CA2199983A1 - Treatment to improve corrosion resistance of autodeposited coatings on metallic surfaces - Google Patents
Treatment to improve corrosion resistance of autodeposited coatings on metallic surfacesInfo
- Publication number
- CA2199983A1 CA2199983A1 CA002199983A CA2199983A CA2199983A1 CA 2199983 A1 CA2199983 A1 CA 2199983A1 CA 002199983 A CA002199983 A CA 002199983A CA 2199983 A CA2199983 A CA 2199983A CA 2199983 A1 CA2199983 A1 CA 2199983A1
- Authority
- CA
- Canada
- Prior art keywords
- group
- vinyl
- total weight
- weight percent
- symbol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
- B05D7/142—Auto-deposited coatings, i.e. autophoretic coatings
- B05D7/144—After-treatment of auto-deposited coatings
Abstract
A process enhances corrosion resistance of autodeposited coatings on metallic surfaces by contacting the uncured coating on the metallic surface with a reaction rinse solution containing complex fluoride anions. In a preferred use, because the protective properties of the autodeposited coatings are improved on both cold rolled and galvanized steel, both may be processed simultaneously, providing practical and economic advantages.
Description
9~ A A ~ A ~ PCT/US95/11404 TREATME?~T TO IM~ROVE CORROSION RESISTANOE OF AUTODEPOSITED
COATINGS ON METAL~C SURFAOES
BACKGROUND OF THE rNVENTION
s Field ofthe Inventinn This invention rdates to the h~ of ~l~todeposited co~ r~ in order to retain longer or to P 'r~Anre the collos;on rc~ e provided by the CO~ pc on metallic sur-faces, particularly fc.,;f~,lous articles, inc~urlinP zinc coated (also called "galvanized") steel.
o Sta~ c"L of Rela~ed Art Autod~po.,;h~ is a generic term used to descri~e the deposition of a subs~;~mi~lly uniforrn orgar~ic binder co~ lP film on a metal surface, ~enerally preferab~y pre-c~n~A without the use of externally imposed electric current in the deposition process.
o~t,o~ .. involves the use of an aqueous coating co~ oS;I;on co..lh;..;.lP dispersed ts organic resin, usually at relatively low solids conce..hallon such as ~ to 12 %, normally less than 10 %, to for;m a coating of relatively high solids COI~C~ ahol~ usually greater than 10 %, on a metallic surface i,..l~ ed therein, with the coating i~ Gsulg in thick-ness and mass the longer the time that the met~tliC surface is ill~lllc.ae~ in the coating ~llll~oai~ion. Because the 3t~tode~Gs;lion ~lOCLSS iS driven ~ ;r~lly, rather than elec-20 trically, it coats whw~ r the solution wets the surface ofthe aulJall~e, depositing a rda-tively ~uru--u coating on even ~lh;C~lC or co.~ , shapes or designs of the substrate.
In generaL ~tudP~os;~;..D Cc,~ G, l;0~5 are ~ lc acid r~ol~l;nl~ ha~ g solid I
W096110461 0 ~ ~ ~ F~S95lll4o4 resin particles dispersed therein in very finely di~ided forrn. The coating forrned while the metal substrate used is in~,l.e~ed in the bath is generally wet and fairly weak, ~AIthollEh suffisiently strong to I~lAil~t5l;ll itself against gravity and moderate spraying forces. In this state the coating is described as "uncured". To make an autodeposition s coated object suitable for normal practical use, the uncured coating is dried, usually with the aid of heat. The coating is then described as "curedN.
Basic co~ctihlents of an A~ltodepositing composition are water, resin solids dis-persed in the ~u~ous medium of the comptjsilion, and activator, that is, an ingredient or ingte~l;c.ll~ which convert the composition into one which will form on a metallic surface 10 a resinous coating which increases in thickness or areal density as long as the surface is inl,lle,sed in the composition. Various types of activators or activating systems are known. The activating system generally comprises an acidic oxidizing system, foreA&~le: hydrogen peroxide and HF; HNO3; a ferric ion contAinin~ compound and HF;and other ~l..~h~alions of (i) soluble metal cG..l~;n;ng compounds such as, for example, 15 silver fluoride, ferrous oxide, cupric sulfate, cobqltous nitrate, silver ac~t~te ferrous phosphate, chromium fluoride, s~tlmil~m fluoride, stannous fluoride, lead dioxide, and silver nitrate, in an amount between about 0.025 and about ~0 grams per liter (hereinafter often abbreviated as "g/l,"), with (ii) one or more acids such as hydrofluoric, sulfuric, hydrochloric, nitric, and phosphoric acids and organic acids such as, for example, acetic, 20 chloroacetic, and trichloroacetic acids.
Autodeposition composition can be used to form coatings which have good aes-thetic prope~ lies and which protect the underlying metallic substrate from being degrad-ed, e.g., corroded by water. Many applications however require the autodeposited coat-ing have particularly good propel lies for use. Various means have been developed to irn-25 prove the propel lies of autodeposited coatings including:(a) chemical prel-~al...enl ofthe met~llic surface prior to forming the coatings;
~b) selection of specific particular resins which form the coating and (c) chemical post-l, e à~ of the freshly formed or uncured coating.
U.S. Patent 4,800,106, the entire disclosure of which, except to the extent that it 30 may be inconsistent with any explicit ~l~len~e~,t herein, is hereby incorporated herein by reference, describes a number of references dealing with various treatments of uncured ~ulodeposited coal;n~,s inclu~ing the l~.,al ...~.~l of freshly formed autodeposited coatings wo 96rl046l PCI/IJS95/11404 with acidic, ~qu~us solution of one or more chromium compounds to improve corrosion resist~nce. While chemiç~l lt.~ e.~s such as "reaction rinses" (which are defined as any rinses c~nl~in;l~g deliberately added ingredie.~ls other than water and air), following - autodeposition coAtingc can provide for improved corrosion resict~rlce~ gloss or other s prope.lies, o~entimes the ~leS~ creates problems such as waste disposal problems.
Thus the use of chromium cGn~ ;-,g compounds in post~ ,AI~lf l~t raises a disposal and en~"ro-..~ .lAI proble.ll or disadvantage because the chromium must first be removed or otherwise treated before disposal to waste.
In the past, cold rolled steel and galvanized steel often required dilrcrent autode-10 posited co~ requiring di~re"t post-l~e.~nle..~ i.e. di~.enl reaction rinses for the coatin~c. One object of the present invention is to provide a process which incl~ldes a reaction rinse which will retain, or improve, the corrosion resistance properties of the autodeposited coating while employing non-chromium cont~ining materials which are en~iron...~ -~ally acceptable, raising no disposal problems.
s A further object of the present invention is to provide a single reaction rinse for ~1 ;n~ on a variety of metal substrates, paricularly on both cold rolled steel and galva-nized steel. In this way a single reaction rinse may be used for composite objects that contain two or more distinct types of metal surface areas and autodeposited coatings . . thereon, so that cimlllt~neollc processing of such composite objects can be more efficient-Iy carried out.
DESCRIPTION OF THE INVENTION
General Principles of Description Except in the claims and the operating examples, or where otherwise expressly indicated, all numerical quantities in this description indicating amounts of material or 2s conditions of reaction and/or use are to be understood as modified by the word "about"
in describing the broadest scope of the invention. Practice within the numerical limits stated is generally p~t;rt"~d. Also, unless c~, cssly stated to the contrary: percent, "parts of", and ratio values are by weight; the term "polymer" includes "oligomer", "copoly-mer", "terpolymer", and the like; the description of a group or class of materials as suit-30 able or p,~re-,ed for a given purpose in connection with the invention implies that mix-tures of any two or more ofthe members ofthe group or class are equally suitable or pre-ferred; desc i~,on of con~tinlçnt~ in chemical terms refers to the conctituents at the time WO 96110461 ~ 3 PCT/US95/11404 of addition to any combination specified in the description, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed; speci-fication of materials in ionic form implies the presence of sufficient counterions to produce electrical neutrality for the composition as a whole (any counterions thus impli-s citly specified should preferably be selected from among other constit-lents explicitly specified in ionic form, to the extent possible; otherwise such counterions may be freely selected, except for avoiding counterions that act adversely to the objects of the inven-tion); and the term "mole" and its variations may be applied to ele ..~ -t~l ionic, and any other chemical species defined by number and type of atoms present, as well as to 10 compounds with well defined molecules.
Summary of the Invention In accordance with this invention, the corrosion resict~nce of a metal substratecoated with a dried and optionally cured autodeposited coating is improved from the level that would be achieved by rinsing the wet, uncured autodeposited coating with plain 15 water, by treating the uncured coating on the metallic substrate with an aqueous rinse so-lution that comprises, preferably consisls essçnti~lly of, or still more prefe~ably consisls of, water and anions that consist of (i) at least four fluorine atoms and (ii) at least one atom of an element selected from the group cons;sling of tit~nillm~ zirconium, h~fnium~
siIicon, and boron and, optionally, ~iii) one or more oxygen atoms; the rinse solution may 20 also contain other ingredients, for such purposes as pH adjuctment or in general any other inyedients that do not act adversely to the objects of the invention. The anions may be introduced into the rinse solution by addition of the corresponding acids or of salts in~llldinE the anions; in either case, the stoichiometric equivalent as the specified anions is con~idered for the purposes of this description to be present when any such ma-25 terial is dissolved in a ll r~ el~l rinse solution, irrespective of the actual degree of ioni-zation in the solution.
Description of P, ere" ed Embodiments Except for use of a specific type of reaction rinse as described herein, a process accoldillg to this invention preferably is like those of prior art autodeposition processes.
30 Thus, in a co r'~e process, before autodeposition coating the metal substrate is prefer-ably cleaned, generally using an ~lk~lin~., cornmercially available cleaner. The cleaning is carried out by spraying, immersion or any other effective method or colnbinalion of W0 96110461 ' ~ PCr/US95/11404 methods, afller which the coated workpiece preferably is rinsed with water to remove any residual cl~ning solution, prior to deposition of the coating The autodeposited film is preferably applied by i"~ ..sion of the substrate into a coating bath cont~ining the desired polymer latex, emulsion or dispersion for a time sufficient to coat the substrate s with a wet film thickness that preferably is, with increas;ng preference in the order given, at least 2, 4, 5, 6.0, 6.5, 6.8, 7.1, 7.4, 8.0, 9.0, 10, 11, 12, 13, 14, or 15 micrometers (here-ina~er often abbreviated "Il") and jnd~pc~d&~ y preferably is, with inereasing pref~rence in the order given, not more than 50, 40, 30, 28, 27, 26, or 25 Il. The time and tem-perature during autodeposition will vary dependil g on the nature of the particular resins 10 in the coating After the coating is deposited, a reaction rinse is applied in the present invention to improve the cGll~sion re~;~t~nce ofthe lata fonned cured coating The chemical composition of the a~todeposition bath may be selected without limit from all the con,po~ilions that produce coalhlgs useful for any purpose, in particular including those compositions taught in U. S. Patents 3,585,084, 3,709,743, 3,776,848, 4,180,603, 4,191,676, 4,313,861, 4,347,172, 4,366,195, 4,657,788, all of which, to the extent that they desc.il~ c~ ;ons suitable for autodeposition baths and are not incon-sistent with any explicit s~le .-e~l herein are hereby incorporated herein by reference.
~ l~r~ d cGd~ which are treated acco,~li ,g to the process of the present inven-tion are formed from an autodepositing composition in which particles of resin are dis-20 persed in an aqueous acidic solution which is plepared by combining hydrofluoric acidand a soluble ferric iron-cont~ining ingredient, most preferable ferric fluoride.
U.S. Patent Nos. 4,347,172 and 4,411,937 which disclose the preferred activatingsystem disclose the optional use in the composition of an oxidizing agent in an amount to provide from about 0.01 to about 0.2 oxidizing equivalent per liter of composition.
25 F.~ p~i of suitable o~udi~"~g agents are hydrogen peroxide, dicl,lo,nate, perm~ng~n~te, nitrate, persulfate, perborate, p-benzoquinone and p-nitrophenol. Hydrogen peroxide is most pr~f~ d.
With respect to particular resins that can be used in the coating composition ofthe present invention, one ~ler~lle;d class can be p.e~,a,ed by copolynle,~il-g (A) vinyli-30 dene chloride monomer with (B) ,llonolne, ~ such as meth~crylic acid, methyl methacryl-ate, acrylonitrile, and vinyl chloride and (C) a water soluble ionic material such as sodi-um sulfoethyl methacrylate. .Alth-~ugh the constin~ ts CGllllJIiSil~g the above-desired res-~ ~ ~t ~ 3 in can vary over a relatively wide range, in general the resin will comprise the polymer-- ized constituents in the following amounts I) between 45 and 99 %, based on the total weight of ."ono~ used, of vinylidene chloride n~onG~
COATINGS ON METAL~C SURFAOES
BACKGROUND OF THE rNVENTION
s Field ofthe Inventinn This invention rdates to the h~ of ~l~todeposited co~ r~ in order to retain longer or to P 'r~Anre the collos;on rc~ e provided by the CO~ pc on metallic sur-faces, particularly fc.,;f~,lous articles, inc~urlinP zinc coated (also called "galvanized") steel.
o Sta~ c"L of Rela~ed Art Autod~po.,;h~ is a generic term used to descri~e the deposition of a subs~;~mi~lly uniforrn orgar~ic binder co~ lP film on a metal surface, ~enerally preferab~y pre-c~n~A without the use of externally imposed electric current in the deposition process.
o~t,o~ .. involves the use of an aqueous coating co~ oS;I;on co..lh;..;.lP dispersed ts organic resin, usually at relatively low solids conce..hallon such as ~ to 12 %, normally less than 10 %, to for;m a coating of relatively high solids COI~C~ ahol~ usually greater than 10 %, on a metallic surface i,..l~ ed therein, with the coating i~ Gsulg in thick-ness and mass the longer the time that the met~tliC surface is ill~lllc.ae~ in the coating ~llll~oai~ion. Because the 3t~tode~Gs;lion ~lOCLSS iS driven ~ ;r~lly, rather than elec-20 trically, it coats whw~ r the solution wets the surface ofthe aulJall~e, depositing a rda-tively ~uru--u coating on even ~lh;C~lC or co.~ , shapes or designs of the substrate.
