CN102369246A - Method for treating and/or coating a substrate with non-chrome materials - Google Patents
Method for treating and/or coating a substrate with non-chrome materials Download PDFInfo
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- CN102369246A CN102369246A CN2010800143081A CN201080014308A CN102369246A CN 102369246 A CN102369246 A CN 102369246A CN 2010800143081 A CN2010800143081 A CN 2010800143081A CN 201080014308 A CN201080014308 A CN 201080014308A CN 102369246 A CN102369246 A CN 102369246A
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- base material
- coating composition
- acid
- electrodepositable coating
- water rinse
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
- C09D5/4442—Binder characterised by functional groups
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/22—Light metals
Abstract
The present invention is directed to a method for coating a substrate comprising: (a) applying a caustic cleaner to at least a portion of the substrate; (b) rinsing at least a portion of the substrate that was subjected to step (a) with water; (c) applying an acid cleaner onto at least a portion of the caustically cleaned substrate; (d) rinsing at least a portion of the substrate that was subjected to step (c) with water; and (e) applying a conversion coating comprising zirconium onto at least a portion of the acid cleaned substrate; and wherein at least one of the materials used in steps (c) and (e) is substantially chrome free. The present invention is also directed to a substrate such as an aluminum substrate, that has been coated using the aforementioned method.
Description
Statement about the federal funding research project
The present invention makes through the support contract FA8650-05-C-5010 of government that The Air Force Research Laboratory gives.United States Government has some rights and interests to the present invention.
Invention field
Relate generally to of the present invention is with the method for Chrome-free material processing and/or coated substrate.
Background information
The common pre-treatment and the primer coating compositions that are used for aerospace industry contain chromium, such as the sexavalence lattice, will deposit the base material on it so that give coating with erosion resistance.Yet, because the toxicity relevant, and considering following government regulations to the sexavalent chrome consumption that in coating, uses with sexavalent chrome, people need reduce and/or eliminate chromic use in the pre-treatment of aerospace industry use and primer coating.
Summary of the invention
The present invention relates to a kind of method of coated substrate, it comprises: (a) the causticity sanitising agent is applied at least a portion of base material; (b) with at least a portion base material of water rinse through step (a); (c) sour sanitising agent is applied to the base material of at least a portion of process causticity cleaning; (d) with at least a portion base material of water rinse through step (c); And the conversion coatings that (e) will contain zirconium is applied at least a portion base material that acid cleaned; And wherein used at least a material is substantially devoid of chromium in step (c) and (e).The invention still further relates to base material, such as aluminium base, it applies through aforesaid method.
The invention still further relates to a kind of method of coated substrate, it comprises: (a) the causticity sanitising agent is applied at least a portion of base material; (b) with at least a portion base material of water rinse through step (a); (c) sour sanitising agent is applied to the base material of at least a portion of process causticity cleaning; (d) with at least a portion base material of water rinse through step (c); And the conversion coatings that (e) will contain zirconium is applied at least a portion base material that acid cleaned; And the material that wherein uses in step (c) and (e) is substantially devoid of chromium.
The invention still further relates to a kind of method of coated substrate, it is made up of following steps basically: (a) the causticity sanitising agent is applied at least a portion of base material; (b) with at least a portion base material of water rinse through step (a); (c) sour sanitising agent is applied to the base material of at least a portion of process causticity cleaning; (d) with at least a portion base material of water rinse through step (c); The conversion coatings that (e) will contain zirconium is applied at least a portion base material that acid cleaned; (f) with at least a portion base material of water rinse through step (e); And (g) electrodepositable coating composition is applied at least a portion of conversion coatings, wherein this electrodepositable coating composition comprises corrosion inhibitor; And wherein at step (c), (e) material with (g) middle use is substantially devoid of chromium.
Detailed Description Of The Invention
Unless otherwise prescribed, at all numerical value of this use, such as those expression sizes, scopes, quantity or per-cent, all should be considered to have prefix " pact ", even the specially appearance of this prefix.Plural number comprises odd number, and vice versa.For example, though listed " a kind of " causticity sanitising agent at this, " a kind of " sour sanitising agent, " a kind of " conversion coatings, " a kind of " electrodepositable coating, " a kind of " corrosion inhibitor, also can use the combination (just, a plurality of) of causticity sanitising agent and sour sanitising agent.
In this use, " a plurality of " refer to two kinds or more kinds of.
In this use, " comprising " refers to " including, but are not limited to " with similar term.
When referring to any numerical range, said scope should be understood to include any subrange between any numerical value and/or said minimum and the peak.
In this use, term " curing " refers to a coating, and wherein any crosslinkable component of compsn is carried out crosslinked at least in part.In certain embodiments, the cross-linking density of crosslinkable component (just, degree of crosslinking) scope is fully crosslinked 5% to 100%, such as 35% to 85%, or, sometimes, 50% to 85%.Those skilled in the art understand the existence of degree of crosslinking (just, cross-linking density) and can measure according to the whole bag of tricks, and such as dynamic mechanical analysis (DMTA), it uses Polymer Laboratories MK III DMTA analyzer under nitrogen, to carry out.
In this use, molecular weight refers to number-average molecular weight (M
w), it passes through gel permeation chromatography.
