JP4156559B2 - リン酸クロム水溶液の製造方法 - Google Patents
リン酸クロム水溶液の製造方法 Download PDFInfo
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- JP4156559B2 JP4156559B2 JP2004142871A JP2004142871A JP4156559B2 JP 4156559 B2 JP4156559 B2 JP 4156559B2 JP 2004142871 A JP2004142871 A JP 2004142871A JP 2004142871 A JP2004142871 A JP 2004142871A JP 4156559 B2 JP4156559 B2 JP 4156559B2
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- chromium
- chromium phosphate
- present
- solution
- 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
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- 229910000151 chromium(III) phosphate Inorganic materials 0.000 title claims description 46
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 57
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000011651 chromium Substances 0.000 claims description 20
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 16
- 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 claims description 16
- 235000006408 oxalic acid Nutrition 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000003638 chemical reducing agent Substances 0.000 description 12
- 235000011007 phosphoric acid Nutrition 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 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 6
- 238000011282 treatment Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- XHFVDZNDZCNTLT-UHFFFAOYSA-H chromium(3+);tricarbonate Chemical compound [Cr+3].[Cr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XHFVDZNDZCNTLT-UHFFFAOYSA-H 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 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 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006479 redox reaction 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
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 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
- 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
クロム酸水溶液に予めリン酸を混合し、反応系内の酸性度を高めておき、次いでメチルアルコールを添加することを特徴とする組成式Cr(H 3-3/n PO 4 ) n (式中、nは2≦n≦3の数である)で表されるリン酸クロム水溶液の製造方法を提供するものである。
先に述べた特許文献2では、六価のクロムを確実に三価のクロムに還元させるために、硝酸クロム水溶液中に或る程度以上の量のTOCが必要であることが記載されている。しかし本発明者らがTOCに関して詳細に検討を行ったところ、TOCの量を増やすと、リン酸クロム水溶液を金属の表面処理剤として用いた場合に十分な光沢が得られないことが判明した。本発明のリン酸クロム水溶液を、後述する製造方法で製造すれば、TOCが低レベルであっても、六価のクロムを確実に消滅させることができる。本発明のリン酸クロム水溶液におけるTOCの下限値に特に制限はないが、後述する製造方法を用いるとTOCを0.05重量%という極めて低いレベルにすることができる。
10H2CrO4+10xH3PO4+3(CH2OH)2 → 10Cr(H3-3/xPO4)x+6CO2+34H2O
コンデンサー付きのガラス製反応槽に60%クロム酸水溶液242.9gを入れた。これに水121.5gと571.4gの75%リン酸を投入し、充分撹拌してクロム酸及びリン酸の混合水溶液を作成した。これとは別に、あらかじめ98.5%のエチレングリコール27.5gに水75.2gを加え、26%に希釈しておいたエチレングリコール水溶液を3時間かけて添加した。その後熟成を30分継続した。このときの温度は108℃であった。熟成後、残存のCr6+をチェックし、エチレングリコール水溶液を追加してさらに熟成を継続した。ジフェニルカルバジット法にてCr6+の発色がなくなったことを確認して反応終了とした。得られたリン酸クロム水溶液の組成は以下の通りであった。
コンデンサー付きのガラス製反応槽に、水を387.3g入れ、更に三酸化クロム酸122.8gを投入し、充分撹拌して溶解した。次いで320.0gの75%リン酸を投入し、クロム酸及びリン酸の混合水溶液を作成した。これとは別に、あらかじめ99.5%のメチルアルコール19.7gに水177.1gを加え、10%に希釈しておいたメチルアルコール水溶液を3時間かけて添加した。その後熟成を30分継続した。このときの温度は108℃であった。熟成後、残存のCr6+をチェックし、メチルアルコール水溶液を追加してさらに熟成を継続した。ジフェニルカルバジット法にてCr6+の発色がなくなったことを確認して反応終了とした。得られたリン酸クロム水溶液の組成は以下の通りであった。