In generaL ~tudP~os;~;..D Cc,~ G, l;0~5 are ~ lc acid r~ol~l;nl~ ha~ g solid I
W096110461 0 ~ ~ ~ F~S95lll4o4 resin particles dispersed therein in very finely di~ided forrn. The coating forrned while the metal substrate used is in~,l.e~ed in the bath is generally wet and fairly weak, ~AIthollEh suffisiently strong to I~lAil~t5l;ll itself against gravity and moderate spraying forces. In this state the coating is described as "uncured". To make an autodeposition s coated object suitable for normal practical use, the uncured coating is dried, usually with the aid of heat. The coating is then described as "curedN.
Basic co~ctihlents of an A~ltodepositing composition are water, resin solids dis-persed in the ~u~ous medium of the comptjsilion, and activator, that is, an ingredient or ingte~l;c.ll~ which convert the composition into one which will form on a metallic surface 10 a resinous coating which increases in thickness or areal density as long as the surface is inl,lle,sed in the composition. Various types of activators or activating systems are known. The activating system generally comprises an acidic oxidizing system, foreA&~le: hydrogen peroxide and HF; HNO3; a ferric ion contAinin~ compound and HF;and other ~l..~h~alions of (i) soluble metal cG..l~;n;ng compounds such as, for example, 15 silver fluoride, ferrous oxide, cupric sulfate, cobqltous nitrate, silver ac~t~te ferrous phosphate, chromium fluoride, s~tlmil~m fluoride, stannous fluoride, lead dioxide, and silver nitrate, in an amount between about 0.025 and about ~0 grams per liter (hereinafter often abbreviated as "g/l,"), with (ii) one or more acids such as hydrofluoric, sulfuric, hydrochloric, nitric, and phosphoric acids and organic acids such as, for example, acetic, 20 chloroacetic, and trichloroacetic acids.
Autodeposition composition can be used to form coatings which have good aes-thetic prope~ lies and which protect the underlying metallic substrate from being degrad-ed, e.g., corroded by water. Many applications however require the autodeposited coat-ing have particularly good propel lies for use. Various means have been developed to irn-25 prove the propel lies of autodeposited coatings including:(a) chemical prel-~al...enl ofthe met~llic surface prior to forming the coatings;
~b) selection of specific particular resins which form the coating and (c) chemical post-l, e à~ of the freshly formed or uncured coating.
U.S. Patent 4,800,106, the entire disclosure of which, except to the extent that it 30 may be inconsistent with any explicit ~l~len~e~,t herein, is hereby incorporated herein by reference, describes a number of references dealing with various treatments of uncured ~ulodeposited coal;n~,s inclu~ing the l~.,al ...~.~l of freshly formed autodeposited coatings wo 96rl046l PCI/IJS95/11404 with acidic, ~qu~us solution of one or more chromium compounds to improve corrosion resist~nce. While chemiç~l lt.~ e.~s such as "reaction rinses" (which are defined as any rinses c~nl~in;l~g deliberately added ingredie.~ls other than water and air), following - autodeposition coAtingc can provide for improved corrosion resict~rlce~ gloss or other s prope.lies, o~entimes the ~leS~ creates problems such as waste disposal problems.
Thus the use of chromium cGn~ ;-,g compounds in post~ ,AI~lf l~t raises a disposal and en~"ro-..~ .lAI proble.ll or disadvantage because the chromium must first be removed or otherwise treated before disposal to waste.
In the past, cold rolled steel and galvanized steel often required dilrcrent autode-10 posited co~ requiring di~re"t post-l~e.~nle..~ i.e. di~.enl reaction rinses for the coatin~c. One object of the present invention is to provide a process which incl~ldes a reaction rinse which will retain, or improve, the corrosion resistance properties of the autodeposited coating while employing non-chromium cont~ining materials which are en~iron...~ -~ally acceptable, raising no disposal problems.
s A further object of the present invention is to provide a single reaction rinse for ~1 ;n~ on a variety of metal substrates, paricularly on both cold rolled steel and galva-nized steel. In this way a single reaction rinse may be used for composite objects that contain two or more distinct types of metal surface areas and autodeposited coatings . . thereon, so that cimlllt~neollc processing of such composite objects can be more efficient-Iy carried out.
DESCRIPTION OF THE INVENTION
General Principles of Description Except in the claims and the operating examples, or where otherwise expressly indicated, all numerical quantities in this description indicating amounts of material or 2s conditions of reaction and/or use are to be understood as modified by the word "about"
in describing the broadest scope of the invention. Practice within the numerical limits stated is generally p~t;rt"~d. Also, unless c~, cssly stated to the contrary: percent, "parts of", and ratio values are by weight; the term "polymer" includes "oligomer", "copoly-mer", "terpolymer", and the like; the description of a group or class of materials as suit-30 able or p,~re-,ed for a given purpose in connection with the invention implies that mix-tures of any two or more ofthe members ofthe group or class are equally suitable or pre-ferred; desc i~,on of con~tinlçnt~ in chemical terms refers to the conctituents at the time WO 96110461 ~ 3 PCT/US95/11404 of addition to any combination specified in the description, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed; speci-fication of materials in ionic form implies the presence of sufficient counterions to produce electrical neutrality for the composition as a whole (any counterions thus impli-s citly specified should preferably be selected from among other constit-lents explicitly specified in ionic form, to the extent possible; otherwise such counterions may be freely selected, except for avoiding counterions that act adversely to the objects of the inven-tion); and the term "mole" and its variations may be applied to ele ..~ -t~l ionic, and any other chemical species defined by number and type of atoms present, as well as to 10 compounds with well defined molecules.
Summary of the Invention In accordance with this invention, the corrosion resict~nce of a metal substratecoated with a dried and optionally cured autodeposited coating is improved from the level that would be achieved by rinsing the wet, uncured autodeposited coating with plain 15 water, by treating the uncured coating on the metallic substrate with an aqueous rinse so-lution that comprises, preferably consisls essçnti~lly of, or still more prefe~ably consisls of, water and anions that consist of (i) at least four fluorine atoms and (ii) at least one atom of an element selected from the group cons;sling of tit~nillm~ zirconium, h~fnium~
siIicon, and boron and, optionally, ~iii) one or more oxygen atoms; the rinse solution may 20 also contain other ingredients, for such purposes as pH adjuctment or in general any other inyedients that do not act adversely to the objects of the invention. The anions may be introduced into the rinse solution by addition of the corresponding acids or of salts in~llldinE the anions; in either case, the stoichiometric equivalent as the specified anions is con~idered for the purposes of this description to be present when any such ma-25 terial is dissolved in a ll r~ el~l rinse solution, irrespective of the actual degree of ioni-zation in the solution.
Description of P, ere" ed Embodiments Except for use of a specific type of reaction rinse as described herein, a process accoldillg to this invention preferably is like those of prior art autodeposition processes.
30 Thus, in a co r'~e process, before autodeposition coating the metal substrate is prefer-ably cleaned, generally using an ~lk~lin~., cornmercially available cleaner. The cleaning is carried out by spraying, immersion or any other effective method or colnbinalion of W0 96110461 ' ~ PCr/US95/11404 methods, afller which the coated workpiece preferably is rinsed with water to remove any residual cl~ning solution, prior to deposition of the coating The autodeposited film is preferably applied by i"~ ..sion of the substrate into a coating bath cont~ining the desired polymer latex, emulsion or dispersion for a time sufficient to coat the substrate s with a wet film thickness that preferably is, with increas;ng preference in the order given, at least 2, 4, 5, 6.0, 6.5, 6.8, 7.1, 7.4, 8.0, 9.0, 10, 11, 12, 13, 14, or 15 micrometers (here-ina~er often abbreviated "Il") and jnd~pc~d&~ y preferably is, with inereasing pref~rence in the order given, not more than 50, 40, 30, 28, 27, 26, or 25 Il. The time and tem-perature during autodeposition will vary dependil g on the nature of the particular resins 10 in the coating After the coating is deposited, a reaction rinse is applied in the present invention to improve the cGll~sion re~;~t~nce ofthe lata fonned cured coating The chemical composition of the a~todeposition bath may be selected without limit from all the con,po~ilions that produce coalhlgs useful for any purpose, in particular including those compositions taught in U. S. Patents 3,585,084, 3,709,743, 3,776,848, 4,180,603, 4,191,676, 4,313,861, 4,347,172, 4,366,195, 4,657,788, all of which, to the extent that they desc.il~ c~ ;ons suitable for autodeposition baths and are not incon-sistent with any explicit s~le .-e~l herein are hereby incorporated herein by reference.
~ l~r~ d cGd~ which are treated acco,~li ,g to the process of the present inven-tion are formed from an autodepositing composition in which particles of resin are dis-20 persed in an aqueous acidic solution which is plepared by combining hydrofluoric acidand a soluble ferric iron-cont~ining ingredient, most preferable ferric fluoride.
U.S. Patent Nos. 4,347,172 and 4,411,937 which disclose the preferred activatingsystem disclose the optional use in the composition of an oxidizing agent in an amount to provide from about 0.01 to about 0.2 oxidizing equivalent per liter of composition.
25 F.~ p~i of suitable o~udi~"~g agents are hydrogen peroxide, dicl,lo,nate, perm~ng~n~te, nitrate, persulfate, perborate, p-benzoquinone and p-nitrophenol. Hydrogen peroxide is most pr~f~ d.
With respect to particular resins that can be used in the coating composition ofthe present invention, one ~ler~lle;d class can be p.e~,a,ed by copolynle,~il-g (A) vinyli-30 dene chloride monomer with (B) ,llonolne, ~ such as meth~crylic acid, methyl methacryl-ate, acrylonitrile, and vinyl chloride and (C) a water soluble ionic material such as sodi-um sulfoethyl methacrylate. .Alth-~ugh the constin~ ts CGllllJIiSil~g the above-desired res-~ ~ ~t ~ 3 in can vary over a relatively wide range, in general the resin will comprise the polymer-- ized constituents in the following amounts I) between 45 and 99 %, based on the total weight of ."ono~ used, of vinylidene chloride n~onG~
2) from about 0 5 to 30 weight percent based on the total weight of (1) and (2) of a second relatively more hydrophilic ethylenically unsaturated monomeric material wherein such ...- n~ ;c material has a solubility in both the water phase and the oil phase of the polymer latex of at least I weight percent at the tc.,.~e. alllre of poly",e~ ion; and 10 3) from about 0.1 to about ~ weight percent based on the total weight of other mono-mers of an ionic, si~ificnntly water-soluble material which is copol~-"e.i~able with (2) and is selected from the group of sulfonic acids and their salts having the formula:
R-Z-Q-(SO3)M~, wherein the moiety "R" is selected from the group cor~sistin~ of vinyl and substi-tuted vinyl, for example, alkyl-substituted vinyl; the symbol "Z" represents a di-functional linking group which will activate the double bond in the vinyl group;-Q- is a divalent hydrocarbon moiety having its valence bonds on dirrerent carbon atoms; and the symbol "M~ ,plesellls a cation.
20 Examples of resins plepared from such monomers are disclosed in U S Patent No 3,617,368 The relatively hydrophilic monomers of (2) above include those materiaJs which are readily copolymerizable with (1) in aqueous dispersion, that is, which copolymerize within a period of about 40 hours at a temperature ranging from the freezing point of the 25 IllollGllRlic serum up to about 100 C, and which have a solubility in both the water and the oil phase of the polymer latex of at least I weight percent at the temperature of po-lymerization. Exemp1ary of prefell~id materials, particularly when used in conjunction with ..~ono~e. ic vinylidene chloride, are methacrylic acid and methyl methacrylate Oth-er monomers which may be advantageously employed include the hydroxyethyl and 30 propyl acrylates, hydroxyethylmeSh~crylate, ethyl hexylacrylate, acrylic acid, acryloni-trile, meth~crylonitrile, acrylamide, and the lower alkyl and dialkylacrylamides, acrolein, methyl vinyl ketone, and vinyl acetate.
WO 96110461 ~ PCI/US95/11404 -These monomers, which can be employed in amounts of from 0.5 to 30 weight percent, based on the total weight ofthe nonionic monomers used, provide for the neces-- sary reactivity with the copolymerizable ionic material of (3) and also provide for the re-quired water solubility of the interpolymer in water. Thus, such materials may be re-ferred to as "go-between" ,-,ono,nc.~. It is to be understood that the optimum amount of such relatively hydrophilic ,llonoll-e,~ may vary somewhat within the presc,ibed range ~e~ g upon the amount of h~dluphobic ",ono",el used in p~epalin~, the resin, as weD
as upon the amount and type ofthe copol~",cli~ble ionic monomer used.
The copol~",~.i~ble ionic monomers used in preparing the aforementioned type resins are those monomeric materials which contain in their structure both an ionizable group and a reactive double bond, are c~ c~tly soluble in water, are copolymerizable with the hydlophilic Inor~om~r conctit~ent (2) and in which the substituent on the double bond is chemically stable under the conditions normally encountered in emulsion polym-enzation.
s Examples of the afore.,.e.,lioned divalent hydrocarbon moiety Q having its val-ence bonds on di~l.,.lt carbon atoms include alkylene and arylene divalent hydrocarbon moieties. ~hhou~h the alkylene group can contain up to about 20 carbon atoms, it pref-erably has 1 to about 8 carbon atoms.
The solubility of the defined copol~l"e.i~able ionic material as described herein iS strongly irlfllJenced by the cation M~. Exemplary cations are the hydrated protons characterstic of aqueous free acids, alkali metal ions, ammonium, sulfonium and substi-tuted ammonium and sulfonium ions, incl.~tling quaternary ammonium ions. Preferred are the free acids, alkali metals, particularly sodium and pot~ssil~m, and ammonium.