Generally refer to those at this any monomer () of quoting and can carry out monomer polymerized with another polymerizable compound such as another monomer or polymkeric substance.Except as otherwise noted, should be by clear, in case monomer component reacts to form compound each other, this compound will comprise the residue of monomer component.
Coated technique
As stated, the present invention relates to Chrome-free coating system coated substrate, such as the method for aluminium base.Unlike the additive method of coated with aluminum base material, method disclosed herein need not used any material (for example, sanitising agent, water, conversion coatings, electrodepositable coating composition) that contains chromium.Therefore, in certain embodiments, the material that in one or more step that is described below, uses is substantially devoid of chromium.In this use, " being substantially devoid of chromium " refers to the user and chromium is not added in the material wittingly.For example, in some embodiments, all material that in following step, uses is substantially devoid of chromium.In other embodiments, the one or more materials that in following step, use (for example, conversion coatings and/or electrodepositable coating composition) are substantially free of chromium, and the other materials (for example, sour sanitising agent) that uses in other steps simultaneously can contain chromium.Based on the object of the invention, the material that in step (a) to (g), uses can use technology known in the art to be applied on the base material, such as spraying and/or dipping technique.
This method at first applies the causticity sanitising agent at least a portion base material and begin from step (a).The causticity sanitising agent is used for removing and deoils and/or other pollutent (for example, dirt or dust), and it can before being applied to another coating composition on the base material, deposit to substrate surface in moulding and/or press back process.Can be used for the causticity sanitising agent that causticity sanitising agent of the present invention can be any silicate known in the art and/or non--silicate.Suitable silicate and/or non--silicate causticity sanitising agent comprise that METALAST CLEANER 1000 is (from METALAST International; Inc. company buys); RIDOLENE 298 (buying) from HENKEL company; CHEMKLEEN 275 (from PPG Industries, Inc company buys), perhaps their combination.
After step (a), at least a portion base material that will pass through step (a) carries out the processing of step (b) rinse stage, and water, carries out rinsing such as deionized water, so that from substrate surface flush away at least a portion causticity sanitising agent.
After step (b), (c) sour sanitising agent is applied at least a portion base material that alkalescence had cleaned.This acid sanitising agent is applied to the surface, so that the etching substrate surface.In certain embodiments, this acid sanitising agent is used for substrate surface is carried out deoxygenation (for example, removing the oxide skin that substrate surface forms), so that promote the uniform deposition of conversion coatings, is described below, and promotes the adhesion of conversion coatings to base material simultaneously.The appropriate acid sanitising agent that can be used for present method disclosed herein comprises, but is not limited to phosphoric acid, sulfuric acid, nitric acid, hydrofluoric acid, LNC DEOXIDIZER (buying from Oakite), TURCO DEOXIDIZER 6 (buying from Henkel), perhaps their combination.
After step (c), at least a portion base material that will pass through step (c) carries out the processing of step (d) rinse stage, and water, carries out rinsing such as deionized water, so that from substrate surface flush away at least a portion acid sanitising agent.
After step (d), (e) the conversion coatings compsn (pretreatment coating compsn) that will contain zirconium deposits at least a portion base material that acid had been cleaned then.In some embodiments, this conversion coatings comprises the pre-treatment body lotion, and it comprises 1,000 ten thousand/(ppm) to 10, and the zirconium of 000ppm is based on the gross weight of pre-treatment body lotion.In certain embodiments, this conversion coatings compsn can further comprise chromium.Traditional chromium (not containing zirconium) conversion coatings that contains is known in the art, and it also can be used for the present invention simultaneously.The instance that contains the chromium conversion coatings of this quasi-tradition comprises ALODINE1200S (buying from Henkel) and/or METLAST TCP-HF (available from Metalast International Inc).
Additionally, in some embodiments, for the application of the conversion coatings that replaces describing the last period, substrate surface can use technology known in the art to carry out anodize.
After step (e), at least a portion base material that will pass through step (e) carries out the processing of step (f) rinse stage, and water, carries out rinsing such as deionized water, so that from the excessive conversion coatings compsn of substrate surface flush away at least a portion.
