CN116457498A - Aqueous composition containing zirconium, molybdenum and acid functional polymers for treating metal surfaces - Google Patents
Aqueous composition containing zirconium, molybdenum and acid functional polymers for treating metal surfaces Download PDFInfo
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- CN116457498A CN116457498A CN202180074279.6A CN202180074279A CN116457498A CN 116457498 A CN116457498 A CN 116457498A CN 202180074279 A CN202180074279 A CN 202180074279A CN 116457498 A CN116457498 A CN 116457498A
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- 239000000203 mixture Substances 0.000 title claims abstract description 152
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 54
- 239000002184 metal Substances 0.000 title claims abstract description 54
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 29
- 229910052750 molybdenum Inorganic materials 0.000 title claims description 22
- 239000011733 molybdenum Substances 0.000 title claims description 22
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title description 12
- 239000002253 acid Substances 0.000 title description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title description 4
- 229920001002 functional polymer Polymers 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 96
- 239000000758 substrate Substances 0.000 claims abstract description 76
- 229920000642 polymer Polymers 0.000 claims abstract description 64
- 230000002378 acidificating effect Effects 0.000 claims abstract description 63
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 13
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims abstract description 10
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 9
- -1 zirconium ions Chemical class 0.000 claims description 52
- 238000000576 coating method Methods 0.000 claims description 38
- 229910052782 aluminium Inorganic materials 0.000 claims description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 33
- 229910000838 Al alloy Inorganic materials 0.000 claims description 26
- 238000007739 conversion coating Methods 0.000 claims description 25
- 238000005260 corrosion Methods 0.000 claims description 25
- 230000007797 corrosion Effects 0.000 claims description 25
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 17
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims description 4
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 18
- 239000011248 coating agent Substances 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000000178 monomer Substances 0.000 description 17
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- 239000011247 coating layer Substances 0.000 description 10
- 150000002222 fluorine compounds Chemical class 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
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- 229910000676 Si alloy Inorganic materials 0.000 description 4
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 2
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- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
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- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 description 2
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical Treatment Of Metals (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a method for treating at least one metallic surface of a substrate, comprising at least a step of contacting the surface with an acidic aqueous composition (a) having a value in the range of 2.5 to <5.0 and comprising Zr ions (a) in an amount in the range of 10 to 200 calculated as metal, at least one polymer (P) selected from poly (meth) acrylic acid and (meth) acrylic copolymers having carboxylic acid groups as component (b) and mixtures thereof, and Mo ions (c) in an amount in the range of 0.5 to 10ppm calculated as metal, wherein the relative weight ratio of Zr ions (a) to Mo ions (c) in each case is in the range of 40:1 to 75:1 calculated as metal; the use of the corresponding acidic aqueous composition (a) per se in the treatment of metal surfaces and substrates comprising the surfaces thus treated.
Description
The invention relates to a method for treating at least one metallic surface of a substrate, comprising at least the step of contacting the surface with an acidic aqueous composition (a) having a pH value in the range of 2.5 to <5.0 and comprising Zr ions (a) in an amount in the range of 10 to 200ppm calculated as metal, as component (b) at least one polymer (P) selected from poly (meth) acrylic acid and (meth) acrylic copolymers having carboxylic acid groups and mixtures thereof, and Mo ions (c) in an amount in the range of 0.5 to 10ppm calculated as metal, wherein the relative weight ratio of Zr ions (a) to Mo ions (c) in each case is in the range of 40:1 to 7.5:1 calculated as metal, the use of the acidic aqueous composition (a) in treating metallic surfaces and substrates comprising the surfaces treated thereby per se.
Background
Aluminum materials made from aluminum and/or aluminum alloys are typically subjected to a pretreatment process that resists corrosion and promotes adhesion. The pretreatment process is typically preceded by pickling the aluminum material. This pretreatment of aluminum materials is used, for example, not only in various indoor and outdoor areas of building construction components made of aluminum and/or aluminum alloys, but also in vehicle parts made of aluminum and/or aluminum alloys, such as wheels. After the pretreatment, other coatings are typically applied to the pretreated aluminum material.
WO 2010/100187 A1 discloses a two-step process for treating a metal surface, such as a surface made of aluminum or an aluminum alloy. In a first step, the surface is contacted with an aqueous composition containing silane/silanol/(poly) siloxane. In a subsequent second step, the surface is contacted with an aqueous composition containing a phosphonic acid compound, such as a phosphonate/phosphonic acid. Thus, the (poly) siloxane and phosphonate coating is continuously formed. Such conventional two-step processes typically involve considerable expense and are therefore disadvantageous due to increased time, energy and labor consumption.
Conventional aqueous solutions used in pretreatment processes for aluminum materials are based on complex fluorides such as titanium and/or zirconium complex fluorides to form conversion coatings on the surfaces thereof prior to application of any other coating. Subsequently, a further aqueous solution comprising a phosphonate compound may be applied thereafter, so that the pretreatment is carried out in a two-step process. However, the use of such a two-step process is disadvantageous for the reasons outlined above. Alternatively, the complex fluoride-based aqueous solution may additionally contain phosphonate compounds, such that the pretreatment is performed in total in a one-step process. However, the use of phosphonates is undesirable for ecological reasons, since phosphonates are regarded as pollutants. This is also disadvantageous from an economic point of view due to the waste water treatment and thus the requirements for purifying the waste water.
However, the presently known one-step pretreatment methods using complex fluorides such as titanium and/or zirconium complex fluorides do not always give satisfactory results with regard to adequate corrosion protection, in particular with regard to the undesirable occurrence of filiform corrosion and/or with regard to adequate adhesion properties.
For example, in U.S. patent No.4,921,552, a method of coating an aluminum material or an alloy thereof is disclosed. Coating compositions for this purpose contain, inter alia, polyacrylic acid polymers and H 2 ZrF 6 . In U.S. patent No.4,191,596, another method for coating aluminum materials or alloys thereof is disclosed. Coating compositions for this purpose contain, inter alia, polyacrylic acid polymers or esters thereof and H 2 TiF 6 、H 2 ZrF 6 And H 2 SiF 6 At least one of them. Furthermore, WO 97/13588A1 discloses a watch coated with a metal selected from the group consisting of aluminum and aluminum alloysA method of forming a surface, the method comprising contacting the surface with a liquid containing H 2 TiF 6 、H 2 ZrF 6 、HBF 4 And H 2 SiF 6 Contacting the aqueous acidic solution of at least one of the above. After the rinsing step, the surface is then further coated with an aqueous polymer composition. Furthermore, WO 2020/049132A1, WO 2020/049134 A1 and WO 2019/053023 A1 each relate to a method of treating at least one surface of a substrate, wherein the surface is at least partially made of aluminum and/or an aluminum alloy. Each of these methods comprises the step of contacting the surface with an aqueous composition containing at least one linear polymer containing, inter alia, phosphonic acid groups.
