CN101875794A - The method that is used for stabilizing metal pigments against gassing - Google Patents

Abstract

The present invention relates to a kind of deactivation matter that is applicable to passivating metallic surfaces.This deactivation matter comprises a kind of following polymkeric substance that comprises: (a) at least one nitro, and/or pyridine group, and/or phenolic hydroxyl group; (b) at least one is selected from phosphorus-containing groups and/or carboxylic acid group's group, and wherein this at least one phosphorus-containing groups is selected from the phosphonate radical that phosphate radical, orthophosphite or non-nitrogen replace.

Description

The method that is used for stabilizing metal pigments against gassing

Technical field

The application is dividing an application of Chinese invention patent application 200580022080.X.The present invention relates to a kind of polymerizable compound that has corrosion or hydrolysis inhibitor and surface-modifying agent effect concurrently that can be used as Metal Flake pigment.The invention still further relates to the coating composition that comprises these treated metallic pigment.

Background technology

Metal Flake pigment, for example aluminum slice pigment is widely used in decorative paint, for this coating provides metal effect.This metal effect is subjected to needing the welcome of the user in the automobile market of " glamour is covered with paint, lacquer, colour wash, etc. (glamourfinishes) " especially.

Automotive coatings can be used single even pigmented layer.As selection, they can have two different layers, i.e. the first highly colored layer (undercoat) and coating less or do not have painted coating (Clear coating) on it.This two-layer coating is called as " basecoat/clearcoat layers " in industry.The coating of " basecoat/clearcoat layers " has been introduced the glossiness and the color depth of higher degree, can produce welcome especially outward appearance.Metal Flake pigment is usually added in the bottom coating composition.

Because worry the discharging of organic solvent in the application and the course of processing, the automobile finish of water-based is obtaining to use widely in automotive industry.Yet the shortcoming of water-miscible paint is that the medium of its use can the corroding metal lamellar pigment.The hydrolysis of metallic pigment for example, can take place in water-miscible paint.In addition, the pH value scope of water-borne acrylic type coating composition can be 8.0～9.0 usually, and the pH value scope of common polyurethane coating composition can be 7.5～8.0.In alkaline pH value environment, aluminium pigment can be oxidized.Oxidation is exactly a kind of form of corrosive, can destroy mirror like particulate metal coloring character.When the paint application that has oxidized Metal Flake pigment on matrix the time, this coating can show fades, and its metal effect also can weaken.

In addition, the hydrolysis of metallic surface or oxidation meeting cause producing hydrogen in the water-miscible paint.The amount that produces hydrogen has shown the oxidation of metallic pigment (or corrosion) degree.If this coating composition is stored in the closed container, hydrogen can be accumulated under pressure.

Because continue the pH value environment of the alkalescence of contact coating composition, the hydrolysis meeting of aluminium pigment was quickened along with the time in the presence of water.The coating composition of containing metal lamellar pigment can store 6 months or the longer time usually before using, can cause the pigment obvious corrosion like this.If this corrosion continues not discovered, can cause this coating composition not use.

In industry,, carried out considerable effort in order to handle or the corrosion of " passivation " metallic pigment surface to prevent from water-based paint compositions, to cause by water.For example, the known surface of aluminium pigment that chromiumcoating is applied to is to prevent the generation of top described corrosion and hydrogen.Yet chromium is virose, and therefore the metallic pigment particle for this chromium coating need carry out special operational and treatment procedures.

Therefore, provide a kind of passive metal pigment and reduce simultaneously or the coating composition of eliminating existing at least some problems of known passivation technology fully is very useful of can being used for.

Summary of the invention

In one embodiment, the present invention relates to a kind of polymkeric substance that is applicable to passivating metallic surfaces.This polymkeric substance comprises (a) at least one nitro, and/or the pyridine group, and/or phenolic hydroxyl group; (b) at least one is selected from phosphorus-containing groups and/or carboxylic acid group's group, and wherein this at least one phosphorus-containing groups is selected from the phosphonate radical that phosphate radical, orthophosphite or non-nitrogen replace.

And, the invention provides a kind of metallic pigment of passivation, it comprises at least a metallic pigment particle and a kind of deactivation matter that forms on this at least a metallic pigment particulate at least a portion.This deactivation matter can comprise a kind of polymkeric substance, and this polymkeric substance comprises (a) at least one nitro, and/or the pyridine group, and/or phenolic hydroxyl group; (b) at least one is selected from phosphorus-containing groups and/or carboxylic acid group's group, and wherein this at least one phosphorus-containing groups is selected from the phosphonate radical that phosphate radical, orthophosphite or non-nitrogen replace.

In another embodiment, the present invention relates to a kind of coating composition, it comprises diluent media, film-forming polymer and at least a with the deactivation matter metallic pigment particle crossed of partially disposed at least.This deactivation matter can comprise a kind of polymkeric substance, and this polymkeric substance comprises (a) at least one nitro, and/or the pyridine group, and/or phenolic hydroxyl group; (b) at least one is selected from phosphorus-containing groups and/or carboxylic acid group's group, and wherein this at least one phosphorus-containing groups is selected from the phosphonate radical that phosphate radical, orthophosphite or non-nitrogen replace.

Another embodiment provides a kind of coating composition, and it comprises aqueous diluent medium, film-forming polymer and at least a with the deactivation matter metallic pigment particle crossed of partially disposed at least.This deactivation matter can comprise a kind of polymkeric substance that comprises the reaction product of following reactant: the diglycidyl ether of polyvalent alcohol, contain nitro-compound, be selected from least a nitro-compound that contains in the compound that contains alkyl, aryl and/or alkaryl nitro; And P contained compound, comprise the phosphonate radical that phosphate radical and/or non-nitrogen replace.

The present invention also provides a kind of method of passivating metallic surfaces, and it comprises makes this metallic surface contact with a kind of deactivation matter.This deactivation matter comprises a kind of polymkeric substance, and this polymkeric substance comprises (a) at least one nitro, and/or the pyridine group, and/or phenolic hydroxyl group; (b) at least one is selected from phosphorus-containing groups and/or carboxylic acid group's group, and wherein this at least one phosphorus-containing groups is selected from the phosphonate radical that phosphate radical, orthophosphite or non-nitrogen replace.

Embodiment

All be appreciated that the modification that adds term " about " in all cases at the numeral of these used all expression sizes of in specification sheets and claims, using, physical properties, processing parameter, component concentration, reaction conditions etc.Therefore, unless point out on the contrary, in following specification sheets and claims given numerical value can be according to the present invention the desired character that obtains different and changing.At bottom line, and be not used in the scope that the application of Equivalent principle is defined as claim, each numerical value all should be at least makes an explanation by using common rounding method according to the value of the significant figure of being reported.And all scopes in this announcement all are appreciated that starting point and the end point values that comprises scope, comprise arbitrarily and all are included in wherein among a small circle.For example, certain scope " 1～10 " should be considered to comprise any of (being included) between minimum value 1 and the maximum value 10 and all among a small circle; Promptly all are initial with the minimum value more than or equal to 1, and be less than or equal to that 10 maximum value finishes all among a small circle, for example 5.5～10,3.7～6.4, or 1～7.8, these also only mention seldom several examples.In this used molecular weight quantity,, all can use polystyrene to obtain by gel permeation chromatography as canonical measure no matter be Mn or Mw.And, the term " polymer " shown in it " comprise oligopolymer, homopolymer and multipolymer.Term " surface modification " and " modified surface " comprise all and any between metallic surface and compound or composition according to disclosed invention carry out in conjunction with, interact or reaction.Term " passivation " represents all that with " deactivation method " this surface has been modified to reduce it corrodes and/or generate hydrogen when contacting with water trend.All reference of being mentioned in this file all are appreciated that all to include and are used for reference.As used herein term " non-nitrogen substituted phosphonates " mean as shown in the formula group:

R wherein ₁It is any group that does not comprise nitrogen.

Being applicable to that deactivation matter of the present invention generally includes contains at least two substituent polymkeric substance.In a kind of embodiment of indefiniteness, first substituting group can comprise at least one nitro, and/or at least one pyridine group, and/or at least one phenolic hydroxyl group.Second substituting group can comprise at least one phosphorus-containing groups and/or at least one carboxylic acid group.

In broad practice of the present invention, this passivation polymer can be the straight or branched polymkeric substance.This polymkeric substance can be or can derived from, for example acrylic polymers, polyester polymers, polyether polyols with reduced unsaturation, epoxy polymer, polyolefin polymer, polyether polymer, maybe can be to comprise above-mentioned one or more multipolymer.In one embodiment, this polymkeric substance can be or can comprise addition polymer and polycondensate derived from a kind of polymkeric substance that comprises hydroxyl or epoxy group(ing), perhaps also can use this mixture of polymers.The hydroxyl equivalent scope of this polymkeric substance can be 100～1000, for example 200～400; Or the epoxide equivalent scope is 100～2000, for example 300～600.