After step (f), (g) with electrodepositable coating composition, it comprises corrosion inhibitor; Deposit at least a portion base material; Said at least a portion base material has used technology known in the art, such as anodic electrodeposition or cathode electrodeposition technology, comes above that and deposits conversion coatings.In some embodiments, this electrodepositable coating composition is the electrodepositable coating composition of negatively charged ion.In certain embodiments, the suitable corrosion inhibitor that can be used for this electrodepositable coating composition comprises nitrogen-containing heterocycle compound.Being suitable for use in this type of examples for compounds among the present invention, is azoles system (azo les) ， oxazole, thiazole, thiazoline, imidazoles, diazole, pyridine, indolizine, and triazine, tetrazolium, tolytriazole (tolutriazole), or their mixture.Suitable triazole comprises, for example, and 1,2,3-triazoles, 1,2,4-triazole, benzotriazole and their verivate, perhaps their combination.Be suitable for use in the 1,2,3-triazoles verivate among the present invention, comprise the 1-methyl isophthalic acid, 2,3-triazole, 1-phenyl-1,2,3-triazoles, 4-methyl-2-phenyl-1; 2, the 3-triazole, 1-benzyl-1,2,3-triazoles, 4-hydroxyl-1,2,3-triazoles, 1-amino-1,2; The 3-triazole, 1-benzamido--4-methyl isophthalic acid, 2,3-triazole, 1-amino-4,5-phenylbenzene-1,2,3-triazoles, 1; 2,3-triazole aldehyde, 2-methyl isophthalic acid, 2,3-triazole-4-carboxylic acid and 4-cyanic acid-1,2,3-triazoles, perhaps their combination.Be applicable to of the present inventionly 1,2, the 4-triazole derivative comprises the 1-methyl isophthalic acid, 2, and the 4-triazole; 1,3-phenylbenzene-1,2,4-triazole, 5-amino-3-methyl isophthalic acid, 2; The 4-triazole, 3-sulfydryl-1,2,4-triazole, 1,2; 4-triazole-3-carboxylic acid, 1-phenyl-1,2,4-triazole-5-ketone, 1-phenyl urazole, perhaps their combination.The suitable example of diazole and thiazole comprises 2-mercaptobenzothiazole, 2, and 5-dimercapto-1,3,4 thiadiazoles and verivate thereof, perhaps their combination.Be applicable to the verivate of benzotriazole of the present invention, comprise the 1-Methylbenzotriazole, 5,6-dimethylbiphenyl triazole; 2-phenyl benzotriazole, I-hydroxybenzotriazole, 1-benzotriazole carboxylic acid methyl ester; 2-(3 ', 5 '-dibutyl-2 '-phenylor) benzotriazole, perhaps their combination.In certain embodiments, the azole compounds consumption in electrodepositable coating composition is >=0.5wt%, based on the total resin solids of electrodepositable coating composition.In certain embodiments, the azole compounds consumption in electrodepositable coating composition is≤5wt%, based on the total resin solids of electrodepositable coating composition.In certain embodiments, the azole compounds amount ranges in the electrodepositable coating composition is the arbitrary combination of numerical value described in the aforementioned sentence, comprises that said numerical value is originally in interior.For example, in some embodiments, the azole compounds consumption is that 2wt% is to 4wt%, based on the total resin solids of electrodepositable coating composition.
Additionally, in some embodiments, in order to replace the application of the described electrodepositable coating composition of last paragraph, color is given coating composition (describing in detail hereinafter) and can be used technology known in the art to be applied on the base material.
In some embodiments, this method is made up of step (a) to (g) basically, and wherein at step (c), the material that uses in (e) and (g) is substantially devoid of chromium.
The base material of coating system
Aforesaid method can be used on the various base materials.Can comprise metal base with the suitable substrate that the present invention uses, the metal alloy base and the base material of metallize are such as the plastics of nickel plating.In some embodiments, this metal or metal alloy can be steel and/or aluminium.For example, this steel substrate can be a CRS, electro-galvanized steel, and/or hot dip galvanization steel.2XXX, 5XXX, 6XXX, or the duraluminum of 7XXX series, and alloy plating also can be used as base material.Be used for base material of the present invention and also can comprise titanium and/or titanium alloy.In some embodiments, this base material can comprise the part of vehicle, such as automobile body (for example, without restriction, car door; Body panels, box-shaped deck lid, top board, guard shield; Top and/or interlayer, rivet, take-off and landing device assembly, and/or be used for the crust of aircraft) and/or the framework of vehicle.In this use, " vehicle " or its variant include, but not limited to civilian, commercialization and military spacecraft, and/or land vehicle, and such as car, motorcycle, and truck.
Various coating composition described here can be used as the part that can deposit to the coating system on the base material and applies.This coating system typically comprises many coatings.Deposit to coating composition on the base material (for example, priming paint-finish paint, color is given, and/or transparent basically coating composition; Be described below) be cured basically or exsiccant the time, formed coating usually through methods known in the art (for example, through heat heating).
Depend on industry (for example, aerospace or automobile), various coatings are given coating such as priming paint-top coat layer or color, can be applied on the electrodepositable coating of at least a portion.For example, at aerospace industry, color is given coating, such as DESOPHANE (from PPG Industries, Inc buys), is deposited on the electrodepositable coating of at least a portion.In certain embodiments, prime coat such as DESOPRIME (from PPG Industries, Inc buys), is configured to electrodepositable coating and color and gives between the coating.
Be used for the common coating system of automotive industry, priming paint-top coat layer is such as DPX-1791; DPX-1804, DSPX-1537, GPXH-5379; OPP-2645; PCV-70118, and 1177-225A (from PPG Industries, Inc buys) typically is deposited on the electrodepositable coating of at least a portion.This priming paint-topcoat is used to strengthen the resistance to chipping (for example, color is given coating composition and/or substantial transparent coating composition) of after-applied coating, and the outward appearance that is of value to after-applied coating.In this use; " priming paint-finish paint " refers to, the paint base composition under after-applied coating composition, and comprised as thermoplastics and/or crosslinked (for example; Thermoset) material of film-forming resin, it generally is known in the organic coating compositions field.
It should be noted that in some embodiments this priming paint-topcoat does not use in coating system.Therefore, color is given coating and can be deposited on the electrodepositable coating of at least a portion.
In some embodiments, color is given coating composition (below be called " stratum basale (basecoat) ") and is deposited at least a portion priming paint topcoat (if existence).Any stratum basale coating composition well known in the prior art all can be used among the present invention.It should be noted that this coating composition typically comprises tinting material.
