EP2828419B1 - Aqueous, surface-active, corrosion protection formulation, and as well as an oil-containing, water-miscible emulsion concentrate - Google Patents
Aqueous, surface-active, corrosion protection formulation, and as well as an oil-containing, water-miscible emulsion concentrate Download PDFInfo
- Publication number
- EP2828419B1 EP2828419B1 EP13709100.5A EP13709100A EP2828419B1 EP 2828419 B1 EP2828419 B1 EP 2828419B1 EP 13709100 A EP13709100 A EP 13709100A EP 2828419 B1 EP2828419 B1 EP 2828419B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon atoms
- corrosion protection
- protection system
- component
- corrosion
- 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.)
- Active
Links
- 238000005260 corrosion Methods 0.000 title claims description 82
- 230000007797 corrosion Effects 0.000 title claims description 81
- 239000000839 emulsion Substances 0.000 title claims description 22
- 239000012141 concentrate Substances 0.000 title claims description 20
- 239000000203 mixture Substances 0.000 title description 9
- 238000009472 formulation Methods 0.000 title description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 41
- 150000001412 amines Chemical class 0.000 claims description 35
- 238000002360 preparation method Methods 0.000 claims description 22
- 150000001735 carboxylic acids Chemical class 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 150000002191 fatty alcohols Chemical class 0.000 claims description 16
- -1 aliphatic phosphonic acids Chemical class 0.000 claims description 15
- 150000003973 alkyl amines Chemical group 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 11
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 10
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- 239000003995 emulsifying agent Substances 0.000 claims description 10
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- XZOYHFBNQHPJRQ-UHFFFAOYSA-N 7-methyloctanoic acid Chemical compound CC(C)CCCCCC(O)=O XZOYHFBNQHPJRQ-UHFFFAOYSA-N 0.000 claims description 7
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229960002446 octanoic acid Drugs 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001302 tertiary amino group Chemical group 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- 150000001983 dialkylethers Chemical class 0.000 claims description 2
- 239000010696 ester oil Substances 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims 11
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 238000005555 metalworking Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000003112 inhibitor Substances 0.000 description 10
- 239000012530 fluid Substances 0.000 description 7
- 239000011550 stock solution Substances 0.000 description 7
- 150000003009 phosphonic acids Chemical class 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000005068 cooling lubricant Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 description 3
- 150000002830 nitrogen compounds Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910001060 Gray iron Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- PVGXGEMQALWHPA-UHFFFAOYSA-N 4,10-diethyl-1,7-dioxa-4,10-diazacyclododecane Chemical compound CCN1CCOCCN(CC)CCOCC1 PVGXGEMQALWHPA-UHFFFAOYSA-N 0.000 description 1
- RGDWYHPHCVBFQJ-UHFFFAOYSA-N 4,10-dimethyl-1,7-dioxa-4,10-diazacyclododecane Chemical compound CN1CCOCCN(C)CCOCC1 RGDWYHPHCVBFQJ-UHFFFAOYSA-N 0.000 description 1
- CFDQAEZGYUCNEI-UHFFFAOYSA-N 7,13-diethyl-1,4,10-trioxa-7,13-diazacyclopentadecane Chemical compound CCN1CCOCCOCCN(CC)CCOCC1 CFDQAEZGYUCNEI-UHFFFAOYSA-N 0.000 description 1
- JKAINOIUNISDMC-UHFFFAOYSA-N 7,13-dimethyl-1,4,10-trioxa-7,13-diazacyclopentadecane Chemical compound CN1CCOCCOCCN(C)CCOCC1 JKAINOIUNISDMC-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000013011 aqueous formulation Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229940079842 sodium cumenesulfonate Drugs 0.000 description 1
- QEKATQBVVAZOAY-UHFFFAOYSA-M sodium;4-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=C(S([O-])(=O)=O)C=C1 QEKATQBVVAZOAY-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
- C10G75/02—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
- C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/36—Organic compounds containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
- C23G1/26—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions using inhibitors
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/106—Naphthenic fractions
- C10M2203/1065—Naphthenic fractions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/0406—Ethers; Acetals; Ortho-esters; Ortho-carbonates used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/2805—Esters used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/049—Phosphite
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
-
- C11D2111/16—
Definitions
- the corrosion protection system comprises carboxylic and / or phosphonic acids and at least one amine having at least one oxybis (alkylamine) unit.
- Such anticorrosive systems effectively protect metal surfaces from corrosion and have high water solubility, which is indispensable for the formulation of aqueous concentrates for metalworking and metalworking fluids.
- the present invention relates to an aqueous surface-active and corrosion-protective preparation comprising the corrosion protection system and an emulsifier system and an oily, water-miscible emulsion concentrate which, when diluted with water, provides ready-to-use corrosion protection, cleaning and cooling lubricant emulsions.
- corrosion-prone metals such as iron, aluminum, zinc, copper or their alloys against corrosion
- a permanent corrosion-protective coating such as a paint due to their processing condition or because of their field of application.
- Examples include metal parts during technical processing stages such as machining or non-cutting shaping or cleaning and finished metal components such as heat exchangers or pipelines, which come into contact during their function with corrosive aqueous media.
- the metal surfaces are brought into contact with corrosion inhibitors, which cause a temporary corrosion protection.
- Inorganic corrosion inhibitors may be based, for example, on chromates, nitrites or phosphates, but these are more or less disadvantageous for toxicological and ecological reasons.
- Organic corrosion inhibitors are often based on carboxylates, amines, amides or on nitrogen-containing heterocyclic compounds.
- Carboxylic acids as such prove in practice to be insufficiently long-term effective if the pH is lowered by an acid entry into the inhibitor baths or by microbiological processes to such an extent that the carboxylic acids are present in the less active acid form instead of in the salt form.
- Corrosion-inhibiting carboxylic acids are therefore often used in the form of their salts or as a corrosion protection system consisting of the carboxylic acid and a base.
- Particularly well-known in the art are corrosion protection systems consisting of carboxylic acids and alkanolamines, which have an increased inhibitory effect compared to systems of carboxylic acid and alkalis based on sodium hydroxide solution or ammonia.
- the DE 102007004325 describes an emulsifier system for the production of coolant emulsions suitable for use in the machining of light metals or aluminum alloyed metals.
- the emulsifier system comprises a corrosion protection system consisting of light metal inhibitors such as carboxylic acids and phosphonic acids, which in addition to avoid the so-called fountain blacks contains chelating tertiary organic amine compounds having phosphonic acid groups.
- the corrosion protection system contains alkanolamines, preferably mono- and trialkanolamines, as bases for providing particularly effective inhibiting carboxylic and phosphonic acid salts.
- the DE 4444878 discloses a water-soluble inhibitor system based on monocarboxylic acids and aromatic hydroxy compounds with a pK s value for the Hydroxy group in the range of 7.0 to 11, wherein both components are in a certain weight ratio to each other.
- the JP2005015617 discloses an aqueous anticorrosion composition for metalworking comprising an aliphatic carboxylic acid in combination with an amine, preferably bis (2-dimethylaminoethyl) ether or N, N, N ', N'-tetramethyl-2,2'-oxybis (ethylamine) , contains.
- the DE 19747895 discloses a corrosion protection system for the neutral pH range based on a combination of one or more carboxylic acids and one or several nitrogen compounds selected from organic amines or nitrogen-containing heterocycles, wherein the nitrogen compounds have a pK a value for at least one protolysis stage is in the range 6-9 , wherein both components are in a certain weight ratio to each other.
- Preferred nitrogen compounds may for example be selected from linear or cyclic alkylenediamines, alkylene triamines and alkylene tetraamines.
- the object of the present invention is to provide an aqueous surface-active and corrosion-protective preparation suitable for the production of aqueous metal treatment and metalworking fluids, in particular cleaners and lubricants, that metals, in particular iron and iron alloys, in comparison with the prior art in contact with the Treatment and processing fluid more effectively protects against corrosion.
- an aqueous surface-active and corrosion-protective preparation according to the present claim 1.
- the inventive aqueous surface-active and corrosion-protective preparation provides excellent protection against corrosion of iron and iron alloys and of aluminum and Aluminum alloys in contact with aqueous liquids, in particular liquids for metal treatment or metalworking.
- the corrosion protection system (I) is characterized by its good water solubility, which makes it possible to distribute the corrosion protection system in the form of highly concentrated aqueous preparations.
- Each preparation for example a ready-to-use metal treatment or metalworking fluid or its concentrate, which contains the two components a) and b), thus comprises the corrosion protection system (I).
- a solution of the anticorrosive system is formulated into a metalworking or metalworking fluid to impart the desired anticorrosive properties.
- corrosion protection systems which store the components a) and b) in an aqueous phase are therefore preferred.
- At least one amine of the following structural formula (1) is contained: wherein the radicals R 1 , R 2 , R 3 and R 4 are independently selected from branched or unbranched alkyl radicals having not more than 8 carbon atoms and - ((CH 2 ) o -X) p -R 5 , where o is a natural whole Number in the range of 1 to 3, p is a natural integer in the range of 1 to 6, X is either an oxygen or a nitrogen atom, and R 5 is selected from hydrogen, methyl, ethyl or propyl; with m and n as natural integers in the range of 1 to 3.
- radicals R 1 , R 2 , R 3 and R 4 of the structural formula (1) may be selected from those containing the two nitrogen atoms of the oxybis (alkylamine) moiety bridge, so that the radical R 1 and / or the radical R 2 are each structurally identical to the radical R 3 or R 4 , wherein bridging radicals R 1 or R 2 or R 3 or R 4 are selected from alkylene, polyoxyalkylenes or polyaminoalkylenes with not more than 6 carbon atoms.
- Such a preferred bridged amine in a corrosion protection system (I) has the following general structural formula (1a): wherein the radicals R 1 and R 2 are independently selected from branched or unbranched alkyl radicals having not more than 8 carbon atoms and - ((CH 2 ) o -X) p -R 5 , where o is a natural integer in the range of 1 to 3, p is a natural integer in the range of 1 to 6, X is either an oxygen or a nitrogen atom, and R 5 is selected from hydrogen, methyl, ethyl or propyl; with m and n as natural integers in the range of 1 to 3; and wherein q, r and s are integer numbers in the range of 1 to 3 and Z is either a carbon, oxygen or nitrogen atom.
- amines of the structural formula (1a) for which the radicals R 1 and R 2 are independently selected from branched or unbranched alkyl radicals having not more than 8 carbon atoms, preferably not more than 4 carbon atoms, for the m, n, q and r is 2, and s is not greater than 3, where Z is an oxygen or nitrogen atom.
- bridged amines are N, N'-dimethyl-1,7-dioxa-4,10-diazacyclododecane, N, N'-diethyl-1,7-dioxa-4,10-diazacyclododecane, N, N'-dimethyl 1,4,10-trioxa-7,13-diazacyclopentadecane and N, N'-diethyl-1,4,10-trioxa-7,13-diazacyclopentadecane.
- the radicals R 1 , R 2 , R 3 and R 4 of the structural formula (1) are independently selected from branched or unbranched alkyl radicals with no more as 8 carbon atoms, more preferably not more than 4 carbon atoms, wherein the natural integers m and n are equal to 2.
- the radicals R 1 , R 2 , R 3 and R 4 of the structural formula (1) are independently selected from branched or unbranched alkyl radicals with no more as 8 carbon atoms, more preferably not more than 4 carbon atoms, wherein the natural integers m and n are equal to 2.
- a preferred corrosion protection system (I) contains at least 50% by weight, more preferably at least 80% by weight, only those organic amines according to component b) which are selected from amines of the general structural formula (1) according to component b) , particularly preferably from such amines of general structural formula (1) according to component b), for which the radicals R 1 , R 2 , R 3 and R 4 are independently selected from branched or unbranched alkyl radicals having not more than 4 carbon atom, wherein the natural integers m and n are 2, and more preferably are selected from N, N, N ', N'-tetramethyl-2,2'-oxybis (ethylamine) and / or N, N, N', N '-Tetraethyl-2,2'-oxybis (ethylamine).
- the aliphatic carboxylic acids according to component a) of the corrosion protection system (I) having at least 6 but not more than 14 carbon atoms can be mono- or polybasic, saturated or unsaturated, linear or branched aliphatic carboxylic acids, but are preferably selected from aliphatic monocarboxylic acids having at least 6 but not more than 12 carbon atoms, in particular from caprylic acid, ethylhexanoic acid, isononanoic acid and / or isodecanoic acid.
- carboxylic acids according to component a) with inserted into the carbon chain oxygen heteroatoms are preferably selected ether carboxylic acids of the general formula R- (OC 2 H 4 ) n -OCH 2 COOH, where R is a linear or branched, saturated or unsaturated alkyl radical having 6 to Is 16 carbon atoms, n represents a number in the range of 1 to 5 and R and n are to be matched to one another such that the sum of the carbon and oxygen atoms is not greater than 25, neglecting the carboxyl group.
- the ether carboxylic acids may be technical mixtures of molecules with different radicals R and different values for n. An example of this is the technical Laurylethercarbonklare, in which R for is a mixture of linear, saturated alkyl groups having 12 and 14 carbon atoms and n is about 2.5.
- the aliphatic phosphonic acids having at least 4 but not more than 18 carbon atoms contained in the corrosion protection system (I) according to component a) may be mono- or polybasic, saturated or unsaturated, linear or branched aliphatic phosphonic acids, but are preferably selected from saturated straight-chain or linear branched monophosphonic acids. Mixtures of different acids may be particularly advantageous, the alkyl monophosphonic acids are particularly suitable in their straight-chain form. Further preferred are alkyl monophosphonic acids having 6 to 12 carbon atoms.
- carboxylic acids as component a) is always preferable for ecological reasons, if the use of phosphonic acids is not able to significantly improve the temporary corrosion protection in metal treatment or metalworking.
- component a) is therefore selected from aliphatic monocarboxylic acids having at least 6 but not more than 12 carbon atoms, in particular from caprylic acid, ethylhexanoic acid, isononanoic acid and / or isodecanoic acid, and / or carboxylic acids with into the carbon chain inserted oxygen heteroatoms having between 6 and 26 atoms in the carbon heteroatom chain, in particular ether carboxylic acids of the general formula R- (OC 2 H 4 ) n -OCH 2 COOH, wherein R is a linear or branched, saturated or unsaturated alkyl radical 6 to 16 carbon atoms, n represents a number in the range of 1 to 5 and R and n are coordinated so that the sum of the C and O atoms is neglecting the carboxyl group is not greater than 25.
- component a) is selected from aliphatic monocarboxylic acids having at least 6 but not more than 12 carbon atoms, in particular from caprylic acid, ethylhexanoic acid, isononanoic acid and / or isodecanoic acid.
- the weight-based proportion of carboxylic acids according to component a) is selected from aliphatic monocarboxylic acids having at least 6 but not more than 12 carbon atoms, in particular the weight-related proportion of caprylic acid, ethylhexanoic acid, isononanoic acid and / or isodecanoic acid, on the total amount of carboxylic acids and phosphonic acids in the corrosion protection system, including those carboxylic acids and phosphonic acids which are not compounds according to component a), at least 50 wt .-%, particularly preferably at least 80 wt .-% is.
- components a) and b) of the corrosion protection system (I) can undergo acid-base reactions with one another and, in aqueous solution, also have a protolysis equilibrium with their respective deprotonated or protonated form.
- the molar ratio of the total amount of carboxyl and / or phosphonic acid groups of components a) to oxybis (alkylamine) units of the at least one amine of component b) is not less than 1: 3 in order to ensure a minimum amount of the amine according to component b) is present in the corrosion protection system as ammonium salt.
- this molar ratio is not less than 2: 3.
- the total amount of carboxyl and / or phosphonic acid groups of components a) relative to the proportion of amines according to component b) should not exceed values for which the effectiveness of the corrosion protection is clearly evident decreases.
- the molar ratio of the total amount of carboxyl and / or phosphonic acid groups of components a) to oxybis (alkylamine) units of the at least one amine of component b) is not greater than 5: 1, more preferably not greater than 3: 1, particularly preferably not greater than 2: 1.
- the corrosion protection system (I) is suitable to be used in aqueous emulsions, especially in cleaning, anticorrosion and cooling lubricant emulsions, to prevent metal corrosion.
- An advantage of using a corrosion protection system based on components a) and b) is that for a sufficient corrosion protection, a comparatively small amount of these two active components must be present in the aqueous metal working and metal treatment system.
- the emulsifier system (II) of the aqueous surface-active and anti-corrosive preparation according to the invention additionally comprises alkoxylated fatty amines as component e) to improve the filterability of emulsions prepared from these preparations.
- alkoxylated fatty amines consisting of one or more alkoxylated saturated and / or unsaturated aliphatic amines having an aliphatic chain length of at least 8, preferably at least 10 and more preferably at least 12, but not more than 20, preferably not more than 18 and most preferably not used more than 16 carbon atoms.
- the fatty amines used should be ethoxylated with at least 8, preferably not more than 10, but not more than 16, preferably not more than 14 and most preferably 12 ethylene oxide units. In particular, is suitable for increasing the Filterability of ready-to-use emulsions 12 times ethoxylated cocoamine prepared from these formulations.
- the proportion of components a) to e) of the preparation according to the invention for an application-ready anticorrosive cleaner solution is preferably in the range from 0.5 to 10% by weight, the total proportion of components a) and b) of the anticorrosion system (I) preferably being at least 0.1 wt .-% is.
- the preparation according to the invention can also be a concentrate for the production of anticorrosion cleaner solutions in which the proportion of components a) to e) is preferably in the range from 40 to 95% by weight, the total amount of components a) and b) being of the corrosion protection system (I) in the preparation according to the invention is preferably at least 10 wt .-%.
- the aqueous surface-active and corrosion-protective preparation may additionally be admixed with a water component of not more than 60% by weight, so that a total of one oil-containing, water-miscible emulsion concentrate for metalworking, in particular a concentrate for a coolant lubricant or anticorrosion emulsion, realized.
- the corrosion protection system (I) and the emulsifier system (II) of the oil-containing, water-miscible emulsion concentrate according to the invention are identical to those described for the corrosion protection system and the aqueous surface-active and corrosion-protective preparation according to the invention.
- the emulsifier system (II) of the oil-containing, water-miscible emulsion concentrate according to the invention as described above for the aqueous surface-active and anti-corrosive preparation, alkoxylated fatty amines as component e), preferably with a weight fraction in the concentrate of at least 1 wt .-%, more preferably at least 2 wt .-%, but preferably not more than 10 wt .-%, particularly preferably not more than 8 wt .-%.
- the oil component (III) of the oily, water-miscible emulsion concentrate according to the invention is preferably selected from paraffinic or naphthenic mineral oils, dialkyl ethers having 12 to 20 carbon atoms and / or ester oils.
- auxiliaries or active ingredients may be mentioned: lubricating additives in general and in particular so-called “extreme pressure” additives (so-called EP additives) and biocides in each case in an amount of preferably 0.1 to 2 wt .-% in the concentrate; Buffer systems, in particular based on boric acid, in an amount based on the particular acid form of preferably 2 to 10 wt .-% in the concentrate; Neutralizing agent based on alkanolamines, solubilizers such as glycols, glycerol or sodium cumenesulfonate each in an amount of preferably 1 to 6 wt .-% in the concentrate.
- so-called "extreme pressure" additives so-called EP additives
- biocides in each case in an amount of preferably 0.1 to 2 wt .-% in the concentrate
- Buffer systems in particular based on boric acid, in an amount based on the particular acid form of preferably 2 to 10 wt .-% in the
- the invention relates to the ready-to-use oil-in-water emulsion which is obtainable by adding from about 0.5 to about 10 parts by weight of the above-described oily, water-miscible concentrate with about 99.5 to about 90 parts by weight of water. Due to the self-emulsifying properties of the emulsion concentrate, the ready-to-use emulsion forms spontaneously upon addition of water or after slight mechanical agitation such as stirring. This emulsion can be used for example as a cleaning, corrosion protection or cooling lubricant emulsion.
- oil-containing, water-miscible emulsion concentrate according to the invention and the ready-to-use oil-in-water emulsions preparable therefrom by dilution with water are particularly suitable for the treatment and processing of iron and iron alloys and of aluminum and aluminum alloys.
- the mode of action of the corrosion protection system (I) is shown by way of example and compared with systems known in the prior art.
- a corrosion protection test according to DIN 51360-2 is carried out in which gray cast iron chips (type GG25) are wetted on a round filter with freshly prepared dilute aqueous solutions containing various corrosion protection systems based on an amine and isononanoic acid.
- Table 1 lists the compositions of concentrated aqueous corrosion protection systems (stock solutions) based on an amine and isononanoic acid.
- stock solutions of the corrosion protection systems with an active component content of 20% by weight in water with a hardness of 20 ° dH (3.04 mmol CaCl 2 , 0.54 mmol MgSO 4 )
- Amine component Wt .-% carboxylic acid
- V2 triethanolamine 9.71 isononanoic 10.29 V3 N, N, N ', N'-tetramethyl-1,6-hexamethylenediamine 10.43 isononanoic 9.57
- Table 2 shows the degree of rust formation as a function of the active content of the solutions based on the assessment of the corrosion marks on the filter paper after 2 hours exposure of the chips at 20 ° C.
- the corrosion protection system (I) containing the amine with a Oxybis (alkylamine) unit already shows a significant corrosion protection effect from a weight fraction of 6% based on the stock solution B1. At a weight fraction of at least 7% based on the stock solution B1, only slight corrosion phenomena on the filter paper are detectable, while for the other corrosion protection systems a moderate (V3) to further strong (V1, V2) corrosion can be observed.
- the corrosion protection system (B1) containing the amine with the oxybis (alkylamine) unit is also superior to the corrosion protection system (V3) containing the hexamethylene-bridged tertiary diamine.
Description
Das Korrosionsschutzsystem umfasst Carbon- und/oder Phosphonsäuren sowie zumindest ein Amin mit mindestens einer Oxybis(alkylamin)-Einheit. Derartige Korrosionsschutzsysteme schützen Metalloberflächen effektiv vor Korrosion und weisen eine hohe Wasserlöslichkeit auf, die für die Formulierung wässriger Konzentrate für Metallbehandlungs- und Metallbearbeitungsflüssigkeiten unabdingbar ist. Die vorliegende Erfindung betrifft eine wässrige oberflächenaktive und korrosionsschützende Zubereitung enthaltend das Korrosionsschutzsystem und ein Emulgatorsystem sowie eine ölhaltiges, wassermischbares Emulsionskonzentrat, das durch Verdünnung mit Wasser anwendungsfertige Korrosionsschutz-, Reiniger- und Kühlschmierstoffemulsionen liefert.The corrosion protection system comprises carboxylic and / or phosphonic acids and at least one amine having at least one oxybis (alkylamine) unit. Such anticorrosive systems effectively protect metal surfaces from corrosion and have high water solubility, which is indispensable for the formulation of aqueous concentrates for metalworking and metalworking fluids. The present invention relates to an aqueous surface-active and corrosion-protective preparation comprising the corrosion protection system and an emulsifier system and an oily, water-miscible emulsion concentrate which, when diluted with water, provides ready-to-use corrosion protection, cleaning and cooling lubricant emulsions.
Der Schutz korrosionsgefährdeter Metalle wie beispielsweise Eisen, Aluminium, Zink, Kupfer oder deren Legierungen vor Korrosion ist eine weitgefächerte technische Aufgabe. Sie stellt sich insbesondere dann, wenn die Metallteile aufgrund ihres Bearbeitungszustandes oder aufgrund ihres Einsatzgebietes nicht oder noch nicht mit einem permanent korrosionsschützenden Überzug wie beispielsweise einem Lack bedeckt sind. Beispiele hierfür sind Metallteile während technischer Bearbeitungsstufen wie beispielsweise spanabhebende oder spanlose Formgebung oder Reinigung sowie fertige Metallbauteile wie beispielsweise Wärmetauscher oder Rohrleitungen, die während ihrer Funktion mit korrosiven wässrigen Medien in Berührung kommen. Um eine Korrosion während oder zwischen den einzelnen Bearbeitungsschritten bzw. während des bestimmungsgemäßen Gebrauchs zu verhindern oder einzudämmen, bringt man die Metalloberflächen mit Korrosionsinhibitoren in Berührung, die einen temporären Korrosionsschutz bewirken. Dabei ist es häufig aus Gründen des Umweltschutzes wünschenswert, dass die Korrosionsinhibitoren in wässriger Phase mit den Metalloberflächen in Kontakt gebracht werden können. Zudem beruhen die meisten Metallbehandlung- oder Metallbearbeitungsflüssigkeiten auf wässrigen Zubereitungen, so dass die Wasserlöslichkeit eines Korrosionsinhibitors für die Formulierung dieser Zubereitungen unabdingbar ist. Daher ist es eine wünschenswerte Eigenschaft von Korrosionsinhibitoren, wasserlöslich zu sein.The protection of corrosion-prone metals such as iron, aluminum, zinc, copper or their alloys against corrosion is a widespread technical task. It arises in particular when the metal parts are not or not yet covered with a permanent corrosion-protective coating such as a paint due to their processing condition or because of their field of application. Examples include metal parts during technical processing stages such as machining or non-cutting shaping or cleaning and finished metal components such as heat exchangers or pipelines, which come into contact during their function with corrosive aqueous media. In order to prevent or limit corrosion during or between the individual processing steps or during normal use, the metal surfaces are brought into contact with corrosion inhibitors, which cause a temporary corrosion protection. It is often desirable for reasons of environmental protection that the corrosion inhibitors in the aqueous phase can be brought into contact with the metal surfaces. In addition, most metalworking or metalworking fluids are based on aqueous formulations so that the water solubility of a corrosion inhibitor for the formulation of these Preparations is essential. Therefore, it is a desirable property of corrosion inhibitors to be water soluble.
Als wasserlösliche Korrosionsinhibitoren sind eine Vielzahl anorganischer und organischer Verbindungen bekannt. Anorganische Korrosionsinhibitoren können beispielsweise auf Chromaten, Nitriten oder Phosphaten aufgebaut sein, die jedoch aus toxikologischen und aus ökologischen Gründen mehr oder weniger nachteilig sind. Organische Korrosionsinhibitoren basieren häufig auf Carboxylaten, Aminen, Amiden oder auf stickstoffhaltigen heterozyklischen Verbindungen. Carbonsäuren als solche erweisen sich in der Praxis jedoch als nicht hinreichend langzeitwirksam, wenn durch einen Säureeintrag in die Inhibitorbäder oder durch mikrobiologische Prozesse der pH-Wert soweit abgesenkt wird, dass die Carbonsäuren statt in der Salzform in der weniger wirksamen Säureform vorliegen. Korrosionsinhibierende Carbonsäuren werden daher häufig in Form ihrer Salze eingesetzt bzw. als Korrosionsschutzsystem bestehend aus der Carbonsäure und einer Base. Im Stand der Technik bekannt sind insbesondere Korrosionsschutzsysteme bestehend aus Carbonsäuren und Alkanolaminen, die im Vergleich zu Systemen aus Carbonsäure und Alkalien auf Basis von Natronlauge oder Ammoniak eine erhöhte Inhibitorwirkung aufweisen.As water-soluble corrosion inhibitors, a variety of inorganic and organic compounds are known. Inorganic corrosion inhibitors may be based, for example, on chromates, nitrites or phosphates, but these are more or less disadvantageous for toxicological and ecological reasons. Organic corrosion inhibitors are often based on carboxylates, amines, amides or on nitrogen-containing heterocyclic compounds. Carboxylic acids as such, however, prove in practice to be insufficiently long-term effective if the pH is lowered by an acid entry into the inhibitor baths or by microbiological processes to such an extent that the carboxylic acids are present in the less active acid form instead of in the salt form. Corrosion-inhibiting carboxylic acids are therefore often used in the form of their salts or as a corrosion protection system consisting of the carboxylic acid and a base. Particularly well-known in the art are corrosion protection systems consisting of carboxylic acids and alkanolamines, which have an increased inhibitory effect compared to systems of carboxylic acid and alkalis based on sodium hydroxide solution or ammonia.
Die
Die
Die Aufgabe der vorliegenden Erfindung besteht darin, eine wässrige oberflächenaktive und korrosionsschützende Zubereitung geeignet für die Herstellung wässriger Metallbehandlungs- und Metallbearbeitungsflüssigkeiten, insbesondere von Reinigern und Schmiermitteln, bereitzustellen, dass Metalle, insbesondere Eisen und Eisenlegierungen, im Vergleich zum Stand der Technik bei Kontakt mit der Behandlungs- und Bearbeitungsflüssigkeit effektiver vor Korrosion schützt.The object of the present invention is to provide an aqueous surface-active and corrosion-protective preparation suitable for the production of aqueous metal treatment and metalworking fluids, in particular cleaners and lubricants, that metals, in particular iron and iron alloys, in comparison with the prior art in contact with the Treatment and processing fluid more effectively protects against corrosion.
Diese Aufgabe wird gelöst durch eine wässrige oberflächenaktive und korrosionsschützende Zubereitung gemäß dem vorliegendem Anspruch 1. Das erfindungsgemäße wässrige oberflächenaktive und korrosionsschützende Zubereitung bewirkt einen hervorragenden Schutz vor Korrosion von Eisen und Eisenlegierungen sowie von Aluminium und Aluminiumlegierungen bei Kontakt mit wässrigen Flüssigkeiten, insbesondere Flüssigkeiten zur Metallbehandlung oder Metallbearbeitung. Weiterhin zeichnet sich das Korrosionsschutzsystem (I) durch seine gute Wasserlöslichkeit aus, die es erlaubt das Korrosionsschutzsystem in Form hochkonzentrierter wässriger Zubereitungen zu vertreiben.This object is achieved by an aqueous surface-active and corrosion-protective preparation according to the present claim 1. The inventive aqueous surface-active and corrosion-protective preparation provides excellent protection against corrosion of iron and iron alloys and of aluminum and Aluminum alloys in contact with aqueous liquids, in particular liquids for metal treatment or metalworking. Furthermore, the corrosion protection system (I) is characterized by its good water solubility, which makes it possible to distribute the corrosion protection system in the form of highly concentrated aqueous preparations.
Jede Zubereitung, beispielsweise eine anwendungsfertige Metallbehandlungs- oder Metallbearbeitungsflüssigkeit oder deren Konzentrat, die die beiden Komponenten a) und b) enthält, umfasst damit das Korrosionsschutzsystem (I). Üblicherweise wird eine Lösung des Korrosionsschutzsystems zu einer Metallbehandlungs- oder Metallbearbeitungsflüssigkeit hinzuformuliert, um die gewünschten Korrosionsschutzeigenschaften zu vermitteln. Erfindungsgemäß sind daher für eine gute Kompatibilität mit wässrigen Metallbehandlungs- und Metallbearbeitungsflüssigkeiten Korrosionsschutzsysteme, die die Komponenten a) und b) in wässriger Phase bevorraten.Each preparation, for example a ready-to-use metal treatment or metalworking fluid or its concentrate, which contains the two components a) and b), thus comprises the corrosion protection system (I). Typically, a solution of the anticorrosive system is formulated into a metalworking or metalworking fluid to impart the desired anticorrosive properties. For compatibility with aqueous metal treatment and metalworking fluids according to the invention, corrosion protection systems which store the components a) and b) in an aqueous phase are therefore preferred.
In einem bevorzugten Korrosionsschutzsystem (I) ist als Komponente b) zumindest ein Amin der folgenden Strukturformel (1) enthalten:
Alternativ können die Reste R1, R2, R3 und R4 der Strukturformel (1) aus solchen Resten ausgewählt sein, die die beiden Stickstoffatome der Oxybis(alkylamin)-Einheit verbrücken, so dass der Rest R1 und/oder der Rest R2 jeweils strukturidentisch mit dem Rest R3 oder R4 ist, wobei verbrückende Reste R1 oder R2 bzw. R3 oder R4 ausgewählt sind aus Alkylenen, Polyoxyalkylenen oder Polyaminoalkylenen mit nicht mehr als 6 Kohlenstoffatomen. Ein solches bevorzugtes verbrücktes Amin in einem Korrosionsschutzsystem (I) hat folgende allgemeine Strukturformel (1a):
Besonders bevorzugt sind Amine der Strukturformel (1a) für die die Reste R1 und R2 unabhängig voneinander ausgewählt sind aus verzweigten oder unverzweigten Alkylresten mit nicht mehr als 8 Kohlenstoffatomen, vorzugsweise nicht mehr als 4 Kohlenstoffatomen, für die m, n, q und r gleich 2 sind, und s nicht größer als 3 ist, wobei Z ein Sauerstoff- oder Stickstoffatom ist. Insbesondere bevorzugte verbrückte Amine sind N,N'-Dimethyl-1,7-dioxa-4,10-diazacyclododecan, N,N'-Diethyl-1,7-dioxa-4,10-diazacyclododecan, N,N'-Dimethyl-1,4,10-trioxa-7,13-diazacyclopentadecan und N,N'-Diethyl-1,4,10-trioxa-7,13-diazacyclopentadecan.Particularly preferred are amines of the structural formula (1a) for which the radicals R 1 and R 2 are independently selected from branched or unbranched alkyl radicals having not more than 8 carbon atoms, preferably not more than 4 carbon atoms, for the m, n, q and r is 2, and s is not greater than 3, where Z is an oxygen or nitrogen atom. Particularly preferred bridged amines are N, N'-dimethyl-1,7-dioxa-4,10-diazacyclododecane, N, N'-diethyl-1,7-dioxa-4,10-diazacyclododecane, N, N'-dimethyl 1,4,10-trioxa-7,13-diazacyclopentadecane and N, N'-diethyl-1,4,10-trioxa-7,13-diazacyclopentadecane.
Besonders bevorzugt sind die Reste R1, R2, R3 und R4 der Strukturformel (1) unabhängig voneinander ausgewählt aus verzweigten oder unverzweigten Alkylresten mit nicht mehr als 8 Kohlenstoffatom, besonders bevorzugt nicht mehr als 4 Kohlenstoffatomen, wobei die natürlichen ganzen Zahlen m und n gleich 2 sind. Insbesondere bevorzugt sind N,N,N',N'-Tetramethyl-2,2'-oxybis(ethylamin) und N,N,N',N'-Tetraethyl-2,2'-oxybis(ethylamin).Particularly preferably, the radicals R 1 , R 2 , R 3 and R 4 of the structural formula (1) are independently selected from branched or unbranched alkyl radicals with no more as 8 carbon atoms, more preferably not more than 4 carbon atoms, wherein the natural integers m and n are equal to 2. Especially preferred are N, N, N ', N'-tetramethyl-2,2'-oxybis (ethylamine) and N, N, N', N'-tetraethyl-2,2'-oxybis (ethylamine).
Ein bevorzugtes Korrosionsschutzsystem (I) enthält zu zumindest 50 Gew.-%, besonders bevorzugt zu zumindest 80 Gew.-%, nur solche organischen Amine gemäß Komponente b), die ausgewählt sind aus Aminen der allgemeinen Strukturformel (1) gemäß der Komponente b), besonders bevorzugt aus solchen Aminen der allgemeinen Strukturformel (1) gemäß der Komponente b), für die die Reste R1, R2, R3 und R4 unabhängig voneinander ausgewählt sind aus verzweigten oder unverzweigten Alkylresten mit nicht mehr als 4 Kohlenstoffatom, wobei die natürlichen ganzen Zahlen m und n gleich 2 sind, und insbesondere bevorzugt ausgewählt sind aus N,N,N',N'-Tetramethyl-2,2'-oxybis(ethylamin) und/oder N,N,N',N'-Tetraethyl-2,2'-oxybis(ethylamin).A preferred corrosion protection system (I) contains at least 50% by weight, more preferably at least 80% by weight, only those organic amines according to component b) which are selected from amines of the general structural formula (1) according to component b) , particularly preferably from such amines of general structural formula (1) according to component b), for which the radicals R 1 , R 2 , R 3 and R 4 are independently selected from branched or unbranched alkyl radicals having not more than 4 carbon atom, wherein the natural integers m and n are 2, and more preferably are selected from N, N, N ', N'-tetramethyl-2,2'-oxybis (ethylamine) and / or N, N, N', N '-Tetraethyl-2,2'-oxybis (ethylamine).
Die aliphatischen Carbonsäuren gemäß Komponente a) des Korrosionsschutzsystems (I) mit zumindest 6, jedoch nicht mehr als 14 Kohlenstoffatomen können ein- oder mehrbasische, gesättigte oder ungesättigte, lineare oder verzweigte aliphatische Carbonsäuren darstellen, vorzugsweise sind sie jedoch ausgewählt aus aliphatischen Monocarbonsäuren mit zumindest 6, jedoch nicht mehr als 12 Kohlenstoffatomen, insbesondere aus Caprylsäure, Ethylhexansäure, Isononansäure und/oder Isodecansäure.The aliphatic carboxylic acids according to component a) of the corrosion protection system (I) having at least 6 but not more than 14 carbon atoms can be mono- or polybasic, saturated or unsaturated, linear or branched aliphatic carboxylic acids, but are preferably selected from aliphatic monocarboxylic acids having at least 6 but not more than 12 carbon atoms, in particular from caprylic acid, ethylhexanoic acid, isononanoic acid and / or isodecanoic acid.
Als Carbonsäuren gemäß Komponente a) mit in die Kohlenstoffkette eingeschobenen Sauerstoff-Heteroatomen wählt man vorzugsweise Ethercarbonsäuren der allgemeinen Formel R-(O-C2H4)n-OCH2COOH, wobei R für einen linearen oder verzweigten, gesättigten oder ungesättigten Alkylrest mit 6 bis 16 Kohlenstoffatomen steht, n eine Zahl im Bereich von 1 bis 5 darstellt und R und n so aufeinander abzustimmen sind, dass die Summe der Kohlenstoff- und Sauerstoffatome unter Vernachlässigung der Carboxylgruppe nicht größer als 25 ist. Dabei können die Ethercarbonsäuren technische Gemische aus Molekülen mit unterschiedlichen Resten R und unterschiedlichen Werten für n sein. Ein Beispiel hierfür ist die technische Laurylethercarbonsäure, bei der R für ein Gemisch aus linearen, gesättigten Alkylgruppen mit 12 und 14 Kohlenstoffatomen steht und n etwa 2,5 ist.As carboxylic acids according to component a) with inserted into the carbon chain oxygen heteroatoms are preferably selected ether carboxylic acids of the general formula R- (OC 2 H 4 ) n -OCH 2 COOH, where R is a linear or branched, saturated or unsaturated alkyl radical having 6 to Is 16 carbon atoms, n represents a number in the range of 1 to 5 and R and n are to be matched to one another such that the sum of the carbon and oxygen atoms is not greater than 25, neglecting the carboxyl group. The ether carboxylic acids may be technical mixtures of molecules with different radicals R and different values for n. An example of this is the technical Laurylethercarbonsäure, in which R for is a mixture of linear, saturated alkyl groups having 12 and 14 carbon atoms and n is about 2.5.
Die im Korrosionsschutzsystem (I) gemäß Komponente a) enthaltenen aliphatischen Phosphonsäuren mit zumindest 4, jedoch nicht mehr als 18 Kohlenstoffatomen, können ein- oder mehrbasische, gesättigte oder ungesättigte, lineare oder verzweigte aliphatische Phosphonsäuren darstellen, vorzugsweise sind sie jedoch ausgewählt aus gesättigten geradkettigen oder verzweigten Monophosphonsäuren. Gemische unterschiedlicher Säuren können besonders vorteilhaft sein, wobei die Alkylmonophosphonsäuren besonders in ihrer geradkettigen Form geeignet sind. Weiterhin bevorzugt sind Alkylmonophosphonsäuren mit 6 bis 12 Kohlenstoffatomen.The aliphatic phosphonic acids having at least 4 but not more than 18 carbon atoms contained in the corrosion protection system (I) according to component a) may be mono- or polybasic, saturated or unsaturated, linear or branched aliphatic phosphonic acids, but are preferably selected from saturated straight-chain or linear branched monophosphonic acids. Mixtures of different acids may be particularly advantageous, the alkyl monophosphonic acids are particularly suitable in their straight-chain form. Further preferred are alkyl monophosphonic acids having 6 to 12 carbon atoms.
Die Verwendung von Carbonsäuren als Komponente a) ist aus ökologischen Gründen immer dann zu bevorzugen, wenn die Verwendung von Phosphonsäuren den temporären Korrosionsschutz bei der Metallbehandlung oder Metallbearbeitung nicht signifikant zu verbessern vermag.The use of carboxylic acids as component a) is always preferable for ecological reasons, if the use of phosphonic acids is not able to significantly improve the temporary corrosion protection in metal treatment or metalworking.
In einer bevorzugten Ausführungsform des Korrosionsschutzsystems (I) ist die Komponente a) daher ausgewählt aus aliphatischen Monocarbonsäuren mit zumindest 6, jedoch nicht mehr als 12 Kohlenstoffatomen, insbesondere aus Caprylsäure, Ethylhexansäure, Isononansäure und/oder Isodecansäure, und/oder Carbonsäuren mit in die Kohlenstoffkette eingeschobenen Sauerstoff-Heteroatomen, die zwischen 6 und 26 Atome in der Kohlenstoff-Heteroatomkette aufweisen, insbesondere Ethercarbonsäuren der allgemeinen Formel R-(O-C2H4)n-OCH2COOH, wobei R für einen linearen oder verzweigten, gesättigten oder ungesättigten Alkylrest mit 6 bis 16 C-Atomen steht, n eine Zahl im Bereich von 1 bis 5 darstellt und R und n so aufeinander abzustimmen sind, dass die Summe der C- und O-Atome unter Vernachlässigung der Carboxylgruppe nicht größer als 25 ist.In a preferred embodiment of the corrosion protection system (I), component a) is therefore selected from aliphatic monocarboxylic acids having at least 6 but not more than 12 carbon atoms, in particular from caprylic acid, ethylhexanoic acid, isononanoic acid and / or isodecanoic acid, and / or carboxylic acids with into the carbon chain inserted oxygen heteroatoms having between 6 and 26 atoms in the carbon heteroatom chain, in particular ether carboxylic acids of the general formula R- (OC 2 H 4 ) n -OCH 2 COOH, wherein R is a linear or branched, saturated or unsaturated alkyl radical 6 to 16 carbon atoms, n represents a number in the range of 1 to 5 and R and n are coordinated so that the sum of the C and O atoms is neglecting the carboxyl group is not greater than 25.
In einem besonders bevorzugten Korrosionsschutzsystem (I) ist die Komponente a) ausgewählt aus aliphatischen Monocarbonsäuren mit zumindest 6, jedoch nicht mehr als 12 Kohlenstoffatomen, insbesondere aus Caprylsäure, Ethylhexansäure, Isononansäure und/oder Isodecansäure.In a particularly preferred corrosion protection system (I), component a) is selected from aliphatic monocarboxylic acids having at least 6 but not more than 12 carbon atoms, in particular from caprylic acid, ethylhexanoic acid, isononanoic acid and / or isodecanoic acid.
Diesbezüglich besonders bevorzugt ist eine Ausführungsform des Korrosionsschutzsystems, bei dem der gewichtsbezogene Anteil von Carbonsäuren gemäß Komponente a) ausgewählt aus aliphatischen Monocarbonsäuren mit zumindest 6, jedoch nicht mehr als 12 Kohlenstoffatomen, insbesondere der gewichtsbezogene Anteil von Caprylsäure, Ethylhexansäure, Isononansäure und/oder Isodecansäure, am Gesamtanteil an Carbonsäuren und Phosphonsäuren im Korrosionsschutzsystem, also auch solchen Carbonsäuren und Phosphonsäuren, die keine Verbindungen gemäß Komponente a) sind, zumindest 50 Gew.-%, besonders bevorzugt zumindest 80 Gew.-% beträgt.Particularly preferred in this regard is an embodiment of the corrosion protection system in which the weight-based proportion of carboxylic acids according to component a) is selected from aliphatic monocarboxylic acids having at least 6 but not more than 12 carbon atoms, in particular the weight-related proportion of caprylic acid, ethylhexanoic acid, isononanoic acid and / or isodecanoic acid, on the total amount of carboxylic acids and phosphonic acids in the corrosion protection system, including those carboxylic acids and phosphonic acids which are not compounds according to component a), at least 50 wt .-%, particularly preferably at least 80 wt .-% is.
Dem Fachmann ist bekannt, dass die Komponenten a) und b) des Korrosionsschutzsystems (I) miteinander Säure-Base Reaktionen eingehen können und in wässriger Lösung zudem im Protolyse-Gleichgewicht mit ihrer jeweiligen deprotonierten bzw. protonierten Form stehen.It is known to the person skilled in the art that components a) and b) of the corrosion protection system (I) can undergo acid-base reactions with one another and, in aqueous solution, also have a protolysis equilibrium with their respective deprotonated or protonated form.
Es hat sich in diesem Zusammenhang gezeigt, dass sowohl die Wasserlöslichkeit als auch die Korrosionschutzwirkung positiv durch die Anwesenheit von Ammoniumsalzen, die aus der Neutralisationsreaktion der Komponenten a) und b) hervorgehen, beeinflusst wird. Erfindungsgemäß ist daher, dass das molare Verhältnis der Gesamtmenge an Carboxyl- und/oder Phosphonsäure-Gruppen der Komponenten a) zu Oxybis(alkylamin)-Einheiten des zumindest einen Amins der Komponente b) nicht kleiner als 1 : 3 ist, um zu gewährleisten, dass eine Mindestmenge des Amins gemäß Komponente b) im Korrosionsschutzsystem als Ammoniumsalz vorliegt. Besonders bevorzugt ist dieses molare Verhältnis nicht kleiner als 2 : 3. Umgekehrt sollte die Gesamtmenge an Carboxyl- und/oder Phosphonsäure-Gruppen der Komponenten a) relativ zum Anteil der Amine gemäß Komponente b) keine Werte überschreiten, für die die Effektivität des Korrosionsschutz deutlich abnimmt. Hierfür ist erfindungsgemäß, dass das molare Verhältnis der Gesamtmenge an Carboxyl- und/oder Phosphonsäure-Gruppen der Komponenten a) zu Oxybis(alkylamin)-Einheiten des zumindest einen Amins der Komponente b) nicht größer als 5 : 1, besonders bevorzugt nicht größer als 3 : 1, insbesondere bevorzugt nicht größer als 2 : 1 ist.It has been found in this context that both the water solubility and the anticorrosive effect are positively influenced by the presence of ammonium salts resulting from the neutralization reaction of components a) and b). According to the invention, therefore, that the molar ratio of the total amount of carboxyl and / or phosphonic acid groups of components a) to oxybis (alkylamine) units of the at least one amine of component b) is not less than 1: 3 in order to ensure a minimum amount of the amine according to component b) is present in the corrosion protection system as ammonium salt. In particular, this molar ratio is not less than 2: 3. Conversely, the total amount of carboxyl and / or phosphonic acid groups of components a) relative to the proportion of amines according to component b) should not exceed values for which the effectiveness of the corrosion protection is clearly evident decreases. For this purpose, the molar ratio of the total amount of carboxyl and / or phosphonic acid groups of components a) to oxybis (alkylamine) units of the at least one amine of component b) is not greater than 5: 1, more preferably not greater than 3: 1, particularly preferably not greater than 2: 1.
In besonderem Maße ist das Korrosionsschutzsystem (I) geeignet, um in wässrigen Emulsionen, speziell in Reinigungs-, Korrosionsschutz- und Kühlschmierstoffemulsionen, zur Verhinderung der Metallkorrosion verwendet zu werden. Ein Vorteil der Verwendung eines Korrosionsschutzsystems basierend auf den Komponenten a) und b) besteht darin, dass für eine hinreichenden Korrosionsschutz eine vergleichsweise geringe Menge dieser beiden Aktivkomponenten im wässrigen System zur Metallbearbeitung und Metallbehandlung enthalten sein muss.In particular, the corrosion protection system (I) is suitable to be used in aqueous emulsions, especially in cleaning, anticorrosion and cooling lubricant emulsions, to prevent metal corrosion. An advantage of using a corrosion protection system based on components a) and b) is that for a sufficient corrosion protection, a comparatively small amount of these two active components must be present in the aqueous metal working and metal treatment system.
Die vorliegende Erfindung umfasst daher eine wässrige oberflächenaktive und korrosionsschützende Zubereitung, die neben Wasser und dem zuvor beschriebenen Korrosionsschutzsystem enthaltend die Komponenten a) und b), als Korrosionsschutzsystem (I) bezeichnet, wobei das molare Verhältnis der Gesamtmenge an Carboxyl- und/oder Phosphonsäure-Gruppen der Komponenten a) zu Oxybis(alkylamin)-Einheiten des zumindest einen Amins der Komponente b) nicht grösser als 5:1, jedoch nicht kleiner als 1:3 ist, ein Emulgatorsystem (II) bestehend aus
- c) Ethoxylaten/Propoxylaten von Fettalkoholen mit 8 bis 18 Kohlenstoffatomen im Alkohol mit 2 bis 6 Ethylenoxideinheiten und 4 bis 8 Propylenoxideinheiten und
- d) Fettalkoholen und/oder Fettalkoholpropoxylaten mit 12 bis 24 C Atomen im Alkohol und 0 bis 3 Propylenoxideinheiten und/oder dem Destillationsrückstand dieser Fettalkohole enthält.
- c) ethoxylates / propoxylates of fatty alcohols having 8 to 18 carbon atoms in the alcohol with 2 to 6 ethylene oxide units and 4 to 8 propylene oxide units and
- d) fatty alcohols and / or fatty alcohol propoxylates having 12 to 24 C atoms in the alcohol and 0 to 3 propylene oxide units and / or the distillation residue of these fatty alcohols.
In einem weiteren Aspekt enthält das Emulgatorsystem (II) der erfindungsgemäßen wässrigen oberflächenaktiven und korrosionsschützenden Zubereitung zur Verbesserung der Filtrierbarkeit von aus diesen Zubereitungen hergestellten Emulsionen zusätzlich alkoxylierte Fettamine als Komponente e). Hierfür werden bevorzugt alkoxylierte Fettamine bestehend aus einem oder mehreren alkoxylierten gesättigten und/oder ungesättigten aliphatischen Aminen mit einer aliphatischen Kettenlänge von mindestens 8, vorzugsweise mindestens 10 und besonders bevorzugt mindestens 12, allerdings nicht mehr als 20, vorzugsweise nicht mehr als 18 und besonders bevorzugt nicht mehr als 16 Kohlenstoffatomen verwendet. Die verwendeten Fettamine sollten mit mindestens 8, vorzugsweise mit mindestens 10, aber nicht mit mehr als 16, vorzugsweise nicht mit mehr als 14 und besonders bevorzugt mit 12 Ethylenoxideinheiten ethoxyliert sein. Insbesondere eignet sich zur Erhöhung der Filtrierbarkeit von aus diesen Zubereitungen hergestellten anwendungsfertigen Emulsionen 12fach ethoxyliertes Kokosamin.In a further aspect, the emulsifier system (II) of the aqueous surface-active and anti-corrosive preparation according to the invention additionally comprises alkoxylated fatty amines as component e) to improve the filterability of emulsions prepared from these preparations. For this purpose, preferably alkoxylated fatty amines consisting of one or more alkoxylated saturated and / or unsaturated aliphatic amines having an aliphatic chain length of at least 8, preferably at least 10 and more preferably at least 12, but not more than 20, preferably not more than 18 and most preferably not used more than 16 carbon atoms. The fatty amines used should be ethoxylated with at least 8, preferably not more than 10, but not more than 16, preferably not more than 14 and most preferably 12 ethylene oxide units. In particular, is suitable for increasing the Filterability of ready-to-use emulsions 12 times ethoxylated cocoamine prepared from these formulations.
Der Anteil der Komponenten a) bis e) der erfindungsgemäßen Zubereitung liegt für eine anwendungsfertige korrosionsschützende Reinigerlösung vorzugsweise im Bereich von 0,5 bis 10 Gew.-%, wobei der Gesamtanteil der Komponenten a) und b) des Korrosionsschutzsystems (I) vorzugsweise bei zumindest 0,1 Gew.-% liegt.The proportion of components a) to e) of the preparation according to the invention for an application-ready anticorrosive cleaner solution is preferably in the range from 0.5 to 10% by weight, the total proportion of components a) and b) of the anticorrosion system (I) preferably being at least 0.1 wt .-% is.
Die erfindungsgemäße Zubereitung kann jedoch auch ein Konzentrat für die Herstellung von korrosionsschützenden Reinigerlösungen darstellen, bei dem der Anteil der Komponenten a) bis e) vorzugsweise im Bereich von 40 bis 95 Gew.-% liegt, wobei der Gesamtanteil der Komponenten a) und b) des Korrosionsschutzsystems (I) in der erfindungsgemäßen Zubereitung vorzugsweise bei zumindest 10 Gew.-% liegt.However, the preparation according to the invention can also be a concentrate for the production of anticorrosion cleaner solutions in which the proportion of components a) to e) is preferably in the range from 40 to 95% by weight, the total amount of components a) and b) being of the corrosion protection system (I) in the preparation according to the invention is preferably at least 10 wt .-%.
Der wässrigen oberflächenaktiven und korrosionsschützenden Zubereitung kann als Konzentrat mit einem Wasser Anteil von nicht mehr als 60 Gew.-% zusätzlich eine Ölkomponente (III) hinzugegeben werden, so dass insgesamt ein ölhaltiges, wassermischbares Emulsionskonzentrat für die Metallbearbeitung, insbesondere ein Konzentrat für eine Kühlschmierstoff- oder Korrosionsschutzemulsion, realisiert vorliegt.The aqueous surface-active and corrosion-protective preparation may additionally be admixed with a water component of not more than 60% by weight, so that a total of one oil-containing, water-miscible emulsion concentrate for metalworking, in particular a concentrate for a coolant lubricant or anticorrosion emulsion, realized.
Die vorliegende Erfindung betrifft daher auch ein erfindungsgemäßes ölhaltiges, wassermischbares Emulsionskonzentrat enthaltend
- i) 2 bis 20 Gew.-% eines Korrosionsschutzsystem (I) bestehend aus
- a) zumindest einer aliphatischen Carbonsäure mit zumindest 6, jedoch nicht mehr als 14 Kohlenstoffatomen und/oder zumindest einer Carbonsäure mit in die Kohlenstoffkette eingeschobenen Sauerstoff-Heteroatomen, die zwischen 6 und 26 Atome in der Kohlenstoff-Heteroatomkette aufweist, und/oder zumindest einer aliphatischen Phosphonsäure mit zumindest 4, jedoch nicht mehr als 18 Kohlenstoffatomen,
- b) zumindest einem Amin, das zumindest eine Oxybis(alkylamin)-Einheit mit tertiären Amino-Gruppen aufweist, wobei die Alkylketten dieser Einheit jeweils aus nicht mehr als 4 Kohlenstoffatomen bestehen,
- ii) 2 bis 50 Gew.-% eines Emulgatorsystems (II) bestehend aus
- c) Ethoxylaten/Propoxylaten von Fettalkoholen mit 8 bis 18 Kohlenstoffatomen im Alkohol mit 2 bis 6 Ethylenoxideinheiten und 4 bis 8 Propylenoxideinheiten und
- d) Fettalkoholen und/oder Fettalkoholpropoxylaten mit 12 bis 24 C Atomen im Alkohol und 0 bis 3 Propylenoxideinheiten und/oder dem Destillationsrückstand dieser Fettalkohole,
- iii) 5 bis 50 Gew.-% einer Ölkomponente (III),
- i) 2 to 20 wt .-% of a corrosion protection system (I) consisting of
- a) at least one aliphatic carboxylic acid having at least 6, but not more than 14 carbon atoms and / or at least one carboxylic acid having inserted into the carbon chain oxygen heteroatoms having between 6 and 26 atoms in the carbon heteroatom chain, and / or at least one aliphatic Phosphonic acid having at least 4 but not more than 18 carbon atoms,
- b) at least one amine having at least one oxybis (alkylamine) moiety having tertiary amino groups, wherein the alkyl chains of this moiety each consist of not more than 4 carbon atoms,
- ii) 2 to 50 wt .-% of an emulsifier system (II) consisting of
- c) ethoxylates / propoxylates of fatty alcohols having 8 to 18 carbon atoms in the alcohol with 2 to 6 ethylene oxide units and 4 to 8 propylene oxide units and
- d) fatty alcohols and / or fatty alcohol propoxylates having 12 to 24 C atoms in the alcohol and 0 to 3 propylene oxide units and / or the distillation residue of these fatty alcohols,
- iii) from 5 to 50% by weight of an oil component (III),
Bezüglich des Korrosionsschutzsystems (I) und des Emulgatorsystems (II) der erfindungsgemäßen ölhaltigen, wassermischbaren Emulsionskonzentrates sind die bevorzugten Ausführungsformen identisch mit denen, die für das Korrosionsschutzsystem und die erfindungsgemäße wässrige oberflächenaktive und korrosionsschützende Zubereitung beschrieben wurden.With regard to the corrosion protection system (I) and the emulsifier system (II) of the oil-containing, water-miscible emulsion concentrate according to the invention, the preferred embodiments are identical to those described for the corrosion protection system and the aqueous surface-active and corrosion-protective preparation according to the invention.
Insofern kann das Emulgatorsystem (II) des erfindungsgemäßen ölhaltigen, wassermischbaren Emulsionskonzentrates, wie zuvor für die wässrigen oberflächenaktiven und korrosionsschützenden Zubereitung beschrieben, alkoxylierte Fettamine als Komponente e) enthalten, vorzugsweise mit einem Gewichtsanteil im Konzentrat von mindestens 1 Gew.-%, besonders bevorzugt mindestens 2 Gew.-%, aber vorzugsweise nicht mehr als 10 Gew.-%, besonders bevorzugt nicht mehr als 8 Gew.-%.In this respect, the emulsifier system (II) of the oil-containing, water-miscible emulsion concentrate according to the invention, as described above for the aqueous surface-active and anti-corrosive preparation, alkoxylated fatty amines as component e), preferably with a weight fraction in the concentrate of at least 1 wt .-%, more preferably at least 2 wt .-%, but preferably not more than 10 wt .-%, particularly preferably not more than 8 wt .-%.
Die Ölkomponente (III) des erfindungsgemäßen ölhaltigen, wassermischbaren Emulsionskonzentrates ist vorzugsweise ausgewählt aus paraffinischen oder naphtenischen Mineralölen, Dialkylethern mit 12 bis 20 Kohlenstoffatomen und/oder Esterölen.The oil component (III) of the oily, water-miscible emulsion concentrate according to the invention is preferably selected from paraffinic or naphthenic mineral oils, dialkyl ethers having 12 to 20 carbon atoms and / or ester oils.
Als fakultative weitere Hilfs- oder Wirkstoffe sind zu nennen: Schmieradditive allgemein und insbesondere sogenannte "Extreme-Pressure"-Additive (sogenannte EP-Additive) sowie Biozide jeweils in einer Menge von vorzugsweise 0,1 bis 2 Gew.-% im Konzentrat; Puffersysteme, insbesondere auf Basis von Borsäure, in einer Menge bezogen auf die jeweilige Säureform von vorzugsweise 2 bis 10 Gew.-% im Konzentrat; Neutralisationsmittel auf Basis von Alkanolaminen, Lösevermittler wie beispielsweise Glykole, Glycerin oder Na-Cumolsulfonat jeweils in einer Menge von vorzugsweise 1 bis 6 Gew.-% im Konzentrat.As optional further auxiliaries or active ingredients may be mentioned: lubricating additives in general and in particular so-called "extreme pressure" additives (so-called EP additives) and biocides in each case in an amount of preferably 0.1 to 2 wt .-% in the concentrate; Buffer systems, in particular based on boric acid, in an amount based on the particular acid form of preferably 2 to 10 wt .-% in the concentrate; Neutralizing agent based on alkanolamines, solubilizers such as glycols, glycerol or sodium cumenesulfonate each in an amount of preferably 1 to 6 wt .-% in the concentrate.
Weiterhin betrifft die Erfindung die anwendungsfertige Öl-in-Wasser-Emulsion, die dadurch erhältlich ist, dass man etwa 0,5 bis etwa 10 Gewichtsteile des vorstehend beschriebenen ölhaltigen, wassermischbaren Konzentrats mit etwa 99,5 bis etwa 90 Gewichtsteile Wasser versetzt. Aufgrund der selbstemulgierenden Eigenschaften des Emulsionskonzentrats bildet sich die anwendungsfertige Emulsion beim Versetzen mit Wasser spontan oder nach geringfügiger mechanischer Bewegung wie beispielsweise Rühren. Diese Emulsion kann beispielsweise als Reinigungs-, Korrosionsschutz- oder Kühlschmierstoffemulsion eingesetzt werden.Furthermore, the invention relates to the ready-to-use oil-in-water emulsion which is obtainable by adding from about 0.5 to about 10 parts by weight of the above-described oily, water-miscible concentrate with about 99.5 to about 90 parts by weight of water. Due to the self-emulsifying properties of the emulsion concentrate, the ready-to-use emulsion forms spontaneously upon addition of water or after slight mechanical agitation such as stirring. This emulsion can be used for example as a cleaning, corrosion protection or cooling lubricant emulsion.
Das erfindungsgemäße ölhaltige, wassermischbare Emulsionskonzentrat sowie die daraus durch Verdünnung mit Wasser herstellbaren anwendungsfertigen Öl-in-Wasser-Emulsionen eignen sich insbesondere für die Behandlung und Bearbeitung von Eisen und Eisenlegierungen sowie von Aluminium und Aluminiumlegierungen.The oil-containing, water-miscible emulsion concentrate according to the invention and the ready-to-use oil-in-water emulsions preparable therefrom by dilution with water are particularly suitable for the treatment and processing of iron and iron alloys and of aluminum and aluminum alloys.
Im Folgenden wird die Wirkungsweise des Korrosionsschützsystem (I) beispielhaft dargestellt und mit im Stand der Technik bekannten Systemen verglichen. Durchgeführt wird hierfür ein Korrosionsschutztest nach DIN 51360-2 bei dem Graugussspäne (Typ GG25) auf einem Rundfilter mit frisch hergestellten verdünnten wässrigen Lösungen enthaltend verschiedene Korrosionsschutzsysteme auf Basis eines Amins und Isononansäure benetzt werden.In the following, the mode of action of the corrosion protection system (I) is shown by way of example and compared with systems known in the prior art. For this purpose, a corrosion protection test according to DIN 51360-2 is carried out in which gray cast iron chips (type GG25) are wetted on a round filter with freshly prepared dilute aqueous solutions containing various corrosion protection systems based on an amine and isononanoic acid.
In der Tabelle 1 sind die Zusammensetzungen konzentrierter wässriger Korrosionsschutzsysteme (Stammlösungen) auf Basis eines Amins und Isononansäure aufgeführt.
Die Stammlösungen der Tabelle 1 wurden mit Wasser mit einer Härte von 20°dH (3,04 mmol CaCl2; 0,54 mmol MgSO4) weiter verdünnt und die Graugussspäne auf dem Filterpapier mit dieser verdünnten Lösung benetzt.The stock solutions of Table 1 were mixed with water with a hardness of 20 ° dH, further diluted and wets the cast iron chips on the filter paper with this diluted solution (3.04 mM CaCl2 0.54 mmol MgSO 4).
Tabelle 2 gibt den Grad der Rostbildung in Abhängigkeit vom Aktivgehalt der Lösungen anhand der Beurteilung der Korrosionsabzeichnungen auf dem Filterpapier nach zweistündiger Exposition der Späne bei 20 °C wieder.Table 2 shows the degree of rust formation as a function of the active content of the solutions based on the assessment of the corrosion marks on the filter paper after 2 hours exposure of the chips at 20 ° C.
Anhand der in der Tabelle 2 dargelegten Korrosionsergebnisse wird deutlich, dass das Korrosionsschutzsystem (I) enthaltend das Amin mit einer Oxybis(alkylamin)-Einheit bereits ab einem Gewichtsanteil von 6% bezogen auf die Stammlösung B1 eine deutliche Korrosionsschutzwirkung zeigt. Bei einem Gewichtsanteil von zumindest 7% bezogen auf die Stammlösung B1 sind nur noch leichte Korrosionserscheinungen auf dem Filterpapier nachweisbar, während für die übrigen Korrosionschutzsysteme weiterhin eine mäßige (V3) bis weiterhin starke (V1, V2) Korrosion zu beobachten ist. Das Korrosionsschutzsystem (B1) enthaltend das Amin mit der Oxybis(alkylamin)-Einheit ist auch dem Korrosionsschutzsystem (V3) enthaltend das Hexamethylen-verbrückte tertiäre Diamin überlegen.
Beurteilung der Korrosion gemäß DIN 51 360:
- 0 keine Korrosion / unverändert
- 1 Spuren von Korrosion / höchstens 3 Korrosionsabzeichnungen
- 2 leichte Korrosion / nicht mehr als 1 % der Oberfläche verfärbt
- 3 mäßige Korrosion / nicht mehr als 5% der Oberfläche verfärbt
- 4 starke Korrosion / über 5% der Oberfläche verfärbt
- 0 no corrosion / unchanged
- 1 traces of corrosion / maximum of 3 corrosion marks
- 2 slight corrosion / not more than 1% of the surface discolored
- 3 moderate corrosion / not more than 5% of the surface discolored
- 4 strong corrosion / over 5% of the surface discolored
Claims (8)
- An aqueous, surface-active and anti-corrosion preparation containing, in addition to water,i) a corrosion protection system (I) comprisinga) aliphatic carboxylic acids having at least 6 but no more than 14 carbon atoms and/or carboxylic acids having oxygen heteroatoms inserted in the carbon chain, which have between 6 and 26 atoms in the carbon heteroatom chain, and/or aliphatic phosphonic acids having at least 4 but no more than 18 carbon atoms,b) at least one amine which has at least one oxybis(alkylamine) unit having tertiary amino groups, wherein the alkyl chains of this unit each consist of no more than 4 carbon atoms, wherein the molar ratio of the total amount of carboxyl acid groups and/or phosphonic acid groups of components a) to oxybis(alkylamine) units of the at least one amine of component b) is no greater than 5:1 but no smaller than 1:3,ii) an emulsifier system (II) consisting ofc) ethoxylates/propoxylates of fatty alcohols having from 8 to 18 carbon atoms in the alcohol having from 2 to 6 ethylene oxide units and from 4 to 8 propylene oxide units andd) fatty alcohols and/or fatty alcohol propoxylates having from 12 to 24 C atoms in the alcohol and from 0 to 3 propylene oxide units and/or the distillation residue of these fatty alcohols.
- The preparation according to claim 1, characterized in that the molar ratio of the total amount of carboxyl acid groups and/or phosphonic acid groups of components a) to oxybis(alkylamine) units of the at least one amine of component b) of the relevant corrosion protection system (I) is no greater than 3:1 but no smaller than 2:3.
- The preparation according to one or both of the preceding claims, characterized in that at least one amine of the following structural formula (1) is contained as component b) of the corrosion protection system (I):
and/or the functional groups R1, R2, R3 and R4 being selected from functional groups of this kind which bridge the two nitrogen atoms of the oxybis(alkylamine) unit such that the functional group R1 and/or the functional group R2 are each structurally identical to the functional group R3 or R4, bridging functional groups R1 or R2 and R3 or R4 being selected from alkylenes, polyoxyalkylenes or polyaminoalkylenes having no more than 6 carbon atoms; where m and n are natural integers in the range of from 1 to 3. - The preparation according to claim 3, characterized in that at least one amine of structural formula (1) is contained as component b) of the corrosion protection system (I), functional groups R1, R2, R3 and R4 being selected, independently of one another, from branched or unbranched alkyl functional groups having no more than 8, preferably no more than 4, carbon atoms, and the natural integers m and n being equal to 2.
- The preparation according to one or more of the preceding claims, characterized in that, based on the total proportion of the amines according to component b) of the corrosion protection system (I), at least 50 wt.%, preferably at least 80 wt.%, of the amines of component b) of the corrosion protection system (I) are selected from amines of structural formula (I) according to one of claims 3 or 4.
- The preparation according to one or more of the preceding claims, characterized in that component a) of the corrosion protection system (I) is selected from aliphatic branched or unbranched monocarboxylic acids, which are preferably selected from caprylic acid, ethylhexanoic acid, isononanoic acid and isodecanoic acid.
- An oil-containing, water-miscible emulsion concentrate containingi) from 2 to 20 wt.% of a corrosion protection system (I) comprisinga) aliphatic carboxylic acids having at least 6 but no more than 14 carbon atoms and/or carboxylic acids having oxygen heteroatoms inserted in the carbon chain, which have between 6 and 26 atoms in the carbon heteroatom chain, and/or aliphatic phosphonic acids having at least 4 but no more than 18 carbon atoms,b) at least one amine which has at least one oxybis(alkylamine) unit having tertiary amino groups, wherein the alkyl chains of this unit each consist of no more than 4 carbon atoms, wherein the weight ratio of components a) and b) can vary from 1:0.2 to 0.3:1ii) from 2 to 50 wt. % of an emulsifier system (II) consisting ofc) ethoxylates/propoxylates of fatty alcohols having from 8 to 18 carbon atoms in the alcohol having from 2 to 6 ethylene oxide units and from 4 to 8 propylene oxide units andd) fatty alcohols and/or fatty alcohol propoxylates having from 12 to 24 carbon atoms in the alcohol and from 0 to 3 propylene oxide units and/or the distillation residue of these fatty alcohols, wherein the weight ratio of components c) and d) can vary from 1:0.3 to 0.3:1, andiii) from 5 to 50 wt.% of an oil component (III), and optionally further auxiliary agents and active ingredients (IV), wherein the sum of the constituents I) to IV) makes up from 60 to 95 wt.% and the remaining weight proportion is water.
- The oil-containing, water-miscible emulsion concentrate according to claim 7, characterized in that paraffinic or naphthenic mineral oils, dialkyl ethers having from 12 to 20 carbon atoms and/or ester oils are used as the oil component (III).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL13709100T PL2828419T3 (en) | 2012-03-23 | 2013-03-13 | Aqueous, surface-active, corrosion protection formulation, and as well as an oil-containing, water-miscible emulsion concentrate |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102012204683A DE102012204683A1 (en) | 2012-03-23 | 2012-03-23 | Corrosion protection system for the treatment of metal surfaces |
| PCT/EP2013/055074 WO2013139650A1 (en) | 2012-03-23 | 2013-03-13 | Corrosion-protection system for treating metal surfaces |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2828419A1 EP2828419A1 (en) | 2015-01-28 |
| EP2828419B1 true EP2828419B1 (en) | 2018-02-28 |
Family
ID=47878036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP13709100.5A Active EP2828419B1 (en) | 2012-03-23 | 2013-03-13 | Aqueous, surface-active, corrosion protection formulation, and as well as an oil-containing, water-miscible emulsion concentrate |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US9890462B2 (en) |
| EP (1) | EP2828419B1 (en) |
| JP (1) | JP6216366B2 (en) |
| KR (1) | KR20140137378A (en) |
| CN (1) | CN104508186B (en) |
| AU (1) | AU2013234535B2 (en) |
| CA (1) | CA2867413C (en) |
| DE (1) | DE102012204683A1 (en) |
| ES (1) | ES2663255T3 (en) |
| PL (1) | PL2828419T3 (en) |
| TR (1) | TR201806934T4 (en) |
| WO (1) | WO2013139650A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160362598A1 (en) * | 2015-06-10 | 2016-12-15 | Baker Hughes Incorporated | Decreasing corrosion on metal surfaces |
| US9828566B2 (en) * | 2015-07-06 | 2017-11-28 | Afton Checmical Corporation | Boron free corrosion inhibitors for metalworking fluids |
| GB201709767D0 (en) * | 2017-06-19 | 2017-08-02 | Ecolab Usa Inc | Naphthenate inhibition |
| DE102020104085A1 (en) * | 2020-02-17 | 2021-08-19 | Metall-Chemie Technologies Gmbh | Phosphonic acids based on natural substances as acidic corrosion inhibitors |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3365661A (en) | 1965-04-26 | 1968-01-23 | Anaconda Wire & Cable Co | Method and apparatus for locating leaks in a cable by determining the distance to a short circuit in the cable |
| USB336566I5 (en) * | 1973-02-28 | 1975-01-28 | ||
| GB1486197A (en) * | 1973-09-29 | 1977-09-21 | Nippon Light Metal Res Labor | Water-soluble metal working lubricating composition |
| US4687634A (en) * | 1986-10-31 | 1987-08-18 | Ronco Laboratories, Inc. | Process for inhibiting corrosion of metal surfaces |
| US5489618A (en) * | 1993-11-29 | 1996-02-06 | Osi Specialties, Inc. | Process for preparing polyurethane foam |
| DE69508185T2 (en) * | 1994-11-08 | 1999-07-08 | Betz Europ Inc | Process using a water-soluble corrosion inhibitor based on salt from dicarboxylic acids, cyclic amines and alkanolamines. |
| DE4444878A1 (en) | 1994-12-16 | 1996-06-20 | Henkel Kgaa | Nitrogen-free corrosion inhibitors with a good buffer effect |
| JPH10324982A (en) * | 1997-05-26 | 1998-12-08 | Daiwa Kasei Kenkyusho:Kk | Corrosion and discoloration suppressor |
| DE19747895A1 (en) | 1997-10-30 | 1999-05-06 | Henkel Kgaa | Metal treatment liquid for the neutral pH range |
| US6667283B2 (en) * | 1999-01-15 | 2003-12-23 | Ecolab Inc. | Antimicrobial, high load bearing conveyor lubricant |
| JP2005015617A (en) * | 2003-06-26 | 2005-01-20 | Neos Co Ltd | Water-soluble metal working fluid composition |
| FR2883294B1 (en) * | 2005-03-18 | 2009-03-06 | Imaje Sa Sa | INK COMPOSITION FOR CONTINUOUS JET PRINTING DEVICE |
| JP5204390B2 (en) | 2006-09-27 | 2013-06-05 | ユシロ化学工業株式会社 | Water-soluble metal processing agent, coolant and preparation method thereof, method for preventing microbial degradation of water-soluble metal processing agent, and metal processing |
| DE102007004325A1 (en) | 2007-01-23 | 2008-07-24 | Henkel Ag & Co. Kgaa | Cooling lubricant for the aqueous machining of aluminum-alloyed magnesium |
-
2012
- 2012-03-23 DE DE102012204683A patent/DE102012204683A1/en not_active Ceased
-
2013
- 2013-03-13 TR TR2018/06934T patent/TR201806934T4/en unknown
- 2013-03-13 WO PCT/EP2013/055074 patent/WO2013139650A1/en active Application Filing
- 2013-03-13 JP JP2015500843A patent/JP6216366B2/en not_active Expired - Fee Related
- 2013-03-13 KR KR1020147026449A patent/KR20140137378A/en not_active Application Discontinuation
- 2013-03-13 PL PL13709100T patent/PL2828419T3/en unknown
- 2013-03-13 CA CA2867413A patent/CA2867413C/en not_active Expired - Fee Related
- 2013-03-13 ES ES13709100.5T patent/ES2663255T3/en active Active
- 2013-03-13 CN CN201380014773.9A patent/CN104508186B/en active Active
- 2013-03-13 EP EP13709100.5A patent/EP2828419B1/en active Active
- 2013-03-13 AU AU2013234535A patent/AU2013234535B2/en not_active Ceased
-
2014
- 2014-09-22 US US14/492,207 patent/US9890462B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CA2867413A1 (en) | 2013-09-26 |
| US9890462B2 (en) | 2018-02-13 |
| PL2828419T3 (en) | 2018-08-31 |
| AU2013234535A1 (en) | 2014-10-09 |
| CN104508186B (en) | 2018-02-06 |
| KR20140137378A (en) | 2014-12-02 |
| WO2013139650A1 (en) | 2013-09-26 |
| JP2015513004A (en) | 2015-04-30 |
| DE102012204683A1 (en) | 2013-09-26 |
| CN104508186A (en) | 2015-04-08 |
| JP6216366B2 (en) | 2017-10-18 |
| AU2013234535B2 (en) | 2017-03-30 |
| TR201806934T4 (en) | 2018-06-21 |
| CA2867413C (en) | 2020-09-08 |
| EP2828419A1 (en) | 2015-01-28 |
| ES2663255T3 (en) | 2018-04-11 |
| US20150011445A1 (en) | 2015-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1652909B2 (en) | Corrosion-inhibiting agent for functional fluids, water-miscible lubricating concentrate and its use. | |
| DE3540246A1 (en) | USE OF ALKOXYHYDROXY FATTY ACIDS AS CORROSION INHIBITORS IN OILS AND OIL-BASED EMULSIONS | |
| DE102008064004B4 (en) | Water-based hydraulic fluids containing dithiodi (arylcarboxylic acids) or their alkali metal, alkaline earth metal or ammonium salts | |
| EP1102830B1 (en) | Water-miscible cooling lubricant concentrate | |
| EP2033964A2 (en) | Corrosion inhibitor | |
| EP2828419B1 (en) | Aqueous, surface-active, corrosion protection formulation, and as well as an oil-containing, water-miscible emulsion concentrate | |
| EP0103737B1 (en) | Corrosion inhibitors for c02 and h2s in water in oil emulsions | |
| EP0584711B1 (en) | Alkenyl succinic acid derivatives as metal working agents | |
| EP0060455B1 (en) | Inhibitors against corrosion by carbon dioxide and hydrogen sulfide in water-in-oil emulsions | |
| WO2001042532A2 (en) | Metal treatment fluid for the neutral ph-range | |
| EP2111440A1 (en) | Cooling lubricant with high dispersing properties for the wet machining of light alloys | |
| EP0231524B1 (en) | Application of alkylbenzoylacrylic acids as corrosion inhibitors | |
| WO2008089857A1 (en) | Cooling lubricant for the wet machining of aluminium alloyed magnesium | |
| WO1999023281A1 (en) | METAL PROCESSING LIQUID FOR THE NEUTRAL pH RANGE | |
| DE10043040A1 (en) | Use of N-alkyl-beta-alanine derivatives for the production of cleaning anti-corrosion agents | |
| DE3701719A1 (en) | Corrosion protection agent, containing mixtures with amido acids | |
| EP0109549B1 (en) | Corrosion inhibitors for aqueous solutions for the treatment of metals, and process for their preparation | |
| DE1521710A1 (en) | Anti-corrosive agents | |
| EP0501368B1 (en) | Use of alkenylsuccinic acid half-amides | |
| DE60022626T2 (en) | MECHANICAL WORK IN THE PRESENCE OF A MULTIFUNCTIONAL REFRIGERANT | |
| DE3416857A1 (en) | Phenoxyalkanecarboxylic acid alkanolamine salts as water-soluble corrosion inhibitors | |
| EP2031093A2 (en) | Corrosion inhibitors containing non-ionic tensides | |
| DE3208748A1 (en) | Epoxide-phosphoric acid adducts and process for their preparation | |
| EP0464473B1 (en) | Alkenylsuccinic monoamide salts and their use as corrosion inhibitors and emulsifiers for metal working oils | |
| EP0109548A1 (en) | Corrosion inhibitors for aqueous solutions for the treatment of metals, and process for their preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 20140212 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| AX | Request for extension of the european patent |
Extension state: BA ME |
|
| RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: TEMME, ANDREAS |
|
| DAX | Request for extension of the european patent (deleted) | ||
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| INTG | Intention to grant announced |
Effective date: 20171012 |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH Ref country code: CH Ref legal event code: EP |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 974223 Country of ref document: AT Kind code of ref document: T Effective date: 20180315 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 6 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502013009550 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2663255 Country of ref document: ES Kind code of ref document: T3 Effective date: 20180411 |
|
| REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20180228 |
|
| REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180228 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180228 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180228 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180528 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180228 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180228 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180228 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180228 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180528 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180529 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180228 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180228 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180228 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180228 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502013009550 Country of ref document: DE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180228 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180228 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180228 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180228 |
|
| REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20180331 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180313 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180313 |
|
| 26N | No opposition filed |
Effective date: 20181129 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180228 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180331 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PL Payment date: 20190418 Year of fee payment: 9 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20130313 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180228 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180228 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20180628 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: TR Payment date: 20220311 Year of fee payment: 10 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200313 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20230324 Year of fee payment: 11 Ref country code: CZ Payment date: 20230306 Year of fee payment: 11 Ref country code: AT Payment date: 20230322 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20230314 Year of fee payment: 11 Ref country code: GB Payment date: 20230322 Year of fee payment: 11 Ref country code: DE Payment date: 20230321 Year of fee payment: 11 |
|
| P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230530 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20230328 Year of fee payment: 11 Ref country code: ES Payment date: 20230529 Year of fee payment: 11 Ref country code: CH Payment date: 20230401 Year of fee payment: 11 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20240321 Year of fee payment: 12 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240320 Year of fee payment: 12 Ref country code: CZ Payment date: 20240304 Year of fee payment: 12 Ref country code: GB Payment date: 20240320 Year of fee payment: 12 |