The example of the polymkeric substance of operable hydroxyl is including, but not limited to the polycondensate of hydroxyl, for example polyester of hydroxy functional groups.The operable example that contains the polymkeric substance of epoxy group(ing) comprises the polyglycidyl ether of polyvalent alcohol, Epicholorohydrin or dichlorohydrine and Fatty Alcohol(C12-C14 and C12-C18) and alicyclic ring alcohol (for example ethylene glycol, glycol ether, triglycol, propylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol, butyleneglycol, pentanediol, glycerol, 1 for example, 2,6-hexanetriol, tetramethylolmethane and 2,2-two (4-hydroxy-cyclohexyl) propane) reaction product.

The addition polymer of operable hydroxyl or epoxy group(ing) comprises the hydroxyl of ethylenically unsaturated monomers or the polymkeric substance or the multipolymer of epoxy functional.The monomeric example that has hydroxy functional group that is fit to comprises (methyl) Hydroxyethyl Acrylate, (methyl) vinylformic acid hydroxy propyl ester, (methyl) vinylformic acid hydroxyl butyl ester and vinyl carbinol.The monomeric example that has epoxy functionality that is fit to comprises (methyl) glycidyl acrylate.This addition polymer can be any homopolymer in these hydroxyls or the epoxy functional monomer, perhaps can be the multipolymer of the ethylenically unsaturated monomers of one or more and at least a other non-hydroxyl or epoxy functional in these hydroxyls or the epoxy functional monomer.These other monomeric example is including, but not limited to (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, vinylbenzene and vinyl monomer, for example vinylbenzene, Vinyl toluene and vinyl acetate.

The example of operable epoxy compounds comprises and the same simple compounds such as oxyethane, propylene oxide, butylene oxide ring, cyclohexene oxide.

The example of operable epoxy compounds also comprises by epihalohydrin (for example Epicholorohydrin or epibromohydrin) and polyphenol react resulting epoxidized polyether under the alkali existence condition.The polyphenol that is fit to comprises: 2,2-two (4-hydroxyphenyl) propane (being dihydroxyphenyl propane), 1,1-two (4-hydroxyphenyl) Trimethylmethane, 2,2-two (4-hydroxyl tert-butyl-phenyl) propane, 4,4-dihydroxy benaophenonel, 1,1-two (4-hydroxyphenyl) ethane, two (2-hydroxyl naphthyl) methane, 1,5-dihydroxy naphthlene, 1, the hydrogenated derivatives of 1-two (4-hydroxyl-3-allyl phenyl) ethane and this compounds.The polyglycidyl ether that can prepare the polyphenol of various molecular weight for example changes the molar ratio of Epicholorohydrin and polyphenol in a known way.

The example of operable epoxy compounds also comprises the polyglycidyl ether of monocycle polyphenol, the polyglycidyl ether of Resorcinol, pyrogallol, Resorcinol and pyrocatechol for example, and a glycidyl ether of monohydric phenol, for example phenyl glycidyl ether, Alpha-Naphthyl glycidyl ether, betanaphthyl glycidyl ether and the corresponding compound that on aromatic ring, has an alkyl substituent.

The example of other indefiniteness of operable epoxy compounds comprises the glycidyl ether of aromatic alcohol, for example phenmethyl glycidyl ether and phenyl glycidyl ether, the perhaps polyglycidyl ether of polyvalent alcohol, Epicholorohydrin or dichlorohydrine and Fatty Alcohol(C12-C14 and C12-C18) or alicyclic ring alcohol (for example ethylene glycol, glycol ether, triglycol, dipropylene glycol, tripropylene glycol, propylene glycol, butyleneglycol, pentanediol, glycerol, 1 for example, 2,6-hexanetriol, tetramethylolmethane and 2,2-two (4-hydroxy-cyclohexyl) propane) reaction product.

The example of more indefinitenesses of operable epoxy compounds also comprises many glycidyl esters of polycarboxylic acid, many glycidyl esters of for example common known hexanodioic acid, phthalic acid etc.Other spendable epoxy compounds comprises single glycidyl ester of monocarboxylic acid, for example single glycidyl ester of phenylformic acid glycidyl ester, naphthoic acid glycidyl ester and substituted benzoic acid and naphthoic acid.

Also can use the polyaddition resin that comprises epoxy group(ing).This material can be prepared from by epoxide-functional monomer and polymerisable alkene addition polymerization unsaturated and/or vinyl monomer.This epoxide-functional monomer is for example glycidyl acrylate, glycidyl methacrylate and glycidyl allyl ether usually.Unsaturated and/or the vinyl monomer of this polymerisable alkene is vinylbenzene, alpha-methyl styrene, α-ethyl styrene, Vinyl toluene, t-butyl styrene, acrylamide, Methacrylamide, vinyl cyanide, methacrylonitrile, ethyl acrylonitrile, Jia Jibingxisuanyizhi, methyl methacrylate, isopropyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, 2-EHA, methacrylic acid 2-ethylhexyl, isobornyl methacrylate for example, or the like.

Selectively, the main chain of this polymkeric substance can comprise a kind of vinylformic acid, carbamate, polyester, Synolac or epoxy polymer or oligopolymer.The main chain of this polymkeric substance can comprise at least two isocyanate group or protection or end capped isocyanate group thereon when synthetic.This can be incorporated in the main polymer chain by the monomer copolymerization that will have isocyanic acid or blocked isocyanate functional group and realize, perhaps realizes by one or more groups (for example hydroxyl or amido) are reacted on polymkeric substance with isocyanic ester or blocked isocyanate functional group.The reaction of isocyanic ester or blocked isocyanate functional group and first substituting group or the second substituent isocyano active function groups can form suitable linking group.

The illustrative examples that contains the carbamate main chain of isocyanic ester or blocked isocyanate functional group comprises the urethane polymer that has terminal isocyanic ester or blocked isocyanate functional group.This urethane polymer can be synthetic by known technology, for example mass polymerization, for example solution polymerization, by polyisocyanates with the active polyfunctional compound of polyisocyanates (comprising for example polyol, polyamines and amino alcohol) polymerization is made, but the equivalents sum of isocyanic ester that must use and potential isocyanate groups surpasses the used equivalents to the active polyfunctional compound of polyisocyanates.This polyisocyanates can be an isophorone diisocyanate for example, to phenylene vulcabond, xenyl 4,4 ' vulcabond, between eylylene diisocyanate, tolylene diisocyanate, 3,3 '-dimethyl-4,4 '-diphenylene vulcabond, 1, the 4-tetramethylene diisocyanate, 1, the 6-hexamethylene diisocyanate, 2,2,4-trimethyl cyclohexane-1, the 6-vulcabond, 1,3-two-[2-(isocyanato-) propyl group] benzene (is also referred to as the tetramethyl xylene group diisocyanate, TMXDI), methylene radical two-(phenyl isocyanate), l,5 naphthylene diisocyanate, two-(isocyanatoethyl fumarate), methylene radical two-(4-cyclohexyl isocyanate) and biuret or any isocyanuric acid ester in these.

Can comprise any glycol, triol or contain more multi-functional alcohols the active polyfunctional compound of polyisocyanates, for example ethylene glycol, propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane, polyester polyol, polyether polyhydroxy-compound or the like; Polyamine, for example quadrol and diethylenetriamine; Perhaps amino alcohol, for example diethanolamine and thanomin.

Polyisocyanates or can have more than two functional groups (comprising end capped functional group) to a kind of among the active polyfunctional compound of polyisocyanates.This reactant can distribute makes polyurethane copolymer have the terminal isocyanate functional group.

The illustrative examples of isocyanic ester or the functional acrylic acid or the like of blocked isocyanate is the multipolymer that comprises the ethylenically unsaturated monomers of isocyanic ester or blocked isocyanate groups.This multipolymer can be prepared for example radical polymerization, cationoid polymerisation or the anionoid polymerization in for example batch technology or semi-batch technology by using routine techniques.For example, can carry out polyreaction, optionally in batch technology, can add a kind of chain-transfer agent by in bulk solution or organic solution, under radical source (for example organo-peroxide or azo-compound) existence condition, heating this ethylenically unsaturated monomers; Perhaps, in semi-batch technology, can in reactor heating, add monomer and initiator with control speed as selecting.

In a kind of embodiment of indefiniteness, first substituting group can comprise nitro (NO ₂).This nitro substituent can form by making the isocyanic ester radical reaction that contains on nitro material and the main polymer chain.This example that can be used for forming the substituent material that meets above-mentioned requirements comprises any compound that contains nitro with isocyanate reactive group (for example hydroxyl, amido, sulfydryl or Oxyranyle).Useful contain the compound that nitro-compound comprises that the alkyl, aryl or the alkaryl that include isocyanate reactive group replaces.Typically, the nitro-compound that contains that is used for indefiniteness of the present invention comprises 2-methyl-2-nitro-propanol, 2-nitro-1-propyl alcohol, 2-nitroethyl alcohol, 4-N-methyl-p-nitroaniline, 5-oil of mirbane methyl alcohol, 4-nitrothiphenol, 2-nitrobenzoic acid, 4-nitrobenzoic acid, 2-4-dinitrobenzoic acid and/or its mixture.