It is further noted that, with one ofthe ions above, and the usual choices for R and 2s Z, the solubility of the monomer depçn~s on Q. As intlicate-l, this group can be either aliphatic or aromatic and its size will determine the hydrophilic/ hydrophobic balance in the molecule, that is, if Q is relatively small, the monomer is water soluble, but as Q be-comes progressively larger, the surface activity of such monomer increases until it be-comes a soap and l-him~tely a water insoluble wax. It is to be understood, however, that the limiting size of Q depends on R, Z, and M~. As exemplary of the above, it has been found that sodium sulfoethyl rneth~rrylate is a highly acceptable copolymerizable ionic material for use in the present invention.
~ ~ S ~ 3 Further, the selection of R and Z is governed by the reactivity needed, and the se-- lection of Q is usually determined by the reaction used to attach the sulfonic acid to the base monomer (or vice versa) ~locesses for ple~.aling latexes con~aining resins ofthe afore.,.e,llioned type are s known, such latexes being commercially available and belng referred to herein as "self-stabilizing latexes", that is, latexes, the polymeric particles of which contain in the poly-mer molecule fi-nctio~ groups that are effective in ...~ a~ the polyrneric particles L~.~ in the ~queous phase ofthe latex. As mentioned above, such latexes do not re-quire the pres~nce of an external surfactant to m~int~in the particles in their dispersed state. Latexes of this type generally have a surface tension very close to that of water (about 72 dynes/cm). It has been observed that autodepositing compositions con~ining such latexes forrn coatin~ which build up at a relatively fast rate.
An ~y~mpl~ry method for ple~alu~g such latexes involves plep~lion of an aque-ous dispeKion by an essenti~lly continuous, carefully controlled addition of the requisite pol~,l,e~i~lion cor-stituer-t~ (incluAing polyrnerization initiator systems, if desired) to the aqueous me~ium having the desired pH value, followed by the subsequent addition of the necessary pol~"l~,.;~lion initiator, to form a polymeric seed latex in order to aid in the control of particle size. When forming such polyrneric seed latexes, very small arnounts of conventional surf~ct~ntc, such as alkali soaps or the like, may be incorporated in the aqueous medium to further aid in the attainrnent of particles of desired size. The addition of such surf~ct~tltc however, is not critical for the production of the highly stab-le, internally stabilized, aqueous colloidal dispersions of polymeric particles of the type described above. In any event, additions of surfactants are lirnited so that the total arnount present in the aqueous phase of the final coating solution is less than the critical micelle co,-~enl~aliorl, as taught in U.S. Patent No. 4,191,676. Following the formation of the polymeric seed latex, the rem~ining polymerization constituents are simultaneous-ly and con~inuo-lcly added under carefully controlled conditions to the aqueous meAillm Highly stable polymer latexes for use in the present invention are characterizedby the virtual absence of undesirable coa~lh-m which often results when polymeric la-texes are stabilized by conventional water soluble surfact~nts. Thus, such latexes com-bine the highly beneficial prope,lies of optimum colloidal stability, reduced viscosities at relatively high polymer solids content, low foarning tendencies, and excellent product WO96/10461 ~ 2 ~ PCI/US95/11404 wur~ y and reproducibility Such highly stable latexes which are internally stabilized are disclosed, for eY~mrle~ in U S Patent No 3,617,368 One prefc..~,d embodiment of this invention co--lt,--ses the use of vinylidene chJoride-cor~ g latexes in which a water soluble ionic material such as, for e~mrle, s sodium sulfoethyl methqcrylate is copolymerized with the comono..,ers con.p.ising the copolymer. Sodium sulfoethyl methacrylate is particularly effective for use with mono-meric vinylidene chloride and the relatively hydrophilic ...ono.~.a methyl l~.ell.ae,ylate or ...~ a~;-ylic acid when used in the amounts and in the manner called for by the present invention Particularly ~,refelled latexes for use in this invention are latexes with about 35 to about 60 weight % solids co-n~ , a polymeric composition pn,parc~ by em~-lQ;cn polymerization of vinylidene chloride with one or more comonomers selected from the group concisti~ of vinyl chloride, acrylic acid, a lower alkyl acrylate (such as methyl acrylate, ethyl acrylate, butyl acrylate), meth~crylic acid, methyl meth~crylate, acryloni-1S trile, ell~c-ylonitrile, acrylamide, and meth~rrylamide and stabilized with sulfonic acid or sulfonic acid salt of the formula R-Z-(CH2)n-(S03) M+, wherein R rep. ~se.,ls vinyl or lower alkyl-substituted vinyl; Z ~ epre3en~s one of the difunctional groups:
o o o o -C- , -C-O- , -O-C- , or -C-N (T) -, where T reples~.~ls hydrogen or an alkyl group; n is an integer from 1 to 20, preferably I to 6, and M~ is hydrogen or an alkali metal cation, preferably sodium or potassium One subgroup of prere.led polymers are those having at least 50 % by weight of vinylidene chloride, but less than 70 %, 5 to 35 % vinyl chloride, and 5 to 20 % of a 2s vinyl compound sPle~e~ from the group consisting of acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, ...elh~t~ylic acid, methyl meth~srylate, acrylonitrile, meth~crylo-nitrile, acrylamide and meth~crylamide, and co.,-b;"alions thereof, and 1 to 3 % by weight of sulfoethyl rneth~crylate One particularly plert;.led group of latexes, however, are latexes co..~ g about30 to about 70 % of solids forrned by emulsion polyll,e.i~alion of about 50 to about 99 %, more preferably at least 80 %, of vinylidene chloride, based on total weight of poly-mer, and about 0 1 to about 5 % by weight of sulfoethyl meth~çrylate, with optionally other comono"~ selected from the group cons;sling of vinyl chloride, acrylic and WO96/10461 ~ ~ ~P !~ ~ Q ~ ~ PCT/US95111404 methacrylic monomers such as acrylonitriles, acrylamides, methacrylamides and mixtures thereof in amounts between about 5 and about 50 % by weight~ and s ~l,sliv~ ly free of unpolyrnerized surfactant or protective colloid. Most ~,ere.ably, the vinylidene chloride copolyrner is crystalline in nature. Exemplary crysta!line resins are describedinU.S.PatentNo 3,922,451 andaforementionedU.S.PatentNo. 3,617~368.
In general, crystalline vinylidene chloride-co.~ resins have a relatively high pro-portion of vinylidene chloride, for example, at least about 80 % thereof.
~ntemaUy ~ 7ed polymers or resins include as part of their chemical structure a surfactant group which functions to mi~int~in polymer particles or resin solids in a dis-10 pased state in an aqueous m~ m this being the function also p~;-Ço,.ed by an "extern-al surfactant", that is, by a material which has surface-active prope, lies and which is ab-sorbed on the surface of resin solids, such as those in colloidal dispersion. As is known, the l)resence of an external surfactant tends to increase the water sensitivity of co~tin~c formed from aqueous resin dispersions cont~inin~ the same and to adversely affect de-si~red properties ofthe coa~ gc As described in U.S. Patent No. 4,191,676, the ~,resence of an undue arnount of surfactant in autodepositing compositions can deter the build-up of resin particles on the metallic surface being coated. In addition, the p. esence of undue amounts of surfactant can also adversely affect desired coating properties, for example, corrosion resistant properties. An advantage of internally stabilized vinylidene chloride-cont~ininE polymers is that stable aqueous dispersions, jnclu-ling acidic aqueous disper-sions of the type needed for autodepositing compositions, can be prepared without utiliz-ing external s~-Ç~ nc (It is noted that there is a tendency in the literature to use inter-changeably the following tenns in connection with describing surface active materials which are used in polymerization processes for preparing polymers of the type to which the present invention relates: surfactant, wetting agent, emulsifier or emulsifying agent, and dis~ g agent. As used herein, the term "surfactant" is inten~ed to be synonymous w.ith the afore~lcnlioned.) Various types of internally stabilized vinylidene chloride-cont~ining polymers are known and species thereof are available commercially. E~a nples of such latexes are the SARANTM latexes such as, for exarnple, SARANTM 143 and SARANrM 112 available from ~T~.nl.cl.;re Chemical Corp., T.çxin~on, M~cc~chllsettcJ USA and the SERFENElM
latexes available from Morton Chemic~l In accordance with the present invention, these WO96/10461 ~ 2` ~ PCT/US9S/11404 commercial latexes can be used to excellent advantage. and internally stabilized latexes in general are preferred.
Various surf~ct~nts which function to m~intain polyrneric particles in dispersed-state in aqueous medium include organic compounds which contain ionizabie groups in 5 which the anionic group is bound to the pl inc;pal organic moiety of the compound, with the cationic group being a conctitl~ent such as, for eAar,.ple, hydrogen, an alkali metal, and arn,lloni.lm. Speaking generally, e ~e~..pl -~ y anionic groups of widely used surfact-ants contain sulfilr or phosyhorous~ for eA~-nple, in the form of sulf~tes, thiosulfate~, sul-fonates, s~lfin~tes, sulr;~ ec~ phosph~tes~ pyrophosphates and phosphon~tes. Such 10surf~ct~ntc cGIllplis~ inorganic ionizable groups linked to an organic moiety.~ltho~ h various ways may be used to introduce into the molecular structure of the vinylidene chloride resin such ionizable groups, it is believed that the most widely used method for prepa~ g such resins will involve reacting vinylidene chloride with a onolllt;lic surfactant and optionally one or more other monomers. In such reaction, the 5monomeric surfactant cGIll~Jlises a material which is polyllle-i~ble with mQnomçric vi-nylidene chloride or with a mono~llc.ic material which is polymerizable with monomeric vinylidene chloride and which is ionizable in the reaction mixture and in the acidic aque-ous me~ m comprising an autodepositing composition.
Among other p.e~-.ed subclasses of resin for use in this invention are: disper-20sions of copolymers of 50 to 90 % of butyl acrylate and I to 2 % by weight of sulfoethyl methacrylate based on the total weight of polymer; latexes of vinylidene chloride-con-taining polymers internally stabilized with sulfoethyl methacrylate and free of other s~.racla..l, and including optionally vinyl chloride and one or more acrylic comonomers;
vinylidene chloride-co..l~it,i.~g copolymer havingl5 to 20 % of vinyl chloride, 2 to 5 %
2s butyl acrylate, 3 to 10 weight % acrylonitrile, and 1 to 2 % of sulfoethyl methacrylate.
~his particular copolymer will have less than 70 % by weight of vinylidene chloride copolymer based upon total weight of comonolllers (including the sulfoethyl methacryl-ate) used in the emulsion poly~.leli,alion.
The conc~ la~ion ofthe resin in the coating composition can vary over a wide 30 range. The lower concel~llalion limit of the resin particles in the composition is dictated by the amount of resin needed to provide sufficient material to form a resinous coating.
The upper limit is dictated by the amount of resin particles which can be dispersed in the Q ~ ~
acidic aqueous composition. In general, the higher the amount of resin particles in the composition, the heavier the coating forrned, other factors being the same. Although coating compositions can be form~ ted with a range of about 5 to about 550 grams per liter (he. ~inaller often abbreviated "g/L") of resin solids, the amount of the resin solids s will tend to vary dcp~A;.~g on the other ingredients comprising the composition and also on the specific latex or resin used. For most uses, the concenl~ dlion of binder resin solids in an autodeposition co..,pos;lion or bath used as part of a process accGrding to this in-vention pler~.~bly is, with inc,~asi,.g prerel ence in the order given, at lease 0.5, 1.0, 2.0, 3.0, 3.5, 4.0, 4.5, 4.7, or 4.9 % and indenpendently ~,ere~ably is, with increasing prefer-ence in the order given, not more than 40, 30, 20, 17, 14, 12, 11, 10.5, or 10.0 %.
Optional ingredients can be added to the composition as desired. For ~--~. Ie, it is believed that the present invention will be used most widely in applications where it is desired to apply p.~ d coatin~ to the metallic substrate. For this purpose, suit-able pigments can be included in the composition. Exalnples of pi~mçnts that can. be 15 used are carbon black phth~locyanine blue, phthalocyanine green, quinacridone red, ben-zidene yellow, and tit~nillm dioxide. The pi,~ment should be added to the compositionin an amount which imparts to the coating the desired color and/or the desired depth or degree of hue. It should be understood that the specific amount used will be governed . . by the specific pigment used and the color of coating desired. Excellent results have 20 been achieved by using the aqueous dispersion in an amount such that the composition contains about 0.2 to about 3 g of furnace black/100 g of resin solids.
Many pi~m~nts are available in aqueous dispersions which may include surfact-ants or dispersing agents for ."~ the pigment particles in dispersed state. When utilizing such pi~nent dispersions, they should be selected so that the surfactant concen-2s tration in the aqueous phase ofthe composition is below the critical micelle concentration("CMC"), preferably below the surfactant concentration which corresponds to the inflec-tion point on a graph of surface tension versus the logarithm of surfactant concentration in the composition. A suitable pigmented composition is illustrated in examples herein.
Colored c~al;~ ~,c can be produced also by the use of dyes, examples of which in-30 clude rhodamine derived dyes, methyl violet, safranine, anthraquinone derived dyes, nig-rosine, and alizarin cyanine green. These are but a few exarnples of dyes that can be used.
WO96/10461 ~ s~ ~ ~ PCT/US95/11404 Examples of other additives that may be used in the autodepositing composition are those generally known to be used in formul~ting paint compositions, for example, W
stabilizers, viscosity modifiers, etc.
If a surfactant is added to the composition, either as a colnl,ol1enl ofthe latex, or 5 with a pi~ nt dispersion, or with other ingredients or additives, the total amount of sur-factant in the aqueous phase of the composition should be .nAil~A;l~ed below the CMC.
Fl~f~lably~ the ~queol-~ phase of the composition c~nlains little or no surfactant.
If an external surfactant is utili7etl the pre~.led surf~ct~nts are anionic.
Examples of suitable anionic surf~ct~nts are the alkyl, alkyVaryl or naphth~lene sul-10 fonates, for example, sodium dioctylsulfosucçin~te and sodium dodecylben2elle sulfon-ate.
In prep~ing the autodepositing composition, the con~tituçnts thereof can be ad-rnixed in any suitable way, for example, as des.,li~ed in U. S. Patent No. 4,191,676. In prep~.ng a bath of pi~mented coating composition for use on an industrial scale, it is pl~f~lled that the bath be prepa,ed by admixing:
A) an aqueous conce,ltlale comprising about 350 to ab~ut 550 g/l of resin particles, preferable the aforementioned vinylidene chloride-co..~ l;n~
resin particles, and about 10 to about 550 g/l of pigment; and . . B) an aqueous concell~rate p~pared from about 0.4 to about 210 g/l of HF
and a water soluble ferric-cont~ining compound in an amount equivalent to about i to about 100 gA of ferric iron.
The bath can be pl e~,al ed by stirring water into concen~l a~e (A) and thereafter admL~cing therewith the required arnount of concentrate (B) ~,vith stirring to provide a homogenous composltion.
2s The complex fluoride anions required in a reaction rinse accordu1g to the inven-tion are preferably added to the ~r~...enl solution in the forrn of nickel, ferric, or cobalt salts, more preferably cobalt salts, and the anions themselves are preferably fluoborate (i.e., BF;), fluosil;~te (i.e., SiF62), fluotitanate (i.e., TiF6-2), or fluozirconate (i.e., ZrF6~2) with the latter most prerelled.
The conce,l~.~ion of the total of the complex fluoride anions present in the aque-ous liquid rinse composition used according to the invention preferably is, with increas-ing ~"t;re,el1ce in the order given, at least 0.002, 0.004, 0.008, 0.016, 0.023, 0.033, 0.040, WO96/10461 ~'2 ~ Pcr/uS95/11404 0.047, 0.054, 0.061, or 0 068 moles per liter ("M") and independently preferably is, with inc,~sing plerere~lcc in the order given, not more than 1.0, 0.7, 0.4, 0.20, 0.15, 0.100, 0.090, 0.080, 0.075, or 0.072 M. The pH of the rinse soluition used according to this in-vention p,~.~ly is, with ;n~;,~si.~g p,eferellce in the order given, not less than 1.0, 1.5, ! 8 2.0, 2.5, 3.0, 3.1, 3.2, 3.3, 3.4, or 3.5 and independently preferably is, with increasing p,~f~rellce in the order given, not more than 9, 8, 7.0, 6.5, 6.0, 5.8, 5.6, 5.4, 5.2, 5.0, 4.9, 4.8, 4.7, 4.6, or 4.5.
The rinse solution may be co~taGted, accoldil~g to the invention, with a wet un-cured ~utodçposiled coating by any convenient method or combination of methods, such as spraying, cu~ain co~tin~, or ilnl,lel~;ol~, with the latter normally pref~"~. ~efc.ably the time of contact between the rinse s~,lt~tion and the wet uncured autodepositied coating is, with increasing p,eferènce in the order given, not less than 5, 10, 20, 30, 40, 45, 50, 55, or 60 seconds (hereinafter often abbreviated "secN) and independently preferably is, with increasing prëfel ence in the order given, not more than 600, 400, 200, 120, 1 10, 100, 95, or 90 sec. The tell.pelalule ofthe rinse solution during contact with a wet un-cured autodepo~iled coating may be any te~"?c~al~lre at which the rinse solution is liquid but normally preferably is, with increasing plef.,rence in the order given, not less than 10, 15, 18, or 20 C and indepen-lently preferably is, with increasing preference in the order given, not more than 60, 45, 35, 30, 27, 25, or 23 C.
A~er the reaction rinse ~ l"e,lt, the wet autodeposited coating as modified by contact with the reaction rinse is so~.~el;~es rinsed again with water, preferably deionized water if any, before being dried and, if desired as is usually pl efel ~ ed, cured by he~ting~t an elevated te.l")elal~lre so selected that the protective p, Opel lies of the coating are fully dcv~loped but not adversely affected. The tel~,pe.al~re and time of tre~tme~t will depend on the nature ofthe particular resin in the autodeposited coating and the thickness of the coating. With autodeposition baths con~ ;ng most types of organic binder resins, in-cluding the most ~>leÇ~ d poly{vinylidene chloride} resins, during or a~er drying, the autodeposited coatings preferably are heated to a temperature that is, ~ith increasing plêfelellce in the order given, at least 22, 30, 40, S0, 60, 70, 80, 90, 100, 110, or 120 C and independently preferably is, with increasing preferellce in the order given, not morethan200, 180, 160, 150, 140, 135, 130, 128, or 126 C. Times of heating for cur-ing plefel~ly range from S seconds up to 30 mirnltec, dependent on the macs of the coat-WO 96/10461 ~ PCT/US9S/11404 ed article. Preferably, the coating is heated for a period of time until the metallic sub-strate has reached the temperature of the heated environl.lent, typically in a forced air baking oven.
- The dried, cured coated articles are found to have excellent corrosion reCist~nce s when tested in soak tests or the neutral salt spray ("NSS") test, such as ASTM B-l 17 and scab corrosion cycles. Autodeposited ~ g~ treated according to the present invention are particularly effective on both cold rolled steel and galvanized steel, thereby allowing the two types to be processed together.
To further illustrate the various objects and advantages of the present invention, the following examples, in which all parts and percentaEes are by weight unless other-wise indicated, are provided. It is understood that their purpose is entirely illustrative and in no way intended to limit the scope of the invention.
Example 1 This example illustrates the preparation of a metallic surface having an autode-posited resinous coating. The met~llic surface comprised steel panels, both cold rolled steel (CRS) and zinc galvanized steel (GS) panels, which were cleaned with a conven-tional alkaline cleaner composition and nnsed with water prior to being coated by irnrner-sion in the autodepositing composition at arnbient temperature (about 21 C) for about 90 seconds. The autodepositing i"-n~e.~ion bath had the following composition: 60 grams per liter (he,e;llaner abbreviated as "g/L") of internally stabilized copolyrner of vinylidene chloride, 2.5 g/L of carbon black, 0.4 g/L of HF, 1.5 gtL of ferric iron, and the balance water.
Example 2 In this exarnple, the uncured coated panels from example I are treated with a re-2s action rinse inunersion bath after first being rinsed with water. The reaction rinse with-out cobalt cations contained 0.5 % by weight of H2ZrF6 and was adjusted to the pH
shown in the following tables with ammonia if needed. In the exarnples employing the cobalt salt of hydrofluorozirconic acid, the concentration is shown in the tables below;
the pH was 3.5 for all the concenllalions shown.
After hnlne,~;on in the reaction rinse bath for one rninute, the panels were then rinsed with water (deionized) and the panels were then cured for 20 minutes in an oven at a telllpelal~lre of 105 C.
- -WO 96/10461 ~ PCT/US95/11404 Example 3 This e,~ . ~!e illustrates the results of corrosion resistance testing of various pan-els. Table 1 below illustrates salt spray performance and cyclic scab pe.ru~ ance on galvanized steel, and Tables 2 - 7 i~dic~te pe.fo-~l,ance on other tests as noted.
The letters "GM" and the numbers and letters immediately following these lettersin the h6~riin~c of Tables 2 - 7 refer res~e~ rely to the General Motors Corporation and to various specific corrosion tests that are part of pe~rGI"~ance specific~tions at that company. Test details are readily available from General Motors. Briefly, the tests reported here are described as follows:
10 1. Cyclic CorroSiQn - GM 9511P
Af'~er prepa.alion (1) the s&"lples are heated in an oven at 60C. for 1 hour fol-lowed by (2) 30 minutes at -25 C. The samples are then (3) immersed in a 5 % NaCI
solution at room te"lpe~ re for 15 minutes, followed by (4) ambient drying for 75 minuteS The samples are then (5) held for 22.5 hours in a humidity challlber at 85 %
relative humidity ("RH") and 60 C. The fo,egoing is generally conducted over a 5-day period after which the 5 steps may be repeated for any desired number of cycles.2. Cyclic Corrosion - GM 9540P. Cycle B
A~er p,e~)a,aLion~ the samples are treated at 25C. and 50 % RH environment for 8 hours, including 4 sprays at 90 minutes intervals with a solution cont~ining 0.9 %
NaCI, 0.1 % CaCI2, and 0.25 % NaHCO3 in deionized water. The samples are then sub-jected to an 8 hour fog, 100 % RH at 40 C, followed by 8 hours at 60 C and less than 20 % RH. The entire treatment is repeated for the desired number of cycles, usually 40 cycles.
WO96/10461 ~ ~ fi ~ PCT/US9~/11404 Table 1 Reaction Rinse Concentration pH Corrosion Tes~ l~atings (Paint Del~l;nalion from Scribe, mm) NSS (336 hr) 20 Cycles Scâb H~ZrF~ 0.5 % 3 0 - 2 H2ZrF~s 0 5 % 4 0 - 2 H2ZrF6 0.5 % 5 0 - 2 1.5 CoZrF6 4.5 g/L 3.5 0 - 2 1.5 CoZrF6 9.0 ,~/L 3.5 0 - 2 0.8 CoZrF6 18 g/L 3.5 0 - I 0.6 ~able 2 (20 Cycles GM 9511 P on Cold Rolled Steel) Reaction Coat- TotalWidth Creepback Gravel Rating Rinse ing (mm) Thick-ness"u Aver- Ma~imum Minimum Impact After age Dam- 20 a~e~Cycles 0 5%H2ZrF6 23 2.8 5.9 1 5 9 10 %
pH 5 20 3.3 6.0 1.0 9 rusted CoZrF6 23 3.7 5.9 1.5 9 10 %
4.5 g/L 23 2.8 8.2 1.0 9 rusted *Impact damage was measured as specified in GM 9508 P.
-0 2 ~ 9 ~ pCr~US95/11404 wo 96110461 Table 3 (20 Cycles GM 951 1 P on Galvanized Steel) -`
Reaction Coating TotalWidth Creepback(mm) Gravel Rating Rinse Thick-ness,ll Average Ma~imum Minimum Before After 0.5% H2ZrF6 13 1.5 3.1 0.2 8 8 pH 5 17 0.6 1.9 0.2 8 8 CoZrF6 15 0.7 2.6 0.2 8 8 4.5 g/L 13 0.4 3.1 0.2 8 8 Table 4 (40 Cycles GM 9540 P, Cycle B, on Cold Rolled Steel) Reaction Coating Total Width Creepback (mm) Field RinseThickness, ~1 Average Ma~imum Minimum 0.5% 20 6.6 9.8 4.2 10 % n~sted H~rF6 pH 5 20 6.5 9.5 3.8 CoZrF6 20 12.1 22.6 4.5 20 % rusted 4.5 glL 23 9.6 14.8 3.9 W096/10461 ~ ~` q ~ ~ ~ 8 3 PCI~/US9!i111404 Table 5 (40 Cycles Gm 9540 P, Cycle B, on Galvanized Steel) Reaction Coating Total Width Creepback (mm) Field RinseThickness, 11 Avera~e Masimum Minimum 0.5% 10 0.7 4.2 0.2 60 % rusted H2ZrF6 pH S 11 1.0 2.7 0.2 CoZrF6 16 0.7 2.2 0.2 10 % rusted 4.5 g/L 15 0.8 2.6 0.2 Table 6 (5 cycles GM 9505 P, Cycle J, on Cold Rolled Steel) ReactionCoatingMasimum Creepback from Scribe RinseThickness,~ (mm) Right Left Total 0.5% H2ZrF6 23 2.6 2.9 5.5 P 20 2.7 2.8 5.5 CoZrF6 20 3.4 3.0 6.4 4.5 g/L 20 2.4 2.9 5.3 - -WO96/10461 tl 2~ PCT/US95/11404 Table 7 --(5 Cycles GM 9505 P, Cycle J, on Galvani~ed Steel) Reaction CoatingMa~imum Creepbllck from Scribe Rinse Thickness, ~ (mm) Ri~ht Left Total 0.5% H2ZrF6 13 2.8 3.1 5.9 P 15 3.0 2.7 5.7 CoZrF6 14 0.2 0.2 0.4 4.S g/L 12 0.2 0.2 0.4 3. Cyclic Corrosion - GM 9505P. Cycle J
A~er plCp~a~iOn, the samples are (I) held in a freezer at -30 C for 2 hours, fol-lowed by ambient conditions for 2 hours and subsequently (2) in an oven at 70 C for 2 hours. The samples are then (3) subjected to a 5 % NaCI solution salt spray for 2 hours s and then (4) held in a humidity cl.~llber at 38 C and 95 % RH for 64 hours. The sam-ples are then (S) held in an oven at 60 C for I hour followed by (6) a freezer at -30 C
for 30 mi~ teS The samples are then subjected to (7) im nersion in a 5 % NaCI solution at room temperature for 15 minutes and then (8) held at ambient conditions for 1.25 hours, followed by (9) a humidity chamber at 60C and 85 % RH for 6.5 hours, followed ~o (10) by 38 C for 64 hours. Steps (1) - (4) above are then repeated to complete the cycle which is generally concluded in a 2-week period.
R-Z-Q-(SO3)M~, wherein the moiety "R" is selected from the group cor~sistin~ of vinyl and substi-tuted vinyl, for example, alkyl-substituted vinyl; the symbol "Z" represents a di-functional linking group which will activate the double bond in the vinyl group;-Q- is a divalent hydrocarbon moiety having its valence bonds on dirrerent carbon atoms; and the symbol "M~ ,plesellls a cation.
