JPS62238379A - Additive for chemical dissolving solution for metallic surface - Google Patents
Additive for chemical dissolving solution for metallic surfaceInfo
- Publication number
- JPS62238379A JPS62238379A JP7964386A JP7964386A JPS62238379A JP S62238379 A JPS62238379 A JP S62238379A JP 7964386 A JP7964386 A JP 7964386A JP 7964386 A JP7964386 A JP 7964386A JP S62238379 A JPS62238379 A JP S62238379A
- Authority
- JP
- Japan
- Prior art keywords
- additive
- acid
- solution
- salt
- added
- 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
- 239000000654 additive Substances 0.000 title claims abstract description 39
- 230000000996 additive effect Effects 0.000 title claims abstract description 27
- 239000000126 substance Substances 0.000 title claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 229920000768 polyamine Polymers 0.000 claims abstract description 11
- 239000013522 chelant Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 32
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 abstract description 4
- 229910000831 Steel Inorganic materials 0.000 abstract description 3
- 239000010959 steel Substances 0.000 abstract description 3
- 150000003464 sulfur compounds Chemical class 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 12
- -1 fatty acid salts Chemical class 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- 238000004090 dissolution Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 9
- 238000005530 etching Methods 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical class CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical class CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 3
- 229950006389 thiodiglycol Drugs 0.000 description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 3
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 2
- YCLSOMLVSHPPFV-UHFFFAOYSA-N 3-(2-carboxyethyldisulfanyl)propanoic acid Chemical compound OC(=O)CCSSCCC(O)=O YCLSOMLVSHPPFV-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-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
- 206010011878 Deafness Diseases 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Chemical class 0.000 description 2
- 239000003490 Thiodipropionic acid Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 231100000895 deafness Toxicity 0.000 description 2
- 208000016354 hearing loss disease Diseases 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical class [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 235000019303 thiodipropionic acid Nutrition 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 1
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- HKNNAYPWWDWHFR-UHFFFAOYSA-N 1-sulfanylbutan-1-ol Chemical compound CCCC(O)S HKNNAYPWWDWHFR-UHFFFAOYSA-N 0.000 description 1
- AEUVIXACNOXTBX-UHFFFAOYSA-N 1-sulfanylpropan-1-ol Chemical compound CCC(O)S AEUVIXACNOXTBX-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- DLLMHEDYJQACRM-UHFFFAOYSA-N 2-(carboxymethyldisulfanyl)acetic acid Chemical compound OC(=O)CSSCC(O)=O DLLMHEDYJQACRM-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- CFPHMAVQAJGVPV-UHFFFAOYSA-N 2-sulfanylbutanoic acid Chemical compound CCC(S)C(O)=O CFPHMAVQAJGVPV-UHFFFAOYSA-N 0.000 description 1
- IMGGANUNCHXAQF-UHFFFAOYSA-N 2-sulfanylpentanoic acid Chemical compound CCCC(S)C(O)=O IMGGANUNCHXAQF-UHFFFAOYSA-N 0.000 description 1
- IYGAMTQMILRCCI-UHFFFAOYSA-N 3-aminopropane-1-thiol Chemical compound NCCCS IYGAMTQMILRCCI-UHFFFAOYSA-N 0.000 description 1
- RIRRYXTXJAZPMP-UHFFFAOYSA-N 4-aminobutane-1-thiol Chemical compound NCCCCS RIRRYXTXJAZPMP-UHFFFAOYSA-N 0.000 description 1
- ACAYZXFEFNEADF-UHFFFAOYSA-N 5-(4-carboxybutylsulfanyl)pentanoic acid Chemical compound OC(=O)CCCCSCCCCC(O)=O ACAYZXFEFNEADF-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 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
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 241000287828 Gallus gallus Species 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
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- KFFQABQEJATQAT-UHFFFAOYSA-N N,N'-dibutylthiourea Chemical compound CCCCNC(=S)NCCCC KFFQABQEJATQAT-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- 229920002518 Polyallylamine hydrochloride Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241001474791 Proboscis Species 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 159000000021 acetate salts Chemical class 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 229960001748 allylthiourea Drugs 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 description 1
- KYNFOMQIXZUKRK-UHFFFAOYSA-N bishydroxyethyldisulfide Natural products OCCSSCCO KYNFOMQIXZUKRK-UHFFFAOYSA-N 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- DLEPCXYNAPUMDZ-UHFFFAOYSA-N butan-2-ylphosphonic acid Chemical compound CCC(C)P(O)(O)=O DLEPCXYNAPUMDZ-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DUYAAUVXQSMXQP-UHFFFAOYSA-N ethanethioic S-acid Chemical class CC(S)=O DUYAAUVXQSMXQP-UHFFFAOYSA-N 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 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 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 230000001965 increasing effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 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
- 210000003127 knee Anatomy 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229960003151 mercaptamine Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IMENJLNZKOMSMC-UHFFFAOYSA-N n'-[2-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCNCCN IMENJLNZKOMSMC-UHFFFAOYSA-N 0.000 description 1
- RUSNFULRUJHOPI-UHFFFAOYSA-N n'-[2-[2-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCNCCNCCN RUSNFULRUJHOPI-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical class OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical class NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- ing And Chemical Polishing (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は金属製品の製造工程において、その表面を溶解
させるための化学溶解液に添加使用する添加剤に係り、
本添加剤を添加しない場合に比して、より良好な仕上り
面を得せしめるものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an additive that is added to a chemical solution for dissolving the surface of a metal product in the manufacturing process of the metal product.
This results in a better surface finish than when this additive is not added.
背景技術とその問題点
金属とくに軟鋼、ステンレス鋼、鉄−ニッケル系合金、
鉄−ニッケルーコバルト系合金など鉄系合金を最終製品
にする工程において、屡々エツチング、化学研磨、電解
研磨などの化学溶解処理が施こされている。Background technology and its problems Metals, especially mild steel, stainless steel, iron-nickel alloys,
In the process of turning iron alloys such as iron-nickel-cobalt alloys into final products, chemical dissolution treatments such as etching, chemical polishing, and electrolytic polishing are often performed.
これら金属表面の溶解処理に使用される化学溶解液は、
通常塩酸、硫醗、燐酸、弗酸などの鉱酸の単独、あるい
はそれらの混酸に酸化剤として硝酸、クロム酸またはそ
の塩、過酸化水素、第二鉄塩（塩化第２鉄、硫酸第二鉄
、硝酸第二鉄等）などを加えた水溶液が使用されている
が、本発明にいう化学溶解液とは、塩酸、硫！、燐酸、
硝酸の単独あるいは混酸と、第二鉄塩例えば塩化第二鉄
との混合液（以下化学溶解液または単に溶解液と略す）
をいう。The chemical solution used for dissolving these metal surfaces is
Normally, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and hydrofluoric acid are used singly or in combination with nitric acid, chromic acid or their salts, hydrogen peroxide, ferric salts (ferric chloride, sulfuric acid, etc.) as oxidizing agents. Although an aqueous solution containing iron, ferric nitrate, etc.) is used, the chemical solution referred to in the present invention refers to hydrochloric acid, sulfuric acid, etc. ,phosphoric acid,
A mixed solution of nitric acid alone or a mixed acid and a ferric salt such as ferric chloride (hereinafter abbreviated as chemical solution or simply solution)
means.
なお、これら溶解液は、金属とのぬれ特性を付与するた
めに、界面活性剤やポリオール類などの水溶性高分子等
を添加してもよい。Incidentally, a surfactant, a water-soluble polymer such as polyols, etc. may be added to these solutions in order to impart wetting properties with the metal.
一般に、これら溶解液の使用は、金属の仕上り面に、多
くの場合局部腐食による多数の孔食（ビット）を生じて
おり、製品として要求される表面平滑性、光沢性を充分
には満足せしめ得ないという問題点がある。In general, the use of these solutions often causes a large number of pitting corrosion (bits) on the finished surface of the metal due to local corrosion, and the surface smoothness and gloss required for the product are not fully satisfied. The problem is that you can't get it.
本発明は、金属の溶解速度に影響することなく、前記問
題点を解消し、金属表面を良好ならしめる金属表面の化
学溶解液用添加剤（以下単に添加剤と略す）を提供する
ものである。The present invention provides an additive for a chemical solution for metal surfaces (hereinafter simply referred to as the additive) that solves the above-mentioned problems and improves the metal surface without affecting the dissolution rate of the metal. .
問題解決の手段
本発明は、金属表面を溶解処理する時、上記問題を解決
するため、化学溶解液に添加する添加剤であって、該添
加剤はＡ〕ポリアミンまたはそのる。Means for Solving the Problem The present invention provides an additive that is added to a chemical solution when dissolving a metal surface in order to solve the above-mentioned problems, and the additive is A] polyamine or the like.
以下、本発明の金属表面の化学溶解液用添加剤を構成す
る各成分について詳述する。Each component constituting the additive for a chemical solution for metal surfaces of the present invention will be described in detail below.
は
Ａ〕 ポリアミン吻岬−−桔まもその塩この化合物は金
属表面の孔食抑制効果を有し、次のような（Ｉ）および
（Ｉｔ）よりなるグループより選ばれたチ転和かも一種
以上の混合物である。is A] Polyamine proboscis - salt of Kimamo This compound has the effect of inhibiting pitting corrosion on metal surfaces, and may be a type of compound selected from the group consisting of (I) and (It) as follows. It is a mixture of the above.
（Ｉ）一般式 で表わされる７リーのぎりアミン類。(I) General formula 7 Li nogiri amines represented by
（ＩＩ） 上記一般式で表わされるポリアミン類の塩
酸。(II) Hydrochloric acid of polyamines represented by the above general formula.
燐酸或は炭素数２〜４の脂肪酸塩類。Phosphoric acid or fatty acid salts having 2 to 4 carbon atoms.
■ ｍ＝１ 、Ａ 、ｅ＝ｏの時Ｒ１＊ Ｒ２ｅ Ｒ５
＊ Ｒ６＝水素を表し、ｔｈ ＝ ２ 、 ｓａ ＝
ｌ及びｄ＝２〜９の整数。■ When m=1, A, e=o R1* R2e R5
*R6=represents hydrogen, th=2, sa=
l and d = integers from 2 to 9.
■ ｇ＝ｉ 、 ｂ＝ｏでＲ１ｔ Ｒｆｆｉ ＊ ＲＪ
ｅ Ｒ４＝水素で、Ｒ４＝ ＣＨ２−ＣＨ，−ＮＨ２
を表し、ｍ＝２．（：、ｄ：各々１．％：２〜２００の
整数。■ R1t Rffi * RJ with g=i and b=o
e R4=hydrogen, R4= CH2-CH, -NH2
represents m=2. (:, d: 1.% each: an integer from 2 to 200.
■ ａ 、 Ｃ、ｄ ＝ ０ テＲ，、Ｒ６＝ −ＣＨ
，−ＣＭ −Ｒ３＝ −ＣＨ２−ＮＨ２、ｂ＝ ５０〜
４０００ （７）整数。■ a, C, d = 0 teR,, R6= -CH
, -CM -R3= -CH2-NH2, b= 50~
4000 (7) Integer.
■ ｌ、、ｅ＝ＱでＲ１ｚ Ｒ２＃ Ｒ５ｔ Ｒ８＝水
素を表す。■ l,, e=Q represents R1z R2# R5t R8=hydrogen.
旙＝６ 、 ｍ＝ｌ 、α＝１及びｄ＝２の整数。旙=6 m=l , α=1 and d=2 integers.
これら化合物の具体例としては、ジエチレントリアミン
、トリエチレンテトラミン、テトラエチレンペンタミン
、ペンタエチレンへキサミン、ヘキサエチレンへブタミ
ン、ヘプタエチレンオクタミン、オクタエチレンノナミ
ン、ノナエチレンデカミンなどのポリアルキレンポリア
ミン類、及びその塩酸塩、燐酸塩、酢酸塩、プロピオン
酸塩などのポリアルキレンポリアミン塩類、ポリエチレ
ンイミン類及びその塩酸塩、ｊｓ酸塩、酢酸塩、プロピ
オン酸塩などのポリエチレンイミン塩類、ポリ了りルア
ミン或はその塩酸塩、燐酸塩、酢酸塩、プロピオン酸塩
などのポリアリルアミン塩類、ビスへキサメチレントリ
アミン及びその塩酸塩。Specific examples of these compounds include polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethylenehebutamine, heptaethyleneoctamine, octaethylenenonamine, and nonaethylenedecamine; Polyalkylenepolyamine salts such as its hydrochloride, phosphate, acetate, propionate, polyethyleneimine and its hydrochloride, polyethyleneimine salt such as its salt, acetate, propionate, polyesterylamine or Polyallylamine salts such as its hydrochloride, phosphate, acetate, propionate, bishexamethylene triamine and its hydrochloride.
燐酸塩、酢酸塩、プロピオン酸塩などを例示される。Examples include phosphates, acetates, and propionates.
Ｂ〕有機硫黄化合物
この化合物は金属表面の孔食抑制作用の他表面の荒れ防
止及び光沢作用を有しており、次の一般式（１）および
〔■〕よりなるグループより選ばれたすき＊呑を一種以
上の混合物である。B] Organic sulfur compound This compound has the effect of suppressing pitting corrosion on metal surfaces, as well as preventing surface roughness and brightening. is a mixture of more than one type.
（１） Ｒ７−（Ｓｑ Ｒｓ
■ Ｒγｔ Ｒ＋ ニー（ＣＨｚｋＲｅで同一または異
なってもよい。(1) R7-(Sq Rs ■ Rγt R+ knee (may be the same or different in CHzkRe).
Ｒ，＝−ＯＨ、−ＮＨ，、−ＣＯＯＨであり、鶏＝１〜
４及び聾＝１〜２の整数。R, = -OH, -NH,, -COOH, and chicken = 1~
4 and deafness = integer from 1 to 2.
Ｒ９が一〇〇〇Ｈの場合はＣ６までのアルカノールアミ
ン塩、まなは−ＮＨ２の場合は無機酸塩あるいは炭素数
１〜３の有機醗塩でもよい。When R9 is 1000H, it may be an alkanolamine salt up to C6, and when R9 is -NH2, it may be an inorganic acid salt or an organic salt having 1 to 3 carbon atoms.
■ Ｒ７：Ｈｔたはアルカリ金属塩＊ Ｒｓ 堅ＣＨ２
％Ｒｘ。■ R7: Ht or alkali metal salt *Rs hard CH2
%Rx.
であり、
Ｒ１，： −ＣＯＯＨ、−ＯＨ、−ＮＨ，であり、蕩＝
１〜３及び聾＝１の整数、
ＲＩＯが−ＣＯＯＨの場合は、炭素数６までのアルカノ
ールアミン塩、ま之は−ＮＨ２の場合は、無機酸塩ある
いは炭素数１〜３の有機醜塩であってもよい。and R1,: -COOH, -OH, -NH, and 蕩=
An integer of 1 to 3 and deafness = 1. If RIO is -COOH, it is an alkanolamine salt with up to 6 carbon atoms, and if RIO is -NH2, it is an inorganic acid salt or an organic ugly salt with 1 to 3 carbon atoms. There may be.
Ｒ１１ｅ Ｒ１２”同一ま之は異なっていてもよく、各
々水素、炭素数１〜８のアルキル基、アルケニル基、ア
リル基、アルキルアリル基、アラルＲ１３：■″１なは
■で示され、
Ｒ１４＋ Ｒ１５＝ Ｒ１１ｐ Ｒ１２と同内容である
。R11e R12" The same or different values may be different, and each is represented by hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkenyl group, an allyl group, an alkylaryl group, an aral R13:■"1 is represented by ■, R14+ R15 = R11p Same content as R12.
■：炭素数１〜３のアルキル基、アルケニル基
これら化合物の具体例は（１）に属するものとして〔１
１〕〜〔■５〕が挙げられる。■: Alkyl group, alkenyl group having 1 to 3 carbon atoms Specific examples of these compounds belong to (1) [1
1] to [■5].
（ＩＩ ） メルカプトエタノール、メルカプトプロ
パツール、メルカプトブタノール、チオジグリコール、
チオジェタノール、チオジブロバノール。(II) Mercaptoethanol, mercaptopropanol, mercaptobutanol, thiodiglycol,
Thiogetanol, Thiodibrobanol.
チオジプタノール、ジチオジグリコール、ジチオジェタ
ノール、ジチオジブロバノール、ジチオシフタノールな
どのチオアルコール類。Thioalcohols such as thiodiptanol, dithiodiglycol, dithiodigetanol, dithiodibrobanol, and dithiosyphtanol.
〔Ｉ２〕 メルカプトエチルアミン、メルカプドブ田
ビルアミン、メルカプトブチルアミン、チオジエチルア
ミン、チオジブ四ビルアミン、チオジプチルアミン、ジ
チオジエチルアミン、ジチオジプロピルアミン、ジチオ
ジプチルアミンなどのチオアミン類。[I2] Thioamines such as mercaptoethylamine, mercaptobutabylamine, mercaptobutylamine, thiodiethylamine, thiodibuteterbylamine, thiodiptylamine, dithiodiethylamine, dithiodipropylamine, and dithiodiptylamine.
〔Ｉ３〕 これら（１１） 、 （１２）の塩酸、燐
酸及び酢酸塩。[I3] Hydrochloric acid, phosphoric acid and acetate salts of these (11) and (12).
（［４） メルカプト酢酸、メルカプトプロピオン酸
、メルカプト酪酸、メルカプト吉草酸、チオジ酢酸、チ
オジプロピオン酸、チオジ酪酸、チオジ吉草酸、ジチオ
ジ酢酸、ジチオジプロピオン酸、ジチオジ酪酸、ジチオ
ジ吉草酸などのチオ酸類。([4) Thioacetic acids such as mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptovaleric acid, thiodiacetic acid, thiodipropionic acid, thiodibutyric acid, thiodivaleric acid, dithiodiacetic acid, dithiodipropionic acid, dithiodibutyric acid, dithiodivaleric acid, etc. Acids.
（１５） これら“（：Ｉ４）のモノ、ジオトリエタ
ノールアミン塩。(15) These mono- and di-triethanolamine salts of (:I4).
ＣＦ／）に属するものとして、チオ尿素、モノ、ジ。As belonging to CF/), thiourea, mono, di.
トリメチルチオ尿素、ジエチルチオ尿素、ジブチル千オ
尿素、アリルチオ尿素、とドロキシエチルアリルチオ尿
素、ジトリルチオ尿素、ジフェニルチオ尿素、チオアセ
トアミドなどが例示される。Examples include trimethylthiourea, diethylthiourea, dibutylthiourea, allylthiourea, droxyethylallylthiourea, ditolylthiourea, diphenylthiourea, and thioacetamide.
Ｃ〕有機キレート化合物
この化合物は金属の結晶粒界腐食抑制並びに孔食抑制効
果を有するものであり、次の■〜■よりなるグループか
ら選ばれた一種以上の混合物である。C] Organic chelate compound This compound has the effect of suppressing grain boundary corrosion and pitting corrosion of metals, and is a mixture of one or more types selected from the group consisting of the following (1) to (2).
■ 分子中に水酸基とカルボキシル基を各々１ヶ以上含
有するオキシカルボン酸類。■ Oxycarboxylic acids containing one or more hydroxyl groups and one or more carboxyl groups in the molecule.
■ 分子中に７ミノ基とカルボキシル基！−々１ヶ以上
を含有するアミノカルボン酸類。■ 7-mino group and carboxyl group in the molecule! Aminocarboxylic acids containing one or more of -.
■ 分子中にホスホノ基とカルボキシル基を各々少なく
とも１ヶ以上を含有するホスホ／カルボン酸類。(2) Phospho/carboxylic acids containing at least one phosphono group and at least one carboxyl group in the molecule.
■ 分子中にホスホノ基と水酸基を各々１ヶ以上含有す
るオキシホスホン酸類。■ Oxyphosphonic acids containing one or more phosphono groups and one or more hydroxyl groups in the molecule.
■ 分子中にアミ７基とホスホノ基を各々１ヶ以上含有
するアミノホスホン酸類。■ Aminophosphonic acids containing one or more each of amine7 groups and one or more phosphono groups in the molecule.
■ 上記■〜■のアルカリ金属塩、アンモニウム塩、炭
素数１〜４の低級アミンまたは炭素数１〜６までのアル
カノールアミン塩。(2) Alkali metal salts, ammonium salts, lower amines having 1 to 4 carbon atoms, or alkanolamine salts having 1 to 6 carbon atoms as described in (1) to (2) above.
以下１行余白□−一−
酸、酒石ｍ、クエン酸、グルコン酸、サリチル酸などの
オキシカルボン酸類、イミノジ酢酸、ニトリロトリ酢酸
、エチレンジアミンテトラ酢酸などのアミノカルボン酸
類、及び２ホスホノブタン１．２，４．）リカルボン酸
、アミノトリ（メチレンホスホン酸）、エチレンジアミ
ンテトラ（メチレンホスホン酸）、１−ヒドロキシエチ
リデン−１，１−ジホスホン酸などのホスホノカルボン
酸類、アミノ或はヒドロキシホスホン酸類、及びこれら
のカリウム、ナトリウムなどアルカリ金属塩。1 line margin below □ -1- Acid, tartaric acid, oxycarboxylic acids such as citric acid, gluconic acid, and salicylic acid, aminocarboxylic acids such as iminodiacetic acid, nitrilotriacetic acid, and ethylenediaminetetraacetic acid, and 2-phosphonobutane 1,2,4 ．． ) Phosphonocarboxylic acids such as lycarboxylic acid, aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, amino or hydroxyphosphonic acids, and potassium and sodium thereof such as alkali metal salts.
アンモニウム塩、エチルアミン、プロピルアミン、エチ
レンジ・アミンまたはモノ、ジオトリエタノールアミン
塩などがあげられる。Examples include ammonium salts, ethylamine, propylamine, ethylenediamine or mono- and ditriethanolamine salts.
本発明添加剤は、Ａ）ポリアミンまたはその塩、Ｂ〕有
機硫黄化合物および、Ｃ〕有機キレート化合物の３成分
を、個々に別々の形で、または２種以上の混合物、ある
いはまた使用し易い水溶液として化学溶解液に添加して
使用される。いずれにせよ、これら３成分が化学溶解液
中に共存することが必要とされる。The additive of the present invention comprises three components: A) a polyamine or its salt, B] an organic sulfur compound, and C] an organic chelate compound, individually, in a mixture of two or more, or in an easy-to-use aqueous solution. It is used by adding it to a chemical solution. In any case, these three components are required to coexist in the chemical solution.
むろん、界面活性剤やポリオール類を、必要に応じて添
加併用でき、そうすると溶解液のぬれ特性の改善に役立
つ。Of course, surfactants and polyols can be added and used together if necessary, and this helps to improve the wetting properties of the solution.
本発明添加剤の使用量は、溶解液ｌｌ中に、Ａ）０ 、
０１ ｆ／１以上、Ｂ） ｏ、ｏｔｙ／Ａ’以上、ｃ）
ｏ、ｏ２ｇ／！１２ｙ／１１せることが適当とされる
。なおＡ〕。The amount of the additive of the present invention used is A) 0,
01 f/1 or more, B) o, oty/A' or more, c)
o, o2g/! 12y/11 is considered appropriate. Furthermore, A].
