JP2909517B2 - Method for cleaning after passivation of phosphate layer - Google Patents
Method for cleaning after passivation of phosphate layerInfo
- Publication number
- JP2909517B2 JP2909517B2 JP2179367A JP17936790A JP2909517B2 JP 2909517 B2 JP2909517 B2 JP 2909517B2 JP 2179367 A JP2179367 A JP 2179367A JP 17936790 A JP17936790 A JP 17936790A JP 2909517 B2 JP2909517 B2 JP 2909517B2
- Authority
- JP
- Japan
- Prior art keywords
- passivation
- washed
- metal
- aqueous solution
- post
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/20—Pretreatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- External Artificial Organs (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Materials For Medical Uses (AREA)
- Solid Thermionic Cathode (AREA)
- Detergent Compositions (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Saccharide Compounds (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は金属、特に鋼、亜鉛めっき鋼、亜鉛合金めっ
き鋼及びアルミニウムの上のリン酸塩層を塗料又は接着
剤の塗布前に無クロム水溶液で不動態化後洗浄する方法
に関する。The present invention relates to a method for coating phosphate layers on metals, in particular steel, galvanized steel, galvanized steel and aluminum, before the application of paints or adhesives. A method for cleaning after passivation with an aqueous solution.
リン酸塩化工程は金属表面を後の塗料塗布に対して改
善するために工業的に大規模に行われる。これにより得
られたリン酸塩層は特に塗膜の金属への接着を向上し、
耐食性を増大し、塗膜の損傷部分から始まる塗膜下への
腐食の侵入が阻止される。リン酸塩層の保護特性は水性
不動態化後洗浄を行うことにより一層向上する。The phosphating process is performed on an industrial scale on a large scale to improve the metal surface against subsequent paint application. The resulting phosphate layer improves the adhesion of the coating, especially to metal,
Increases corrosion resistance and prevents penetration of corrosion beneath the coating starting from the damaged portion of the coating. The protective properties of the phosphate layer are further improved by washing after aqueous passivation.
望ましい利用技術的特性は６価及び／又は３価クロム
系不動態化後洗浄剤により得られる。しかし、３価クロ
ム化合物及び特に６価クロム化合物の毒性が欠点であ
る。Desirable technical properties are obtained with hexavalent and / or trivalent chromium-based post-passivating detergents. However, the toxicity of trivalent chromium compounds and especially hexavalent chromium compounds is a disadvantage.
US−Ａ−4376000にはポリビニルフェノール系の無ク
ロム後洗浄剤が開示されているが、この後洗浄剤は比較
的高い濃度で使用しなければならないので、特に分解の
ために多量の酸素を必要とするために、望ましくない汚
水が発生する。US-A-4376000 discloses a polyvinylphenol-based chromium-free post-cleaning agent, but since the post-cleaning agent must be used at a relatively high concentration, it requires a large amount of oxygen particularly for decomposition. As a result, undesirable sewage is generated.
US−Ａ−3695942には転化層の後処理に可溶性ジルコ
ニウム化合物を使用することが開示されている。この後
洗浄剤はジルコニウムの外にカチオンとしてアルカリと
アンモニウムを含有している。特にアルカリ土類金属カ
チオンが存在しないように用心されている。この後洗浄
剤はpH値が３〜8.5であるが、クロム含有後洗浄剤の品
質水準には達していない。US-A-3695942 discloses the use of a soluble zirconium compound for post-treatment of a conversion layer. After this, the detergent contains alkali and ammonium as cations in addition to zirconium. In particular, care is taken to avoid the presence of alkaline earth metal cations. Although the pH of this post-washing agent is between 3 and 8.5, it does not reach the quality level of chromium-containing post-washing agents.