In certain embodiments, the coating composition of substantial transparent (below be called " transparent layer (clearcoat) ") is deposited at least a portion stratum basale coating." substantial transparent " coating in this use is a substantial transparent, and is not opaque.In certain embodiments, the coating composition of substantial transparent can comprise tinting material, yet its consumption can not make it after curing, cause clear coating composition opaque (not being substantial transparent).Any transparent layer coating composition well known in the prior art all can be used among the present invention.For example, at United States Patent(USP) No. 5,989, the transparent layer coating composition of 642,6,245,855,6,387,519 and 7,005,472 descriptions all can be used for this coating system.In certain embodiments, the coating composition of substantial transparent can also comprise particle, and such as silica granule, it is dispersed in this transparent layer coating composition and (such as after curing, is in the surface of transparent layer coating composition).In some embodiments, comprise the coating composition of polymkeric substance described here, can be used as the transparent layer coating composition.
One or more coating compositions described here can comprise tinting material and/or other optional material, and it is known in the prescription field of surface coatings.In this use, term " tinting material " refers to anyly can give the material that color and/or other opaqueness and/or other visual effect are given compsn.This tinting material can join in the coating by any suitable form, such as discrete particles, and dispersion-s, solution and/or thin slice (for example, aluminum slice).The mixture of single tinting material or two kinds or more kinds of tinting materials all can be used in the coating composition described here.
The instance of tinting material comprises pigment, dyestuff and stain (tints), such as in paint industry, use those and/or in Color Manufacturers Association (DCMA), list those, and special effect compositions.Tinting material can comprise, for example, finely divided pressed powder, but its be insoluble under working conditions, be wettable.Tinting material can be organic or inorganic, and can be accumulative or non--accumulative.Tinting material can join in the coating through use grinding vehicle, grinds vehicle such as acrylic acid or the like, and its use is well known to those skilled in the art.
The instance of pigment and/or color compositions includes, but not limited to the thick pigment of carbazole dioxazine, azo, monoazo, two azos; Naphthols AS, salt (color lake), benzimidazolone, condenses (condensation), metal complex, iso-dihydro-indole; Isoindoline and many ring phthalocyanines, quinacridone ， perylene, pyrene ketone (perinone), diketopyrrolopyrrolecocrystals, thioindigo; Anthraquinone, indanthrone, anthracene pyrimidine, flavanthrone, pyranthrone, anthanthrone dioxazine, triaryl carbonium ion, quinone and phthalein ketone (quinophthalone) pigment, diketopyrrolopyrrolecocrystals red (" DPPBO is red "), titanium oxide, carbon black and their mixture.Term " pigment " can exchange use with " colored filler ".
It is solvents and/or water base that the instance of dyestuff includes, but not limited to those, such as phthalocyanine green or phthalocyanine blue, and red stone, bismuth vannadate, anthraquinone ， perylene, aluminium and quinacridone.
The instance of stain comprises; But be not limited to; Be dispersed in the pigment in water base or the water-soluble carrier, such as available from Degussa, the AQUA-CHEM 896 of Inc.; Available from Eastman Chemical, the CHARISMA COLORANTS of the Accurate Dispersions department of Inc and MAXITONER INDUSTRIAL COLORANTS.
As stated, tinting material can be the dispersion-s form, and it includes but not limited to, nanoparticle dispersion.Nanoparticle dispersion can comprise the nanoparticle colorants and/or the coloring agent particle of one or more high dispersing, and it has produced perceived color and/or opaqueness and/or the visual effect of wanting.Nanoparticle dispersion can comprise tinting material, and such as pigment or dyestuff, its granularity is lower than 150nm, such as being lower than 70nm, perhaps is lower than 30nm.Nanoparticle can be through the grinding medium that is lower than the 0.5mm granularity grinds the coarse fodder pigment dyestuff or mineral dye is produced with having.At United States Patent(USP) No. 6,875, the instance to nanoparticle dispersion and preparation method thereof in 800 defines.Nanoparticle dispersion can also be through crystallization, deposition, and vapour phase condensation and chemistry grind the mode of (just, being partly dissolved) and produce.In order to make the nanoparticle coalescence again that minimizes in the coating, can use the nanoparticle dispersion of resin-coated.In this use, " nanoparticle dispersion of resin-coated " refers to, an external phase, and wherein be scattered here and there discrete " compound microparticle ", said " compound microparticle " comprise nanoparticle and are coated in the resin on the nanoparticle.The nanoparticle of resin-coated and the instance of method of manufacture thereof; The open 2005-0287348 of U.S. Patent application that submits on June 24th, 2004; The U.S. Provisional Application No.60/482 that on June 24th, 2003 submitted to; The U.S. Patent Application Serial No.11/337 that submitted on January 20th, 167 and 2006, on the books in 062.
