JPH1081977A - Chromate treating solution and treatment - Google Patents
Chromate treating solution and treatmentInfo
- Publication number
- JPH1081977A JPH1081977A JP25249296A JP25249296A JPH1081977A JP H1081977 A JPH1081977 A JP H1081977A JP 25249296 A JP25249296 A JP 25249296A JP 25249296 A JP25249296 A JP 25249296A JP H1081977 A JPH1081977 A JP H1081977A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- chromium
- chromate treatment
- treating solution
- 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
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000011651 chromium Substances 0.000 claims abstract description 32
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 5
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 5
- -1 phosphoric acid compound Chemical class 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 239000002952 polymeric resin Substances 0.000 claims 1
- 229920003002 synthetic resin Polymers 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 abstract description 7
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011975 tartaric acid Substances 0.000 abstract description 5
- 235000002906 tartaric acid Nutrition 0.000 abstract description 5
- 238000001879 gelation Methods 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- PMJNEQWWZRSFCE-UHFFFAOYSA-N 3-ethoxy-3-oxo-2-(thiophen-2-ylmethyl)propanoic acid Chemical compound CCOC(=O)C(C(O)=O)CC1=CC=CS1 PMJNEQWWZRSFCE-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- VBSTXRUAXCTZBQ-UHFFFAOYSA-N 1-hexyl-4-phenylpiperazine Chemical compound C1CN(CCCCCC)CCN1C1=CC=CC=C1 VBSTXRUAXCTZBQ-UHFFFAOYSA-N 0.000 description 1
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- JACRWUWPXAESPB-QMMMGPOBSA-N Tropic acid Natural products OC[C@H](C(O)=O)C1=CC=CC=C1 JACRWUWPXAESPB-QMMMGPOBSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- UKXSKSHDVLQNKG-UHFFFAOYSA-N benzilic acid Chemical compound C=1C=CC=CC=1C(O)(C(=O)O)C1=CC=CC=C1 UKXSKSHDVLQNKG-UHFFFAOYSA-N 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229920001577 copolymer Polymers 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
- 238000010828 elution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、クロメ−ト皮膜から６
価クロムがほとんど溶出しないクロメ−ト皮膜を形成で
きるクロメ−ト処理液および処理方法に関する。BACKGROUND OF THE INVENTION The present invention relates to a method for producing a chromate film from a chromate film.
The present invention relates to a chromate treating solution and a treating method capable of forming a chromate film from which chromium (VI) hardly elutes.
【０００２】[0002]
【従来技術】近年、亜鉛やアルミニウムまたはこれらの
合金等のめっき鋼板、銅めっき鋼板、アルミニウム板等
のクロメ−ト処理液は、クロム酸、クロム酸塩、重クロ
ム酸塩のような水溶性クロム化合物の水溶液に水溶性も
しくは水分散性有機樹脂を添加して、被処理材に塗布後
水洗することなく乾燥する塗布型のものが主流になって
いる。この処理液では含有クロムがすべて６価クロムで
あると、クロムが溶出し易く、また、吸湿性になるた
め、通常、６価クロムの一部を還元剤で不溶性の３価ク
ロムに還元して、クロメ−ト皮膜の耐食性、耐湿性を高
めている。2. Description of the Related Art In recent years, chromate treatment solutions for plated steel sheets such as zinc and aluminum or alloys thereof, copper-plated steel sheets, aluminum sheets, etc. are made of water-soluble chromium such as chromate, chromate and dichromate. The mainstream is a coating type in which a water-soluble or water-dispersible organic resin is added to an aqueous solution of a compound, applied to a material to be treated, and then dried without being washed with water. In this treatment liquid, if the chromium content is all hexavalent chromium, the chromium is easily eluted and becomes hygroscopic. Therefore, usually, a part of hexavalent chromium is reduced to insoluble trivalent chromium with a reducing agent. In addition, the corrosion resistance and moisture resistance of the chromate film are enhanced.