実施例1で用いたエチレングリコールに代えてグルコースを用いる以外は実施例1と同様にしてリン酸クロム水溶液を得た。得られたリン酸クロム水溶液の組成は以下の通りであった。
実施例1、2及び比較例1で得られたリン酸クロム水溶液を用いてクロメート処理液を建浴し、亜鉛めっき鋼板のテストピースを浸漬、乾燥してクロメート処理を行った。処理後の光沢の程度を評価した結果を以下の表4に示す。表4中、○は光沢が良好であることを示し、×は光沢が充分でないことを示す。
Claims (1)
- 組成式Cr(H 3-3/n PO 4 ) n (式中、nは2≦n≦3の数を示す)で表され、六価のクロムが実質的に存在していないリン酸クロムを含む水溶液であって、全有機炭素がクロムに対して3.5重量%以下で且つ該水溶液中のシュウ酸の含有量が0.5重量%以下であることを特徴とする金属の表面処理用又はクロメート用リン酸クロム水溶液の製造方法であって、
クロム酸水溶液に予めリン酸を混合し、反応系内の酸性度を高めておき、次いでメチルアルコールを添加することを特徴とする組成式Cr(H 3-3/n PO 4 ) n (式中、nは2≦n≦3の数である)で表されるリン酸クロム水溶液の製造方法。
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004142871A JP4156559B2 (ja) | 2004-05-12 | 2004-05-12 | リン酸クロム水溶液の製造方法 |
CA002545320A CA2545320A1 (en) | 2003-12-10 | 2004-11-22 | Aqueous solution of chromium salt and method for producing same |
BRPI0416838-0A BRPI0416838A (pt) | 2003-12-10 | 2004-11-22 | solução aquosa de sal de cromo e método para produção da mesma |
KR1020127017977A KR101265801B1 (ko) | 2003-12-10 | 2004-11-22 | 크롬염 수용액 및 그의 제조 방법 |
KR1020067011319A KR101190369B1 (ko) | 2003-12-10 | 2004-11-22 | 크롬염 수용액 및 그의 제조 방법 |
US10/578,626 US7641721B2 (en) | 2003-12-10 | 2004-11-22 | Aqueous solution of chromium salt and method for producing same |
PCT/JP2004/017353 WO2005056478A1 (ja) | 2003-12-10 | 2004-11-22 | クロム塩水溶液及びその製造方法 |
EP04820113A EP1712524A4 (en) | 2003-12-10 | 2004-11-22 | AQUEOUS CHROMIUM SALT SOLUTION AND MANUFACTURING METHOD THEREFOR |
TW093136279A TWI285224B (en) | 2003-12-10 | 2004-11-25 | Aqueous solution of chromium salt and method for producing same |
US12/646,048 US8083842B2 (en) | 2003-12-10 | 2009-12-23 | Aqueous solution of chromium salt and method for producing same |
US13/338,012 US20120199787A1 (en) | 2003-12-10 | 2011-12-27 | Aqueous solution of chromium salt and method for producing same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004142871A JP4156559B2 (ja) | 2004-05-12 | 2004-05-12 | リン酸クロム水溶液の製造方法 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP2008145628A Division JP4659855B2 (ja) | 2008-06-03 | 2008-06-03 | リン酸クロム水溶液 |
Publications (3)
Publication Number | Publication Date |
---|---|
JP2005325384A JP2005325384A (ja) | 2005-11-24 |
JP2005325384A5 JP2005325384A5 (ja) | 2006-01-12 |
JP4156559B2 true JP4156559B2 (ja) | 2008-09-24 |
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Family Applications (1)
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JP2004142871A Expired - Lifetime JP4156559B2 (ja) | 2003-12-10 | 2004-05-12 | リン酸クロム水溶液の製造方法 |
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Country | Link |
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JP (1) | JP4156559B2 (ja) |
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2004
- 2004-05-12 JP JP2004142871A patent/JP4156559B2/ja not_active Expired - Lifetime
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JP2005325384A (ja) | 2005-11-24 |
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