JP4845050B2 - Concentrated liquid composition for hexavalent chromium-free surface conversion treatment with improved stability - Google Patents
Concentrated liquid composition for hexavalent chromium-free surface conversion treatment with improved stability Download PDFInfo
- Publication number
- JP4845050B2 JP4845050B2 JP2007261009A JP2007261009A JP4845050B2 JP 4845050 B2 JP4845050 B2 JP 4845050B2 JP 2007261009 A JP2007261009 A JP 2007261009A JP 2007261009 A JP2007261009 A JP 2007261009A JP 4845050 B2 JP4845050 B2 JP 4845050B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- composition
- conversion treatment
- chemical conversion
- oxalic acid
- 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 - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 44
- 239000007788 liquid Substances 0.000 title claims description 36
- 238000006243 chemical reaction Methods 0.000 title claims description 30
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 78
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 52
- 150000007524 organic acids Chemical class 0.000 claims description 38
- 239000000126 substance Substances 0.000 claims description 31
- 235000006408 oxalic acid Nutrition 0.000 claims description 26
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 22
- 229910021645 metal ion Inorganic materials 0.000 claims description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 claims description 5
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 27
- 239000007789 gas Substances 0.000 description 25
- 239000012141 concentrate Substances 0.000 description 20
- 229910002651 NO3 Inorganic materials 0.000 description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- -1 nitrate ions Chemical class 0.000 description 12
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 8
- 229940093915 gynecological organic acid Drugs 0.000 description 8
- 235000005985 organic acids Nutrition 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 235000006708 antioxidants Nutrition 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 238000003287 bathing Methods 0.000 description 5
- 239000001630 malic acid Substances 0.000 description 5
- 235000011090 malic acid Nutrition 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910001430 chromium ion Inorganic materials 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000012085 test solution Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Images
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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Landscapes
- Chemical Treatment Of Metals (AREA)
Description
本発明は、金属イオンを含み安定性を高めた6価クロムフリー表面化成処理用濃縮液組成物、例えば、金属イオンとして3価クロムイオンと有機酸と硝酸イオンとから成る貯蔵性を高めた6価クロムフリー表面化成処理用濃縮液組成物に関する。 The present invention provides a hexavalent chromium-free concentrated chemical composition for surface chemical conversion treatment that contains metal ions and has improved stability, for example, improved storage properties comprising trivalent chromium ions, organic acids, and nitrate ions as metal ions. The present invention relates to a concentrated chromium-free surface chemical conversion concentrate composition.
本発明を金属イオンによる表面化成処理としていわゆるクロメート処理を例にとって、以下、説明する。
鋼材に対する表面化成処理の1種に、亜鉛系めっき鋼材の防錆処理として化成処理用金属イオンに6価クロムイオンを使用したクロメート処理がある。ところが最近は6価クロムが人体に有害であるという理由から、金属イオンとして3価クロムイオンを有機酸とともに使用するクロメート処理に移行されつつある。
The present invention will be described below by taking a so-called chromate treatment as an example of the surface chemical conversion treatment with metal ions.
One type of surface chemical conversion treatment for steel materials is chromate treatment in which hexavalent chromium ions are used as metal ions for chemical conversion treatment as a rust prevention treatment for zinc-based plated steel materials. However, recently, because hexavalent chromium is harmful to the human body, it is being shifted to chromate treatment using trivalent chromium ions together with organic acids as metal ions.
なお、従来の6価クロメート処理液は、濃縮液組成物の形態でも貯蔵安定性に優れた薬剤であって、密閉式の容器で保存しておけば、長期間保存しても性状に変化は無く、新しく液を調製した時と変わらない性能を得ることができる。 In addition, the conventional hexavalent chromate treatment liquid is a drug having excellent storage stability even in the form of a concentrated liquid composition, and if stored in a sealed container, the properties change even if stored for a long period of time. And the same performance as when a new solution is prepared.
ここに、3価クロメート処理液としては、例えば、特許文献1の例2には、3価クロムを有機酸とともに使用する場合の例として、有機酸としてマロン酸を用いた下記組成が開示されている。 Here, as a trivalent chromate treatment solution, for example, in Example 2 of Patent Document 1, the following composition using malonic acid as an organic acid is disclosed as an example of using trivalent chromium together with an organic acid. Yes.