US−Ａ−3895970はリン酸塩化のための、簡単な又は
複雑なフッ化物を主成分とした酸性の水性後処理剤を開
示し、ジルコニウム化合物の群からフッ化ジルコニウム
クロムとフッ化ジルコニウムを挙げている。フッ化ジル
コニウムクロム以外はこの特許明細書に挙げられた生成
物は中程度の要件を満たすに過ぎない。フッ化ジルコニ
ウムクロムは前記の毒性の欠点を有する。U.S. Pat. No. 3,895,970 discloses a simple or complex fluoride-based acidic aqueous post-treatment agent for phosphorylation, citing zirconium chromium fluoride and zirconium fluoride from the group of zirconium compounds. ing. With the exception of zirconium chromium fluoride, the products mentioned in this patent only fulfill moderate requirements. Zirconium chromium fluoride has the aforementioned toxicity disadvantages.
本発明の課題は金属上のリン酸塩層を塗料又は接着剤
の塗布前に不動態化後洗浄する方法であって、公知の方
法の欠点をもたず、高い耐食性と塗料又は接着剤の極め
て良好な接着性の点で傑出し、環境を全く又はほとんど
汚染しないようにした方法を提供することである。The object of the present invention is a method for cleaning the phosphate layer on the metal after passivation before applying the paint or adhesive, without the disadvantages of the known methods, with a high corrosion resistance and a low paint or adhesive strength. The object is to provide a method which is outstanding in terms of very good adhesion and which does not pollute the environment at all.
本発明の課題は冒頭に述べた種類の方法において、A
l:Zr:Fがモル比で（0.15〜0.67）:1:（５〜７）である
フルオロジルコニウム酸アルミニウムを含有し、Al＋Zr
＋Ｆの合計濃度が0.1〜2.0g/であり、pH値が３〜５に
調整された水溶液でリン酸塩化金属表面を洗浄すること
により達成される。The object of the present invention is to provide a method of the type mentioned at the beginning
l: Zr: F contains aluminum fluorozirconate in a molar ratio of (0.15 to 0.67): 1: (5 to 7), and Al + Zr
This is achieved by washing the metal phosphated surface with an aqueous solution having a total concentration of + F of 0.1 to 2.0 g / and a pH value adjusted to 3 to 5.
本発明の好適態様によれば、Al＋Zr＋Ｆの合計濃度が
0.2〜0.8g/である水溶液でリン酸塩塩化金属表面を洗
浄する。According to a preferred embodiment of the present invention, the total concentration of Al + Zr + F is
Wash the phosphate metal chloride surface with an aqueous solution that is 0.2-0.8 g /.
本発明の方法は金属、特に鋼、亜鉛めっき鋼、亜鉛合
金めっき鋼、アルミニウムめっき鋼、亜鉛、亜鉛合金、
アルミニウム及びアルミニウム合金の上のすべてのリン
酸塩層に適している。これについて特にリン酸亜鉛、リ
ン酸鉄、リン酸マンガン、リン酸カルシウム、リン酸マ
グネシウム、リン酸ニッケル、リン酸コバルト、リン酸
鉄亜鉛、リン酸マンガン亜鉛、リン酸カルシウム亜鉛及
びその他、２種又はそれ以上の二価カチオンを有する層
が挙げられる。本発明の方法はMn、Ni、Co及びMgといっ
たカチオンをさらに加え又は加えないで低亜鉛リン酸塩
化工程で生成したリン酸塩層に特に適している。The method of the present invention may be applied to metals, particularly steel, galvanized steel, zinc alloy-plated steel, aluminized steel, zinc, zinc alloy,
Suitable for all phosphate layers on aluminum and aluminum alloys. In particular, zinc phosphate, iron phosphate, manganese phosphate, calcium phosphate, magnesium phosphate, nickel phosphate, cobalt phosphate, zinc iron phosphate, zinc manganese phosphate, zinc zinc calcium phosphate and other two or more types Examples include a layer having a divalent cation. The method of the present invention is particularly suitable for phosphate layers formed in a low zinc phosphatization step with or without additional cations such as Mn, Ni, Co and Mg.
リン酸塩化後、金属表面は例えば浸漬、噴霧、カーテ
ンフロー又はロールにより本発明の方法に従って後処理
される前に水で洗浄するのが好ましい。After phosphatization, the metal surface is preferably washed with water before being post-treated according to the method of the invention, for example by dipping, spraying, curtain flow or rolls.