20 Examples of resins plepared from such monomers are disclosed in U S Patent No 3,617,368 The relatively hydrophilic monomers of (2) above include those materiaJs which are readily copolymerizable with (1) in aqueous dispersion, that is, which copolymerize within a period of about 40 hours at a temperature ranging from the freezing point of the 25 IllollGllRlic serum up to about 100 C, and which have a solubility in both the water and the oil phase of the polymer latex of at least I weight percent at the temperature of po-lymerization. Exemp1ary of prefell~id materials, particularly when used in conjunction with ..~ono~e. ic vinylidene chloride, are methacrylic acid and methyl methacrylate Oth-er monomers which may be advantageously employed include the hydroxyethyl and 30 propyl acrylates, hydroxyethylmeSh~crylate, ethyl hexylacrylate, acrylic acid, acryloni-trile, meth~crylonitrile, acrylamide, and the lower alkyl and dialkylacrylamides, acrolein, methyl vinyl ketone, and vinyl acetate.
WO 96110461 ~ PCI/US95/11404 -These monomers, which can be employed in amounts of from 0.5 to 30 weight percent, based on the total weight ofthe nonionic monomers used, provide for the neces-- sary reactivity with the copolymerizable ionic material of (3) and also provide for the re-quired water solubility of the interpolymer in water. Thus, such materials may be re-ferred to as "go-between" ,-,ono,nc.~. It is to be understood that the optimum amount of such relatively hydrophilic ,llonoll-e,~ may vary somewhat within the presc,ibed range ~e~ g upon the amount of h~dluphobic ",ono",el used in p~epalin~, the resin, as weD
as upon the amount and type ofthe copol~",cli~ble ionic monomer used.
The copol~",~.i~ble ionic monomers used in preparing the aforementioned type resins are those monomeric materials which contain in their structure both an ionizable group and a reactive double bond, are c~ c~tly soluble in water, are copolymerizable with the hydlophilic Inor~om~r conctit~ent (2) and in which the substituent on the double bond is chemically stable under the conditions normally encountered in emulsion polym-enzation.
s Examples of the afore.,.e.,lioned divalent hydrocarbon moiety Q having its val-ence bonds on di~l.,.lt carbon atoms include alkylene and arylene divalent hydrocarbon moieties. ~hhou~h the alkylene group can contain up to about 20 carbon atoms, it pref-erably has 1 to about 8 carbon atoms.
The solubility of the defined copol~l"e.i~able ionic material as described herein iS strongly irlfllJenced by the cation M~. Exemplary cations are the hydrated protons characterstic of aqueous free acids, alkali metal ions, ammonium, sulfonium and substi-tuted ammonium and sulfonium ions, incl.~tling quaternary ammonium ions. Preferred are the free acids, alkali metals, particularly sodium and pot~ssil~m, and ammonium.
It is further noted that, with one ofthe ions above, and the usual choices for R and 2s Z, the solubility of the monomer depçn~s on Q. As intlicate-l, this group can be either aliphatic or aromatic and its size will determine the hydrophilic/ hydrophobic balance in the molecule, that is, if Q is relatively small, the monomer is water soluble, but as Q be-comes progressively larger, the surface activity of such monomer increases until it be-comes a soap and l-him~tely a water insoluble wax. It is to be understood, however, that the limiting size of Q depends on R, Z, and M~. As exemplary of the above, it has been found that sodium sulfoethyl rneth~rrylate is a highly acceptable copolymerizable ionic material for use in the present invention.
~ ~ S ~ 3 Further, the selection of R and Z is governed by the reactivity needed, and the se-- lection of Q is usually determined by the reaction used to attach the sulfonic acid to the base monomer (or vice versa) ~locesses for ple~.aling latexes con~aining resins ofthe afore.,.e,llioned type are s known, such latexes being commercially available and belng referred to herein as "self-stabilizing latexes", that is, latexes, the polymeric particles of which contain in the poly-mer molecule fi-nctio~ groups that are effective in ...~ a~ the polyrneric particles L~.~ in the ~queous phase ofthe latex. As mentioned above, such latexes do not re-quire the pres~nce of an external surfactant to m~int~in the particles in their dispersed state. Latexes of this type generally have a surface tension very close to that of water (about 72 dynes/cm). It has been observed that autodepositing compositions con~ining such latexes forrn coatin~ which build up at a relatively fast rate.
An ~y~mpl~ry method for ple~alu~g such latexes involves plep~lion of an aque-ous dispeKion by an essenti~lly continuous, carefully controlled addition of the requisite pol~,l,e~i~lion cor-stituer-t~ (incluAing polyrnerization initiator systems, if desired) to the aqueous me~ium having the desired pH value, followed by the subsequent addition of the necessary pol~"l~,.;~lion initiator, to form a polymeric seed latex in order to aid in the control of particle size. When forming such polyrneric seed latexes, very small arnounts of conventional surf~ct~ntc, such as alkali soaps or the like, may be incorporated in the aqueous medium to further aid in the attainrnent of particles of desired size. The addition of such surf~ct~tltc however, is not critical for the production of the highly stab-le, internally stabilized, aqueous colloidal dispersions of polymeric particles of the type described above. In any event, additions of surfactants are lirnited so that the total arnount present in the aqueous phase of the final coating solution is less than the critical micelle co,-~enl~aliorl, as taught in U.S. Patent No. 4,191,676. Following the formation of the polymeric seed latex, the rem~ining polymerization constituents are simultaneous-ly and con~inuo-lcly added under carefully controlled conditions to the aqueous meAillm Highly stable polymer latexes for use in the present invention are characterizedby the virtual absence of undesirable coa~lh-m which often results when polymeric la-texes are stabilized by conventional water soluble surfact~nts. Thus, such latexes com-bine the highly beneficial prope,lies of optimum colloidal stability, reduced viscosities at relatively high polymer solids content, low foarning tendencies, and excellent product WO96/10461 ~ 2 ~ PCI/US95/11404 wur~ y and reproducibility Such highly stable latexes which are internally stabilized are disclosed, for eY~mrle~ in U S Patent No 3,617,368 One prefc..~,d embodiment of this invention co--lt,--ses the use of vinylidene chJoride-cor~ g latexes in which a water soluble ionic material such as, for e~mrle, s sodium sulfoethyl methqcrylate is copolymerized with the comono..,ers con.p.ising the copolymer. Sodium sulfoethyl methacrylate is particularly effective for use with mono-meric vinylidene chloride and the relatively hydrophilic ...ono.~.a methyl l~.ell.ae,ylate or ...~ a~;-ylic acid when used in the amounts and in the manner called for by the present invention Particularly ~,refelled latexes for use in this invention are latexes with about 35 to about 60 weight % solids co-n~ , a polymeric composition pn,parc~ by em~-lQ;cn polymerization of vinylidene chloride with one or more comonomers selected from the group concisti~ of vinyl chloride, acrylic acid, a lower alkyl acrylate (such as methyl acrylate, ethyl acrylate, butyl acrylate), meth~crylic acid, methyl meth~crylate, acryloni-1S trile, ell~c-ylonitrile, acrylamide, and meth~rrylamide and stabilized with sulfonic acid or sulfonic acid salt of the formula R-Z-(CH2)n-(S03) M+, wherein R rep. ~se.,ls vinyl or lower alkyl-substituted vinyl; Z ~ epre3en~s one of the difunctional groups:
o o o o -C- , -C-O- , -O-C- , or -C-N (T) -, where T reples~.~ls hydrogen or an alkyl group; n is an integer from 1 to 20, preferably I to 6, and M~ is hydrogen or an alkali metal cation, preferably sodium or potassium One subgroup of prere.led polymers are those having at least 50 % by weight of vinylidene chloride, but less than 70 %, 5 to 35 % vinyl chloride, and 5 to 20 % of a 2s vinyl compound sPle~e~ from the group consisting of acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, ...elh~t~ylic acid, methyl meth~srylate, acrylonitrile, meth~crylo-nitrile, acrylamide and meth~crylamide, and co.,-b;"alions thereof, and 1 to 3 % by weight of sulfoethyl rneth~crylate One particularly plert;.led group of latexes, however, are latexes co..~ g about30 to about 70 % of solids forrned by emulsion polyll,e.i~alion of about 50 to about 99 %, more preferably at least 80 %, of vinylidene chloride, based on total weight of poly-mer, and about 0 1 to about 5 % by weight of sulfoethyl meth~çrylate, with optionally other comono"~ selected from the group cons;sling of vinyl chloride, acrylic and WO96/10461 ~ ~ ~P !~ ~ Q ~ ~ PCT/US95111404 methacrylic monomers such as acrylonitriles, acrylamides, methacrylamides and mixtures thereof in amounts between about 5 and about 50 % by weight~ and s ~l,sliv~ ly free of unpolyrnerized surfactant or protective colloid. Most ~,ere.ably, the vinylidene chloride copolyrner is crystalline in nature. Exemplary crysta!line resins are describedinU.S.PatentNo 3,922,451 andaforementionedU.S.PatentNo. 3,617~368.
In general, crystalline vinylidene chloride-co.~ resins have a relatively high pro-portion of vinylidene chloride, for example, at least about 80 % thereof.
~ntemaUy ~ 7ed polymers or resins include as part of their chemical structure a surfactant group which functions to mi~int~in polymer particles or resin solids in a dis-10 pased state in an aqueous m~ m this being the function also p~;-Ço,.ed by an "extern-al surfactant", that is, by a material which has surface-active prope, lies and which is ab-sorbed on the surface of resin solids, such as those in colloidal dispersion. As is known, the l)resence of an external surfactant tends to increase the water sensitivity of co~tin~c formed from aqueous resin dispersions cont~inin~ the same and to adversely affect de-si~red properties ofthe coa~ gc As described in U.S. Patent No. 4,191,676, the ~,resence of an undue arnount of surfactant in autodepositing compositions can deter the build-up of resin particles on the metallic surface being coated. In addition, the p. esence of undue amounts of surfactant can also adversely affect desired coating properties, for example, corrosion resistant properties. An advantage of internally stabilized vinylidene chloride-cont~ininE polymers is that stable aqueous dispersions, jnclu-ling acidic aqueous disper-sions of the type needed for autodepositing compositions, can be prepared without utiliz-ing external s~-Ç~ nc (It is noted that there is a tendency in the literature to use inter-changeably the following tenns in connection with describing surface active materials which are used in polymerization processes for preparing polymers of the type to which the present invention relates: surfactant, wetting agent, emulsifier or emulsifying agent, and dis~ g agent. As used herein, the term "surfactant" is inten~ed to be synonymous w.ith the afore~lcnlioned.) Various types of internally stabilized vinylidene chloride-cont~ining polymers are known and species thereof are available commercially. E~a nples of such latexes are the SARANTM latexes such as, for exarnple, SARANTM 143 and SARANrM 112 available from ~T~.nl.cl.;re Chemical Corp., T.çxin~on, M~cc~chllsettcJ USA and the SERFENElM
latexes available from Morton Chemic~l In accordance with the present invention, these WO96/10461 ~ 2` ~ PCT/US9S/11404 commercial latexes can be used to excellent advantage. and internally stabilized latexes in general are preferred.
Various surf~ct~nts which function to m~intain polyrneric particles in dispersed-state in aqueous medium include organic compounds which contain ionizabie groups in 5 which the anionic group is bound to the pl inc;pal organic moiety of the compound, with the cationic group being a conctitl~ent such as, for eAar,.ple, hydrogen, an alkali metal, and arn,lloni.lm. Speaking generally, e ~e~..pl -~ y anionic groups of widely used surfact-ants contain sulfilr or phosyhorous~ for eA~-nple, in the form of sulf~tes, thiosulfate~, sul-fonates, s~lfin~tes, sulr;~ ec~ phosph~tes~ pyrophosphates and phosphon~tes. Such 10surf~ct~ntc cGIllplis~ inorganic ionizable groups linked to an organic moiety.~ltho~ h various ways may be used to introduce into the molecular structure of the vinylidene chloride resin such ionizable groups, it is believed that the most widely used method for prepa~ g such resins will involve reacting vinylidene chloride with a onolllt;lic surfactant and optionally one or more other monomers. In such reaction, the 5monomeric surfactant cGIll~Jlises a material which is polyllle-i~ble with mQnomçric vi-nylidene chloride or with a mono~llc.ic material which is polymerizable with monomeric vinylidene chloride and which is ionizable in the reaction mixture and in the acidic aque-ous me~ m comprising an autodepositing composition.
Among other p.e~-.ed subclasses of resin for use in this invention are: disper-20sions of copolymers of 50 to 90 % of butyl acrylate and I to 2 % by weight of sulfoethyl methacrylate based on the total weight of polymer; latexes of vinylidene chloride-con-taining polymers internally stabilized with sulfoethyl methacrylate and free of other s~.racla..l, and including optionally vinyl chloride and one or more acrylic comonomers;
vinylidene chloride-co..l~it,i.~g copolymer havingl5 to 20 % of vinyl chloride, 2 to 5 %
2s butyl acrylate, 3 to 10 weight % acrylonitrile, and 1 to 2 % of sulfoethyl methacrylate.
~his particular copolymer will have less than 70 % by weight of vinylidene chloride copolymer based upon total weight of comonolllers (including the sulfoethyl methacryl-ate) used in the emulsion poly~.leli,alion.
The conc~ la~ion ofthe resin in the coating composition can vary over a wide 30 range. The lower concel~llalion limit of the resin particles in the composition is dictated by the amount of resin needed to provide sufficient material to form a resinous coating.
The upper limit is dictated by the amount of resin particles which can be dispersed in the Q ~ ~
acidic aqueous composition. In general, the higher the amount of resin particles in the composition, the heavier the coating forrned, other factors being the same. Although coating compositions can be form~ ted with a range of about 5 to about 550 grams per liter (he. ~inaller often abbreviated "g/L") of resin solids, the amount of the resin solids s will tend to vary dcp~A;.~g on the other ingredients comprising the composition and also on the specific latex or resin used. For most uses, the concenl~ dlion of binder resin solids in an autodeposition co..,pos;lion or bath used as part of a process accGrding to this in-vention pler~.~bly is, with inc,~asi,.g prerel ence in the order given, at lease 0.5, 1.0, 2.0, 3.0, 3.5, 4.0, 4.5, 4.7, or 4.9 % and indenpendently ~,ere~ably is, with increasing prefer-ence in the order given, not more than 40, 30, 20, 17, 14, 12, 11, 10.5, or 10.0 %.