50 g/L CrCl3・6H2O
100 g/L NaNO3
31.2g/L マロン酸
50 g / L CrCl 3・ 6H 2 O
100 g / L NaNO 3
31.2g / L malonic acid
上述のようなクロメート処理液は、使用に際して所定割合で各薬剤を含有する水溶液を調製している。これを建浴と云う。実験室では、その都度、建浴を行うことで実験を行っている。しかし、工業的に上述のようなクロメート処理を行う場合、その処理を行う現場でその都度、各種薬剤を調合することは煩雑であるため、通常は、予め調製された濃縮液をその都度、水で希釈して所定濃度のクロメート処理液とすることで建浴している。 The chromate treatment liquid as described above prepares an aqueous solution containing each drug at a predetermined ratio when used. This is called bathing. In the laboratory, experiments are conducted by performing bathing each time. However, when the chromate treatment as described above is industrially performed, it is complicated to prepare various chemicals each time the treatment is performed. Therefore, a concentrated solution prepared in advance is usually used each time. It is constructed by diluting with a chromate treatment solution of a predetermined concentration.
ところで、本発明者らは、特許文献1の開示するクロメート処理液の効果を確認するために実験を続けていたところ、たまたま予備に調製して放置されていた濃縮液からガス成分が発生していることに気が付いた。このまま放置すれば、容器の破壊、クロメート処理液の劣化が予想された。 By the way, when the present inventors continued the experiment to confirm the effect of the chromate treatment solution disclosed in Patent Document 1, a gas component was generated from the concentrated solution that happened to be prepared and allowed to stand. I realized that If left as it is, destruction of the container and deterioration of the chromate treatment liquid were expected.
このようなことはこれまで経験されなかったことである。すなわち、従来の6価クロメート濃縮液組成物の場合は、すでに述べたように、通常の条件下では、長期間密閉状態で保存してもガスの発生は認められず、性能低下も起こらない。 This has never been experienced before. That is, in the case of the conventional hexavalent chromate concentrate composition, as described above, no gas is generated and performance is not deteriorated even when stored in a sealed state for a long time under normal conditions.
そこで、さらに検討を重ねた結果、有機酸を使用した3価クロメート濃縮液組成物は、貯蔵安定性が非常に悪い不安定な薬剤であって、高温状況下 (35℃以上) で保存すると保存容器中にガスが充満して容器が膨れたり (変形したり) する傾向があることが判明した。 Therefore, as a result of further investigation, the trivalent chromate concentrate composition using organic acids is an unstable drug with very poor storage stability and is preserved when stored under high temperature conditions (35 ℃ or higher). It turned out that the container tends to be filled with gas and swell (deform).
もちろん、建浴してしまうと十分に希釈されているため、また短時間で使い切ってしまうため、ガス発生などの問題はなく、その限りでは性状は安定である。
したがって、3価クロメート処理をさらに普及させるためには、貯蔵安定性に優れた3価クロメート濃縮液組成物の開発が望まれる。
Of course, when the bath is built, it is sufficiently diluted and used up in a short time, so there is no problem of gas generation, etc., and as long as the property is stable.
Therefore, in order to further spread the trivalent chromate treatment, it is desired to develop a trivalent chromate concentrate composition having excellent storage stability.
このように、3価クロメート処理液でも建浴した液(希釈した液)ならばガスの発生は認められないが、原液(濃縮液)では高温状況下で密閉式容器にて長期間保存すると、ガスが発生し、容器の変形を引き起こす傾向が認められる。また、その劣化速度は保存する温度に影響を受け、高温であればあるほど劣化速度は速くなることが判明した。このようなことは従来は知られることはなかった。 In this way, generation of gas is not observed if it is a liquid (diluted liquid) that is also a trivalent chromate treatment liquid, but if it is stored for a long time in a sealed container under high temperature conditions in a stock solution (concentrated liquid), There is a tendency to generate gas and cause deformation of the container. Further, it has been found that the deterioration rate is affected by the storage temperature, and that the higher the temperature, the faster the deterioration rate. This has never been known before.
発生するガスの主な成分は、下記反応式で示すように、硝酸クロムの硝酸成分とマロン酸の反応による炭酸ガスであり、他にも窒素ガスや酸素ガスも発生すると考えられる。
2C3O4H4+4(NO3 - ) →6CO2 ↑+2N2↑+2O2↑+4H2O
そこで、本発明者らは、かかるガス発生の問題を回避する手段について検討したところ、まず考えられることは、濃縮液を収容する容器にガス抜きキャップを使用することである。
As shown in the following reaction formula, the main component of the generated gas is carbon dioxide gas due to the reaction between the nitric acid component of chromium nitrate and malonic acid, and it is considered that nitrogen gas and oxygen gas are also generated.
2C 3 O 4 H 4 +4 ( NO 3 -) → 6CO 2 ↑ + 2N 2 ↑ + 2O 2 ↑ + 4H 2 O
Therefore, the present inventors examined a means for avoiding such a problem of gas generation. The first thing that can be considered is to use a degassing cap for a container that contains the concentrate.
確かに、ガス抜き用キャップを使用すれば容器の変形は回避できるが、容器が倒れた状態で放置されるとキャップのガス抜き穴から液が徐々に漏れることがあり、その対策が求められ、コスト増加は避けられない。また、ガス抜きキャップを使用しても、ガス発生それ自体を防止できない以上、濃縮液の劣化は避けられない。 Certainly, if the cap for venting is used, deformation of the container can be avoided, but if the container is left in a collapsed state, the liquid may gradually leak from the venting hole of the cap, and countermeasures are required. An increase in cost is inevitable. Even if a gas vent cap is used, deterioration of the concentrate is inevitable as long as gas generation itself cannot be prevented.
ここに、本発明者らは、マロン酸とシュウ酸とを混合してシュウ酸を主成分とする有機酸として、好ましくはこれにさらにヒドロキノンなどの酸化防止剤を混合して硝酸クロム
に配合した場合にはほとんどガスの発生が見られないことが判明した。ここに「主成分として」とはより多く含むということで、本発明の場合、マロン酸とシュウ酸との混合有機酸ではシュウ酸の量がマロン酸の量より多い混合有機酸ということである。
Here, the present inventors mixed malonic acid and oxalic acid to form an organic acid mainly composed of oxalic acid, preferably further mixed with an antioxidant such as hydroquinone and mixed with chromium nitrate. In some cases, it was found that almost no gas was generated. Here, “as a main component” means that it contains more, and in the case of the present invention, in the mixed organic acid of malonic acid and oxalic acid, the amount of oxalic acid is a mixed organic acid greater than the amount of malonic acid. .
また、有機酸としてマロン酸に代えてシュウ酸を配合した場合、ガスの発生は実質上見られないことも判明した。
一般的に有機酸を使用する3価クロメート液には、耐食性能を向上させるため、マロン酸やシュウ酸といったクロムを錯体化させる成分が含有されることがある。したがって、それから分かるように、本発明において有機酸として配合されるマロン酸やシュウ酸は、クロメート皮膜の形成に何ら有害作用を及ぼすことはなく、むしろ耐食性が改善されることから、その実用上の意義は大きい。
It has also been found that when oxalic acid is blended in place of malonic acid as the organic acid, gas generation is virtually not observed.
In general, a trivalent chromate solution using an organic acid may contain a component complexing chromium, such as malonic acid or oxalic acid, in order to improve corrosion resistance. Therefore, as can be seen, malonic acid and oxalic acid blended as organic acids in the present invention have no adverse effect on the formation of the chromate film, but rather improve the corrosion resistance. Significance is great.
なお、本発明者らの知見によれば、硝酸クロムとマロン酸を高濃度で単に混合した場合にガス発生が見られる。
また、有機酸としてマロン酸に代えてシュウ酸を配合する場合は、金属イオンをシュウ酸により錯体化することで液の安定化を図ることができるのである。
According to the knowledge of the present inventors, gas generation is observed when chromium nitrate and malonic acid are simply mixed at a high concentration.
When oxalic acid is blended instead of malonic acid as the organic acid, the solution can be stabilized by complexing metal ions with oxalic acid.
さらに、本発明者らは、表面化成処理液濃縮組成物からガスが発生するのは、硝酸塩イオンが含有されていることであるから、濃縮液組成物としては硝酸塩イオンを配合することなく、金属イオンなどは塩化物イオンとして供給し、建浴時に、硝酸塩を配合することで、長期間の貯蔵安定性が確保できることを知った。表面化成処理液濃縮組成物の言わば分割貯蔵という考えである。希釈率ばかりでなく、それぞれの組成物の配合割合を予め指定しておけば、現場での建浴時にも容易に表面化成処理液を調製可能である。 Furthermore, since the present inventors generate nitrate gas from the surface chemical conversion liquid concentrated composition because it contains nitrate ions, the concentrated liquid composition does not contain nitrate ions. I knew that long-term storage stability could be secured by supplying ions as chloride ions and adding nitrate during the bath. This is the idea of divided storage of the surface chemical conversion liquid concentrated composition. If the blending ratio of each composition is specified in advance as well as the dilution rate, the surface chemical conversion treatment liquid can be easily prepared even at the time of on-site bathing.
ここで、「濃縮液」という場合、各成分の濃度は、希釈率2〜100 倍で希釈して建浴することを目安とした濃度であって、具体的には、前述の3価クロメート処理液を例にとると、そのときの濃縮液の組成は、例えば下記の通りである。 Here, in the case of “concentrated liquid”, the concentration of each component is a concentration based on diluting at a dilution rate of 2 to 100 times and as a guide, and specifically, the above-described trivalent chromate treatment. Taking the liquid as an example, the composition of the concentrated liquid at that time is, for example, as follows.
CrCl3・6H2O : 250g/L
NaNO3 : 500g/L
マロン酸 : 156g/L
ここに、本発明は、次の通りである。
CrCl 3・ 6H 2 O: 250g / L
NaNO 3 : 500g / L
Malonic acid: 156g / L
Here, the present invention is as follows.
(1) 金属イオンと、有機酸と、硝酸イオンと、ハイドロキノンとを含有する6価クロムフリーの表面化成処理用濃縮液組成物であって、前記有機酸が、(i)シュウ酸からなること、および(ii)シュウ酸とマロン酸とからなりシュウ酸の量がマロン酸の量より多い混合有機酸からなることの一方を満たすことを特徴とする貯蔵性を高めた6価クロムフリーの表面化成処理用濃縮液組成物。 (1) A hexavalent chromium-free concentrated composition for surface chemical conversion treatment containing a metal ion, an organic acid, a nitrate ion and hydroquinone , wherein the organic acid comprises (i) oxalic acid. And (ii) a hexavalent chromium-free surface-improved storability characterized by satisfying one of the following: consisting of oxalic acid and malonic acid and a mixed organic acid in which the amount of oxalic acid is greater than the amount of malonic acid Concentrated liquid composition for treatment.
(2) ハイドロキノンの濃度が0.01〜1.2g/Lである、上記(1) 記載の表面化成処理用濃縮液組成物。
(3) 前記有機酸の組成が、シュウ酸2水和物5〜15%から成る、上記(1) 記載の表面化成処理用濃縮液組成物。
(2) The concentrated composition for surface chemical conversion treatment according to (1) above, wherein the concentration of hydroquinone is 0.01 to 1.2 g / L.
(3) The concentrated liquid composition for surface chemical conversion treatment according to the above (1), wherein the composition of the organic acid comprises 5 to 15% oxalic acid dihydrate.
高温環境下 (50℃) にて保存した場合、従来の3価クロメート濃縮液組成物では1週間程度でガスの発生 (容器の変形) が確認されていたのに対し、本発明によれば、そのような高温環境下で1ヶ月以上経過しても性状が安定な有機酸を含有する3価クロメート濃縮液組成物を提供することが可能である。 When stored in a high temperature environment (50 ° C.), the conventional trivalent chromate concentrate composition showed gas generation (container deformation) in about one week, whereas according to the present invention, It is possible to provide a trivalent chromate concentrate composition containing an organic acid having stable properties even after one month or more has passed under such a high temperature environment.
また、ガスの発生がほとんどないためにガス抜きキャップを使用する必要がなく、マロン酸に比べ安価なシュウ酸をマロン酸の一部または全部に代替して使用できる点からもコスト低減が可能になる。 In addition, since there is almost no gas generation, there is no need to use a vent cap, and it is possible to reduce costs because oxalic acid, which is cheaper than malonic acid, can be used in place of part or all of malonic acid. Become.
すでに述べたように、有機酸を含有する3価クロメート処理液は通常は濃縮液組成物として調製され、これを例えば10倍に希釈した水溶液として建浴するのである。なお、本明細書において組成割合などは、特にことわりがない限り、質量および質量%でもって規定する。 As described above, the trivalent chromate treatment liquid containing an organic acid is usually prepared as a concentrated liquid composition, and is constructed as an aqueous solution diluted 10 times, for example. In the present specification, the composition ratio and the like are defined by mass and mass% unless otherwise specified.
ここに、本発明によれば、金属イオンとして3価クロムが代表例であるが、本発明はそれに限定されず、例えば、Na、Mg、Al、Si、K、Ca、Ti、V 、Mn、Fe、Co、Ni、Cu、Zn、Mo、Sn、Ba、W 、Biなどの金属のイオンを例示できる。これらの金属イオンの1種または2種以上を含有するものであってもよい。 Here, according to the present invention, trivalent chromium is a representative example of the metal ion, but the present invention is not limited thereto. For example, Na, Mg, Al, Si, K, Ca, Ti, V, Mn, Examples include ions of metals such as Fe, Co, Ni, Cu, Zn, Mo, Sn, Ba, W, and Bi. You may contain 1 type, or 2 or more types of these metal ions.
濃縮液組成物として、金属イオンは、通常の条件下では、イオン濃度として、0.1 〜20g/L 、好ましくは、1〜10g/L 含有されている。
本発明は、硝酸イオン、有機酸および金属イオンを含む表面化成処理液においてガス発生が見られる濃縮液組成物について、ガス発生を防止することにあり、その対象とする濃縮組成物に含まれる有機酸の例としては、シュウ酸が主成分として含有される。具体的には、例えば、濃縮液組成物全体に対して、シュウ酸2水和物が5 〜15%含有される。5%未満では、所期の効果はなく、一方、15%を超えると、希釈して建浴したときに処理外観を悪化させる原因となってしまう。
As a concentrate composition, metal ions are contained in an ion concentration of 0.1 to 20 g / L, preferably 1 to 10 g / L under normal conditions.
The present invention is to prevent gas generation in a concentrated liquid composition in which gas generation is observed in a surface chemical conversion treatment liquid containing nitrate ions, organic acids, and metal ions, and the organic contained in the target concentrated composition. As an example of the acid, oxalic acid is contained as a main component. Specifically, for example, oxalic acid dihydrate is contained in an amount of 5 to 15% with respect to the entire concentrated liquid composition. If it is less than 5%, the desired effect is not obtained. On the other hand, if it exceeds 15%, the appearance of the treatment will be deteriorated when diluted and bathed.
有機酸の濃度は一般には120 〜360g/L、好ましくは150 〜200g/L、である。
本発明の別の態様にあっては、上記有機酸としては、すでに述べたマロン酸の他に、リンゴ酸およびクエン酸の例がある。そのような有機酸を含む表面化成処理濃縮液組成物について、本発明によれば、シュウ酸、必要によりさらにヒドロキノンのような酸化防止剤を添加する。
The concentration of the organic acid is generally 120 to 360 g / L, preferably 150 to 200 g / L.
In another aspect of the present invention, examples of the organic acid include malic acid and citric acid in addition to the malonic acid already described. According to the present invention, the surface chemical conversion treatment concentrate composition containing such an organic acid is added with oxalic acid and, if necessary, an antioxidant such as hydroquinone.
有機酸としてマロン酸が用いられる6価クロムフリーの表面化成処理濃縮液組成物の場合には、マロン酸とシュウ酸との混合有機酸が、あるいはシュウ酸単独の有機酸が用いられる。 In the case of a hexavalent chromium-free surface chemical conversion concentrate composition in which malonic acid is used as the organic acid, a mixed organic acid of malonic acid and oxalic acid or an organic acid of oxalic acid alone is used.
このときの濃縮液における具体的濃度は、例えば、マロン酸とシュウ酸の混合有機酸では、120 〜360g/L、好ましくは、150 〜200g/Lである。シュウ酸単独の場合には、60〜180g/L、好ましくは、100 〜130g/Lである。 The specific concentration in the concentrated liquid at this time is, for example, 120 to 360 g / L, preferably 150 to 200 g / L for a mixed organic acid of malonic acid and oxalic acid. In the case of oxalic acid alone, it is 60 to 180 g / L, preferably 100 to 130 g / L.
有機酸としてリンゴ酸あるいはクエン酸が使用されている6価クロムフリーの表面化成処理濃縮液組成物の場合には、それぞれリンゴ酸あるいはクエン酸とシュウ酸との混合有機酸が、あるいはシュウ酸単独有機酸が用いられる。 In the case of a hexavalent chromium-free surface chemical conversion concentrated liquid composition in which malic acid or citric acid is used as the organic acid, malic acid or a mixed organic acid of citric acid and oxalic acid or oxalic acid alone Organic acids are used.
このときの濃縮液における具体的濃度は、例えば、りんご酸あるいはクエン酸とシュウ酸の混合有機酸では、120 〜360g/L、好ましくは、150 〜200g/Lである。シュウ酸単独の有機酸の場合には、60〜180g/L、好ましくは、100 〜130g/Lである。 The specific concentration in the concentrated liquid at this time is, for example, 120 to 360 g / L, preferably 150 to 200 g / L for malic acid or a mixed organic acid of citric acid and oxalic acid. In the case of an organic acid containing oxalic acid alone, it is 60 to 180 g / L, preferably 100 to 130 g / L.
ここで、3価クロムを用いる場合、3価クロムは、3価クロムがイオン化しておればその供給形態は特に制限されないが、一般には、例えば、硝酸塩あるいは塩化物の形態で配合される。硝酸塩の形態以外の場合には、硝酸イオンの供給源を一緒に配合する必要がある。 Here, in the case of using trivalent chromium, the supply form of trivalent chromium is not particularly limited as long as the trivalent chromium is ionized. However, in general, for example, it is blended in the form of nitrate or chloride. In cases other than the nitrate form, it is necessary to formulate a source of nitrate ions together.
例えば、亜鉛上に化成被膜を形成させるには亜鉛めっき表面を適度にエッチングして亜鉛を溶解させる必要があるが、そのときに硝酸イオンは特に効果的であり、通常、化成処理液には硝酸イオンを含有させている。したがって、金属イオンも、硝酸塩の形で供給されるのが好ましいが、上述のように硝酸塩は別途供給してもよい。 For example, in order to form a chemical conversion film on zinc, it is necessary to appropriately etch the zinc plating surface to dissolve zinc. At that time, nitrate ions are particularly effective. Contains ions. Accordingly, metal ions are preferably supplied in the form of nitrates, but nitrates may be supplied separately as described above.
濃縮液における硝酸イオンの具体的濃度は、硝酸イオンとして50〜300g/L、好ましくは、150 〜200g/Lである。
また、硝酸クロムとマロン酸を混合しても、酸化防止剤として例えばヒドロキノンを添加することによりガスの発生を効果的に抑制できる。
The specific concentration of nitrate ions in the concentrate is 50 to 300 g / L, preferably 150 to 200 g / L, as nitrate ions.
Even when chromium nitrate and malonic acid are mixed, generation of gas can be effectively suppressed by adding, for example, hydroquinone as an antioxidant.
このときのヒドロキノンの濃縮物における具体的濃度は、0.01〜1.2g/L、好ましくは、0.4 〜1.0g/Lである。
ここに、本発明の好適態様によれば、6価クロムフリー表面化成処理用濃縮液組成物は、シュウ酸2水和物5〜15%、マロン酸5〜15%、ヒドロキノン( 酸化防止剤)0.01 〜1 %から成るが、シュウ酸2水和物の組成限定理由はすでに述べた通りであるが、マロン酸の場合には、その範囲を外れると、希釈して化成処理液を建浴した場合に、所期の効果を得ることができない。酸化防止剤としてのヒドロキノンは、0.01%未満では、ガス発生を防止できず、1 %を超えると、建浴したときに化成処理性が十分でなくなるから、上記範囲に限定した。
The specific concentration in the hydroquinone concentrate at this time is 0.01 to 1.2 g / L, preferably 0.4 to 1.0 g / L.
Here, according to a preferred embodiment of the present invention, a concentrated liquid composition for hexavalent chromium-free surface chemical conversion treatment comprises oxalic acid dihydrate 5 to 15%, malonic acid 5 to 15%, hydroquinone (antioxidant) The reason for limiting the composition of oxalic acid dihydrate is as described above. However, in the case of malonic acid, when it was out of the range, it was diluted and the chemical conversion solution was built. In some cases, the desired effect cannot be obtained. When hydroquinone as an antioxidant is less than 0.01%, gas generation cannot be prevented, and when it exceeds 1%, the chemical conversion treatment property becomes insufficient when it is constructed, so it is limited to the above range.
本発明にかかる3価クロメート濃縮液組成物には、その他、金属塩、pH調整剤、等、従来の3価クロメート処理液に含まれる薬剤を適宜含有してもよい。
次に、本発明は、別の面からは、6価クロムフリーの表面化成処理用濃縮液組成物の安定化方法と云うこともでき、その場合には、表面化成処理用濃縮液組成物を、金属イオンと、有機酸と、そして金属イオンが塩化物として供給される場合には、さらに塩化物イオンとから調製し、水で希釈して建浴する際に、硝酸塩を配合するようにしてもよい。
In addition, the trivalent chromate concentrate composition according to the present invention may appropriately contain chemicals contained in the conventional trivalent chromate treatment liquid, such as metal salts and pH adjusters.
Next, from another aspect, the present invention can also be referred to as a method for stabilizing a concentrated solution composition for surface chemical conversion treatment that is free of hexavalent chromium. When metal ions, organic acids, and metal ions are supplied as chlorides, prepare further from chloride ions, and dilute with water to add nitrate when building. Also good.
濃縮液組成物の貯蔵安定性を阻害する要因の一つが、硝酸イオンであるから、濃縮液の形態では硝酸イオンを含まないようにする、つまり建浴時に初めて投入する (分割投入という) のである。もちろん、硝酸イオンは、化成被膜を形成する際の基地である鋼表面あるいは亜鉛めっき表面のエッチングとその上における被膜形成に有効であるから、硝酸イオンは通常の化成処理液では不可避の成分である。 Since one of the factors that hinders the storage stability of the concentrate composition is nitrate ions, it should not contain nitrate ions in the form of concentrates, that is, it is introduced for the first time during bathing (called split injection). . Of course, nitrate ions are effective for etching the steel surface or galvanized surface, which is the base for forming a chemical conversion film, and for forming a film thereon, so nitrate ions are an inevitable component in ordinary chemical conversion solutions. .
ここに、そのような態様にあっては、本発明は、6価クロムフリーの表面化成処理用液の調製方法と云うこともでき、その場合には、表面化成処理用濃縮液組成物を、金属イオンと、有機酸と、塩化物イオンとから調製し、水で希釈して建浴する際に、硝酸塩を配合するのである。 Here, in such an embodiment, the present invention can also be referred to as a method for preparing a hexavalent chromium-free surface chemical conversion treatment liquid. It is prepared from metal ions, organic acids, and chloride ions, and nitrates are blended when diluting with water and bathing.
本例では、表1に示す各組成をもって3価クロメート濃縮液組成物を調製し、これを試験液とした。
試験要領は、図1に模式的に示すが、まず、上述のようにして調製した3価クロメート濃縮液組成物のに各試験液10を、内蓋のついた密閉型の1L 容器12に試験液を1L 秤量して注入し、内蓋( 図示せず) および外蓋16をしっかりと嵌めて密封状態にした。
In this example, a trivalent chromate concentrate composition was prepared with each composition shown in Table 1, and this was used as a test solution.
The test procedure is shown schematically in FIG. 1. First, each
50℃に保温した湯浴20に容器12が最低8割方は浸漬するようにして、その経時変化 (容器の変形) を目視にて判定した。湯浴20はヒータ22によって50℃の一定温度に維持されており、ノズル24から空気を吹き込んで浴を攪拌し、浴の温度を可及的一定に保っている。
At least 80% of the
比較例として、ハイドロキノンに代えて、L−アスコルビン酸、カテコール、レゾルシンをそれぞれ酸化防止剤として用いたが、ガス発生を防止する効果は見られなかった。
さらに比較例として、有機酸のマロン酸に代えて、リンゴ酸、クエン酸を使用したがガスの発生は避けられなかった。
As a comparative example, L-ascorbic acid, catechol, and resorcin were used as antioxidants in place of hydroquinone, but no effect of preventing gas generation was observed.
Further, as a comparative example, malic acid and citric acid were used in place of the organic acid malonic acid, but the generation of gas was inevitable.
このときの試験結果は、表1にまとめて示す。
容器内の濃縮液の様子は、次の基準で目視判定した。
〇: 30日、40日または 50日経過後も液性状は安定しており、当初の状態を保持していた。
×: 3日または7日経過後に、液内にはガス発生が見られ、容器が全体的に膨張しており、一部のものは蓋が外れていた。
The test results at this time are summarized in Table 1.
The state of the concentrated liquid in the container was visually determined according to the following criteria.
〇: The liquid properties were stable after 30 days, 40 days or 50 days, and the original state was maintained.
X: After 3 days or 7 days, gas generation was observed in the liquid, the container was expanded as a whole, and some of the containers were uncovered.
したがって、本発明によれば、以上の結果から、高温環境下 (50℃) にて保存した場合、従来の3価クロメート濃縮液組成物では1週間程度でガスの発生 (容器の変形) が確認されていたのに対し、本発明では高温環境下で1ヶ月以上経過しても、その後の希釈で性状が安定な有機酸含有3価クロメート液を提供することが可能であることが分かる。 Therefore, according to the present invention, from the above results, when stored in a high temperature environment (50 ° C.), the conventional trivalent chromate concentrate composition confirms gas generation (deformation of the container) in about one week. On the other hand, it can be seen that the present invention can provide an organic acid-containing trivalent chromate solution having stable properties by subsequent dilution even after one month or more has passed in a high temperature environment.
実施例4は、いわゆる分割投入の例であり、硝酸塩は建浴のときに添加しており、表1に示すのは、硝酸塩を含まない濃縮液についての結果である。 Example 4 is an example of so-called split injection, and nitrate is added at the time of building bath, and Table 1 shows the results for a concentrated solution not containing nitrate.