本発明の方法において使用される後洗浄剤は化学的に
は弱酸性のフルオロジルコニウム酸アルミニウムに分類
される。その製造は例えば、まず金属ジルコニウム又は
炭酸ジルコニウムを水に溶解させてフルオロジルコン酸
錯体を生成させるようにして行われる。次いで金属アル
ミニウム又は水酸化アルミニウムを加え、溶解させる。
この方法が好適ではあるが、別の方法でも洗浄剤を製造
することができる。The post-cleaning agents used in the method of the present invention are chemically classified as weakly acidic aluminum fluorozirconates. The production is performed, for example, by first dissolving metal zirconium or zirconium carbonate in water to form a fluorozirconate complex. Next, aluminum metal or aluminum hydroxide is added and dissolved.
Although this method is preferred, the cleaning agent can be produced by another method.
本発明の別の好適態様によれば、リン酸塩化金属表面
は安息香酸イオン、カプリル酸イオン、エチルヘキサン
酸イオン及びサリチル酸イオンの各アニオンの少なくと
も１種を0.05〜0.5g/の合計濃度でさらに含有する水
溶液で洗浄される。アニオンは相当する酸又は塩として
添加することができる。According to another preferred embodiment of the present invention, the metal phosphated surface further comprises at least one of each anion of benzoate ion, caprylate ion, ethylhexanoate ion and salicylate ion at a total concentration of 0.05 to 0.5 g /. It is washed with the contained aqueous solution. Anions can be added as the corresponding acid or salt.
後洗浄剤のpH値の調整は揮発性塩基のカチオンによっ
て調整するのが好ましい。このためには特にアンモニウ
ム、エタノールアンモニウム、ジエタノールアンモニウ
ム及びトリエタノールアンモニウムが挙げられる。The pH value of the post-cleaning agent is preferably adjusted by the cation of a volatile base. This includes in particular ammonium, ethanolammonium, diethanolammonium and triethanolammonium.
リン酸塩化金属表面への不動態化後洗浄剤の付与は浸
漬、カーテンフロー、噴霧及び例えばロールによる湿潤
によって行うことができる。処理時間は約１秒間〜２分
間である。処理温度は室温から約80℃までとすることが
でき、20℃と50℃の間の温度が通常は好ましい。後洗浄
浴の調整には完全脱塩水又は低塩水が好ましく用いられ
る。塩含有量の高い水は後洗浄浴の調整には好ましくな
い。Application of the post-passivating detergent to the metal phosphatized surface can be effected by dipping, curtain flow, spraying and wetting, for example by rolls. The processing time is about 1 second to 2 minutes. Processing temperatures can be from room temperature to about 80 ° C, with temperatures between 20 ° C and 50 ° C being usually preferred. For adjusting the post-wash bath, completely demineralized water or low-brine water is preferably used. Water with a high salt content is not preferred for adjusting the post-wash bath.
本発明の別の好適態様によれば、リン酸塩化金属表面
は完全脱塩水で最終洗浄される。According to another preferred embodiment of the invention, the metal phosphated surface is finally washed with completely demineralized water.
本発明の方法は塗料又は接着剤の塗布前にリン酸塩化
金属表面に調整するために用いられる。この方法により
金属基材上への有機被膜の接着が向上し、腐食応力下で
のブリスター形成に対する有機被膜の抵抗性が改善さ
れ、被膜の損傷部分から始まる腐食の侵入が阻止され
る。本発明の方法は陰極電着塗料、粉体塗料、低溶剤ハ
イソリッドラッカー及び水を主溶剤としたラッカーと組
合わせると特に有利である。The method of the present invention is used to condition a metal phosphated surface prior to application of a paint or adhesive. This method improves the adhesion of the organic coating on the metal substrate, improves the resistance of the organic coating to blister formation under corrosive stress, and prevents the ingress of corrosion starting from damaged portions of the coating. The process according to the invention is particularly advantageous in combination with cathodic electrodeposition coatings, powder coatings, low-solvent high-solid lacquers and lacquers based on water.
本発明の方法を以下の実施例について例示的に詳細に
説明する。The method of the present invention is described in detail by way of example with reference to the following examples.
鋼、電気亜鉛めっき鋼及びAlMgSiからそれぞれつくっ
た脱脂シートをマンガン変性低亜鉛リン酸塩化法により
55℃で２分間噴霧した。リン酸塩化溶液の組成は次の通
りであった。Degreased sheet made from steel, electrogalvanized steel and AlMgSi by manganese-modified low zinc phosphate method
Sprayed at 55 ° C for 2 minutes. The composition of the phosphatization solution was as follows.
Zn 0.7 g/ Fe III 0.04g/ Mn 1.0 g/ P2O5 13g/ Ni 1.0 g/ No3 2.1g/ Na 2.9 g/ Ｆ 0.3g/ NH4 0.15g/ NO2 0.07g/ ３種の金属基材上に微結晶性で均一に被覆した2.5〜3
g/m2のリン酸塩層が形成された。次いで各シートを水で
洗浄した後、不動態化後洗浄を行った。不動態化後洗浄
は30℃で１分間の処理時間で噴霧により行った。最終処
理として完全脱塩水による洗浄を行った。各シートの塗
装のために陰極電着下塗り、充填剤及び上塗りを用い
た。各塗膜は別々に焼付けした。塗膜の合計厚さは約90
μｍであった。Zn 0.7 g / Fe III 0.04 g / Mn 1.0 g / P 2 O 5 13 g / Ni 1.0 g / No 3 2.1 g / Na 2.9 g / F 0.3 g / NH 4 0.15 g / NO 2 0.07 g / Three metals 2.5 to 3 microcrystalline and uniformly coated on the substrate
A phosphate layer of g / m 2 was formed. Next, each sheet was washed with water, and then washed after passivation. Post-passivation washing was performed by spraying at 30 ° C. for a treatment time of 1 minute. Washing with complete demineralized water was performed as a final treatment. Cathodic electrodeposition undercoat, filler and overcoat were used for coating each sheet. Each coating was baked separately. The total thickness of the coating is about 90
μm.
次いで各シートを鋼針により金属基材に達するまで引
掻き、各種の試験を行った。結果は第１表〜第３表にま
とめて示されている。Then, each sheet was scratched with a steel needle until it reached the metal substrate, and various tests were performed. The results are summarized in Tables 1 to 3.
本発明の方法で用いる後洗浄剤はAl0.855％＋Zr8.62
％＋F10.7％の水性濃厚液を完全脱塩水により希釈して
製造した。次いでpH値をアンモニウムで3.5〜4.0に調整
した。得られた後洗浄剤の組成は次の通りであった:Al
0.014g/＋Zr0.14g/＋F0.17g/＋NH30.026g/。The post-cleaning agent used in the method of the present invention is Al 0.855% + Zr 8.62
% + F10.7% aqueous concentrate was diluted with completely demineralized water. The pH value was then adjusted to 3.5-4.0 with ammonium. The composition of the resulting detergent was as follows: Al
0.014 g / + Zr 0.14 g / + F 0.17 g / + NH 3 0.026 g /.
比較試験のために次の溶液を用いた。 The following solutions were used for comparative testing.
Cr30.2g/＋Cr III0.037g/を含有したCr VI−Cr I
II含有後処理溶液（pH値3.5〜4.0） Cr III0.047g/、Zr0.083g/及びF0.121g/を含有
したフルオロジルコン酸クロム溶液（pH値3.5〜4.0）及
び 濃度0.68g/のポリビニルフェノール溶液（pH値3.5
〜4.0） 各シート試験片の試験はDIN50021SS（1008時間）によ
る塩水噴霧試験、ASTMD2803（1008時間）及び20サイク
ルのゼネラル・モータース試験法TM54−26（GM−Scad−
Test）により行った。塗膜下への侵入をmm単位で測定し
た。Cr VI-Cr I containing Cr 3 0.2g / + Cr III 0.037g /
II-containing post-treatment solution (pH 3.5-4.0) Chromium fluorozirconate solution (pH 3.5-4.0) containing Cr 0.047g /, Zr 0.083g / and F0.121g / and polyvinyl phenol with a concentration of 0.68g / Solution (pH 3.5
4.04.0) The test of each sheet test piece is performed by salt spray test according to DIN50021SS (1008 hours), ASTM D2803 (1008 hours) and 20 cycles of General Motors test method TM54-26 (GM-Scad-
Test). The penetration under the coating was measured in mm.
表中の値を比較するとわかるとおり、本発明の方法は
いずれの場合も３種の同時に試験を行った比較例の最高
値と少なくとも同程度に良好な値を示した。 As can be seen from the comparison of the values in the table, the method of the present invention showed at least as good a value as the highest value of the comparative examples in which three kinds of tests were conducted simultaneously in each case.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 ゲルハルト・ミューラー ドイツ連邦共和国6450ハナウ・アム・マ イン・ホップフェンシュトラーセ29 (72)発明者 ホルスト・ゲヒメカー ドイツ連邦共和国6080グロース‐ゲラウ ２ ネッカーリング47 (72)発明者 バーナー・ラウシュ ドイツ連邦共和国6370オバーウルセル６ ウルセマーシュトラーセ43 (58)調査した分野(Int.Cl.6，ＤＢ名) C23C 22/00 - 22/86 B05D 3/10,7/14 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Gerhard Müller Germany 6450 Hanau am Main Hopfenstrasse 29 (72) Inventor Horst Geheimeker Germany 6080 Gross-Gerau 2 Neckarling 47 ( 72) Inventor Berner Rausch Germany 6370 Oberursel 6 Urse Marstrasse 43 (58) Field studied (Int. Cl. 6 , DB name) C23C 22/00-22/86 B05D 3/10, 7/14
Claims (9)
アルミニウムから成る群から選ばれた金属の上のリン酸
塩層を塗料又は接着剤の塗布前に無クロム水溶液で不動
態化後洗浄する方法において、 Al:Zr:Fがモル比で（0.15〜0.67）:1:（５〜７）である
フルオロジルコニウム酸アルミニウムを含有し、Al＋Zr
＋Ｆの合計濃度が0.1〜2.0g/であり、pH値が３〜５に
調整された水溶液でリン酸塩化金属表面を洗浄すること
を特徴とするリン酸塩層を不動態化後洗浄する方法。1. The method of claim 1, wherein the phosphate layer on the metal selected from the group consisting of steel, galvanized steel, galvanized steel and aluminum is passivated and washed with a chromium-free aqueous solution prior to the application of the paint or adhesive. Al: Zr: F containing aluminum fluorozirconate in a molar ratio of (0.15-0.67): 1: (5-7), wherein Al + Zr
A method for cleaning a phosphate layer after passivation, wherein the surface of the metal phosphate is washed with an aqueous solution having a total concentration of + F of 0.1 to 2.0 g / and a pH value adjusted to 3 to 5. .
る水溶液でリン酸塩化金属表面を洗浄することを特徴と
する請求項１の方法。2. The method according to claim 1, wherein the metal phosphated surface is washed with an aqueous solution having a total concentration of Al + Zr + F of 0.2 to 0.8 g /.
ルヘキサン酸イオン及びサリチル酸イオンの各アニオン
の少なくとも１種を0.05〜0.5g/の合計濃度でさらに
含有する水溶液でリン酸塩化金属表面を洗浄する請求項
１又は２の方法。3. The metal phosphated surface is washed with an aqueous solution further containing at least one of anions of benzoate ion, caprylate ion, ethylhexanoate ion and salicylate ion at a total concentration of 0.05 to 0.5 g /. 3. The method of claim 1 or claim 2.
ウム、ジエタノールアンモニウム及びトリエタノールア
ンモニウムから成る群から選ばれた揮発性塩基のカチオ
ンによって調整されている水溶液でリン酸塩化金属表面
を洗浄する請求項１〜３のいずれかの方法。4. The metal phosphate surface is washed with an aqueous solution whose pH value is adjusted by the cation of a volatile base selected from the group consisting of ammonium, ethanolammonium, diethanolammonium and triethanolammonium. Any of the three methods.
浄を行う請求項１〜４のいずれかの方法。5. The method according to claim 1, wherein a post-passivation wash is followed by a final wash with completely demineralized water.
する請求項１〜５のいずれかの方法。6. The method according to claim 1, wherein a cathodic electrodeposition coating is applied after the post-passivation washing.
請求項１〜５のいずれかの方法。7. The method according to claim 1, wherein the powder coating is applied after cleaning after passivation.
ラッカーを塗布する請求項１〜５のいずれかの方法。8. The method according to claim 1, wherein a low solvent high solid lacquer is applied after the post-passivation cleaning.
ッカーを塗布する請求項１〜５のいずれかの方法。9. The method according to claim 1, wherein a lacquer containing water as a main solvent is applied after washing after passivation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3924984.0 | 1989-07-28 | ||
| DE3924984A DE3924984A1 (en) | 1989-07-28 | 1989-07-28 | METHOD FOR PASSIVATING RINSING OF PHOSPHATE LAYERS |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0361385A JPH0361385A (en) | 1991-03-18 |
| JP2909517B2 true JP2909517B2 (en) | 1999-06-23 |
Family
ID=6386020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2179367A Expired - Fee Related JP2909517B2 (en) | 1989-07-28 | 1990-07-06 | Method for cleaning after passivation of phosphate layer |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0410497B1 (en) |
| JP (1) | JP2909517B2 (en) |
| AT (1) | ATE81533T1 (en) |
| BR (1) | BR9003594A (en) |
| CA (1) | CA2018631C (en) |
| DD (1) | DD298436A5 (en) |
| DE (2) | DE3924984A1 (en) |
| ES (1) | ES2035699T3 (en) |
| PL (1) | PL164742B1 (en) |
| PT (1) | PT94843B (en) |
| ZA (1) | ZA905922B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4017187A1 (en) * | 1990-05-29 | 1991-12-05 | Metallgesellschaft Ag | METHOD FOR REFILLING CONVERSION LAYERS |
| DE4017186A1 (en) * | 1990-05-29 | 1991-12-05 | Metallgesellschaft Ag | GENERATION OF CONVERSION OVERHEADS ON ZINC OR ZINC ALLOY SURFACES |
| US5209788A (en) * | 1990-11-21 | 1993-05-11 | Ppg Industries, Inc. | Non-chrome final rinse for phosphated metal |
| DE19511573A1 (en) * | 1995-03-29 | 1996-10-02 | Henkel Kgaa | Process for phosphating with metal-containing rinsing |
| DE19834796A1 (en) | 1998-08-01 | 2000-02-03 | Henkel Kgaa | Process for phosphating, rinsing and cathodic electrocoating |
| DE19854091C2 (en) * | 1998-11-24 | 2002-07-18 | Audi Ag | Process for the pre-treatment of bodies before painting |
| DE10010355A1 (en) * | 2000-03-07 | 2001-09-13 | Chemetall Gmbh | Applying phosphate coatings to metallic surfaces comprises wetting with an aqueous acidic phosphatizing solution containing zinc ions, manganese ions and phosphate ions, and drying the solution |
| KR20020051991A (en) * | 2000-12-23 | 2002-07-02 | 이구택 | Method of producing corrosion- resistance steel sheet coated with zirconium and silane coupling agent |
| WO2002066702A1 (en) | 2001-02-16 | 2002-08-29 | Henkel Kommanditgesellschaft Auf Atkien | Process for treating multi-metal articles |
| EP2405031A1 (en) * | 2010-07-07 | 2012-01-11 | Mattthias Koch | Method for coating shaped bodies and coated shaped body |
| CN103097583B (en) * | 2010-09-15 | 2015-11-25 | 杰富意钢铁株式会社 | Steel plate for container and manufacture method thereof |
| US10435806B2 (en) | 2015-10-12 | 2019-10-08 | Prc-Desoto International, Inc. | Methods for electrolytically depositing pretreatment compositions |
| DE102016206417A1 (en) | 2016-04-15 | 2017-10-19 | Henkel Ag & Co. Kgaa | PROMOTION TREATMENT FOR SUPPRESSING PLANT-ORIENTED PHOSPHATOR TRANSPORT IN A PROCESS FOR DIVING LACQUER |
| DE102016206418A1 (en) * | 2016-04-15 | 2017-10-19 | Henkel Ag & Co. Kgaa | SUPPRESSION OF PLANT-SPECIFIC PHOSPHATE EXTRACTION IN A PROCESS FOR DIPPING LACQUER |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3695942A (en) * | 1970-12-02 | 1972-10-03 | Amchem Prod | Zirconium rinse for phosphate coated metal surfaces |
| US3966502A (en) * | 1972-08-17 | 1976-06-29 | Amchem Products, Inc. | Zirconium rinse for phosphate coated metal surfaces |
| US3852123A (en) * | 1972-11-20 | 1974-12-03 | Pennwalt Corp | Sealing rinses for phosphate coatings on metal |
| US3895970A (en) * | 1973-06-11 | 1975-07-22 | Pennwalt Corp | Sealing rinse for phosphate coatings of metal |
| US4496404A (en) * | 1984-05-18 | 1985-01-29 | Parker Chemical Company | Composition and process for treatment of ferrous substrates |
| US4650526A (en) * | 1986-03-18 | 1987-03-17 | Man-Gill Chemical Company | Post treatment of phosphated metal surfaces by aluminum zirconium metallo-organic complexes |
-
1989
- 1989-07-28 DE DE3924984A patent/DE3924984A1/en not_active Withdrawn
-
1990
- 1990-06-08 CA CA002018631A patent/CA2018631C/en not_active Expired - Fee Related
- 1990-06-26 AT AT90201689T patent/ATE81533T1/en not_active IP Right Cessation
- 1990-06-26 ES ES199090201689T patent/ES2035699T3/en not_active Expired - Lifetime
- 1990-06-26 DE DE9090201689T patent/DE59000357D1/en not_active Expired - Lifetime
- 1990-06-26 EP EP90201689A patent/EP0410497B1/en not_active Expired - Lifetime
- 1990-07-06 JP JP2179367A patent/JP2909517B2/en not_active Expired - Fee Related
- 1990-07-23 DD DD90343003A patent/DD298436A5/en not_active IP Right Cessation
- 1990-07-25 BR BR909003594A patent/BR9003594A/en unknown
- 1990-07-27 ZA ZA905922A patent/ZA905922B/en unknown
- 1990-07-27 PL PL90286243A patent/PL164742B1/en not_active IP Right Cessation
- 1990-07-27 PT PT94843A patent/PT94843B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| PL164742B1 (en) | 1994-10-31 |
| BR9003594A (en) | 1991-08-27 |
| DD298436A5 (en) | 1992-02-20 |
| ZA905922B (en) | 1992-03-25 |
| DE3924984A1 (en) | 1991-01-31 |
| CA2018631A1 (en) | 1991-01-28 |
| PT94843B (en) | 1997-03-31 |
| ES2035699T3 (en) | 1993-04-16 |
| DE59000357D1 (en) | 1992-11-19 |
| CA2018631C (en) | 1999-05-11 |
| JPH0361385A (en) | 1991-03-18 |
| ATE81533T1 (en) | 1992-10-15 |
| PT94843A (en) | 1991-04-18 |
| PL286243A1 (en) | 1991-04-22 |
| EP0410497A1 (en) | 1991-01-30 |
| EP0410497B1 (en) | 1992-10-14 |
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