NO116350B - - Google Patents
Info
- Publication number
- NO116350B NO116350B NO16558766A NO16558766A NO116350B NO 116350 B NO116350 B NO 116350B NO 16558766 A NO16558766 A NO 16558766A NO 16558766 A NO16558766 A NO 16558766A NO 116350 B NO116350 B NO 116350B
- Authority
- NO
- Norway
- Prior art keywords
- resin
- water
- soluble
- paint
- film
- Prior art date
Links
- 239000011347 resin Substances 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 36
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000003973 paint Substances 0.000 claims description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000003957 anion exchange resin Substances 0.000 claims description 4
- 239000003729 cation exchange resin Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005349 anion exchange Methods 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- -1 methylene sulfonic acid Chemical compound 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012866 water-soluble synthetic resin Substances 0.000 description 1
- 229920006186 water-soluble synthetic resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/20—Electrolytic after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Description
Fremgangsmåte ved elektrolytisk avsetning av vannoppløselig harpiksmaling på en film av anodisk oxydert aluminium. Method of electrolytic deposition of water-soluble resin paint on a film of anodically oxidized aluminium.
Foreliggende oppfinnelse angår en fremgangsmåte ved elektrolytisk avsetning av en vannopplbselig harpiksmaling på en film av anodisk"oxydert aluminium, hvor harpiksmalingen forbehandles med en ioneutvekslerharpiks fbr elektropletteringen finner sted. The present invention relates to a method by electrolytic deposition of a water-soluble resin paint on a film of anodically oxidized aluminum, where the resin paint is pretreated with an ion exchange resin before the electroplating takes place.
Den kjente teknikk med anodisk oxydasjon av aluminium har gått ut på å utfOre den anodiske oxydasjon ved hjelp av en elektrolytt såsom svovelsyre, oxalsyre eller kromsyre og deretter utglatte den anodiske oxyderte overflate ved behandling av de på overflaten dannede porer med damp eller lignende for å lukke porene. Denne teknikk gir imidlertid ikke produkter-med tilstrekkelig stor korrosjonsfasthet og dielektrisk styrke for praktiske formål. The known technique of anodic oxidation of aluminum has consisted of carrying out the anodic oxidation with the aid of an electrolyte such as sulfuric acid, oxalic acid or chromic acid and then smoothing the anodic oxidized surface by treating the pores formed on the surface with steam or the like to close the pores. However, this technique does not produce products with sufficiently high corrosion resistance and dielectric strength for practical purposes.
I de senere år har det vært foreslått å foreta elektrolytiskKfr. kl. 48a-13/0d mv setning av vunnopplbsc: 1. ige harpikser på aluininiumoxyd filmer fremstilt ved anodisk oxydasjon og påfblgende utgletting av den jorbse overflate ved A' lukke porene. Nærmere bestemt går forslage; ut på å vaske den porose aluminiumoxydfilm med vann straks etter fit den elektrolytiske oxydasjon er utfort, dyj.pe filmen i en opp-IHsninc nv v;mnopplci3elig narpiks, lade opp harpikspartiklene ved . ).;"t,Jrykning av an likespenning, hvorved harpiksen som folge av eloktromotoriske krefter adsorberes i den porSse film, slik at der dannes en sa::imenhengende harpiksfilm, og deretter utglatte ovsr-flaten ved oppvHrmning slik at overflatens porer lukkes. j In recent years, it has been proposed to carry out electrolytic Kfr. at 48a-13/0d etc. statement of winning results: 1. ige resins on aluminum oxide films produced by anodic oxidation and subsequent smoothing of the earth's surface at A' close the pores. More specifically, proposals go; to wash the porous aluminum oxide film with water immediately after the electrolytic oxidation has been carried out, dip the film in an up-IHsninc nv;mnopplci3elig narpiks, charge the resin particles at . Applying a direct voltage, whereby the resin is adsorbed in the porous film as a result of electromotive forces, so that a continuous resin film is formed, and then the surface is smoothed by heating so that the pores of the surface are closed.
Fordi den ved unodisk oxydasjon fremstilte aluminiumoxydfilmiBecause it produced aluminum oxide film by non-ionic oxidation
i dette tilfelle dyppes ned i opplesningen av den vannopplbselige harpiks, blondes elektrolyten for aluininiuuet inn i harpiksopp-Ibisningen. Av grunner som ennu ikke er klarlagt, dannes derved en spesiell forbindelse i harpiksopplbsningen. Når denne harpiks av-j settes elektrolytisk fra harpiksopplbsningen, oppstår der intet strbmfall under elektropletteringen, og aluminiumoxydfilmen frem-bringer stby, samtidig med at der dannes tallrike bobler. Når så strbmtilfbrselen avstenges og arbeidsstykket tas ut, finnes alu- j iiiiniumoxydfilmen å vn.-re dekket med uregelmessige, eruptive granu-| -ler. Produktet er således verdllbst som handelsvare, og det mang Uer dielektrisk styrke og resistens overfor alkalier, foruten at harpiksmalingen er lost bundet til overflaten. Når harpiksfilmen fjernes, vLser det seg at aluminiumoxydfilmen er bdelagt av sprekker. Det har derfor ikkeVisrt praktisk mulig å fremstille anodisk in this case, the water-soluble resin is dipped into the reading, the electrolyte for the aluminum is diluted into the resin recording. For reasons that have not yet been clarified, a special compound is thereby formed in the resin solution. When this resin is deposited electrolytically from the resin solution, no current drop occurs during the electroplating, and the aluminum oxide film produces dust, at the same time as numerous bubbles are formed. When the power supply is turned off and the workpiece is removed, the aluminum oxide film is found to be covered with irregular, eruptive granules. - laughs. The product is thus valuable as a commercial product, and it has a lot of dielectric strength and resistance to alkalis, apart from the fact that the resin paint is loosely bound to the surface. When the resin film is removed, it turns out that the aluminum oxide film is damaged by cracks. It has therefore not been practically possible to manufacture anodic
i oxyderte gjenstander med tilstrekkelig korrosjonsfasthet og dielektrisk styrke ved elektrolytisk .avsetning av vannopplbselig harpiks på aluminiumoxydfilmer fremstilt ved anodisk oxydasjon. j Disse mangler avhjelpes nu ved hjelp av den foreliggende oppfinnelse. in oxidized objects with sufficient corrosion resistance and dielectric strength by electrolytic deposition of water-soluble resin on aluminum oxide films produced by anodic oxidation. j These deficiencies are now remedied by means of the present invention.
Ved hjelp av oppfinnelsen tilveiebringes der således en fren-gangsmåte ved elektrolytisk avsetning av vannopplbselig harpiksmaling på en film av anodisk oxydert aluminium, hvilken fremgange - måte utmerker seg ved at en vannopplbselig harpiksmaling behandle s med en basisk anionutvekslerharpiks eller forst behandles med en basisk anionutvekslerharpiks og deretter med en sur kationut-■vekslerharp.iks, et anodisk oxydert aluminiumlegeme dyppes ned i den således forbehandlede vannopplbselige harpiksmaling, og harpiksen avsettes elektrolytisk på aluminiumlegenet. With the help of the invention, there is thus provided a process by electrolytic deposition of water-soluble resin paint on a film of anodically oxidized aluminum, which process is distinguished by the fact that a water-soluble resin paint is treated with a basic anion exchange resin or first treated with a basic anion exchange resin and then with an acidic cation exchange resin, an anodically oxidized aluminum body is dipped into the thus pretreated water-soluble resin paint, and the resin is electrolytically deposited on the aluminum body.
Herved oppnåes det, at der dannes en jevn og gjennomsiktig j harpiksfilm ved elektropletteringen,3lik at der iVieo ferdige produkter med god korronjonsfnsthet og utmerket elektrisk isola-sjonsevne. In this way, it is achieved that a uniform and transparent j resin film is formed during the electroplating,3 similar to that in Vieo finished products with good corrosion resistance and excellent electrical insulation.
De vannopplonel j ge r-iirp iksmfil Inger som anvendes ved fremgangsmåten ifblge oppfinnelsen, er nv kjente typer og er fortrinnsvis ucryliske harpikser somi er gjor+- vannopplbselige med ammoniakk, j aminer eller lignende. The water-soluble resins used in the method according to the invention are currently known types and are preferably ucrylic resins which are made water-soluble with ammonia, amines or the like.
Basiske anionutvetr;--! erharni kser som knn anvendes ved frem- i gnngsmåten ifolge oppfinnelsen, innbefatter ds av styrentypen, i polyvinylpyridintypen, ffrjioltypen og av typen alifatisk amin, med jet hvilket som helst av <lo fblgcnde ulvekslbare radikaler: Basic anion scavengers;--! Compounds that can be used in the process according to the invention include those of the styrene type, of the polyvinylpyridine type, of the fluorocarbon type and of the aliphatic amine type, with any of the following non-exchangeable radicals:
Sure kationutvekslerharpjksnr som kan anvendes ved fremgangsmåten ifblge oppfinnelsen, innbefatter de av styrentypen, fenol-' Acidic cation exchange resins which can be used in the method according to the invention include those of the styrene type, phenolic
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typen, methylensulfonsyretypen, i cryltypen og fosfonsyretypen med et av radikalene -SO^J og -COCM3om utvekslbart radikal. type, the methylene sulfonic acid type, in the cryl type and the phosphonic acid type with one of the radicals -SO^J and -COCM3 as an exchangeable radical.
Egnede basiske anionutvekslerharpikser som kan anvendes ved fremgangsmåten ifblge oppfinnelsen, er både de av den sterkt basiske type og de av den svakt basiske type. Suitable basic anion exchange resins which can be used in the method according to the invention are both those of the strongly basic type and those of the weakly basic type.
Slike basiske anic.-iittveku Lerharpikser regenereres med ifeOH og anvendes som en harpiks -..v typen fl-OH ved behandlingen rv uen • vannopplbselige harpiksna 1 i n.=c. hlAr el c-ktropletteringen stopper opp som folge av opphopning uv ammoniakk, aminer eller andre ; vannopplbseliggjbrende ;.:IJler for den vannopplbselige harpiks, Such basic anic.-iittveku Clay resins are regenerated with ifeOH and used as a resin -..v type fl-OH in the treatment rv uen • water-soluble resins na 1 in n.=c. hlAr el c-ctroplating stops as a result of accumulation of ammonia, amines or others; water-soluble ;.:IJler for the water-soluble resin,
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i behandles anionutvekslerh^rf iksen med en sur kationutvekslemor-i i piks av typen R-H. j 1 i i Oppfinnelsen illustreres ytterligere i de fblgende eksempler. i i ' Eksempel 1^in the anion exchange h^rf the ice is treated with an acidic cation exchange mother-i in piks of the type R-H. j 1 i i The invention is further illustrated in the following examples. i i ' Example 1^
"SA-10A" (hondels.-ff".iet u\ en sterkt basisk anionutveksl er-i i harpiks) regenereres i-isd iiaOH på vanlig i.vite til typen R-OH, og j j en opplbsning av vannopplbselig syntetisk harpiks med et narpiks.- "SA-10A" (hondels.-ff.iet u\ a strongly basic anion exchange er-i i i i resin) is regenerated i-is iiaOH in ordinary i.vite to the type R-OH, and is a solution of water-soluble synthetic resin with a narc.-
innhold på 15 1°ledes gjennom ioneutvekslérharpiksen ved SV = 30 (SV = 1 betyr at en behandlingsopplbsning av samme mengde som harpikssoylen ledes gjennom /denne i lopet av en time). content of 15 1° is passed through the ion exchange resin at SV = 30 (SV = 1 means that a treatment solution of the same amount as the resin soil is passed through / this in the course of one hour).
En avfettet og vasket aluminiumplate elektrolyseres i en elektrolytt bestående av en 15 #'ig svovelsyreopplbsning ved anvendelse av en strømtetthet på 1,5 A/dm 2 i 30 minutter, hvorved der ved anodisk oxydasjon dannes en film av aluminiumoxyd på aluminiumplaten. A degreased and washed aluminum plate is electrolysed in an electrolyte consisting of a 15% sulfuric acid solution using a current density of 1.5 A/dm 2 for 30 minutes, whereby a film of aluminum oxide is formed on the aluminum plate by anodic oxidation.
Platen dyppes deretter ned i en 15 #'ig opplbshing av den vannopplbselige harpiks som på forhånd er behandlet med ioneutvekslérharpiksen som ovenfor beskrevet, og platen forbindes med The plate is then dipped into a 15 # solution of the water-soluble resin that has been previously treated with the ion exchange resin as described above, and the plate is connected with
en likespenningskildes anode. Katoden forbindes med en uopplbsel.g metallplate, og aluminiumplaten elektropletteres ved anvendelse av en spenning i området fra 50 til 100 volt og en strbmtetthet på 200/mA/dm i 60 sekunder. Platen tas ut av harpiksopplbsningei, vaskes' med vann for å fjerne overskuddet av avsatt harpiks og tbrres ved 150°C i 30 minutter. the anode of a DC voltage source. The cathode is connected to an inert metal plate, and the aluminum plate is electroplated using a voltage in the range of 50 to 100 volts and a current density of 200/mA/dm for 60 seconds. The plate is taken out of the resin solution, washed with water to remove the excess of deposited resin and dried at 150°C for 30 minutes.
Den ovenfor beskrevne fremgangsmåte har alltid vist seg å g:. ferdige produkter som er glatte, oppviser stor korrosjonsfasthet og har et godt vedheftende belegg og et behagelig utseende. The method described above has always been shown to g:. finished products that are smooth, exhibit high corrosion resistance and have a well-adherent coating and a pleasing appearance.
Eksempel 2Example 2
På samme måte som i eksempel 1 behandles en vannopplbselig 'acrylisk harpiks med "SA-10A". Den ledes deretter ved SV = 60 igjennom en harpikssbyle av "CS-101" (handelsnavnet på en svakt sur kationutvekslerharpiks) som vaskes med ammoniakk eller emine : enten alene eller i blanding med et alkoholisk opplbsningsmiddel,<:>deretter vaskes med vann og til slutt regenereres på kjent måte I med HC1 til typen R-H.. In the same way as in example 1, a water-soluble acrylic resin is treated with "SA-10A". It is then passed at SV = 60 through a resin bath of "CS-101" (the trade name of a weakly acidic cation exchange resin) which is washed with ammonia or amine: either alone or in admixture with an alcoholic solvent,<:>then washed with water and until finally, I is regenerated in a known manner with HC1 to the type R-H..
Elektrolytisk avsetning av således forbehandlet harpiks fra en opplbsning derav på anodisk oxydert aluminium fremstilt på Electrolytic deposition of thus pretreated resin from a solution thereof on anodically oxidized aluminum produced on
iden i eksempel 1 beskrevne måte, ga alltid produkter med jevn fi .m-tykkelse, god korrosjonsfasthet og adhesjon og et behagelig utseende. in the manner described in example 1, always produced products with uniform fi.m thickness, good corrosion resistance and adhesion and a pleasant appearance.
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Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP694866 | 1966-02-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO116350B true NO116350B (en) | 1969-03-10 |
Family
ID=11652439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO16558766A NO116350B (en) | 1966-02-08 | 1966-11-15 |
Country Status (3)
| Country | Link |
|---|---|
| CH (1) | CH472507A (en) |
| FR (1) | FR1504209A (en) |
| NO (1) | NO116350B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4965946A (en) * | 1972-10-28 | 1974-06-26 | ||
| DE3618157A1 (en) * | 1986-05-30 | 1987-12-03 | Basf Lacke & Farben | AQUEOUS ELECTRO-DIP PAINT BATH FOR CATHODIC ELECTRO-DIP PAINT AND METHOD FOR THEIR PRODUCTION |
-
1966
- 1966-11-15 NO NO16558766A patent/NO116350B/no unknown
- 1966-11-25 CH CH1692266A patent/CH472507A/en not_active IP Right Cessation
- 1966-12-08 FR FR86730A patent/FR1504209A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR1504209A (en) | 1967-12-01 |
| CH472507A (en) | 1969-05-15 |
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