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007261009A JP4845050B2 (en) | 2007-10-04 | 2007-10-04 | Concentrated liquid composition for hexavalent chromium-free surface conversion treatment with improved stability |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007261009A JP4845050B2 (en) | 2007-10-04 | 2007-10-04 | Concentrated liquid composition for hexavalent chromium-free surface conversion treatment with improved stability |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2003418347A Division JP2005179702A (en) | 2003-12-16 | 2003-12-16 | Hexavalent chromium-free concentrate composition for surface chemical conversion having enhanced stability |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2008019512A JP2008019512A (en) | 2008-01-31 |
JP4845050B2 true JP4845050B2 (en) | 2011-12-28 |
Family
ID=39075687
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2007261009A Expired - Lifetime JP4845050B2 (en) | 2007-10-04 | 2007-10-04 | Concentrated liquid composition for hexavalent chromium-free surface conversion treatment with improved stability |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4845050B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010087442A1 (en) * | 2009-01-30 | 2010-08-05 | ユケン工業株式会社 | Composition for chemical conversion coating, and member equipped with chemical conversion coating film comprising the composition |
WO2013011950A1 (en) * | 2011-07-15 | 2013-01-24 | ユケン工業株式会社 | Aqueous acidic composition for forming chromium-containing conversion coating on ferrous member, and ferrous member having conversion coating formed using said composition |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2654440B1 (en) * | 1989-11-16 | 1993-07-30 | Produits Ind Cie Fse | PROCESS FOR THE CHEMICAL CONVERSION OF METAL SUBSTRATES, BATH USED IN THIS PROCESS AND CONCENTRATE FOR THE PREPARATION OF THE BATH. |
DE10005113A1 (en) * | 2000-02-07 | 2001-08-09 | Henkel Kgaa | Corrosion inhibitor and corrosion protection method for metal surfaces |
JP2002249884A (en) * | 2001-02-23 | 2002-09-06 | Nippon Light Metal Co Ltd | Substrate treatment method for imparting-alkali corrosion resistance to aluminum material |
JP3332374B1 (en) * | 2001-11-30 | 2002-10-07 | ディップソール株式会社 | A treatment solution for forming a hexavalent chromium-free rust preventive film on zinc and zinc alloy plating, a hexavalent chromium-free rust preventive film, and a method for forming the same. |
JP2003193286A (en) * | 2001-12-27 | 2003-07-09 | Ishihara Chem Co Ltd | Gold - tin alloy plating bath |
-
2007
- 2007-10-04 JP JP2007261009A patent/JP4845050B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JP2008019512A (en) | 2008-01-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8070886B2 (en) | Treatment solution for forming of black trivalent chromium chemical coating on zinc or zinc alloy and method of forming black trivalent chromium chemical coating on zinc or zinc alloy | |
JP3332373B1 (en) | A treatment solution for forming a hexavalent chromium-free rust preventive film on zinc and zinc alloy plating, a hexavalent chromium-free rust preventive film, and a method for forming the same. | |
JP5198727B2 (en) | Treatment solution for forming black hexavalent chromium-free conversion coating on zinc or zinc alloy | |
CA2450644A1 (en) | Treating solution for metal surface treatment and a method for surface treatment | |
CN102268667A (en) | Corrosion-resistant trivalent-chromium chemical conversion coating and solution for trivalent-chromium chemical treatment | |
JP4845050B2 (en) | Concentrated liquid composition for hexavalent chromium-free surface conversion treatment with improved stability | |
JPH06306652A (en) | Corrosion inhibitor for metal and corrosion inhibiting method for metal | |
JP2005126797A (en) | Trivalent chromate liquid, and method of forming hexavalent chromium-free corrosion resistant film on zinc-nickel alloy plating using the liquid | |
JP2010209456A (en) | Immersion treatment liquid for rust prevention of plated chromium film, and rust-preventing treatment method | |
JP2005179702A (en) | Hexavalent chromium-free concentrate composition for surface chemical conversion having enhanced stability | |
JP5336742B2 (en) | Chemical conversion treatment method for forming a trivalent chromium chemical conversion coating having good heat and corrosion resistance on zinc or zinc alloy plating | |
JP2001279462A (en) | Surface treating agent and surface treating method for zinc or zinc alloy | |
TWI421383B (en) | Ferrous ion-containing aqueous solution | |
JP4384471B2 (en) | Method of forming hexavalent chromium-free corrosion-resistant film on zinc-nickel alloy plating | |
JP2005008948A (en) | Composition for surface treatment of aluminum and aluminum alloy | |
JP2016108640A (en) | Method and solution for passivating stainless steel component | |
US3850767A (en) | Electrolytic treatment of stainless steel having an oxidic film | |
JP2008261017A (en) | Blackened corrosion resistant film, machine device provided with the corrosion resistant film, and method for forming corrosion resistant film | |
Karthik et al. | Corrosion Behaviour of Carbon Steel in DTPMP-ST-Zn 2 System: An Eco-Friendly System | |
JP5799037B2 (en) | Film formation method by plasma electrolytic oxidation | |
JP5300113B2 (en) | Metal surface treatment agent, metal surface treatment method using metal surface treatment agent, and iron component subjected to surface treatment | |
JP2003519290A (en) | Luster / passivation of metal surfaces without risk of nitrogen oxide release | |
JP2006028547A (en) | Surface treatment liquid and method for preparation thereof | |
JP4159879B2 (en) | Acid bath for zinc-manganese alloy electrodeposition | |
JP2005232504A (en) | Solution and method for blackening zinc or zinc alloy |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100929 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20101102 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101224 |
|
RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20110708 |
|
RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20110726 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110914 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20111005 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20141021 Year of fee payment: 3 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 4845050 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
EXPY | Cancellation because of completion of term |