【０００３】還元剤としては、澱粉、ポリビニルアルコ
−ル、ホルマリンのような有機化合物や過酸化水素のよ
うな無機化合物を用いていたが、これらの還元剤で６価
クロムの３価クロムへの還元率を５０％より大きくする
と、還元率の上昇に伴ってｐＨも上昇するため、３価ク
ロムが水酸化クロム等に変化して、処理液のゲル化や沈
降が生じ、被処理材への塗布が困難になる。このため、
６価クロムの還元率は５０％以下にしていたが、この程
度の還元率ではクロメ−ト皮膜中の６価クロムが溶出し
て、黄色のシミが発生したり、取り扱い者に悪影響を与
えたりするという問題があった。[0003] Organic compounds such as starch, polyvinyl alcohol and formalin and inorganic compounds such as hydrogen peroxide have been used as reducing agents. These reducing agents convert hexavalent chromium into trivalent chromium. If the reduction ratio is larger than 50%, the pH also increases with the increase in the reduction ratio, so that trivalent chromium changes to chromium hydroxide and the like, and the treatment solution gels and precipitates, and Application becomes difficult. For this reason,
The hexavalent chromium reduction rate was set to 50% or less, but at such a reduction rate, hexavalent chromium in the chromate film was eluted, causing yellow spots or adversely affecting the operator. There was a problem of doing.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、６価クロム
の３価クロムへの還元率を５０％より大きくしても、処
理液がゲル化しないクロメ−ト処理液および処理方法を
提供するものである。SUMMARY OF THE INVENTION The present invention provides a chromate treatment solution and a treatment method in which the treatment solution does not gel even when the reduction ratio of hexavalent chromium to trivalent chromium is greater than 50%. Things.
【０００５】[0005]
【課題を解決するための手段】本発明は、水溶性クロム
化合物と、水溶性もしくは水分散性有機樹脂とを含有す
るクロメ−ト処理液において、オキシカルボン酸化合物
またはこれとリン酸もしくはリン酸化合物とにより６価
クロムを３価クロムに還元した。クロメ−ト処理液は被
処理材に塗布した後、水洗することなく乾燥する。According to the present invention, there is provided a chromatized solution containing a water-soluble chromium compound and a water-soluble or water-dispersible organic resin, comprising an oxycarboxylic acid compound or phosphoric acid or phosphoric acid. The compound reduced hexavalent chromium to trivalent chromium. After the chromate treatment liquid is applied to the material to be treated, it is dried without washing.
【０００６】[0006]
【作用】本発明者らは、６価クロムの還元率を５０％以
上にしても有機樹脂含有クロメ−ト処理液がゲル化しな
い還元剤について、種々検討したところ、オキシカルボ
ン酸化合物を用いると、６価クロム全量を３価クロムに
還元しても、処理液が安定していることを見いだした。
ここで、オキシカルボン酸化合物を用いると、処理液が
ゲル化しない理由は明確ではないが、オキシカルボン酸
化合物の水酸基が６価クロムを３価クロムに還元し、カ
ルボキシル基が３価クロムの化合物に配位して、ゲル化
を防止するものと考えられる。The present inventors have conducted various studies on a reducing agent that does not cause the chromatized solution containing an organic resin to gel even when the reduction ratio of hexavalent chromium is 50% or more. It was found that the treatment liquid was stable even when the total amount of hexavalent chromium was reduced to trivalent chromium.
Here, when the oxycarboxylic acid compound is used, the reason why the treatment liquid does not gel is not clear, but the hydroxyl group of the oxycarboxylic acid compound reduces hexavalent chromium to trivalent chromium, and the compound having a carboxyl group of trivalent chromium. Is considered to prevent gelation.
【０００７】オキシカルボン酸化合物としては、酒石
酸、マロン酸、クエン酸、乳酸、グルコ−ル酸、グリセ
リン酸、トロパ酸、ベンジル酸、ヒドロキシ吉草酸等が
挙げられるが、これらの還元剤は単独または併用しても
よい。還元性は化合物により異なるので、添加量は３価
クロムへの還元を把握しながら行う。Examples of the oxycarboxylic acid compound include tartaric acid, malonic acid, citric acid, lactic acid, gluconic acid, glyceric acid, tropic acid, benzylic acid and hydroxyvaleric acid. These reducing agents may be used alone or in combination. You may use together. Since the reducibility differs depending on the compound, the addition amount is determined while grasping the reduction to trivalent chromium.
【０００８】水溶性クロム化合物の濃度は、全Ｃｒが１
〜２０ｇ／Ｌにするのが望ましい。１ｇ／Ｌ未満では耐
食性が不充分で、２０ｇ／Ｌより多いと、ゲル化し易い
傾向にある。６価クロムの還元は目的により設定すれば
よいが、Ｃｒ6+／全Ｃｒの比率で０.１以下にすると、
６価クロムの溶出をほぼ完全に防止でき、また、クロメ
−ト皮膜を無色にすることができる。有機樹脂は２０ｇ
／Ｌ未満であると、均一な皮膜形成が困難で、５００ｇ
／Ｌより多くすると、粘性が高くなり、塗布困難になる
ので、２０〜５００ｇ／Ｌにするのが好ましい。[0008] The concentration of the water-soluble chromium compound is
Desirably, it is ２０20 g / L. If it is less than 1 g / L, the corrosion resistance is insufficient, and if it is more than 20 g / L, it tends to gel. The reduction of hexavalent chromium may be set according to the purpose, but if the ratio of Cr 6+ / total Cr is set to 0.1 or less,
The elution of hexavalent chromium can be almost completely prevented, and the chromate film can be made colorless. 20 g of organic resin
/ L is less than 500 g, it is difficult to form a uniform film.
If the ratio is more than / L, the viscosity becomes high and coating becomes difficult. Therefore, the amount is preferably 20 to 500 g / L.
【０００９】オキシカルボン酸化合物による還元は、処
理液にリン酸またはリン酸化合物を添加すると、少ない
添加量で図１に示すように還元を促進することができ、
また、クロメ−ト皮膜を難溶性のリン酸クロム皮膜にす
ることができる。リン酸化合物としてはリン酸二水素ア
ンモニウム等のような水易溶性のものを用いるが、添加
量はＰ／全Ｃｒ＝０.１〜４.０になるようにする。０.
１未満であると、皮膜難溶化による耐食性の向上が小さ
く、４.０を超えると、処理液の安定性が低下するよう
になる。In the reduction with an oxycarboxylic acid compound, when phosphoric acid or a phosphoric acid compound is added to the treatment solution, the reduction can be promoted with a small addition amount as shown in FIG.
Further, the chromate film can be made of a hardly soluble chromium phosphate film. As the phosphoric acid compound, a water-soluble compound such as ammonium dihydrogen phosphate is used, and the amount of addition is adjusted so that P / total Cr = 0.1 to 4.0. 0.
When it is less than 1, the improvement in corrosion resistance due to insolubilization of the film is small, and when it is more than 4.0, the stability of the treatment liquid is reduced.
【００１０】なお、有機樹脂含有クロメ−ト処理液に
は、潤滑剤として、融点が１００℃以上の高分子樹脂粉
末を添加し、プレス加工等の際のクロメ−ト皮膜潤滑性
を高めることが従来より行われているが、このクロメ−
ト処理液にもポリエチレン、ポリプロピレン、フッ素樹
脂のような融点が１００℃以上の樹脂粉末を添加しても
よい。Incidentally, a high molecular resin powder having a melting point of 100 ° C. or more is added as a lubricant to the organic resin-containing chromate treatment liquid to improve the lubricity of the chromate film at the time of press working or the like. This has been done conventionally,
A resin powder having a melting point of 100 ° C. or more, such as polyethylene, polypropylene, and fluororesin, may be added to the treating solution.
【００１１】被処理材への処理液塗布は、従来の塗布型
クロメ−ト処理の場合と同様に公知方法、例えば、ロ−
ルコ−ト法、エア−カ−テン法、静電霧化法、スクイズ
ロ−ルコ−ト法などにより行い、水洗せずに乾燥する方
法で行う。The treatment liquid is applied to the material to be treated in the same manner as in the case of the conventional coating type chromate treatment.
It is carried out by a coating method, an air curtain method, an electrostatic atomization method, a squeeze roll coating method, etc., and a method of drying without washing with water.
【００１２】[0012]
【実施例】クロム酸アンモニウム水溶液に異なるオキシ
カルボン酸化合物を添加して、６価クロムの一部を３価
クロムに還元した後、メチルメタクリレ−トとエチルア
クリレ−トの共重合体のアクリルエマルジョンを添加
し、さらに、ノニオン系乳化剤、シリコ−ン変性ポリエ
−テル系消泡剤を添加した。このようにして調製したク
ロメ−ト処理液を電気亜鉛めっき鋼板にロ−ルコ−タ−
で塗布し、到達板温１５０℃で乾燥した。表１にクロメ
−ト処理液組成、安定性およびクロメ−ト皮膜を示す。
なお、クロメ−ト処理液の安定性は温度４０℃の処理液
をロ−ルコ−タ−にセットして、２４時間運転し、処理
液中に樹脂のゲル化や沈降の認められなかったものを記
号○、認められたものを記号×で評価した。EXAMPLE A different oxycarboxylic acid compound was added to an aqueous solution of ammonium chromate to partially reduce hexavalent chromium to trivalent chromium, and then an acrylic emulsion of a copolymer of methyl methacrylate and ethyl acrylate was used. Was added, and a nonionic emulsifier and a silicone-modified polyether-based antifoaming agent were further added. The chromate treatment solution thus prepared is roll-coated on an electrogalvanized steel sheet.
And dried at an ultimate plate temperature of 150 ° C. Table 1 shows the composition, stability and chromate film of the chromate treatment solution.
In addition, the stability of the chromate treatment solution was such that the treatment solution at a temperature of 40 ° C. was set on a roll coater and operated for 24 hours, and no gelling or sedimentation of the resin was observed in the treatment solution. Was evaluated with the symbol 、, and those recognized were evaluated with the symbol x.
【００１３】[0013]
【表１】 [Table 1]
【００１４】次に、表１で処理液安定性の良好なもので
処理したクロメ−ト処理鋼板について、次のような性能
試験を実施した。この結果を表２に示す。 （１）耐Ｃｒ6+溶出性試験 クロメ−ト処理鋼板の試験片を９０℃の熱水に３分浸漬
して、Ｃｒ6+溶出量を測定し、溶出量が１ｍｇ／ｍ2未
満のものを記号○で、１ｍｇ／ｍ2以上、５ｍｇ／ｍ2未
満のものを記号△で、５ｍｇ／ｍ2以上のものを記号×
で評価した。 （２）未加工部耐食性試験 塩水噴霧試験（ＪＩＳ Ｚ ２３７１）を１００時間実
施して、白錆発生率が全面積の５％未満のものを記号◎
で、５％以上、１０％未満のものを記号○で、１０％以
上、３０％未満のものを記号△で、３０％以上のものを
記号×で評価した。Next, the following performance tests were carried out on the chromate-treated steel sheet treated with one having good treatment liquid stability as shown in Table 1. Table 2 shows the results. (1) Cr 6+ resistance test A test piece of a chromate-treated steel sheet was immersed in hot water at 90 ° C. for 3 minutes, and the Cr 6+ dissolution amount was measured, and the dissolution amount was less than 1 mg / m 2. Is indicated by the symbol ○, and 1 mg / m 2 or more and less than 5 mg / m 2 is indicated by the symbol △, and 5 mg / m 2 or more is indicated by the symbol X.
Was evaluated. (2) Corrosion resistance test of unprocessed portion A salt spray test (JIS Z 2371) was performed for 100 hours.
, Those of 5% or more and less than 10% were evaluated with the symbol で, those of 10% or more and less than 30% were evaluated with the symbol 、, and those of 30% or more were evaluated with the symbol x.
【００１５】（３）加工部耐食性試験 ドロ−ビ−ド（摺動変形）試験を、加圧力２００ｋｇ
ｆ、引き抜き速度５００ｍｍ／ｍｉｎの条件で実施した
後、上記塩水噴霧試験を１００時間実施し、赤錆が発生
しないものを記号◎で、赤錆発生率が全面積の１０％未
満のものを記号○で、１０％以上、３０％未満のものを
記号△で、３０％以上のものを記号×で評価した。 （４）潤滑性試験 表面性測定機によりステンレス鋼板（ＳＵＳ３０４、Ｂ
Ａ仕上げ）表面に対する動摩擦係数を荷重２００ｇｆ、
移動速度６０ｍ／ｍｉｎの条件で測定し、動摩擦係数が
０.１５未満のものを記号◎で、０.１５以上、０.２５
未満のものを記号○で、０.２５以上、０.３５未満のも
のを記号△で、０.３５以上のものを記号×で評価し
た。[0015] (3) Corrosion resistance test of the processed part A test (a sliding deformation) was carried out by applying a pressure of 200 kg.
f. After the extraction was performed under the conditions of a drawing speed of 500 mm / min, the above salt spray test was performed for 100 hours. And 10% or more and less than 30% were evaluated with a symbol △, and 30% or more were evaluated with a symbol x. (4) Lubricity test A stainless steel plate (SUS304, B
A finish) The coefficient of kinetic friction on the surface was determined to be 200 gf,
Measured under the condition of a moving speed of 60 m / min, and those with a dynamic friction coefficient of less than 0.15 are marked with a symbol ◎, 0.15 or more and 0.25.
Those with less than were evaluated with the symbol 、, those with 0.25 or more and those with less than 0.35 were evaluated with the symbol △, and those with 0.35 or more were evaluated with the symbol x.
【００１６】[0016]
【表２】 [Table 2]
【００１７】実施例２ 実施例１において、クロム酸アンモニウム水溶液の代わ
りにクロム酸二ナトリウム水溶液を用い、また、オキシ
カルボン酸化合物は酒石酸にして、クロメ−ト処理液を
調製した。そして、調製後処理液の一部にリン酸やポリ
エチレン樹脂粉末（融点１２５℃）を添加した。この処
理液組成を表３に示す。また、実施例１と同様の性能試
験を実施した結果を表４に示す。Example 2 In Example 1, an aqueous solution of disodium chromate was used instead of the aqueous solution of ammonium chromate, and tartaric acid was used as the oxycarboxylic acid compound to prepare a chromate treatment solution. Then, phosphoric acid or polyethylene resin powder (melting point 125 ° C.) was added to a part of the treatment liquid after preparation. Table 3 shows the composition of the treatment liquid. Table 4 shows the results of performance tests performed in the same manner as in Example 1.
【００１８】[0018]
【表３】 [Table 3]
【００１９】[0019]
【表４】 [Table 4]
【００２０】[0020]
【発明の効果】以上のように、有機樹脂含有塗布型クロ
メ−ト処理液において、６価クロムの還元剤にオキシカ
ルボン酸化合物を用いると、６価クロムの３価クロムへ
の還元率を５０％以上にしても、処理液のゲル化や沈殿
は生じない。As described above, when an oxycarboxylic acid compound is used as the hexavalent chromium reducing agent in the organic resin-containing coating type chromate treatment liquid, the reduction rate of hexavalent chromium to trivalent chromium is reduced to 50%. %, No gelation or precipitation of the processing solution occurs.
【図１】はクロメ−ト処理液中の６価クロムを酒石酸添
加により還元した場合とさらにリン酸を添加して還元し
た場合の３価クロムへの還元率と酒石酸添加量との関係
を示すグラフである。FIG. 1 shows the relationship between the rate of reduction to trivalent chromium and the amount of tartaric acid when hexavalent chromium in the chromatized solution was reduced by adding tartaric acid and when further reduced by adding phosphoric acid. It is a graph.
Claims (7)
は水分散性有機樹脂とを含有するクロメ−ト処理液にお
いて、オキシカルボン酸化合物により６価クロムを３価
クロムに還元したことを特徴とするクロメ−ト処理液。1. A chromate treatment solution containing a water-soluble chromium compound and a water-soluble or water-dispersible organic resin, wherein hexavalent chromium is reduced to trivalent chromium by an oxycarboxylic acid compound. Chromate treatment solution.
比率で０.１以下にすることを特徴とする請求項１に記
載のクロメ−ト処理液。2. The chromate treatment liquid according to claim 1, wherein the reduction of hexavalent chromium is reduced to 0.1 or less in a ratio of Cr 6+ / total Cr.
特徴とする請求項１に記載のクロメ−ト処理液。3. The chromate treatment liquid according to claim 1, wherein the total Cr is 1 to 20 g / L.
ことを特徴とする請求項１に記載のクロメ−ト処理液。4. The chromate treatment liquid according to claim 1, wherein the amount of the organic resin is 20 to 500 g / L.
またはリン酸化合物をＰ／全Ｃｒ＝０.１〜４.０の比率
で添加したことを特徴とするクロメ−ト処理液。5. A chromate treatment solution, wherein phosphoric acid or a phosphoric acid compound is added to the chromate treatment solution according to claim 1 in a ratio of P / total Cr = 0.1 to 4.0.
処理液に融点が１００℃以上の高分子樹脂粉末を添加し
たことを特徴とするクロメ−ト処理液。6. A chromate treatment liquid, wherein a polymer resin powder having a melting point of 100 ° C. or more is added to the chromate treatment liquid according to claim 1 or 5.
メ−ト処理液を被処理材に塗布した後、水洗することな
く乾燥することを特徴とするクロメ−ト処理方法。7. A chromate treatment method comprising applying the chromate treatment liquid according to any one of claims 1 to 6 to a material to be treated and drying without washing with water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25249296A JP3411452B2 (en) | 1996-09-03 | 1996-09-03 | Chromate treatment solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25249296A JP3411452B2 (en) | 1996-09-03 | 1996-09-03 | Chromate treatment solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1081977A true JPH1081977A (en) | 1998-03-31 |
| JP3411452B2 JP3411452B2 (en) | 2003-06-03 |
Family
ID=17238133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25249296A Expired - Fee Related JP3411452B2 (en) | 1996-09-03 | 1996-09-03 | Chromate treatment solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3411452B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6190464B1 (en) | 1998-09-24 | 2001-02-20 | Nisshin Steel Co., Ltd. | Chromating solution and chromated metal sheet |
| WO2008029953A1 (en) | 2006-09-07 | 2008-03-13 | Nippon Steel Corporation | AQUEOUS TREATMENT LIQUID FOR Sn-PLATED STEEL SHEET HAVING EXCELLENT CORROSION RESISTANCE AND COATING ADHESION, AND METHOD FOR PRODUCING SURFACE-TREATED STEEL SHEET |
-
1996
- 1996-09-03 JP JP25249296A patent/JP3411452B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6190464B1 (en) | 1998-09-24 | 2001-02-20 | Nisshin Steel Co., Ltd. | Chromating solution and chromated metal sheet |
| US6329067B2 (en) | 1998-09-24 | 2001-12-11 | Nisshin Steel Co., Ltd. | Chromating solution and chromated metal sheet |
| WO2008029953A1 (en) | 2006-09-07 | 2008-03-13 | Nippon Steel Corporation | AQUEOUS TREATMENT LIQUID FOR Sn-PLATED STEEL SHEET HAVING EXCELLENT CORROSION RESISTANCE AND COATING ADHESION, AND METHOD FOR PRODUCING SURFACE-TREATED STEEL SHEET |
| US8097306B2 (en) | 2006-09-07 | 2012-01-17 | Nippon Steel Corporation | Aqueous treating solution for Sn-based plated steel sheet excellent in corrosion resistance and paint adhesion, and production method of surface-treated steel sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3411452B2 (en) | 2003-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1274156A (en) | Chromate coating of zinc surfaces | |
| US4637840A (en) | Coated aluminum-zinc alloy plated sheet steel | |
| EP2294248B1 (en) | Midly alkaline thin inorganic corrosion protective coating for metal substrates | |
| JP2001303267A (en) | Non-chromium anti-rust treatment agent for aluminum, anti-rust treatment method, and anti-rust treated aluminum products | |
| US4966634A (en) | Composition of the surface treatment for metal and the treatment method | |
| US6146473A (en) | Metal surface treatment composition containing an acrylic resin comprising a n-heterocycle ring, treatment method, and treated metal material | |
| GB1129302A (en) | Aqueous metal-coating composition | |
| JP2002226981A (en) | Rust prevention agent for galvanized steel sheet and galvanized steel sheet | |
| US4247344A (en) | Rust preventing treatment of metal-plated steel materials | |
| JP3411452B2 (en) | Chromate treatment solution | |
| JPH1081976A (en) | Chromate treating solution and treatment | |
| US6329067B2 (en) | Chromating solution and chromated metal sheet | |
| JP2002105658A (en) | Galvanized steel sheet having excellent blackening resistance and corrosion resistance after working, chemically treating solution and chemical conversion treatment method | |
| JP2000178761A (en) | Surface treatment agent for galvanized steel sheet and galvanized steel sheet | |
| JPH0833867A (en) | Surface treatment method for aluminum thin plate for cap | |
| JPS6158552B2 (en) | ||
| JP2002327280A (en) | Metal surface treatment agent | |
| JP3615781B2 (en) | Method for producing trivalent chromium compound sol, surface treatment agent for metal material containing the sol, and surface treatment method | |
| JP2002060959A (en) | Galvanized steel sheet excellent in corrosion resistance and adhesive strength of coating, chemically treating solution and chemical conversion treating method | |
| KR910003484B1 (en) | Metal Surface Treatment Compositions and Treatment Methods | |
| US6071435A (en) | Composition and process for treating a zinciferous surface | |
| KR0143479B1 (en) | Chromate solution | |
| JP2000219974A (en) | Surface treatment agent and surface treated steel sheet | |
| JP3881392B2 (en) | Metal surface treatment composition and metal surface treatment method | |
| JPH10176279A (en) | Production of structural hot-dip coated steel excellent in resistance to white rust and chromium (vi) ion elution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20021022 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20030311 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080320 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090320 Year of fee payment: 6 |
|
| LAPS | Cancellation because of no payment of annual fees |