The instance of operable special effect compositions comprises pigment and/or the compsn that has produced one or more appearance, said appearance such as reflection, pearliness, metalluster, phosphorescence, fluorescence, photochromic, photosensitive, thermochromism phenomenon, with angle variable color (goniochromism) and/or color-change.Other special effect compositions can provide other appreciable performance, such as opaqueness or texture.In nonrestrictive embodiment, special effect compositions can produce gamut (color shift), makes that coating color changes when coating is checked with different angles.The instance of color effect compositions is at United States Patent(USP) No. 6,894, and 086 describes to some extent.Other example color effect compositions can comprise the mica and/or the synthetic mica of clear-coated; The silica that applies; The aluminum oxide that applies, transparent liquid crystal pigment, liquid crystal coating; The interference that wherein produces, rather than because any compsn of the interference that the RI difference between material surface and the air produces owing to the RI difference in the material.
In some nonrestrictive embodiment, photosensitive composition and/or photochromic composition, it is exposed to the meeting of following time of one or more light source change its color reversiblely, also can be used for coating composition described here.Photochromic and/or photosensitive composition can get off to activate through the radiation that is exposed to provision wavelengths.When compsn was excited, its molecular structure changed, and the structure of change shows the color that is different from the compsn initial color that makes new advances.When removing radiation, photochromic and/or photosensitive composition can be got back to holddown, under this state, returns to initial color.In a non-limiting embodiments, photochromic and/or photosensitive composition can be colourless at unactivated state, at the excited state Show Color.In several minutes, complete color change can take place at millisecond, such as from 20 seconds to 60 seconds.Instance photochromic and/or photosensitive composition comprises photochromic dyes.
In non-limiting embodiments, photosensitive composition and/or photochromic composition can interrelate with the polymer materials of polymkeric substance and/or polymerizable components and/or combine at least in part, such as passing through covalent linkage.With the photosensitive compsn can from coating, move and crystallization different to some coating in the base material; According to a non-limiting embodiments of the present invention; And/or at least part bonded photosensitive composition and/or photochromic composition relevant with polymkeric substance and/or polymerizable components have the minimum migration from coating.The U. S. application series number No.10/892 that the instance of photosensitive composition and/or photochromic composition and method of manufacture thereof was submitted on July 16th, 2004 describes in 919 to some extent.
Usually, tinting material can any amount exist, and its consumption is enough to give vision and/or the color effects of desireing.Tinting material can account for 1 to 65wt% of compsn, such as 3 to 40wt% or 5 to 35wt%, based on composition total weight.
Coating composition can comprise other optional material that the topcoating formulation art is known, such as softening agent, and inhibitor, hindered amine as light stabilizer; UV light absorber and stablizer, tensio-active agent, flowing regulator; Thixotropic agent is such as wilkinite, pigment, filler; Organic cosolvent, catalyzer comprises phosphonic acids and other conventional auxiliary agent.
What should further understand is, forms one or more coating compositions of various coatings described here, can be " single component " (" 1K "), " two-pack " (" 2K "), perhaps multi-component compsn.After the 1K compsn will be understood to be in manufacturing, between the shelf lives or the like, all coating compositions all remain on the compsn of same container.2K compsn or multi-component combination will be understood that wherein various components using always before all independent compsn of preserving.1K or 2K coating composition all can such as heating, forced air or the like, be applied on the base material through any ordinary method, and solidify.
The coating composition that forms various coatings described here can use any technology known in the art to deposit or be applied on the base material.For example, coating composition can be applied on the base material through any of the whole bag of tricks, in the whole bag of tricks, includes, but not limited to spraying, brushes dipping, and roller coat.When being applied to a plurality of coating compositions on the base material; It should be noted that; Coating composition can be applied at least a portion of below coating composition, perhaps below after coating composition has cured, perhaps below before coating composition solidifying.If when coating composition was applied on the also uncured below coating composition, one or more uncured coating compositions can solidify simultaneously.
Coating composition can use any technology known in the art to be cured, such as, but be not limited to, heat energy, infrared, ionize or actinic radiation, perhaps their any combination.In certain embodiments, curing operation carries out under temperature >=10 ℃.In other embodiments, this is solidificated under temperature≤246 ℃ and carries out.In certain embodiments, curing can be carried out in the TR of the arbitrary combination of numerical value described in the aforementioned sentence, comprises that said numerical value is originally in interior.For example, this curing can be carried out under 120 ℃-150 ℃ of temperature.It should be noted, yet lower or higher temperature can be used as the essential curing mechanism that activates.
In certain embodiments, coating composition described here is cryogenic, the coating composition of moisture curable.In this use, term " low temperature, moisture curable " refers to, after being applied to base material; Coating composition can be cured in the presence of ambient air, and the relative humidity of air is 10% to 100%, such as 25% to 80%; Temperature is-10 ℃ to 120 ℃, such as 5 ℃ to 80 ℃, 10 ℃ to 60 ℃ of certain situations; And, in other cases, 15 ℃ to 40 ℃.
The desciccator diaphragm thickness scope of coating described here is 0.1 micron to 500 microns.In other embodiments, desciccator diaphragm thickness can be≤125 microns, such as≤80 microns.For example, desciccator diaphragm thickness scope is 15 microns to 60 microns.
In some embodiment that the present invention describes in detail, what those skilled in the art should understand is all can develop according to the spirit of whole instruction of the present invention various modifications and conversion that scheme is detailed.Therefore, some scheme disclosed herein only is illustrative, rather than restrictive, and protection scope of the present invention is provided by the entire scope of claim and all equivalent form of values thereof.
Embodiment
Example I
2024-T3 exposed aluminium panel carries out hydro-peening with CHEMKLEEN 275 solution at 130 ° of F and cleaned in 2 minutes, and said CHEMKLEEN 275 is for deriving from the alkaline cleansing agent of PPG Industries.After alkali cleaning, panel carries out thorough rinsing with deionized water.Panel was impregnated into acidic solution two minutes at 120 ° of F then.Acidic solution is through adopting 85% phosphoric acid of deionized water dilution 198.1 grams; 8.5 70% nitric acid of gram; 16.5 the TRITON CF-10 (available from Dow Chemical Company) of the TRITON X-100 (available from Dow Chemical Company) of gram and 11.1 grams arrives the five gallon bottle volume, uses CHEMFIL Buffer (available from the PPG Industries) pH 3.0 that neutralizes to obtain then.After in acid solution, handling, panel carries out thorough rinsing with deionized water, carries out blow dried with the warm air air draft.
Panel carries out electropaining then and covers in galvanic deposit body lotion (being described below), in body lotion, receive 50% Ultrafiltration afterwards.Galvanic deposit was carried out for 90 seconds at 100 to 170 volts, and bath temperature is 24-27 ℃.After galvanic deposit, panel all toasted 30 minutes down at 93 ℃ (200 ° of F) in coal gas heating baking oven.The electropaining cladding boards receives the 5% neutral salt atomizing of ASTM B117 then and handled 3000 hours.
The bath lotion composition that uses in the example I
Resin 1: the preparation of phosphated epoxy resin dispersion
819.2 part bisphenol A diglycidyl ether (EEW 188), 263.5 parts of dihydroxyphenyl propanes and 209.4 parts of 2-n-butoxy-1-alcoholic acid mixtures are heated to 115 ℃.This time, add 0.8 part ethyl triphenyl phosphorus iodide.Mixture at least 165 ℃ of heating, and was kept one hour.Mixture allows to be cooled to 88 ℃, and 51.3 parts of EKTASOLVE EEH solvents and 23.2 parts of 2-n-butoxy-1-ethanol are added.At 88 ℃, add by 32.1 part of 85% adjacent phosphoric acid 18.9 parts of phenyl-phosphonic acids and 6.9 parts of slurry that EKTASOLVE EEH forms.Reaction mixture maintains at least 120 ℃ and reaches 30 minutes subsequently.At this moment, mixture is cooled to 100 ℃, adds 71.5 parts deionized water gradually.In case add entry, keep about 100 ℃ to reach 2 hours.Reaction mixture is cooled to 90 ℃ then, adds 90.0 parts of HSDB 338s, adds 413.0 parts of CYMEL 1130 and 3.0 parts of deionized waters subsequently.After 30 minutes mixing, 1800.0 parts mixture is inverted in the deionized water of the stirring of diluting 1506.0 parts.348.0 parts other deionized water is added, generate the dispersion-s of homogeneous, it has 39.5% solids content at 110 ℃ after 1 hour.
This galvanic deposit body lotion is prepared as follows:
| Composition | Weight part |
| Phosphated epoxy resin dispersion | 1522 |
| Pigment paste 1 | 331 |
| Deionized water | 1947 |
1The gray paint paste, ACPP-1120, available from PPG Industries, Inc., 50% solid content.
The thorough blend of mentioned component is produced and is had 19% solids content, the resin blend of pigment ratio 0.2.
Example II
2024-T3 exposed aluminium panel carries out hydro-peening with CHEMKLEEN 275 solution at 130 ° of F and cleaned in 2 minutes, and said CHEMKLEEN 275 is for deriving from the alkaline cleansing agent of PPG Industries.After alkali cleaning, panel carries out thorough rinsing with deionized water.Panel was impregnated into acidic solution two minutes at 120 ° of F then.Acidic solution is through adopting 85% phosphoric acid of deionized water dilution 198.1 grams; 8.5 70% nitric acid of gram; 16.5 the TRITON CF-10 (available from Dow Chemical Company) of the TRITON X-100 (available from Dow Chemical Company) of gram and 11.1 grams arrives the five gallon bottle volume, uses CHEMFIL Buffer (available from the PPG Industries) pH 3.0 that neutralizes to obtain then.After pickling, panel carries out thorough rinsing with deionized water.Then panel is immersed and fluoridize in the zirconic acid, reach two minutes at 100 ° of F.Fluoridize zirconic acid to the five gallon bottle volume through adopting deionized water to dilute 45% of 16.6 grams, and, obtain acid bath liquid with CHEMFIL Buffer (available from the PPG Industries) pH4.5 that neutralizes.After in acidic solution, handling, panel carries out thorough rinsing with deionized water, carries out blow dried with the warm air air draft.
Panel carries out electropaining then and covers in electrodeposition bath (being described below), in body lotion, receive 50% Ultrafiltration afterwards.Galvanic deposit was carried out for 90 seconds at 100 to 170 volts, and bath temperature is 24-27 ℃.After galvanic deposit, panel all toasted 30 minutes down at 93 ℃ (200 ° of F) in coal gas heating baking oven.5% neutral salt that the electropaining cladding boards receives ASTM B117 then atomized 3000 hours.
The bath lotion composition that uses in the example II
Resin II: phosphated epoxy resin dispersion preparation
819.2 part bisphenol A diglycidyl ether (EEW 188), 263.5 parts of dihydroxyphenyl propanes and 209.4 parts of 2-n-butoxy-1-alcoholic acid mixtures are heated to 115 ℃.This time, add 0.8 part ethyl triphenyl phosphorus iodide.Mixture at least 165 ℃ of heating, and was kept one hour.Mixture allows to be cooled to 88 ℃, and 51.3 parts of EKTASOLVE EEH solvents and 23.2 parts of 2-n-butoxy-1-ethanol are added.At 88 ℃, add by 32.1 part of 85% adjacent phosphoric acid 18.9 parts of phenyl-phosphonic acids and 6.9 parts of slurry that EKTASOLVE EEH forms.Reaction mixture maintains at least 120 ℃ and reaches 30 minutes subsequently.At this moment, mixture is cooled to 100 ℃, adds 71.5 parts deionized water gradually.In case add entry, keep about 100 ℃ to reach 2 hours.Reaction mixture is cooled to 90 ℃ then, adds 90.0 parts of HSDB 338s, adds 413.0 parts of CYMEL 1130 and 3.0 parts of deionized waters subsequently.After 30 minutes mixing, 1800.0 parts mixture is inverted in the deionized water of the stirring of diluting 1506.0 parts.348.0 parts other deionized water is added, generate the dispersion-s of homogeneous, it has 39.5% solids content at 110 ℃ after 1 hour.
The resin blend of above-mentioned phosphated epoxy resin is prepared as follows:
| Composition | Weight part |
| Phosphated epoxy resin dispersion+corrosion inhibitor of embodiment 1 | 1522 |
| Pigment paste 1 | 331 |
| Deionized water | 1947 |
1The gray paint paste, ACPP-1120, available from PPG Industries, Inc., 50% solid content.
The thorough blend of mentioned component is produced and is had 19% solids content, the resin blend of pigment ratio 0.2.
Test result is summed up
Test result shows that when comparing with the panel of example I, the panel of example I I has shown (that is less foaming, of improved corrosive nature; Surface layer and cut), corrosion still less and indenture still less at the cut place.
Claims (20)
1. the method for a coated substrate, it comprises: (a) the causticity sanitising agent is applied at least a portion of base material; (b) with at least a portion base material of water rinse through step (a); (c) sour sanitising agent is applied to the base material of at least a portion of process causticity cleaning; (d) with at least a portion base material of water rinse through step (c); And the conversion coatings compsn that (e) will contain zirconium deposits at least a portion base material that acid cleaned; And at least a material that wherein uses in step (c) and (e) is substantially devoid of chromium.
2. the process of claim 1 wherein that this method further comprises: (f) with at least a portion base material of water rinse through step (e); And (g) electrodepositable coating composition is deposited at least a portion of conversion coatings, wherein this electrodepositable coating composition comprises corrosion inhibitor.
3. the method for claim 2, wherein electrodepositable coating composition is substantially devoid of chromium.
4. the method for claim 2, wherein corrosion inhibitor comprises azole compounds.
5. the method for claim 4, wherein azole compounds comprises benzotriazole, 3-sulfydryl-1,2,4-triazole, 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4 thiadiazoles, 1-Methylbenzotriazole or their combination.
6. the method for claim 2; Wherein electrodepositable coating composition comprises the not phosphated epoxy resin of agglomerative, and wherein phosphated epoxy resin comprises the mixture of the reaction product of polymeric rings oxygen compound and phosphoric acid, organic phospho acid, organic Hypophosporous Acid, 50 or their combination.
7. the process of claim 1 wherein sour detergent package phosphoric acid, sulfonic acid, hydrofluoric acid, nitric acid or their combination.
8. the process of claim 1 wherein that the conversion coatings compsn is substantially devoid of chromium.
9. the method for a coated substrate, it comprises: (a) the causticity sanitising agent is applied at least a portion of base material; (b) with at least a portion base material of water rinse through step (a); (c) sour sanitising agent is applied to the base material of at least a portion of process causticity cleaning; (d) with at least a portion base material of water rinse through step (c); And the conversion coatings compsn that (e) will contain zirconium deposits at least a portion base material that acid cleaned; And the material that wherein uses in step (c) and (e) is substantially devoid of chromium.
10. the method for claim 9, wherein this method further comprises: (f) with at least a portion base material of water rinse through step (e); And (g) electrodepositable coating composition is deposited at least a portion of conversion coatings, wherein this electrodepositable coating composition comprises corrosion inhibitor;
11. the method for claim 10, wherein corrosion inhibitor comprises azole compounds.
12. the method for claim 11, wherein azole compounds comprises benzotriazole, 3-sulfydryl-1,2,4-triazole, 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4 thiadiazoles, 1-Methylbenzotriazole or their combination.
13. the method for claim 10; Wherein electrodepositable coating composition comprises the not phosphated epoxy resin of agglomerative, and wherein phosphated epoxy resin comprises the mixture of the reaction product of polymeric rings oxygen compound and phosphoric acid, organic phospho acid, organic Hypophosporous Acid, 50 or their combination.
14. the method for claim 9, the material that wherein uses in step (c) and (e) is substantially devoid of chromium.
15. the method for a coated substrate, it is made up of following steps basically: (a) the causticity sanitising agent is applied at least a portion of base material; (b) with at least a portion base material of water rinse through step (a); (c) sour sanitising agent is applied to the base material of at least a portion of process causticity cleaning; (d) with at least a portion base material of water rinse through step (c); The conversion coatings compsn that (e) will contain zirconium is applied at least a portion base material that acid cleaned; (f) with at least a portion base material of water rinse through step (e); And (g) electrodepositable coating composition is applied at least a portion of conversion coatings compsn, wherein this electrodepositable coating composition comprises corrosion inhibitor; And wherein at step (c), (e) material with (g) middle use is substantially devoid of chromium.
16. the method for claim 15, wherein corrosion inhibitor comprises azole compounds.
17. the method for claim 16, wherein azole compounds comprises benzotriazole, 3-sulfydryl-1,2,4-triazole, 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4 thiadiazoles, 1-Methylbenzotriazole or their combination.
18. the method for claim 15; Wherein electrodepositable coating composition comprises the not phosphated epoxy resin of agglomerative, and wherein phosphated epoxy resin comprises the mixture of the reaction product of polymeric rings oxygen compound and phosphoric acid, organic phospho acid, organic Hypophosporous Acid, 50 or their combination.
19. the base material that applies according to the method for claim 1.
20. the base material of claim 19, wherein base material is an aluminium.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/414,719 US20100243108A1 (en) | 2009-03-31 | 2009-03-31 | Method for treating and/or coating a substrate with non-chrome materials |
| US12/414,719 | 2009-03-31 | ||
| PCT/US2010/022206 WO2010117479A1 (en) | 2009-03-31 | 2010-01-27 | Method for treating and/or coating a substrate with non-chrome materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102369246A true CN102369246A (en) | 2012-03-07 |
| CN102369246B CN102369246B (en) | 2014-07-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201080014308.1A Expired - Fee Related CN102369246B (en) | 2009-03-31 | 2010-01-27 | Method for treating and/or coating a substrate with non-chrome materials |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US20100243108A1 (en) |
| EP (1) | EP2414463A1 (en) |
| JP (2) | JP5539491B2 (en) |
| KR (1) | KR101379053B1 (en) |
| CN (1) | CN102369246B (en) |
| BR (1) | BRPI1006183A2 (en) |
| CA (1) | CA2754819C (en) |
| HK (1) | HK1163728A1 (en) |
| MX (1) | MX2011010321A (en) |
| RU (1) | RU2503697C2 (en) |
| WO (1) | WO2010117479A1 (en) |
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| CN111154347A (en) * | 2020-01-09 | 2020-05-15 | 浙江工业大学 | Autophoretic coating and method for improving performance of autophoretic coating |
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| EP2623639A1 (en) | 2012-02-02 | 2013-08-07 | Hydro Aluminium Deutschland GmbH | Aluminium alloy strip with improved surface visual appearance and method for producing thereof |
| ES2924127T3 (en) | 2012-08-29 | 2022-10-04 | Ppg Ind Ohio Inc | Lithium-containing zirconium pretreatment compositions, associated methods for treating metal substrates, and related coated metal substrates |
| US10125424B2 (en) | 2012-08-29 | 2018-11-13 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
| KR101716066B1 (en) | 2012-10-11 | 2017-03-13 | 피알시-데소토 인터내쇼날, 인코포레이티드 | Coating/sealant systems, aqueous resinous dispersions, methods for making aqueous resinous dispersions, and methods of electrocoating |
| US9273399B2 (en) | 2013-03-15 | 2016-03-01 | Ppg Industries Ohio, Inc. | Pretreatment compositions and methods for coating a battery electrode |
| US9303167B2 (en) | 2013-03-15 | 2016-04-05 | Ppg Industries Ohio, Inc. | Method for preparing and treating a steel substrate |
| BR112015023836A2 (en) * | 2013-03-16 | 2017-07-18 | Prc Desoto Int Inc | composition for application to a metallic substrate, coated article and method for manufacturing a coated article |
| RU2631226C2 (en) | 2013-05-14 | 2017-09-19 | Прк-Десото Интернэшнл, Инк. | Permanganate-based conversion coating compositions |
| US9267041B2 (en) * | 2014-03-28 | 2016-02-23 | Goodrich Corporation | Anti-corrosion and/or passivation compositions for metal containing substrates and methods for making, enhancing, and applying the same |
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Also Published As
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| CA2754819C (en) | 2015-05-12 |
| HK1163728A1 (en) | 2012-09-14 |
| BRPI1006183A2 (en) | 2016-03-01 |
| JP5539491B2 (en) | 2014-07-02 |
| RU2011143773A (en) | 2013-05-10 |
| JP2014040676A (en) | 2014-03-06 |
| KR20120001792A (en) | 2012-01-04 |
| JP2012522129A (en) | 2012-09-20 |
| EP2414463A1 (en) | 2012-02-08 |
| CN102369246B (en) | 2014-07-30 |
| KR101379053B1 (en) | 2014-03-28 |
| RU2503697C2 (en) | 2014-01-10 |
| US20100243108A1 (en) | 2010-09-30 |
| WO2010117479A1 (en) | 2010-10-14 |
| MX2011010321A (en) | 2011-10-11 |
| CA2754819A1 (en) | 2010-10-14 |
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