Ｂ）、Ｃ）（７）３成分の合計濃度は、１００ ｙ／Ｉ
Ｉ以下にすることが望ましい。この濃度以上にしても増
量効果が乏しく経済的でなφ。また、溶解液中のＡ）、
Ｂ）、Ｃ）３成分の重量比は、Ａ）１〜５に対し、Ｂ〕
１〜１０Ｓ ｃ〕２〜２ｏの割合が適当とされる。The total concentration of the three components B), C) (7) is 100 y/I
It is desirable to keep it below I. Even if the concentration is higher than this, the increasing effect is poor and it is not economical. In addition, A) in the solution,
The weight ratio of the three components B) and C) is A) 1 to 5 to B]
A ratio of 1 to 10S c]2 to 2o is considered appropriate.
本発明添加剤を加えた化学溶解液の使用方法は、以下実
施例を挙げる。Examples of how to use the chemical solution containing the additive of the present invention will be given below.
実施例１
実施例１及びその比較例に供した化合物及び添加剤割合
は第１表の通りである。Example 1 The compounds and additive ratios used in Example 1 and its comparative example are shown in Table 1.
Ａ〕ポリアミンとしてペンタエチレンヘキサミンを、Ｂ
）有機硫黄化合物としてチオジグリコー示割合の添加剤
α〜ｆを得る。A] Pentaethylenehexamine as the polyamine, B
) Additives α to f having the proportions of thiodiglycol as the organic sulfur compound are obtained.
この添加剤を５ｙ／（ｔとなるように溶解液に添加し、
試験属１〜６に供用した。この時のＡ）、Ｂ〕。Add this additive to the solution so that it becomes 5y/(t,
It was used for test genera 1 to 6. A), B] at this time.
及びＣ〕の濃度は各々０．５ｆ／ｌ 、 ０．５ｆ／ｌ
及び１、ｏｙ７ｇである。他方、上記添加剤Ｃ及び−に
用いた化合物Ａ）ｔ Ｂ）−ｃ）なる３成分を溶解液に
別々に添加した場合を、試験ム７および８でそれぞれ実
施した。and C] concentrations are 0.5 f/l and 0.5 f/l, respectively.
and 1, oy7g. On the other hand, in Tests 7 and 8, the three components A), B), and C) used for the additives C and - were separately added to the solution.
試験Ａ７？各々ノ濃度は、Ａ） ｏ、ｓｙ／ｌ 、 Ｂ
）０．５ｙ／（ｊ 、 Ｃ：） １．０ｙ／１１であり
、試験＆８の各々の濃度は、Ａ） ０．１ｙ／ｌ、 Ｂ
） ０．１ｙ／１１ 、 Ｃ）０．５ｙ／（ｌである。Exam A7? The respective concentrations are A) o, sy/l, B
) 0.5y/(j, C:) 1.0y/11, and the concentrations of each of test &8 are: A) 0.1y/l, B
) 0.1y/11, C) 0.5y/(l).
また試験Ａ９，１０およヒ１１は、添加剤−に用いた化
合物Ａ）ｅ Ｂ）ｐ ｃ）のうちの−ずれかを、単独に
他の２成分を混合して溶解液に添加した場合である。そ
の各々の濃度は、試験Ａ９はＡ〕を単独の形の添加で０
．ｆ／１３とし、Ｂ） １０９とＣ）２０ｙとは混合し
て添加濃度を０．３ノ／ｌとした。この時のＢ〕及びＣ
〕の濃度は０．１ｆ／ｌ及び０．２ ｆ／ｌとなる。Tests A9, 10 and 11 were conducted when one of the compounds A) e B) p c) used as the additive was mixed with the other two components and added to the solution. It is. The concentration of each of them was 0 for test A9 when A] was added in the sole form.
．． f/13, and B) 109 and C) 20y were mixed to give an additive concentration of 0.3 n/l. B] and C at this time
) are 0.1 f/l and 0.2 f/l.
試験Ｊｆ６１０はＢ〕を単独の形の添加で０．１１／１
とし、Ａ）１０ｙとＣ）２０ｙとを混合して、添加濃度
を０．３ｙ／ｌとした場合である。Test Jf610 is 0.11/1 when B] is added in a single form.
This is the case where A) 10y and C) 20y are mixed and the added concentration is 0.3y/l.
試験墓１１はＣ〕を単独の形の添加で０．２ｙ／（１と
し、Ａ）ＬｏｐとＢ）ｌＯｐと水３０ｇとを混合して、
添加濃度を０．５ｙ／（ｌとした場合であり、この時の
Ａ）ｔＢ）濃度はそれぞれ０．１ｆ／ｌである。Test Tomb 11 was prepared by adding C] in the form of 0.2y/(1), mixing A) Lop, B) lOp, and 30 g of water.
This is the case where the added concentration is 0.5y/(l), and the A), tB) and concentrations at this time are each 0.1f/l.
試験Ａ ｉ２は、添加剤−と比較例６の界面活性剤とを
併用した場合で、添加濃度は、添加剤−１界面活性剤共
に５ ｙ／ｌである。この時のＡ）ｔＢ）及びＣ〕の濃
度は各々０．５ ｇ／（１、０，５ｙ／（ｌ及び１１／
ｌである。Test A i2 is a case where Additive-1 and the surfactant of Comparative Example 6 are used together, and the additive concentration is 5 y/l for both Additive-1 surfactant. At this time, the concentrations of A)tB) and C] are 0.5 g/(1, 0,5y/(l and 11/
It is l.
加削−、ポリエチレングリコール共に５ｙ／６である。Both machining and polyethylene glycol are 5y/6.
この時のＡ）、Ｂ）及びＣ〕は試９４１２と同様である
。At this time, A), B), and C] are the same as Test 9412.
比較例は、第１表に示すように添加剤を加えない溶解液
のみの場合と、Ａ〕ペンタエチレンへキサジン、Ｂ）チ
オジグリコールの各々単独、及び両方混合の場合、並び
にしばしば溶解液に添加使用される界面活性剤たる脂肪
酸エステル糸アニオン活性剤（商品名サンアルファー）
を、ポリオール類の例としてポリエチレングリコールＪ
ＩＦｘ４００ＩＤ各々の単独の添加の場合について実施
した。各々の添加濃度は５ ｆ／ｌとした。As shown in Table 1, the comparative examples include cases in which only the dissolution solution is used without additives, cases in which A] pentaethylene hexazine and B) thiodiglycol are used alone, and both are mixed together, and cases in which the dissolution solution is often added to the dissolution solution. Fatty acid ester thread anion activator (product name: Sun Alpha), which is a surfactant used as an additive.
and polyethylene glycol J as an example of polyols.
The case of adding each IFx400ID alone was carried out. The concentration of each addition was 5 f/l.
試験に用い念金属試片は、５Ｓ４１材（普通鋼）Ｆｅ−
４２％Ｎ１合金及びＳＵＳ ３０４材（Ｆｅ −Ｎｉ−
Ｃｒスｆ＞レスｆｊｉ４）である。その寸法は各々長さ
５０Ｘ幅３０×厚さ２．３ｎ、同じ＜ ４（）Ｘ２０Ｘ
１．８ｍ及び４０Ｘ２０ｘ２ｍに成形加工したもので、
砥石（＊ １２０）で研磨したのち、水洗し、ア七トン
で脱脂し乾燥し、表向を清浄にしたものを供試材料とし
た。The metal specimen used in the test was 5S41 material (common steel) Fe-
42%N1 alloy and SUS 304 material (Fe-Ni-
Crsuf>resfji4). Its dimensions are each length 50x width 30x thickness 2.3n, the same <4()x20x
It is molded to 1.8m and 40x20x2m,
After polishing with a whetstone (*120), it was washed with water, degreased with Ashiton, dried, and the surface was cleaned, and the sample material was used.
試験方法は、溶解液として１５０ ｙ／ｌ塩化第二鉄と
１５ｆ／ｌ塩酸を含む混合液を用い、上記添加剤を加え
、よく混和し、６０’Ｃに加温、攪拌しながら金属試片
を２分間浸漬し、金属表面を溶解（エツチング）した。The test method is to use a mixed solution containing 150 y/l ferric chloride and 15 f/l hydrochloric acid as a dissolving solution, add the above additives, mix well, heat to 60'C, and remove the metal specimen while stirring. was immersed for 2 minutes to dissolve (etch) the metal surface.
ついで下記の評価を行った。Then, the following evaluation was performed.
即ち処理金属試片に対するエツチングの評価は、（１）
溶解速度の測定、表面状態として（２）表面の粗さ、（
３）孔食数の測定及び（４）光沢性を観察した。評価（
１）の溶解速度は、添加剤がその金属の溶解に影響する
か否かについて調査するものであり、その測定方法は、
金属試片のエツチング前後の重量を秤り、その重量差よ
り溶解挺を知り、又エツチング前の金属試片の表面積を
求めておき、次式により単位面＠ （、？ｌ１１２）
、単位時間（２）当妙の溶解速度を算出する。In other words, the etching evaluation for the treated metal specimen is (1)
Measurement of dissolution rate, surface conditions include (2) surface roughness, (
3) Measurement of the number of pitting corrosion and (4) Observation of glossiness. evaluation(
The dissolution rate in 1) is to investigate whether additives affect the dissolution of the metal, and the measurement method is as follows:
Weigh the weight of the metal specimen before and after etching, determine the melting depth from the difference in weight, and calculate the surface area of the metal specimen before etching, using the following formula to calculate the unit area @ (,?l112)
, unit time (2) Calculate the dissolution rate of Tomyo.
（Ｐ−Ｑ）−
溶解速度（勢１２・Ｈ）＝□
但し、Ｐ＝エツチング前の金属試片の重量（ＩＩＩｙ）
Ｑ＝エツチング後の金属試片の重ｉｔ （”Ｆ）Ｓ：エ
ツチング前の金属試片の表面積（１２）Ｔ：エツチング
時間（分）
評価（２）の表面の粗さは平滑性の程度を示すものであ
や、触針式表面粗さ計を用いて中心線平均粗さくＲ，）
を測定し、それを表示した。(P-Q) - Dissolution rate (12H) = □ However, P = Weight of metal specimen before etching (IIIy)
Q = Weight of metal specimen after etching it (''F) S: Surface area of metal specimen before etching (12) T: Etching time (minutes) The roughness of the surface in evaluation (2) indicates the degree of smoothness. The center line average roughness R,) was measured using a stylus type surface roughness meter.
measured and displayed.
評価（３）の孔食は顕微鏡（Ｘ４００）で観察し、その
視野５Ｑａｌ”当９の孔食数を数え、評価はＷ：孔食な
し、Ｘ：４個以下、Ｙ８５〜１０個、ＺニーＪ１４−個
以上と表示判定した。The pitting corrosion of evaluation (3) was observed with a microscope (X400), and the number of pitting corrosion in the field of view 5Qal'' was counted. The display was determined to be J14- or more.
評価（４）の光沢性は肉眼で評価し、◎：金属光沢優、
○：光沢良好、△：光沢なし、×：光沢なく黒っぽいと
表示判定した。The glossiness of evaluation (4) was evaluated with the naked eye: ◎: Excellent metallic luster;
◯: Good gloss, △: No gloss, ×: No gloss and blackish.
塩、Ｂ〕有機硫黄化合物及びＣ〕有機キレート化合物の
３成分が各々別々に添加された場合、あるいは混合して
添加された場合であっても、溶解液中に前記３成分が存
在していることによって、処理された金属表面は非常に
良好に仕上っているか−また界面活性剤やポリエチレン
グリコールの併用は、金属表面仕上りに侮辱支障のな―
ことも明らかである。Even when the three components of salt, B] organic sulfur compound, and C] organic chelate compound are added separately or in a mixture, the three components are present in the solution. Does the treated metal surface have a very good finish? Also, the combined use of surfactants and polyethylene glycol does not harm the metal surface finish.
It is also clear that
実施例２
実施例２及びその比較例に供した化合物名、及び添加剤
の調製割合は第３表の通ゆである。Example 2 The names of the compounds used in Example 2 and its comparative examples and the preparation ratios of additives are as shown in Table 3.
Ａ〕ポリアミン←÷−セま〜その塩としてポリアリルア
ミン塩酸塩（分子量約３万）と、Ｃ〕有機キレート化合
物としてエチレンジアミング酢酸２Ｎα塩、及び代表的
な種々のＢ〕有機硫黄１ヒ合物を選び、第３表で示す割
合のｇ ／％／ ｉの添加剤を作製した。A] polyamine ←÷-sema ~ polyallylamine hydrochloride (molecular weight approximately 30,000) as its salt, C] ethylene diamine acetic acid 2Nα salt as an organic chelate compound, and various representative B] organic sulfur compounds. were selected, and additives of g/%/i in the proportions shown in Table 3 were prepared.
比較例は第３表中比較例８〜１１で示したように、実施
例で用いたＡ）ｔ Ｂ）及びＣ〕各化合物の単独と、Ａ
〕とＣ〕の混合物について比較した。Comparative Examples are as shown in Comparative Examples 8 to 11 in Table 3, A), B) and C] each compound used in the Examples alone, and
] and C] were compared.
溶解液への添加濃度を５０ｙ／ｌ（この時の本発明のＡ
：） 、 Ｂ）及びＣ〕の各々の濃度は７．５ｙ／（１
，２，５ｙ／１１及び５１／ｌとなる）とした以外は、
実ように本発明添加剤は金属表面仕上りを良好ならしめ
ている。The concentration added to the solution was 50 y/l (at this time, A of the present invention
:), B) and C] is 7.5y/(1
, 2,5y/11 and 51/l).
Indeed, the additive of the present invention improves the metal surface finish.
実施例３
実施例３及びその比較例に供した化合物名、及び添加剤
の調製割合は第５表通りである。Example 3 The names of the compounds used in Example 3 and its comparative examples and the preparation ratios of additives are shown in Table 5.
Ｂ〕有機硫黄化合物としてチオジプロピオン酸のトリエ
タノールアミン塩と、Ｃ〕有機キレート化合物としてヒ
ドロキシェチリデンジホスホン酸およびＡ〕ポリアミン
Ｗまりその塩の代表的なものを種々選び、第５表で示す
割合のα〜ノの添加剤を作製した。B] triethanolamine salt of thiodipropionic acid as an organic sulfur compound, C] hydroxyethylidene diphosphonic acid as an organic chelate compound, and A] various representative polyamine W marison salts were selected and shown in Table 5. Additives α to No. were prepared in the proportions shown.
比較例は第５表中比較例１２〜１５で示したように、実
施例で用いたＡ）ｔ Ｂ）及びＣ〕の各々単独とＢ）Ｉ
Ｃ）の混合物について代表例として比較した。As shown in Comparative Examples 12 to 15 in Table 5, Comparative Examples include each of A)t, B) and C] used in Examples alone and B)I.
The mixture of C) was compared as a representative example.
溶解液への添加濃度は１５０ｆＩ／ｌ！（この時の本発
明のＡ）＃ Ｂ）及びＣ〕の各々の濃度は３ ｆ／ｌ
。The concentration added to the solution is 150 fI/l! (At this time, the concentration of each of A), #B) and C] of the present invention is 3 f/l
.
及びＣ） ０．０７５ ｇ／ｌ ）と１ ｙ／／ｌ （
Ａ〕ｏ、ｏ２Ｆ／６ 。and C) 0.075 g/l ) and 1 y//l (
A]o, o2F/6.
Ｂ） ｏ、１ｓｙ＃ 、 ｃ） ｏ、１５ｙ／ｌ ）以
外は、実施例１と同様の処理とした。The same treatment as in Example 1 was carried out except for B) o, 1sy#, c) o, 15y/l).
仕上り面を与えている。It gives a finished surface.
実施例４
溶解液として、硫酸と酸化剤としての塩化第二鉄の混合
液（１５０ｙ／ｌ塩化第二鉄と５０ｙ／ｌ硫酸を含む液
）を用いた。Example 4 A mixed solution of sulfuric acid and ferric chloride as an oxidizing agent (a solution containing 150 y/l ferric chloride and 50 y/l sulfuric acid) was used as the dissolving solution.
及びＣ〕の各濃度は：Ｈ／（１、ｌｙ／ｌ及び２９４で
あり、試験Ａ３７のＡ）？ Ｂ）及びＣ〕の各濃度は０
．４ ｙ／ｌ 、 ３１７１及び３ ｆ／ｌである。and C] are: H/(1, ly/l and 294, A of test A37)? Each concentration of B) and C] is 0.
．． 4 y/l, 3171 and 3 f/l.
試験Ａ３８は実施例３の添加剤Ｃに用いたＡ〕＋ Ｂ）
及びＣ〕の各々を別々に溶解液に添加した場合であり、
混合添加した場合と同様の効果を示している。Test A38 was A]+B) used for Additive C in Example 3.
and C] are separately added to the solution,
It shows the same effect as when mixed and added.
比較例中比較例１６は４０％脂肪酸エステル系界面活性
剤ｚｏｙ／ｌとなるように添加したもの、比較例１７は
無添加の場合である。これ以外は実施７表に示す。Among the comparative examples, Comparative Example 16 was a case in which the fatty acid ester surfactant was added at a concentration of 40% zoy/l, and Comparative Example 17 was a case in which no additive was added. Other details are shown in Table 7.
実施例５
溶解液として塩化第二鉄溶液と硝酸の混合液（２００ｐ
／ｌ塩化第二鉄と５０１７１硝酸を含む液）を用いて前
記実施例で用いた本発明添加剤の数例を選び、添加濃度
２０１７１として、第８表の試験屋３９〜試Ｆｋ４４２
の比較例として、第８表の比較例１８に４０％脂肪酸エ
ステル系界面活性剤２０ ｙ／（１となるように添加し
たもの、及び比較例１９は無添加の場合である。処理条
件は液１ｆｆ１３０″Ｃで攪拌しながら試験片を１分間
浸漬処理し前記同様評価した、用いた添加剤とその結果
を第８表に示す。Example 5 A mixed solution of ferric chloride solution and nitric acid (200p
Several examples of the additives of the present invention used in the above examples were selected using a liquid containing ferric chloride and 50171 nitric acid, and the additive concentration was set to 20171, and the additives were added to Tester 39 to Test Fk442 in Table 8.
As a comparative example, 40% fatty acid ester surfactant was added to Comparative Example 18 in Table 8 so that 20 y/(1) was added, and Comparative Example 19 was a case in which no additive was added. The test pieces were immersed for 1 minute while stirring at 1ff 130''C and evaluated in the same manner as described above.Table 8 shows the additives used and the results.
第 ３ 表
※２有機硫黄化合物名は１
α２：２メルカプトエタノール
ｂ２：３メルカプトプロピルアミン
ｃ２：３メルカプトプロピオン酸
ｄ２：チオジェタノール
＃２：チオジエチルアミン
ル２： ヒドロキシェチルアリルチ鳳
ｔｚ ： ４０％フェニルチオウレアブチルセロソル
ブ溶液ノ゛２ニジチオジェタノール
に２：チオアセトアミド
発明の効果
本発明の金属溶解液用添加剤は、実施例に限定されるも
のではなく、鉱酸と酸化剤として第二鉄塩との混合溶解
液に、適量添加されることによって、金属の溶解速度を
低下させることなしに、被処理全日は光沢ある均一で平
滑な表面が得られ、孔食の数も大巾に減少出来、エツチ
ングの寸法情度が向上するという優れた効果を有してお
り、該金属の後処理を容易ならしめ、低起泡性のため、
廃液処理も容易である。また、孔食の発生の減少により
、不良率の低減ができ、高価な金属の損失を軽減出来る
有益な発明である。Table 3 *2 Names of organic sulfur compounds are 1 α2:2 Mercaptoethanol b2:3 Mercaptopropylamine C2:3 Mercaptopropionic acid d2: Thiogetanol #2: Thiodiethylamine 2: Hydroxyethylallyl z: 40 % phenylthioureabutyl cellosolve solution: 2: dithiodiethanol: 2: thioacetamide Effects of the invention The additive for metal solution of the present invention is not limited to the examples, but includes a mineral acid and ferric iron as an oxidizing agent. By adding an appropriate amount to the mixed solution with salt, a glossy, uniform, and smooth surface can be obtained throughout the treatment process without reducing the metal dissolution rate, and the number of pitting corrosion is also greatly reduced. It has the excellent effect of improving the dimensional accuracy of etching and making the post-processing of the metal easier, and has low foaming properties.
Waste liquid treatment is also easy. Furthermore, by reducing the occurrence of pitting corrosion, it is possible to reduce the defective rate and reduce the loss of expensive metals, which is a useful invention.
Claims (1)
レート化合物の３成分を主成分とすることを特徴とする
金属表面の化学溶解液用添加剤An additive for a chemical solution for metal surfaces, which is characterized by containing three main components: polyamine or its salt, an organic sulfur compound, and an organic chelate compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7964386A JPS62238379A (en) | 1986-04-07 | 1986-04-07 | Additive for chemical dissolving solution for metallic surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7964386A JPS62238379A (en) | 1986-04-07 | 1986-04-07 | Additive for chemical dissolving solution for metallic surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62238379A true JPS62238379A (en) | 1987-10-19 |
| JPH0377279B2 JPH0377279B2 (en) | 1991-12-10 |
Family
ID=13695789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7964386A Granted JPS62238379A (en) | 1986-04-07 | 1986-04-07 | Additive for chemical dissolving solution for metallic surface |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62238379A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6379983A (en) * | 1986-09-24 | 1988-04-09 | Sumitomo Special Metals Co Ltd | Chemically dissolving and treating solution for metal |
| JP2000001799A (en) * | 1998-06-17 | 2000-01-07 | Teikoku Micro Kk | Electrolytic cleaning composition for die, and die cleaning device using the composition |
| JP2008144228A (en) * | 2006-12-08 | 2008-06-26 | Sanshin Chem Ind Co Ltd | Chemical dissolution control agent for metal, chemically dissolving solution for metal, and chemically dissolving method for metal |
| JP2013189990A (en) * | 2012-03-12 | 2013-09-26 | Ntn Corp | Rolling bearing |
| US11111595B2 (en) | 2016-02-18 | 2021-09-07 | Nippon Steel Corporation | Apparatus for electrolytic etching and dissolution and method for extracting metal compound particles |
| US11137326B2 (en) | 2016-02-18 | 2021-10-05 | Nippon Steel Corporation | Method for extracting metal compound particles, method for analyzing the metal compound particles, and electrolytic solution used therefor |
-
1986
- 1986-04-07 JP JP7964386A patent/JPS62238379A/en active Granted
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6379983A (en) * | 1986-09-24 | 1988-04-09 | Sumitomo Special Metals Co Ltd | Chemically dissolving and treating solution for metal |
| JPH0258358B2 (en) * | 1986-09-24 | 1990-12-07 | Sumitomo Tokushu Kinzoku Kk | |
| JP2000001799A (en) * | 1998-06-17 | 2000-01-07 | Teikoku Micro Kk | Electrolytic cleaning composition for die, and die cleaning device using the composition |
| JP2008144228A (en) * | 2006-12-08 | 2008-06-26 | Sanshin Chem Ind Co Ltd | Chemical dissolution control agent for metal, chemically dissolving solution for metal, and chemically dissolving method for metal |
| JP2013189990A (en) * | 2012-03-12 | 2013-09-26 | Ntn Corp | Rolling bearing |
| US11111595B2 (en) | 2016-02-18 | 2021-09-07 | Nippon Steel Corporation | Apparatus for electrolytic etching and dissolution and method for extracting metal compound particles |
| US11137326B2 (en) | 2016-02-18 | 2021-10-05 | Nippon Steel Corporation | Method for extracting metal compound particles, method for analyzing the metal compound particles, and electrolytic solution used therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0377279B2 (en) | 1991-12-10 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |