JP2902554B2 - Coolant composition - Google Patents
Coolant compositionInfo
- Publication number
- JP2902554B2 JP2902554B2 JP6098691A JP9869194A JP2902554B2 JP 2902554 B2 JP2902554 B2 JP 2902554B2 JP 6098691 A JP6098691 A JP 6098691A JP 9869194 A JP9869194 A JP 9869194A JP 2902554 B2 JP2902554 B2 JP 2902554B2
- Authority
- JP
- Japan
- Prior art keywords
- calcium
- magnesium
- compound
- test
- 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 - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims description 26
- 239000002826 coolant Substances 0.000 title claims description 11
- 229940043430 calcium compound Drugs 0.000 claims description 34
- 150000001674 calcium compounds Chemical class 0.000 claims description 34
- 150000002681 magnesium compounds Chemical class 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 13
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 150000002334 glycols Chemical class 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 230000000994 depressogenic effect Effects 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000003557 thiazoles Chemical class 0.000 claims description 3
- 150000003852 triazoles Chemical class 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 34
- 239000000110 cooling liquid Substances 0.000 description 20
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 20
- 238000005260 corrosion Methods 0.000 description 18
- 230000007797 corrosion Effects 0.000 description 18
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 12
- 239000011575 calcium Substances 0.000 description 12
- 229910052791 calcium Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- 239000000498 cooling water Substances 0.000 description 7
- 229920000137 polyphosphoric acid Polymers 0.000 description 7
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 230000003449 preventive effect Effects 0.000 description 5
- 230000002265 prevention Effects 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002528 anti-freeze Effects 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 2
- 241000257303 Hymenoptera Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- -1 molybdates Chemical class 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 2
- 235000010234 sodium benzoate Nutrition 0.000 description 2
- 239000004299 sodium benzoate Substances 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VRKHTAYPELFGPP-UHFFFAOYSA-N 10-[(1,3-dimethylpyrrolidin-3-yl)methyl]phenothiazine Chemical compound C1N(C)CCC1(C)CN1C2=CC=CC=C2SC2=CC=CC=C21 VRKHTAYPELFGPP-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 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
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 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
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229930195712 glutamate Natural products 0.000 description 1
- 229940049906 glutamate Drugs 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940001447 lactate Drugs 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-M mandelate Chemical compound [O-]C(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000004005 nitrosamines Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229940114926 stearate Drugs 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940086735 succinate Drugs 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、自動車などの内燃機関
の冷却水中に混合され、冷却水の凍結を防止する冷却液
組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cooling liquid composition which is mixed in cooling water of an internal combustion engine such as an automobile to prevent the cooling water from freezing.
【０００２】[0002]
【従来の技術】従来、自動車エンジンの冷却水には、ア
ルコール類やグリコール類などの融点降下剤を主成分と
する冷却液が添加され、冬季の凍結が防止されている。
ところがアルコール類やグリコール類には防錆作用が全
くないばかりか、高温で循環中に酸素と接触することに
より酸化され、生成した酸化物が冷却水流路を構成する
金属の腐食を促進するという不具合がある。2. Description of the Related Art Conventionally, a cooling liquid mainly containing a melting point depressant such as alcohols or glycols has been added to cooling water of an automobile engine to prevent freezing in winter.
However, alcohols and glycols not only have no rust-preventive action, but are oxidized by contact with oxygen during circulation at high temperatures, and the resulting oxides promote the corrosion of the metal that forms the cooling water flow path. There is.
【０００３】そこで冷却液には一般に、リン酸塩，ホウ
酸塩，炭酸塩，硫酸塩，硝酸塩，モリブデン酸塩，安息
香酸塩，ケイ酸塩，ベンゾトリアゾール，メルカプトベ
ンゾチアゾールのナトリウム塩，トリルトリアゾール，
トリエタノールアミン塩などから選ばれる防錆剤が添加
され、冷却水に所定量混合された使用時における金属の
腐食が防止されている。[0003] Therefore, the cooling liquid is generally phosphate, borate, carbonate, sulfate, nitrate, molybdate, benzoate, silicate, benzotriazole, sodium salt of mercaptobenzothiazole, tolyltriazole. ,
A rust preventive selected from triethanolamine salts and the like is added to prevent corrosion of metal when used in a predetermined amount mixed with cooling water.
【０００４】ところが省資源・省エネルギーの目的でア
ルミニウム部品が多用されるに伴い、従来の冷却液では
アルミニウム系金属に対する防食性が不十分であること
が明らかとなった。例えばホウ酸塩は鋳鉄材質に対して
は優れた防食性を有するが、アルミニウム系金属材質に
対しては効果が無い。However, as aluminum parts are frequently used for the purpose of saving resources and energy, it has become clear that the conventional coolant does not have sufficient corrosion resistance to aluminum-based metals. For example, borate has excellent anticorrosion properties on cast iron materials, but has no effect on aluminum-based metal materials.
【０００５】またトリエタノールアミンのリン酸塩は、
鉄系金属とアルミニウム系金属の両方に対して防食性を
有している。しかし亜硝酸塩との共存により反応してニ
トロソアミンを生成し、防食性の耐久性に問題がある。
またケイ酸塩もアルミニウム系金属に対する防食性を有
しているが、長時間の貯蔵又は使用中にゲル化分離して
防食性が低下するという問題がある。The phosphate of triethanolamine is
It has anticorrosion properties against both iron-based metals and aluminum-based metals. However, it reacts with nitrite to produce nitrosamines, which is problematic in durability against corrosion.
Silicates also have an anticorrosion property against aluminum-based metals, but have a problem in that they are gelated and separated during long-term storage or use, and the anticorrosion properties are reduced.
【０００６】そこで特開平1-306492号公報には、アミン
類やケイ酸塩の代わりにマグネシウム化合物やメルカプ
トベンゾチアゾールのナトリウム塩などを防錆剤として
用い、さらにｐＨを6.5 〜9.0 の範囲とした不凍液が開
示されている。この不凍液によれば、アルミニウム系金
属に対する十分な防食性を有している。Therefore, JP-A-1-306492 discloses that a magnesium compound or a sodium salt of mercaptobenzothiazole is used as a rust preventive in place of amines or silicates, and the pH is adjusted to a range of 6.5 to 9.0. An antifreeze is disclosed. This antifreeze has sufficient anticorrosion properties against aluminum-based metals.
【０００７】[0007]
【発明が解決しようとする課題】しかし上記公報に記載
された不凍液では、マグネシウム化合物の添加量が0.00
1 〜0.08重量％程度と多く、その分他の防錆剤の添加量
が制約されたりコストも高いという問題がある。また、
エンジンの高出力化に伴い、エンジンによっては金属の
表面温度が非常に高くなるものがある。このようなエン
ジンの冷却水の場合は、マグネシウム化合物などの添加
量が多くなると、エンジンヘッド上へのスケール状堆積
物量の増大をまねき、エンジン放熱性の低下を引き起こ
す可能性がある。However, in the antifreeze described in the above publication, the addition amount of the magnesium compound is 0.00
The amount is as large as about 1 to 0.08% by weight, so that there is a problem that the amount of other rust preventives to be added is restricted and the cost is high. Also,
As the output of the engine increases, the surface temperature of the metal of some engines becomes extremely high. In the case of such engine cooling water, an increase in the amount of the magnesium compound or the like leads to an increase in the amount of scale-like deposits on the engine head, which may cause a decrease in engine heat radiation.
【０００８】本発明はこのような事情に鑑みてなされた
ものであり、マグネシウム化合物などの防錆剤の添加量
を少量としても高い防錆性を確保することを目的とす
る。The present invention has been made in view of such circumstances, and an object of the present invention is to ensure high rust resistance even when the amount of a rust inhibitor such as a magnesium compound is small.
【０００９】[0009]
【課題を解決するための手段】上記課題を解決する本発
明の冷却液組成物は、アルコール類及びグリコール類か
ら選ばれる融点降下剤と、リン酸塩，ホウ酸塩，硝酸
塩，モリブデン酸塩，安息香酸塩，ケイ酸塩，トリアゾ
ール類，チアゾール類，セバチン酸及びオクチル酸から
選ばれる少なくとも１種の防錆剤とを含み、さらにカル
シウム化合物とマグネシウム化合物をそれぞれ金属元素
濃度として０．００００５〜０．０２重量％含むことを
特徴とする。The coolant composition of the present invention for solving the above-mentioned problems comprises a melting point depressant selected from alcohols and glycols, a phosphate, a borate, a nitrate, a molybdate, It contains at least one rust inhibitor selected from benzoates, silicates, triazoles, thiazoles, sebacic acid and octylic acid, and further contains calcium compounds and magnesium compounds in a metal element concentration of 0.00005 to 0, respectively. 0.02% by weight.
【００１０】また、さらに望ましい本発明の冷却液組成
物は、アルコール類及びグリコール類から選ばれる融点
降下剤と、リン酸塩，ホウ酸塩，硝酸塩，モリブデン酸
塩，安息香酸塩，ケイ酸塩，トリアゾール類，チアゾー
ル類，セバチン酸及びオクチル酸から選ばれる少なくと
も１種の防錆剤とを含み、さらにカルシウム化合物とマ
グネシウム化合物をそれぞれ金属元素濃度として0.0000
5 〜0.02重量％含むことを特徴とする。[0010] Further, a more preferable cooling liquid composition of the present invention comprises a melting point depressant selected from alcohols and glycols, phosphates, borates, nitrates, molybdates, benzoates and silicates. And at least one rust preventive selected from triazoles, thiazoles, sebacic acid and octylic acid, and further containing calcium compounds and magnesium compounds at a metal element concentration of 0.0000
It is characterized by containing 5 to 0.02% by weight.
【００１１】融点降下剤であるアルコール類及びグリコ
ール類としては、メタノール，エタノール，２−プロパ
ノール，モノエチレングリコール，プロピレングリコー
ルなどを単独で、或いは２種以上混合して用いることが
できる。カルシウム化合物及びマグネシウム化合物とし
ては、それぞれ酸化物，水酸化物，過マンガン酸塩，ク
ロム酸塩，フッ化物，ヨウ化物，炭酸塩，硝酸塩，硫酸
塩，チタン酸塩，タングステン酸塩，ホウ酸塩，リン酸
塩，リン酸二水素塩，蟻酸塩，酢酸塩，プロピオン酸
塩，酪酸塩，吉草酸塩，ラウリン酸塩，ステアリン酸
塩，オレイン酸塩，グルタミン酸塩，乳酸塩，コハク酸
塩，リンゴ酸塩，酒石酸塩，マレイン酸塩，クエン酸
塩，シュウ酸塩，マロン酸塩，セバシン酸塩，安息香酸
塩，フタル酸塩，サリチル酸塩，マンデル酸塩などを用
いることができる。As alcohols and glycols which are melting point depressants, methanol, ethanol, 2-propanol, monoethylene glycol, propylene glycol and the like can be used alone or as a mixture of two or more. Calcium compounds and magnesium compounds include oxides, hydroxides, permanganates, chromates, fluorides, iodides, carbonates, nitrates, sulfates, titanates, tungstates, borates, respectively. , Phosphate, dihydrogen phosphate , formate, acetate, propionate, butyrate, valerate, laurate, stearate, oleate, glutamate, lactate, succinate, Malate, tartrate, maleate, citrate, oxalate, malonate, sebacate, benzoate, phthalate, salicylate, mandelate and the like can be used.
【００１２】カルシウム化合物は、冷却液原液中に金属
元素濃度として0.00005 〜0.02重量％含まれている。こ
の量が0.00005 重量％より少なくなると防錆性が急に低
下し、0.02重量％を越えて添加しても効果が飽和し他の
成分の添加量が制限されるため好ましくない。特に望ま
しくは0.0002〜0.01重量％の範囲である。カルシウム化
合物とマグネシウム化合物を併用する場合は、それぞれ
の添加量が金属元素濃度として0.00005 〜0.02重量％と
される。なお、併用の場合におけるカルシウム化合物と
マグネシウム化合物の混合割合は、金属元素重量比でカ
ルシウム化合物／マグネシウム化合物＝１／２が望まし
い。The calcium compound is contained in the stock solution of the cooling liquid at a concentration of 0.00005 to 0.02% by weight as a metal element concentration. If this amount is less than 0.00005% by weight, the rust-prevention properties suddenly decrease, and even if added in excess of 0.02% by weight, the effect is saturated and the amount of other components added is not preferred. Particularly preferably, it is in the range of 0.0002 to 0.01% by weight. When a calcium compound and a magnesium compound are used in combination, the amount of each added is set to 0.00005 to 0.02% by weight as the metal element concentration. In addition, the mixing ratio of the calcium compound and the magnesium compound in the case of the combined use is desirably that the calcium compound / magnesium compound = 1/2 by the metal element weight ratio.
【００１３】ところで、カルシウム化合物やマグネシウ
ム化合物は、過度の添加により製品コストの上昇を招く
とともにスケール状の堆積物を形成する恐れがある。そ
こで本発明の冷却液組成物では、さらにポリリン酸及び
カルボン酸の少なくとも一方を含むことが望ましい。こ
れによりカルシウム化合物やマグネシウム化合物の添加
量を低減しても同等の防錆性能が得られる。By the way, the calcium compound and the magnesium compound may cause an increase in product cost due to excessive addition, and may form scale-like deposits. Therefore, the coolant composition of the present invention preferably further contains at least one of polyphosphoric acid and carboxylic acid. As a result, even if the amount of the calcium compound or the magnesium compound is reduced, the same rust prevention performance can be obtained.
【００１４】ポリリン酸としては、ピロリン酸、トリポ
リリン酸、１ーヒドロキシエチリデンー１，１ージホス
ホン酸、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、フィチン酸などが例示
される。またカルボン酸としては、オリゴマーあるいは
ポリマー状態のカルボン酸が用いられ、ポリアクリル
酸、オリゴマレイン酸、マレイン酸／アクリル酸コポリ
マなどが例示される。Examples of polyphosphoric acid include pyrophosphoric acid, tripolyphosphoric acid, 1-hydroxyethylidene-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, phytic acid and the like. As the carboxylic acid, an oligomer or a polymer carboxylic acid is used, and examples thereof include polyacrylic acid, oligomaleic acid, and maleic acid / acrylic acid copolymer.
【００１５】ポリリン酸及びカルボン酸の添加量は、ど
ちらか一方又は両者の合計で、0.005 〜0.5 重量％の範
囲が好ましい。添加量が0.005 重量％より少ないと効果
が得られず、0.5 重量％より多くなっても効果が飽和し
他の防錆剤の添加量がその分少なくなるため好ましくな
い。The addition amount of polyphosphoric acid and carboxylic acid is preferably in the range of 0.005 to 0.5% by weight in total of either or both. If the amount is less than 0.005% by weight, no effect is obtained. If the amount is more than 0.5% by weight, the effect is saturated, and the amount of other rust preventives added is undesirably reduced.
【００１６】[0016]
【作用】本発明の冷却液組成物は、冷却水中に通常２０
〜６０体積％混合されて使用される。ここで本発明の冷
却液組成物では、カルシウム化合物又はマグネシウム化
合物を所定範囲で含むため、理由は不明であるが防錆性
が向上する。そして従来のマグネシウム化合物を含むも
のと比較すると、本発明ではカルシウム化合物又はマグ
ネシウム化合物の添加量は従来より少量で同等の防錆性
能が得られ、同量とすれば防錆性能は一段と向上する。The cooling liquid composition of the present invention usually contains 20
６０60% by volume are mixed and used. Here, in the cooling liquid composition of the present invention, the calcium compound or the magnesium compound is contained in a predetermined range, so that the rust prevention property is improved for unknown reasons. Compared with a conventional compound containing a magnesium compound, in the present invention, the same amount of the calcium compound or the magnesium compound is added as compared with the conventional case, and the same rust prevention performance can be obtained.
【００１７】そしてカルシウム化合物とマグネシウム化
合物を併用すれば、さらに少量の添加量で従来と同等の
防錆性能を得ることができ、同量とすれば防錆性能は格
段に向上する。さらに、カルシウム化合物とマグネシウ
ム化合物の少なくとも一方と、ポリリン酸及びカルボン
酸の少なくとも一方とを含む構成とすれば、カルシウム
化合物とマグネシウム化合物の添加量を少量としても同
等の防錆性を維持できる。If a calcium compound and a magnesium compound are used in combination, the same rust-preventive performance can be obtained with a smaller amount of addition, and if the amounts are the same, the rust-preventive performance is remarkably improved. Furthermore, if the composition contains at least one of a calcium compound and a magnesium compound and at least one of a polyphosphoric acid and a carboxylic acid, the same rust prevention can be maintained even if the added amounts of the calcium compound and the magnesium compound are small.
【００１８】[0018]
【実施例】以下、実施例及び比較例により具体的に説明
する。なお、以下にいう％は特にことわらない限り重量
％を意味する。 ＜第１シリーズの実施例＞ （実施例１）表１にも示すように、モノエチレングリコ
ール90.0% ，水1.9859% ，硝酸ナトリウム0.4%，モリブ
デン酸ナトリウム0.5%，ベンゾトリアゾール0.4%，安息
香酸ナトリウム5.0%，メルカプトベンゾチアゾール0.2
%，オルトリン酸0.8%，水酸化カリウム0.7%及び硝酸カ
ルシウム４水和物0.0141% （金属カルシウム濃度として
0.0024% ）を混合し、実施例１の冷却液組成物とした。The present invention will be specifically described below with reference to examples and comparative examples. In addition,% described below means% by weight unless otherwise specified. <Examples of First Series> (Example 1) As shown in Table 1, monoethylene glycol 90.0%, water 1.9859%, sodium nitrate 0.4%, sodium molybdate 0.5%, benzotriazole 0.4%, sodium benzoate 5.0%, mercaptobenzothiazole 0.2
%, Orthophosphoric acid 0.8%, potassium hydroxide 0.7% and calcium nitrate tetrahydrate 0.0141% (as metal calcium concentration
0.0024%) to obtain a cooling liquid composition of Example 1.
【００１９】この冷却液組成物について、ASTM D4340-8
4(Corrosion of Cast AluminiumAlloys in Engine Cool
ants Under Heat-Rejecting Conditions)（アルミニウ
ム合金伝熱面腐食試験）に基づく腐食試験を行い、腐食
量測定と外観判定の結果を表１に示す。また試験前と試
験後の冷却水のｐＨを測定し、併せて表１に示す。なお
試験条件は、下記のとおりである。The cooling liquid composition was prepared according to ASTM D4340-8.
4 (Corrosion of Cast AluminumAlloys in Engine Cool
A corrosion test was performed based on ants Under Heat-Rejecting Conditions (aluminum alloy heat transfer surface corrosion test), and the results of the corrosion amount measurement and the appearance judgment are shown in Table 1. The pH of the cooling water before and after the test was measured, and the results are shown in Table 1. The test conditions are as follows.
【００２０】 冷却液濃度 ： ２５体積％ 試験片 ： アルミニウム合金鋳物(AC-2
A) 試験片温度 ： 135 ℃ 液量 ： 500ml 試験時間 ： 168Hr 試験液中のcl- 量 ： 100ppm 加圧圧力 ： 193kPa （実施例２） 硝酸カルシウム４水和物の量を0.0212% （金属カルシウ
ム濃度として0.0036%）としたこと以外は実施例１と同
様である。同様に試験を行い、結果を表１に示す。 （実施例３） 硝酸カルシウム４水和物の代わりに硫酸カルシウム２水
和物を0.0052%（金属カルシウム濃度として0.0012% ）
用いたこと以外は実施例１と同様である。同様に試験を
行い、結果を表１に示す。 （実施例４） 硝酸カルシウム４水和物の代わりに硫酸カルシウム２水
和物を0.0303% （金属カルシウム濃度として0.0072% ）
用いたこと以外は実施例１と同様である。同様に試験を
行い、結果を表１に示す。 （実施例５） 硝酸カルシウム４水和物を0.0012% （金属カルシウム濃
度として0.0002% ）用い、硝酸マグネシウム６水和物を
0.0042% （金属マグネシウム濃度として0.0004% ）用い
たこと以外は実施例１と同様である。同様に試験を行
い、結果を表１に示す。 （実施例６） 硝酸カルシウム４水和物を0.0035% （金属カルシウム濃
度として0.0006% ）用い、硝酸マグネシウム６水和物を
0.0127% （金属マグネシウム濃度として0.0012% ）用い
たこと以外は実施例１と同様である。同様に試験を行
い、結果を表１に示す。 （実施例７） 硝酸カルシウム４水和物を0.0071% （金属カルシウム濃
度として0.0012% ）用い、硝酸マグネシウム６水和物を
0.0253% （金属マグネシウム濃度として0.0024% ）用い
たこと以外は実施例１と同様である。同様に試験を行
い、結果を表１に示す。 （実施例８） 表１にも示すように、モノエチレングリコール95.0% ，
水2.7176% ，硝酸カルシウム４水和物0.0071% （金属カ
ルシウム濃度として0.0012% ），硝酸マグネシウム６水
和物0.0253% （金属マグネシウム濃度として0.0024%
），硝酸ナトリウム0.25% ，トリルトリアゾール0.1
%，オルトリン酸0.6%，水酸化カリウム0.65%，ケイ酸ナ
トリウム0.35% 及びテトラホウ酸ナトリウム0.3%を混合
し、実施例８の冷却液組成物とした。そして実施例１と
同様に試験を行い、結果を表１に示す。 （実施例９） 表１にも示すように、モノエチレングリコール90.0% ，
水2.9676% ，硝酸カルシウム４水和物0.0071% （金属カ
ルシウム濃度として0.0012% ），硝酸マグネシウム６水
和物0.0253% （金属マグネシウム濃度として0.0024%
），硝酸ナトリウム0.25% ，ベンゾトリアゾール0.1
%，水酸化ナトリウム1.3%，ケイ酸ナトリウム0.15% ，
テトラホウ酸ナトリウム1.2%，セバチン酸1.5%及びオク
チル酸2.5%を混合し、実施例９の冷却液組成物とした。
そして実施例１と同様に試験を行い、結果を表１に示
す。 （比較例１） カルシウム化合物及びマグネシウム化合物を含まないこ
と以外は実施例１と同様である。同様に試験を行い、結
果を表１に示す。 （比較例２） カルシウム化合物及びマグネシウム化合物を含まないこ
と以外は実施例８と同様である。同様に試験を行い、結
果を表１に示す。 （比較例３） カルシウム化合物及びマグネシウム化合物を含まないこ
と以外は実施例９と同様である。同様に試験を行い、結
果を表１に示す。 （比較例４） カルシウム化合物の代わりに硝酸マグネシウム６水和物
を0.0253% （金属マグネシウム濃度として0.0024% ）用
いたこと以外は実施例１と同様である。同様に試験を行
い、結果を表１に示す。 （比較例５） カルシウム化合物の代わりに硝酸マグネシウム６水和物
を0.0759% （金属マグネシウム濃度として0.0072% ）
用いたこと以外は実施例１と同様である。同様に試験を
行い、結果を表１に示す。Coolant concentration: 25% by volume Test piece: Aluminum alloy casting (AC-2
A) Test piece temperature: 135 ° C Liquid volume: 500 ml Test time: 168 Hr Cl - amount in test solution: 100 ppm Pressurizing pressure: 193 kPa (Example 2) The amount of calcium nitrate tetrahydrate was reduced to 0.0212% (metal calcium concentration). The same as in Example 1 except that 0.0036% was set as the value. The test was performed in the same manner, and the results are shown in Table 1. (Example 3) Instead of calcium nitrate tetrahydrate, calcium sulfate dihydrate was 0.0052% (the concentration of metal calcium was 0.0012%)
It is the same as Example 1 except that it was used. The test was performed in the same manner, and the results are shown in Table 1. (Example 4) 0.0303% of calcium sulfate dihydrate instead of calcium nitrate tetrahydrate (0.0072% in terms of metal calcium concentration)
It is the same as Example 1 except that it was used. The test was performed in the same manner, and the results are shown in Table 1. (Example 5) Magnesium nitrate hexahydrate was prepared using 0.0012% of calcium nitrate tetrahydrate (0.0002% in terms of metal calcium concentration).
The same as Example 1 except that 0.0042% (0.0004% as the concentration of metallic magnesium) was used. The test was performed in the same manner, and the results are shown in Table 1. (Example 6) 0.0035% of calcium nitrate tetrahydrate (0.0006% as a calcium metal concentration) was used, and magnesium nitrate hexahydrate was used.
It is the same as Example 1 except that 0.0127% (0.0012% as the concentration of metallic magnesium) was used. The test was performed in the same manner, and the results are shown in Table 1. (Example 7) 0.0071% of calcium nitrate tetrahydrate (0.0012% as the concentration of metal calcium) was used, and magnesium nitrate hexahydrate was used.
Same as Example 1 except that 0.0253% (concentration of metal magnesium was 0.0024%) was used. The test was performed in the same manner, and the results are shown in Table 1. (Example 8) As shown in Table 1, 95.0% of monoethylene glycol,
2.7176% water, 0.0071% calcium nitrate tetrahydrate (0.0012% metal calcium concentration), 0.0253% magnesium nitrate hexahydrate (0.0024% metal magnesium concentration)
), Sodium nitrate 0.25%, tolyltriazole 0.1
%, Orthophosphoric acid 0.6%, potassium hydroxide 0.65%, sodium silicate 0.35% and sodium tetraborate 0.3% were mixed to obtain a cooling liquid composition of Example 8. Then, a test was conducted in the same manner as in Example 1, and the results are shown in Table 1. (Example 9) As also shown in Table 1, monoethylene glycol 90.0%,
2.9676% water, 0.0071% calcium nitrate tetrahydrate (0.0012% as calcium metal concentration), 0.0253% from magnesium nitrate hexahydrate (0.0024% as magnesium metal concentration)
), Sodium nitrate 0.25%, benzotriazole 0.1
%, Sodium hydroxide 1.3%, sodium silicate 0.15%,
1.2% of sodium tetraborate, 1.5% of sebacic acid and 2.5% of octylic acid were mixed to obtain a cooling liquid composition of Example 9.
Then, a test was conducted in the same manner as in Example 1, and the results are shown in Table 1. (Comparative example 1) It is the same as Example 1 except not containing a calcium compound and a magnesium compound. The test was performed in the same manner, and the results are shown in Table 1. (Comparative example 2) It is the same as Example 8 except not containing a calcium compound and a magnesium compound. The test was performed in the same manner, and the results are shown in Table 1. (Comparative example 3) It is the same as that of Example 9 except not containing a calcium compound and a magnesium compound. The test was performed in the same manner, and the results are shown in Table 1. (Comparative Example 4) Same as Example 1 except that magnesium nitrate hexahydrate was used in place of the calcium compound at 0.0253% (the concentration of metal magnesium was 0.0024%). The test was performed in the same manner, and the results are shown in Table 1. (Comparative Example 5) Instead of a calcium compound, 0.0759% of magnesium nitrate hexahydrate (0.0072% as a magnesium metal concentration)
It is the same as Example 1 except that it was used. The test was performed in the same manner, and the results are shown in Table 1.
【００２１】[0021]
【表１】 [Table 1]
【００２２】（評価）比較例４〜５と実施例１〜４を比
較すると、カルシウム化合物の方が少量の添加で腐食量
が大きく低減し、マグネシウム化合物に比べて効果が大
きいことが明らかである。またカルシウム化合物は、硝
酸塩よりも硫酸塩の方が効果が大きいこともわかる。そ
して実施例の冷却液を用いた場合には、試験片の外観変
化もほとんどない。(Evaluation) Comparing Comparative Examples 4 to 5 with Examples 1 to 4, it is clear that the addition of a small amount of the calcium compound greatly reduces the amount of corrosion and is more effective than the magnesium compound. . It can also be seen that sulfate is more effective than nitrate for calcium compounds. When the cooling liquid of the example was used, there was almost no change in the appearance of the test piece.
【００２３】さらに実施例５〜７とも比較すると、カル
シウム化合物とマグネシウム化合物とを併用することに
より、その合計添加量がさらに少量でも腐食量は極めて
少なく、高い耐食性を示していることが明らかである。
そして併用の効果は、他の組成例である比較例２と実施
例８の比較、及び比較例３と実施例９の比較からも明ら
かである。Further, when compared with Examples 5 to 7, it is clear that the combined use of a calcium compound and a magnesium compound shows a very small amount of corrosion even when the total added amount is even smaller, and shows high corrosion resistance. .
The effect of the combined use is also evident from a comparison between Comparative Example 2 and Example 8, which are other composition examples, and a comparison between Comparative Example 3 and Example 9.
【００２４】さらに、試験前後のｐＨの変化はほとんど
ないことから、実施例及び比較例の冷却液には無駄な反
応が生じていないと判断され、長期の使用に耐え得るこ
とがわかる。 ＜第２シリーズの実施例＞ （実施例10）表２にも示すように、モノエチレングリコ
ール90.0% ，水1.9476% ，硝酸ナトリウム0.4%，モリブ
デン酸ナトリウム0.5%，ベンゾトリアゾール0.4%，安息
香酸ナトリウム5.0%，メルカプトベンゾチアゾール0.2
%，オルトリン酸0.8%，水酸化カリウム0.7%，硝酸カル
シウム４水和物0.0071% （金属カルシウム濃度として0.
0012% ），硝酸マグネシウム６水和物0.0253% （金属マ
グネシウム濃度として0.0024% ）及び１−ヒドロキシエ
チリデン−１，１−ジホスホン酸0.02% を混合し、実施
例10の冷却液組成物とした。Further, since there was almost no change in pH before and after the test, it was determined that no useless reaction occurred in the coolants of the examples and comparative examples, and it was found that the coolants could be used for a long time. <Example of Second Series> (Example 10) As shown in Table 2, monoethylene glycol 90.0%, water 1.9476%, sodium nitrate 0.4%, sodium molybdate 0.5%, benzotriazole 0.4%, sodium benzoate 5.0%, mercaptobenzothiazole 0.2
%, Orthophosphoric acid 0.8%, potassium hydroxide 0.7%, calcium nitrate tetrahydrate 0.0071%.
0012%), 0.0253% of magnesium nitrate hexahydrate (0.0024% as magnesium metal concentration) and 0.02% of 1-hydroxyethylidene-1,1-diphosphonic acid were mixed to obtain a cooling liquid composition of Example 10.
【００２５】この冷却液組成物について、ASTM D4340-8
4(Corrosion of Cast AluminiumAlloys in Engine Cool
ants Under Heat-Rejecting Conditions)（アルミニウ
ム合金伝熱面腐食試験）に基づく腐食試験を行い、腐食
量測定と外観判定の結果を表２に示す。 冷却液濃度 ： ２５体積％ 試験片 ： アルミニウム合金鋳物(AC-2
A) 試験片温度 ： 135 ℃又は170 ℃ 液量 ： 500ml 試験時間 ： 168Hr 試験液中のcl- 量 ： 100ppm 加圧圧力 ： 193kPa なおASTM試験法では、温度条件は135 ℃のみであるが、
より過酷な試験を行うために170 ℃の温度条件でも同じ
試験を行った。また、この冷却液組成物を30体積％含む
水溶液のｐＨは7.3 であった。 （実施例11）硝酸カルシウム４水和物を0.0213% （金属
カルシウム濃度として0.0036% ）用い、マグネシウム化
合物を用いなかったこと以外は実施例10と同様である。
同様に試験を行い、結果を表２に示す。なお、この冷却
液組成物を30体積％含む水溶液のｐＨは7.3 であった。 （実施例12）硝酸マグネシウム６水和物を0.0759% （金
属マグネシウム濃度として0.0072%）用い、カルシウム
化合物を用いなかったこと以外は実施例10と同様であ
る。同様に試験を行い、結果を表２に示す。なお、この
冷却液組成物を30体積％含む水溶液のｐＨは7.3 であっ
た。 （実施例13）１−ヒドロキシエチリデン−１，１−ジホ
スホン酸を用いず、硝酸カルシウム４水和物0.0213%
（金属カルシウム濃度として0.0036% ）と硝酸マグネシ
ウム６水和物を0.0759% （金属マグネシウム濃度として
0.0072% ）用いたこと以外は実施例10と同様である。同
様に試験を行い、結果を表２に示す。なお、この冷却液
組成物を30体積％含む水溶液のｐＨは7.3 であった。 （比較例６）カルシウム化合物とマグネシウム化合物を
用いなかったこと以外は実施例10と同様である。同様に
試験を行い、結果を表２に示す。なお、この冷却液組成
物を30体積％含む水溶液のｐＨは7.3 であった。The cooling liquid composition was prepared according to ASTM D4340-8
4 (Corrosion of Cast AluminumAlloys in Engine Cool
A corrosion test based on ants Under Heat-Rejecting Conditions (aluminum alloy heat transfer surface corrosion test) was performed, and the results of the corrosion amount measurement and appearance judgment are shown in Table 2. Coolant concentration: 25% by volume Test piece: Aluminum alloy casting (AC-2
A) Test piece temperature: 135 ° C or 170 ° C Liquid volume: 500ml Test time: 168Hr Cl - amount in test solution: 100ppm Pressurizing pressure: 193kPa In the ASTM test method, the temperature condition is only 135 ° C.
The same test was performed at a temperature of 170 ° C. to perform a more severe test. The pH of an aqueous solution containing 30% by volume of the cooling liquid composition was 7.3. (Example 11) The same as Example 10 except that 0.0213% of calcium nitrate tetrahydrate (0.0036% as the concentration of calcium metal) was used and no magnesium compound was used.
The test was performed in the same manner, and the results are shown in Table 2. The pH of the aqueous solution containing 30% by volume of the cooling liquid composition was 7.3. (Example 12) The same as Example 10 except that 0.0759% of magnesium nitrate hexahydrate (0.0072% as a concentration of magnesium metal) was used and no calcium compound was used. The test was performed in the same manner, and the results are shown in Table 2. The pH of the aqueous solution containing 30% by volume of the cooling liquid composition was 7.3. (Example 13) Without using 1-hydroxyethylidene-1,1-diphosphonic acid, calcium nitrate tetrahydrate 0.0213%
(0.0036% metal calcium concentration) and 0.0759% magnesium nitrate hexahydrate (magnesium metal concentration
The same as Example 10 except that 0.0072%) was used. The test was performed in the same manner, and the results are shown in Table 2. The pH of the aqueous solution containing 30% by volume of the cooling liquid composition was 7.3. (Comparative Example 6) The same as Example 10 except that the calcium compound and the magnesium compound were not used. The test was performed in the same manner, and the results are shown in Table 2. The pH of the aqueous solution containing 30% by volume of the cooling liquid composition was 7.3.
【００２６】[0026]
【表２】 [Table 2]
【００２７】（評価）比較例１，比較例５〜６及び実施
例２，７，13と実施例10〜12の比較より、カルシウム及
びマグネシウムの少なくとも一方と１−ヒドロキシエチ
リデン−１，１−ジホスホン酸とが共存することによ
り、過酷な試験においても腐食量が減少し防食性に優れ
ることがわかり、ポリリン酸とカルシウム化合物又はマ
グネシウム化合物の共存による相乗効果が明らかであ
る。(Evaluation) From a comparison between Comparative Examples 1, 5 and 6 and Examples 2, 7, 13 and Examples 10 and 12, at least one of calcium and magnesium was compared with 1-hydroxyethylidene-1,1-diphosphone. It can be seen that the coexistence of an acid reduces the amount of corrosion even in a severe test and is excellent in anticorrosion properties, and a synergistic effect of coexistence of polyphosphoric acid and a calcium compound or a magnesium compound is apparent.
【００２８】一方、実施例７と実施例１３の比較より、
カルシウム化合物とマグネシウム化合物を増量しても防
食性が改善されることがわかるが、実施例13の場合はス
ケール状堆積物が形成される心配がある。つまり、ポリ
リン酸をカルシウム化合物又はマグネシウム化合物と共
存させることにより、カルシウム化合物又はマグネシウ
ム化合物の量を少なくしても多い場合と同等の防食性が
得られるので、スケール状堆積物の形成が防止され、エ
ンジンの放熱性を長期間維持することができる。On the other hand, a comparison between Example 7 and Example 13 shows that
It can be seen that even if the calcium compound and the magnesium compound are increased, the anticorrosion property is improved, but in the case of Example 13, there is a concern that a scale-like deposit is formed. In other words, by allowing the polyphosphoric acid to coexist with the calcium compound or the magnesium compound, the same anticorrosive property as when the amount of the calcium compound or the magnesium compound is reduced is obtained, so that the formation of scale-like deposits is prevented, The heat radiation of the engine can be maintained for a long time.
【００２９】[0029]
【発明の効果】すなわち本発明の冷却液組成物によれ
ば、アルミニウム系金属の腐食を確実に抑制することが
できる。そしてカルシウム化合物の少量の添加により高
い耐食性が得られるので、他の成分の添加量の規制が緩
和され配合設計の自由度が高い。またカルシウム化合物
とマグネシウム化合物を併用すれば、配合設計の自由度
はさらに高くなる。したがって各種用途に応じた冷却液
を容易に配合設計することができ、製品化までの工数が
短縮されるとともに安価となる。As described above, according to the coolant composition of the present invention, the corrosion of aluminum-based metal can be surely suppressed. Since a high corrosion resistance can be obtained by adding a small amount of a calcium compound, the regulation of the addition amount of other components is relaxed, and the degree of freedom in the blending design is high. When a calcium compound and a magnesium compound are used in combination, the degree of freedom in the formulation design is further increased. Therefore, it is possible to easily mix and design the cooling liquid according to various uses, thereby reducing the man-hours required for commercialization and reducing the cost.
【００３０】また本発明の冷却液組成物は、ポリリン酸
又はカルボン酸をカルシウム化合物及びマグネシウム化
合物の少なくとも一方と共存させることにより、カルシ
ウム化合物又はマグネシウム化合物の量を少なくしても
多い場合と同等の防食性が得られる。したがって、カル
シウム化合物又はマグネシウム化合物の過度の添加によ
るスケール状堆積物の形成が抑制されるので、エンジン
の放熱性を長期間高く維持することができる。Further, the coolant composition of the present invention has a polyphosphoric acid or a carboxylic acid coexisting with at least one of a calcium compound and a magnesium compound, so that the amount of the calcium compound or the magnesium compound can be reduced even if the amount is large. Provides anticorrosion properties. Therefore, the formation of scale-like deposits due to excessive addition of the calcium compound or the magnesium compound is suppressed, and the heat radiation of the engine can be maintained high for a long period of time.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 谷川 正峰 愛知県豊田市トヨタ町１番地 トヨタ自 動車株式会社内 (72)発明者 伊藤 寿記 愛知県豊田市トヨタ町１番地 トヨタ自 動車株式会社内 (72)発明者 田見 秀行 静岡県清水市吉川813番地 日本ケミカ ル工業株式会社内 (72)発明者 八重田 一人 静岡県清水市吉川813番地 日本ケミカ ル工業株式会社内 (56)参考文献 特開 昭51−75641（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masamine Tanikawa 1 Toyota Town, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation (72) Inventor Toshiki Ito 1 Toyota Town, Toyota City, Toyota City, Aichi Prefecture Toyota Motor Corporation (72) Inventor Hideyuki Tami 813 Yoshikawa, Shimizu City, Shizuoka Prefecture, Japan Nippon Chemical Industry Co., Ltd. Kaisho 51-75641 (JP, A)
Claims (1)
れる融点降下剤と、リン酸塩，ホウ酸塩，硝酸塩，モリ
ブデン酸塩，安息香酸塩，ケイ酸塩，トリアゾール類，
チアゾール類，セバチン酸及びオクチル酸から選ばれる
少なくとも１種の防錆剤とを含み、さらにカルシウム化
合物とマグネシウム化合物をそれぞれ金属元素濃度とし
て０．００００５〜０．０２重量％含むことを特徴とす
る冷却液組成物。1. A melting point depressant selected from alcohols and glycols, phosphate, borate, nitrate, molybdate, benzoate, silicate, triazole,
A cooling agent containing at least one rust inhibitor selected from thiazoles, sebacic acid and octylic acid, and further containing 0.00005 to 0.02% by weight of a calcium compound and a magnesium compound as metal element concentrations , respectively. Liquid composition.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6098691A JP2902554B2 (en) | 1993-07-02 | 1994-05-12 | Coolant composition |
| US08/559,199 US5718836A (en) | 1994-05-12 | 1995-11-13 | Liquid coolant compositions with anti-corrosive property containing magnesium and calcium compounds |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-164715 | 1993-07-02 | ||
| JP16471593 | 1993-07-02 | ||
| JP6098691A JP2902554B2 (en) | 1993-07-02 | 1994-05-12 | Coolant composition |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9103065A Division JP2884336B2 (en) | 1997-04-21 | 1997-04-21 | Coolant composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0770558A JPH0770558A (en) | 1995-03-14 |
| JP2902554B2 true JP2902554B2 (en) | 1999-06-07 |
Family
ID=26439809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6098691A Expired - Fee Related JP2902554B2 (en) | 1993-07-02 | 1994-05-12 | Coolant composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2902554B2 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999057218A1 (en) * | 1998-05-06 | 1999-11-11 | Shishiai-Kabushikigaisha | Dilute coolant |
| KR100549298B1 (en) * | 2001-02-09 | 2006-02-03 | 애큐랩주식회사 | Corrosion inhibitor and its feeding method in cooling system |
| CA2546332A1 (en) * | 2003-11-13 | 2005-05-26 | Vladisav Milovanovic | The nontoxic watery solution against freezing and corrosion and the regenerator for the utilized antifreeze |
| JP5044544B2 (en) * | 2006-03-31 | 2012-10-10 | シーシーアイ株式会社 | Coolant composition |
| EP2255147A4 (en) * | 2008-03-03 | 2013-10-16 | Prestone Products Corp | Heat transfer system comprising brazed aluminum, method, heat transfer fluid, and additive package |
| JP5465941B2 (en) * | 2009-07-16 | 2014-04-09 | 共栄社化学株式会社 | Metal protective liquid |
| CN102747373B (en) * | 2012-07-13 | 2014-07-16 | 李舰 | Sorbitol and maltitol inhibitor and preparation method thereof |
| KR102241565B1 (en) * | 2013-02-13 | 2021-04-16 | 바스프 에스이 | Anti-freeze concentrate having corrosion protection and aqueous coolant composition produced therefrom |
| JP6332603B2 (en) * | 2014-02-24 | 2018-05-30 | 株式会社スリーボンド | Rust preventive composition |
| JP6537847B2 (en) * | 2015-03-02 | 2019-07-03 | シーシーアイ株式会社 | Coolant composition |
| CA3038677A1 (en) * | 2016-10-04 | 2018-04-12 | Commonwealth Scientific And Industrial Research Organisation | Methods for inhibiting corrosion |
| WO2022230306A1 (en) * | 2021-04-26 | 2022-11-03 | オルガノ株式会社 | Metal corrosion inhibitor composition for chillers and method for operating chiller |
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1994
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