Finally, WO 2017/046139 A1 discloses a method of pre-treating a workpiece, in particular having an aluminum or aluminum alloy surface, wherein the method in particular comprises the step of applying an acidic and chromium-free aqueous solution to the workpiece, the solution comprising Zr in the form of a complex fluoride and Mo in the form of a molybdate. However, the solutions disclosed therein have not always obtained satisfactory results with respect to adequate corrosion protection, in particular with respect to the undesired occurrence of filiform corrosion and/or with respect to adequate adhesion properties, in particular when powder coating compositions such as (meth) acrylic powder coating compositions are subsequently applied to the conversion coating formed by using the solutions mentioned above.
It is therefore desirable to provide a method of treating a metal substrate, in particular a metal substrate made at least in part of aluminum and/or an aluminum alloy, which method allows the formation of a single conversion coating layer in a single step, is economically and ecologically advantageous, and which provides good corrosion resistance properties and is not detrimental with respect to adhesion properties when other coatings are applied to the formed conversion coating layer.
Problem(s)
It is therefore a potential object of the present invention to provide a method of treating a metal substrate, in particular a metal substrate made at least partly of aluminum and/or an aluminum alloy, which method allows the formation of a single conversion coating layer in a single step, in particular allows the avoidance of conventionally used phosphonate treatment steps, is economically and ecologically advantageous, and which provides good corrosion resistance properties and is not detrimental with respect to adhesion properties when other coatings are applied to the formed conversion coating layer.
Solution scheme
This object is solved by the subject matter of the claims of the present application and by the preferred embodiments thereof disclosed in the present specification, i.e. by the subject matter described herein.
The first subject of the invention is a method for treating at least one surface of a substrate, wherein said surface is at least partially made of at least one metal, in particular of aluminum and/or an aluminum alloy, comprising at least step (1), i.e
(1) Contacting at least one surface of the substrate with an acidic aqueous composition (A),
wherein the acidic aqueous composition (A) has a pH in the range of 2.5 to <5.0 and comprises
(a) Zirconium ions in an amount in the range of 10 to 200ppm calculated as metal,
(b) At least one polymer (P), wherein the polymer (P) is selected from the group consisting of poly (meth) acrylic acid and (meth) acrylic copolymers having carboxylic acid groups and mixtures thereof, and
(c) Molybdenum ions in an amount in the range of 0.5 to 10ppm calculated as metal,
wherein the relative weight ratio of zirconium ions (a) to molybdenum ions (c) is in the range from 40:1 to 7.5:1, calculated as metal in each case.
By the contacting step (1), a conversion coating film is formed on the surface of the substrate.
Another subject of the invention is an acidic aqueous composition (a), wherein said acidic aqueous composition (a) is a composition for use in the contacting step of the process of the invention as defined above.
Another subject of the invention is the use of the acidic aqueous composition (a) according to the invention for treating at least one surface of a substrate, wherein the surface is at least partially made of at least one metal, preferably at least partially made of aluminum and/or an aluminum alloy, preferably to provide corrosion protection to the surface and/or the substrate and/or to provide increased adhesion of a conversion coating formed on the surface by treatment to other coatings applied to the conversion coating, in particular to other (meth) acrylic based coatings such as (meth) acrylic based powder coatings.
Another subject of the invention is a substrate comprising at least one surface, wherein the surface is at least partially made of at least one metal, preferably at least partially made of aluminum and/or an aluminum alloy, wherein the surface has been treated according to the process of the invention and/or by the acidic composition (A) of the invention.
It has surprisingly been found that the properties of the conversion coating formed by the contacting step (1), in particular the ability to be used as adhesion promoter for other coatings applied thereon, can be significantly improved by the presence of the polymer (P) used according to the invention as component (b), zirconium ion (a) and molybdenum ion (c) in the composition (A).
It has further surprisingly been found that the presence of the polymer (P) used according to the invention as component (b), zirconium ion (a) and molybdenum ion (c) in the composition (a) also significantly reduces the corrosive subsurface migration (subsurface migration) and/or diffusion. In particular, it has been found that filiform corrosion is significantly reduced.
Furthermore, it has surprisingly been found that the process of the present invention is economically advantageous because it can be carried out in a shorter time, energy and labor, since it allows the formation of a single conversion coating in a single step. In particular, by using the process of the present invention, no additional treatment steps conventionally used, such as phosphonate treatment steps, are required. Furthermore, it has surprisingly been found that the process of the invention is also ecologically advantageous, since harmful components such as chromium-containing compounds, in particular Cr (VI) ions, and/or phosphonates do not have to be present in the composition and nevertheless excellent adhesion and corrosion resistance properties are obtained.
Furthermore, it has been found that when Mo ions are used in the aqueous composition in amounts ranging as defined above and below and when Zr/Mo weight ratios as defined above and below are used, undesired yellowing of the formed conversion coating layer can be avoided.
Detailed Description
The term "comprising", in the sense of the present invention, particularly in connection with the process of the present invention, the composition (a) of the present invention (used) and the masterbatch of the present invention, preferably has the meaning "consisting of …". In this case, for example, with respect to the composition (a) of the present invention, one or more of the other optional components mentioned below may be contained in the composition in addition to the essential components (a) and (b) and (c) and water) therein. In each case, in its preferred embodiment mentioned below, all components may be present. The same applies to other subjects of the invention.
The method of the invention
The process according to the invention is a process for treating at least one surface of a substrate, wherein the surface is at least partly made of at least one metal, in particular at least partly made of aluminium and/or an aluminium alloy, which process comprises at least a contacting step (1).
Preferably, the process of the present invention does not contain any step involving phosphonate treatment. More preferably, the process of the present invention does not contain any further steps involving any treatment, wherein any further conversion coating film is applied to the substrate, even if the conversion coating film is obtained after the contacting step (1).
Preferably, the process of the present invention does not contain any step involving any treatment with chromium ions, such as Cr (VI) ions.
Substrate material
At least one region of the substrate surface is made of at least one metal, preferably aluminum and/or an aluminum alloy. Other examples of metals are different types of steel. The substrate surface may be composed of different regions comprising different metals and/or alloys. However, at least one region of the substrate surface is preferably aluminum and/or an aluminum alloy. Preferably, the entire surface of the substrate is made of aluminum and/or an aluminum alloy.
More preferably, the substrate itself is composed of aluminum and/or an aluminum alloy, even more preferably an aluminum alloy.
In the case of aluminum alloys, the alloys preferably contain greater than 50 wt.% aluminum based on the total weight of the alloy. The method of the invention is particularly suitable for all aluminium alloys containing more than 50 wt% aluminium, in particular for aluminium magnesium alloys including but not limited to AA5005, and aluminium magnesium silicon alloys including but not limited to AA6014, AA6060 and AA6063, for cast alloys-such as AlSi7Mg, alSi9Mg, alSi10Mg, alSi11Mg, alSi12 Mg-and for wrought alloys-such as alsimag. Aluminum magnesium alloys (including AA 5005) and aluminum magnesium silicon alloys (including AA6060 and AA 6063) are commonly used in the aluminum processing (finishing) field and/or in wheel handling and/or other vehicle components such as electric vehicle components like battery housings. However, the method is mainly applicable to all alloys of the so-called AA1000, AA2000, AA3000, AA4000, AA5000, AA6000, AA7000 and AA8000 series. A preferred example of the AA 2000-series is AA2024.A preferred example of the AA7000 series is AA7075.AA2024 and AA7075 are commonly used in the aerospace industry.
The most optional aluminum alloy is selected from the group consisting of aluminum magnesium alloy, aluminum magnesium silicon alloy, aluminum copper alloy, aluminum zinc alloy, and aluminum zinc copper alloy.
The substrate may be a wheel or other component such as an automotive component, including a vehicle component, as well as an electric vehicle component such as a battery pack housing, a work piece, and a coil. The use of coils is described, for example, in WO2017/046139 A1. In these cases, the substrate is preferably made of an aluminum magnesium alloy or an aluminum magnesium silicon alloy. The substrate may be a component useful in constructing an aircraft. In this case, the substrate is preferably made of an aluminum copper alloy or an aluminum zinc alloy.
Contact step (1)
Step (1) of the process of the present invention is a contacting step in which at least one surface of the substrate is contacted with the acidic aqueous composition (a).
The surface to be treated may be cleaned and/or etched by means of an acidic, basic or pH neutral cleaning composition prior to treatment with the acidic aqueous composition (a). The treatment procedure according to step (1), i.e. "contacting" may for example comprise a spraying and/or dip coating procedure. The composition (a) may also be applied manually by flooding the surface or by rolling or even by wiping or brushing.
The treatment time, i.e. the period of time during which the surface is contacted with the acidic aqueous composition (a) used in the method of treating a surface according to the invention, is preferably from 15 seconds to 20 minutes, more preferably from 30 seconds to 10 minutes, most preferably from 45 seconds to 5 minutes, for example from 1 to 3 minutes.
The temperature of the acidic aqueous composition (a) used in the treatment process of the present invention is preferably 5 to 50 ℃, more preferably 15 to 45 ℃, most preferably 25 to 40 ℃.
By carrying out the process step (1) of the present invention, a conversion coating film is formed on the surface of the substrate, which has been contacted with the acidic aqueous composition (A). Preferably, the coating layer is preferably formed after drying, preferably with the following coating weights as determined by XRF (X-ray fluorescence spectroscopy):
each calculated as metal of 0.5 to 100mg/m 2 More preferably 0.75 to 50mg/m 2 Even more preferably 1 to 40mg/m 2 Still more preferably 2 to 35mg/m 2 Still more preferably 5 to 30mg/m 2 In particular from 10 to 26mg/m 2 Zirconium ions and molybdenum ions used as components (a) and (c).
Optional further steps of the method of the invention
Prior to step (1), one or more of the following optional steps may be performed in this order: step (A-1): cleaning and optionally subsequently rinsing the surface of the substrate,
step (B-1): subjecting the substrate surface to an acid wash, i.e. etching, and subsequently rinsing the substrate surface, step (C-1): contacting the substrate surface with an aqueous composition comprising at least one mineral acid, said aqueous composition being different from composition (a) or alternatively with an aqueous alkaline composition or a pH neutral aqueous composition and step (D-1): rinsing the substrate surface obtained after the contacting according to step (C-1) and/or (B-1).
Alternatively, steps (A-1) and (B-1) may be carried out in one step, which is preferable. Preferably, both steps (A-1) and (B-1) are performed.
The optional step (C-1) is used to remove alumina, undesired alloy components, skin layers, brush dust, etc. from the substrate surface and thereby activate the surface for subsequent conversion treatment in step (1) of the method according to the invention. This step represents an etching step.
Preferably, the at least one mineral acid of the composition in step (C-1) is sulfuric acid and/or nitric acid, more preferably sulfuric acid. The content of the at least one mineral acid is preferably in the range of 1.5 to 75g/l, more preferably 2 to 60g/l, most preferably 3 to 55 g/l. The composition used in step (C-1) preferably additionally comprises one or more metal ions selected from the group of titanium, zirconium, hafnium ions and mixtures thereof. In the treatment means, the duration of the treatment with the composition in step (C-1) is preferably in the range of 30 seconds to 10 minutes, more preferably 40 seconds to 6 minutes, most preferably 45 seconds to 4 minutes. The treatment temperature is preferably in the range of 20 to 55 ℃, more preferably 25 to 50 ℃, most preferably 30 to 45 ℃. In the treatment coil, the duration of the treatment is preferably in the range of 3 seconds to 1 minute, most preferably 5 to 20 seconds.
The rinsing step (D-1) and the optional rinsing as part of step (A-1) are preferably carried out by using deionized water or tap water. Preferably, step (D-1) is performed by using deionized water.
After carrying out the necessary step (1) of the process of the invention, one or more of the following optional steps may be carried out in this order:
step (2): rinsing the substrate surface obtained after the contacting according to step (1),
step (3): contacting the surface of the substrate obtained after step (1) or after optional step (2) with an aqueous acidic composition (B) which is the same as or different from composition (A),
step (4): rinsing the substrate surface obtained after the contacting according to step (3), and step (5): the substrate surface obtained after the contacting according to step (1), after the rinsing according to step (2), after the contacting according to step (3) or after the rinsing of step (4) is dried.
After step (1) of the process according to the invention, the substrate surface obtained after the contacting according to step (1) may be rinsed, preferably with deionized water or tap water (optional step (2)). After optional step (3) of the process according to the invention, the substrate surface obtained after the contacting according to optional step (3) may be rinsed, preferably with water (optional step (4)).
Rinsing steps (2) and (4) may be performed to remove from the substrate excess components, such as polymer (P) and/or damaging ions, present in composition (a) used in step (1) and optionally in composition used in optional step (3).
In a preferred embodiment, the rinsing step (2) is performed after step (1). In another preferred embodiment, the rinsing step (2) is not performed. In both embodiments, an additional drying step (5) is preferably carried out. By the drying step (5), at least the conversion coating film present on the surface of the substrate is dried and becomes a coating layer.
The aqueous composition (B) applied in optional step (3) of the method according to the invention may for example be another composition as used in step (1), i.e. a composition different from the composition (a) used in step (1), but need not necessarily be identical to the composition (a).
The substrate surface used in the present invention may be coated by other, i.e. subsequent, coatings. Thus, the process of the invention may comprise at least one further optional step, namely
Step (6): applying at least one coating composition to the surface of the substrate obtained after step (1) or after any of the optional steps (2) to (5) to form a coating film on the surface, said coating film being different from the conversion coating film obtained after step (1).
The coating composition used in step (6) is different from compositions (a) and (B) and preferably comprises at least one polymer suitable as binder, said polymer being different from polymer (P). Examples of such polymers other than the polymer (P) are in particular polyesters, polyurethanes, epoxy-based polymers (epoxy resins) and/or (meth) acrylic copolymers and/or polyvinylidene difluoride (PVDF). If applicable, these polymers are used in combination with crosslinking agents such as blocked polyisocyanates and/or aminoplast resins.
Preferably, step (6) is performed. The coating composition used in step (6) may be a powder coating composition. Alternatively, it may be a solvent-based or aqueous coating composition. Preferably, a powder coating composition is used. Any conventional powder coating composition may be used in this step. The coating composition used may in particular be a primer coating composition or a clear coat composition.
Preferably, the inventive method comprises said step (6) as an additional coating step of applying at least one coating composition to the substrate surface obtained after the contacting step (1), i.e. to the substrate surface as a result of having a conversion coating layer at already performed step (1), to form at least one further coating layer on the surface, wherein optionally a rinsing step (2) is performed after step (1) before said coating step (6). Irrespective of whether the optional rinsing step (2) is carried out or not, the drying step (5) is preferably carried out subsequently before the coating step (6).
The treated surface is preferably rinsed to remove excess polymer (P) and optionally undesired ions before applying the further coating according to step (6).
The subsequent coating wet-on-wet land may be applied to the metal surface as treated in the treatment method according to the present invention. However, it is also possible to dry the metal surface as treated in step (5) according to the invention and then apply any other coating.
Composition (A) used in step (1) of the process of the present invention
The acidic aqueous composition (a) used in step (1) preferably does not contain any chromium ions such as Cr (VI) cations.
The acidic aqueous composition (a) used in step (1) preferably does not contain any phosphonate anions.
The term "aqueous" in relation to the composition (a) used in the present invention preferably means that the composition (a) is a composition containing at least 50 wt. -%, preferably at least 60 wt. -%, more preferably at least 70 wt. -%, in particular at least 80 wt. -%, most preferably at least 90 wt. -% of water based on the total content of organic and inorganic solvents (including water). Thus, composition (a) may contain at least one organic solvent in addition to water, however, in an amount lower than the amount of water present.
Preferably, the acidic aqueous composition (a) contains at least 50 wt.%, preferably at least 60 wt.%, more preferably at least 70 wt.%, in particular at least 80 wt.%, most preferably at least 90 wt.% of water, based in each case on the total weight thereof.
The acidic aqueous composition (a) has a pH in the range of 2.5 to < 5.0. Preferably, the pH is measured at room temperature (23 ℃). The pH of the acidic aqueous composition is preferably in the range of 2.6 to 4.8, preferably 2.8 to 4.6, more preferably 3.0 to 4.4, even more preferably 3.1 to 4.3, especially 3.2 to 4.2, most preferably 3.2 to 3.8. If desired, the pH is preferably adjusted by using nitric acid, ammonia and/or sodium carbonate.
The acidic aqueous composition (a) can be used as an dip coating bath. However, it may also be applied by virtually any conventional coating procedure, such as spraying, roll coating, brushing, wiping, etc., as outlined above in connection with step (1). Spraying is preferred.
The acidic aqueous composition (a) used in the present invention may contain other components including ions as outlined in the detailed description below. The term "further comprising" as used herein throughout the specification in view of the components of the acidic aqueous composition means "in addition to the essential components (a) and (b) and (c) and water". Thus, such "other" compounds comprise ions different from the essential components (a) and (b) and (c).
The term "component" as used herein is interchangeable.
The total amount of all components present in the composition (A) of the invention adds up to 100% by weight.
The composition (a) may be a dispersion or a solution. Preferably, it is a solution.
Preferably, the acidic aqueous composition (a) has a temperature in the range of 18 to 35 ℃, more preferably 20 to 35 ℃, especially 20 to 30 ℃.
Preferably, the acidic aqueous composition (A) comprises
Zirconium ions as component (a) in amounts in the range from 15 to 150ppm, more preferably from 16 to 125ppm, still more preferably from 17 to 100ppm, even more preferably from 18 to 75ppm, still more preferably from 20 to 65ppm, still more preferably from 20 to 35ppm, in each case calculated as metal,
and/or, preferably and, in each case calculated as metal, molybdenum ions in an amount in the range from 1 to 8ppm, more preferably from 1.5 to 6ppm, still more preferably from 1.5 to 5ppm, even more preferably from 1.5 to 4ppm, still more preferably from 2.0 to 3.5ppm, still more preferably > 2 to 3 ppm.
The relative weight ratio of zirconium ions (a) to molybdenum ions (c) in the composition (a) is in the range from 40:1 to 7.5:1, calculated as metal in each case.
Preferably, the relative weight ratio of zirconium ions (a) to molybdenum ions (c), calculated as metal in each case, is in the range of from 35:1 to 8:1, more preferably from 25:1 to 8.5:1, still more preferably from 15:1 to 9:1, even more preferably from 12.5:1 to 9.5:1, still more preferably from 12:5 to 10:1.
Zirconium ion as component (a)
The composition (A) contains zirconium ions in an amount in the range of 10 to 200ppm calculated as metal.
Preferably, the acidic aqueous composition (a) comprises zirconium ions in an amount in the range of from 15 to 150ppm, more preferably from 16 to 125ppm, still more preferably from 17 to 100ppm, even more preferably from 18 to 75ppm, still more preferably from 20 to 65ppm, still more preferably from 20 to 35ppm, in each case calculated as metal.
Preferably, the amount (in ppm) of component (a) in composition (a) is lower than the amount (in ppm) of component (b).
Preferably, a precursor metal compound is used to generate ions as component (a) in composition (a). Preferably, the precursor metal compound is water soluble. The solubility was determined at a temperature of 20℃and at atmospheric pressure (1.013 bar).
The content of component (a) can be monitored and determined by means of ICP-OES (optical emission spectroscopy and inductively coupled plasma). The method is described in detail below.
Particularly preferred zirconium compounds are complex fluorides of these metals. The term "complex fluoride" encompasses single and multiple protonated forms and deprotonated forms. Mixtures of such complex fluorides may also be used. In the sense of the present invention, a complex fluoride is a complex of zirconium formed with fluoride ions in composition (a), for example by complexation of fluoride anions with zirconium cations in the presence of water.
In addition, zirconyl compounds, such as zirconyl nitrate and zirconyl acetate; or zirconium is added in the form of zirconium carbonate or nitrate, the latter being particularly preferred.
Preferably, however, zirconium ions (a) are incorporated into composition (a) in the form of their complex fluorides. The polymer (P) as component (b)
The composition (a) contains at least one polymer (P), wherein the polymer (P) is selected from poly (meth) acrylic acid and (meth) acrylic copolymers having carboxylic acid groups and mixtures thereof. Thus, the polymer (P) is selected from poly (meth) acrylic acid (having carboxylic acid groups, as it is seen by the term "poly (meth) acrylic acid" itself), carboxylic acid group containing (meth) acrylic copolymers and mixtures thereof.
The polymer (P) is preferably soluble in the acidic composition (A). The solubility was determined at a temperature of 20℃and at atmospheric pressure (1.013 bar).
The polymer (P) is preferably present in the composition (a) in an amount ranging from 50 to 2000ppm, preferably ranging from 60 to 1500ppm, more preferably ranging from 70 to 1000ppm, even more preferably ranging from 80 to 750ppm, still more preferably ranging from 90 to 650ppm, still more preferably ranging from 100 to 600ppm, even more preferably ranging from 105 to 500ppm, still more preferably ranging from 125 to 400ppm, still more preferably ranging from 135 to 300ppm, most preferably ranging from 150 to 250 ppm.
Preferably, the polymer (P) does not contain any phosphonic acid and/or phosphonate groups.
Preferably, the at least one polymer (P) has a weight average molecular weight (M) in the range of 40 000 to 350 g/mol, preferably 50 to 340 g/mol, more preferably 60 to 330 g/mol, still more preferably 65 to 320000g/mol, still more preferably 70 to 310 g/mol, still more preferably 70 to 300 000, still more preferably 75 to 275 g/mol w ). The weight average molecular weight is determined by the method described in the "methods" section below.
Preferably, the polydispersity of the polymer (P) is above a value of 2.0, more preferably above a value of 2.5. Preferably, the polydispersity is in the range of > 1.0 to 4.0. Polydispersity is determined by the method described in the "methods" section below.
The polymer (P) has carboxylic acid groups. The polymer (P) is selected from poly (meth) acrylic acid and (meth) acrylic copolymers having carboxylic acid groups, and mixtures thereof. Preferably, the polymer (P) is poly (meth) acrylic acid, more preferably polyacrylic acid.
In any case, the polymer (P) is prepared by using (meth) acrylic monomers.
The term "(meth) acryl" means "acryl" and/or "methacryl". Similarly, "(meth) acrylate" means acrylate and/or methacrylate. The polymer (P) is preferably a "(meth) acryl polymer", which is formed of "acryl monomer" and/or "methacryl monomer", but may additionally contain non-acryl and non-methacryl monomer units, and if the polymer (P) is a copolymer, other ethylenically unsaturated monomers such as vinyl monomers are additionally used. Preferably, the backbone of the (meth) acryl copolymer (P) is formed of more than 50 mole percent, even more preferably of more than 75 mole percent of the (meth) acryl monomer.
Preferably, the polymer (P) is a (meth) acrylic copolymer and comprises a polymer backbone having carboxylic acid groups and at least one side chain attached to the polymer backbone.
The polymer (P) is preferably a linear polymer. If the polymer (P) is a copolymer, the monomer units present in the polymer (P) may be in two or more blocks or statistically arranged in a gradient along the polymer backbone of the polymer (P). These arrangements may also be combined. Preferably, the polymer (P) has a statistical distribution, if it is a copolymer and can be prepared by conventional radical polymerization. If the polymer (P) is a block copolymer, it can preferably be prepared by controlled radical polymerization.
Preferably, the polymer (P) contains monomer units (S1) present in the polymer, which each contain side chains (S1) comprising at least one carboxylic acid group in an amount of from 50 to 100mol%, more preferably from 75 to 100mol%, even more preferably from 90 to 100mol%, in particular 100mol%, based in each case on the total amount of all monomer units of the polymer (P), wherein the sum of all monomer units present in the polymer (P) adds up to 100mol%. At 100mol% the polymer (P) is a homopolymer comprising in total the monomer units (S1) present in the polymer, each of which contains side chains (S1) comprising at least one carboxylic acid group, which is most optional.
The functional groups of the side chains (S1) not only allow the crosslinking reaction to take place when the other coating film is applied on top of the conversion coating film obtained after step (1) of the process of the invention, when the coating composition for forming the other coating film comprises a suitable film-forming polymer and/or a crosslinking agent which in turn has functional groups reactive to the functional groups of the side chains (S1), but also the functional groups of the side chains (S1) are additionally related to ensure that the polymer (P) has a sufficient solubility in water and thus in the aqueous composition (a).
Preferably, the at least one monomer used for preparing the polymer (P) is chosen from the group consisting of (meth) acrylic monomers preferably having at least one COOH-group. Examples are acrylic acid and methacrylic acid. Alternatively or additionally, other monomers containing carboxylic acid groups may be used in their preparation, for example maleic acid and/or maleic anhydride, in particular when the polymer (P) is a copolymer.
If the polymer (P) is a copolymer, it may additionally contain other monomer units than (m 1). These may contain side chains which in turn contain OH-groups. Examples of suitable monomers for introducing such side chains are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, monoglyceride (meth) acrylate, N- (2-hydroxypropyl) (meth) acrylamide, allyl alcohol, hydroxystyrene, hydroxyalkyl vinyl ethers such as hydroxybutyl vinyl ether and vinylbenzyl alcohol.
Molybdenum ion as component (c)
Composition (A) contains molybdenum ions in an amount in the range of 0.5 to 10ppm calculated as metal.
Preferably, the acidic aqueous composition (a) comprises molybdenum ions in an amount in the range of from 1 to 8ppm, more preferably from 1.5 to 6ppm, still more preferably from 1.5 to 5ppm, even more preferably from 1.5 to 4ppm, still more preferably from 2.0 to 3.5ppm, in particular > 2 to 3ppm, calculated as metal in each case.
For the preparation of the aqueous composition (A), it is preferred to use a water-soluble (at a temperature of 20℃and atmospheric pressure (1.013 bar)) molybdenum salt. Preferably, the molybdenum ion (c) is incorporated in the composition (a) in the form of at least one molybdate, preferably at least one ammonium molybdate.
Other optional Components
The acidic aqueous composition (a) used in the present invention preferably contains free fluoride. These may result from the presence of component (a), i.e. in particular when a complex fluoride of Zr is present as component (a) in (a), but may also or alternatively result from the presence of other optional components as described hereinafter. Preferably, the acidic aqueous composition (a) contains free fluoride ions in an amount in the range of from 1 to 500ppm, more preferably from 1.5 to 200ppm, even more preferably from 2 to 100ppm, especially from 2.5 to 50 ppm. The free fluoride content was determined by means of a fluoride ion-sensitive electrode according to the method disclosed in the "methods" section.
Optionally, the aqueous composition (a) further comprises at least one metal cation selected from the group of cations of metals of sub-groups 1 to 3 (copper, zinc and scandium) and sub-groups 4 and 8 (titanium, vanadium, chromium, manganese, iron, cobalt and nickel) of the periodic table (comprising the lanthanide series) and of main group 2 (alkaline earth metal group) of the periodic table, lithium, bismuth and tin. The metal cations mentioned in the foregoing are generally introduced in the form of their water-soluble compounds, preferably their water-soluble salts. Preferred cations are selected from the group consisting of cations of cerium and other lanthanides, chromium, iron, calcium, cobalt, copper, magnesium, manganese, nickel, niobium, tantalum, yttrium, vanadium, lithium, titanium, hafnium, bismuth, zinc, and tin. Such metal cations are different from components (a) and (c).
Optionally, the aqueous composition (a) further comprises at least one pH adjusting substance, preferably selected from the group consisting of nitric acid, sulfuric acid, methanesulfonic acid, acetic acid, ammonia, sodium hydroxide and sodium carbonate, wherein nitric acid, ammonia and sodium carbonate are preferred. Depending on the pH of the acidic aqueous composition (a), the above compounds may be in their fully or partially deprotonated form or in protonated form.
Optionally, the aqueous composition (a) further comprises at least one water-soluble fluorine compound. Examples of such water-soluble fluorine compounds are fluoride and hydrofluoric acid. In particular, when component (a) is not present in composition (a) in the form of a complex fluoride of zirconium, the compound is present in composition (a).
Optionally, the aqueous composition (a) further comprises at least one corrosion inhibitor. Examples are L-cysteine and other amino acids, benzotriazole and mixtures thereof. Preferably, at least one corrosion inhibitor does not comprise any type of metal ion.
The composition (A) of the invention
Another subject of the invention is an acidic aqueous composition (a) which is the composition used in the contacting step (1) of the process of the invention defined above.
The composition (a) used in the present invention and the components contained therein, in particular components (a), (b) and water, used herein above in connection with the process of the present invention and the contacting step (1) of said process, and all the preferred embodiments described for optional components are also preferred embodiments of the acidic aqueous composition (a) itself.
The inventive masterbatch
Another subject of the invention is a masterbatch, by dilution of which the acidic aqueous composition (A) according to the invention is produced by water and, if applicable, by adjustment of the pH.
The composition (a) of the invention, and the components contained therein, in particular components (a) and (b) and (c) other than water, used herein above in connection with the process of the invention and the contacting step (1) of the process, and all the preferred embodiments described herein above in connection with the acidic aqueous composition (a) itself are also preferred embodiments of the inventive masterbatch.
If the masterbatch is used for producing the acidic aqueous composition (a) according to the invention, the masterbatch generally contains the components of the acidic aqueous composition (a), i.e. components (a) and (b) and (c), to be produced in the desired proportions, but at higher concentrations. The masterbatch is preferably diluted with water to the concentration of the ingredients as disclosed above to form the acidic aqueous composition (a). The pH of the acidic aqueous composition may be adjusted after dilution of the masterbatch, if desired.
Of course, any of the optional components may be further added to the water, wherein the masterbatch is diluted or after the masterbatch is diluted with water. However, it is preferred that the masterbatch already contains all the necessary components.
Preferably, the masterbatch is diluted with water and/or an aqueous solution in a ratio of 1:5,000 to 1:10, more preferably 1:1,000 to 1:10, most preferably 1:300 to 1:10, even more preferably 1:150 to 1:50.
Application of the invention
Another subject of the invention is the use of the acidic aqueous composition (a) according to the invention for treating at least one surface of a substrate, wherein said surface is at least partially made of at least one metal, preferably at least partially made of aluminum and/or an aluminum alloy, preferably to provide corrosion protection to the surface and/or the substrate and/or to provide increased adhesion of a conversion coating formed by treatment on the surface to other coatings applied to the conversion coating.
The inventive composition (A) used in connection with the inventive process and in the contacting step (1) of the process, as well as the inventive masterbatch, and the components contained in the neutralization composition, in particular components (a) and (b) and (c) other than water, and the optional components, as well as all the preferred embodiments described hereinabove in connection with the acidic aqueous composition (A) itself, are also preferred embodiments for the inventive use.
The substrate of the present invention
Another subject of the invention is a substrate comprising at least one surface, wherein the surface is at least partially made of at least one metal, preferably at least partially made of aluminum and/or an aluminum alloy, wherein the surface has been treated according to the process of the invention and/or by the acidic composition (A) of the invention. By the treatment of the present invention, a conversion coating film is formed and thus present on the substrate. Thus, the substrate of the present invention represents a coated substrate.
The compositions (A) according to the invention, as well as the masterbatches according to the invention, and the components contained in the neutralization compositions, in particular components (a) and (b) and (c) other than water, and also the optional components, described hereinabove in connection with the process according to the invention and the contacting step (1) of the process, and all the preferred embodiments described hereinabove in connection with the acidic aqueous composition (A) itself and the use according to the invention are also preferred embodiments of the substrates according to the invention.
In particular, the coated substrate has a concentration of 0.5 to 100mg/m as determined by XRF (X-ray fluorescence spectroscopy) after drying 2 More preferably 0.75 to 50mg/m 2 Even more preferably 1 to 40mg/m 2 Still more preferably 2 to 35mg/m 2 Still more preferably 5 to 30mg/m 2 In particular from 10 to 26mg/m 2 As coating weights of zirconium and molybdenum ions of components (a) and (c), each calculated as metal.
Method
1. Determination of the average molecular weight M w And M n
Number average molecular weight and weight average molecular weight (M n And M w ) Each measured according to the following protocol: the samples were analyzed by SEC (size exclusion chromatography) equipped with a MALS detector. The absolute molar mass is obtained with a dn/dC value equal to 0.1875mL/g selected to give a recovery mass of about 90%. The polymer sample was dissolved in the mobile phase and the resulting solution was filtered with a Millipore filter 0.45 μm. The elution conditions were as follows. Mobile phase: h 2 O100 vol%, 0.1M NaCl,25mM NaH 2 PO 4 ，25mM Na 2 HPO 4 ；100ppm NaN 3 The method comprises the steps of carrying out a first treatment on the surface of the Flow rate: 1mL/min; column: varian Aquagel OH mixing H,8 μm,3 x 30cm; a detector: RI (concentration detector Agilent) +MALLS (Multi-angle laser light Scattering) Mini Dawn Tristar +UV at 290 nm; sample concentration: about 0.5 wt.% in the mobile phase; injection circuit: 100. Mu.L. Polydispersity P is obtainable from M n And M w And (5) calculating a value.
2. Free fluoride content determination
The free fluoride content was determined by means of fluoride ion selective electrodes. The electrodes were calibrated using at least three mother liquor solutions with known fluoride concentrations. The calibration process results in the establishment of a calibration curve. The fluoride content was then determined by using a curve.
3.ICP-OES
The amounts of certain elements in the sample under analysis, such as zirconium and molybdenum present as components (a) and (c), were determined using inductively coupled plasma atomic emission spectrometry (ICP-OES) according to DIN EN ISO 11885 (date: 2009, 9, 1). The sample was subjected to thermal excitation in an argon plasma generated by a high frequency field, and the light emitted due to the electron transition became visible as spectral lines of the respective wavelengths and analyzed using an optical system. There is a linear correlation between the intensity of the emitted light and the concentration of the element. Calibration measurements are performed as a function of the particular sample under analysis, using known elemental standards (reference standards) prior to implementation. These calibrations can be used to determine the concentration of unknown solutions such as the concentration of amounts of titanium, zirconium and hafnium.
Cross-hatch adhesion test of 4.DIN EN ISO 2409 (06-2013)
The cross-hatch adhesion test was used to determine the adhesion strength of the coating on the substrate according to DIN EN ISO 2409 (06-2013). The cutting tool spacing was 2mm. The evaluation was based on a characteristic cross-hatch adhesion value in the range of 0 (very good adhesion) to 5 (very poor adhesion). The method is used to measure dry adhesion. The cross-hatch adhesion test was also performed after storing the samples in water having a temperature of 63 ℃ for 48 hours to determine wet adhesion. The cross-hatch adhesion test can also be carried out after up to 240 hours of exposure in the condensation climate test according to DIN EN ISO 6270-2CH (correction of 09-2005 and 10-2007). Each of the three tests was performed and the average value was determined.
5. Filiform Corrosion (FFC)
The wire-form corrosion is measured to determine the corrosion resistance of the coating on the substrate. According to MBN 10494-6,
5.5 (version 2016-03) the assay was performed over a 672 hour duration. The maximum thread Length (LF) and/or average filiform subsurface erosion (UF) were measured in [ mm ].
Copper-catalyzed acetate fog (CASS) test of 6.DIN EN ISO 9227 (09-2012)
The copper catalyzed acetate fog test was used to determine the corrosion resistance of a coating on a substrate. According to DIN EN ISO 9227 (09-2012), the sample under analysis is placed in a chamber in which there is a continuous fine mist of a common salt solution at a concentration of 5%, which salt solution is mixed with acetic acid and copper chloride at a controlled pH at a temperature of 50℃over a period of time, for example over a duration of 168, 240 or 264 hours, respectively. The spray was deposited on the sample under analysis, which was covered with a corrosive film of brine. Still prior to CASS testing, if the coating on the sample being investigated is notched down into the substrate, the degree of underfilm corrosion of the sample can be investigated according to DIN EN ISO 4628-8 (03-2013) because the substrate is corroded along the score line during CASS testing. As a result of the progressive process of corrosion, the coating rusted to a greater or lesser extent during testing. The extent of rust (in mm) is a measure of the resistance of the coating. Each test was performed three times and the average value was determined. Both the average of corrosion ("c" value) and delamination ("d" value) can be determined.
Examples
The following examples further illustrate the invention but should not be construed as limiting its scope.
1. Preparation of acidic aqueous compositions
1.1 a number of acidic aqueous compositions (1L each) have been prepared. All aqueous compositions contain H in an amount corresponding to the value calculated as zirconium ppm as metal 2 ZrF 6 As illustrated in table 1 below. All aqueous compositions further contained ammonium heptamolybdate in an amount corresponding to the molybdenum ppm value calculated as metal as illustrated in table 1 below. The compositions each further comprisePA 110S as Polymer, which is M with 250,000g/mol w Is a commercially available polyacrylic acid.
In table 1a, the acidic aqueous compositions prepared in this way are summarized.
Table 1a:
1.2 many other acidic aqueous compositions (1L each) have been prepared by using the same ingredients as described in item 1.1. However, different amounts/pH values are used.
In table 1b, the acidic aqueous compositions prepared in this way are summarized.
Table 1b:
2. pretreatment method
As the base material, an aluminum alloy base material (base material T1; AA 5005) was used. A5505 is an aluminum magnesium alloy substrate.
By using commercially available products for the substrateS5201/1 cleaning (3 minutes at 63 ℃ C.). Then, the mixture was rinsed twice with tap water (30 seconds each). Next, an etching step is performed. Etching is carried out by using commercially available products 4325 (containing nitric acid; 50g/L; chemetall GmbH) and the commercially available product +.>A mixture of Additive H7274 (containing fluoride; 7.5g/L; chemetall GmbH) was carried out (60 seconds). After etching, rinsing with tap water (30 seconds) followed by deionized water (30 seconds). />
Then, a contact step is performed, even if the surface of the substrate is contacted with one of the acidic aqueous compositions described in items 1.1 and 1.2 above, to form a conversion coating layer on the surface of the substrate. The contacting step was carried out in each case by spraying one of the acidic aqueous compositions onto the substrate surface for 60 seconds. The acidic aqueous composition was heated to 25 ℃ prior to spraying. As Reference Example (RE), a conventional two-step contact pretreatment was performed: the aqueous commercial composition without any polymer was preparedX4707) is used in the first contact step, then after rinsing with a solution (++>X4661).
After the contacting step, a drying step (15 minutes at 60 to 70 ℃) is carried out after a period of air blowing.
Thereafter, a paint layer is applied to the conversion-coated substrate T1. An acrylic coating material, a commercially available acrylic powder coating material (PY 1005 from FreiLacke) was used. The dry layer thickness of these coatings obtained is in the range of 80 to 100 μm.
3. Properties of the coated substrate
Many properties of the coated substrate obtained by the method described in item 2 above have been studied. These properties were determined according to the test methods described above. The results are shown in tables 2a and 2 b. In addition, the coating weight has been measured by XRF.
Table 2a: substrate T1
As is evident from table 2a, excellent adhesion and corrosion resistance properties are obtained when using the one-step treatment process and using the aqueous composition of the present invention. Adhesion and corrosion resistance properties were significantly better than those of reference example RE.
Table 2b: substrate T1
As is evident from table 2b, excellent adhesion and corrosion resistance properties are obtained when using the one-step treatment process and using the aqueous composition of the present invention. The adhesion and corrosion resistance properties when using composition A5 were significantly better than when the process was performed using comparative example A4, which comparative example A4 utilized both having too high a Mo ion content and a Zr/Mo weight ratio outside the range of 40:1 to 7.5:1. Furthermore, in the case of using composition A4, an undesired yellow color of the resulting paint layer was observed. It has been found that this undesired yellowing is observed when the amount of Mo ions is too high/not satisfying the Zr/Mo weight ratio mentioned above.
Claims (15)
1. A method of treating at least one surface of a substrate, wherein the surface is at least partially made of at least one metal, in particular at least partially made of aluminum and/or an aluminum alloy, the method comprising at least step (1), i.e
(1) Contacting at least one surface of the substrate with an acidic aqueous composition (A),
wherein the acidic aqueous composition (A) has a pH in the range of 2.5 to <5.0 and comprises (a) zirconium ions in an amount in the range of 10 to 200ppm calculated as metal,
(b) At least one polymer (P), wherein the polymer (P) is selected from poly (meth) acrylic acid and (meth) acrylic copolymers having carboxylic acid groups and mixtures thereof, and
(c) Molybdenum ions in an amount in the range of 0.5 to 10ppm calculated as metal,
wherein the relative weight ratio of zirconium ions (a) to molybdenum ions (c) is in the range from 40:1 to 7.5:1, calculated as metal in each case.
2. The method according to claim 1, wherein the relative weight ratio of zirconium ions (a) to molybdenum ions (c) is in the range of from 35:1 to 8:1, preferably from 25:1 to 8.5:1, more preferably from 15:1 to 9:1, even more preferably from 12.5:1 to 9.5:1, still more preferably from 12:5 to 10:1, calculated as metal in each case.
3. The method of claim 1 and/or 2, wherein the acidic aqueous composition (a) comprises
Zirconium ions in an amount in the range from 15 to 150ppm, preferably from 16 to 125ppm, more preferably from 17 to 100ppm, even more preferably from 18 to 75ppm, still more preferably from 20 to 65ppm, still more preferably from 20 to 35ppm,
And/or, preferably and,
molybdenum ions in an amount in the range of from 1 to 8ppm, preferably from 1.5 to 6ppm, more preferably from 1.5 to 5ppm, even more preferably from 1.5 to 4ppm, still more preferably from 2.0 to 3.5ppm, still more preferably > 2 to 3ppm, calculated as metal in each case.
4. The process according to one or more of the preceding claims, wherein the acidic aqueous composition (a) has a pH value in the range of 2.6 to 4.8, preferably 2.8 to 4.6, more preferably 3.0 to 4.4, even more preferably 3.1 to 4.3, still more preferably 3.2 to 4.2, most preferably 3.2 to 3.8.
5. The process according to one or more of the preceding claims, wherein the acidic aqueous composition (a) has a temperature in the range of 18 to 35 ℃, more preferably 20 to 35 ℃, still more preferably 20 to 30 ℃.
6. The method according to one or more of the preceding claims, wherein the at least one polymer (P) has a weight average molecular weight (M) in the range of 40 to 350 g/mol, preferably 50 to 340 g/mol, more preferably 60 to 330 g/mol, still more preferably 65 to 320 g/mol, still more preferably 70 to 310 g/mol, still more preferably 70 to 300 000, still more preferably 75 to 275000g/mol w )。
7. The process according to one or more of the preceding claims, wherein the polymer (P) is poly (meth) acrylic acid, preferably polyacrylic acid.
8. The process according to one or more of the preceding claims, wherein polymer (P) is present in composition (a) in an amount ranging from 50 to 2000ppm, preferably ranging from 60 to 1500ppm, more preferably ranging from 70 to 1000ppm, even more preferably ranging from 80 to 750ppm, still more preferably ranging from 90 to 650ppm, still more preferably ranging from 100 to 600ppm, even more preferably from 105 to 500ppm, still more preferably from 125 to 400ppm, still more preferably from 135 to 300ppm, most preferably from 150 to 250 ppm.
9. The method according to one or more of the preceding claims, wherein the zirconium ion (a) is incorporated in composition (a) in the form of its complex fluoride.
10. The process according to one or more of the preceding claims, wherein the molybdenum ions (c) are incorporated in composition (a) in the form of at least one molybdate, preferably at least one ammonium molybdate.
11. The process according to one or more of the preceding claims, wherein the acidic aqueous composition (a) contains free fluoride ions in an amount ranging from 1 to 500ppm, preferably from 1.5 to 200ppm, more preferably from 2 to 100ppm, in particular from 2.5 to 50 ppm.
12. The process according to one or more of the preceding claims, wherein polymer (P) does not contain any phosphonic acid and/or phosphonate groups.
13. An acidic aqueous composition (a) as defined in any one or more of the preceding claims.
14. Use of an acidic aqueous composition (a) according to claim 13 in treating at least one surface of a substrate, wherein the surface is at least partly made of at least one metal, preferably at least partly made of aluminum and/or an aluminum alloy, preferably to provide corrosion protection for the surface and/or the substrate and/or to provide increased adhesion of a conversion coating formed by treatment on the surface to other coatings applied to the conversion coating.
15. A substrate comprising at least one surface, wherein the surface is at least partially made of at least one metal, preferably of aluminum and/or an aluminum alloy, wherein the at least one surface has been treated according to the method according to one or more of claims 1-12 and/or by the acidic composition (a) according to claim 13 above.
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| EP20204599.3 | 2020-10-29 | ||
| EP20204599 | 2020-10-29 | ||
| PCT/EP2021/079972 WO2022090388A1 (en) | 2020-10-29 | 2021-10-28 | Zr, mo and acid-functional polymer containing aqueous compositions for treatment of metallic surfaces |
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| US (1) | US20230366097A1 (en) |
| EP (1) | EP4237597A1 (en) |
| JP (1) | JP2023547651A (en) |
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| CN (1) | CN116457498A (en) |
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| US4191596A (en) | 1978-09-06 | 1980-03-04 | Union Carbide Corporation | Method and compositions for coating aluminum |
| US4921552A (en) | 1988-05-03 | 1990-05-01 | Betz Laboratories, Inc. | Composition and method for non-chromate coating of aluminum |
| US5641542A (en) | 1995-10-11 | 1997-06-24 | Betzdearborn Inc. | Chromium-free aluminum treatment |
| DE102009001372B4 (en) | 2009-03-06 | 2011-01-27 | Chemetall Gmbh | Process for coating metallic surfaces in a multistage process and use of the products coated by the process |
| US9303167B2 (en) * | 2013-03-15 | 2016-04-05 | Ppg Industries Ohio, Inc. | Method for preparing and treating a steel substrate |
| CN108350579A (en) | 2015-09-15 | 2018-07-31 | 凯密特尔有限责任公司 | With the composition pre-treating aluminium surface containing zirconium and molybdenum |
| BR112019004899B1 (en) * | 2016-09-15 | 2023-01-17 | Chemetall Gmbh | PROCESS FOR ANTI-CORROSIVE PRE-TREATMENT OF A METALLIC SURFACE, AND USE OF A METALLIC SUBSTRATE |
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| US11958989B2 (en) | 2018-09-07 | 2024-04-16 | Rhodia Operations | Method for treating surfaces of aluminum containing substrates |
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| CN109943836A (en) * | 2019-04-30 | 2019-06-28 | 华南理工大学 | A kind of aluminum alloy surface chrome-free tanning agent and its application |
-
2021
- 2021-10-28 JP JP2023526517A patent/JP2023547651A/en active Pending
- 2021-10-28 MX MX2023004774A patent/MX2023004774A/en unknown
- 2021-10-28 CA CA3196574A patent/CA3196574A1/en active Pending
- 2021-10-28 US US18/250,008 patent/US20230366097A1/en active Pending
- 2021-10-28 CN CN202180074279.6A patent/CN116457498A/en active Pending
- 2021-10-28 TW TW110139976A patent/TW202225482A/en unknown
- 2021-10-28 KR KR1020237017634A patent/KR20230095098A/en unknown
- 2021-10-28 EP EP21799054.8A patent/EP4237597A1/en active Pending
- 2021-10-28 WO PCT/EP2021/079972 patent/WO2022090388A1/en active Application Filing
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| TW202225482A (en) | 2022-07-01 |
| JP2023547651A (en) | 2023-11-13 |
| US20230366097A1 (en) | 2023-11-16 |
| CA3196574A1 (en) | 2022-05-05 |
| EP4237597A1 (en) | 2023-09-06 |
| KR20230095098A (en) | 2023-06-28 |
| WO2022090388A1 (en) | 2022-05-05 |
| MX2023004774A (en) | 2023-05-09 |
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