In the embodiment of another indefiniteness, first substituting group can comprise at least one pyridine group and/or at least one phenolic hydroxyl group.The example that is applicable to the material that forms the pyridine group is including, but not limited to 2,6-pyridine dimethanol, 2-pyridine propyl alcohol, 3-pyridine propyl alcohol, pyridine proprionic acid, Yi Yansuan, pyridine carboxylic acid, pyridine dicarboxylic acid, nicotinic acid, dinicotinic acid, cinchomeronic acid, pyridinedicarboxylic acid or its mixture.The example that is applicable to the material that forms phenolic hydroxyl group is including, but not limited to gallic acid, chavicol, polyhydroxy phenol, for example Resorcinol, pyrocatechol, Phloroglucinol, pyrogallol, 1,2,4-benzene triol or its mixture.

In the embodiment of an indefiniteness, second substituting group comprises a phosphorus-containing groups, and for example phosphate radical, non-nitrogen replace the organosilane ester and/or the bi-ester of phosphite of phosphonate radical, ortho-phosphoric acid, phosphoric acid.For example, this phosphate compounds can be the type described in the US patent 4565716.Organophosphite is the derivative of phosphorous acid, rather than is used to prepare the phosphoric acid of organophosphate.Described in exemplary organophosphate such as the United States Patent (USP) 4808231.

That the example that can be used for the phosphoric acid ester in the present invention practice comprises is single-and two-C ₄-C ₁₈Alkyl ester, for example mono phosphoric acid ester-and dibutylester, mono phosphoric acid ester and diamyl ester, mono phosphoric acid ester-and dihexyl, mono phosphoric acid ester-and two heptyl esters, mono phosphoric acid ester-and dioctyl ester, mono phosphoric acid ester-and two the ninth of the ten Heavenly Stems ester, mono phosphoric acid ester-and two (n-Hexadecane) esters and mono phosphoric acid ester-and two (octadecane) ester; With aryl ester that in aryl, comprises 6～10 carbon atoms and aralkyl ester, mono phosphoric acid ester-and diphenyl and mono phosphoric acid ester-and benzhydryl ester for example.

In the embodiment of a specific indefiniteness, be used for this passivation polymer of the present invention and comprise a kind of epoxy polymer, it has at least one nitro substituent and at least one phosphate group, wherein epoxy group(ing): nitro: the equivalence ratio of phosphoric acid is 3.8/0.3/4.8～3.8/3/0.8.In the embodiment of another indefiniteness, epoxy group(ing): nitro: the equivalence ratio of phosphoric acid can be 3.8/0.8/4.2～3.8/1/3.2.

Have been found that metallic pigment and passivation polymer (for example above-mentioned those) are in contact with one another the hydrolysis or the oxidation that can reduce or prevent pigment, and therefore can reduce and eliminate fully the generation of hydrogen.In addition, since comprise metallic pigment that this polymer treatment in the use coating composition crosses can't be to the moistureproofness generation adverse influence of the dry film (coating) that forms by this waterborne compositions.

The metallic pigment that a kind of exemplary water-based paint compositions of the present invention generally includes film-forming polymer, moisture diluent media and handled through passivation polymer of the present invention to small part.By adding the deactivation matter of the present invention of significant quantity, can stop or reduce this pigment and water-bearing media and react and emit the tendency of gaseous substance.

The example that is applicable to the metallic pigment of water-based paint compositions of the present invention comprises any metallic pigment of making coating composition painted of becoming known for usually.The example is including, but not limited to metallic pigment, for example Metal Flake pigment, comprise aluminium, copper, zinc, iron and/or brass and by other wrought metal and alloy to small part, for example nickel, tin, silver, chromium, Al-zn-mg-cu alloy, aluminum-zinc alloy and aluminium-magnesium alloy etc.In addition, water-based paint compositions of the present invention can also comprise in other pigment that much becomes known for coating composition one or more, for example various colorific pigment and/or filler pigment.The example of this pigment including, but not limited to: based on the common known pigment of metal oxide, metal hydroxides, metallic sulfide, metal sulfate, metal carbonate, carbon black, potter's clay, phthalocyanine blue and phthalocyanine green, organic red and organic dye.

The deactivation matter (for example aforementioned those) that can use various technologies will comprise passivation polymer of the present invention joins in the coating composition (such as, but be not limited to water-based paint compositions of the present invention)." water-based " coating composition is meant that wherein diluent media mainly is the coating composition of water-bearing media, and promptly water-based paint compositions does not contain or do not contain substantially organic solvent.The connotation that " does not contain organic solvent substantially " is that it is less than the 20wt.% of coating composition gross weight if wherein contain organic solvent, for example is less than 10wt.%, for example is less than 5wt.%, for example is less than 2wt.%, for example is less than 1wt.%.Those skilled in the art will recognize that in the embodiment of an indefiniteness of the present invention, this water-based paint compositions can comprise that a small amount of organic solvent is used for improving one or more coating properties, for example improve the flowability or the levelling property of application composition, perhaps reduce viscosity as required.A kind of method of adding the deactivation matter that comprises polymkeric substance of the present invention is before joining pigment in the water-based paint compositions metallic pigment to be contacted with deactivation matter.This can realize that perhaps it can add in the stage more early, for example in the actual production process of pigment by deactivation matter of the present invention being added in the pigment slurry (for example usually commercially available to pigment).Selectively, can be only by its " pure substance " be added, promptly as the another kind of component in the water-based paint compositions prescription, deactivation matter is incorporated in the water-based paint compositions of the present invention, for example in the mixing process of film-forming resin, metallic pigment and water-bearing media and other routine and inessential component (for example linking agent, solubility promoter, thickening material and filler).No matter deactivation matter of the present invention joins in the water-based paint compositions of the present invention in which way, the normally used amount of this compound should be able to effectively reduce or eliminate the gas release of metallic pigment in water-bearing media.For example, the scope of the amount of deactivation matter can be the deactivation matter solid in the weight 5wt.%～200wt.% of pigment solids, the scope of 10wt.%～100wt.% for example, the scope of 10wt.%～80wt.% for example, the for example scope of 15wt.%～50wt.%, for example scope of 16wt.%～25wt.%.

A kind of exemplary composition that does not contain organic solvent substantially of the present invention can be a kind of thermoplasticity film-forming composition, and perhaps selectable is a kind of thermoset composition.Be meant that at this used " thermoset composition " it is irreversible that curing in a single day of this compound or crosslinked its " are fixed ", wherein the polymer chain of polymeric constituent is linked together by covalent linkage.This character is often relevant by the crosslinking reaction that for example heating or irradiation cause with the component of composition usually.Hawley，Gessner?G.，The?Condensed?Chemical?Dictionary，Ninth?Edition.，page?856；Surface?Coatings，vol.2，Oil?and?Colour?Chemists’Association，Australia，TAFE?Educational?Books(1974)。Curing or crosslinking reaction also can be carried out under envrionment conditions.In case curing or crosslinked, thermoset composition can not melt under heating, and is insoluble in solvent yet.As a comparison, " thermoplastic compounds " comprises and can't help the polymeric component that covalent linkage connects, therefore can obtain liquid fluidity under heating, and can be dissolved in solvent.Saunders，K.J.，Organic?Polymer?Chemisty，pp.41-42，Chapman?and?Hall，London(1973)。

A kind of exemplary coating composition of the present invention comprises diluent media, resin glue system, comprises the deactivation matter and at least a metallic pigment particle of polymkeric substance of the present invention.For example, this granules of pigments can be handled through deactivation matter of the present invention to small part.

This diluent media can be solvent borne diluent media or moisture (for example water-based) diluent media." solvent borne " is meant that this diluent media is a kind of water-free material, for example organic solvent basically.

The resin glue system comprises (a) at least a film-forming polymer of active function groups and (b) at least a linking agent that comprises the functional group that can react with the functional group of film-forming polymer of containing usually.

This film-forming polymer (a) can comprise the known polymkeric substance that contains active group in the various topcoatings field, as long as this polymkeric substance can be well dispersed in the diluent media.The example of the indefiniteness that is fit to can comprise acrylic polymers, polyester polymers, polyether polyols with reduced unsaturation, polyether polymer, polysiloxane extracting mixture, polyepoxide polymer, and multipolymer and mixture.And this polymkeric substance can comprise various active functional group, for example is selected from functional group at least a in hydroxyl, carboxyl, epoxy group(ing), amido, amide group, carbamate groups, isocyanate group and the combination thereof.

