polyester coating materials composition, blue, about 70 ℃ of the second-order transition temperature of cured coating film) to each bottom coating, form the thick dry film of about 15 μ m, and under 220 ℃ maximum base material temperature, solidify 40 seconds to obtain each coated test panel.

The film performance test

According to following test method, the anticorrosive coating composition that use obtains by embodiment 1-20, comparative example 1-10 and reference example 1-2, each the coated test panel that obtains in above-mentioned coating explanation 1-3 stand the film performance test.Test-results is presented in the table 2.

Test method

Resistance to boiling water: will cut into each the coated test panel that is of a size of 5cm * 10cm and immerse in about 100 ℃ boiling water 2 hours, and then take out the outward appearance of filming that on the face side that applies panel, forms to estimate, and stand cross cut band method respectively to estimate.Described cross cut band method such as JIS K-5400 8.5.2 (1990) definition.That is, with cutting at interval 1mm and 100 grids bonding glass paper tape is adhered to the face side of each coated test panel, follow following this band of firmly peeling off and have filming of grid with evaluation.

◎: on filming, do not have the unusual for example bubble and the generation of albefaction, residual 100 grids.

Zero: on filming, do not have the unusual for example bubble and the generation of albefaction, a residual 91-99 grid.

△: the generation of slight bubble or albefaction, a residual 91-99 grid are arranged on filming, and perhaps unusually for example bubble and albefaction do not produce but a residual 71-90 grid on filming.

*: a large amount of or significant bubble generation is arranged, perhaps residual 70 grids or still less on filming.

Alkali resistance:

The back side and the cutting surface that will cut into each the coated test panel that is of a size of 5cm * 10cm seal with anticorrosive coating composition, and form the cross cut that arrives base material in the face side central authorities that apply panel.The coating panel that obtains immersed in 40 ℃ 5% the aqueous sodium hydroxide solution 48 hours, then take out, clean also at room temperature dry, to estimate the outward appearance of filming on the film coated surface side, and further bonding glass paper tape is adhered to the cross cut part, then firmly peel off this band with estimate obtain film in peel off width (side) from the cross cut part.

◎: not having bubble to produce, peel off width from the band of cutting part is below the 1.5mm.

Zero: do not have bubble to produce, peel off width but below the 3mm greater than 1.5mm from the band of cutting part.

△: having slight bubble to produce, peel off width from the band of cutting part is below the 3mm, does not perhaps have bubble to produce, and peels off width greater than 3mm from the band of cutting part.

*: there is bubble to produce, peel off width greater than 3mm from the band of cutting part.

Acid resistance:

The back side and the cutting surface that will cut into each the coated test panel that is of a size of 5cm * 10cm seal with anticorrosive coating composition, and form the cross cut that arrives base material in the face side central authorities that apply panel.The coating panel that obtains was immersed in 40 ℃ 5% the aqueous sulfuric acid 48 hours, then take out, clean also at room temperature dry, to estimate the outward appearance of filming on the film coated surface side, and further the glass paper tape is adhered to the cross cut part, then firmly peel off this band with estimate obtain film in peel off width (side) from the cross cut part.

◎: not having bubble to produce, peel off width from the band of cutting part is below the 1.5mm.

Zero: do not have bubble to produce, peel off width but below the 3mm greater than 1.5mm from the band of cutting part.

△: having slight bubble to produce, peel off width from the band of cutting part is below the 3mm, does not perhaps have bubble to produce, peel off width greater than 3mm from the band of cutting part.

*: there is bubble to produce, peel off width greater than 3mm from the band of cutting part.

The scratch resistance trace:

Under 20 ℃ room temperature, use coin scratch hardness test device (selling) by Jido-ka GikenKogyo K.K., the edge of ten Yen of copper coins is remained on 45 ° angle on the filming of face side of each coated test panel, follow these ten Yen of about 30mm of copper coin of speed tractive with 10mm/sec, under the load of 3kg, push simultaneously, on filming, form cut, and the degree of following evaluation cut.

◎: do not expose substrate metal in the cut part.

Zero: expose substrate metal slightly in the cut part.

△: expose substrate metal in large quantities in the cut part.

*: almost do not film residual and clearly expose substrate metal in cut part.

The composite anticorrosive test:

Be prepared as follows each the coated test panel that uses in the composite anticorrosive test.Use xenon lamp accelerated weathering test instrument, make to cut into each the coated test panel that is of a size of 7cm * 15cm and stand 500 hours accelerated weathering test.

Use shears to cut the coated test panel that obtains at each 5mm place, edge of distance avris, so that the burr in the edge part of the long side of each coated test panel is facing to the face side on the right side of filming on the face side, and facing to the rear side in the left side of filming on the face side.Then, the back of using cutting knife forms the cross cut of arrival base material of the live width of groove angle with 30 ° and 0.5mm in each face side central authorities that apply panel, then the upper end-face edge that will apply panel with anticorrosive coating composition partly seals, and make this upper end-face edge partly stand the folding processing of 3T, i.e. this processing comprises: will apply panel and fold, the face side of described coating panel outwardly, 3 had with the plate of described coating panel same thickness put into folding coating panel, and use vice with the folding coating panel that obtains of 180 ° angle to obtain each test panel.

According to JIS K-5621 (1990) the coating panel that obtains is carried out the cyclic corrosion test, the test of wherein said cyclic corrosion comprises by will be by the single circulation that following step in turn constitutes 1200 hours 200 circulations altogether of carrying out round-robin: 30 ℃ down 5% salt-fog tests 0.5 hour, 95% or higher RH under in the humidity test device under 30 ℃ test 1.5 hours, 50 ℃ of dryings 2 hours, and 30 ℃ of dryings 2 hours.The coating panel that obtains is stood unprocessed planar section, edge section, cross cut part and 3T respectively fold-evaluation of situation is carried out in the processing part.

