CA2374539A1

CA2374539A1 - Chromium-free anticorrosive and anticorrosive method

Info

Publication number: CA2374539A1
Application number: CA002374539A
Authority: CA
Inventors: Stefan Kupper; Jorg Sander; Karsten Hackbarth; Christina Hirsch; Veit Lachmann; Petra Reessing; Reinhard Seidel
Original assignee: Individual
Current assignee: Henkel AG and Co KGaA
Priority date: 1999-05-20
Filing date: 2000-05-11
Publication date: 2000-11-30
Also published as: AU5065600A; DE19923084A1; WO2000071626A1; EP1187883A1; AU780777B2

Abstract

The invention relates to a chromium-free aqueous anticorrosive which is suitable for producing thin organic layers on surfaces of steel, metallized (e.g. galvanized or alloy-galvanized) steel and aluminum. The inventive anticorrosive contains as the essential components a) 0.5 to 100 g/l hexafluorine anions of titanium (IV), silicon (IV) and/or zirconium (IV); b) 20 to 100 g/l phosphoric acid; c) 0 to 100 g/l of one or more compounds of cobalt, nickel, vanadium, iron, manganese, molybdenum or tungsten; d) 0.5 to 30 wt.- %. of at least one water-soluble or water-dispersible film-forming organic polymer or copolymer; e) 0.1 to 10 wt.- % of an organosphonic acid; f) optionally further auxiliaries and additives. The inventive compositions are especially useful for the anticorrosive treatment of metal strips. They are preferably applied in such a manner that a dry layer is produced on the surface in a mass surface density of 0.1 to 5 g/m2.

Description

20-Nuv-O1 08:04 F~um-HENKEL/COGNIS CORP, PATENT DEPT, 8102788548 T-080 P.04/25 H 38()U
'I May 1999 CHROMIUM-FREE ANTICORROSIVE AND ANTICORROSIVE METHOD
Q.~~~~~.~G~~oa~b~~~~~~b~~~~~~~b~b~~~'~~~9b'b~a~bbb~~~~b'~'b'~~~b The present invention relates to a chromieun-free crryauic/inorgans.c anti-corrosive agent anti an anti-corrosive process for treating Surfaces ox steel, which are cp~icually provsaed with a metali~.c caring of zinc, aluminum. copper, nickel, etc., or of aluminum anct its S alloys. rt i3 particularly suitzbla for surfa~p treatment in sxrip plants (coil-coat~ag) for apptyzng thlS SL1173trdt~' 3.I1 LtIG vlomestic snd architectural areas and in rhp automobile indu9Lry.
Fir the temporary corrosion protection of galvanized or alloy-galvanlzeci '.,ICCl. strip3, rhe9e arc ofccn either simply rubhe~i with oil or, in the event that more intense corrosive stresses are expecLCd, ykiuaphatized or chromatsrect. Before rQCSivin~ a final coating Of organic binders (primer, lacquers, electrodeposi~ad lacq~xer3), a muh s-tage procQSS is generally performed. When usin4 galvanized metal strips or al.umanum and h s alloys iu ilea domestic appliance or arc_nitectural industries, optionally after previous removal of chs oil layer, LhC metal surface is first provided with an anr_s-corrosive layer. The best method for arszi-corrosive treatment known lscm the ptsor art is chromstizing in which Zrie mpr.al surface is coated with a ?t) chromiumtIII1 and/or chromium(vI)-contalnitiy layer, generally at a rate of about 5 to 15 mgJm=. Ph~spnatizinQ, as aTi alternative measure for anti-corrosive treatment, has two kluds of disadvantages. On the one hanri the appearance of the metal surface may be altered in an uncteslrabln umr~rmr . ~n ttte other hand, phosphatizin~ i s a procedure which is very costly in terms of the equipment required bccau~e, depending on the eu,t~strazo m~.terial, an additional activation Stage and, generally aftex phospriatizing, a passma~img stagy ss requsrad.
over and abnvp the actual anticorrosive effect, inorganic coazz.ng ensures qoo6 adheszou c.C the Frrimer which is appli4d thereto. There again, r_he primer not only has a beneficial effect on the antl.-corrcsivc effect of the Inorganic conversion layer, the primer layer in its turn also provides a goad adherent substrate for Lt~C topcoat lacquer.

20-Nov-01 09:04 From-HENKEL/COGNIS CORP, PATENT DEPT, 0102700540 T-OGO P.05/25 _ 2 To an increasing extent, metal strip producers are supplying sheet . mccal with a functiorsal preliminary coating which facilitates mechanical processing such as punching, drilling, bending, sizaping and/or deep drawing. only after final assembly of the workpiece is this finally provided with a topcoat lacquer. bunatiorsal precoaLS.ng must provide the srieet metal not only with corrosion-inhibiting properties but also properties which Facilitate mechanical processing. In order to produce thc~c l5yers, processes faced on chromium-containing lU inorganic/organrc compositions and also chromium-tree, Cx~lus3vely organic preparations are known, wherein the latter have only a l~.mited anti.-corrosive effs~ct.
In the automobile industry, galvanized steel sheeting which has been 1!~ pracoatad with thin orr~anic~ films is being used to an increasing ~XL~ill:. Thrsc suhstrate3 en.~urc a good snti-corrooivc cfFect, to bo precise even in the bodywork sector, which cannot be acn~.eved in a conventional lacquering process, or only with difficulty. The use of she a types of procoated materials enah'IpQ ~~Rr-tntensive secondary 2) ants-corrosive measures such as cavity sealing and joiu~. scalz.i.g to be reduced or even avoided altogether. To facilitate the subsequent processing stops such as spnr_ wPl~inr~ hr electrodeposltion lacquering, the organic films frequently also ec~smaite yigswemts and fillers which increase the aieotr~.cal conductivity. These types of materials are 25 krsomn, for eaamplQ, under the names nnraRrPPITS, BonazincT°°, DurazincT°°
or t~ranoCOatT°°. Materials C:UdL~i1 ,Z ii thl3 W~ty hGYG for cxam~lo, aver a conversion layer which is a chromatizing or phospnat~.zing layer, a thrn organic coatinrl wh~.ch consists, for example, of spoxide or polyurethane reslus, palyamidc9 or polyacrylazes. The organs.c layers are gFnprally .0 applied with a thickness of about u.j to about 5 ym_ These tailings on metal stxips are generally produced in a two-stagc process which ~.s costly in torms of eduipmonr., in which first the inorganic conversion layer is produee4 and then the U~yasi3.c polymor film is ap8lied in a second treatment stage.
..5 It is known trial attempts have alreauy taCCU a4ade to use single stage coating processes in which the inorganic conversion treatment and coacirg with an organic poa.yrn~r fi lm take place in a sin511e treatment solution.
~! 0 For example, tos-A-5 3a4 504 describes a coating process fos galvani2ed steel iu wluoli the Substrate is brougta into contact with a rrPar_ment solution with the following composzt~.on: 0.1 to 10 g/1 ur a tGtxafluoro or hexaflunrn acid of boron, silicon, titanium cad zirconium or 35 tsylitvfluoric acid, about O.O1S to about 6 g/1 of '~atin~g of cobalt.