For example, the polymkeric substance of the hydroxyl of Shi Heing can comprise acrylic acid or the like polyol, polyester polyol, urethane polyol, polyether polyhydroxy-compound and composition thereof.

The hydroxyl that is fit to and/or the acrylic polymers of carboxyl can be prepared by polymerisable ethylenically unsaturated monomers, it is (methyl) vinylformic acid and/or (methyl) acrylic acid hydroxy alkyl ester and one or more other polymerisable ethylenically unsaturated monomers ((methyl) acrylic acid alkyl ester for example normally, comprise (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate and 2-EHA, and vinyl aromatic compounds, for example vinylbenzene, alpha-methyl styrene and Vinyl toluene) multipolymer.

In an embodiment of the present invention, acrylic polymers can be by the unsaturated beta-hydroxy esters functional monomer of alkene, for example aforesaid those preparations and getting.

Can copolymerization take place by making the monomer that contains Oxyranyle and other polymerisable ethylenically unsaturated monomers (for example above-mentioned those), epoxy-functional is joined in the acrylic copolymer by polymerisable ethylenically unsaturated monomers preparation.The monomer that contains Oxyranyle is (methyl) glycidyl acrylate and glycidyl allyl ether for example.Describe the preparation of the acrylic polymers of this epoxy functional in United States Patent (USP) 4001156 the 3rd to 6 hurdle in detail.

Can copolymerization take place by the vinyl monomer (for example carbamate-functional alkyl ester of methacrylic acid) that makes for example above-mentioned those polymerisable ethylenically unsaturated monomers and carbamate-functional, carbamate-functional is joined in the acrylic copolymer that is prepared by polymerisable ethylenically unsaturated monomers.The alkyl ester of useful carbamate-functional can be by for example hydroxyalkyl carbamate (for example reaction product of ammonia and ethylene carbonate or Texacar PC) and methacrylic anhydride prepared in reaction.The vinyl monomer of the carbamate-functional that other is useful comprises: the reaction product of hydroxyethyl methylacrylate, isoflurane chalcone diisocyanate and carboxylamine hydroxypropyl acrylate for example; The perhaps reaction product of Rocryl 410, isoflurane chalcone diisocyanate and methyl alcohol.Can also use the vinyl monomer of other carbamate-functional, the reaction product of the acrylic or methacrylic acids monomer (for example Hydroxyethyl acrylate) of isocyanic acid (HNCO) and hydroxyl-functional for example, and described in the United States Patent (USP) 3479328 those.Also can react, and carbamate-functional is incorporated in the acrylic polymers by acrylic polymers and the low-molecular-weight alkyl carbamate (for example Urethylane) that makes hydroxyl-functional.Also can (transcarbamoylation) react, and the carbamate pendant groups is incorporated in the acrylic polymers by " transcarbamylaseization " that the acrylic polymers of hydroxyl-functional wherein and low molecular weight carbamate derived from alcohols or glycol ethers take place.Carbamate groups becomes functional acrylic polymers of carbamate and initial alcohols or glycol ethers with the hydroxyl exchange student.And the acrylic polymers of hydroxyl-functional can react with isocyanic acid the carbamate side group is provided.Equally, the acrylic polymers of hydroxyl-functional can react with urea the carbamate side group is provided.

Can for example be prepared under organo-peroxide or azo-compound (for example benzoyl peroxide or N, N-idol two (the isopropyl cyanides)) existence condition at suitable catalyzer by well known to a person skilled in the art solution polymerization technique by the polymkeric substance of polymerisable ethylenically unsaturated monomers preparation.Polyreaction can be with the common technology of this area at monomer in wherein carrying out in the soluble organic solvent.Selectively, can prepare these polymkeric substance by water miscible liquid well known in the art or aqueous dispersion polymerization technology.Select the preparation of suitable reactant ratio and reaction conditions to have the acrylic polymers of required functional pendant groups.

In film-forming composition of the present invention, also can use polyester polymers.Useful polyester polymers generally includes the condensation product of polyvalent alcohol and polycarboxylic acid.The polyvalent alcohol that is fit to can comprise ethylene glycol, neopentyl glycol, TriMethylolPropane(TMP) and tetramethylolmethane.The polycarboxylic acid that is fit to can comprise hexanodioic acid, 1,4-cyclohexyl dicarboxylic acid and hexahydro-phthalic acid.Except the above-mentioned polycarboxylic acid of mentioning, also can use the functional equivalent of carboxylic acid, for example the lower alkyl esters of the acid anhydrides of its existence or carboxylic acid, for example methyl esters.Also can use a spot of monocarboxylic acid, for example stearic acid in addition.Select the preparation of suitable reactant ratio and reaction conditions to have the polyester polymers of required functional pendant groups (being carboxyl or hydroxy functional group).

For example, can react with 1: 2 mol ratio with dibasic alcohol (for example neopentyl glycol), prepare the polyester of hydroxyl by the acid anhydrides (for example hexahydrophthalic anhydride) that makes di-carboxylic acid.When needs improve dry air, can use suitable drying oil fatty acid, it comprises those that are derived from Toenol 1140, soya-bean oil, Yatall MA, synourin oil or tung oil.

Can by at first form can with form the polyester that hydroxyalkyl carbamate that the polyprotonic acid that uses in the polyester and polyol react prepares carbamate-functional.Selectively, can react by the polyester that makes isocyanic acid and hydroxyl-functional, and terminal carbamate functional group is joined in the polyester.And, can react by making hydroxyl polyester and urea, and carbamate-functional is joined in the polyester.In addition, can also carbamate groups be incorporated in the polyester by the transcarbamylase reaction.The 2nd hurdle the 40th of United States Patent (USP) 5593733 walks to the method for having described the polyester for preparing those amido-containing acid ester functional groups that are fit in the 4th hurdle the 9th row.

The polyether polyols with reduced unsaturation that comprises isocyanate end or hydroxyl also can be as the polymkeric substance in the coating composition of the present invention.Operable urethane polyol or the end capped urethane of NCO be by polyol that comprises polymeric polyhydroxy compound and polyisocyanates react the preparation those.The also operable polyureas that comprises isocyanate end or primary amine and/or secondary amine is those by the react preparation and getting of polyamine that comprises the polymerization polyamine and polyisocyanates.Regulate the equivalence ratio of this hydroxyl/isocyanate base or amino/isocyanate group and select appropriate reaction conditions, obtain required terminal group.The example of the polyisocyanates that is fit to comprises that the 5th hurdle the 26th of United States Patent (USP) 4046729 walks to those described in the 6th hurdle the 28th row, now uses this content introducing for referencial use herein.The example of the polyol that is fit to comprises that the 7th hurdle the 52nd of United States Patent (USP) 4046729 walks to those described in the 10th hurdle the 35th row.The example of the polyamine that is fit to comprises that the 6th hurdle the 61st of United States Patent (USP) 4046729 walks to described in capable those of the 3rd hurdle the 13rd to 50 of the 7th hurdle the 32nd row and United States Patent (USP) 3799854.

Can react by making polyisocyanates and the polyester that has hydroxy functional group and comprise the carbamate side group, carbamate-functional is incorporated in the polyether polyols with reduced unsaturation.Selectively, can prepare urethane by polyisocyanates and polyester polyol and hydroxyalkyl carbamate or isocyanic acid are reacted as independent reactant.The example of the polyisocyanates that is fit to is aromatic isocyanic ester, for example 4,4 '-'-diphenylmethane diisocyanate, 1,3-phenylene vulcabond and toluene diisocyanate, with aliphatic polyisocyanates, for example 1,4-tetramethylene diisocyanate and 1,6-hexamethylene diisocyanate.Also can use alicyclic vulcabond, for example 1,4-cyclohexyl diisocyanate and isoflurane chalcone diisocyanate.

The example of the polyether polyhydroxy-compound that is fit to comprises the polyalkylene ether polyol, for example has following structural formula (I) or (II) those:

Or

Wherein substituent R is hydrogen or the low alkyl group that comprises 1～5 carbon atom, comprises the mixing substituting group, and the value of n is generally 2～6, and m value scope is 8～100 or higher.Exemplary polyalkylene ether polyol comprises poly-(oxygen tetramethylene) glycol, poly-(oxygen four ethylidene) glycol, poly-(oxygen-propylene) glycol, poly-(oxygen-1,2-butylidene) glycol.

Also can use by various polyols (glycol for example, ethylene glycol, 1 for example, 6-hexylene glycol, dihydroxyphenyl propane etc., or other more high-grade polyol, for example TriMethylolPropane(TMP), tetramethylolmethane etc.) through the polyether polyhydroxy-compound of alkoxylate preparation.The polyol of operable above-mentioned higher functional group can be for example alkoxylate by the compound of for example sucrose or Sorbitol Powder etc. prepare.Normally used a kind of alkoxylating method is that polyol and alkylene oxide (for example propylene oxide or oxyethane) react under the condition of acidity or basic catalyst existence.The example of polyethers comprise can trade(brand)name TERATHANE and TERACOL available from E.I.Du Pont de Nemours and Company, those of Inc..

