JPH0456782A - Black chromating solution for zn-ni alloy plating - Google Patents
Black chromating solution for zn-ni alloy platingInfo
- Publication number
- JPH0456782A JPH0456782A JP16526990A JP16526990A JPH0456782A JP H0456782 A JPH0456782 A JP H0456782A JP 16526990 A JP16526990 A JP 16526990A JP 16526990 A JP16526990 A JP 16526990A JP H0456782 A JPH0456782 A JP H0456782A
- Authority
- JP
- Japan
- Prior art keywords
- black
- alloy plating
- soln
- hexavalent chromium
- chromate
- 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.)
- Granted
Links
- 238000007747 plating Methods 0.000 title claims abstract description 23
- 238000004532 chromating Methods 0.000 title abstract description 5
- 229910000990 Ni alloy Inorganic materials 0.000 title description 8
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 38
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 28
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001384 succinic acid Substances 0.000 claims abstract description 14
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 9
- 229910007567 Zn-Ni Inorganic materials 0.000 claims abstract description 7
- 229910007614 Zn—Ni Inorganic materials 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 17
- 230000007797 corrosion Effects 0.000 abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 229910052759 nickel Inorganic materials 0.000 description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 11
- 239000011701 zinc Substances 0.000 description 11
- 229910052725 zinc Inorganic materials 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- 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 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 239000002253 acid Substances 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 235000019646 color tone Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C23C22/05—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
- C23C22/24—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 hexavalent chromium compounds
- C23C22/26—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 hexavalent chromium compounds containing also organic compounds
- C23C22/27—Acids
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、亜鉛・ニッケル合金めっき上に高耐食性黒色
クロメート皮膜を形成するのに用いるクロメート処理液
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a chromate treatment solution used to form a highly corrosion-resistant black chromate film on zinc-nickel alloy plating.
亜鉛めっきのクロメート処理は装飾と防食の目的で、自
動車・家電製品等各分野で使用されている。しかし、亜
鉛めっきを従来のクロメート処理液で処理した物は、厳
しい環境下、例えば、過熱状態にあるエンジンルーム内
、あるいは、凍結防止用融解塩が散布されている道路上
などでは耐食性が十分ではないという欠点がある。Chromate treatment of zinc plating is used for decorative and anti-corrosion purposes in various fields such as automobiles and home appliances. However, zinc plating treated with a conventional chromate treatment solution does not have sufficient corrosion resistance in harsh environments, such as in an overheated engine room or on roads where molten antifreeze salt is sprayed. There is a drawback that there is no
そこで、高耐食性を有するものとして、ニッケル析出率
５〜１５重量％の１ｎ−Ｎｉ合金めっきのクロメート処
理が注目されてきている。その中でも、自動車部品等の
凹凸形状のある物は処理部位によりニッケル析出率に分
布が生６しるため、ニッケル析出率５〜１０％のもので
ないとめっき後のクロメート化成の均一性が無いことが
わかった。そして、５〜１０％の処理物は無色、干渉色
、緑色（ブロンズ）の色調のものとして亜鉛めっきより
高耐食性の処理物として採用され始めている。Therefore, chromate treatment of 1n-Ni alloy plating with a nickel precipitation rate of 5 to 15% by weight has been attracting attention as a material having high corrosion resistance. Among these, for objects with uneven shapes such as automobile parts, the nickel precipitation rate varies depending on the treated area6, so unless the nickel precipitation rate is 5 to 10%, the chromate formation after plating will not be uniform. I understand. 5 to 10% of the treated product is colorless, has an interference color, or has a green (bronze) tone, and is beginning to be adopted as a treated product with higher corrosion resistance than zinc plating.
ところが、ニッケル析出率５〜ＩＱ％の処理物に亜鉛め
っき黒色クロメート処理液を適用して黒色化したものは
、耐食性が亜鉛めっきと同等で、期待された高耐食性は
得られないのが現状である。However, when a zinc plating black chromate treatment solution is applied to a treated product with a nickel precipitation rate of 5 to IQ% to make it black, the corrosion resistance is equivalent to that of zinc plating, and the expected high corrosion resistance cannot be obtained. be.
一方、近年の色調のモノトーン化、高級化の傾向により
黒色化処理物の使用範囲が拡大しつつあり、高耐食性の
黒色処理物は需要が増大している。On the other hand, the range of use of blackened products is expanding due to the recent trend toward monotone color tones and higher quality products, and the demand for highly corrosion-resistant blackened products is increasing.
そこで、ニッケル析出率を少なくして、黒色化する方法
や、ギ酸・クエン酸・酒石酸を用いる方法が開発されて
きた。しかしながら、前者は５〜１０％のニッケル析出
率では黒色化が不十分であり、後者は、処理液が化学的
に不安定で、液成分が分解してしまうため実用的ではな
いという問題がある。Therefore, methods have been developed to reduce the nickel precipitation rate and turn the material black, as well as methods using formic acid, citric acid, and tartaric acid. However, the former has the problem that blackening is insufficient at a nickel precipitation rate of 5 to 10%, and the latter is not practical because the treatment liquid is chemically unstable and the liquid components decompose. .
本発明は、実用的なニッケル析出率のＺｎ−Ｎｉ合金め
っきに高耐食性の黒色クロメート皮膜を形成できる処理
液を提供することを目的とする。An object of the present invention is to provide a treatment solution that can form a highly corrosion-resistant black chromate film on Zn-Ni alloy plating with a practical nickel precipitation rate.
二課題を解決するた必の手段〕
本発明は、Ｃｒ６−及び５０４’−、特にコハク酸とＡ
ｇ−を併用することによって、高耐食性黒色クロメート
化成皮膜を形成させることができ、かつその処理液が化
学的に安定であるという知見に基づいてなされたのであ
る。Necessary Means for Solving the Two Problems] The present invention provides a method for combining Cr6- and 504'-, especially succinic acid and A
This was done based on the knowledge that a highly corrosion-resistant black chromate conversion film can be formed by using g- in combination, and that the treatment solution is chemically stable.
すなわち、本発明は、六価クロムを１〜５０ｇ／ｌ、硫
酸根を１〜５０ｇ／β、溶解性銀を０．１〜０．５ｇ／
ｌ及びコハク酸を０．５〜６０ｇ／Ｒの濃度で含有し、
かつｐＨが０．５〜２．５の範囲にあるＺｎ−ＩＪｉ合
金めっき用高耐食性黒色クロメート処理液を提供する。That is, the present invention uses 1 to 50 g/l of hexavalent chromium, 1 to 50 g/β of sulfate, and 0.1 to 0.5 g/l of soluble silver.
1 and succinic acid at a concentration of 0.5 to 60 g/R,
The present invention provides a highly corrosion-resistant black chromate treatment solution for Zn-IJi alloy plating, which has a pH in the range of 0.5 to 2.5.
ここで六価クロム源となる化合物としては、クロム酸ま
たはその塩または重クロム酸塩の１種以上を用いること
ができ、硫酸根源としては、硫酸またはその塩（例えば
、ナ、トリウム、カリウム、アンモニウムなどの塩）を
１種以上用いることができ、溶解性銀源としては、硫酸
銀等の溶解性銀塩を用いることができる。Here, as the compound serving as the hexavalent chromium source, one or more of chromic acid, its salt, or dichromate can be used, and as the sulfuric acid source, sulfuric acid or its salt (for example, sodium, thorium, potassium, As the soluble silver source, soluble silver salts such as silver sulfate can be used.
本発明において六価クロムの量がＩｇ／β未満では連続
的に安定な黒色化ができず、一方、５０ｇ／βより多い
としみを生じ不経済になる。In the present invention, if the amount of hexavalent chromium is less than Ig/β, continuous and stable blackening cannot be achieved, whereas if it is more than 50 g/β, stains occur and become uneconomical.
本発明では硫酸根と六価クロムとの比率を任意とするこ
とができるが、硫酸根／六価クロムの重量比率を０．８
／ １〜２／１とするのがよい。つまり、０．８未満
では５〜１０％Ｎｌ物が着色しないという問題があり、
一方２より多いと黒色化しないという問題があるからで
ある。また、溶解性銀の濃度は０．１ｇ／ｆｌより少な
いと黒色化せず、０．５ｇ／βより多いと黒色化しても
耐食性が亜鉛めっきの黒色クロメートと同等になってし
まうからである。In the present invention, the ratio of sulfate radicals to hexavalent chromium can be set arbitrarily, but the weight ratio of sulfate radicals/hexavalent chromium is 0.8.
/1 to 2/1 is preferable. In other words, if it is less than 0.8, there is a problem that 5 to 10% Nl will not be colored.
On the other hand, if the number is more than 2, there is a problem that blackening does not occur. Further, if the concentration of soluble silver is less than 0.1 g/fl, blackening will not occur, and if it is more than 0.5 g/β, even if blackening occurs, the corrosion resistance will be equivalent to that of black chromate of zinc plating.
本発明では、硫酸根、六価クロム及び溶解性銀にコハク
酸を併用することを特徴とする。つまり、コハク酸以外
の他のジカルボン酸ではギ酸、クエン酸、酒石酸と同様
にクロム酸液中で化学的に不安定で、分解してしまうの
で実用性がないからである。コハク酸はクロム酸溶液中
で安定であり、これを用いることによりニッケル５〜１
０％のＺｎ−Ｎｉ合金めっきに目的の高耐食性黒色クロ
メートを形成させることができると共に、化学的に安定
な処理液を得ることができるのである。本発明でコハク
酸の量が０．５ｇ／ｊ２より少いと皮膜が薄く耐食性が
悪くなり、一方６０ｇ／ｆよりも多くなると溶解しにく
くなる。The present invention is characterized in that succinic acid is used in combination with sulfate, hexavalent chromium, and soluble silver. In other words, dicarboxylic acids other than succinic acid are chemically unstable and decompose in a chromic acid solution, similar to formic acid, citric acid, and tartaric acid, so they are not practical. Succinic acid is stable in chromic acid solution, and by using it, nickel 5 to 1
The desired highly corrosion-resistant black chromate can be formed on 0% Zn-Ni alloy plating, and a chemically stable treatment solution can be obtained. In the present invention, if the amount of succinic acid is less than 0.5 g/j2, the film will be thin and corrosion resistance will be poor, while if it is more than 60 g/f, it will be difficult to dissolve.
尚、コハク酸としては、酸自体に加えて、ナトリウム、
カリウムなどの塩も使用することができる。塩を使う場
合の添加量は酸に換算して行う。In addition to the acid itself, succinic acid contains sodium,
Salts such as potassium can also be used. When using salt, the amount to be added is calculated in terms of acid.
本発明で用いるクロメート化処理液のｐＨを０．５〜２
．５にすることも重要である。この範囲にｐＨを調整す
るためには水酸化アルカリ、硫酸、クロム酸を用いるの
がよい。The pH of the chromate treatment solution used in the present invention is 0.5 to 2.
．． It is also important to set it to 5. In order to adjust the pH within this range, it is preferable to use alkali hydroxide, sulfuric acid, or chromic acid.
本発明では、上記必須成分の残分は水であるが、メチル
アミン、エチレンジアミン、ジエチレントリアミン等の
アミン類などをさらに加えることができる。In the present invention, the remainder of the above essential components is water, but amines such as methylamine, ethylenediamine, diethylenetriamine, etc. can be further added.
本発明の処理液を用いて黒色クロメートを施す基体は、
Ｚｎ−Ｎｉ合金からなるもの又はＺｎ−Ｎｉ合金被膜を
有するものであり、このうちニッケル含有率が５〜１０
重量％のものに対して行うのが好ましい。The substrate to which black chromate is applied using the treatment solution of the present invention is:
It is made of Zn-Ni alloy or has a Zn-Ni alloy coating, of which the nickel content is 5 to 10.
Preferably, it is carried out on a weight percent basis.
クロメート化方法としては、本発明クロメート処理液に
合金めっき物を浸漬する方法が一般的であり、例えば、
１５〜５０℃の液温で３０〜３００秒、好ましくは３０
〜１８０秒浸漬して、厚さ０．５〜３μｍ１好ましくは
１〜２μｍのクロメート皮膜を形成させるのがよい。A common method for chromating is to immerse the alloy plated material in the chromate treatment solution of the present invention, for example,
30 to 300 seconds at a liquid temperature of 15 to 50°C, preferably 30
It is preferable to form a chromate film with a thickness of 0.5 to 3 μm, preferably 1 to 2 μm, by dipping for ~180 seconds.
従って、基体に常法により亜鉛−ニッケルめっきを施し
く２μ以上、好ましくは５〜２０μ厚）だ後、上記方法
で黒色クロメート被膜を形成させることができる。尚、
亜鉛めっきではクロメート皮膜の光沢を増すために、通
常、被処理物を稀硝酸溶液に浸漬させることが行なわれ
るが、本発明ではこのような前処理は無用である。上記
以外の条件や処理操作は、従来の亜鉛めっきの黒色クロ
メート処理方法に準じて行なうことができる。Therefore, after zinc-nickel plating is applied to the substrate by a conventional method to a thickness of 2 microns or more, preferably 5 to 20 microns, a black chromate film can be formed by the above method. still,
In zinc plating, the object to be treated is usually immersed in a dilute nitric acid solution in order to increase the gloss of the chromate film, but such pretreatment is unnecessary in the present invention. Conditions and treatment operations other than those described above can be performed in accordance with conventional black chromate treatment methods for zinc plating.
本発明によれば、亜鉛・ニッケル合金ｔつき表面に優れ
た黒色外観と耐熱性、防食性、を兼ね備えているクロメ
ート皮膜を形成させる化学的・実用的に安定な処理液を
得ることができる。従って、発明の方法により黒色クロ
メート皮膜を形成された物は幅広く使用できる。According to the present invention, it is possible to obtain a chemically and practically stable treatment solution that forms a chromate film having excellent black appearance, heat resistance, and corrosion resistance on a surface coated with a zinc-nickel alloy. Therefore, products with a black chromate film formed by the method of the invention can be widely used.
次に実施例により本発明を説明する。Next, the present invention will be explained with reference to examples.
実施例１
鋼板に亜鉛・ニッケル合金めっきにッケル含有量３，５
，９．１２％）を８μｍの厚みに施したものを下記のク
ロメート処理液に浸漬した。この結果、ニッケル含有率
３％、５％及び９％のものについては良好な黒色のクロ
メート皮膜が形成された。しかし、１２％のものにはク
ロメート皮膜が形成されなかった。Example 1 Steel plate with zinc-nickel alloy plating with nickel content of 3.5
, 9.12%) to a thickness of 8 μm was immersed in the following chromate treatment solution. As a result, good black chromate films were formed with nickel contents of 3%, 5% and 9%. However, no chromate film was formed in the case of 12%.
［：ｒ０３１０ｇ／β （六価クロム： ５．２ｇ
＃りＮａ２５Ｏ，Ｌｏｇ／β （硫酸根： ６．８ｇ＃
りＡｇＮＯｓ ０．５ｇ／ ｊ２ （溶解性銀
： ０．３２ｇ／β）コハク酸 ５ｇ／β
ｐｉ（１，２
硫酸根／六価クロム：１．３
実施例２
鋼板に亜鉛・ニッケル合金めっきにッケル含有量７％）
を１０μｍの厚みに施したものを、下記のクロメート処
理液に浸漬したところ、黒色クロメート皮膜が形成され
た。[:r0310g/β (hexavalent chromium: 5.2g
#riNa25O, Log/β (sulfate group: 6.8g #
AgNOs 0.5 g/j2 (Soluble silver: 0.32 g/β) Succinic acid 5 g/β pi (1,2 sulfuric acid radical/hexavalent chromium: 1.3 Example 2 Zinc-nickel alloy plating on a steel sheet content 7%)
When it was immersed in the following chromate treatment solution, a black chromate film was formed.
Ｎａ２Ｃｒ２Ｏ７１５ｇ＃！ 、 （六価クロム：
６．Ｏｇ／β）Ｈ２ＳＯ４３ｇ／ ｐ （硫酸根：
２．９ｇ／ｊ７）Ｎａ２Ｓ［１４５ｇ／ １ （硫酸
根： ３．４ｇ／Ａ）ＡｇｚＳ［］４０．４ｇ／β
（溶解性銀 ： ０．２８ｇ／ ｆ！、 ）コハク酸
１０ｇ／β
ｐＨ１，８
硫酸根／六価クロム：１．０
このようにして得られた黒色クロメート処理物について
、塩水噴霧試験（ＪＩＳ−２−２３７１）を行った結果
、６００時間後でも白錆の発生はみられず、また２００
０時間後でも赤錆の発生はみられなかった。Na2Cr2O715g#! , (Hexavalent chromium:
6. Og/β) H2SO43g/p (sulfate group:
2.9g/j7) Na2S[145g/1 (sulfate group: 3.4g/A)AgzS[]40.4g/β
(Soluble silver: 0.28g/f!,) Succinic acid
10g/β pH 1.8 Sulfate radical/hexavalent chromium: 1.0 The black chromate treated product thus obtained was subjected to a salt spray test (JIS-2-2371), and as a result, no white rust occurred even after 600 hours. No occurrence was observed, and 200
No red rust was observed even after 0 hours.
実施例３
鋼板に亜鉛・ニッケル合金めっきにッケル含有量７％）
を１０μｍの厚みに施したものを、下記のクロメート処
理液に浸漬したところ、黒色クロメート皮膜が形成され
た。Example 3 Zinc/nickel alloy plating on steel plate with 7% nickel content)
When it was immersed in the following chromate treatment solution, a black chromate film was formed.
Ｃｒ０３１０ｇ／ｉ’ （六価りｏム：５．２ｇ／β
）Ｎａ２Ｃｒ２０ｉ ４０ｇ／β （六価クロム：
１５．８ｇ／ Ｒ）Ｎａ２ｓｏ４４０ｇ／４１！
（硫酸根： ２７． Ｏｇ／ ｌ ）ＡｇＮＯ：＋
０．５ｇ／β （溶解性銀： ０．３２ｇ／β）コハク
酸 １５ｇ／ Ｒ
ｐＨ１，５
硫酸根／六価クロム：１．３
実施例４
鋼板に亜鉛・ニッケル合金めっきにッケル含有量７％）
を１０μｍの厚みに施したものを、下記のクロメート処
理液に浸漬したところ、黒色クロメート皮膜が形成され
た。Cr0310g/i' (hexavalent om: 5.2g/β
) Na2Cr20i 40g/β (Hexavalent chromium:
15.8g/R) Na2so440g/41!
(Sulfate root: 27.Og/l)AgNO:+
0.5g/β (Soluble silver: 0.32g/β) Succinic acid 15g/R pH 1.5 Sulfate radical/hexavalent chromium: 1.3 Example 4 Nickel content 7% in zinc-nickel alloy plating on steel sheet )
When it was immersed in the following chromate treatment solution, a black chromate film was formed.
Ｃｒ０３１０ｇ／ ４２ （六価クロム： ５．２
ｇ＃りＮａ２Ｃｒ２０ｉ １０ｇ／ Ｒ（六価クロム
： ４．Ｏｇ／β）Ｎａ２Ｓ０４２５ｇ／ ｎ （
硫酸根： １７． Ｏｇ／ ＩＩ ）ＡｇＮＯ３０，８
ｇ／β （溶解性銀： ０．５ｇ／ｌコハク酸 １０ｇ
／β
ｐＨ１，５
硫酸根／六価クロム：１，８
比較例
鋼板に亜鉛めっきを８μｍの厚みに施したものに、黒色
クロメート処理を行った。Cr0310g/42 (Hexavalent chromium: 5.2
g#riNa2Cr20i 10g/R (hexavalent chromium: 4.Og/β)Na2S0425g/n (
Sulfate root: 17. Og/II) AgNO30,8
g/β (Soluble silver: 0.5g/l succinic acid 10g
/β pH 1,5 Sulfate radical/hexavalent chromium: 1,8 Comparative Example A steel sheet plated with zinc to a thickness of 8 μm was subjected to black chromate treatment.
実施例及び比較例の条件及び結果をまとめて表−１に示
す。これにより本発明で従来技術である亜鉛の黒色クロ
メート処理法による黒色クロメート皮膜に比べ耐食性に
優れた皮膜を得られることがわかる。The conditions and results of Examples and Comparative Examples are summarized in Table-1. This shows that the present invention can provide a film with superior corrosion resistance compared to the black chromate film obtained by the conventional black chromate treatment method for zinc.
表−１ ＊塩水噴霧試験結果 （ＪＩＳ Ｚ２３７１）Table-1 *Salt spray test results (JIS Z2371)
Claims (2)
ｇ／ｌ、溶解性銀を０．１〜０．５ｇ／ｌ及びコハク酸
を０．５〜６０ｇ／ｌの濃度で含有し、かつｐＨが０．
５〜２．５の範囲にあることを特徴とするＺｎ−Ｎｉ合
金めっき用黒色クロメート処理液。(1) 1 to 50 g/l of hexavalent chromium, 1 to 50 g/l of sulfate
g/l, soluble silver at a concentration of 0.1-0.5 g/l and succinic acid at a concentration of 0.5-60 g/l, and a pH of 0.
A black chromate treatment liquid for Zn-Ni alloy plating, characterized in that the chromate treatment liquid is in the range of 5 to 2.5.
の範囲にある請求項（１）記載の黒色クロメート処理液
。(2) Weight ratio of sulfate radical/hexavalent chromium is 0.8 to 2.0
The black chromate treatment liquid according to claim (1), which falls within the range of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2165269A JP2953750B2 (en) | 1990-06-22 | 1990-06-22 | Black chromate treatment solution for Zn-Ni alloy plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2165269A JP2953750B2 (en) | 1990-06-22 | 1990-06-22 | Black chromate treatment solution for Zn-Ni alloy plating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0456782A true JPH0456782A (en) | 1992-02-24 |
| JP2953750B2 JP2953750B2 (en) | 1999-09-27 |
Family
ID=15809125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2165269A Expired - Lifetime JP2953750B2 (en) | 1990-06-22 | 1990-06-22 | Black chromate treatment solution for Zn-Ni alloy plating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2953750B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5565042A (en) * | 1994-12-27 | 1996-10-15 | Dipsol Chemicals Co., Ltd. | Black chromate solution |
| EP0805222A1 (en) * | 1996-05-01 | 1997-11-05 | Dipsol Chemicals Co., Ltd. | Solution and process for black chromating |
| US5735972A (en) * | 1996-05-23 | 1998-04-07 | Dipsol Chemicals Co., Ltd. | Black chromate-treatment solution for Zn-Ni alloy plated film |
-
1990
- 1990-06-22 JP JP2165269A patent/JP2953750B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5565042A (en) * | 1994-12-27 | 1996-10-15 | Dipsol Chemicals Co., Ltd. | Black chromate solution |
| EP0805222A1 (en) * | 1996-05-01 | 1997-11-05 | Dipsol Chemicals Co., Ltd. | Solution and process for black chromating |
| US5735972A (en) * | 1996-05-23 | 1998-04-07 | Dipsol Chemicals Co., Ltd. | Black chromate-treatment solution for Zn-Ni alloy plated film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2953750B2 (en) | 1999-09-27 |
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