WO1992001029A1 - Aqueous coolant - Google Patents

Aqueous coolant Download PDF

Info

Publication number
WO1992001029A1
WO1992001029A1 PCT/US1991/004429 US9104429W WO9201029A1 WO 1992001029 A1 WO1992001029 A1 WO 1992001029A1 US 9104429 W US9104429 W US 9104429W WO 9201029 A1 WO9201029 A1 WO 9201029A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
coolant
composition
glycerine
amino
Prior art date
Application number
PCT/US1991/004429
Other languages
French (fr)
Inventor
Robert A. Thordsen
Original Assignee
Quaker Chemical Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Quaker Chemical Corporation filed Critical Quaker Chemical Corporation
Publication of WO1992001029A1 publication Critical patent/WO1992001029A1/en

Links

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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
    • 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
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
    • 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
    • C10M2207/022—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two hydroxy groups
    • 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
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • 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
    • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
    • 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
    • C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more 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
    • C10M2207/22—Acids obtained from polymerised unsaturated 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
    • 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
    • C10M2215/044—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms having cycloaliphatic groups
    • 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
    • C10M2215/08—Amides
    • 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
    • C10M2215/08—Amides
    • C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
    • 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
    • C10M2215/28—Amides; Imides
    • 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
    • C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles

Definitions

  • This invention relates to an aqueous coolant for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking. More particularly, the present invention relates to an aqueous coolant for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking, for example, machining and grinding and any metal-removing or metal- forming operation, comprising a composition containing sebacic acid, glycerine, isononanoic acid and 6-[(l- oxoisonony1) mino]hexanoic acid.
  • Aqueous coolants for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking operations or procedures, for example, machining and grinding and metal- removing or metal-forming operations are generally well known in the art.
  • prior art aqueous coolants typically contain undesired ingredients, including free amines, for example, monoethanolamine, diethanolamine and triethanolamine, nitrites, phosphates, sulfur, chlorine or boron. These ingredients may impart undesirable properties to the coolant.
  • free amines for example, monoethanolamine, diethanolamine and triethanolamine, nitrites, phosphates, sulfur, chlorine or boron.
  • These ingredients may impart undesirable properties to the coolant.
  • coolants containing free amines may cause dermatitis to the skin of an individual who comes in contact with the free a ine-containing coolant.
  • the free amines in the free amine-containing coolants may also result in the coolants having objectionable odors.
  • free amines and nitrites in aqueous coolants containing both free amines and nitrites may react to form nitrosamines, which are known carcinogens.
  • the free amines may also react with nitrous oxides in the air to form nitrosamines.
  • the free amines typically used, mono-, di- and triethanolamine are themselves health hazards, causing burning to mucous membranes and skin. These undesired ingredients may also cause waste disposal difficulties of the coolant after use.
  • U.S. Patent 4,452,715 discloses an aqueous alcohol coolant composition having a pH of about 9 to about 10.5 to inhibit the corrosion of iron and solder.
  • the composition may contain chlorine and free amines, but is free of phosphate and borate compounds and comprises an inorgance silicate, a water-soluble nitrite, a water-soluble triazole or thiazole and a water-soluble carbonate.
  • U.S. Patent 4,348,302 discloses an anticorrosive agent stable to hard water consisting of an alkali metal salt, alkaline earth metal salt or amine salt of an amido carboxylic acid.
  • the anticorro ⁇ ives may be used in admixture with known metal processing liquids for aqueous oil emulsions and can be applied in the form of aqueous solutions, dispersions or emulsions.
  • U.S. Patent 4,342,658 discloses a water-based hydraulic fluid or metalworking composition comprising a mixture of a phosphate ester, a polyethylene ester, polyester of an oxyalkaline compound and an alkyl dialkanolamide.
  • This reference discloses using sebacic acid to prepare the alkyl dialkanolamide ⁇ and glycerol which are ethoxylated and subsequently esterified to produce the esters of ethoxylated aliphatic alcohols, useful as components of the hydraulic fluids.
  • Additives may be used in the disclosed compositions, including amines and nitrites.
  • U.S. Patent 4,578,208 discloses compositions for cleaning and passivating metals comprising at least one phosphoric acid ester, at least one alkanolamine and/or alkanolamine salt, at least one ⁇ prayable non-ionic surfactant and optionally building, complexing agents and/or biocides.
  • the aqueous cleaning solutions of the invention have a pH range of about 7.5 to about 10.5.
  • the present invention overcomes the aforementioned problems associated with the prior art aqueous coolants containing free amines, nitrites, phosphates, sulfur, chlorine or boron.
  • the aqueous compositions and coolants containing the composition of the present invention effectively and efficiently cool and protect a metal workpiece from corrosion and rust during metalworking, and have improved corrosion protection properties over the aqueous coolants of the prior art.
  • the aqueous compositions and coolants containing the composition of the present invention also effectively and efficiently cool and protect the metalworking apparatus or device used to work the metal during the metalworking operations or procedures.
  • the aqueous coolant and/or composition of the present invention contains no free amines, nitrites, phosphates, sulfur, chlorine or boron.
  • One aspect of the invention relates to a composition
  • a composition comprising about 5 to about 20% sebacic acid, about 2 to about 15% glycerine, about 9 to about 27% isononanoic acid, about 1 to about 3% 6-[(1-oxoisononyl)- amino]hexanoic acid, an amount of KOH to provide the composition with a pH of about 10 to about 10.5, and water.
  • Another aspect of the invention relates to a process for cooling and protecting a metal workpiece from corrosion and rust during metalworking comprising providing a concentrate comprising about 5 to about 20% sebacic acid, about 2 to about 15% glycerine, about 9 to about 27% isononanoic acid, about 1 to about 3% 6-[ (1-oxoisononyl)- amino]hexanoic acid, an amount of KOH to provide the concentrate with a pH of about 10 to about 10.5, and water, diluting the concentrate with additional water to about 1:20 to about 1:40 to provide a coolant having a pH of about 9.5 or less, and working the metal in the presence of the coolant.
  • Still another aspect of the invention relates to a process for cooling and protecting a metal workpiece from corrosion and rust during metalworking comprising providing a coolant comprising about 0.125 to about 1% sebacic acid, about 0.05 to about 0.75% glycerine, about 0.225 to about 1.35% isononanoic acid, about 0.025 to about 0.15% 6-[(l- oxoisononyl)amino]hexanoic acid, an amount of KOH to provide the coolant with a pH of about 9.5 or less, and water, and working the metal in the presence of the coolant.
  • a coolant comprising about 0.125 to about 1% sebacic acid, about 0.05 to about 0.75% glycerine, about 0.225 to about 1.35% isononanoic acid, about 0.025 to about 0.15% 6-[(l- oxoisononyl)amino]hexanoic acid, an amount of KOH to provide the coolant with a pH of about 9.5
  • % or “percent” means the weight percent of the particular ingredient or component in the composition or coolant as described unless otherwise indicated or clear from the context of the description.
  • the present invention relates to an aqueous composition and a coolant formed therefrom for cooling and protecting a metal workpiece from corrosion and rust during metalworking.
  • the present invention also relates to an aqueous composition and coolant formed therefrom for cooling and protecting a metalworking apparatus or device from corrosion and rust during metalworking.
  • the "coolant” of the present invention is an aqueous dilution of the "composition" of the present invention.
  • composition is a concentrate which should be diluted with water to form a "coolant" when used in metalworking procedures.
  • the concentrated composition is the form of the present invention preferred for preparation and shipping.
  • aqueous coolants for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking contain undesirable ingredients or chemicals, for example, free amines, nitrites, phosphates, sulfur, chlorine and/or boron. These chemicals or ingredients may cause difficulty during use of the coolant or during disposal.
  • coolants containing free amines may cause dermititis to the user and may have an obnoxious odor.
  • free amines and nitrites may react to form carcinogenic nitrosamines and free amines and nitrous oxides from the air may react to form carcinogenic nitrosamines, and the free amines typically used, for example, mono-, di- and triethanolamine, are themselves health hazards, causing burning of the skin and mucous membranes.
  • the primary ingredients in the composition used to make the aqueous coolant of the present invention include about 5 to about 20% sebacic acid, about 2 to about 15% glycerine, about 9 to about 27% isononanoic acid and about 1 to about 3% 6-[ (l-oxoisononyl)amino]hexanoic acid, based upon the total weight of the composition.
  • Additional primary ingredients include an amount of KOH to provide the composition with a pH of about 10 to about 10.5, and water.
  • Isononanoic acid and 6-[ (l-oxoisononyl)amino]- hexanoic acid have the following formulas I and II, respectively:
  • Isononanoic acid is commercially available from Exxon Chemicals, for example. 6-[ (l-oxoisononyl)amino]- hexanoic acid is commercially available from Hoechst- Celanese, for example. 6-[ (l-oxoisononyl)amino]hexanoic acid may be prepared by reacting -caprolactam with isononanoic acid chloride according to the procedure in U.S. Patent 4,348,302.
  • a suitable mixture of isononanoic acid and 6-[ (l-oxoisononyl)amino]hexanoic acid is commercially available from Hoechst-Celanese under the trademark HOSTACOR* TP-2291. Because the isononanoic acid and 6-[ (l-oxoisononyl)amino]hexanoic acid are premixed in the HOSTACOR ® TP-2291 product, the use of this product is the preferred manner of incorporating these two primary ingredients in the composition of the present invention.
  • the sebacic acid and glycerine used in the composition of the present invention may generally be obtained from various commercial suppliers.
  • the KOH used in the present invention is preferably an aqueous solution of KOH, for example, 45% aqueous KOH.
  • the KOH used in the present invention preferably contains no chlorine-containing impurities.
  • This chlorine-free KOH is generally referred to as "electronic grade" KOH.
  • the water used in the composition of the present invention may be chlorine-free tap water, distilled water or deionized water or mixtures thereof.
  • the amount of water used in the composition is an amount so that the sum of the ingredients of the composition is 100%.
  • the composition comprises about 7 to about 15% sebacic acid, about 2 to about 6% glycerine, about 13.5 to about 18% isononanoic acid and about 1.5 to about 2% 6-[ (l-oxoisononyl)amino]- hexanoic acid, based upon the total weight of the composition.
  • composition of the present invention is about 9.67% sebacic acid, about 3.9% glycerine, about 17.41% isononanoic acid, about 1.93% 6-[(l-oxoisononyl)amino]hexanoic acid, about 25.56% of 45% aqueous KOH and about 37.39% water, based upon the total weight of the composition.
  • composition may further comprise optional ingredients.
  • optional ingredients include ingredients designed to improve characteristics of the composition and/or coolant, such as corr ⁇ siv-ity, stability and fragrance.
  • the optional ingredients of the composition of the present invention include a non-ferrous corrosion inhibitor, present in an amount of about 0.01 to about 0.5%, based on the total weight of the composition.
  • a non-ferrous corrosion inhibitor to be used in accordance with the present invention is benzotriazole.
  • a suitable, commercially available form of benzotriazole to be used as a non-ferrous corrosion inhibitor in the present invention is COBRATEC ® , marketed by PMC Specialties Group, Inc.
  • Other non-ferrous corrosion inhibitors suitable to be used in the composition of the present invention would be readily apparent to one skilled in the art.
  • dimer ester Another optional ingredient which may be used in the composition of the present invention is a dimer ester.
  • the dimer ester is present in the composition in an amount of about 0 to about 5%, based upon the total weight of the composition.
  • a suitable, commercially available dimer ester is EMERY ® 2902 or EMERY ® 2908 water-active lubricant basestocks, marketed by Emery Chemicals.
  • biocide present in an amount of about 0 to about 4%, based on the total weight of the composition.
  • suitable biocides to be used in the present invention include 5-hydroxymethoxymethyl-l-aza-3 ,7-dioxabicyclo- (3.3.0)octane, 5-hydroxymethyl-l-aza-3 ,7-dioxabicyclo- (3.3.0)octane and 5-hydroxypoly[methyleneoxy(74% C,, 21% C,, 4% C , 1% C 5 )]methyl-l-aza-3,7-dioxabicyclo(3.3.0)octane.
  • a suitable, commercially available biocide to be used in the present invention is BIOBAN ® N-95, marketed by ANGUS Chemical Co.
  • Other biocides to be used in the composition of the present invention would be readily apparent to one skilled in the art.
  • Still another optional ingredient to be used in the composition of the present invention is a perfume, present in an amount of up.to about 0.5% based on the total weight of the composition.
  • the perfume is intended to impart a pleasant fragrance to the composition and/or the aqueous coolant.
  • An example of a suitable perfume to be used in the present invention is an orange perfume, commercially available from Alpine Aromatics International.
  • Other perfumes to be used in the composition of the present invention would be readily apparent to one skilled in the art.
  • Another optional ingredient to be used in the composition of the present invention is a lubricant, for example, an ethoxylated and propoxylated polyalkylglycol, such as poly GWS 660, commercially available from Olin Chemical.
  • Other optional ingredients to be used in the composition of the present invention intended to impart desirable properties to the composition and/or coolant would be readily apparent to one skilled in the art.
  • the optional ingredients include about 0.1 to about 0.5% of a non-ferrous corrosion inhibitor, about 1 to about 5% of a dimer ester and about 1 to about 4% of a biocide.
  • the composition used to prepare the aqueous coolant for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking may be prepared according to a number of procedures.
  • all of the primary ingredients namely, sebacic acid, glycerine, isononanoic acid and 6-[ (l-oxoisononyl)amino]hexanoic acid are added to the water.
  • the optional ingredients for example, a non- ferrous corrosion inhibitor, a dimer ester and a perfume, may also be added to the water at this stage of the preparation of the composition.
  • the biocide should not yet be added to the mixture.
  • the pH is adjusted with KOH until a pH of about 10 to about 10.5 is obtained.
  • the isononanoic acid and 6-[ (l-oxoisononyl)amino]hexanoic acid are present as the corresponding potassium salts.
  • the sebacic acid is generally present as the dipotassium salt.
  • This neutralization/basification process is exothermic due to the heat of neutralization.
  • the temperature of the mixture generally rises to about 130-150*F during the neutralization/basification process.
  • the mixture should be allowed to cool to below about 100*F, at which time, if desired, the biocide may be added to the mixture. After all of the desired ingredients are combined and the mixture is allowed to cool, the result is the composition.
  • the composition of the present invention is used to prepare an aqueous coolant for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking.
  • the composition is diluted with additional water.
  • the composition is diluted with water at a ratio of about 1 part composition to about 20 parts water to about 1 part composition to about 40 parts water. It is critical that the resulting aqueous coolant has a pH of about 9.5 or less and more preferably, a pH of about 7.4 to about 8.1.
  • a process for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking operations and/or procedures includes, for example, machining and grinding and any metal-removing or metal-forming operation.
  • metalworking apparatus or device includes, for example, a grinding wheel, a drill and a cutting wheel.
  • Suitable metals to be cooled and protected by the aqueous coolant of the present invention comprise ferrous metals, for example, cast iron and steel, and non-ferrous metals, such as aluminum. Examples of other metals to be cooled and protected by the aqueous coolant of the present invention during metalworking operations or procedures would be readily apparent to one skilled in the art.
  • a concentrate namely the aforementioned composition, comprising primary ingredients including about 5 to about 20% sebacic acid, about 2 to about 15% glycerine, about 9 to about 27% isononanoic acid and about 1 to about 3%
  • the concentrate further comprises an amount of KOH to provide the concentrate with a pH of about 10 to about 10.5, and water.
  • KOH potassium hydroxide
  • the concentrate is diluted with additional water to provide a coolant.
  • the concentrate is diluted with additional water at a ratio of about 1 part concentrate to about 20 parts water to about 1 part concentrate to about 40 parts water.
  • the resulting coolant must have a pH of about 9.5 or less.
  • the metal is worked in the presence of the coolant, thereby cooling and protecting the metal workpiece and a metalworking apparatus or device from corrosion and rust.
  • the concentrate comprises about 7 to about 15% sebacic acid, about 2 to about 6% glycerine, about 13.5 to about 18% isononanoic acid and about 1.5 to about 2%
  • the concentrate comprises about 7.5 to about 10% sebacic acid, about 3.9 to about 4% glycerine, about 17.41 to about 18% isononanoic acid and about 1.93 to about 2% 6-[(l-oxoisononyl)amino]hexanoic acid, based upon the total weight of the concentrate.
  • the concentrate comprises about 9.67% sebacic acid, about 3.9% glycerine, about 17.41% isononanoic acid, about 1.93% 6-[ (l-oxoisononyl)amino]hexanoic acid, about 25.56% of 45% aqueous KOH and about 37.39% water, based upon the total weight of the concentrate.
  • the concentrate may comprise optional ingredients to enhance the stability and other characteristics of the concentrate.
  • the concentrate in addition to the aforementioned primary ingredients, may further comprise about 0.01 to about 0.5% of a non-ferrous corrosion inhibititor, about 0 to about 5% of a dimer ester, about 0 to about 4% of a biocide and up to about 0.5% of a perfume, based upon the total weight of the concentrate.
  • These optional ingredients generally correspond to the optional ingredients contained in the composition, discussed hereinbefore. Accordingly, the discussion regarding the optional ingredients for the composition is incorporated herein by reference.
  • the concentrate comprises about 0.1 to about 0.5% of a non-ferrous corrosion inhibitor, about 1 to about 5% of a dimer ester and about 1 to about 4% of a biocide.
  • the process for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking comprises initially beginning with the coolant. This obviates the need for initially preparing the concentrate and/or composition, followed by diluting the concentrate and/or composition with additional water.
  • the coolant comprises primary ingredients, including about 0.125 to about 1% sebacic acid, about 0.05 to about 0.75% glycerine, about 0.225 to about 1.35% isononanoic acid and about 0.025 to about 0.15% 6- [(l-oxoisononyl)a ino]hexanoic acid, based on the total weight of the coolant.
  • the coolant further comprises primary ingredients of an amount of KOH to provide the coolant with a pH of about 9.5 or less, and water.
  • the process further comprises working the metal in the presence of the coolant, thereby cooling and protecting the metal workpiece and the metalworking apparatus or device from corrosion and rust.
  • These primary ingredients correspond to the primary ingredients for the composition and the concentrate, discussed hereinbefore. Accordingly, the discussion regarding the primary ingredients for the composition and the concentrate are incorporated herein by reference.
  • the coolant comprises about 0.175 to about 0.75% sebacic acid, about 0.05 to about 0.3% glycerine, about 0.338 to about 0.9% isononanoic acid and about 0.038 to about 0.1% 6-[(l- oxoisononyl)amino]hexanoic acid, based on the total weight of the coolant.
  • the coolant comprises about 0.188 to about 0.5% sebacic acid, about 0.098 to about 0.2% glycerine, about 0.435 to about 0.9% isononanoic acid and about 0.048 to about 0.1% 6- [(l-oxoisononyl)amino]hexanoic acid, based on the total weight of the coolant.
  • the coolant comprises about 0.242 to about 0.484% sebacic acid, about 0.098 to about 0.195% glycerine, about 0.435 to about 0.871% isononanoic acid ajnd about 0.048 to about 0.097% 6-[ (l-oxoisononyl)amino]- hexanoic acid.
  • the coolant in the process of the present alternate embodiment may comprise optional ingredients. These optional ingredients correspond to the optional ingredients described with reference to the composition and the concentrate.
  • a preferred range of these optional ingredients in the coolant is about 2.5 x 10 -4 to about 0.25% of a non-ferrous corrosion inhibitor, about 0 to about 0.25% of a dimer ester, about 0 to about 0.2% of a biocide and up to about 0.025% of a perfume. More preferably, the coolant comprises about 2.5 x
  • compositions and/or aqueous coolants of the present invention are evaluated using a "Modified Herbert Rust Test.”
  • This test is designed as a relative determination of the corrosion thre ⁇ hhold concentration of metalworking fluids on cast iron.
  • the test comprises grinding the surface of a test block which comprises a 1-3/4-inch type "S" cast iron pipe plug to a near mirror finish. The test block is then cleaned with isopropyl alcohol.
  • the desired aqueous coolant is formulated and placed in a 4-oz. jar.
  • Cast iron chips (1 gram) obtained from machining and grinding operations are added to the jars and the aqueous coolant and the cast iron chip/coolant mixture i ⁇ ⁇ ha en and allowed to soak for 5 minutes.
  • the resulting mixture i ⁇ poured over the cast iron test block, retaining the chips on the surface of the blocks. Excess liquid from the block is then drained and the block is placed into a humidity cabinet containing 1/2 inch distilled water. After allowing the block to stand for 18 hours in the humidity cabinet, the chips are ⁇ craped from the surface of the block and the percentage of blush rust and degree of contact rust is recorded.
  • Example 1 A ⁇ erie ⁇ of aqueou ⁇ coolants were prepared as indicated in Table 1. Table 1 al ⁇ o ⁇ et ⁇ forth the la ⁇ t dilution at which the block did not rust, unles ⁇ otherwi ⁇ e indicated. The higher the dilution, the more effective the coolant in preventing ru ⁇ t.
  • Sebacic Acid 10 15 5 5 15 20 2.5 5 7.5
  • OAHA indicates 6-[(l-oxoi ⁇ ononyl)aalnojhexanolc acid; P Indicates pass; and F indicates fail
  • OAHA 6-[(l-oxoisononyl)amino)hexanoic acid; P Indicates pass; and F indicates fall
  • aqueous coolants 12, 22 and 23 are the most effective coolants for cooling and protecting a metal workpiece from corrosion and rust during metalworking.
  • Aqueous coolants 12, 22 and 23 are effective at a greater dilution (1:40, or a 2.5% v/v concentration) than the other aqueous coolants set forth in Table 1.
  • compositions are not commercially acceptable in view of cost consideration ⁇ .
  • some of the prior art type of commercially available coolant ⁇ lose their effectivenes ⁇ over time, due to a breakdown or leaching out or other decrease in effectiveness of the ingredients.
  • the coolant ⁇ of the pre ⁇ ent invention not only are capable of effective cooling and corro ⁇ ion protection at high dilution ratio ⁇ of 1:30 and greater, but also, they are stable and effective for a long period of time.
  • the coolants of the pre ⁇ ent invention do not appear to break down, leach out or have their effectivene ⁇ dimini ⁇ hed compared to the prior art commercial coolant ⁇ .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

An aqueous composition and a diluted aqueous coolant containing sebacic acid, glycerine, isononanoic acid and 6-[(1-oxoisononyl)amino]hexanoic acid are provided. The aqueous coolant is used for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking. The coolant contains no free amines, nitrites, phosphates, sulfur, chlorine or boron.

Description

AQUEOUS COOLANT Background of the Invention
Field of the Invention
This invention relates to an aqueous coolant for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking. More particularly, the present invention relates to an aqueous coolant for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking, for example, machining and grinding and any metal-removing or metal- forming operation, comprising a composition containing sebacic acid, glycerine, isononanoic acid and 6-[(l- oxoisonony1) mino]hexanoic acid.
Description of the Prior Art
Aqueous coolants for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking operations or procedures, for example, machining and grinding and metal- removing or metal-forming operations are generally well known in the art. However, prior art aqueous coolants typically contain undesired ingredients, including free amines, for example, monoethanolamine, diethanolamine and triethanolamine, nitrites, phosphates, sulfur, chlorine or boron. These ingredients may impart undesirable properties to the coolant. For example, coolants containing free amines may cause dermatitis to the skin of an individual who comes in contact with the free a ine-containing coolant. The free amines in the free amine-containing coolants may also result in the coolants having objectionable odors. Furthermore, free amines and nitrites in aqueous coolants containing both free amines and nitrites may react to form nitrosamines, which are known carcinogens. The free amines may also react with nitrous oxides in the air to form nitrosamines. In addition, the free amines typically used, mono-, di- and triethanolamine, are themselves health hazards, causing burning to mucous membranes and skin. These undesired ingredients may also cause waste disposal difficulties of the coolant after use.
U.S. Patent 4,452,715 discloses an aqueous alcohol coolant composition having a pH of about 9 to about 10.5 to inhibit the corrosion of iron and solder. The composition may contain chlorine and free amines, but is free of phosphate and borate compounds and comprises an inorgance silicate, a water-soluble nitrite, a water-soluble triazole or thiazole and a water-soluble carbonate.
U.S. Patent 4,348,302 discloses an anticorrosive agent stable to hard water consisting of an alkali metal salt, alkaline earth metal salt or amine salt of an amido carboxylic acid. According to this reference, the anticorroεives may be used in admixture with known metal processing liquids for aqueous oil emulsions and can be applied in the form of aqueous solutions, dispersions or emulsions.
U.S. Patent 4,342,658 discloses a water-based hydraulic fluid or metalworking composition comprising a mixture of a phosphate ester, a polyethylene ester, polyester of an oxyalkaline compound and an alkyl dialkanolamide. This reference discloses using sebacic acid to prepare the alkyl dialkanolamideε and glycerol which are ethoxylated and subsequently esterified to produce the esters of ethoxylated aliphatic alcohols, useful as components of the hydraulic fluids. Additives may be used in the disclosed compositions, including amines and nitrites.
U.S. Patent 4,578,208 discloses compositions for cleaning and passivating metals comprising at least one phosphoric acid ester, at least one alkanolamine and/or alkanolamine salt, at least one εprayable non-ionic surfactant and optionally building, complexing agents and/or biocides. The aqueous cleaning solutions of the invention have a pH range of about 7.5 to about 10.5.
The present invention overcomes the aforementioned problems associated with the prior art aqueous coolants containing free amines, nitrites, phosphates, sulfur, chlorine or boron. The aqueous compositions and coolants containing the composition of the present invention effectively and efficiently cool and protect a metal workpiece from corrosion and rust during metalworking, and have improved corrosion protection properties over the aqueous coolants of the prior art. The aqueous compositions and coolants containing the composition of the present invention also effectively and efficiently cool and protect the metalworking apparatus or device used to work the metal during the metalworking operations or procedures. The aqueous coolant and/or composition of the present invention contains no free amines, nitrites, phosphates, sulfur, chlorine or boron. Summary of the Invention One aspect of the invention relates to a composition comprising about 5 to about 20% sebacic acid, about 2 to about 15% glycerine, about 9 to about 27% isononanoic acid, about 1 to about 3% 6-[(1-oxoisononyl)- amino]hexanoic acid, an amount of KOH to provide the composition with a pH of about 10 to about 10.5, and water.
Another aspect of the invention relates to a process for cooling and protecting a metal workpiece from corrosion and rust during metalworking comprising providing a concentrate comprising about 5 to about 20% sebacic acid, about 2 to about 15% glycerine, about 9 to about 27% isononanoic acid, about 1 to about 3% 6-[ (1-oxoisononyl)- amino]hexanoic acid, an amount of KOH to provide the concentrate with a pH of about 10 to about 10.5, and water, diluting the concentrate with additional water to about 1:20 to about 1:40 to provide a coolant having a pH of about 9.5 or less, and working the metal in the presence of the coolant. Still another aspect of the invention relates to a process for cooling and protecting a metal workpiece from corrosion and rust during metalworking comprising providing a coolant comprising about 0.125 to about 1% sebacic acid, about 0.05 to about 0.75% glycerine, about 0.225 to about 1.35% isononanoic acid, about 0.025 to about 0.15% 6-[(l- oxoisononyl)amino]hexanoic acid, an amount of KOH to provide the coolant with a pH of about 9.5 or less, and water, and working the metal in the presence of the coolant.
As used herein, "%" or "percent" means the weight percent of the particular ingredient or component in the composition or coolant as described unless otherwise indicated or clear from the context of the description. Detailed Description of the Preferred Embodiments The present invention relates to an aqueous composition and a coolant formed therefrom for cooling and protecting a metal workpiece from corrosion and rust during metalworking. The present invention also relates to an aqueous composition and coolant formed therefrom for cooling and protecting a metalworking apparatus or device from corrosion and rust during metalworking. The "coolant" of the present invention is an aqueous dilution of the "composition" of the present invention. Thus, the
"composition" is a concentrate which should be diluted with water to form a "coolant" when used in metalworking procedures. The concentrated composition is the form of the present invention preferred for preparation and shipping. Generally,' prior art aqueous coolants for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking contain undesirable ingredients or chemicals, for example, free amines, nitrites, phosphates, sulfur, chlorine and/or boron. These chemicals or ingredients may cause difficulty during use of the coolant or during disposal. For example, coolants containing free amines may cause dermititis to the user and may have an obnoxious odor. Furthermore, as indicated hereinbefore, free amines and nitrites may react to form carcinogenic nitrosamines and free amines and nitrous oxides from the air may react to form carcinogenic nitrosamines, and the free amines typically used, for example, mono-, di- and triethanolamine, are themselves health hazards, causing burning of the skin and mucous membranes. The primary ingredients in the composition used to make the aqueous coolant of the present invention include about 5 to about 20% sebacic acid, about 2 to about 15% glycerine, about 9 to about 27% isononanoic acid and about 1 to about 3% 6-[ (l-oxoisononyl)amino]hexanoic acid, based upon the total weight of the composition. Additional primary ingredients include an amount of KOH to provide the composition with a pH of about 10 to about 10.5, and water.
Isononanoic acid and 6-[ (l-oxoisononyl)amino]- hexanoic acid have the following formulas I and II, respectively:
CH, O
3\ II
CHCH CH,CH,CH,CH C-OH (I) /
CH3
CH, O O
\ II II
CHCH2CH2CH2CH2CH2C-NH-CH2CH2CH2CH2CH2C-OH (II) CH3
Isononanoic acid is commercially available from Exxon Chemicals, for example. 6-[ (l-oxoisononyl)amino]- hexanoic acid is commercially available from Hoechst- Celanese, for example. 6-[ (l-oxoisononyl)amino]hexanoic acid may be prepared by reacting -caprolactam with isononanoic acid chloride according to the procedure in U.S. Patent 4,348,302. In addition, a suitable mixture of isononanoic acid and 6-[ (l-oxoisononyl)amino]hexanoic acid is commercially available from Hoechst-Celanese under the trademark HOSTACOR* TP-2291. Because the isononanoic acid and 6-[ (l-oxoisononyl)amino]hexanoic acid are premixed in the HOSTACOR® TP-2291 product, the use of this product is the preferred manner of incorporating these two primary ingredients in the composition of the present invention. The sebacic acid and glycerine used in the composition of the present invention may generally be obtained from various commercial suppliers. The KOH used in the present invention is preferably an aqueous solution of KOH, for example, 45% aqueous KOH. In addition, the KOH used in the present invention preferably contains no chlorine-containing impurities. This chlorine-free KOH is generally referred to as "electronic grade" KOH. The water used in the composition of the present invention may be chlorine-free tap water, distilled water or deionized water or mixtures thereof. The amount of water used in the composition is an amount so that the sum of the ingredients of the composition is 100%.
In a preferred embodiment, the composition comprises about 7 to about 15% sebacic acid, about 2 to about 6% glycerine, about 13.5 to about 18% isononanoic acid and about 1.5 to about 2% 6-[ (l-oxoisononyl)amino]- hexanoic acid, based upon the total weight of the composition.
An even more preferred range of components of the composition of the present invention is about 9.67% sebacic acid, about 3.9% glycerine, about 17.41% isononanoic acid, about 1.93% 6-[(l-oxoisononyl)amino]hexanoic acid, about 25.56% of 45% aqueous KOH and about 37.39% water, based upon the total weight of the composition.
In addition to the aforementioned primary ingredients, the presence of which is critical to the beneficial properties of the present invention, the composition may further comprise optional ingredients. These optional ingredients include ingredients designed to improve characteristics of the composition and/or coolant, such as corrσsiv-ity, stability and fragrance.
The optional ingredients of the composition of the present invention include a non-ferrous corrosion inhibitor, present in an amount of about 0.01 to about 0.5%, based on the total weight of the composition. An example of a non- ferrous corrosion inhibitor to be used in accordance with the present invention is benzotriazole. A suitable, commercially available form of benzotriazole to be used as a non-ferrous corrosion inhibitor in the present invention is COBRATEC®, marketed by PMC Specialties Group, Inc. Other non-ferrous corrosion inhibitors suitable to be used in the composition of the present invention would be readily apparent to one skilled in the art.
Another optional ingredient which may be used in the composition of the present invention is a dimer ester. The dimer ester is present in the composition in an amount of about 0 to about 5%, based upon the total weight of the composition. A suitable, commercially available dimer ester is EMERY® 2902 or EMERY® 2908 water-active lubricant basestocks, marketed by Emery Chemicals.
Yet another optional ingredient to be used in the composition of the present invention is a biocide, present in an amount of about 0 to about 4%, based on the total weight of the composition. Non-limiting examples of suitable biocides to be used in the present invention include 5-hydroxymethoxymethyl-l-aza-3 ,7-dioxabicyclo- (3.3.0)octane, 5-hydroxymethyl-l-aza-3 ,7-dioxabicyclo- (3.3.0)octane and 5-hydroxypoly[methyleneoxy(74% C,, 21% C,, 4% C , 1% C5)]methyl-l-aza-3,7-dioxabicyclo(3.3.0)octane. A suitable, commercially available biocide to be used in the present invention is BIOBAN® N-95, marketed by ANGUS Chemical Co. Other biocides to be used in the composition of the present invention would be readily apparent to one skilled in the art.
Still another optional ingredient to be used in the composition of the present invention is a perfume, present in an amount of up.to about 0.5% based on the total weight of the composition. The perfume is intended to impart a pleasant fragrance to the composition and/or the aqueous coolant. An example of a suitable perfume to be used in the present invention is an orange perfume, commercially available from Alpine Aromatics International. Other perfumes to be used in the composition of the present invention would be readily apparent to one skilled in the art. Another optional ingredient to be used in the composition of the present invention is a lubricant, for example, an ethoxylated and propoxylated polyalkylglycol, such as poly GWS 660, commercially available from Olin Chemical. Other optional ingredients to be used in the composition of the present invention intended to impart desirable properties to the composition and/or coolant would be readily apparent to one skilled in the art.
In a preferred embodiment of the present invention, the optional ingredients include about 0.1 to about 0.5% of a non-ferrous corrosion inhibitor, about 1 to about 5% of a dimer ester and about 1 to about 4% of a biocide.
The composition used to prepare the aqueous coolant for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking may be prepared according to a number of procedures. In a preferred method for preparing the composition of the present invention, all of the primary ingredients, namely, sebacic acid, glycerine, isononanoic acid and 6-[ (l-oxoisononyl)amino]hexanoic acid are added to the water. The optional ingredients, for example, a non- ferrous corrosion inhibitor, a dimer ester and a perfume, may also be added to the water at this stage of the preparation of the composition. However, of the optional ingredients, the biocide should not yet be added to the mixture. After all of the primary and selected optional ingredients, except the biocide, are combined in water to provide a mixture, the pH is adjusted with KOH until a pH of about 10 to about 10.5 is obtained. After the KOH has been added and a pH of about 10 to about 10.5 is obtained, the isononanoic acid and 6-[ (l-oxoisononyl)amino]hexanoic acid are present as the corresponding potassium salts. The sebacic acid is generally present as the dipotassium salt. This neutralization/basification process is exothermic due to the heat of neutralization. The temperature of the mixture generally rises to about 130-150*F during the neutralization/basification process. The mixture should be allowed to cool to below about 100*F, at which time, if desired, the biocide may be added to the mixture. After all of the desired ingredients are combined and the mixture is allowed to cool, the result is the composition.
As indicated, the composition of the present invention is used to prepare an aqueous coolant for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking. To obtain the aqueous coolant, the composition is diluted with additional water. Preferably, the composition is diluted with water at a ratio of about 1 part composition to about 20 parts water to about 1 part composition to about 40 parts water. It is critical that the resulting aqueous coolant has a pH of about 9.5 or less and more preferably, a pH of about 7.4 to about 8.1.
In accordance with the present invention, there is provided a process for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking operations and/or procedures. Examples of these metalworking operations and/or procedures include, for example, machining and grinding and any metal-removing or metal-forming operation. Examples of a metalworking apparatus or device includes, for example, a grinding wheel, a drill and a cutting wheel. These metalworking operations and/or procedures and metalworking apparatuses and devices are generally well known to those skilled in the art.
Suitable metals to be cooled and protected by the aqueous coolant of the present invention comprise ferrous metals, for example, cast iron and steel, and non-ferrous metals, such as aluminum. Examples of other metals to be cooled and protected by the aqueous coolant of the present invention during metalworking operations or procedures would be readily apparent to one skilled in the art.
According to the process for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking operations and/or procedures, a concentrate, namely the aforementioned composition, is provided, comprising primary ingredients including about 5 to about 20% sebacic acid, about 2 to about 15% glycerine, about 9 to about 27% isononanoic acid and about 1 to about 3%
6-[ (l-oxoisononyl)a ino]hexanoic acid, based upon the total weight of the concentrate. The concentrate further comprises an amount of KOH to provide the concentrate with a pH of about 10 to about 10.5, and water. The disclosure hereinbefore regarding the primary ingredients for the composition is incorporated herein for the concentrate. Further concerning the process for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking, the concentrate is diluted with additional water to provide a coolant. Preferably, the concentrate is diluted with additional water at a ratio of about 1 part concentrate to about 20 parts water to about 1 part concentrate to about 40 parts water. In addition, the resulting coolant must have a pH of about 9.5 or less.
After the coolant has been prepared, the metal is worked in the presence of the coolant, thereby cooling and protecting the metal workpiece and a metalworking apparatus or device from corrosion and rust.
In a preferred embodiment of the present invention, the concentrate comprises about 7 to about 15% sebacic acid, about 2 to about 6% glycerine, about 13.5 to about 18% isononanoic acid and about 1.5 to about 2%
6-[ (l-oxoisononyl)amino]hexanoic acid, based upon the total weight of the concentrate.
In a more preferred embodiment of the present invention, the concentrate comprises about 7.5 to about 10% sebacic acid, about 3.9 to about 4% glycerine, about 17.41 to about 18% isononanoic acid and about 1.93 to about 2% 6-[(l-oxoisononyl)amino]hexanoic acid, based upon the total weight of the concentrate.
In an even more preferred embodiment of the present invention, the concentrate comprises about 9.67% sebacic acid, about 3.9% glycerine, about 17.41% isononanoic acid, about 1.93% 6-[ (l-oxoisononyl)amino]hexanoic acid, about 25.56% of 45% aqueous KOH and about 37.39% water, based upon the total weight of the concentrate.
As with the composition, the concentrate may comprise optional ingredients to enhance the stability and other characteristics of the concentrate. For example, the concentrate, in addition to the aforementioned primary ingredients, may further comprise about 0.01 to about 0.5% of a non-ferrous corrosion inhibititor, about 0 to about 5% of a dimer ester, about 0 to about 4% of a biocide and up to about 0.5% of a perfume, based upon the total weight of the concentrate. These optional ingredients generally correspond to the optional ingredients contained in the composition, discussed hereinbefore. Accordingly, the discussion regarding the optional ingredients for the composition is incorporated herein by reference.
In a preferred embodiment of the process for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking, the concentrate comprises about 0.1 to about 0.5% of a non-ferrous corrosion inhibitor, about 1 to about 5% of a dimer ester and about 1 to about 4% of a biocide.
In an alternate embodiment of the present invention, the process for cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking comprises initially beginning with the coolant. This obviates the need for initially preparing the concentrate and/or composition, followed by diluting the concentrate and/or composition with additional water. The coolant comprises primary ingredients, including about 0.125 to about 1% sebacic acid, about 0.05 to about 0.75% glycerine, about 0.225 to about 1.35% isononanoic acid and about 0.025 to about 0.15% 6- [(l-oxoisononyl)a ino]hexanoic acid, based on the total weight of the coolant. The coolant further comprises primary ingredients of an amount of KOH to provide the coolant with a pH of about 9.5 or less, and water. The process further comprises working the metal in the presence of the coolant, thereby cooling and protecting the metal workpiece and the metalworking apparatus or device from corrosion and rust. These primary ingredients correspond to the primary ingredients for the composition and the concentrate, discussed hereinbefore. Accordingly, the discussion regarding the primary ingredients for the composition and the concentrate are incorporated herein by reference.
In a preferred alternate embodiment, the coolant comprises about 0.175 to about 0.75% sebacic acid, about 0.05 to about 0.3% glycerine, about 0.338 to about 0.9% isononanoic acid and about 0.038 to about 0.1% 6-[(l- oxoisononyl)amino]hexanoic acid, based on the total weight of the coolant. In a more preferred alternate embodiment, the coolant comprises about 0.188 to about 0.5% sebacic acid, about 0.098 to about 0.2% glycerine, about 0.435 to about 0.9% isononanoic acid and about 0.048 to about 0.1% 6- [(l-oxoisononyl)amino]hexanoic acid, based on the total weight of the coolant.
In an even more preferred alternate embodiment of the present invention, the coolant comprises about 0.242 to about 0.484% sebacic acid, about 0.098 to about 0.195% glycerine, about 0.435 to about 0.871% isononanoic acid ajnd about 0.048 to about 0.097% 6-[ (l-oxoisononyl)amino]- hexanoic acid. As with the previous embodiment, the coolant in the process of the present alternate embodiment may comprise optional ingredients. These optional ingredients correspond to the optional ingredients described with reference to the composition and the concentrate. A preferred range of these optional ingredients in the coolant is about 2.5 x 10 -4 to about 0.25% of a non-ferrous corrosion inhibitor, about 0 to about 0.25% of a dimer ester, about 0 to about 0.2% of a biocide and up to about 0.025% of a perfume. More preferably, the coolant comprises about 2.5 x
10 to about 0.25% of a non-ferrous corrosion inhibitor, about 0.025 to about 0.25% of a dimer ester and about 0.025 to about 0.2% of a biocide.
The present invention will now be described in more detail with reference to the following specific, non- limiting examples.
General Parameters for the Examples To evaluate the efficacy of the compositions and/or aqueous coolants of the present invention in cooling and protecting a metal workpiece and a metalworking apparatus or device from corrosion and rust during metalworking, the compositions and/or aqueous coolants are evaluated using a "Modified Herbert Rust Test." This test is designed as a relative determination of the corrosion threεhhold concentration of metalworking fluids on cast iron. The test comprises grinding the surface of a test block which comprises a 1-3/4-inch type "S" cast iron pipe plug to a near mirror finish. The test block is then cleaned with isopropyl alcohol. The desired aqueous coolant is formulated and placed in a 4-oz. jar. Cast iron chips (1 gram) obtained from machining and grinding operations are added to the jars and the aqueous coolant and the cast iron chip/coolant mixture iε εha en and allowed to soak for 5 minutes. The resulting mixture iε poured over the cast iron test block, retaining the chips on the surface of the blocks. Excess liquid from the block is then drained and the block is placed into a humidity cabinet containing 1/2 inch distilled water. After allowing the block to stand for 18 hours in the humidity cabinet, the chips are εcraped from the surface of the block and the percentage of blush rust and degree of contact rust is recorded.
Example 1 A εerieε of aqueouε coolants were prepared as indicated in Table 1. Table 1 alεo εetε forth the laεt dilution at which the block did not rust, unlesε otherwiεe indicated. The higher the dilution, the more effective the coolant in preventing ruεt.
Table 1 Sample No.
Ingredient 10 11 water 44.1 44.1 44.1 44.1 44.1 49.1 49.1 49.1 46.36 46.37 40 5 isononanoic acid 15 10 20 20
OAHA
HOSTACOR* TP-2291 20 10 - - 20 20 20 20
KOH (45%) 22.89 22.89 22.89 22.89 22.89 22.89 22.89 22.89 22.89 20.38 25.53 poly GUS660 4 4 4 4 4 4 4 4 10 Emery 2908 2 2 2 2 2 2 2 2 2 2 2
Cobratec 99 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.25 0.25 0.25
Bioban N-95 2 2 2 2 2 2 2 2 2 2 2
Sebacic Acid 10 15 5 5 15 20 2.5 5 7.5
Glycerine 4 4 4 15 neodecanoic acid pH (5* dilution) 7.6- 8.0- 7.7 8.1 modified Herbert 1:20 P 1:20 P 1:20 P 1:30 F 1:30 F 1:20 P 1:20 F 1:20 P 1:20 P 1:30 P 1:30 P (P/F)
20
OAHA indicates 6-[(l-oxoiβononyl)aalnojhexanolc acid; P Indicates pass; and F indicates fail
Figure imgf000020_0001
OAHA indicates 6-[(l-oxoisononyl)amino)hexanoic acid; P Indicates pass; and F indicates fall
The foregoing Table demonstrates that aqueous coolants 12, 22 and 23 according to the present invention are the most effective coolants for cooling and protecting a metal workpiece from corrosion and rust during metalworking. Aqueous coolants 12, 22 and 23 are effective at a greater dilution (1:40, or a 2.5% v/v concentration) than the other aqueous coolants set forth in Table 1.
At dilutions less than 1:30, the compositions are not commercially acceptable in view of cost considerationε. Moreover, some of the prior art type of commercially available coolantε lose their effectivenesε over time, due to a breakdown or leaching out or other decrease in effectiveness of the ingredients.
The coolantε of the preεent invention not only are capable of effective cooling and corroεion protection at high dilution ratioε of 1:30 and greater, but also, they are stable and effective for a long period of time. The coolants of the preεent invention do not appear to break down, leach out or have their effectiveneεε diminiεhed compared to the prior art commercial coolantε.
The preεent invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof and, accordingly, reference should be made to the appended claims, rather than to the foregoing εpecification as indicating the scope of the invention.

Claims

1. A compoεition compriεing about 5 to about 20% sebacic acid, about 2 to about 15% glycerine, about 9 to about 27% isononanoic acid, about 1 to about 3% 6-[(l- oxoiεononyl)amino]hexanoic acid, an amount of KOH to provide the composition with a pH of about 10 to about 10.5, and water.
2. The composition of claim 1 comprising about 7 to about 15% sebacic acid, about 2 to about 6% glycerine, about 13.5 to about 18% isononanoic acid and about 1.5 to about 2% 6-[ (l-oxoiεononyl)amino]hexanoic acid.
3. The composition of claim 1 compriεing about 7.5 to about 10% εebacic acid, about 3.9 to about 4% glycerine, about 17.41 to about 18% iεononanoic acid and about 1.93 to about 2% 6-[ (1-oxoisononyl) ino]hexanoic acid.
4. The composition of claim 1 further comprising about 0.01 to about 0.5% of a non-ferrous corrosion inhibitor, about 0 to about 5% of a dimer ester, about 0 to about 4% of a biocide and up to about 0.5% of a perfume.
5. The composition of claim 4 comprising about 0.1 to about 0.5% of a non-ferrous corrosion inhibitor, about 1 to about 5% of a dimer ester and about 1 to about 4% of a biocide.
6. The compoεition of claim 1 comprising about 9.67% sebacic acid, about 3.9% glycerine, about 17.41% isononanoic acid, about 1.93% 6-[ (l-oxoisononyl)amino]- hexanoic acid, about 25.56% of 45% aqueous KOH and about 37.39% water.
7. The composition of claim 1 comprising an amount of additional water to dilute the composition to about 1:20 to about 1:40, the diluted composition having a pH of about 9.5 or less.
8. The diluted composition of claim 7 having a pH of about 7.4 to about 8.1.
9. A procesε for cooling and protecting a metal workpiece from corrosion and rust during metalworking comprising (a) providing a concentrate compriεing about
5 to about 20% sebacic acid, about 2 to about 15% glycerine, about 9 to about 27% iεononanoic acid, about 1 to about 3% 6-[ (l-oxoisononyl)amino]hexanoic acid, an amount of KOH to provide the concentrate with a pH of about 10 to about 10.5, and water;
(b) diluting the concentrate with additional water to about 1:20 to about 1:40 to provide a coolant having a pH of about 9.5 or lesε; and
(c) working the metal in the preεence of the coolant.
10. The process of claim 9 wherein the concentrate compriseε about 7 to about 15% sebacic acid, about 2 to about 6% glycerine, about 13.5 to about 18% isononanoic acid and about 1.5 to about 2% 6-[(l- oxoiεononyl)amino]hexanoic acid.
11. The process of claim 9 wherein the concentrate comprises about 7.5 to about 10% sebacic acid, about 3.9 to about 4% glycerine, about 17.41 to about 18% isononanoic acid and about 1.93 to about 2% 6-[(l-oxoisononyl)amino]hexanoic acid.
12. The procesε of claim 11 wherein the concentrate further compriεeε about 0.01 to about 0.5% of a non-ferrouε corroεion inhibitor, about 0 to about 5% of a dimer eεter, about 0 to about 4% of a biocide and up to about 0.5% of a perfume.
13. The process of claim 12 wherein the concentrate comprises about 0.1 to about 0.5% of a non- ferrous corrosion inhibitor, about 1 to about 5% of a dimer ester and about 1 to about 4% of a biocide.
14. The procesε of claim 9 wherein the concentrate compriseε about 9.67% sebacic acid, about 3.9% glycerine, about 17.41% isononanoic acid, about 1.93% 6-[ (l-oxoisononyl)amino]hexanoic acid, about 25.56% of 45% aqueouε KOH and about 37.39% water.
15. A proceεε for cooling and protecting a metal workpiece from corroεion and ruεt during metalworking comprising (a) providing a coolant compriεing about 0.125 to about 1% εebacic acid, about 0.05 to about 0.75% glycerine, about 0.225 to about 1.35% iεononanoic acid, about 0.025 to about 0.15% 6-[ (l-oxoisononyl)amino]hexanoic acid, an amount of KOH to provide the coolant with a pH of about 9.5 or less, and water; and
(b) working the metal in the presence of the coolant.
16. The process of claim 15 wherein the coolant comprises about 0.175 to about 0.75% sebacic acid, about
0.05 to about 0.3% glycerine, about 0.338 to about 0.9% isononanoic acid and about 0.038 to about 0.1% 6-[(l- oxoiεononyl)amino]hexanoic acid.
17. The process of claim 15 wherein the coolant compriseε about 0.188 to about 0.5% εebacic acid, about
0.098 to about 0.2% glycerine, about 0.435 to about 0.9% iεonanonanoic acid and about 0.048 to about 0.1% 6-[ (l-oxoiεononyl)amino]hexanoic acid.
18. The proceεε of claim 15 wherein the coolant
-4 further compriεes about 2.5 x 10 to about 0.25% of a non- ferrouε corrosion inhibitor, about 0 to about 0.25% of a dimer ester, about 0 to about 0.2% of a biocide and up to about 0.025% of a perfume.
19. The proceεε of claim 18 wherein the coolant
—3 comprises about 2.5 x 10 to about 0.25% of a non-ferrouε corroεion inhibitor, about 0.025 to about 0.25% of a dimer ester and about 0.025 to about 0.2% of a biocide.
20. The process of claim 9 wherein the coolant compriεeε about'0.242 to about 0.484% sebacic acid, about 0.098 to about 0.195% glycerine, about 0.435 to about 0.871% isononanoic acid and about 0.048 to about 0.097% 6-[(l-oxoisononyl)amino]hexanoic acid.
PCT/US1991/004429 1990-07-03 1991-06-21 Aqueous coolant WO1992001029A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US54788590A 1990-07-03 1990-07-03
US547,885 1995-10-25

Publications (1)

Publication Number Publication Date
WO1992001029A1 true WO1992001029A1 (en) 1992-01-23

Family

ID=24186545

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1991/004429 WO1992001029A1 (en) 1990-07-03 1991-06-21 Aqueous coolant

Country Status (2)

Country Link
AU (1) AU8057491A (en)
WO (1) WO1992001029A1 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0556087A1 (en) * 1992-02-14 1993-08-18 Elf Atochem S.A. Corrosion inhibitor composition based on carboxylic acid and its use in inhibiting corrosion
EP0573287A1 (en) * 1992-06-03 1993-12-08 Texaco Development Corporation Heat transfer fluid corrosion inhibitors
WO1994017221A1 (en) * 1993-01-22 1994-08-04 Buckman Laboratories International, Inc. Chemical agents and method for the inhibition of corrosion and deposit formation in water systems
EP1010740A1 (en) * 1998-12-16 2000-06-21 Setuza a.s. Concentrated and diluted cooling liquid
WO2006092376A1 (en) 2005-02-28 2006-09-08 Basf Aktiengesellschaft Glycerin-containing antifreezing agent concentrates with corrosion protection
WO2009026916A2 (en) * 2007-08-30 2009-03-05 Technische Universität Braunschweig Cooling lubricant
WO2018035477A1 (en) 2016-08-19 2018-02-22 Arena Pharmaceuticals, Inc. 5-ht2c receptor agonists and compositions and methods of use
CN112812755A (en) * 2020-12-23 2021-05-18 杭州富通电线电缆有限公司 Copper rod manufacturing method
LU101645B1 (en) * 2020-02-17 2021-08-17 Metall Chemie Tech Gmbh Amino Acids as Green Neutralizing Agent for Acidic Corrosion Inhibitors

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4448702A (en) * 1981-10-12 1984-05-15 Lang & Co., Chemisch-Technische Produkte Kommanditgesellschaft Freezing-point-lowering composition and method
US4493780A (en) * 1981-03-30 1985-01-15 Basf Wyandotte Corporation Water-based hydraulic fluids having improved lubricity and corrosion inhibiting properties
US4587028A (en) * 1984-10-15 1986-05-06 Texaco Inc. Non-silicate antifreeze formulations
US4647392A (en) * 1985-12-27 1987-03-03 Texaco Inc. Monobasic-dibasic acid/salt antifreeze corrosion inhibitor
US4717495A (en) * 1984-11-30 1988-01-05 Fleetguard, Inc. Diesel engine cooling system compositions
US4759864A (en) * 1987-09-04 1988-07-26 Texaco Inc. & S.A. Texaco Petro, N.V. Corrosion-inhibited antifreeze formulation
US4770803A (en) * 1986-07-03 1988-09-13 The Lubrizol Corporation Aqueous compositions containing carboxylic salts
US4869841A (en) * 1982-12-27 1989-09-26 Bp Chimie S.A. Process for the treatment of aqueous fluids to reduce corrosion comprising dicarboxylic aliphatic acid salt and polyol
US4946616A (en) * 1988-11-14 1990-08-07 The Dow Chemical Company Heat transfer fluids containing dicarboxylic acid mixtures as corrosion inhibitors

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4493780A (en) * 1981-03-30 1985-01-15 Basf Wyandotte Corporation Water-based hydraulic fluids having improved lubricity and corrosion inhibiting properties
US4448702A (en) * 1981-10-12 1984-05-15 Lang & Co., Chemisch-Technische Produkte Kommanditgesellschaft Freezing-point-lowering composition and method
US4869841A (en) * 1982-12-27 1989-09-26 Bp Chimie S.A. Process for the treatment of aqueous fluids to reduce corrosion comprising dicarboxylic aliphatic acid salt and polyol
US4587028A (en) * 1984-10-15 1986-05-06 Texaco Inc. Non-silicate antifreeze formulations
US4717495A (en) * 1984-11-30 1988-01-05 Fleetguard, Inc. Diesel engine cooling system compositions
US4647392A (en) * 1985-12-27 1987-03-03 Texaco Inc. Monobasic-dibasic acid/salt antifreeze corrosion inhibitor
US4770803A (en) * 1986-07-03 1988-09-13 The Lubrizol Corporation Aqueous compositions containing carboxylic salts
US4759864A (en) * 1987-09-04 1988-07-26 Texaco Inc. & S.A. Texaco Petro, N.V. Corrosion-inhibited antifreeze formulation
US4946616A (en) * 1988-11-14 1990-08-07 The Dow Chemical Company Heat transfer fluids containing dicarboxylic acid mixtures as corrosion inhibitors

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0556087A1 (en) * 1992-02-14 1993-08-18 Elf Atochem S.A. Corrosion inhibitor composition based on carboxylic acid and its use in inhibiting corrosion
US5507861A (en) * 1992-02-14 1996-04-16 Elf Atochem S.A. And Haber Partners Sarl Carboxylic acid-based corrosion-inhibiting composition and application thereof in corrosion prevention
EP0573287A1 (en) * 1992-06-03 1993-12-08 Texaco Development Corporation Heat transfer fluid corrosion inhibitors
WO1994017221A1 (en) * 1993-01-22 1994-08-04 Buckman Laboratories International, Inc. Chemical agents and method for the inhibition of corrosion and deposit formation in water systems
EP1010740A1 (en) * 1998-12-16 2000-06-21 Setuza a.s. Concentrated and diluted cooling liquid
US8454854B2 (en) 2005-02-28 2013-06-04 Basf Se Glycerin-containing antifreezing agent concentrates with corrosion protection
US7927505B2 (en) 2005-02-28 2011-04-19 Basf Aktiengesellschaft Glycerin-containing antifreezing agent concentrates with corrosion protection
WO2006092376A1 (en) 2005-02-28 2006-09-08 Basf Aktiengesellschaft Glycerin-containing antifreezing agent concentrates with corrosion protection
KR101437690B1 (en) * 2005-02-28 2014-09-03 바스프 에스이 Glycerol-containing antifreeze concentrates with corrosion protection
WO2009026916A2 (en) * 2007-08-30 2009-03-05 Technische Universität Braunschweig Cooling lubricant
WO2009026916A3 (en) * 2007-08-30 2009-06-18 Univ Braunschweig Tech Cooling lubricant
WO2018035477A1 (en) 2016-08-19 2018-02-22 Arena Pharmaceuticals, Inc. 5-ht2c receptor agonists and compositions and methods of use
LU101645B1 (en) * 2020-02-17 2021-08-17 Metall Chemie Tech Gmbh Amino Acids as Green Neutralizing Agent for Acidic Corrosion Inhibitors
WO2021165311A1 (en) * 2020-02-17 2021-08-26 Metall Chemie Technologies Gmbh Amino acids as green neutralizing agent for acidic corrosion inhibitors
CN112812755A (en) * 2020-12-23 2021-05-18 杭州富通电线电缆有限公司 Copper rod manufacturing method

Also Published As

Publication number Publication date
AU8057491A (en) 1992-02-04

Similar Documents

Publication Publication Date Title
CA1084688A (en) Corrosion inhibitor for metal surfaces
EP0069960B1 (en) Machining fluid of water soluble type using organic surfactants
US4313837A (en) Using molybdates to inhibit corrosion in water-based metalworking fluids
JP2009536254A (en) Metal working fluid containing neutralized fatty acids
CN106916615B (en) Composite corrosion inhibitor of water-based cutting fluid, preparation method and water-based cutting fluid
WO1992001029A1 (en) Aqueous coolant
CA1169337A (en) Process and compositions for the passivation of iron and steel surfaces
JPS59147093A (en) Method of machining cast iron and aqueous condensate solution therefor
JPH0119958B2 (en)
WO1999061683A1 (en) Corrosion inhibiting compositions and aqueous metal working compositions
JP2000154392A (en) Cutting oil composition
JPH0237959B2 (en)
JPS6116352B2 (en)
JPH10110183A (en) Grinding agent
DE19959588A1 (en) Metal treatment liquid for the neutral pH range
CA1161026A (en) Inherently bactericidal metal working fluid
JP2003041285A (en) Water-soluble cutting and grinding oil for aluminum or its alloy
US5468412A (en) Low foaming aqueous cleaning and passivating treatment for metals
WO2000052230A1 (en) Corrosion inhibitor and process
WO2000014190A1 (en) A method for mechanical working in the presence of a cobalt-containing metal
JP7019224B1 (en) Water-soluble rust inhibitor composition and its usage
EP1115817A1 (en) Mechanical working in the presence of a metal containing copper or aluminum
JP3148395B2 (en) Lubricant composition
JPS6115119B2 (en)
JP6216665B2 (en) Water-soluble functional fluid with rot resistance

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BB BG BR CA CS FI HU JP KP KR LK MC MG MN MW NO PL RO SD SU

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE BF BJ CF CG CH CI CM DE DK ES FR GA GB GN GR IT LU ML MR NL SE SN TD TG

NENP Non-entry into the national phase

Ref country code: CA