Optional ingredients can be added to the composition as desired. For ~--~. Ie, it is believed that the present invention will be used most widely in applications where it is desired to apply p.~ d coatin~ to the metallic substrate. For this purpose, suit-able pigments can be included in the composition. Exalnples of pi~mçnts that can. be 15 used are carbon black phth~locyanine blue, phthalocyanine green, quinacridone red, ben-zidene yellow, and tit~nillm dioxide. The pi,~ment should be added to the compositionin an amount which imparts to the coating the desired color and/or the desired depth or degree of hue. It should be understood that the specific amount used will be governed . . by the specific pigment used and the color of coating desired. Excellent results have 20 been achieved by using the aqueous dispersion in an amount such that the composition contains about 0.2 to about 3 g of furnace black/100 g of resin solids.
Many pi~m~nts are available in aqueous dispersions which may include surfact-ants or dispersing agents for ."~ the pigment particles in dispersed state. When utilizing such pi~nent dispersions, they should be selected so that the surfactant concen-2s tration in the aqueous phase ofthe composition is below the critical micelle concentration("CMC"), preferably below the surfactant concentration which corresponds to the inflec-tion point on a graph of surface tension versus the logarithm of surfactant concentration in the composition. A suitable pigmented composition is illustrated in examples herein.
Colored c~al;~ ~,c can be produced also by the use of dyes, examples of which in-30 clude rhodamine derived dyes, methyl violet, safranine, anthraquinone derived dyes, nig-rosine, and alizarin cyanine green. These are but a few exarnples of dyes that can be used.
WO96/10461 ~ s~ ~ ~ PCT/US95/11404 Examples of other additives that may be used in the autodepositing composition are those generally known to be used in formul~ting paint compositions, for example, W
stabilizers, viscosity modifiers, etc.
If a surfactant is added to the composition, either as a colnl,ol1enl ofthe latex, or 5 with a pi~ nt dispersion, or with other ingredients or additives, the total amount of sur-factant in the aqueous phase of the composition should be .nAil~A;l~ed below the CMC.
Fl~f~lably~ the ~queol-~ phase of the composition c~nlains little or no surfactant.
If an external surfactant is utili7etl the pre~.led surf~ct~nts are anionic.
Examples of suitable anionic surf~ct~nts are the alkyl, alkyVaryl or naphth~lene sul-10 fonates, for example, sodium dioctylsulfosucçin~te and sodium dodecylben2elle sulfon-ate.
In prep~ing the autodepositing composition, the con~tituçnts thereof can be ad-rnixed in any suitable way, for example, as des.,li~ed in U. S. Patent No. 4,191,676. In prep~.ng a bath of pi~mented coating composition for use on an industrial scale, it is pl~f~lled that the bath be prepa,ed by admixing:
A) an aqueous conce,ltlale comprising about 350 to ab~ut 550 g/l of resin particles, preferable the aforementioned vinylidene chloride-co..~ l;n~
resin particles, and about 10 to about 550 g/l of pigment; and . . B) an aqueous concell~rate p~pared from about 0.4 to about 210 g/l of HF
and a water soluble ferric-cont~ining compound in an amount equivalent to about i to about 100 gA of ferric iron.
The bath can be pl e~,al ed by stirring water into concen~l a~e (A) and thereafter admL~cing therewith the required arnount of concentrate (B) ~,vith stirring to provide a homogenous composltion.
2s The complex fluoride anions required in a reaction rinse accordu1g to the inven-tion are preferably added to the ~r~...enl solution in the forrn of nickel, ferric, or cobalt salts, more preferably cobalt salts, and the anions themselves are preferably fluoborate (i.e., BF;), fluosil;~te (i.e., SiF62), fluotitanate (i.e., TiF6-2), or fluozirconate (i.e., ZrF6~2) with the latter most prerelled.
The conce,l~.~ion of the total of the complex fluoride anions present in the aque-ous liquid rinse composition used according to the invention preferably is, with increas-ing ~"t;re,el1ce in the order given, at least 0.002, 0.004, 0.008, 0.016, 0.023, 0.033, 0.040, WO96/10461 ~'2 ~ Pcr/uS95/11404 0.047, 0.054, 0.061, or 0 068 moles per liter ("M") and independently preferably is, with inc,~sing plerere~lcc in the order given, not more than 1.0, 0.7, 0.4, 0.20, 0.15, 0.100, 0.090, 0.080, 0.075, or 0.072 M. The pH of the rinse soluition used according to this in-vention p,~.~ly is, with ;n~;,~si.~g p,eferellce in the order given, not less than 1.0, 1.5, ! 8 2.0, 2.5, 3.0, 3.1, 3.2, 3.3, 3.4, or 3.5 and independently preferably is, with increasing p,~f~rellce in the order given, not more than 9, 8, 7.0, 6.5, 6.0, 5.8, 5.6, 5.4, 5.2, 5.0, 4.9, 4.8, 4.7, 4.6, or 4.5.
The rinse solution may be co~taGted, accoldil~g to the invention, with a wet un-cured ~utodçposiled coating by any convenient method or combination of methods, such as spraying, cu~ain co~tin~, or ilnl,lel~;ol~, with the latter normally pref~"~. ~efc.ably the time of contact between the rinse s~,lt~tion and the wet uncured autodepositied coating is, with increasing p,eferènce in the order given, not less than 5, 10, 20, 30, 40, 45, 50, 55, or 60 seconds (hereinafter often abbreviated "secN) and independently preferably is, with increasing prëfel ence in the order given, not more than 600, 400, 200, 120, 1 10, 100, 95, or 90 sec. The tell.pelalule ofthe rinse solution during contact with a wet un-cured autodepo~iled coating may be any te~"?c~al~lre at which the rinse solution is liquid but normally preferably is, with increasing plef.,rence in the order given, not less than 10, 15, 18, or 20 C and indepen-lently preferably is, with increasing preference in the order given, not more than 60, 45, 35, 30, 27, 25, or 23 C.
A~er the reaction rinse ~ l"e,lt, the wet autodeposited coating as modified by contact with the reaction rinse is so~.~el;~es rinsed again with water, preferably deionized water if any, before being dried and, if desired as is usually pl efel ~ ed, cured by he~ting~t an elevated te.l")elal~lre so selected that the protective p, Opel lies of the coating are fully dcv~loped but not adversely affected. The tel~,pe.al~re and time of tre~tme~t will depend on the nature ofthe particular resin in the autodeposited coating and the thickness of the coating. With autodeposition baths con~ ;ng most types of organic binder resins, in-cluding the most ~>leÇ~ d poly{vinylidene chloride} resins, during or a~er drying, the autodeposited coatings preferably are heated to a temperature that is, ~ith increasing plêfelellce in the order given, at least 22, 30, 40, S0, 60, 70, 80, 90, 100, 110, or 120 C and independently preferably is, with increasing preferellce in the order given, not morethan200, 180, 160, 150, 140, 135, 130, 128, or 126 C. Times of heating for cur-ing plefel~ly range from S seconds up to 30 mirnltec, dependent on the macs of the coat-WO 96/10461 ~ PCT/US9S/11404 ed article. Preferably, the coating is heated for a period of time until the metallic sub-strate has reached the temperature of the heated environl.lent, typically in a forced air baking oven.
- The dried, cured coated articles are found to have excellent corrosion reCist~nce s when tested in soak tests or the neutral salt spray ("NSS") test, such as ASTM B-l 17 and scab corrosion cycles. Autodeposited ~ g~ treated according to the present invention are particularly effective on both cold rolled steel and galvanized steel, thereby allowing the two types to be processed together.
To further illustrate the various objects and advantages of the present invention, the following examples, in which all parts and percentaEes are by weight unless other-wise indicated, are provided. It is understood that their purpose is entirely illustrative and in no way intended to limit the scope of the invention.
Example 1 This example illustrates the preparation of a metallic surface having an autode-posited resinous coating. The met~llic surface comprised steel panels, both cold rolled steel (CRS) and zinc galvanized steel (GS) panels, which were cleaned with a conven-tional alkaline cleaner composition and nnsed with water prior to being coated by irnrner-sion in the autodepositing composition at arnbient temperature (about 21 C) for about 90 seconds. The autodepositing i"-n~e.~ion bath had the following composition: 60 grams per liter (he,e;llaner abbreviated as "g/L") of internally stabilized copolyrner of vinylidene chloride, 2.5 g/L of carbon black, 0.4 g/L of HF, 1.5 gtL of ferric iron, and the balance water.
Example 2 In this exarnple, the uncured coated panels from example I are treated with a re-2s action rinse inunersion bath after first being rinsed with water. The reaction rinse with-out cobalt cations contained 0.5 % by weight of H2ZrF6 and was adjusted to the pH
shown in the following tables with ammonia if needed. In the exarnples employing the cobalt salt of hydrofluorozirconic acid, the concentration is shown in the tables below;
the pH was 3.5 for all the concenllalions shown.
After hnlne,~;on in the reaction rinse bath for one rninute, the panels were then rinsed with water (deionized) and the panels were then cured for 20 minutes in an oven at a telllpelal~lre of 105 C.
- -WO 96/10461 ~ PCT/US95/11404 Example 3 This e,~ . ~!e illustrates the results of corrosion resistance testing of various pan-els. Table 1 below illustrates salt spray performance and cyclic scab pe.ru~ ance on galvanized steel, and Tables 2 - 7 i~dic~te pe.fo-~l,ance on other tests as noted.
The letters "GM" and the numbers and letters immediately following these lettersin the h6~riin~c of Tables 2 - 7 refer res~e~ rely to the General Motors Corporation and to various specific corrosion tests that are part of pe~rGI"~ance specific~tions at that company. Test details are readily available from General Motors. Briefly, the tests reported here are described as follows:
10 1. Cyclic CorroSiQn - GM 9511P
Af'~er prepa.alion (1) the s&"lples are heated in an oven at 60C. for 1 hour fol-lowed by (2) 30 minutes at -25 C. The samples are then (3) immersed in a 5 % NaCI
solution at room te"lpe~ re for 15 minutes, followed by (4) ambient drying for 75 minuteS The samples are then (5) held for 22.5 hours in a humidity challlber at 85 %
relative humidity ("RH") and 60 C. The fo,egoing is generally conducted over a 5-day period after which the 5 steps may be repeated for any desired number of cycles.2. Cyclic Corrosion - GM 9540P. Cycle B
A~er p,e~)a,aLion~ the samples are treated at 25C. and 50 % RH environment for 8 hours, including 4 sprays at 90 minutes intervals with a solution cont~ining 0.9 %
NaCI, 0.1 % CaCI2, and 0.25 % NaHCO3 in deionized water. The samples are then sub-jected to an 8 hour fog, 100 % RH at 40 C, followed by 8 hours at 60 C and less than 20 % RH. The entire treatment is repeated for the desired number of cycles, usually 40 cycles.
WO96/10461 ~ ~ fi ~ PCT/US9~/11404 Table 1 Reaction Rinse Concentration pH Corrosion Tes~ l~atings (Paint Del~l;nalion from Scribe, mm) NSS (336 hr) 20 Cycles Scâb H~ZrF~ 0.5 % 3 0 - 2 H2ZrF~s 0 5 % 4 0 - 2 H2ZrF6 0.5 % 5 0 - 2 1.5 CoZrF6 4.5 g/L 3.5 0 - 2 1.5 CoZrF6 9.0 ,~/L 3.5 0 - 2 0.8 CoZrF6 18 g/L 3.5 0 - I 0.6 ~able 2 (20 Cycles GM 9511 P on Cold Rolled Steel) Reaction Coat- TotalWidth Creepback Gravel Rating Rinse ing (mm) Thick-ness"u Aver- Ma~imum Minimum Impact After age Dam- 20 a~e~Cycles 0 5%H2ZrF6 23 2.8 5.9 1 5 9 10 %
pH 5 20 3.3 6.0 1.0 9 rusted CoZrF6 23 3.7 5.9 1.5 9 10 %
4.5 g/L 23 2.8 8.2 1.0 9 rusted *Impact damage was measured as specified in GM 9508 P.
-0 2 ~ 9 ~ pCr~US95/11404 wo 96110461 Table 3 (20 Cycles GM 951 1 P on Galvanized Steel) -`
Reaction Coating TotalWidth Creepback(mm) Gravel Rating Rinse Thick-ness,ll Average Ma~imum Minimum Before After 0.5% H2ZrF6 13 1.5 3.1 0.2 8 8 pH 5 17 0.6 1.9 0.2 8 8 CoZrF6 15 0.7 2.6 0.2 8 8 4.5 g/L 13 0.4 3.1 0.2 8 8 Table 4 (40 Cycles GM 9540 P, Cycle B, on Cold Rolled Steel) Reaction Coating Total Width Creepback (mm) Field RinseThickness, ~1 Average Ma~imum Minimum 0.5% 20 6.6 9.8 4.2 10 % n~sted H~rF6 pH 5 20 6.5 9.5 3.8 CoZrF6 20 12.1 22.6 4.5 20 % rusted 4.5 glL 23 9.6 14.8 3.9 W096/10461 ~ ~` q ~ ~ ~ 8 3 PCI~/US9!i111404 Table 5 (40 Cycles Gm 9540 P, Cycle B, on Galvanized Steel) Reaction Coating Total Width Creepback (mm) Field RinseThickness, 11 Avera~e Masimum Minimum 0.5% 10 0.7 4.2 0.2 60 % rusted H2ZrF6 pH S 11 1.0 2.7 0.2 CoZrF6 16 0.7 2.2 0.2 10 % rusted 4.5 g/L 15 0.8 2.6 0.2 Table 6 (5 cycles GM 9505 P, Cycle J, on Cold Rolled Steel) ReactionCoatingMasimum Creepback from Scribe RinseThickness,~ (mm) Right Left Total 0.5% H2ZrF6 23 2.6 2.9 5.5 P 20 2.7 2.8 5.5 CoZrF6 20 3.4 3.0 6.4 4.5 g/L 20 2.4 2.9 5.3 - -WO96/10461 tl 2~ PCT/US95/11404 Table 7 --(5 Cycles GM 9505 P, Cycle J, on Galvani~ed Steel) Reaction CoatingMa~imum Creepbllck from Scribe Rinse Thickness, ~ (mm) Ri~ht Left Total 0.5% H2ZrF6 13 2.8 3.1 5.9 P 15 3.0 2.7 5.7 CoZrF6 14 0.2 0.2 0.4 4.S g/L 12 0.2 0.2 0.4 3. Cyclic Corrosion - GM 9505P. Cycle J
A~er plCp~a~iOn, the samples are (I) held in a freezer at -30 C for 2 hours, fol-lowed by ambient conditions for 2 hours and subsequently (2) in an oven at 70 C for 2 hours. The samples are then (3) subjected to a 5 % NaCI solution salt spray for 2 hours s and then (4) held in a humidity cl.~llber at 38 C and 95 % RH for 64 hours. The sam-ples are then (S) held in an oven at 60 C for I hour followed by (6) a freezer at -30 C
for 30 mi~ teS The samples are then subjected to (7) im nersion in a 5 % NaCI solution at room temperature for 15 minutes and then (8) held at ambient conditions for 1.25 hours, followed by (9) a humidity chamber at 60C and 85 % RH for 6.5 hours, followed ~o (10) by 38 C for 64 hours. Steps (1) - (4) above are then repeated to complete the cycle which is generally concluded in a 2-week period.