As previously mentioned, in certain embodiments of the invention, this film-forming composition can also comprise (b) one or more are suitable for functional group and/or any aforementioned polymerization microparticle of polymkeric substance and/or are used to solidify the linking agent that the additive of this film-forming composition reacts if desired.The non-limiting example of the linking agent that is fit to comprises known any aminoplastics in surface-coated field and polyisocyanates, but must be fit to have water-soluble or water dispersible as described below by this linking agent, and polyprotonic acid, multi-anhydride and composition thereof.In use, select linking agent or linking agent mixture according to the functional group relevant (for example hydroxyl and/or carbamate-functional) with the polymerization microparticle.For example when this functional group was hydroxyl, this hydrophilic crosslinked dose can be aminoplastics or polyisocyanate crosslinker.

Be applicable to that the example as the aminoplast(ic) resin of linking agent comprises that those comprise the material of methylol or similar hydroxyalkyl, its part is by by etherificate, providing a kind of aminoplast(ic) resin of water dissolvable/dispersibility with the reaction of lower alcohol (for example methyl alcohol).The aminoplast(ic) resin CYMEL 385 that a kind of suitable aminoplast(ic) resin is a part methylization, it can be available from CytecIndustries, Inc..Water dissolvable/dispersibility and the suitable blocked isocyanate of making linking agent are dimethyl pyrazole end-blocking hexamethylene diisocyanate trimers, and it can be used as BI 7986 available from Baxenden Chemicals, Ltd., Lancashire, England.

Be applicable to that the polyprotonic acid cross-linked material among the present invention can comprise: for example each molecule on average comprises those that surpass 1 acidic group usually, comprises 3 or more sometimes, and 4 or more sometimes, this acidic group can react with epoxy functionalized film-forming polymer.The polyprotonic acid linking agent can have two, three or more functional groups.Operable suitable polyprotonic acid linking agent comprises, for example contains carboxylic acid group's oligopolymer, polymkeric substance and compound, for example acrylic polymers, polyester and urethane and contain compound based on the acidic group of phosphorus.

The example of the polyprotonic acid linking agent that is fit to comprises: for example contain the oligopolymer of ester group and comprise by polyol and ring 1,2-anhydride reaction and the half ester that obtains or by polyol and polyprotonic acid or acid anhydrides preparation and sour functional polyester.These half esters have relatively low molecular weight and the activity suitable to epoxy-functional.The oligopolymer that contains ester group that is fit to comprises that the 4th hurdle the 26th of United States Patent (USP) 4764430 walks to those described in the 5th hurdle the 68th row, is introduced into this paper as a reference at this.

Other useful linking agent comprises sour functional acrylic acid or the like linking agent, is prepared as the polyprotonic acid linking agent with the unsaturated copolymerisable monomer copolymerization of other alkene by methacrylic acid and/or Acrylic Acid Monomer.Selectively, sour functional acrylic acid or the like can be by the acrylic acid or the like and the cyclic anhydride prepared in reaction of hydroxyl-functional.

According to certain embodiments of the present invention, linking agent (b) is water dissolvable/dispersibility normally, it counts 0～at least 10wt.% as the component concentration scope in film-forming composition with total resin solid weight in the film-forming composition, perhaps at least 10～at least 20wt.%, perhaps at least 20～at least 30wt.%.According to certain embodiments of the present invention, linking agent is counted with total resin solid weight in the film-forming composition as component concentration scope in film-forming composition and is less than or equal to 70～is less than or equal to 60wt.%, be less than or equal to 60～be less than or equal to 50wt.%, perhaps be less than or equal to 50～be less than or equal to 40wt.%.The content of this linking agent in film-forming composition can be between the arbitrary combination of these resins within the quoting scope.

The resin glue that is used for undercoat can be based on the material of organic solvent, and for example United States Patent (USP) 4220679 files the 2nd hurdle the 24th row is up to described in the 4th hurdle the 40th row those.And also can use water base paint compositions as the tackiness agent in the bottom coating composition, those described in United States Patent (USP) 4403003, United States Patent (USP) 4147679, the United States Patent (USP) 5071904 for example.

Coating composition can comprise various other components that become known for usually in the water-based paint compositions.The example of various other components comprises: filler, softening agent, antioxidant, mould inhibitor and mycocide, tensio-active agent, various flowing regulators, comprise for example thixotropic agent and anti-molten vertical property additive and/or pigment orientation, precipitated silica for example, fumed silica, organically-modified silicon oxide, wilkinite, organic bentonite, and United States Patent (USP) 4025474 for example, 4055607,4075141,4115472,4147688,4180489,4242384,4268547, such additive described in 4220679 and 4290932 based on polymer micropellet (being also referred to as microgel sometimes).

Can be used for the organic solvent of organic solvent based coating composition of the present invention and/or the example of thinner and comprise alcohols, the low-grade alkane alcohol that for example comprises 1～8 carbon atom comprises methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, hexanol and 2-Ethylhexyl Alcohol; Ethers and ether alcohol class, for example ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, propylene glycol monomethyl ether, diethylene glycol monobutyl ether, dibutyl ethylene glycol ether, dipropylene glycol monomethyl ether and dipropylene glycol monobutyl ether; Ketone, for example methyl ethyl ketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone and methyl N-butyl ketone; Ester class, for example N-BUTYL ACETATE, acetic acid 2-ethoxy ethyl ester and acetic acid 2-ethylhexyl; Aliphatics and clicyclic hydrocarbon, for example various petroleum naphthas and hexanaphthene; And aromatic hydrocarbon, for example toluene and dimethylbenzene.The organic solvent that uses in organic solvent based coating composition of the present invention and/or the amount of thinner can alter a great deal.Yet in the embodiment of an indefiniteness, that the variation range of the amount of organic solvent and/or thinner can be counted based on the gross weight of organic solvent based coating composition is about 10%～about 50%, for example 20%～40%.

Deactivation matter of the present invention also can be used for comprising the powder coating composition of film-forming polymer and pigment (being generally metallic pigment).

Following embodiment has described the present invention, but is not appreciated that the qualification to its scope.Unless otherwise indicated, all percentage compositions and consumption all are understood that it is by weight.

Embodiment

Following embodiment has described the contrast of deflation characteristic that adds the exemplary coating composition that the deactivation matter that comprises polymkeric substance of the present invention is arranged and the deactivation matter that can buy.

The preparation of deactivation matter

Be prepared as follows polymkeric substance that is used for deactivation matter of the present invention and the composition that comprises this polymkeric substance:

Polymkeric substance synthesizes embodiment 1 (PE1)

The following component of use as described below prepares a kind of passivation polymer of the present invention.

Table 1

Component	Content (gram)
		??1?EPON?828 1Propyl ether 6 N of 2 N-Methyl pyrrolidone, 3 2-nitrophenolss, 4 phosphoric acid, 5 propylene glycol, N-dimethylethanolamine 7 deionized waters	??358.5??263.4??106.1??73.1??263.3??43.2??671.0

¹EPON 828 is that epoxy equivalent (weight) is 188 bis-epoxy class, can be available from Shell Oil andChemical Co..

First three is planted component join in the reactor, in nitrogen, be heated to 100 ℃, under this temperature, kept about 1 hour.Reaction mixture is cooled to 30 ℃ temperature, adds component 4 then.Temperature of reaction is brought up to 100 ℃ then, mixture was kept under this temperature about 2 hours.The product that will generate thus under agitation adds component 5,6 and 7 and dilutes then.With the product cool to room temperature.The solid content of reaction product is about 32%, and the pH value is 5.7.

Polymkeric substance synthesizes embodiment 2 (PE2)

Preparation method as the polymkeric substance of embodiment 1 prepares this polymkeric substance, just with the 4-nitrobenzoyl acid substitution 2-nitrophenols wherein of equivalent.

Polymkeric substance synthesizes embodiment 3 (PE3)

Preparation method as the polymkeric substance of embodiment 2 prepares this polymkeric substance, and just the 4-nitrobenzoic acid of half replaces with the Yi Yansuan of equivalent.

Polymkeric substance synthesizes embodiment 4 (PE4)

Preparation method as the polymkeric substance of embodiment 2 prepares this polymkeric substance, just replaces wherein 4-nitrobenzoic acid with the Yi Yansuan of equivalent.

Polymkeric substance synthesizes embodiment 5 (PE5)

Preparation method as the polymkeric substance of embodiment 2 prepares this polymkeric substance, just only uses all EPON 828 of 4-nitrobenzoyl acid substitution, does not use phosphoric acid.

Polymkeric substance synthesizes embodiment 6 (PE6)

Preparation method as the polymkeric substance of embodiment 2 prepares this polymkeric substance, and just the phosphoric acid of 42wt.% replaces with the trimellitic acid 1,2-anhydride of equivalent.

Polymkeric substance synthesizes embodiment 7 (PE7)

Preparation method as the polymkeric substance of embodiment 2 prepares this polymkeric substance, just replaces the 4-nitrobenzoic acid of 50 equivalent % with the reaction product of Tetra hydro Phthalic anhydride and hydroxyethyl ethylidene-urea (by these two kinds of components prepared in reaction 120 ℃ the time).

Polymkeric substance synthesizes embodiment 8 (PE8)

Polymer phase preparation method together as embodiment 2 prepares this polymkeric substance, and just the Unimac 5680 with equivalent replaces the 4-nitrobenzoic acid.

Polymkeric substance synthesizes embodiment 9 (PE9)

Preparation method as the polymkeric substance of embodiment 8 prepares this polymkeric substance, just with EPON 872 (epoxy equivalent (weight) is 645) the replacement EPON 828 of equivalent.

Polymkeric substance synthesizes embodiment 10 (PE10)

Use a kind of acrylate urethane of following component preparation as described below:

Table 2

Content (gram)	Material
		??1?934.0???2?108.0??3?1.2??4?1.2??5?157.2??6?262.2	Hydroxyl value is 120 polyester polyol (by TriMethylolPropane(TMP) (15.2 %), neopentyl glycol (35.3%) and hexanodioic acid (49.5%) preparation) Hydroxyethyl acrylate (HEA) dibutyl tin dilaurate Yoshinox BHT hexamethylene diisocyanate (HDI) butyl acrylate (BA)

Preceding four kinds of components are stirred in flask, simultaneously HDI was being added in 1 hour time under 70 ℃～80 ℃ the temperature.Use 39g butyl acrylate flushing feed hopper then, when the isocyanic ester total overall reaction, reaction mixture was kept 2 hours under 70 ℃ of temperature more then.Then remaining butyl acrylate is added, producing Gardner-Holdt viscosity is 80% solution of X.

Prepare a kind of preemulsion with following component:

Table 3

Content (gram)	Component
		??1?1003.80??2?120.40??3?147.00??4?20.60??5?13.52???6?46.16??7?17.92???8?1246.00	As above 50% aqueous solution (DDBSA/DMEA) the ALIPAL Co 436 of Zhi Bei acrylate polyurethane acroleic acid butyl ester methyl methacrylate (MMA) vinylformic acid Witco 1298 Soft Acid dimethyl ethanol ammonium, anion surfactant, can be available from Rhodia Chemicals AEROSOL OT-75 (dioctyl sodium sulfo-succinate, can be available from Cytec Industries, Inc.) deionized water

This preemulsion is passed through M110MICROFLUIDIZER RTM emulsor at 7000psi pressure next time, form little dispersion liquid.In a round-bottomed flask, in nitrogen, stir this little dispersion liquid, add the component of listing in the following table 4 at 22 ℃.

Table 4

Content (gram)	Component
		??1?429.90??2?2.00??3?2.86??4?2.94??5?21.50	Deionized water saccharosonic acid ferrous ammonium sulphate (1% aqueous solution) hydrogen peroxide (30% aqueous solution) dimethylethanolamine

Add after the component in the table 4, after about 15 minutes, temperature of reaction is elevated to 56 ℃ naturally.Final product has following characteristic:

Total solid content: about 42wt.%;

PH value: about 8.3; With

Brookfield viscosity (50rpm, rotor #1): about 14cps.

Polymkeric substance embodiment 11 (PE11)

Present embodiment has been described a kind of preparation of acrylic polyester polymkeric substance.This acrylic polyester is to be prepared by component as described below.

Polyester (P): this polyester is to prepare in the four neck round-bottomed flasks that thermometer, mechanical stirrer, condenser, drying nitrogen shower nozzle and heating jacket be housed.This polyester is by component preparation listed in the following table 5.

Table 5

Content (gram)	Component
		??1??1103.00??2??800.00??3??480.00??4??688.00??5??6.12??6??6.12??7??1200.00	Stearic acid tetramethylolmethane Ba Dousuan phthalic acid dibutyl tin dilaurate triphenyl phosphite butyl acrylate

Under 230 ℃ temperature the first six being planted component stirs in flask.Distillate is collected in the Dean Rodney Stark trap water trap, this mixture is remained under this temperature, be reduced to up to acidity and be lower than 5.Then this product is cooled to be lower than 80 ℃ temperature, dilutes with butyl acrylate.

The preparation of polyester/acrylic latex

By being stirred together, following component prepares preemulsion:

Table 6

Content (gram)	Component
		??1??1000.0??2??295.0??3??30.0??4??20.0??5??655.0??6??46.4??7??14.3	Deionized water polyester (P) Ethylene glycol dimethacrylate vinylformic acid butyl acrylate Witco 1298 Soft Acid dimethylethanolamine

This preemulsion is passed through MICROFLUIDIZER RTMM110T at 8000psi pressure next time, and transfer in the four neck round-bottomed flasks that overhead, condenser, thermometer and nitrogen atmosphere are housed.Clean MICROFLUIDIZER RTM with the 150.0g deionized water, it is added in the flask.Be dissolved in ferrous ammonium sulphate initiated polymerization in the 120.0g water by adding 4.0g saccharosonic acid and 0.02g, added 70% t-butyl hydroperoxide (being dissolved in the 115.0g water) of 4.0g then at 30 minutes in the clock time.During this period of time temperature of reaction is elevated to 85 ℃ from 24 ℃.The 33.3% dimethyl ethanol amine aqueous solution of interpolation 36g is added on the 2.0g PROXEL GXL (can be available from ICI Americas, the sterilant of Inc.) in the 8.0g water then, and temperature is reduced to 28 ℃.The pH value of the latex of Xing Chenging is 7.9 thus, and non-volatile content is 42.0%, brookfield viscosity be 17cps (rotor #1,50rpm).

Polymkeric substance embodiment 12 (PE12)

Present embodiment has been described a kind of preparation of acrylic acid or the like dispersion liquid.This acrylic acid or the like dispersion liquid is as described below by listed component preparation in the following table 7.

Table 7

Phase I	Content (gram)
		?? Reinforced #1Deionized water dioctyl sulfosuccinate Charging AMethyl methacrylate butyl acrylate methacrylic acid dioctyl sulfosuccinate deionized water Charging BThe deionized water ammonium persulphate	???884.2??17.0???441.6??147.2??11.9??13.6??423.3???339.6??2.5
Phase	Content (gram)
		?? Charging CMethyl methacrylate butyl acrylate Hydroxyethyl acrylate dioctyl sulfosuccinate deionized water Charging DThe deionized water ammonium persulphate	???71.0??35.0??6.9??2.4??75.2???319.8??0.42
Phase I	Content (gram)

Phase I	Content (gram)
		?? Charging EMethyl methacrylate methyl methacrylate butyl acrylate hydroxyethyl methylacrylate dimethylaminoethyl acrylate methyl base vinylformic acid glycol ester dioctyl sulfosuccinate deionized water Charging FDeionized water ammonium persulphate sodium bicarbonate Charging GThe dimethylethanolamine deionized water	???71.0??12.3??30.8??40.2??22.7??34.5??2.4??97.5???319.8??0.54??1.3???10.9??176.0

Reinforced #1 is added in the reactor that thermopair, agitator and reflux exchanger are housed.Then the material in the reactor is heated to 80 ℃ temperature.Then charging A and B (Phase I) were joined in three hours in the reactor, stirred reaction mixture is 30 minutes under 80 ℃ temperature.In 30 minutes time, add charging C and D (Phase) then, stirred 30 minutes at 80 ℃ then.Added charging E and F (Phase I) this moment in 30 minutes, stirred 1 hour, is cooled to envrionment temperature.Then, in 5 minutes, add charging G, and then stirred 10 minutes.

Polymkeric substance embodiment 13 (PE-13)

Present embodiment has been described a kind of method that is prepared polymkeric substance by following component:

Table 8

Component	Content (gram)
		1 neopentanoic acid, 2 neopentyl glycol, 3 FORMREZ 55-56 1??4??Poly?THF 25 dibutyl tin dilaurates, 6 butanols, 7 N-Methyl pyrrolidone, 8 DESMODUR W 39 N-Methyl pyrrolidone, 10 deionized waters, 11 quadrols, 12 dimethylethanolamines	??79.2??14.9??193.3??193.3??1.7??3.87??195.6??28.0??28.0??2366.4??14.2??51.8

¹The hydroxyl-functional polyester, molecular weight 2000 can be available from Witco Chemicals

²The hydroxyl-functional polyester is formed by tetrahydrofuran by polymerization, and molecular weight 2000 can be available from E.I.DuPont de Neumors and Co.