3T processing part: based on the generation of the total length of the rusty part in the 3T processing part and red rust and estimate.

◎: white rust does not take place, white rust perhaps takes place, less than 5mm.

Zero: white rust takes place, greater than 5mm but less than 20mm.

△: white rust is that 20mm is above but less than 40mm.

*: white rust is more than the 40mm, and red rust perhaps takes place.

Edge section: the mean value of the edge creep width of two long sides and check that the generation of red rust estimates with following about determining.

◎: less than 5mm and red rust do not take place.

Zero: 5mm is above but less than 10mm and red rust do not take place.

△: 10mm is above but less than 20mm and red rust do not take place.

*: more than the 20mm, red rust perhaps takes place.

Cross cut part:, following corrosion situation in the cross cut part is estimated based on the mean value of the left and right sides bubble width of the degree of white rust generation length in expose portion and the both sides in cutting part and the generation of red rust with the wide substrate metal of 0.5mm cutting.

◎: the degree of the white rust generation length in the expose portion of substrate metal less than 50% and the bubble width less than 3mm.

Zero: the degree of white rust growth length more than 50% and the bubble width less than 3mm, or the degree of white rust generation length is less than 50% and more than the bubble width 3mm but less than 5mm.

△: the degree of white rust generation length more than 50% and bubble width 5mm above but less than 10mm.

*: the degree of white rust growth length is more than 50%, and more than the bubble width 10mm, red rust takes place perhaps.

Unprocessed planar section:

To with unprocessed planar section in take place discontinuous of the divided portion place, edge of continuous corrosion part and the bubble that distributes, the following evaluation.

◎: do not have bubbling.

Zero: bubble diameter: approximately less than 2mm, number of bubbles: less than 10.

△: bubble diameter: the above and number of bubbles of about 2mm: less than 10, perhaps bubble diameter: less than 2mm and number of bubbles: more than 10.

*: bubble diameter: the above and number of bubbles of about 2mm: more than 10.

Claims (11)

1. coating composition, this coating composition contains (A) not formation resin of filming of phosphoric acid ester group, hydroxyl, (B) linking agent, (C) corrosion-inhibiting pigment mixture and (D) at least a resin in the resin of the resin of phosphoric acid ester group and phosphoric acid salt group; Described corrosion-inhibiting pigment mixture (C) is by the following corrosion-inhibiting pigment mixture that constitutes: (1) is selected from least a vanadium compound and (2) ion-exchange silicon-dioxide of Vanadium Pentoxide in FLAKES, vanadic acid calcium and ammonium meta-vanadate; The total solids level of resin of per 100 weight parts (A) and linking agent (B), respectively, vanadium compound (1) is the scope of 3-50 weight part, and ion-exchange silicon-dioxide (2) is the scope of 3-50 weight part, the total amount of the resin of the resin of the phosphoric acid ester group in the resin of phosphoric acid ester group or phosphate group (D) and phosphoric acid salt group is the scope of 1-30 weight part, and corrosion-inhibiting pigment mixture (C) is the scope of 6-100 weight part.

2. coating composition as claimed in claim 1, the filming of wherein said hydroxyl form at least a in the vibrin of the Resins, epoxy that is selected from hydroxyl and hydroxyl of resin (A).

3. coating composition as claimed in claim 1, wherein said linking agent (B) is for being selected from least a in aminoresin, resol and the optional end capped polyisocyanate compound.

4. coating composition as claimed in claim 1, wherein said ion-exchange silicon-dioxide (2) is for being selected from least a in calcium ion-exchanged silicon-dioxide, magnesium ion exchange silicon-dioxide and the cobalt ion exchange silicon-dioxide.

5. coating composition as claimed in claim 1, wherein except that corrosion-inhibiting pigment mixture (C), described coating composition also contains at least a pigment component in corrosion-inhibiting pigment, TiO 2 pigment and the pigment extender that is selected from except that this corrosion-inhibiting pigment mixture (C).

6. coating composition as claimed in claim 1, wherein said coating composition also contain and are selected from least a in UV light absorber and the ultra-violet stabilizer.

7. coating composition as claimed in claim 1, wherein said coating composition makes the filtrate by following preparation have the pH in the 3-8 scope: with under the total solids level of described resin of claim 1 (A) and linking agent (B) at per 100 weight parts respectively the mixture of the vanadium compound (1) of the formation corrosion-inhibiting pigment mixture (C) in described weight part scope and ion-exchange silicon-dioxide (2) join in the sodium chloride aqueous solution of 5 weight % under 25 ℃ of 10000 weight parts, then stirred 6 hours, under 25 ℃, left standstill 48 hours, and filter the supernatant liquor that obtains.

8. metallic sheet with cured coating film, described cured coating film is formed on the surface of metal sheet by the described coating composition of claim 1, the metal surface treatment process that the surface of described metal sheet stands to choose wantonly.

9. one kind has by the film metallic sheet of the multilayer film that constitutes of cured coating film and the face that forms on cured coating film, described cured coating film is formed on the surface of metal sheet by the described coating composition of claim 1, the metal surface treatment process that the surface of described metal sheet stands to choose wantonly.

10. metallic sheet with cured coating film, described cured coating film is formed on two surfaces of metal sheet two-sided by the described coating composition of claim 1, and two surfaces of described metal sheet two-sided stood the metal surface treatment process chosen wantonly respectively.

11. one kind have by cured coating film and on the one side at least of two cured coating films the film metallic sheet of the multilayer film that constitutes of the face that forms, described cured coating film is formed on two surfaces of metal sheet two-sided by the described coating composition of claim 1, and two surfaces of described metal sheet two-sided stood the metal surface treatment process chosen wantonly respectively.