20-Nuv-O1 0,8:04 Frum-HENKEL/COGNIS CORP, PATENT DEPT, .8102788548 T-080 P.OB/25 F-840 copper, iron, manganese, nickel, strontza.un ox zinc and optionally up to about 3 g/1 of a polymer selected from polyacrylic acl.d, polymethacryllc acid and the~.r esters. The pH of this treatment solution is crithin the ranges from about 4 to ahn»r 5_ w~ 95/14117 also describes a process for treating surfaces of zinc or aluminucn ur ~ticii alloys. In this ca3c, the sarfacca arc brought into contact with a treatment solution with a pH of less than 3 which contain= s complex between a metal oxoion and a heteroion. The metal 1~) oxolor~ is selected from molybdate, tungstate and vanactate. 'the tscteroion is selectea from phosphorus, ale~ninum, Qilirnn, manganese, magnesium, zirconium, titanium, tin, cerium and n.~ckel. Furthermore, the treatment snl»tion algn nnnrains an organic film-groducer which 1s compatiole w~.th rrie other components 1n the sclu~ium. suitaule film-15 prnri«nprs may he, for example, polyacrylates such as in particular pOlylI4C.C.'S Vr iuGtnyl metnacrylatc:, n-butyl acrylatc, hydroxethyl acrylare and glycerinepropoxy traacrylate.
EP-A-~i94 5y3 reCOmmends Lhe treatment of iuaLcl suitaces with a 20 treatment solution which contains the following components: an organic polymcc ui copolymer in which 0.5 to B $ of the monomers contasn groups which can form compounds with metal ions, complex caL~.ons or anions of aluminum, calcium, cerium, coi~alt, molybdenum, rilieon, vanadium, zirconium, titanium, trivalent chromium and zinc, an ox~.aismg agent :5 such as astric acid, perchlori~- arid and hydrogen 8eroxids and an acid such a3 oxalic acid, aCeLic aci.4, Doric rsc~~d, yHuS~r11G3:ic acid, sulfuric arid, nitric acid and hydrochJ_orlc acid.
WD 95/04619 discloses the treatment of metal surfaces with a treatme~m a0 solution ~rnieh contains at least she foll.owind components: fluoro complexes of titanium. zirconium, naxnium, silicon, alumlnuiu and Loro~~, metal ions selected from cnt~alr, magnesium, manganese, zinc, nickel, tin, copper, zirconium, Iron anG strontiusu, Ytiusphata3 or phospAonatc;, and aisd water-soluble or water-dispersible organic fi~.m-producers.
EP-A-792 922 describes a chromium-free corrosion inhibiting coat~.ng cowposition for alumsrsum or aluminum alloys which nnnraans a film-producing organic polymer and (i) a salt selected from esmt~ of rare earth metals, ai kati. aria alkaline earth metal vanadates and also (~.i) a RO borate Salt O= an alkrsla.nc ca~.a_lmuetal. Epoxsde3 inoludiag golyimide-1]~RPC~ Ppoxides, polyuretrianes, acrylic polymers and alkyd-based systems are mentioned, tuc Gaamplc, as preferred polymer. This ceating composition thus has to contain, in addition to the organic frlm-producer, at loa~t one borata and anothor rnmp~nent wh~Ch may be a 95 vanadate.

20-Nuv-O1 0,8:05 Frum-HENKEL/COGNIS CORP~ PATENT DEPT, 8102188548 T-080 P.OP/25 F-840 EP-A-685534 desCrlJ~es a pxocess for prctac~my a steel substrate by means of a thin fi.)_m of an orQariiC/inorgan~c hybrid polymer based 4n an alkoxysilane, another condensable ~r.ganometal compound of the ~ormula M(nR), and also lmeth)acrylic acid and a polymerisation initiator. The Coating 15 ptc~aucGd Ly thermal polymerisation of photopr~lymeriqar.ion.
Zirconium and titaniwn are mentioned as metals for the organon;seal cuwpou~~d. It ~s stated chat a film of this type prnrPCts steel sub3zrates against corrosion and oxic(at~.oni lri aGlCllLIon titc ou~.iSta:Lltc is intAnded re he proteceed by this coating against shock and other efteCLS.
WO 98/4731 desaamLes a process for improving defective pretrgar.erl metal surfaces. For thi9, an aqueous acid solu>rion which contarns fluc.~muCtalate nions, divalent or tetravalent can ons ~f cobalt, magnesium, manganese, =inc, nickel, tin, copper, zirconium. iron mud strontiu:a, phosr~hornR-rnnra~.ninQ inOrgaRiC oxOarilOns and phosphOriate Ions and a water-soJ.ut~le anu/us water-dispcrs~ble organic polyszzor andlnr a polymer-producing xesin 1s applied to the defective metal ::0 xu.cl~si:e. The document provides no data about whRrhPr these tyges of compositions axe also suitable for the first-time coati.ur3 ~f nvn-prccoated metal steps.
still vznpublisherl ~F.--A-1 9754108.9 describes a encomium-free aqueous anti-corrosive agent for es.~aa~ing surfaces of galvanized or alloy galvani~pd steel and of aluminum. It contains, as essential componeries, nexafluoro auiur~s of titanium orsa/or zirconium, vanadi »m ions, cobalt ions, phosphoric acid and also prexeraDly In addztivu dpi organic film-produccr, in part~.cular one teased on Dolyacrylace. This ariti-corrosive agent is particularly sultat~le far else anti-'orrosive treatment of metal strips_ ~PSpite This extensive prior art, there 1s still a need for imprs~ycd c:vd~.ii~g procc9ses for metal surfaces in whi c~.h an inorganic passiv8ting layex and also a thin organic polymer layer can Yea aYplied to the motel 3urfaceo ~.a the saraQ trestmenr step. The coatiriG is intended to facilitate the punching out and restiap.ii~g of Structural parts made from tho coated mer_a1 sr.r~ps. Furthermore, the layers on the metal sut~straze should with»ainl further manufaoturing stops up 1n agsemolinq the a0 products, such as cleaning, optionally phosphatizlng, r~vat.ia~g and welaimy and either be overpaintable with a tnpaoat laCguer or be coatable with an eleczrodeposition lacquer. For protrsc:tlon of the environment and hezlth and cafQry at work reasons, the treatritent process should be performatals without ~)ie use of chromiuca compounds anr3 a5 if possiblA wirte tt~e exclusion of organic solvents. The main T~.elos of 20-Nov-O1 QA;06 From-HENKEL/COGNIS CORP, PATENT DEPT, 6102786649 T-060 P.08/26 applieazien arc the initially mentioned domestic appliance and arcriltectural Inriustries and also the automobile industry.
TAis object is achieved, according to ehe invention, as stated in the ~:lalav3. =t conaista substantially ~n the provision of a chromium-free ants-corros~.ve agent conta~,m ng water and a) O,5 re 1011 gll of hPx~f1 nrn anima c~sf riran~~xm(TV), Sslicon(IV) and/ar zirconium(IV), l~) b) U to lUU g/1 of phosphoric acid, c) 0 to 100 g/1 of one or more compounds selected fxom cobalt, nickel, varvas~zu~t, iron, rtanganosQ, molybdenum and tungsten, d) 0.5 w 30 wl..'~ of at ~.CG~~. UL1C wGLCi-~uluJ~lG ur. water--dispe~aiblc film-producing organic polyJaer or copolymer (with respect to 1~ active substance), a) 0.1 to 10 wt.?~ of an organophosphonic acid, f) optionally further au:ciliary substances and additivoa.
The invention also provides a process for the anticorrosive treatment 2n of RTPP~ whmh is optionally provided with a metallic coating of zinc, aluminum, copper, nickel or similar metal~r or aluma.num or its alloys, which Includes the following essential process steps:
a) thA a»rfac~P of the substrate is placed in COfItaCC With an antl-2~ cvrroaive ogcnz of the type mentioned above for a period between 0.5 and 6o secoac~s ac a treatment temperature between lfl and 50°C, preferaZ'ly between 15 and 35°C; the treatment temperature may be adjustca by supplying heat via trie wnrkniP~P ~r r.he treatment solution, .0 b) excess anti-corrosive agent is optionally removed from the surface and c) the icew is heated for a period from 1 to 120 seconds, by an appropriate heat supply, Wi~ere~.n peak metal temperarures bns.waat~
50°C and 150°C should be reached, wherein cross-linking of the :,0 polymer film and the anchoring thereof to zho mortal surface zakr~~
place at the same time.
In a preferred manner. the ants-corrosive agent is applied to the worJcpiooc surface, preferably rnatal strip surfaca~, by ~!U Tlooc~~.ng/sgueezlng, spraying/ queezzi~g Ur uy au appropriate wiper or roller method of application.
The preferred concentration ranges for components a) to e) in the anti-corrosive agent are:

20-Nov-O1 OA;06 From-HENKEL/CDGNIS CORP, PATEPIT DEPT, ,6102786648 T-060 P.OA/26 F-840 a) 5-50 g/1 of hexafluoro arrons of titanium(TV), ~ilicon(IV) and/or G.i1'LUlllultl ( Tv) , b) 0-50 g/1 of phosphoric acid, c) D-s0 g/1 of ions of cobalt, nickel, vanadium, iron, manganese, s molybdenum, tungsten, 5-30 w~.. ~ of vise yr iLtUL'~ film-producing organ3.c polymers or copolymers (with respect to activ$ substance), e) 0.1-10 wt.$ of an organophosphonic acid.
T)sa pH of the anti-corrosive agent ,is w~.tllln tile range 0.5 Lo 4.fl, preferably within the range 0.7 to 2.5. An acid agent of this type partly Cissolves the metal surface being treated so that a treatment bath c~hich has already bean in use for oome time may contain additional canons wriicn arise From the metal substrates being treated. examples 1~ of these are zinc, aluminum, iron, nickel, silicon, lead and copper.
A person skilled in the arc is familiar with the fact that the preenously mentioned components, In particular the lnorganLc compounds, can enter into reactions witri each other so that they are present in 2C the treatment solution in the form which is stable under the conditions mentioned for pH. Rs an exampls, soma of tho hoxafluoro aniorss era presens: Lei 4he fvrm of ehss free acrd.
Numerous compounds are suitable for use as film-forming organic 2f. polymers or copolymers, but they must sztisfy cwo essenLZal sQlQCtion criteria. on the one h~snd thesy must k~e soluble or d~.spersibla .in sufficient concentration in the strongly acid aqueous solution, which also contains polyvalent Inorganic ions, without this leading to coagulation and/or precipitation of the polymer constituents. nn r.he 3t) oLtsai lsaud, L1lcy must_ c~c~uLaim at~ Ica~t ~c~luC cac»~-lilskablG
i~roup3 which enable the polymer layer to crass-link and adhere to the substrate sufficiently well within a snort t5.me as a result of the supply of heat.
3'i Concrete examples of film--producing polymers are epoxide resins, aminaplastic resins (e. g. melamzne/formalaelzyde res~.ns, urea/formaldehyde resins), tannins, rhennllformal~lRhydR rpQins, palyutets cf vi!lylptscual with sufficient alkyl or substituted r~13:y1-amznomethyl groups in the pnenolic ring to ensure the water-solubility 9~) or water-aispersibil~.ty of 'the polymer. Other examples are water-soluble or water-disperQiYhlr~ pol.ytrethanP pnl ymPry, arrylate )souwpvlynser arid in particular copolymer dispersions, mothacrylaLe homopolymer and/or copolymer dispersions and butadiene copolymer dispersions or styrene copolymer dispersions. In particular, the 4i copolymers bzsGd on olefinacally unsaturated mnnnm9rs may ~'~nraiti 20-Nuv-O1 08:08 Frum-HENKEL/COGNIS CORP, PATENT DEPT, .8102T8B548 T-000 P.10/25 F-840 cross-l~,nKable comonomers Known per se. '1'rie xollowlnq may be mentioned by way of example: acrylic acid, mpthacrylic acid., glycldyl/(meth)acrylate, acrylamx.de, 1V-metnylolacrylamlde, N,N-l5is-alkoxyruethyl cmetm acrylamide and samilar thermally cross-linkable n groups, wherein the alkoxy groups may contain 1 tc~ a carbon atom=.
Furthermore, cross-linking agents known per se may be used in the form of eporide resins, urea derivatives or (blocked) polyisoeyanazes or oligomeric aexivatives thereof. Self-cross-linking or externally cross-linkable (meth)acrylate disrRrsi.ons nr emulsi.nna cr c~mh5nar_ions of 1~7 these with epoxlde resins and/or copolymers of e-tsyc,isvxyxtyiCiiC arc particularly preferred. The last-mentioned copolymers may be represcutrd Ly ~)-cc fVllCiWllll~ C~cllCial fUrmlila: y-(R1-t~-RZ-aminomethyl) hydroxy-styrene, wherein y is 2, 3, S or 6 and Rl is an alkyl group with 1 to 8 carrion azom~, proPcrably a methyl group aria R2 ca.n bQ
represented by the Following general formuJ.a: H(CHQH)pCH2-, wrierein n is an integer betwcQn 1 and 7, ,preferably between 3 2nri 5. ThP avPraqe molecular welgnt of the prevx.ously mentioned pvlymCis is mvrmally in the range between 690 and 20,000, preferably between 800 and 6,000. The tnvlcculur weights of wwtcr-soluble polymer9 are more likely to be found 20 in the lower range, wriile the molecular weights of the water-da.opcrelble polymers era generally found in the middle 2n upper rangp-Further suitable film-producing organic (co)polymers are ~aenzloned in T. 8rock, M_ Grnteklaps, P_ Miq~kP, "t.Phrhuch der LaCkteChnologi.e", Vincentz-Verlag, 1998 in section 2.1.6 Or S~C'LlUll 3.5. TI'ie Y~iader3 a5 mentioned there axe express constituents of this application.
Another important constituent of the compositions are organophosprionates, concrete exampl..s?c hPinr~ the following phOSphonic ac~.ds and diphosphonic adds:
::o 1-hydroxy-1-phenylmethana-l,l-diphosghonic acid 1-uycit~xy-1--phanylmcthane-1,1 diphaaphoaic acid.2Hz0 p-hydroxyphenyl~-1-aminomethane-l,l-diphosphonic acid 35 p-hydroxyphenyl-1-hydroxymQthane-1,1-diphosrhonin acic3_H~O
1--hydroxy-1-phenylmetriane-1,1-azpnospnonic aczct.x2o,NaZ salt 1-hyaroxyphenylcnethanP-1 , 1-ell ph~sphonic acid. H20 1-amZno-1-pnenylmethane-1,1-dlphospktUial< ac:lc.:i 4-aminophenyl-1-hydroxymethane-1,1-diphosphonic acid.HzO
~0 p-aminopheayl 1-aminomethana-1,1-diphosphonic acid p-chlorophenylmethane-1,1-dipnosphonic acrd 1-chloro-1-phenylmcthane-1,1-dzphosphnnir am d_2H~0 p-chlorophenyl-1-hydroxytaethans-1, 1-diptrvspkmuic acid.2H2o 1-chlorophQnylmetnane-1,1-diphosphonic acid.HzO
95 p-chlorophenyl-1~CL2~V141i1CW1Gil~~1, 1-diphosphonic acid 20-Nov-01 09:00 From-HENNEL/COGNIS CORP, PATENT DEPT, 010270054A T-000 P.11/25 4-chlorophenyl-1-chlorometriane diphosprionic acid.2Fiz0 p-hydroxyphenylaminomethylene diphosphonic acid, Na~ salt p-hydroxyphenyl-1-aminomezhane-1,1-diphosphonic acid, containing methylol 3.4°dimetriylprienyl-1-chlaromezriane dlpnosphonic acid 3,4-dimethylphenyl-1-hydro::ymeth3ne diphosphonic acid :3, 4-dimet~lylprietZylam.Lnametriane d~.phospnon.~c acW
3.4-dimethylphenyl-I-chloramethane-i,l-diphasphonic acid.2H20 4-dsmczhylaminophenyl-1-hydroxymethanw diphoaphonic acid 1i~ 4- (N-taenzyl-N, N-B2methylamlno) -phenyl-1-hydroxymec:heur ~iiYyusYluunic:
acid 4-trimethylami.nophenyl-1-hydroxymethane dlphosphonic acid 3, 4, 5-trime>;hoxyplZenyl-1-amlnomethane-l, 1-diphcsYtsussic acid 1-bis-(N-hydraxymethyl)-amino-1-phenylmethane-1,1-diphosphonic acid 1~~ 3, 5-dictsloro-a-hydroxyphenyl-hy~r~xymPrh:~na dipnosphonic aCZd 3, 5-dibrcosac-4-Isyc3icxyphemyl-aminomcthanc ds.~hosphonzc acid 1-amino-1-cxciohexylmethane-1,1-diphosphonic acid 1-hydroxy-1-cyciohexylmethane-1,1--dipriosphonic arid, Na sal.t 1-hydroxy-I-cyclonaxylmethane-1,1-diphnsphnni~ ac-jd, Naj salt 27 [4-(aminomethyl)-cyclonexyl]-1-nydroxymethane-1,1-dz.phosptsusslc: avid 4-methoxybenzoylacetonitrile, phosphonylated N-(hydro:ymeLhyl)-1-aminoechane-1,I-~ti.r.hngphnnin acid 1,j-diaminopropane-1,1-4iphosphonlc acid 3-dsmethylamino-1-aminopropane-1,1-dipriosphonic acid 25 3-monomcehylamino-1-aminopropane-1,1-diphosphnni~ avid 3-(N-dodecylalriino)-1-aminoprvpauc-1,1-~Iiptivsphorszc acid 3-(N,N-dodecylmethylamino)-1-aminogropas?e-1,1-diphosphonic acid 3-(N-dodecylamin~)-1-aminopropane-1,1-dZpnosphonic acid.FiX (X=halogen) 3-(N-damethyldodecylamino)-1-amlnopropane-l,l-diphosphonic aeid.morhyl .0 iodide 2-amino-2-methyl-1-hydroxypropane-1,1-dipriosphonic acid 3-~msno 1 hydroxy-3-phenylpropane-l,1-di.phosphon~.c acid 3-amino-3-phenyl-1-hydroxypropane-1,1-dipnosprionic acid 3-diethylamino-1-hydroxypropane-1,1-diphosphonic acid .:5 3-N, N-d.imethylzmino-1-YsydrnxypropanP-1 , 1-ciiphosphonic acid 3-N-bis- (hydroxyetnyl ) -ammo-1-nyctroxypropdrse-7., 1-c,iiptsosphonic acid 3-(N-dodecylamlno)-1-hydroxypropane-1,1-dlphosphonic acid 1,3-dihydroxy-3-phenylpropano-'I,~-diph~sphomc acid 3-N, N-dimethylasniuupropionic acid.IICI
.I0 3-dimetnylamino-1-hydroxypropane-1,1-diphosphonic acla, Na salt 1, 3-iii hyrlrnxypropane-1~ 1-diphosphonlc acid, Na2 salt 1-1'syriroxy-3-dicthy2aminoproponc-1,1-diphosphoss.ic acid, Na sair 1,3-dihydroxy-3-phsnylpropane-1,1-dipriospnonic aci~t, Na2 salt 1 , 3-cxi.aminobutane--1,1-dzphosphoniC acid 35 1-hydroxy-3 aminabasano-1,1-diphosphonic acLd 20-Nov-01 09:07 From-HENHEL/COGNIS CORP, PATENT DEPT, 0102780540 T-000 P.12/25 3-monoethylamino-1-aminobutane-1,1-dspriosphonic acid C-amino-1-hydXOxybut3rie-1,1-dlphosphoni.C acid 4-N,N-diaiezhylamino-1-hydroxybutane-1,1-diphospnonic acid 6-amino-I-hydroxyhexane-1,1-diphosphonic acid _° l, 6-ci~.hydraxyhexane-1, 1-diphosghonic acid 1, 6-diliyci~vxylicxane-1, 1-dsphvsphvezic acia, Naz salt 1,I1-dshydroxyund2cane-1,1-diphosphonic acid 77-amino-1-hydroxyundecane-1,1-diphosphonic acid m-plvpylphosphonic acid 1(~ butyl-1-phosphoni.c acid hexyl-1-phosphoric acid octyl-1-pho3ghon~c acid Gecane-1-phosphoric aciri dodecyl-1-phosphoric acid 1'.: cetradecyl 1 -pho~phonic cos.d octadecy.i-t-phospnonzc acid oczaaecans monopho9phonsc acid, Na salt eicosarie monaphosphonic acrd, Aia salt x-1,2-dianw nocyclvhcaanc tctrakij(meLhylenepho3phonic acid) 2~ glucamine-bis(mezhylenephosphonic acid) glucama.ne-hiR(mPrhylenephosphonic acid), Na salL
1-uteidoathaisc-1, 1-ds~pho3phoxisc acid metnylenephosphonylaced uramil pyrimiayl-2-aminomethane diphosphonic acid 2l pyridyl-2-aminocneehylene dipbo~phonie acid N,N'-dimetnylureidomezriane oipiiosprionzc acla N-(2-hydroxyethvl>ethylenediamlne-N,N',N'-trismeLhylene-phosphoric acid N t2 hydroxycthyl)othylenediamine-N,N'D3'-trismethylene- phosphoni.r acrd. HxU
?0 ami~oacetic acid-N,N-dimethylenephosphonsc acid 1,2-ciiamsnopropane cezrakis(methylpneph~qphnn~.c acid) z-hyaroxyprcpattc-1, 3-caia~u~.ne tetrakis (methylenepho~phonic acid) 5-hyaroxy-3-oxa-1-aminopentane b1s(metnylenephosphonic acid) imino-bis(methy7PnPphosphonic acid) .5 riitroaamine of imino-bi~(mcshylcs~.eph4sphonic acid) nitro~amine of immo-bis(msthylenephosphonic aria), Na2 salt Y.Y-diphosphono-N-methylbuLyrolactam anslc3imuumi~yleme diphoaphorsic acid formylaminomethane aiphosprion:~c ac.~a <.0 2-iminopspersdone-6,6-dsphosphonic acid.Hz~
2.-imiaopyrrolidone-5,5-ctiphosponic acid N, N' -asmezriyllmlnopyrrolic~vr~-5, ~'411bJ11VJ~j~JOlJIC aCld 1-methyl-2-pyrrolsdons-5,5-diphosphonic acid aminodiacatic acid-N-mgr.hyiph~Rphonic~_ acid ~k5 1,3-aihydrUxy-2-u~eLhylpropanc-N,N-dimechylanephocphonic acid 20-Nav--O1 09:07 From-HENKEL/COGNIS CORP, PATENT DEPT, 0102780549 T-O00 P.13/25 F-940 1,2-aihydroxyproparie-3-amino-bis(methylenephosphoriic acid) 2-hydroxypropane-1,3-diamine rPr,rakis-(metnylensphosphonic acid 3, 6-diora-1, 8-diaml.nooctatie tetrakis-- (methylenephosplioui.c acid) 1,5-diaminopentanete trakis(methylenepriosphonic acid?
methylamino-dimetnylenephosphonic_ acid N-hcxylamsno-dimethylenephosphoni,c acid decyc.lam~.no-aimexhylenephosphonic acid 3-picolylaminodimethy3.enephosphonic acid.H~o meti~arzcpho~phonzc acid lc methariedipnospnonic ac~.a methanediphosphoriic acrd. HzO, Naz salt dichloromeLhanediphosphonic scid.5H~0, Naz malt tetraisopropy3 aichlorometnaneaiphosphoriate 1,I-diphosphonethane-2-carboxylic acid 1~, ethane-1,1-cciphosphonic acid ctharte-1, 1-oiphosphonic acl4, Naa salt ethane-1,2-dzphosphonic acid ethane-1,1,2-criphosphonie acid ethylenedzphosphonso scid, Naa ~alz 2U l,Z~diphosphonaethane-1,2-dicarboxylic acid 1.2-dipnosphorioetharie-1,2-dicarboxylic acid.2Hr0 ethane-1,1,2,2-tetraphosphonic acid.H2~, h~xaguasiidsr~c calc ethane-1,1,2,2-tetrapnospnon~.c acid, hexaguariidine salt ethane-1,1,2,2-tetraphosphonic acid, quanidine salt 2!~ 1-phosphanoethane-1,2,2-tri.caroxylic acid, K gale phospnonoacezic acsa a-chloro-a-phosphonoacetic acid r~-phc~sph~nnarPr i ~ ac~i d 1-phosphuiioptvpariG-2, 3-dirathoxylic acid 3~) I-phosphonopropane-1,2,3-tricarboxylic acid, Na5 salt 1 .-phosphnnnprnpanQ-'1 , ?, 3-r_riaarboxylac ac~_.tri_ HzC7 propane-1,1,3,3-tctraphoaphonic acid, 37a6 salt aminomethane diphosphonic acid dimethylaminomethane diphosphonic acid 3~ N-decylami.nomethane-1,1-dighosphonic acid N-decylaminomethana diphosphonic acid N.N-dimethylaminomethanediphosphonic acid monohydrate dimczhylam-inomczhane dspho~phoaic acid, Naz salt !3-c~ecylamW otnetharie aipnosphonic acrd, Naa salt 4 7 1-amlnoethane-l, 1-diphosptiotiic acid 1-amino-2-chloroethane-1,1-dxphasphonic acid 1-amino-2-phenylechana-l, 1-cfipttvs~akmtiie ac:.id I-monomethylaminoethane-l,l-diphosphonic acid N-mnnnhydrnxymRrhylaminnPrhanP-1,1-diphasphonic acid 1-aminopropnnc-1,1-dipho~phor~ic acid 20-fvov-O1 68:07 Fnom-HENKEL/COGNIS CORP, PATENT DEPT, G10278G548 T-OGO
P.14/25 F-040 1-ama.nnpropane-1,1,3-triphosphonic acid 1-amznobuLassr-1, 1-d.iphosphosiic acid 1-aminohexane-1,1-diphosphonic 1-aminndp~-~np--1,1-diphosphonic acid 1-sfuiuutlesxadecane-1, 1-d~.pho3plZOnic wcid 1-isononanoylamido-1,1--dimethylenemethane phosphonzc acid stearic acid amigo-1,1-a~.methylrnethane phosphoric acid ~:oco fatty ac~,d smido-1,1-dimczhylcaemethane phosphoric ac~.d isonorianoic acid amigo-l,l-dietriylmetnane phosphoriic acl4 iC 1-aminohexyl-1-phosphoric acid 1-~sminooctyl-1-phosphoric ac~,d 1-hydroxyoctyl-1-priosptlonic acid I-hydroxydecyl-1-phosphoric aclcl 1 aminodcoyl-1-phosphoric acid 1'i 1-hyctroxydeeylfaodecyl-1-priospnonl.c ac~a 1--hydroxy-1-dodecyl-1-phasphonic acid 1-lzydroxydodecanA-1-phosphoric acid 1-IlyQroxy-3,6,9-tsiuxadecanc-l,1-diphosphonic acid, Nay salt 12-hydroxy-12-phospkionostearzc acrd, Na salt 7) cocosalkylaminobis(methvlenephosphonzc acid) pliu5phonylaLed polyglycol diacid 4-ethyl-4-methyl-j-oxo-I-aininobexane-1, 1-uiplsc~sYYmnic ac;d 1-nyaroxy-3-oxo-~-ethyl-4-mathylhexane-1,1-diphosphonlc acid 1-rxmino 9-athyl-4-methyl-3-oxohexane-1,1-di.phnRphonic acid 25 1--J'ydroxy-3-oxo-4-ethyl-4-methyll'iexane-7..1-di.plscopliuazic ac.id.IlzO, Na salt e-ethyl-a-methyl-3-oxohex-1-ere-3,1-~iiphosphonic acid 4-methyl-g-ethyl-3-oxohex-1-aua-1,1-diphosphonic acid, Naa salt 1-amino-3-oxo-4,4-dimethyl.haptane-l,l-diphosphon~.c aczCi .a 1-hydroxy-3-cxo-4,4-disnethylheptane-I,I-diphosphonic acid.HzO, Na salz 9,e-dlmethyl-3-uxa-hart-1-ene~l,l-diphosphonic acid 4,4-dimethyl-3-oxo-kept-I-ere--1,1-dapnosphoni.c acid, Na salt 1-ami.n~-3-cxo-9,4-dimathyldecane~l,l-diphosphonic acl.d amlnomettsafse moraophosphoxii.c acid a5 tol,aylaminometharie ptsosprionzc ac~.a p-nydroxyphenyl-1-amznomethanepnosphanic acid semihydrochloride N-ctl~ylamino-(phenylmcchsnediphosphonic aczdl 1-ben2ylamino-1-phenylmetriane-.1-priospnonlc acid 1-riydroxyeztsarse moriophosphonic acid 3o i-hydroxye2hanQ-1-monnF,hnqphnnic acid, Naz salt 1-hydz'Oxyetharie-1, 1-diYhuxYhuiilc acid (II~L~I') 2- jbenzimsctazolyl-- ( 2. 2 ) -] -ethane dl.phosghome aczd monohyctr~scr 2-jbenzimida2olyl.-(2,21-]-ethane diphosphonic acid N--CarboxymBthane-1-anci~ioethane-1,1 dipho~phonic acid 45 1,5-diaminopentane-1,1,5,5-zetraphosprion~.c acla, zrihydcate 20-Huv-O1 08:07 Frum-HENKEL/COGNIS CDRP, PATENT DEPT, 8102788548 T-080 P.15/25 a-oczyl-phosphonosucci.nic acid, a-ti-dodecylaminobenzylphosphon~c acid ø-trifluoromethyl-~S-phosphono)'utyric acid 1 decylpyrrol~.doTie-2,2-d~phosphonic acid pyrroliaone-5,5-diphosphon~c acia 2,2-diphvsphono-N-~lRCylpyrrolidone y, y-aiphosphono-N-metnylbmy~vlac:eam hen7enP phosphoric acrd 1,g-thlazine divxldG-N-methr~nc diphosphonic acs.d 1C p-(1,9-thiazine dioxide)-N-phenylene-hyctraxymeZharie arpnosprionlc acia a-(1,n-thiaxine dioxide)-N-ethane-cr,n-d5ghosphonic acrd 3-(1,9-tniazine dioxhde)-N-1-hydroxyprppane-l,l-diphospriouic acid 6-(l, a-thiazine dioxiriP)-N-1-hydroxyhexane-1.1-diphosphonic acid 11- ( 1, 9-thia2lrie dioxide ) --N-1-hydroxyuudcc:aiZe-1, l-diphosphonia acid 1)~ phosphonomethanegnlfnnic acid, Na3 salt trihydraxe biS (methylenephospnotlo) uaiuvccl~anesulfonLc aczd Lristmethylenephospnono)-acetamido-aminoetnanesulxonic acid azacyclogerstanc-2,2-diphosphonic acid N-methylazacyclopentane-z,l-d~.pnospnonlc acid 2J N-dacylazacyrlnpantane-2,2-diphosphorlic acid N-tetradeCylazacyclvpcu~ame-2,2-diphosphonic aa~.d azacyclohexana-2,2-dsphosphonic acid 1- ( 4, 5-diRy~lio-3H-pyrrole-2-yl ) -pyrrol~cEirlylidene-2. 7-dtphosphoni.c acid hydroxymethane diphosphonic acid, Na2 salt 2S 1-~oxaethunc-l, 2-d.~pho9phoraic a .ri r3 undecanellydrate, Naa salt 1-hydroxypropane-1,1-dipnosphonlc acid 1-hydroxypropane-1,1-W phosphoric acid, Na, salt 1-hycYroxycuLane-1,1-di.phosphonic acid heptadecanehydrate 1-hydroxybutane-1,1-diphosphon5.c acid, Na3 salt _,0 1-hydtvxy~rGtitesne- 1, 1-diphosphon~.e acid, Na, sa l r 1-hydroxyoctane-1,1-di.phosphonic acid, Naa sale cyclic tctraphosphonic acid, Naa sail hexamethyl ester ox cyclic tetraphoSYhonate cyclic HEnP rPtxadecahydrate, Nassalt Tn ~ preferred sway, those representatives of this class o2 sub~tauces are used wt~itli Lontain at lca~t one phosphon~.c arid group arid at least one polar function.
AS further addl.tlves, compositiu~m according to the snvervtion may contain conducrim ty pigm.ents or conductive fillers such as e.g. iron phosphlde (Ferroph~~), vanadi..am carbide, tieanium nitridR, carbon black. graphite, molybdenum sulfide or else barium sulfavc doped with tin v~. antimony. Iron phosphidQ is partinz~larly preferred. The 95 conductivl.ty pigments or fillers are aactea in U~~tGi to improve the 20-Nov-01 D9:08 From-HENKEL/COGNIS CDRP, PATENT DEPT, 0102700549 T-000 P.10/25 weldability or to improvs coating with an electrodeposition lacguer. In addition, silica suspensions, in particular when using anti-corrosive agents for aluminum substrates, may be used. These inorganic 3axilisry subseances sklou.LCi be present in a finely divided form, that is with average particle diameters of between 0.005 and Vim, preferably between O.OS and 2.5 y . Tnc auxiliary ~ub~tanccs arc used in proportions or between U.l and 30 wz.~.
1u Furthermore, the composlt~.ons may contain aC1t11tZVeS Co improve the shaping processes, these besng, for example, wax-eased derivatives eased on natural or synthetic waxes, e.g. polyethylene or Yc~ly~.e~warluvrUCSCkiylcur (PTFE) waxes yr wax Cerivatlves.
1 > Tho pH of r_hs sn].utinns hRinr~ arpli~r_i, r_hat is the original corttpositinn or a varZaezt dilated with more watei, is I;~ezweei~ 0.5 aszi3 4.0, preferably between 0.7 and 2.5. When applying in partic~llar to metal strip surfaces, the application solution is applied in a manner known par sa b;~ roller application ;them-coating), wiping, ~.mmarsion/squeezmg or spray~.ng/squeezmg to an, optionally metal-coated, steel strip or talloyed) aluminum strip. Application is pcrformccc 3t =cmpcraturcm bet~~cea 10 and 50°C, prcfcrsbly bctrreen 7.5 and 35°C. The temperature may be adjusted by supplying heat m a the workpiece or the treatment solution. Finally, dtze to appropriate 25 management of the neat supply, the formation of a film and cross-linkinq of this film and anchoring to the metallic surface all take place at the game time. For this to occur, peak metal temperatures 1PMT) of 50 to 150"C are achieved for a period of between 1 and 12U
sPennds, preferably between 1 and 30 seconds. The weight per unit tree 30 of the coating after drying is teen 0.1 to 5, preferably 0.5 to 2.0 g /mZ .
The layers preduced in chin way may be eoated with the conventional lacquer systems used in the dvmestiC appliance and/or architectural ?5 sectors, that is the application of a liquid primer followed by coating with a l~.quid topcoat may be performed, or else pewder ceazs.ng with a single-layered lacquer may Lake place. l:~urznermore, the anti-corrosive layer according to the invent~.on may be coated directly, chat .~s wi.chous the appla.oation of a primer, with zygical strir toP~nar~~_ The 90 layers prvduceu .u~ tkfis way pLVLcc:L LkiG luetal sAzatim5 and provide adequate protection against corrosion. Thus, for example, when coating (alloy) galvanized steel, the salt spray test in accordance with DIN
~ao2i as .as withstood for more than 250 hours. Likewise, in the ca~c o~
(alloyed) aluminum, a salt spray test in accordance with SIN 5ii0Z1 E5s 20-Nov-01 U8:08 From-HENKEL/COGNIS CORP~ PATENT DEPT, 0102780548 T-000 P.17/25 (g ~.s successfully withstood for more than 250 hours. Also, a climate-controlled test in accordance with DIN 50017 KK for (alloy) galvanized trPpl is wirhar.ond for mnre than 3 weeks without tho formation of white rust. Tne corrosion resistance ox materials which have been treated WILh the ants-eorros.rve compositions according to the invention, wittl or without a primer coating, achiQVO the values whs.eh can be achieved with a conventional treatment. YWe reshaping behaviour 1s lmpfoveCi when compared with substrates which have not been coated in accordance with tn~ invarvtion, furthermore substrates coated in accordance with the Ze znvenz~,on can be catopnoretzcally lacquered unCer the same condLtions and with the same results as materials which have been phosphatized in the way typically used in the automobile .industry- The process ae~urdiuc~ (V (?IC il1VC11liUil ll4Clx alga be used ~.usCracT of tradiLiattz~l chromatizing and phosphatiz~.ng processes when subsequent coating with a 1 ~ fmrr?'!Pr anti -corrns; vP 1 aypr gnr-h aQ rrannr~~rTh and rhP 1 i kP i ~
intended to be pcrformcd.
If treatment according to the invention takes place immediately after a metallic finishing process, e.g. els~ctrolytic ga].vanizing or hot melt 2i~ ctrp galvanzzzng of the steel str ps, then the strips may be placed 1n contact with the treatment solution according to the inventl.on without fi.r.st being ~laar~gp~i. F(nwRVPr, if r. hp mRta1 Rtrip~ r~ hp rrPatPd have been stored amcslo~~ Li'GiI~NUi'tad piicr Lv eaa~iug auGUi'ditly Lo Clic invention, then they have generally been provided with anti-corrosive 2~~ oils or at least have been so heavily cnnraminarPrj char cleansing is iayulscd yiiul to coating accordia5 to tt~e invention. Thin may take place using normal weakly to strongly alkaline cleansers; in the case of aluminum and its alloys also with acrd cleansers.
3~) Wizen being applied to aluminum and aluminum alloys, the anti--corros3.ve composition according to the invention may also contain very low concentrations of org~nopnosphonic acid and optionally may contain n~
arganopriosphonic acid.
3i The invention is explained in mcrP rlPrail in the following iiy using S
fgw work~.ng examples. All data relating to amounts in ttia uauitnrslti.oais are parts by weight unless stated otherwise.
Tlie md~vnsl.ual compQnenta li9s~d irx sable 1 ar4 generally mixod ~n the 4~ sequence given and at room temperature.

20-Nuv-O1 08:06 Frum-HENKEL/COGNIS CORP, PATENT DEPT, 6102786548 T-080 P.16/25 owo 0 r.
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20-Nuv-01 08:09 Frum-HENKEL/COGNIS CORP, PATENT DEPT, 81U2r88548 T-OBO P.21/25 Examples 1 to 3 and 6 and 7 listed in table 1 az:G not in accordance with the .~n~rention, they e::hibxt significant attack by white rust on galvanized steel after about 100 hours in the test according to T~iN 50021 SS. ~xaanples ~, 5 and 15 give good results for anti corrosive effect on aluminum, examples 8 to 14 rive rood results for anti-corrosive effect on galvani2ed steel.

Claims

1. A chromium-free anti-corrosive agent for single-stage coating of metal substrates, containing a) 0.5 to 1,00 g/l of hexafluoro anions of litanium(IV) , Silicon (IV) and/or zirconium(IV) , b) 0 to 100 g/l of phosphoric acid, c) 0 to 100 g/l of one or mare compounds of cobalt, nickel, vanadium, iron, manganese, molybdenum or tungsten, d) 0.5 to 30 wt.% of at least one water-soluble or water-dispersible film-producing organic polymer or copolymer, e) 0.1 to l0.wt.% of an organophosphonic acid, f) optionally further auxiliary substances and additives.

2. An anti-corrosive agent as claimed in claim 1, wherein the film-producing (co)polymer is selected from epoxide resins, styrene copolymers, butadiene copolymers, polyurethanes, melamine resins, (meth)acrylate polymers or mixtures of these.

3. An anti-corrosive agent as claimed in claim 2, wherein the film-producing (co)polymer(s) contain(s) cross-linkable functional groups.

4. An anti-corrosive agent as claimed in claim 3, wherein it also contains a cross-linking agent.

5. An anti-corrosive agent as claimed in at least one of the preceding claims, wherein it contains 0.1 to 30 wt.% of a conductivity pigment and/or a further inorganic auxiliary substance as a further additive.

6. An anti-corrosive agent as claimed in claim 5, wherein the conductivity pigment is selected from carbon black, graphite, molybdenum sulfide, doped barium sulfate, iron phosphide, vanadium carbide, titanium nitride.

7. An anti-corrosive agent as claimed in claim 5 or 6, wherein the conductivity pigment or the further inorganic auxiliary substance has an average particle diameter of 0.005 to 5 µm, preferably 0.05 to 2.5 µm.

8. An anti-corrosive agent as claimed in at least one of the preceding claims, wherein it contains shaping aids based on natural or synthetic waxes, e.g. polyethylene or polytetrafluoroethylene waxes and/or waxes or wax derivatives as further additives.

9. An anti-corrosive agent as claimed in at least one of the preceding claims, wherein it has a pH in the range 0.5 to 4.0, preferably 0.7 to 2.5.

10. A process for the anti-corrosive treatment of (optionally metal-coated) steel or aluminium or its alloys, wherein a) the surface of the metal is placed in contact with an anti-corrosive agent as claimed in at least one of the preceding claims for a period between 0.5 and 60 seconds, b) excess anti-corrosive agent is optionally removed from the surface and c) the treated substrate is heated to peak metal temperatures between 50°C and 150°C for a period of 1 to 120 seconds by the appropriate supply of heat, wherein cross-linking of the polymer film and its anchoring to the metal surface take place at the same time.

11. A process as claimed in claim 10, wherein the metallic coating of steel is selected from hot-melt dip galvanizing alloy galvanizing, electrolytic galvanizinq, copper plating, nickel plating or aluminization.

12. A process as claimed in claim 10 or 11, wherein the corrosion protection agent is applied to the surface of the workpiece by flooding/squeezing, spraying/ squeezing or suitable wiper or roller methode of application.

13. A steel or aluminum strip coated by a process as claimed in claim 10 or 11, wherein the weight per unit area of the layer is between 0.1 and 5, preferably between 0.5 and 2.0 g/m2.

14. A process for the anti-corrosive treatment of aluminum as claimed in one of claims 10 to 13, wherein the anti-corrosive agent as claimed in claims 1 to 9 contain no organophosphonic acid.

15. A steel or aluminum strip coated by a process as claimed in claims 10 to 14, wherein a lacquer undercoat (primer) is not required when coating in a coil-coating process.