³Vulcabond can be available from Bayer corporation

The first seven is planted component join in the reactor, in nitrogen atmosphere, be heated 80 ℃, become evenly up to mixture.It is cooled to 55 ℃ then, in 30 minutes, adds premixed component 8 and 9.Mixture temperature is raise up to 90 ℃.Then mixture is remained on this temperature, become up to 1370 up to isocyanurate equivalent.Add premixed component 10,11 and 12 then.With product restir 30 minutes, cool to room temperature.Total non-volatile content of final product is 24%, and viscosity is lower than 100 centipoises.

The preparation of aqueous composition

Undercoat Embodiment B C 1-10

The moisture argent bottom coating composition that has prepared the passivator that comprises embodiment 1～10.For every kind of bottom coating composition (following Embodiment B C1-10), aluminium pigment slurry, Preblend A1-10, prepare respectively by as described below beginning of following component.Following content is all in weight part (gram).The component of Preblend A1-10 is mixed under light the stirring, and this mixture is stirred 30 minutes up to disperseing fully.Preblend A1 uses the deactivation matter that can buy (LUBRIZOL 2062, can available from Lubrizol Company).

Prepared bottom coating composition (Embodiment B C1～BC10) as described below from following component.Unless otherwise indicated, the content of listing below all is in weight part (gram).Bottom coating composition BC1 is used as contrast, and comprises the deactivation matter that can buy.

Every kind of moisture bottom coating composition among Embodiment B C1～BC10 all is being mixed with by said components under agitation condition.Utilize 50% aqueous solution of the DMEA of appropriate amount that the pH value of every kind of composition is adjusted to 8.4～8.6.Under envrionment conditions,, utilize 50% aqueous solution of the DMEA of appropriate amount once more the pH value of every kind of undercoat to be adjusted to 8.4～8.6 through after 16 hours equilibration period.Utilize deionized water that the viscosity of every kind of composition is reduced to 24～26 seconds atomizing viscosities (Ford #4 cup) then.Then sample is carried out following venting test.

Venting is measured

Every kind among Embodiment B C1～BC10 moisture bottom coating composition is estimated, measured the gas volume that from the aqueous coating that contains aluminum slice, discharges.This testing method is used to measure aluminum slice passivator (inhibitor of promptly exitting) and produces the validity of hydrogen and heat for stoping or suppressing to react between aluminium surface of pigments and the water.This method comprises puts into the venting testing apparatus with the water-borne coatings that contains aluminum slice, and this device is used to measure milliliter (ml) amount of the gas that per 200 gram bottom coating compositions discharged within 7 days.

After above-mentioned final pH value and viscosity adjustment, every kind of bottom coating composition 200 grams are placed in the independent 250ml erlenmeyer flask, cover the fat liquoring adapter glass that has hose connector (Tygon (polyethylene) pipe).A tapered clamp on the folder of the junction of flask and joint.Along the placed around plummet of the erlenmeyer flask of each charging, then each all is placed in 40 ℃ the default thermostatic bath.In thermostatic bath, keep carrying out in 4 hours temperature equilibrium then.

When making composition reach balance, assembling ring stand and drop-burette among the Nalgene tub after thermostatic bath.Ring stand is placed among the Nalgene tub that fills water.The burette holder ring stand of ining succession.For every kind of undercoat, the drop-burette of 250ml is filled water, be upside down among the Nalgene tub that fills water.Drop-burette is inverted and is made the top of inverted drop-burette be arranged under the top of tub horizontal plane.With burette holder burette holder is arrived suitable position.

After equilibration period, polyethylene tube is inserted in the inverted drop-burette, be connected to the hose nipple end of flask in the thermostatic bath then.Write down the inside water surface (ml) of drop-burette then.Write down the initial water surface and in testing apparatus, place the gas volume that the difference between the final water surface after 7 days discharges as undercoat.The subtle change in the test conditions those skilled in the art recognize that, owing to will cause the result of each venting all inequality.Therefore the venting result in the table 11 is appreciated that and has ± error of about 5ml.

Venting data in the following table 11 show that the moisture metal bottom coating composition that comprises aluminum passivation agent of the present invention (being the composition among Embodiment B C2～BC14) compares with the passivator that can buy (Embodiment B C1), and it to the inactivating performance of aluminum slice quite or increase.

Table 11

Undercoat	Discharge gas volume (ml)
		Embodiment B C1*	??12-18
Embodiment B C2	??10
		Embodiment B C3	??0
Embodiment B C4	??3
		Embodiment B C5	??8

Undercoat	Discharge gas volume (ml)
		Embodiment B C6	??0
Embodiment B C7	??4
		Embodiment B C8	??0
Embodiment B C9	??6
		Embodiment B C10*	??15

^*Comparative Examples

Undercoat Embodiment B C11～BC13

Following Embodiment B C11～BC13 has described the preparation of moisture argent bottom coating composition.For every kind of bottom coating composition among Embodiment B C11～BC13, aluminium pigment slurry, Preblend A11-13, prepare respectively by as described below beginning of following component.Following content is all in weight part (gram).The component of Preblend A11-13 is under agitation mixed, and this mixture is stirred 30 minutes up to disperseing fully.Preblend A11 uses the deactivation matter that can buy (LUBRIZOL2062, can available from Lubrizol Company).

Table 12

Preblend A11-13

¹¹The reaction product of EPON828 and phosphoric acid (weight ratio is 83: 17).

¹²Replace the benzotriazole UV light absorber, can be available from Ciba Additives.

¹³Aluminium pigment powder slurry ALPATE 7670NS can be available from Toyal Europe.

¹⁴The solution of LUBRIZOL 2062/ diisopropanolamine (DIPA) of 60/36/4w/w/propylene glycol butyl ether, LUBRIZOL 2062 can be available from Lubrizol Co.

¹⁵Methylated terpolycyantoamino-formaldehyde resin can be available from Cytec Industries, Inc..

Moisture bottom coating composition

Use moisture bottom coating composition separately among following component preparation Embodiment B as described below C11～BC13 then.Unless otherwise indicated, the content of listing below is all in weight part (gram).

Table 13

¹⁶The polymkeric substance of PE=embodiment

¹⁷Mineral turpentine can be available from Shell Chemical Co..

¹⁸Polyurethane aqueous dispersion can be available from Crompton Corp..

¹⁹The polymkeric substance of PE=embodiment

²⁰2% solution of LAPONITE RD in deionized water.LAPONITE RD is a kind of synthesis of clay, can be available from Southern Clay Products, Inc..

²¹Viscolam 330 is a kind of acrylic thickener emulsions, can be available from Lehmann ﹠amp; Voss.

Every kind of moisture bottom coating composition in Embodiment B C11～13 all prepares by mixing said ingredients under agitation condition.Utilize 50% aqueous solution of the DMEA of appropriate amount that the pH value of every kind of composition is adjusted to 8.4～8.6.Utilize deionized water that the viscosity of every kind of moisture bottom coating composition is reduced to 33～37 seconds atomizing viscosities (DIN#4 cup) then.

Venting is measured

According to the venting testing method among previous embodiment BC1～BC10, every kind among Embodiment B C11～BC13 moisture bottom coating composition is estimated.

Venting data in the following table 14 show that moisture metal bottom coating composition that comprises aluminum passivation agent of the present invention (being the composition among Embodiment B C12～BC13) and the contrast passivator that comprises the deactivation matter that can buy (being the composition among the Embodiment B C11) compares, and it to the inactivating performance of aluminum slice quite or increase.

Table 14

Undercoat	Discharge gas volume (ml)
		Embodiment B C11	??9
Embodiment B C12	??0
		Embodiment B C13	??6

Embodiment B C14～BC17

Following Embodiment B C14～BC17 (table 16) has described the preparation of the moisture argent bottom coating composition of the passivator that comprises embodiment A 14～A17 in the table 15 respectively.For every kind of bottom coating composition among Embodiment B C14～BC17, aluminium pigment slurry, Preblend A14-17, prepare respectively by as described below beginning of following component.Following content is all in weight part (gram).The component of Preblend A14-17 is under agitation mixed, and this mixture is stirred 30 minutes up to disperseing fully.

As shown in table 15, comprise known deactivation matter in the Preblend 14,16 and 17, and comprise deactivation matter of the present invention in the Preblend 15.All Preblendes in the table 15 all contain the passivator of the present invention based on aluminium total pigment weight 15wt.%.

Table 15

Preblend A14-17

Undercoat	??A14	??A15	The A16 Comparative Examples	The A17 Comparative Examples
					The DPM glycol ethers	??56	??56	??56	??56
Polypropylene glycol	??57	??57	??57	??57
					??TINUVIN?1130	??16	??16	??16	??16
Aluminum paste	??94	??94	??94	??94
					The aluminum passivation agent
??Lubrizol?2062	??25	??-	??-	??-
					??PE?2 4	??-	??33	??-	??-
Contrast passivator #1 1	??-	??-	??17	??-
					Contrast passivator #2 2	??-	??-	??-	??24
Nitroethane 3	??-	??-	??-	??8
					Phosphorylation Resins, epoxy	??4	??4	??4	??4

¹Deactivation matter described in the embodiment 2 of United States Patent (USP) 5389139.

²Deactivation matter described in the embodiment 1 of United States Patent (USP) 5215579.

³Available from Aldrich Chemical Co..

⁴The polymkeric substance of PE=embodiment

Moisture bottom coating composition

As following table 16 given prepare moisture bottom coating composition (Embodiment B C14～BC17) with Preblend A11～A14.Unless otherwise indicated, the content of listing below all is in weight part (gram), contains the passivator of 15wt.% based on aluminium total pigment weight meter.

Table 16

	The BC14 Comparative Examples	??BC15	The BC16 Comparative Examples	The BC17 Comparative Examples
					Deionized water	??291	??291	??291	??291
??PE-10	??547	??547	??547	??547
					50% aqueous solution of DMEA	??10	??10	??10	??10
??CYMEL?385 1	??205	??205	??205	??205
					N-butoxy propyl alcohol	??153	??153	??153	??153
Mineral turpentine	??23	??23	??23	??23
					Preblend A14	??252	??-	??-	??-
Preblend A15	?-	??260	??-	??-
					Preblend A16	?-	??-	??244	??-
Preblend A17	?-	??-	??-	??259
					The polymkeric substance of embodiment 13	??15	??15	??15	??15
Rheology modifier 2	??61	??61	??61	??61

¹Melamine resin can be available from Cytec Industries, Inc..

²Rheology modifier, 4-methylhexahydrophthalic anhydride, 18.4g hexahydrophthalic anhydride and 38.7g neopentyl glycol hydroxy new pentane acid ester by making 42.9g reacts at 200 ℃ that to be diluted to solid content with methyl iso-butyl ketone (MIBK) then be 80% preparation, and acid number is 165.

Every kind of moisture bottom coating composition among Embodiment B C14～BC17 all prepares by mixing said ingredients under agitation condition.Utilize 50% aqueous solution of the DMEA of appropriate amount that the pH value of every kind of composition is adjusted to 8.4～8.6.Under envrionment conditions,, utilize 50% aqueous solution of the DMEA of appropriate amount once more the pH value of every kind of undercoat to be adjusted to 8.4～8.6 through after 16 hours equilibration period.Utilize deionized water that the viscosity of every kind of composition is reduced to 24～26 seconds atomizing viscosities (Ford #4 cup) then.Then sample is carried out venting test as described below.

Venting is measured

Every kind among Embodiment B C14～BC17 moisture bottom coating composition is estimated according to following testing method, measured the gas volume that from the aqueous coating that contains aluminum slice, discharges.This testing method is used to measure aluminum slice passivator (inhibitor of promptly exitting) and produces the validity of hydrogen and heat for stoping or suppressing to react between aluminium surface of pigments and the water.This method comprises puts into the venting testing apparatus with the water-borne coatings that contains aluminum slice, and this device is used to measure milliliter (ml) amount of the gas that per 250 gram coating discharged within 7 days.

After above-mentioned final pH value and viscosity adjustment, every kind of undercoat 250 gram is placed in the deflation flask, and places 40 ℃ water-bath.As quickly as possible each sample is put into water-bath, up to its become catch all possible release gas after till.Provide in result such as the table 17.

Table 17

Undercoat	Discharge gas volume (ml)
		??BC14*	??24
??BC15	??11.9
		??BC16*	??44.2
??BC17*	??17.4

From the result shown in the table 17 as can be known, deactivation matter of the present invention is compared with other known deactivation matter, and its outgassing behaviour is improved.

Embodiment 2

Present embodiment has been described the influence of deactivation matter of the present invention to the coated products appearance property.

As evaluation coating composition B15 given in the following table 18 and the various appearance properties of B18-20.B18, B19 are identical with B14, B16 and B17 respectively with B20, just contain the passivator of 20wt.%, rather than the passivator of 15wt.%.

Table 18

	?? B18	?? B15	?? B19	?? B20
					Wt.% passivator	??20	??15	??20	??20
??Flip/Flop 1	??1.54	??1.52	??1.44	??1.46
					??L15 2	??132.08	??131.13	??126.91	??126.49
??CO 3	??49	??51	??30	??52
					Discharge quantity 4±5ml	??＜5	??＜5	??33.7	??＜5

¹By using L15, L45 that the X-RITE spectrophotometer obtains and L110 and obtaining according to these data computation flip/flop.This value is big more, and the L15 value is bright more, and the L110 value is dark more.

²Use the brightness of spectrophotometer 15 ° of measurements.This value is big more, and color is beautiful more.

³Autospec=uses the compound average of gloss, image definition and the tangerine peel of conventional Autospec Quality Measurement System (ASTM0631) mensuration.

⁴Discharge quantity is considered to qualified less than 10ml.

Those skilled in the art can easily recognize under the situation that does not break away from the disclosed spiritual scope of aforementioned specification can make some changes to the present invention.Therefore, only play illustration in the particular of this detailed description, and be not used in the scope of the present invention that limits, scope of the present invention is only provided by accompanying Claim and any and complete scopes all its Equivalents.

Claims (17)

1. passive metal pigment comprises:

At least a metallic pigment particle; With

The deactivation matter that on this at least a metallic pigment particulate at least a portion, forms, this deactivation matter comprises polymkeric substance, and wherein said polymkeric substance comprises (a) at least one nitro, and/or the pyridine group, and/or phenolic hydroxyl group; (b) at least one is selected from phosphorus-containing groups and/or carboxylic acid group's group, and wherein this at least one phosphorus-containing groups is selected from the phosphonate radical that phosphate radical, orthophosphite or non-nitrogen replace.

2. pigment as claimed in claim 1, granules of pigments wherein are the tinsel form.

3. pigment as claimed in claim 1, metallic pigment particle wherein comprise following at least a: aluminium, copper, zinc, brass, nickel, tin, silver, chromium, iron and oxide compound thereof or contain aforementioned at least a alloy.

4. pigment as claimed in claim 1, granules of pigments wherein are the aluminum slice form.

5. pigment as claimed in claim 1, at least a granules of pigments wherein comprise aluminium granules of pigments and iron oxide pigment particulate mixture.

6. coating composition comprises:

(a) diluent media;

(b) film-forming polymer; With

(c) at least a usefulness deactivation matter metallic pigment particle crossed of partially disposed at least that comprises polymkeric substance, wherein said polymkeric substance comprises (a) at least one nitro, and/or the pyridine group, and/or phenolic hydroxyl group; (b) at least one is selected from phosphorus-containing groups and/or carboxylic acid group's group, and wherein this at least one phosphorus-containing groups is selected from the phosphonate radical that phosphate radical, orthophosphite or non-nitrogen replace.

7. composition as claimed in claim 6, diluent media wherein are moisture diluent media.

8. composition as claimed in claim 6, diluent media wherein are non-moisture diluent media.

9. composition as claimed in claim 6, at least a metallic pigment particle wherein comprises flaky aluminum.

10. composition as claimed in claim 6, at least a granules of pigments wherein comprise aluminium granules of pigments and iron oxide pigment particulate mixture.

11. a coating composition comprises:

(a) moisture diluent media;

(b) film-forming polymer; With

(c) at least a with the deactivation matter metallic pigment particle crossed of partially disposed at least, wherein this deactivation matter comprises the polymkeric substance of the reaction product that comprises following reactant:

The diglycidyl ether of polyvalent alcohol;

Contain nitro-compound, be selected from least a in the compound that contains alkyl, aryl and/or alkaryl nitro; With

The phosphorous-containigroups groups compound comprises the phosphonate radical that phosphate radical and/or non-nitrogen replace.

12. as the composition of claim 11, at least a granules of pigments wherein is the tinsel form.

13. as the composition of claim 11, at least a metallic pigment particle wherein comprises following at least a: aluminium, copper, zinc, brass, nickel, tin, silver, chromium, iron and oxide compound thereof or contain aforementioned at least a alloy.

14. as the composition of claim 11, granules of pigments wherein is the aluminum slice form.

15. as the composition of claim 11, at least a granules of pigments wherein comprises aluminium granules of pigments and iron oxide pigment particulate mixture.

16. the method for a passivating metallic surfaces, this method comprises:

This metallic surface is contacted with the deactivation matter that comprises polymkeric substance, and wherein said polymkeric substance comprises (a) at least one nitro, and/or the pyridine group, and/or phenolic hydroxyl group; (b) at least one is selected from phosphorus-containing groups and/or carboxylic acid group's group, and wherein this at least one phosphorus-containing groups is selected from the phosphonate radical that phosphate radical, orthophosphite or non-nitrogen replace.

17. as the method for claim 16, metallic surface wherein comprises the pigment of aluminum slice form.