CN101993644B - 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 not metallic sheet with this coating composition of use containing the chromium coating composition 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 due to the photodegradation in outdoor environment and hydrolysis make to film carry out deteriorated after, also effectively improve not only unprocessed planar section in metallic sheet but also the erosion resistance of the part of having processed and edge surface.

Background technology

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

The described article relevant with house are usually by precoat metal plate preparation, for example by comprising the cutting pre-coated steel plate, then stand processing and prepare as the technique of pressing mold and joint.Therefore, the described article relevant with house often have the crackle generation part caused as the metal exposed of cutting surfaces part with due to pressing mold.Described metal exposed part is compared and may be reduced with other parts with the erosion resistance that part occurs 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, from the viewpoint of HUMAN HEALTH and environment protection, result causes problem.

The various chromium corrosion-inhibiting pigments that do not contain are as zinc phosphate, aluminium triphosphate, zinc molybdate etc., commercially available, and proposed the various priming paint that does not contain the combination of chrome pigment that contains.For example, patent documentation 1 discloses by will be by the corrosion-inhibiting pigment mixture constituted of Calucium Silicate powder and vanadic acid phosphorus, or will be added into the carrier component consisted of epoxy resin and resol and the coating composition prepared by the corrosion-inhibiting pigment mixture constituted of calcium carbonate, Calucium Silicate powder, aluminum phosphate 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 coating composition prepared by vibrin by the corrosion-inhibiting pigment mixture that the calcinate of calcium phosphate and vanadium oxide forms.Yet, at patent documentation 1, with the coating composition prepared with using chromium class pigment of filming that in 2, disclosed coating composition forms, compare, 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 often show further 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 the chemical resistant properties of going on business.Therefore, in patent documentation 1 and 2, disclosed corrosion-inhibiting pigment mixture, in the preparation of precoat metal plate, can not replace chromium class corrosion-inhibiting pigment satisfactorily.

Patent documentation 3 discloses the fine particles of silica of the void content by having 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 the cured coating film in 40-125 ℃ of scope of second-order transition temperature.Yet, although formed the filming of disclosed coating composition demonstrates some erosion resistances in patent documentation 3, but the coating composition prepared with using chromium class pigment is compared, show erosion resistance and the poor chemical resistant properties of going on business, in the gratifying especially not erosion resistance of edge surface part.

And, patent documentation 4 discloses a kind of anticorrosion coating composition, the formation resin of filming that said composition contains (A) hydroxyl, (B) linking agent, (C) the corrosion-inhibiting pigment mixture formed by specific vanadium compound, silica dioxide granule and phosphoric acid salt metal-salt, and demonstrate good erosion resistance, 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 deteriorated due to outdoor exposure after in the patience to corrosion reaction, be unsatisfactory aspect 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 not containing chromium coating composition and the metallic sheet that uses this coating composition, the described chromium coating composition that do not contain is for metallic sheet the time, even due to the photodegradation in outdoor environment and hydrolysis make to film carry out deteriorated after, also can form except other unprocessed part, also in the part of having processed and edge surface partial display, going out filming of excellent erosion resistance.

In order to solve the aforementioned problems in the prior, the inventor in depth studies, found a kind of by the corrosion-inhibiting pigment mixture that will be formed by specific vanadium compound and ion-exchange silicon-dioxide, and at least one resin in the resin of the resin of phosphate ester-containing group (phosphate group-containing) and phosphate-containing 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, in outdoor environment during for metallic sheet, can form except other unprocessed planar section, also in the part of having processed and edge surface partial display, going out filming of excellent erosion resistance, result has completed the present invention.

; the invention provides a kind of coating composition; this coating composition contains (A) not formation resin of filming of phosphate ester-containing group, hydroxyl; (B) linking agent; (C) corrosion-inhibiting pigment mixture, and (D) at least one resin [resin (D) that is called hereinafter phosphate ester-containing group or phosphate group] in the resin of the resin of phosphate ester-containing group and phosphate-containing group; Corrosion-inhibiting pigment mixture (C) is by the corrosion-inhibiting pigment mixture constituted as follows: (1) is selected from least one vanadium compound of Vanadium Pentoxide in FLAKES, vanadic acid calcium and ammonium meta-vanadate, and (2) ion-exchange silicon-dioxide; The total solids level of the resin of every 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, in the resin of phosphate ester-containing group or phosphate group (D), the total amount of the resin of the resin of phosphate ester-containing group and phosphate-containing group is the 1-30 weight part, 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, and optional metal surface treatment process is stood on the surface of described metal sheet.

The invention provides and have by the film metallic sheet of the multilayer film that forms 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 aforementioned coating composition, and optional metal surface treatment process is stood on the surface of described metal sheet.

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

The invention provides have by cured coating film and at least one side of two cured coating films the film metallic sheet of the multilayer film that forms 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 respectively optional metal surface treatment process.

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 in the part of having processed and edge surface partial display, go out filming of excellent anticorrosive, these are not difficult to provide containing the chromium anticorrosive coating composition, and in coating composition of the present invention, the resin (D) of contained phosphate ester-containing group or phosphate group plays the effect of strong tackify component, and there is excellent thickening property in sour environment, the improvement of erosion resistance in time in generating chamber's external environment during with specific vanadium compound as the corrosion-inhibiting pigment mixture and the combination of ion-exchange silicon-dioxide.

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

Use the coated metallic sheet of the cured coating film formed by coating composition of the present invention to go out excellent erosion resistance at unprocessed planar section, the part of having processed and edge surface partial display, and compare with the metallic sheet be 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.

Apply, then with the face be formed on described cured coating film, film to apply the metallic sheet prepared by using by the formed cured coating film of coating composition of the present invention, at unprocessed planar section, processing part and edge surface partial display go out excellent erosion resistance.Coating composition of the present invention is coated to metal sheet as coated substrate as on steel plate galvanized or aluminium-zinc alloy coated steel sheet, make it possible to except unprocessed planar section also the edge surface part and 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 phosphate ester-containing group or phosphate group.

Filming of hydroxyl forms resin (A)

In coating composition of the present invention, the film-forming resin of hydroxyl (A) can not be subject to specific limited ground comprise normally used in the coating composition field and have a resin of any hydroxyl of film forming properties, and typically can comprise, such as the resin that is selected from vibrin, epoxy resin, acrylic resin, fluorocarbon resin, vinyl chloride resin etc. of at least one hydroxyl.Be preferably selected from least one organic resin in the epoxy resin 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, such as 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, preferably 2,000～25, number-average molecular weight in 000 scope, the second-order transition temperature (Tg) in 10～100 ℃, preferably 20 ℃～80 ℃ scopes and 2～100mg KOH/g, the preferred interior hydroxyl value of 5～80mg KOH/g scope.

In this manual, the number-average molecular weight of resin is based on the molecular weight of polystyrene standard, the value of calculating in using 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, by Tosoh Corporation, sold 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 consists of the esterification products between polyprotonic acid component and polyol component.The polyprotonic acid component can comprise, as main ingredient, for example be selected from least one 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 above-mentioned acid, can optionally comprise monoprotic acid such as phenylformic acid, β-crotonic acid, p-tert-butyl benzoic acid etc., ternary or more much higher first acid is trimellitic anhydride, tetrahydrotoluene tricarboxylic acid, pyromellitic acid acid anhydride etc. for example.Polyvalent alcohol can comprise, as main ingredient, for example dibasic alcohol is as ethylene glycol, glycol ether, propylene glycol, 1,4-butyleneglycol, neopentyl glycol, 3-methyl pentanediol, 1,4-hexylene glycol, 1,6-hexylene glycol etc., and, except above-mentioned dibasic alcohol, can optionally comprise trivalent alcohol or such as glycerol, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane etc. of more much higher unit's alcohol.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 particularly preferably comprise m-phthalic acid, terephthalic acid and their low alkyl group esterification product.

Synolac is the acid constituents and alkoxide component except above-mentioned oil-free polyester resin, and method itself that can be known according to is by reacting to prepare with fatty acid oil.Fatty acid oil can comprise such as 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%, 5～20% oil length particularly preferably.

Urethane-modified polyester can comprise by the lower molecular weight oil-free polyester resin that makes polyisocyanate compound and above-mentioned oil-free polyester resin or react obtained with the acid constituents that makes to use and alkoxide component in above-mentioned oil-free polyester resin preparation is reacted by known method own the resin prepared.Urethanated alkyd can comprise that the method known by itself by the low-molecular-weight Synolac that makes polyisocyanate compound and above-mentioned Synolac or obtain with each component reaction that makes to use in above-mentioned Synolac preparation reacted the resin prepared.The polyisocyanic acid compound used 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-, tri-isocyanide acyl toluene etc.Urethane-modified resin can preferably include the resin of the modification degree that amount with the polyisocyanate compound that forms urethane-modified resin is the amount below 30 % by weight based on urethane-modified resin.

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

Acrylic acid modified polyester resin can comprise: the vibrin prepared by each component 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 acrylic acid modified polyester resin, with respect to acrylic acid modified polyester resin, the amount of preferred acrylic resins is 0.1～50 % by 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 epoxy resin of resin as filming of hydroxyl, can comprise bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin; And by modified epoxy prepared by epoxy group(ing) in various properties-correcting agent and above-mentioned epoxy resin or hydroxyl reaction.In the preparation of modified epoxy, any stage that can prepare at epoxy resin by the modification of using properties-correcting agent and the terminal stage prepared at epoxy resin are carried out, and are not particularly limited.

Bisphenol-type epoxy resin for example can comprise, optionally at catalyzer, under the existence as alkaline catalysts, makes epoxy chloropropane and bis-phenol stand resin prepared to have high molecular by condensation reaction; With optional, at catalyzer, under the existence 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 epoxy resin can comprise various phenolic resin varnish type epoxy resins, such as phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, phenol glyoxalic type epoxy resin etc.

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

Linking agent (B)

The filming of linking agent (B) and hydroxyl forms resin (A) and react to form cured coating film, and can comprise and can form resin (A) reaction by filming of hydroxyl for example curing linking agent is not particularly limited by heating.Wherein, preferably aminoresin and the optionally polyisocyanate compound of end-blocking.These linking agents may be used singly or in combin.

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

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

Be used as the phenol component of parent material in resole preparation, 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 are as ortho-cresol, p-cresol, p-tert-butylphenol, p-ethyl phenol, 2,3-xylenol, 2,5-xylenol etc., the three-functionality-degree phenolic compound is as phenylic acid, meta-cresol, m-ethylphenol, 3,5-xylenol, meta-methoxy phenol etc., four functionality oxybenzene compounds are 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 separately a kind of or be used in combination.

The aldehydes used in the resol preparation can comprise formaldehyde, paraformaldehyde, trioxane etc., and can use separately a kind of or be used in combination.

The alcohol used in the methylol groups alkyl etherificate by methylolation resol, can preferably include there is 1～8, the preferably monohydroxy-alcohol of 1～4 carbon atom, particularly preferably methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, isopropylcarbinol etc.

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

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

Blocked polyisocyanates compound as linking agent is compound prepared by the free isocyanate groups end-blocking by making with end-capping reagent in polyisocyanate compound.The end-capping reagent used in end-blocking isocyanide acyl group, can comprise such as phenols as phenol, cresols, xylenol etc.; Lactams is as 'epsilon '-hexanolactam, δ-Valerolactim, butyrolactam etc.; Alcohols is as methyl alcohol, ethanol, n-, exclusive OR uncle-butanols, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, phenylcarbinol etc.; Oximes is as formamidoxime, ethylidenehydroxylamine, acetoxime, methyl ethyl ketone oxime, Diacetylmonoxime, diphenylketoxime, cyclohexanone-oxime etc.; And the active methylene group end-capping reagent is as dimethyl malonate, diethyl malonate, methyl aceto acetate, Acetyl Acetone etc.Polyisocyanate compound is with make mixing of end-capping reagent can be easily by 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 the component (A) that makes every 100 weight parts and total solids component (B), it is that 55～95 weight parts, the preferably scope of 60～95 weight parts, and linking agent (B) are 5～45 weight parts, the preferred scope of 5～40 weight parts that the filming of hydroxyl forms resin (A).

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

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

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

In the situation that linking agent (B) is the blocked polyisocyanates compound, the curing catalysts that preferably 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 such as 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.

In the situation that linking agent (B) is two or more linking agent combination, 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 coating composition of the present invention is the corrosion-inhibiting pigment mixture consisted of (1) vanadium compound and (2) ion-exchange silicon-dioxide.

Vanadium compound (1)

Vanadium compound (1) can comprise at least one vanadium compound be selected from Vanadium Pentoxide in FLAKES, vanadic acid calcium and 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 discharged from vanadium compound (1) due to substrate metal react or with the reacting of the ion discharged from other corrosion-inhibiting pigment mixture, effective to the improvement of erosion resistance.

Ion-exchange silicon-dioxide (2)

Ion-exchange silicon-dioxide (2) be by adopt ion-exchange by positively charged ion as calcium ion is incorporated into carefully, the silicon-dioxide fine particle that obtains on the silica supports of porous.Ion-exchange silicon-dioxide can comprise such as calcium ion-exchanged silicon-dioxide, magnesium ion exchange silicon-dioxide, cobalt ion exchange silicon-dioxide etc.

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

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

the resin of phosphate ester-containing group or phosphate group (D)

In the resin (D) of phosphate ester-containing group or phosphate group, the resin of phosphate ester-containing group can comprise phosphate ester-containing group [OPO (OH) (OR ¹)] resin, R wherein ¹mean hydrogen atom, phenyl or there is the alkyl of 1-20 carbon atom, hydrogen atom and there is the alkyl of 1-20 carbon atom particularly, and can comprise with filming of hydroxyl and form resin (A) resin compatible with linking agent (B), such as the acrylic resin of phosphate ester-containing group, the epoxy resin of phosphate ester-containing group, the vibrin of phosphate ester-containing group etc.

The acrylic resin of phosphate ester-containing group can obtain by the unsaturated monomer by the phosphate ester-containing group and other polymerisable unsaturated monomer copolymerization.

The unsaturated monomer of phosphate ester-containing 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 unsaturated monomer such as (methyl) glycidyl acrylate containing epoxy group(ing) etc. etc. mole affixture; Kayamer PM-2, Kayamer PM-21 (trade(brand)name, by Nippon Kayaku company, sold 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.

With the unsaturated monomer copolymerization of phosphate ester-containing group and other polymerisable unsaturated monomer of forming the acrylic resin of phosphate ester-containing group, can comprise, for example, the unsaturated monomer of hydroxyl is 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 is as vinylbenzene, alpha-methyl styrene, Vinyl toluene, α-chloro-styrene etc.; the 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 phosphate ester-containing group can also by phosphate compounds is added to containing the unsaturated monomer of epoxy group(ing) for example the copolymer resin of (methyl) glycidyl acrylate and above-mentioned other polymerisable unsaturated monomer obtain.Phosphate compounds for addition can comprise, such as ortho-phosphoric acid, phosphate ester acid etc.Phosphate ester acid can comprise above illustrative phosphate ester acid.

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

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

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

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

The metallic compound reacted with bound phosphate groups can comprise such as calcium oxide, magnesium oxide, cobalt oxide, nickel oxide, zinc oxide, cerium oxide, lanthanum trioxide etc.

Bound phosphate groups or phosphate group in the resin of phosphate ester-containing 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 the resin of every 100 weight parts (A) and linking agent (B), coating composition of the present invention preferably contains respectively the vanadium compound (1) of 3-50, preferred 5-40 weight part scope, the ion-exchange silicon-dioxide (2) of 3-50, preferred 3-30 weight part scope, 1-30, preferably the phosphate ester-containing group of 1-20 weight part scope or the resin (D) of phosphate group, and 6-100, the preferred corrosion-inhibiting pigment mixture (C) of 10-60 weight part scope.

According to coating composition of the present invention, the vanadium compound (1) of the specified amount separately in 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 phosphate ester-containing group or phosphate group.

Water-soluble from vanadium compound (1) and ion-exchange silicon-dioxide (2), reactivity between corrosion-inhibiting pigment lysate and metal sheet, and erosion resistance viewpoint, hope has 3-8 by the filtrate be prepared as follows, the preferred pH of 5-8 scope: by the total solids level of the resin of every 100 weight parts (A) 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 % by weight under 25 ℃ of 10000 weight parts, then stirred 6 hours, under 25 ℃ standing 48 hours, and filter the supernatant liquor obtained.

; standing the filtrate that pH measures is the filtrate by being prepared as follows: the total solids level by the resin by every 100 weight parts (A) and linking agent (B) under 25 ℃ is respectively the mixture of ion-exchange silicon-dioxide (2) of the amount of the vanadium compound (1) of the amount of 3-50 weight part and 3-50 weight part; join in the sodium chloride aqueous solution of 10000 weight part 5 % by weight; then dissolved, and filtered the solution produced.

Except the resin (D) and the optional curing catalysts used of film-forming resin (A), solidifying agent (B), corrosion-inhibiting pigment mixture (C), phosphate ester-containing group or the phosphate group of hydroxyl, coating composition of the present invention can optionally contain tinting pigment, pigment extender, UV light absorber, ultra-violet stabilizer, organic solvent; The known additives that use in the coating composition field such as additive such as antisettling agent, defoamer, painting face control agent.

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

Pigment extender can comprise, such as talcum, clay, mica, aluminum oxide, calcium carbonate, barium sulfate etc.

UV light absorber can comprise, for example, benzotriazole derivatives is as 2-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl)-2H-benzotriazole, iso-octyl-3-(3-(2H-benzotriazole-2-yl)-5-tert-butyl-hydroxy phenyl) propionic ester, 2-[2-hydroxyl-3, 5-bis-(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 is as 2-[4-(2-hydroxyl-3-dodecyl oxygen propyl group)-oxygen]-2-hydroxy phenyl-4,6-bis-(2,4-3,5-dimethylphenyl-1,3,5-1,3,5-triazine etc., the oxanilide derivative is 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.

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

The organic solvent used in coating composition of the present invention can comprise the optional solvent of ground for the coating property of improving coating composition of the present invention that add, can dissolve or disperse the film-forming resin (A) of hydroxyl and the solvent of linking agent (B), and concrete example as, varsol is as toluene, dimethylbenzene, high point petroleum class hydrocarbon etc., ketones solvent is as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, isophorone etc., esters solvent is as ethyl acetate, butylacetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetic ester etc., alcoholic solvent is as methyl alcohol, ethanol, Virahol, butanols etc., the ether alcohol kind solvent is as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether etc.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 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 manufactures), the variation of the tan δ measured by the temperature dispersion at frequency 110Hz place and definite maximum temperature.

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

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

The second reason is: except the caused effect of the positively charged ion owing to emitting in corrosive environment, also due to the effect of its lip-deep slightly acidic functional group, ion-exchange silicon-dioxide plays the effect that the pH of the wetting environment with approaching in slightly acidic value corrosive environment is controlled consumingly, promote the redox reaction between pentavalent vanadium ion and substrate metal, and further this ion-exchange silicon-dioxide be fixed on film in and the long-term pH retentive control ability to being corroded under corrosive environment, and sacrifice property ground keeps being hydrolyzed under the stronger environment corroded, discharge silicate ion.

The 3rd reason is: in the situation that coated steel plates, although filming, face may become hydrophilic due to deteriorated, and the unprocessed planar section that the material of various promotion corrosion may be filmed from face sees through, but the resin of phosphate ester-containing group or phosphate group (D) plays a role as strong tackify component and has an effect of filming and peeling off near the anode suppressed part that corrosion carries out in sour environment, and in can be effectively and the hydroxyl that in negative electrode, the reduction reaction of oxygen produces and the pH produced can be kept approach neutrality.

Bound phosphate groups and the phosphate group of the resin of phosphate ester-containing group or phosphate group (D) can provide the effect that the pH of environment is remained on to the slightly acidic value.

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

The composition of the vanadium compound (1) of formation corrosion-inhibiting pigment mixture (C) and the resin (D) of ion-exchange silicon-dioxide (2) and phosphate ester-containing group or phosphate group is used, and makes it possible to effectively overcome vanadium compound (1), ion-exchange silicon-dioxide (2) and the phosphorus performance containing the difference of 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 phosphate ester-containing group or phosphate group produces excellent erosion resistance.

, 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 of the effective coated substrate exposure of corrosion-inhibiting pigment mixture (C) component by being formed by vanadium compound (1) and ion-exchange silicon-dioxide (2), also the resin (D) by phosphate ester-containing group or phosphate group is suppressed in sour environment the effect of filming and peeling off near the anode corroded carrying out partly, together with the effect as strong tackify component, even due to the photodegradation in outdoor environment and hydrolysis make to film carry out deteriorated after, also effectively improve the erosion resistance of the not only unprocessed planar section in metallic sheet but also the part of having processed and edge surface part.

metallic sheet

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

The 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, in alloy containing having an appointment " the galvanized iron alloy annealed sheet steel " of 5% aluminium, etc.), nickel-zinc alloy coated steel sheet, stainless steel plate, aluminium sheet, copper coin, Copper Plated Steel, tin plate etc.These metal sheets can optionally stand conventional metal surface treatment process, such as phosphatizing technique as zinc phosphate treatment process, tertiary iron phosphate treatment process etc., combined oxidation membrane treatment process, chromium phosphatizing technique, chromic salt treatment process etc.

Coating composition of the present invention can be coated on metal sheet by conventional cladding process such as rolling method, curtain formula flow coat method, spraying method, spread coating, dip coating etc.The thickness of filming 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 resin used, but, in the situation that 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 batch process can be carried out 10-30 minute usually under the envrionment temperature of 80-200 ℃.

In the situation that do not need heating in the crosslinking reaction of formation while filming, for example, in the situation that the polyisocyanate compound that uses end-blocking not as solidifying agent (B) or use bisphenol-type epoxy resin as resin (A) and use amine compound as linking agent (B), drying can at room temperature be cured according to conventional methods.

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

The coating materials composition that formation face is filmed can comprise for the obtainable composition of the routine of precoat metal plate, for example, polyester resin, Synolac class, silicon modified polyesters resene, organosilicon-modified acrylic resinoid class, fluorocarbon resin borne overcoating material composition.In the very important situation of processing characteristics, use the coating materials composition with excellent machinability for example for the vibrin borne overcoating material composition of processing highly, make it possible to the metallic sheet that acquisition has good especially processing characteristics.There is the metallic sheet that above-mentioned face films in the present invention and demonstrate good film properties on erosion resistance.

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

Filming of being formed by coating composition of the present invention can be formed on the two-sided upper of base material, and on optional face films and can be formed on and film by coating composition of the present invention is formed.Form and film by coating composition of the present invention on the two sides that comprises the back side of base material, 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.

Embodiment

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

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 under 60 ℃, react 3 hours, under vacuum, at 50 ℃, dewater 1 hour, add 100 parts of propyl carbinols and 3 parts of phosphoric acid, under 110～120 ℃, reaction is 2 hours, the solution filter generated, the sodium phosphate that leaches generation be take and obtained solids content as about 50% resole cross-linking agent solution B1.The resin as above obtained 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 preparation of coating composition for the back side:

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 dissolve 80 parts of jER 1009 (trade(brand)names, 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 (with solid, divide and count 20 parts) Desmodur BL-3175 (trade(brand)names, Sumika Bayer Urethane Co., Ltd. sell, the HDI isocyanuric acid ester type polyisocyanate compound solution of methyl ethyl ketone oxime end-blocking, solids content approximately 75%) and 2 parts of TakenateTK-1 (trade(brand)names, Takeda Pharmaceutical Company Limited sells, organic tin end-capping reagent dissociation catalyst, solids content approximately 10%), evenly mix, add mixed solvent 2 and by viscosity controller at about 80sec (Ford Cup#4/25 ℃), to obtain back side coating composition.

The preparation of the resin of phosphate ester-containing group or phosphate group:

Preparation example 3

The preparation of the acrylic resin 1 of phosphate ester-containing group

The 100 parts of butanols of packing in reaction vessel, then in 3 hours, drip 50 parts of vinylbenzene, 35 parts of 2-Ethylhexyl Methacrylates, 15 parts of glycidyl methacrylate and 2.0 part 2,2 '-mixture of Diisopropyl azodicarboxylate, temperature of reactor is remained on to 110 ℃ simultaneously.

Then, add 0.5 part 2,2 '-Diisopropyl azodicarboxylate, then under 110 ℃, react 2 hours, temperature of reactor is remained on to 80 ℃, slowly add 85% ortho-phosphoric acid of 12.2 parts and 10.4 parts of butanols and react 1 hour, until the turbidity disappeared of the mixture produced in reactor is with acrylic resin 1 solution of the phosphate ester-containing group that obtains having 50% solids content.The acrylic resin 1 of phosphate ester-containing group divides the resinous acid value with 54 (with bound phosphate groups content meter 0.096 equivalent/100g resin) as solid.

Preparation example 4

The preparation of the acrylic resin 2 of phosphate ester-containing group

The 100 parts of butanols of packing in reaction vessel, then in 3 hours, drip 53 parts of vinylbenzene, 40 parts of 2-Ethylhexyl Methacrylates, 7 parts of glycidyl methacrylate and 2.0 part 2,2 '-mixture of Diisopropyl azodicarboxylate, temperature of reactor is remained on to 110 ℃ simultaneously.

Then, add 0.5 part 2,2 '-Diisopropyl azodicarboxylate, then under 110 ℃, react 2 hours, temperature of reactor is remained on to 80 ℃, slowly add 85% ortho-phosphoric acid of 5.7 parts and 4.9 parts of butanols and react 1 hour, until in reactor the turbidity disappeared of the mixture that produces with acrylic resin 2 solution of the phosphate ester-containing group that obtains having 50% solids content.The acrylic resin 2 of phosphate ester-containing group divides the resinous acid value with 26 (with bound phosphate groups content meter 0.047 equivalent/100g resin) as solid.

Preparation example 5

The preparation of the acrylic resin 3 of phosphate ester-containing group

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

Then, add 0.5 part 2,2 '-Diisopropyl azodicarboxylate, then under 110 ℃, react 2 hours, temperature of reactor is remained on to 80 ℃, slowly add 85% ortho-phosphoric acid of 25 parts and 17 parts of butanols and react 1 hour, until the turbidity disappeared of the mixture produced in reactor is with acrylic resin 3 solution of the phosphate ester-containing group that obtains having 50% solids content.The acrylic resin 3 of phosphate ester-containing group divides the resinous acid value with 98 (with bound phosphate groups content meter 0.17 equivalent/100g resin) as solid.

Preparation example 6

The preparation of the epoxy resin of phosphate ester-containing 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 stirred and under 70 ℃ heating with by this resin dissolves, 85% ortho-phosphoric acid that adds 5.76 parts, under 70 ℃, reaction is 2 hours, and adds 4 parts of pimelinketone to obtain the epoxy resin solution of 50% phosphate-containing group.The resin of phosphate ester-containing group divides the resinous acid value with 28 (with bound phosphate groups content meter 0.05 equivalent/100g resin) as solid.

Preparation example 7

The preparation of the acrylic resin of phosphate-containing group

Acrylic resin 1 solution and the 5 parts of calcium oxide that pulverize in mortar that add 50% solids content obtained in 100 parts of (with solid, divide and count 50 parts) preparation examples 3 in solid Glass Containers, the glass beads of then packing into, with Skandex (trade(brand)name, by Mitsuwa-Tech Ltd. sell, agitator) disperseed, until this resin solution bleach, at room temperature standing 48 hours, and remove glass beads to obtain the acrylic resin solution of phosphate-containing group.

The preparation of ion-exchange silicon-dioxide

Preparation example 8

The preparation of magnesium ion exchange silicon-dioxide

To the Sylysia710 that adds 10 weight parts in 10000 weight part 5 % by weight magnesium chloride brines (trade(brand)name, by Fuji Silysia Chemical Ltd. sale, silicon-dioxide fine particle, the about 105ml/100g of oil number), under then stirring, mixed 5 hours, filtering and remove solid divides, water fully washs this solid and divides, and carries out drying to obtain magnesium ion exchange silicon-dioxide.

Preparation example 9

The preparation of cobalt ion exchange silicon-dioxide

To the Sylysia710 that adds 10 weight parts in 10000 weight part 5 % by weight cobalt chloride solutions (trade(brand)name, by Fuji Silysia Chemical Ltd. sale, silicon-dioxide fine particle, the about 105ml/100g of oil number), under then stirring, mixed 5 hours, filtering and remove solid divides, water fully washs this solid and divides, and carries 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 dissolve 85 parts of jER 1009 (trade(brand)name, Japan Epoxy Resins Co.Ltd. sale, bisphenol A type epoxy resin, hydroxy-containing resin) and the epoxy resin solution of preparation and 5 parts of Vanadium Pentoxide in FLAKESs, 3 parts of Shieldex AC-3 (trade(brand)name, W.R.Grace & 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, be down 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 HDI isocyanuric acid ester type polyisocyanate compound solution of methyl ethyl ketone oxime end-blocking, solids content approximately 75%), acrylic resin 1 solution of the phosphate ester-containing group obtained in 4 parts of (with solid, divide and count 2 parts) preparation examples 3, 2 parts of Takenate TK-1 (trade(brand)names, Takeda PharmaceuticalCompany Limited sells, organic tin end-capping reagent dissociation catalyst, solids content approximately 10%), evenly mix, add mixed solvent 2 and by 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 table 1.Reference example 1 and 2 means the conventional anticorrosive coating composition that contains chromium class corrosion-inhibiting pigment.In table 1, the resin of each hydroxy-containing resin, linking agent, phosphate ester-containing group or phosphate group and the amount of pigment component mean with solid weight content.Condition is, embodiment 15 does not contain in Takenate TK-1 (trade(brand)name as hereinbefore defined) and embodiment 16 and 19 and contains respectively 1 part of Nacure 5225 (trade(brand)name, sold the amine neutralization solution of Witco 1298 Soft Acid by USKing Industries Ltd.) and replace the Takenate TK-1 of 2 parts.

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

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

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

(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, solid divide 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 & 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 and solidify according to following coating explanation 1-3, 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 (thickness of slab 0.35mm, aluminium-zinc alloy coated steel sheet, the aluminium content in alloy approximately 55%, plating alloy amount 150g/m with coating composition ², be expressed as the GL steel plate in table 2) on, form the thick dry film of 8 μ m, then under the maximum base material temperature of 180 ℃, solidify and film to form the back side in 30 seconds, on the steel plate surface contrary with thering is the back side of filming at the back side that each anticorrosive coating composition that will obtain in the above-described embodiments with excellent coating machine is coated to this steel plate, form the thick dry film of 5 μ m, then under the maximum base material temperature of 220 ℃, solidify 40 seconds to obtain each bottom coating, cooling and apply KP Color 1580B40 (trade(brand)name with excellent coating machine, by Kansai Paint Co., Ltd. sell, polyester coating materials composition, blue, approximately 70 ℃ of the second-order transition temperatures of cured coating film) to each bottom coating, form the approximately thick dry film of 15 μ m, and solidify 40 seconds to obtain each coated test panel under the maximum base material temperature of 220 ℃.

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 zinc-plated amount 250g/m that has stood metal surface treatment process with coating composition ², be expressed as the GI steel plate in table 2) on, form the thick dry film of 8 μ m, then under the maximum base material temperature of 180 ℃, solidify and film to form the back side in 30 seconds, on the steel plate surface contrary with thering is the back side of filming at the back side that each anticorrosive coating composition that will obtain in the above-described embodiments with excellent coating machine is coated to this steel plate, form the thick dry film of 5 μ m, then under the maximum base material temperature of 220 ℃, solidify 40 seconds to obtain each bottom coating, cooling and apply KPColor 1580B40 (trade(brand)name with excellent coating machine, by Kansai Paint Co., Ltd. sell, polyester coating materials composition, blue, approximately 70 ℃ of the second-order transition temperatures of cured coating film) to each bottom coating, form the approximately thick dry film of 15 μ m, and solidify 40 seconds to obtain each coated test panel under the maximum base material temperature of 220 ℃.

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 the maximum base material temperature of 180 ℃, solidify and film to form the back side in 30 seconds, on the steel plate surface contrary with thering is the back side of filming at the back side that each anticorrosive coating composition that will obtain in the above-described embodiments with excellent coating machine is coated to this steel plate, form the thick dry film of 5 μ m, then under the maximum base material temperature of 220 ℃, solidify 40 seconds to obtain each bottom coating, cooling and apply KPColor 1580B40 (trade(brand)name with excellent coating machine, by Kansai Paint Co., Ltd. sell, polyester coating materials composition, blue, approximately 70 ℃ of the second-order transition temperatures of cured coating film) to each bottom coating, form the approximately thick dry film of 15 μ m, and solidify 40 seconds to obtain each coated test panel under the maximum base material temperature of 220 ℃.

the film performance test

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

test method

Resistance to boiling water: will cut in the boiling water that each coated test panel that is of a size of 5cm * 10cm immerses approximately 100 ℃ 2 hours, and then take out the outward appearance of filming formed to estimate on the face side that applies panel, and stand respectively cross cut band method to estimate.Described cross cut band method is defined as JIS K-5400 8.5.2 (1990).That is, with cutting interval 1mm and 100 grids, bonding glass paper tape is adhered to the face side of each coated test panel, then firmly peel off as follows this with to estimate filming with grid.

◎: there is no abnormal for example bubble and the generation of albefaction, residual 100 grids on filming.

Zero: there is no abnormal for example bubble and the generation of albefaction, a residual 91-99 grid on filming.

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

*: on filming, there is a large amount of or significant bubble to occur, or residual 70 grids or still less.

Alkali resistance:

The back side and the cutting surfaces that will cut into each coated test panel that is of a size of 5cm * 10cm seal with anticorrosive coating composition, and form in the face side central authorities that apply panel the cross cut that arrives base material.The coating panel that obtains is immersed in 5% the aqueous sodium hydroxide solution of 40 ℃ 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 with estimate obtain film in peel off width (side) from cross cut part.

◎: there is no Bubble formation, from the band of cutting part, peeling off width is below 1.5mm.

Zero: there is no Bubble formation, from the band of cutting part, peel off that width is greater than 1.5mm but below 3mm.

△: slight Bubble formation being arranged, from the band of cutting part, peel off width is below 3mm, or there is no Bubble formation, peels off width from the band of cutting part and is greater than 3mm.

*: Bubble formation is arranged, peel off width from the band of cutting part and be greater than 3mm.

Acid resistance:

The back side and the cutting surfaces that will cut into each coated test panel that is of a size of 5cm * 10cm seal with anticorrosive coating composition, and form in the face side central authorities that apply panel the cross cut that arrives base material.The coating panel obtained is immersed in 5% the aqueous sulfuric acid of 40 ℃ to 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 with estimate obtain film in peel off width (side) from cross cut part.

◎: there is no Bubble formation, from the band of cutting part, peeling off width is below 1.5mm.

Zero: there is no Bubble formation, from the band of cutting part, peel off that width is greater than 1.5mm but below 3mm.

△: slight Bubble formation being arranged, from the band of cutting part, peel off width is below 3mm, or there is no Bubble formation, peels off width from the band of cutting part and be greater than 3mm.

*: Bubble formation is arranged, peel off width from the band of cutting part and be greater than 3mm.

The scratch resistance trace:

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

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

Zero: in the cut part, expose slightly substrate metal.

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

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

The composite anticorrosive test:

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

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

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

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

◎: white rust does not occur, or white rust occurs, be less than 5mm.

Zero: white rust occurs, be greater than 5mm but be less than 20mm.

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

*: white rust is more than 40mm, or red rust occurs.

Edge section: determine that the mean value of edge creep width of left and right two long sides the generation that checks red rust are to be estimated as follows.

◎: be less than 5mm and red rust does not occur.

Zero: 5mm is above but be less than 10mm and red rust does not occur.

△: 10mm is above but be less than 20mm and red rust does not occur.

*: more than 20mm, or red rust occurs.

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

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

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

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

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

Unprocessed planar section:

To with unprocessed planar section in occur discontinuous of the part place that separates, the edge of continuous corrosion part and the bubble distributed, estimated as follows.

◎: there is no bubbling.

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

△: bubble diameter: the above and number of bubbles of about 2mm: be less than 10, or bubble diameter: be 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. a coating composition, this coating composition contains (A) not formation resin of filming of phosphate ester-containing group, hydroxyl, (B) linking agent, (C) corrosion-inhibiting pigment mixture, and (D) at least one resin in the resin of the resin of phosphate ester-containing group and phosphate-containing group; Described corrosion-inhibiting pigment mixture (C) is by the following corrosion-inhibiting pigment mixture constituted: (1) is selected from least one vanadium compound of Vanadium Pentoxide in FLAKES, vanadic acid calcium and ammonium meta-vanadate, and (2) ion-exchange silicon-dioxide; The total solids level of the resin of every 100 weight parts (A) and linking agent (B), the scope that resin (A) is the 55-95 weight part, the scope that linking agent (B) is the 5-45 weight part, respectively, the scope that vanadium compound (1) is the 3-50 weight part, and ion-exchange silicon-dioxide (2) scope that is the 3-50 weight part, the scope that the total amount of the resin of the phosphate ester-containing group in the resin of phosphate ester-containing group or phosphate group (D) and the resin of phosphate-containing group is the 1-30 weight part, and corrosion-inhibiting pigment mixture (C) scope that is the 6-100 weight part.

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

3. coating composition as claimed in claim 1, wherein said linking agent (B) is at least one in the polyisocyanate compound that is selected from aminoresin, resol and optional end-blocking.

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

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

6. coating composition as claimed in claim 1, wherein said coating composition also contains at least one being selected from UV light absorber and 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: by under the total solids level of the resin at every 100 weight parts claimed in claim 1 (A) and linking agent (B) 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 % by weight under 25 ℃ of 10000 weight parts, then stirred 6 hours, under 25 ℃ standing 48 hours, and filter the supernatant liquor obtained.

8. the metallic sheet with cured coating film, described cured coating film is formed on the surface of metal sheet by coating composition claimed in claim 1, and optional metal surface treatment process is stood on the surface of described metal sheet.

9. one kind has by the film metallic sheet of the multilayer film that forms 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 coating composition claimed in claim 1, and optional metal surface treatment process is stood on the surface of described metal sheet.

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

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