Claims (20)
1. A process of providing a metal substrate with a protective coating containing an organic binder, said process comprising steps of:
(A) contacting the metal substrate with a liquid autodeposition composition for a sufficient time to form on the metal substrate surface a wet adherent film including organic binder deposited from the autodeposition composition:
(B) separating the substrate bearing the wet adherent film formed in step (A) from further contact with the autodeposition composition and contacting the wet adherent film with an aqueous liquid rinse solution comprising water and anions that consist of (i) at least four fluorine atoms and (ii) at least one atom of an element selected from the group consisting of titanium, zirconium, hafnium, silicon, and boron and, optionally, (iii) one or more oxygen atoms; and (C) separating the substrate bearing the wet adherent film as modified by the contacting of step (B) from the aqueous liquid rinse solution used in step (B) and subsequently drying the wet film into place on the substrate to produce a dry film.
(A) contacting the metal substrate with a liquid autodeposition composition for a sufficient time to form on the metal substrate surface a wet adherent film including organic binder deposited from the autodeposition composition:
(B) separating the substrate bearing the wet adherent film formed in step (A) from further contact with the autodeposition composition and contacting the wet adherent film with an aqueous liquid rinse solution comprising water and anions that consist of (i) at least four fluorine atoms and (ii) at least one atom of an element selected from the group consisting of titanium, zirconium, hafnium, silicon, and boron and, optionally, (iii) one or more oxygen atoms; and (C) separating the substrate bearing the wet adherent film as modified by the contacting of step (B) from the aqueous liquid rinse solution used in step (B) and subsequently drying the wet film into place on the substrate to produce a dry film.
2. A process as defined in claim 1 wherein the aqueous liquid rinse solution contains a total of about 0.002 to about 1.0 M of anions selected from the group consisting of fluoborate, fluosilicate, fluotitanate, and fluozirconate anions.
3. A process as defined in claim 2, wherein the aqueous liquid rinse solution has a pH from about 1.8 to about 9 and contains a total of about 0.008 to about 0.7 M of anions selected from the group consisting of fluoborate, fluosilicate, fluotitanate, and fluozirconate anions.
4. A process as defined in claim 4, wherein the aqueous liquid rinse solution has a pH from about 2.5 to about 6.0 and contains a total of about 0.016 to about 0.4 M of anions selected from the group consisting of fluoborate, fluosilicate, fluotitanate, and fluozirconate anions.
5. A process as defined in claim 5, wherein the aqueous liquid rinse solution has a pH from about 3.0 to about 5.4 and contains a total of about 0.023 to about 0.075 M of fluozirconate anions.
6. A process as defined in claim 5, wherein the aqueous liquid rinse solution contains an amount of cobalt cations sufficient to form salts with its total content of fluozirconate anions.
7. A process as defined in claim 4, wherein the aqueous liquid rinse solution contains a total of ferric, nickel, and cobalt cations sufficient to form salts with its total content of fluoborate, fluosilicate, fluotitanate, and fluozirconate anions.
8. A process as defined in claim 3, wherein the aqueous liquid rinse solution contains a total of ferric, nickel, and cobalt cations sufficient to form salts with its content of fluoborate, fluosilicate, fluotitanate, and fluozirconate anions.
9. A process as defined in claim 2, wherein the aqueous liquid rinse solution contains a total of ferric, nickel, and cobalt cations sufficient to form salts with its content of fluoborate, fluosilicate, fluotitanate, and fluozirconate anions.
10. A process as defined in claim 1, wherein the aqueous liquid rinse solution contains a total of ferric, nickel, and cobalt cations sufficient to form salts with its content of fluoborate, fluosilicate, fluotitanate, and fluozirconate anions.
11. A process according to claim 10, wherein the autodeposition composition contains a dispersed resin that is a copolymer of at least one of vinylidene chloride and butyl acrylate.
12. A process according to claim 9, wherein the autodeposition composition contains from about 5 to about 12 % of dispersed resin made by copolymerizing:
1) between about 45 and about 99 %, based on the total weight of monomers used, of vinylidene chloride monomer;
2) from about 0.5 to 30 weight percent, based on the total weight of (1) and (2), of a second relatively more hydrophilic ethylenically unsaturated monomeric material that has a solubility in both the water phase and the oil phase of the polymer latex of at least 1 weight percent at the temperature of polymerization;and 3) from about 0.1 to about 5 weight percent, based on the total weight of other monomers of an ionic, significantly water-soluble material which is copolymerizable with (2) and is selected from the group of sulfonic acids and their salts having the formula:
R-Z-Q-(SO3)-M+, wherein: the moiety "R" is selected from the group consisting of vinyl and substituted vinyl; the symbol "Z" represents a disfunctional linking group which will activate the double bond in the vinyl group; -Q- is a divalent hydrocarbon moiety having its valence bonds on different carbon atoms; and the symbol "M-"
represents a cation.
1) between about 45 and about 99 %, based on the total weight of monomers used, of vinylidene chloride monomer;
2) from about 0.5 to 30 weight percent, based on the total weight of (1) and (2), of a second relatively more hydrophilic ethylenically unsaturated monomeric material that has a solubility in both the water phase and the oil phase of the polymer latex of at least 1 weight percent at the temperature of polymerization;and 3) from about 0.1 to about 5 weight percent, based on the total weight of other monomers of an ionic, significantly water-soluble material which is copolymerizable with (2) and is selected from the group of sulfonic acids and their salts having the formula:
R-Z-Q-(SO3)-M+, wherein: the moiety "R" is selected from the group consisting of vinyl and substituted vinyl; the symbol "Z" represents a disfunctional linking group which will activate the double bond in the vinyl group; -Q- is a divalent hydrocarbon moiety having its valence bonds on different carbon atoms; and the symbol "M-"
represents a cation.
13. A process according to claim 8, wherein the autodeposition composition contains from about 5 to about 12 % of dispersed resin made by copolymerizing:
1) between about 45 and about 99 %, based on the total weight of monomers used, of vinylidene chloride monomer;
2) from about 0.5 to 30 percent, based on the total weight of (1) and (2), of a second relatively more hydrophilic ethylenically unsaturated monomeric material that has a solubility in both the water phase and the oil phase of the polymer latex of at least 1 weight percent at the temperature of polymerization; and 3) from about 0.1 to about 5 percent, based on the total weight of other monomers of an ionic, significantly water-soluble material which is copolymerizable with (2) and is selected from the group of sulfonic acids and their salts having the formula R-Z-Q-(SO3)-M+, wherein: the moiety "R" is selected from the group consisting of vinyl and substituted vinyl; the symbol "Z" represents a difunctional linking group which will activate the double bond in the vinyl group; -Q- is a divalent hydrocarbon moiety having its valence bonds on different carbon atoms; and the symbol "M+"
represents a cation.
1) between about 45 and about 99 %, based on the total weight of monomers used, of vinylidene chloride monomer;
2) from about 0.5 to 30 percent, based on the total weight of (1) and (2), of a second relatively more hydrophilic ethylenically unsaturated monomeric material that has a solubility in both the water phase and the oil phase of the polymer latex of at least 1 weight percent at the temperature of polymerization; and 3) from about 0.1 to about 5 percent, based on the total weight of other monomers of an ionic, significantly water-soluble material which is copolymerizable with (2) and is selected from the group of sulfonic acids and their salts having the formula R-Z-Q-(SO3)-M+, wherein: the moiety "R" is selected from the group consisting of vinyl and substituted vinyl; the symbol "Z" represents a difunctional linking group which will activate the double bond in the vinyl group; -Q- is a divalent hydrocarbon moiety having its valence bonds on different carbon atoms; and the symbol "M+"
represents a cation.
14. A process according to claim 7, wherein the autodeposition composition contains from about 5 to about 12 % of dispersed resin made by copolymerizing:
1) between about 45 and about 99 %, based on the total weight of monomers used, of vinylidene chloride monomer;
2) from about 0.5 to 30 weight percent, based on the total weight of (1) and (2), of a second relatively more hydrophilic ethylenically unsaturated monomeric material that has a solubility in both the water phase and the oil phase of the polymer latex of at least 1 weight percent at the temperature of polymerization;and 3) from about 0.1 to about 5 weight percent, based on the total weight of other monomers of an ionic, significantly water-soluble material which is copolymerizable with (2) and is selected from the group of sulfonic acids and their salts having the formula:
R-Z-Q-(SO3)-M+, wherein: the moiety "R" is selected from the group consisting of vinyl and substituted vinyl; the symbol "Z" represents a difunctional linking group which will activate the double bond in the vinyl group; -Q- is a divalent hydrocarbon moiety having its valence bonds on different carbon atoms; and the symbol "M"
represents a cation.
1) between about 45 and about 99 %, based on the total weight of monomers used, of vinylidene chloride monomer;
2) from about 0.5 to 30 weight percent, based on the total weight of (1) and (2), of a second relatively more hydrophilic ethylenically unsaturated monomeric material that has a solubility in both the water phase and the oil phase of the polymer latex of at least 1 weight percent at the temperature of polymerization;and 3) from about 0.1 to about 5 weight percent, based on the total weight of other monomers of an ionic, significantly water-soluble material which is copolymerizable with (2) and is selected from the group of sulfonic acids and their salts having the formula:
R-Z-Q-(SO3)-M+, wherein: the moiety "R" is selected from the group consisting of vinyl and substituted vinyl; the symbol "Z" represents a difunctional linking group which will activate the double bond in the vinyl group; -Q- is a divalent hydrocarbon moiety having its valence bonds on different carbon atoms; and the symbol "M"
represents a cation.
15. A process according to claim 6, wherein the autodeposition composition contains from about 5 to about 10 % of dispersed resin made by copolymerizing:
1) between about 80 and about 99 %, based on the total weight of monomers used, of vinylidene chloride monomer;
2) from about 0.5 to 19 weight percent, based on the total weight of (1) and (2), of monomers selected from the group consisting of acrylonitriles, acrylamides, and methacrylamides that have a solubility in both the water phase and the oil phaseof the polymer latex of at least 1 weight percent at the temperature of polymerization; and 3) from about 0.1 to about 5 weight percent, based on the total weight of other monomers of an ionic, significantly water-soluble material which is copolymerizable with (2) and is selected from the group of sulfonic acids and their salts having the formula:
R-Z-Q-(SO3)-M+, wherein: the moiety "R" is selected from the group consisting of vinyl and substituted vinyl; the symbol "Z" represents a difunctional linking group which will activate the double bond in the vinyl group; -Q- is a divalent hydrocarbon moiety having its valence bonds on different carbon atoms; and the symbol "M+"
represents a cation.
1) between about 80 and about 99 %, based on the total weight of monomers used, of vinylidene chloride monomer;
2) from about 0.5 to 19 weight percent, based on the total weight of (1) and (2), of monomers selected from the group consisting of acrylonitriles, acrylamides, and methacrylamides that have a solubility in both the water phase and the oil phaseof the polymer latex of at least 1 weight percent at the temperature of polymerization; and 3) from about 0.1 to about 5 weight percent, based on the total weight of other monomers of an ionic, significantly water-soluble material which is copolymerizable with (2) and is selected from the group of sulfonic acids and their salts having the formula:
R-Z-Q-(SO3)-M+, wherein: the moiety "R" is selected from the group consisting of vinyl and substituted vinyl; the symbol "Z" represents a difunctional linking group which will activate the double bond in the vinyl group; -Q- is a divalent hydrocarbon moiety having its valence bonds on different carbon atoms; and the symbol "M+"
represents a cation.
16. A process according to claim 5, wherein the autodeposition composition contains from about 5 to about 10 % of dispersed resin made by copolymerizing:
1) between 45 and 99 %, based on the total weight of monomers used, of vinylidene chloride monomer;
2) from about 0.5 to about 19 weight percent, based on the total weight of (I) and (2), of monomers selected from the group consisting of acrylonitriles, acrylamides, and methacrylamides that have a solubility in both the water phase and the oil phase of the polymer latex of at least 1 weight percent at the temperature of polymerization; and 3) from about 0.1 to about 5 weight percent, based on the total weight of othermonomers of an ionic, significantly water-soluble material which is copolymerizable with (2) and is selected from the group of sulfonic acids and their salts having the formula:
R-Z-Q-(SO3)-M+, wherein: the moiety "R" is selected from the group consisting of vinyl and substituted vinyl; the symbol "Z" represents a difunctional linking group which will activate the double bond in the vinyl group; -Q- is a divalent hydrocarbon moiety having its valence bonds on different carbon atoms, and the symbol "M+"
represents a cation.
1) between 45 and 99 %, based on the total weight of monomers used, of vinylidene chloride monomer;
2) from about 0.5 to about 19 weight percent, based on the total weight of (I) and (2), of monomers selected from the group consisting of acrylonitriles, acrylamides, and methacrylamides that have a solubility in both the water phase and the oil phase of the polymer latex of at least 1 weight percent at the temperature of polymerization; and 3) from about 0.1 to about 5 weight percent, based on the total weight of othermonomers of an ionic, significantly water-soluble material which is copolymerizable with (2) and is selected from the group of sulfonic acids and their salts having the formula:
R-Z-Q-(SO3)-M+, wherein: the moiety "R" is selected from the group consisting of vinyl and substituted vinyl; the symbol "Z" represents a difunctional linking group which will activate the double bond in the vinyl group; -Q- is a divalent hydrocarbon moiety having its valence bonds on different carbon atoms, and the symbol "M+"
represents a cation.
17. A process according to claim 4, wherein the autodeposition composition contains from about 5 to about 12 % of dispersed resin made by copolymerizing 1) between 45 and 99 % based on the total weight of monomers used, of vinylidene chloride monomer;
2) from about 0.5 to 30 weight percent based on the total weight of (1) and (2) of a second relatively more hydrophilic ethylenically unsaturated monomeric material that has a solubility in both the water phase and the oil phase of the polymer latex of at least 1 weight percent at the temperature of polymerization;and 3) from about 0.1 to about 5 weight percent based on the total weight of other monomers of an ionic significantly water-soluble material which is copolymerizable with (2) and is selected from the group of sulfonic acids and their salts having the formula:
R-Z-Q-(SO3)-M+, wherein the moiety "R" is selected from the group consisting of vinyl and substituted vinyl; the symbol "Z" represents a difunctional linking group which will activate the double bond in the vinyl group; -Q- is a divalent hydrocarbon moiety having its valence bonds on different carbon atoms; and the symbol "M+"
represents a cation.
2) from about 0.5 to 30 weight percent based on the total weight of (1) and (2) of a second relatively more hydrophilic ethylenically unsaturated monomeric material that has a solubility in both the water phase and the oil phase of the polymer latex of at least 1 weight percent at the temperature of polymerization;and 3) from about 0.1 to about 5 weight percent based on the total weight of other monomers of an ionic significantly water-soluble material which is copolymerizable with (2) and is selected from the group of sulfonic acids and their salts having the formula:
R-Z-Q-(SO3)-M+, wherein the moiety "R" is selected from the group consisting of vinyl and substituted vinyl; the symbol "Z" represents a difunctional linking group which will activate the double bond in the vinyl group; -Q- is a divalent hydrocarbon moiety having its valence bonds on different carbon atoms; and the symbol "M+"
represents a cation.
18. A process according to claim 3, wherein the autodeposition composition contains from about 5 to about 12 % of dispersed resin made by copolymerizing:
1) between 45 and 99 %, based on the total weight of monomers used, of vinylidene chloride monomer;
2) from about 0.5 to 30 weight percent, based on the total weight of (1) and (2), of a second relatively more hydrophilic ethylenically unsaturated monomeric material that has a solubility in both the water phase and the oil phase of the polymer latex of at least 1 weight percent at the temperature of polymerization;and 3) from about 0.1 to about 5 weight percent, based on the total weight of other monomers of an ionic, significantly water-soluble material which is copolymerizable with (2) and is selected from the group of sulfonic acids and their salts having the formula:
R-Z-Q-(SO3)-M+, wherein: the moiety "R" is selected from the group consisting of vinyl and substituted vinyl; the symbol "Z" represents a difunctional linking group which will activate the double bond in the vinyl group; -Q- is a divalent hydrocarbon moiety having its valence bonds on different carbon atoms; and the symbol "M+"
represents a cation.
1) between 45 and 99 %, based on the total weight of monomers used, of vinylidene chloride monomer;
2) from about 0.5 to 30 weight percent, based on the total weight of (1) and (2), of a second relatively more hydrophilic ethylenically unsaturated monomeric material that has a solubility in both the water phase and the oil phase of the polymer latex of at least 1 weight percent at the temperature of polymerization;and 3) from about 0.1 to about 5 weight percent, based on the total weight of other monomers of an ionic, significantly water-soluble material which is copolymerizable with (2) and is selected from the group of sulfonic acids and their salts having the formula:
R-Z-Q-(SO3)-M+, wherein: the moiety "R" is selected from the group consisting of vinyl and substituted vinyl; the symbol "Z" represents a difunctional linking group which will activate the double bond in the vinyl group; -Q- is a divalent hydrocarbon moiety having its valence bonds on different carbon atoms; and the symbol "M+"
represents a cation.
19. A process according to claim 2, wherein the autodeposition composition contains from about 5 to about 12% of dispersed resin made by copolymerizing:
1) between 45 and 99 %, based on the total weight of monomers used, of vinylidene chloride monomer;
2) from about 0.5 to 30 weight percent, based on the total weight of (1) and (2), of a second relatively more hydrophilic ethylenically unsaturated monomeric material that has a solubility in both the water phase and the oil phase of the polymer latex of at least 1 weight percent at the temperature of polymerization;and 3) from about 0.1 to about 5 weight percent, based on the total weight of other monomers of an ionic, significantly water-soluble material which is copolymerizable with (2) and is selected from the group of sulfonic acids and their salts having the formula:
R-Z-Q-(SO3)-M+, wherein: the moiety "R" is selected from the group consisting of vinyl and substituted vinyl; the symbol "Z" represents a difunctional linking group which will activate the double bond in the vinyl group; -Q- is a divalent hydrocarbon moiety having its valence bonds on different carbon atoms; and the symbol "M+"
represents a cation.
1) between 45 and 99 %, based on the total weight of monomers used, of vinylidene chloride monomer;
2) from about 0.5 to 30 weight percent, based on the total weight of (1) and (2), of a second relatively more hydrophilic ethylenically unsaturated monomeric material that has a solubility in both the water phase and the oil phase of the polymer latex of at least 1 weight percent at the temperature of polymerization;and 3) from about 0.1 to about 5 weight percent, based on the total weight of other monomers of an ionic, significantly water-soluble material which is copolymerizable with (2) and is selected from the group of sulfonic acids and their salts having the formula:
R-Z-Q-(SO3)-M+, wherein: the moiety "R" is selected from the group consisting of vinyl and substituted vinyl; the symbol "Z" represents a difunctional linking group which will activate the double bond in the vinyl group; -Q- is a divalent hydrocarbon moiety having its valence bonds on different carbon atoms; and the symbol "M+"
represents a cation.
20. A process according to claim 1, wherein the autodeposition composition contains a dispersed resin that is a copolymer of at least one of vinylidene chloride and butyl acrylate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US31643794A | 1994-09-30 | 1994-09-30 | |
| US08/316,437 | 1994-09-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2199983A1 true CA2199983A1 (en) | 1996-04-11 |
Family
ID=23229045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002199983A Abandoned CA2199983A1 (en) | 1994-09-30 | 1995-09-18 | Treatment to improve corrosion resistance of autodeposited coatings on metallic surfaces |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0783379A4 (en) |
| JP (1) | JPH08173901A (en) |
| CN (1) | CN1159775A (en) |
| AU (1) | AU691668B2 (en) |
| BR (1) | BR9509053A (en) |
| CA (1) | CA2199983A1 (en) |
| MX (1) | MX9702065A (en) |
| TW (1) | TW308611B (en) |
| WO (1) | WO1996010461A1 (en) |
| ZA (1) | ZA958251B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4310223A1 (en) | 2022-07-18 | 2024-01-24 | Henkel AG & Co. KGaA | Alkaline reaction rinse for decorative autophoretic coatings |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19635615C1 (en) * | 1996-09-03 | 1997-09-18 | Herberts Gmbh | Process for producing multi-layered paint surfaces |
| DE19635616C1 (en) * | 1996-09-03 | 1997-09-18 | Herberts Gmbh | Multi-coat lacquering process giving good adhesion to baked primer coat deposited autophoretically |
| DE102005023728A1 (en) | 2005-05-23 | 2006-11-30 | Basf Coatings Ag | Lacquer-layer-forming corrosion inhibitor and method for its current-free application |
| JP5176337B2 (en) * | 2006-05-12 | 2013-04-03 | 株式会社デンソー | Film structure and method for forming the same |
| DE102006053291A1 (en) | 2006-11-13 | 2008-05-15 | Basf Coatings Ag | Lacquer-layer-forming corrosion protection agent with good adhesion and method for its current-free application |
| DE102007012406A1 (en) | 2007-03-15 | 2008-09-18 | Basf Coatings Ag | Process for corrosion protection equipment of metallic substrates |
| DE102009007633B4 (en) | 2009-02-05 | 2013-09-26 | Basf Coatings Ag | Multi-stage process for painting metallic substrates |
| DE102009007632A1 (en) | 2009-02-05 | 2010-08-12 | Basf Coatings Ag | Coating agent for corrosion-resistant coatings |
| DE102009029334A1 (en) | 2009-09-10 | 2011-03-24 | Henkel Ag & Co. Kgaa | Two-stage process for the corrosion-protective treatment of metal surfaces |
| WO2011061784A1 (en) * | 2009-11-17 | 2011-05-26 | 日本パーカライジング株式会社 | Surface-treatment liquid for autodeposition coating of iron-based and/or zinc-based metal material and surface-treatment method |
| DE102010019245A1 (en) | 2010-05-03 | 2012-01-19 | Basf Coatings Gmbh | Process for autophoretic coating, coating agent and multicoat paint system |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4030945A (en) * | 1966-06-01 | 1977-06-21 | Amchem Products, Inc. | Rinsing coated metallic surfaces |
| US4800106A (en) * | 1987-06-19 | 1989-01-24 | Amchem Products, Inc. | Gloss enhancement of autodeposited coatings |
| AU662758B2 (en) * | 1991-08-30 | 1995-09-14 | Henkel Corporation | Process for treating metal with aqueous acidic composition that is substantially free from chromium (VI) |
-
1995
- 1995-09-18 CA CA002199983A patent/CA2199983A1/en not_active Abandoned
- 1995-09-18 BR BR9509053A patent/BR9509053A/en not_active Application Discontinuation
- 1995-09-18 WO PCT/US1995/011404 patent/WO1996010461A1/en not_active Application Discontinuation
- 1995-09-18 EP EP95933063A patent/EP0783379A4/en not_active Withdrawn
- 1995-09-18 AU AU35856/95A patent/AU691668B2/en not_active Ceased
- 1995-09-18 MX MX9702065A patent/MX9702065A/en unknown
- 1995-09-18 CN CN95195399A patent/CN1159775A/en active Pending
- 1995-09-29 ZA ZA958251A patent/ZA958251B/en unknown
- 1995-09-29 JP JP7253964A patent/JPH08173901A/en active Pending
- 1995-10-11 TW TW084110649A patent/TW308611B/zh active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4310223A1 (en) | 2022-07-18 | 2024-01-24 | Henkel AG & Co. KGaA | Alkaline reaction rinse for decorative autophoretic coatings |
| WO2024017544A1 (en) | 2022-07-18 | 2024-01-25 | Henkel Ag & Co. Kgaa | Alkaline reaction rinse for decorative autophoretic coatings |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0783379A4 (en) | 2000-02-16 |
| JPH08173901A (en) | 1996-07-09 |
| BR9509053A (en) | 1997-09-30 |
| TW308611B (en) | 1997-06-21 |
| ZA958251B (en) | 1996-04-24 |
| WO1996010461A1 (en) | 1996-04-11 |
| AU3585695A (en) | 1996-04-26 |
| EP0783379A1 (en) | 1997-07-16 |
| MX9702065A (en) | 1997-06-28 |
| AU691668B2 (en) | 1998-05-21 |
| CN1159775A (en) | 1997-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1336482C (en) | Treating an autodeposited coating with an alkaline material | |
| US4647480A (en) | Use of additive in aqueous cure of autodeposited coatings | |
| EP0295713B1 (en) | Gloss enhancement of autodeposited coatings | |
| CA2199983A1 (en) | Treatment to improve corrosion resistance of autodeposited coatings on metallic surfaces | |
| EP0568619B1 (en) | Treating an autodeposited coating with an alkaline solution containing anions of multifunctional organic acids | |
| CA1280843C (en) | Vinylidene chloride latex in autodeposition and low temperature cure | |
| WO1994006861A1 (en) | Polymer blends for autodeposited coating | |
| US5164234A (en) | Treating an autodeposited coating with an alkaline solution containing organophosphonate ions | |
| US5760112A (en) | Water-borne autodepositing coating compositions | |
| US5667845A (en) | Treatment to improve corrosion resistance of autodeposited coatings on metallic surfaces | |
| MXPA97002065A (en) | Treatment to improve the corrosion resistance of autodeposited coatings on metali surfaces | |
| US4562098A (en) | Water or steam cure of autodeposited resin coatings on metallic substrates | |
| US5352726A (en) | Autodepositing composition containing vinylidene chloride based resin | |
| CA2152826A1 (en) | Method for applying autodeposition coating | |
| US6312820B1 (en) | Vinylidene chloride resin in autodeposition | |
| US5912297A (en) | Internally stabilized vinylidene chloride resin in autodeposition | |
| EP0312648A2 (en) | Vinylidene chloride latex in autodeposition and low temperature cure | |
| EP0310709A2 (en) | Vinylidene chloride latex in autodeposition and low temperature cure | |
| EP0310708A2 (en) | Vinylidene chloride latex in autodeposition and low temperature cure | |
| JPS607550B2 (en) | Surface treatment method for aluminum products | |
| EP0871549A1 (en) | Composition and process for autodeposition with modifying rinse of wet autodeposited coating film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |