NO771230L - PROCEDURE FOR FINISHING PHOSPHATED METAL SURFACES - Google Patents
PROCEDURE FOR FINISHING PHOSPHATED METAL SURFACESInfo
- Publication number
- NO771230L NO771230L NO771230A NO771230A NO771230L NO 771230 L NO771230 L NO 771230L NO 771230 A NO771230 A NO 771230A NO 771230 A NO771230 A NO 771230A NO 771230 L NO771230 L NO 771230L
- Authority
- NO
- Norway
- Prior art keywords
- acid
- solutions
- phenyl
- vinyl
- phosphonic acid
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 21
- 229910052751 metal Inorganic materials 0.000 title claims description 8
- 239000002184 metal Substances 0.000 title claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 16
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000001530 fumaric acid Substances 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- 239000001384 succinic acid Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 29
- 239000010410 layer Substances 0.000 description 18
- 229910019142 PO4 Inorganic materials 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- 235000021317 phosphate Nutrition 0.000 description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 10
- 239000010452 phosphate Substances 0.000 description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 229910000398 iron phosphate Inorganic materials 0.000 description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000003139 buffering effect Effects 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 150000003009 phosphonic acids Chemical class 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- -1 amine phosphates Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- GSSDUXHQPXODCN-UHFFFAOYSA-N 1-phenylethenylphosphonic acid Chemical compound OP(O)(=O)C(=C)C1=CC=CC=C1 GSSDUXHQPXODCN-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229940042400 direct acting antivirals phosphonic acid derivative Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Description
Oppfinnelsen vedrører en fremgangsmåte til behand-ling av metallfosfat sjikt med oppløsninger av organiske fosfonsyrer. The invention relates to a method for treating a metal phosphate layer with solutions of organic phosphonic acids.
Det er vanlig å fosfatere overflaten av materialer av jern og stål, sink og aluminium for enten å oppnå en bedre klebning for den etterfølgende lakkering eller å oppbygge et underrust som bevirker at ved en skade av lakkfilmen blir korro-sjonen i det vésentlige begrenset til de skadede steder og skrider ikke frem under lakkfilmen. Lakklebningen er spesiell god, når fosfatsjiktene er meget tynne, hvorfor det i økende grad anvendes den såkalte alkalifosfatering. Ved denne fremgangsmåte arbeider man med sure oppløsninger av alkali-, ammonium- eller aminfos-fater og frembringer dermed et fastklebende tynt sjikt av fos-fater og oksyder av metallene, hvorav behandlingsgodsets over-flate består. Disse sjikt.har f.eks. på stålblikk tykkelser på 0>3~1 g/m 2. Underrustbeskyttelsen som oppnås ved påføring av et slikt sjikt kan i forbindelse med en egnet påført lakk være meget god, oppnår imidlertid vanligvis ikke de verdier som oppnås ved påføring av tykkere fosfatsjikt, f.eks. med en såkalt sinkfosfateringsfremgangsmåte. Det er allerede lenge vært kjent at man kan forbedre underrustbeskyttelsen av fosfatsjikt ved at man etterbehandler disse sjikt med oppløsninger,ssom som vesent-lige bestanddeler inneholder kromsyre eller kromater. Denne etsterbehandling er nettopp spesielt virksom ved tynne jernfosfatsjikt. Når de ofte utelates, så ligger dette i ubekvemmeligheter, som er forbundet med anvendelsen av slike oppløsninger. Kromsyre og kromater hører til de kreftfrembringende stoffer, hvorfor betjeningspersonalet ikke bør komme i berøring med de i sprøyte-anlegget dannede sprøytetåker, dvs. må fremfor alt ikke innånde disse. Dessuten må kromat etter dagens bestemmelse praktisk talt fullstendig fjernes fra avvannet (ved reduksjon til Cr<+++>It is common to phosphatize the surface of materials made of iron and steel, zinc and aluminum in order to either achieve a better adhesion for the subsequent painting or to build up an underlying rust which means that, in the event of damage to the paint film, the corrosion is essentially limited to the damaged places and does not progress under the lacquer film. The paint adhesion is particularly good when the phosphate layers are very thin, which is why so-called alkaline phosphating is increasingly being used. In this method, one works with acidic solutions of alkali, ammonium or amine phosphates and thus produces a thin adhesive layer of phosphates and oxides of the metals, of which the surface of the treated goods consists. These layers have e.g. on sheet steel thicknesses of 0>3~1 g/m 2. The rust protection achieved by applying such a layer can, in conjunction with a suitable applied varnish, be very good, but usually does not achieve the values achieved by applying a thicker phosphate layer, f .ex. with a so-called zinc phosphating method. It has already been known for a long time that the rust protection of phosphate layers can be improved by post-treating these layers with solutions that contain chromic acid or chromates as essential components. This ester treatment is particularly effective with thin iron phosphate layers. When they are often omitted, this lies in the inconvenience associated with the use of such solutions. Chromic acid and chromates belong to the carcinogenic substances, which is why the operating staff should not come into contact with the spray mists formed in the spraying plant, i.e. above all must not inhale them. Moreover, according to the current determination, chromate must be practically completely removed from the wastewater (by reduction to Cr<+++>
og etterfølgende utfelling som hydroksyd).and subsequent precipitation as hydroxide).
Det er allerede kjent., istedenfor kromsyrer å anvende vinylfosfonsyre, polyvinylfosfonsyre, blandinger av begge eller blandingspolymerisater av vinylfosfonsyre.med fos-forfrie monomere. Disse forbindelser forbedrer, når de bringes i kontakt med sterkt fortynnede oppløsninger med fosfatsjiktet, underrustbeskyttelsen av et sinkfosfat sjikt (tysk patent nr. I.I82.927). Det har imidlertid vist seg at slike oppløsninger ikke er egnet for våtpassifisering av jernfosfatsjikt, da lakk-vedhengningen er utilfredsstillende og underrustbeskyttelsen ikke er fullstendig tilstrekkelig. It is already known, instead of chromic acids, to use vinylphosphonic acid, polyvinylphosphonic acid, mixtures of both or mixed polymers of vinylphosphonic acid with phosphorus-free monomers. These compounds, when brought into contact with highly dilute solutions with the phosphate layer, improve the rust protection of a zinc phosphate layer (German Patent No. I.I82.927). However, it has been shown that such solutions are not suitable for wet passivation of an iron phosphate layer, as the lacquer adhesion is unsatisfactory and the under rust protection is not completely sufficient.
Det forelå derfor den oppgave å tilveiebringe en fremgangsmåte for etterbehandling av fosfatsjikt, spesielt av de ved alkalifosfat frembragte jernfosfatsjikt, hvor det på tross av unnlatelse av kromat oppnås en virkningsfull korrosjonsbeskyttelse (underrustbeskyttelse) ved god lakkvedhengning. There was therefore the task of providing a method for the post-treatment of phosphate layers, especially of the iron phosphate layers produced by alkali phosphate, where, despite the omission of chromate, effective corrosion protection (underlying rust protection) is achieved through good paint adhesion.
I tysk søknad nr. P 24 55 624.9 foreslås det for løsning av dette problem en fremgangsmåte som erkarakterisertved &t man bringer den fosfaterte metalloverflate i berøring med oppløsninger som minst inneholder et stoff av gruppen bestående av l-fenyl-vinyl-f>osfonsyre-(l), poly-(1-fenylvinyl-fosfonsyre-1) og blandingspolymerisater av 1-fenyl-vinyl-fosfonsyre-(1) In German application no. P 24 55 624.9, a method is proposed to solve this problem which is characterized by bringing the phosphated metal surface into contact with solutions which contain at least one substance from the group consisting of l-phenyl-vinyl-phosphonic acid-( l), poly-(1-phenylvinyl-phosphonic acid-1) and mixed polymers of 1-phenyl-vinyl-phosphonic acid-(1)
og olefinisk umettede monomere. Her henvises også allerede til at for oppnåelse av en god underrustbeskyttelse er det nødvendig med en aciditet av behandlingsoppløsningen og at pH-verdien av disse oppløsninger fortrinnsvis utgjør maksimalt 555. and olefinically unsaturated monomers. Reference is also already made here to the fact that in order to achieve good rust protection, the acidity of the treatment solution is necessary and that the pH value of these solutions preferably amounts to a maximum of 555.
Por vanlig praksis bør en slik etterbehandlings-oppløsning ved produksjon av fosfatert blikkmaterial forbli virksomt lengst mulig, dvs. ha en lengst mulig standtid. Dette betyr at den anvendte oppløsning under behandlingen skal bibe-holde det ønskede pH-område lengst mulig, skjønt det i løpet av behandlingen forbrukes hydrogenioner. Eksempelvis kan det ved innført kalkholdig spylevann som henger ved de fosfaterte materialer, pH-verdien av behandlingsoppløsningen økes. Dessuten forårsaker reaksjonen av behandlingsoppløsningen med den fosfaterte metalloverflate (forbruk av protoner) en økning av pH-verdien som da nødvendiggjør en regenerering eller utveksling av behandlingsoppløsningen. According to normal practice, such a finishing solution in the production of phosphated tin material should remain effective for as long as possible, i.e. have the longest possible shelf life. This means that the solution used during the treatment must maintain the desired pH range for as long as possible, even though hydrogen ions are consumed during the treatment. For example, the pH value of the treatment solution can be increased if calcareous rinse water is introduced that hangs around the phosphated materials. Moreover, the reaction of the treatment solution with the phosphated metal surface (consumption of protons) causes an increase in the pH value which then necessitates a regeneration or exchange of the treatment solution.
Oppfinnelsens gjenstand er en fremgangsmåte til etter behandling av fosfaterte metalloverflater, idet fremgangsmåten erkarakterisert vedat den fosfaterte metalloverflate bringes i berøring med oppløsninger som minst inneholder et stoff fra gruppen bestående av 1-fenyl-vinyl-fosfonsyre-(1), poly-(l-feny1-vinyl-fosfonsyre-1) og blandingspolymerisater av 1-fenyl-vinyl-fosfonsyre-(1) og olefinisk umettede monomere, har' et pH-område fra 4,0 til 5,5 og inneholder fumarsyre og ravsyre som pH-stabilisatorer. The object of the invention is a method for after treatment of phosphated metal surfaces, the method being characterized by bringing the phosphated metal surface into contact with solutions that contain at least one substance from the group consisting of 1-phenyl-vinyl-phosphonic acid-(1), poly-(l- phenyl-1-vinyl-phosphonic acid-1) and mixed polymers of 1-phenyl-vinyl-phosphonic acid-(1) and olefinically unsaturated monomers, have a pH range from 4.0 to 5.5 and contain fumaric acid and succinic acid as pH stabilizers .
Den monomere 1-fenyl-vinyl-fosfonsyre-(1) med formel CI^-C (CgH^-PO^I^ kan samtidig anvendes med sine polymere, idet blandingsforholdet kan svinge innen vide grenser, spesielt i grensene 1:0,1 til.1:10, fortrinnsvis 1:0,5 til 1:2. The monomeric 1-phenyl-vinyl-phosphonic acid-(1) with the formula CI^-C (CgH^-PO^I^ can be used at the same time with its polymers, as the mixing ratio can fluctuate within wide limits, especially in the limits 1:0.1 to.1:10, preferably 1:0.5 to 1:2.
Med denne fremgangsmåte kan den korrosjonsbeskyttende virkning av fosfatsjikt, fortrinnsvis av jernfosfatsjikt, spesielt slike som frembringes med alkalifosfater vesentlig forbedres. With this method, the corrosion-protective effect of a phosphate layer, preferably of an iron phosphate layer, especially those produced with alkali phosphates, can be significantly improved.
De ved fremgangsmåten ifølge oppfinnelsen anvendbare polymere lar ség fremstille etter kjente metoder, f.eks. ved blokkpolymerisasjon med radikaliske startere, som f.eks. benzoyl-peroksyd. Det samme gjelder for blandingspolymerisatene med olefinisk umettede monomere. Derved er det anvendbart et stort antall av umettede forbindelser, f.eks. styren, men også forbindelser som har en sterk polar karakter, som umettede syrer, estere, anhydrider og nitriler som f.eks. akrylsyre, vinylacetat, akrylsyremetylester, maleinsyreanhydrid og acetonitril. Det kan også anvendes blandingspolymerisater av 1-fenyl-vinyl-fosfonsyre-(1), som er oppbygget av mer enn 2 komponenter. Blant blandingspolymerisatene anvendes fortrinnsvis slike med akrylsyre, meta-krylsyre, akrylsyreestere, metakrylsyreestere, spesielt deres (C-^-C^ )-alkylestere eller maleinsyreanhydrid. Ved fremgangsmåten ifølge oppfinnelsen anvendes oppløsningene i polare oppløsnings-midler, spesielt imidlertid vandige oppløsninger. The polymers that can be used in the method according to the invention can be prepared according to known methods, e.g. by block polymerization with radical starters, such as benzoyl peroxide. The same applies to the mixed polymers with olefinically unsaturated monomers. Thereby, a large number of unsaturated compounds can be used, e.g. styrene, but also compounds that have a strong polar character, such as unsaturated acids, esters, anhydrides and nitriles such as e.g. acrylic acid, vinyl acetate, acrylic acid methyl ester, maleic anhydride and acetonitrile. Mixed polymers of 1-phenyl-vinyl-phosphonic acid-(1) can also be used, which are made up of more than 2 components. Among the mixed polymers, those with acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, especially their (C-2-C4)-alkyl esters or maleic anhydride are preferably used. In the method according to the invention, the solutions are used in polar solvents, especially, however, aqueous solutions.
Til anvendelse kommer det sterkt fortynnede oppløs-ninger med 0,01 til 2 g/liter, fortrinnsvis 0,1 til 0,5 g/liter virksomt stoff, oppløst i springvann eller ennu bedre i helav-saltet vann. Highly diluted solutions with 0.01 to 2 g/litre, preferably 0.1 to 0.5 g/litre of active substance, dissolved in tap water or even better in desalted water are used.
Konsentrasjonene av oppløsningene av fumarsyre eller ravsyre ligger derved med fordel i området fra 0,01 til 1 g/liter, fortrinnsvis i området fra 0,05 til 0,2 g/liter. Derved kan man på den ene side anvende de ved fosfatering anvendte gjenstander tørt eller (etter spyling med vann) ennu fuktige. I dette tilfellet er det av fordel med vandige behandlångsopp-løsninger. Ved anvendelse av blandingspolymerisater må det på-ses at oppløseligheten i det anvendte oppløsningsmiddel ennu er tilstrekkelig høy. Derfor anvendes fordelaktig slike blandingspolymerisater hvori minst 30%, fortrinnsvis minst 50% av monomerenheten av blandingspolymerisatet består av 1-fenyl-vinyl-fosfonsyre-(1)i The concentrations of the solutions of fumaric acid or succinic acid are thereby advantageously in the range from 0.01 to 1 g/litre, preferably in the range from 0.05 to 0.2 g/litre. Thereby, on the one hand, the objects used in phosphating can be used dry or (after rinsing with water) still damp. In this case, it is advantageous to use aqueous treatment solutions. When using mixed polymers, it must be ensured that the solubility in the solvent used is still sufficiently high. Therefore, such mixed polymers are advantageously used in which at least 30%, preferably at least 50% of the monomer unit of the mixed polymer consists of 1-phenyl-vinyl-phosphonic acid-(1)i
Istedenfor 1-fenyl-vinyl-fosfonsyre kan man ggså anvende deres i fenylkjernen substituerte derivater, eksempelvis metylhomologe eller klorderivater. Instead of 1-phenyl-vinyl-phosphonic acid, one can also use their derivatives substituted in the phenyl nucleus, for example methyl homologues or chlorine derivatives.
Ved fremgangsmåten ifølge oppfinnelsen kan detWith the method according to the invention, it can
også etterbehandles sinkfosfatsjikt (på jern.eller sink), idet det likeledes iakttas en forbedring av korrosjonsbeskyttelsen. zinc phosphate layer (on iron or zinc) is also post-treated, as an improvement in corrosion protection is also observed.
I alle tilfeller er det fordelaktig at de anvendte oppløsninger er kromatfrie og fosfonsyrederivatene lar seg lett fjerne av avvannet, når man foretar en utfnokning med aluminlumsulfat eller jern(III)-klorid, idet fosfonsyrene adsorberes av hydrok-sydfnokkene og kan fjernes med disse.. For det meste er det ikke nødvendig med spesielle forholdsregler for avvannbehandling, da den omtalte fnokning allikevel foretas for fjerning av fos-fater fra skyllevann fra fosfateringen og man således kan opp-berede brukte oppløsninger av etterbehandlingsmidlet ifølge oppfinnelsen sammen med de fosfatholdige avvann. In all cases, it is advantageous that the solutions used are chromate-free and the phosphonic acid derivatives can be easily removed from the waste water, when de-flocculation is carried out with aluminum sulfate or iron(III) chloride, as the phosphonic acids are adsorbed by the hydroxyl groups and can be removed with these. For the most part, it is not necessary to take special precautions for wastewater treatment, as the aforementioned flocculation is still carried out to remove phosphates from rinse water from the phosphating and one can thus prepare used solutions of the post-treatment agent according to the invention together with the phosphate-containing wastewater.
Innstilling av oppløsningenes pH-verdi til pHSetting the solutions' pH value to pH
4,0 til 5,5 foregår med alkalilut (f.eks. natronlut eller kalilut), ammoniakk eller aminer (f.eks. etanolamin). En videre-gående nøytralisering nedsetter underrustbeskyttelsen. En viss aciditet og dermed forbundet reaksjonsevne er altså nødvendig. 4.0 to 5.5 takes place with alkaline liquor (e.g. caustic soda or potassium hydroxide), ammonia or amines (e.g. ethanolamine). Further neutralization reduces the rust protection. A certain acidity and the associated reactivity are therefore necessary.
Også ved anvendelse av fumarsyre eller ravsyre. oppnås en god underrustbeskyttelse. Det er derved fordelaktig at begge syrer i motsetning til sitronsyre eller vinsyre i for-hold til jern av fosfatovertrekket ikke utfolder komplekserende virkning. Spesielt gunstig er det » at fumarsyre og ravsyre.i forbindelse med de nevnte fosfonsyrer i sin puffervirkning er tydelig overlegne overfor de allerede foreslåtte syrer (sitronsyre, vinsyre, fosforsyre) referert til anvendelsen av samme vektsmengde. Also when using fumaric acid or succinic acid. a good rust protection is achieved. It is therefore advantageous that both acids, in contrast to citric acid or tartaric acid, do not exert a complexing effect in relation to the iron of the phosphate coating. It is particularly advantageous that fumaric acid and succinic acid, in connection with the aforementioned phosphonic acids, are clearly superior in their buffering effect to the already proposed acids (citric acid, tartaric acid, phosphoric acid) referred to the use of the same amount by weight.
Denne puffereffekt fremtrer spesielt når det til innstilling av begynnelses-pH-verdien på 4,0 av behandlingsoppløs-ningen istedenfor alkalilut (f.eks. natronlut eller kalilut) an- This buffering effect is particularly apparent when, to set the initial pH value of 4.0 of the treatment solution, instead of alkaline lye (e.g. caustic soda or potassium lye)
vendes et amin, f.eks. trietanolamin.turns an amine, e.g. triethanolamine.
E ksempel 1.Example 1.
Den gode puffervirkning av ravsyre og fumarsyre sammenlignes til de tidligere foreslåtte syrer ble påvist ved titrering. Hver gang 100 ml vandige oppløsninger (1 til 8), som inneholdt de nedenfor angitte syrer titreres med 0,01 normal NaOH og samtidig måles endringen av pH-verdien. Derved ble The good buffering effect of succinic acid and fumaric acid is compared until the previously proposed acids were demonstrated by titration. Each time 100 ml of aqueous solutions (1 to 8), which contained the acids specified below, are titrated with 0.01 normal NaOH and at the same time the change in the pH value is measured. Thereby became
før titreringene oppløsningene 1, 2, 354, 6 og 7 med få dråper 0,1 normal natronlut og oppløsningene 5 og 8 med få dråper fortynnet trietanolaminoppløsning innstillet på pH-verdien på 4,0. before the titrations solutions 1, 2, 354, 6 and 7 with a few drops of 0.1 normal caustic soda and solutions 5 and 8 with a few drops of dilute triethanolamine solution adjusted to the pH value of 4.0.
Titreringsforløpet fremgår av figuren (absisse:The titration process can be seen in the figure (abscissa:
ml 0,01 normal NaOHi ordinat: pH-verdi). Tegningen viser den relativt langsomme økningen av pH-verdien ved oppløsninger som inneholder fumarsyre og ravsyre. ml 0.01 normal NaOHi ordinate: pH value). The drawing shows the relatively slow increase of the pH value in solutions containing fumaric acid and succinic acid.
Eksempel 2. Example 2.
Kaldvalset stålblikk i dyptrekk-kvalitet ble på vanlig måte fosfatert med en svak sur alkalifosfatoppløsning i sprøytefremgangsmåten. Det oppsto en sjiktvekt på ca. 700 mg/m . Sjiktet ble spylt med vann og deretter etterbehandlet ved 40°C Cold-rolled sheet steel in deep drawing quality was conventionally phosphated with a weakly acidic alkali phosphate solution in the spraying process. A layer weight of approx. 700 mg/m . The layer was rinsed with water and then post-treated at 40°C
i sprøytefremgangsmåte i 30 sekunder med hver gang en av de nedenfor angitte oppløsninger A resp. B. Deretter ble blikkene in the spray method for 30 seconds with each time one of the below stated solutions A resp. B. Then the looks were
tørket med varmluft ved 120°C og grunnet.elektroforatisk. dried with hot air at 120°C and primed.electrophoretic.
(Bindemiddel: Epoksydester) og denne grunning innbrent ved l80°C i 30 minutter. Blikkene ble utstyrt ,med et kryssnitt og ifølge ASTM B 117-64 utsatt for salttåke i 240 timer. Deretter ble den løstsittende del av påstrykningen på kryss-snittet avskrapet med en kunststoffspatel og undervandringen målt. (Binder: Epoxy ester) and this primer baked in at 180°C for 30 minutes. The glasses were equipped with a cross-section and, according to ASTM B 117-64, exposed to salt fog for 240 hours. Then the loose part of the application on the cross-section was scraped off with a plastic spatula and the undertravel was measured.
R esultat.R result.
Det har vist seg at fremgangsmåten ifølge oppfinnelsen (representert ved anvendelse av oppløsning A) bevirker god korrosjonsbeskyttelse på fosfaterte stålblikk. It has been shown that the method according to the invention (represented by the use of solution A) produces good corrosion protection on phosphated steel sheets.
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762615489 DE2615489A1 (en) | 1976-04-09 | 1976-04-09 | PROCESS FOR AFTER-TREATMENT OF PHOSPHATED METAL SURFACES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO771230L true NO771230L (en) | 1977-10-11 |
Family
ID=5974925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO771230A NO771230L (en) | 1976-04-09 | 1977-04-06 | PROCEDURE FOR FINISHING PHOSPHATED METAL SURFACES |
Country Status (9)
| Country | Link |
|---|---|
| AR (1) | AR212820A1 (en) |
| BR (1) | BR7702181A (en) |
| DE (1) | DE2615489A1 (en) |
| DK (1) | DK154177A (en) |
| FR (1) | FR2347457A2 (en) |
| IT (1) | IT1115646B (en) |
| NL (1) | NL7703652A (en) |
| NO (1) | NO771230L (en) |
| SE (1) | SE7704111L (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2632742C3 (en) * | 1976-07-21 | 1980-05-08 | Hoechst Ag, 6000 Frankfurt | Process for phosphating metals and means for producing a phosphating solution |
| US4446028A (en) * | 1982-12-20 | 1984-05-01 | Betz Laboratories, Inc. | Isopropenyl phosphonic acid copolymers used to inhibit scale formation |
| US4446046A (en) * | 1981-06-17 | 1984-05-01 | Betz Laboratories, Inc. | Poly (alkenyl) phosphonic acid and methods of use thereof |
| DE3130628A1 (en) * | 1981-08-01 | 1983-02-17 | Röhm GmbH, 6100 Darmstadt | SUBSTITUTED 1-PHENYL-VINYL-1-PHOSPHONIC ACIDS AND THEIR USE |
| AU637777B2 (en) * | 1989-08-25 | 1993-06-10 | Colgate-Palmolive Company, The | Antibacterial antiplaque oral composition containing novel styrene-phosphonic acid copolymer |
| FR2684550B1 (en) * | 1989-08-25 | 1999-01-22 | Colgate Palmolive Co | ANTI-PLATE ANTIBACTERIAL COMPOSITION COMPRISING A POLYMER OF STYRENE-PHOSPHONIC ACID OR A COPOLYMER OF STYRENE-PHOSPHONIC ACID AND AN ETHYLENICALLY UNSATURATED MONOMER. |
| GR1000848B (en) * | 1989-08-25 | 1993-02-17 | Colgate Palmolive Co | Antiplaque antibacterial oral composition |
| ZA899970B (en) * | 1989-08-25 | 1991-08-28 | Colgate Palmolive Co | Antibacterial antiplaque oral composition containing noval styrene-phosphonic acid copolymer |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL129564C (en) * | 1960-04-16 | 1900-01-01 | ||
| FR80278E (en) * | 1960-04-16 | 1963-04-05 | Hoechst Ag | Method and solution for the treatment of layers of phosphates intended for protection against corrosion |
| FR1442807A (en) * | 1964-08-10 | 1966-06-17 | Parker Ste Continentale | Cold forming of metals |
| FR1498087A (en) * | 1966-11-01 | 1967-10-13 | Dow Chemical Co | Process for treating metals to cause adhesion of polyolefins |
-
1976
- 1976-04-09 DE DE19762615489 patent/DE2615489A1/en not_active Withdrawn
-
1977
- 1977-04-04 NL NL7703652A patent/NL7703652A/en not_active Application Discontinuation
- 1977-04-06 NO NO771230A patent/NO771230L/en unknown
- 1977-04-06 AR AR267142A patent/AR212820A1/en active
- 1977-04-06 BR BR7702181A patent/BR7702181A/en unknown
- 1977-04-06 DK DK154177A patent/DK154177A/en not_active IP Right Cessation
- 1977-04-07 IT IT22259/77A patent/IT1115646B/en active
- 1977-04-07 SE SE7704111A patent/SE7704111L/en unknown
- 1977-04-12 FR FR7710877A patent/FR2347457A2/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| NL7703652A (en) | 1977-10-11 |
| IT1115646B (en) | 1986-02-03 |
| FR2347457A2 (en) | 1977-11-04 |
| AR212820A1 (en) | 1978-10-13 |
| DK154177A (en) | 1977-10-10 |
| BR7702181A (en) | 1978-01-10 |
| SE7704111L (en) | 1977-10-10 |
| FR2347457B2 (en) | 1981-06-19 |
| DE2615489A1 (en) | 1977-10-27 |
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