WO2003080895A1 - Corrosion inhibiting salts, concentrates and metal working fluids containing same - Google Patents

Corrosion inhibiting salts, concentrates and metal working fluids containing same Download PDF

Info

Publication number
WO2003080895A1
WO2003080895A1 PCT/US2003/008245 US0308245W WO03080895A1 WO 2003080895 A1 WO2003080895 A1 WO 2003080895A1 US 0308245 W US0308245 W US 0308245W WO 03080895 A1 WO03080895 A1 WO 03080895A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
composition
formula
carbon atoms
mixture
Prior art date
Application number
PCT/US2003/008245
Other languages
French (fr)
Inventor
Frederick L. Cuneo
Gregory Moran
Maya Naik
Original Assignee
The Lubrizol 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 The Lubrizol Corporation filed Critical The Lubrizol Corporation
Priority to AU2003220376A priority Critical patent/AU2003220376A1/en
Publication of WO2003080895A1 publication Critical patent/WO2003080895A1/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
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C23F11/143—Salts of amines
    • 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
    • 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
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/22—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • C10M2215/222—Triazines
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/226—Morpholines
    • 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • 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
    • C10M2223/04—Phosphate esters
    • 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
    • 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • This invention relates to corrosion inhibiting salts for metal working fluids, and to concentrates and metal working fluids containing such corrosion inhibiting salts.
  • Metal working operations for example, rolling, forging, hot-pressing, blanking, bending, stamping, drawing, cutting, punching, spinning and the like generally employ a lubricant to facilitate the same.
  • Metal working fluids e.g., lubricants, cutting fluids, and the like
  • These metal working fluids are often oil-based, but for many applications there is a desire to replace such oil-based metal working fluids with water-based metal working fluids.
  • a problem with many water-based metal working fluids is that they often contain trace amounts of nitrites. These may be contributed to the fluid by additives used to inhibit corrosion. The presence of such nitrites can lead to the formation of nitrosamines which are carcinogenic and can present a problem for the individuals working with such fluids.
  • the problem therefore is to provide a water-based metal working fluid that is nitrite free.
  • the present invention provides a solution to this problem by providing a corrosion inhibitor for metal working fluids which is nitrite free.
  • This invention relates to a composition, comprising: a salt derived from
  • R 1 and R 2 are independently hydrocarbyl groups; R 3 is an alkylene group; and the total number of carbon atoms in R 1 , R 2 and R 3 is from about 3 to about 20 carbon atoms, and
  • the invention also relates to concentrates and metal working fluids containing the foregoing composition. Detailed Description of the Invention
  • hydrocarbyl refers to groups attached to a molecule having a purely hydrocarbon or predominantly hydrocarbon character within the context of this invention. Such groups include the following:
  • Hetero groups that is, groups which, while predominantly hydrocarbon in character, contain atoms other than carbon in a chain or ring otherwise composed of carbon atoms. Examples include nitrogen, oxygen and sulfur. In general, no more than about three substituents or hetero atoms, and in one embodiment no more than one, will be present for each 10 carbon atoms in the hydrocarbyl group.
  • lower as used herein in conjunction with terms such as hydrocarbyl, alkyl, alkenyl, alkoxy, and the like, is intended to describe such groups which contain a total of up to 7 carbon atoms.
  • water-soluble refers to materials that are soluble in water to the extent of at least 0.5 gram per 100 milliliters of water at 25 m C.
  • the inventive salt compositions are made by reacting (A) an acid- containing composition with (B) at least one alkanol amine. These salt compositions are water-soluble.
  • the weight ratio of (A) to (B) may range from about 1 :1 to about 10:1 , and in one embodiment about 1 :1 to about 5:1.
  • the salt compositions are formed by mixing (A) and (B) together, heating the mixture with agitation at a temperature of about 30 m C to about 60 m C, and in one embodiment about 40 C to about 50 m C, until a clear liquid is formed. The reaction mixture is then cooled to room temperature to provide the inventive salt composition.
  • These salt compositions are useful as corrosion inhibiting additives for water-based metal working fluids. In one embodiment, these salt compositions are also useful as lubricity additives.
  • An advantage of these salt compositions is that they are nitrite free. Another advantage is that they are boron free.
  • the acid-containing composition (A) is comprised of at least one carboxylic acid represented by the formula
  • R 1 and R 2 are independently hydrocarbyl groups; R 3 is an alkylene group; and the total number of carbon atoms in R 1 , R 2 and R 3 is from about 3 to about 20 carbon atoms.
  • R 1 and R 2 independently may contain 1 to about 8 carbon atoms, and in one embodiment 1 to about 4 carbon atoms.
  • R 1 and R 2 may independently be straight chain or branched chain groups.
  • R 1 and R 2 may together form a cyclic group.
  • R 1 and R 2 are each alkyl groups.
  • R 1 and R 2 are methyl groups.
  • R 3 may contain 1 to about 10 carbon atoms, and in one embodiment, 1 to about 8 carbon atoms.
  • R 3 may be a straight chain alkylene group, or it may have hydrocarbyl (e.g., alkyl) groups attached to it.
  • useful compounds include isnonanoic acid, neodecanoic acid, and the like.
  • the concentration of this acid in the acid-containing composition (A) may range from about 1 to about 99 percent by weight based on the weight of the acid-containing composition (A), and in one embodiment about 5 to about 70 percent by weight, and in one embodiment from about 10 to about 40 percent by weight.
  • the acid-containing composition (A) may further comprise at least one phosphate ester.
  • the phosphate ester may be a compound represented by the formulae
  • R 1 is a hydrocarbyl group
  • R 2 is an alkylene group
  • n is a number in the range of about 1 to about 10, and in one embodiment about 2 to about 6.
  • R 1 may contain 1 to about 10 carbon atoms, and in one embodiment 1 to about 8 carbon atoms.
  • R 1 may be a straight chain or branched chain group.
  • R 1 is an alkyl group.
  • R 2 may contain 1 to about 10 carbon atoms, and in one embodiment about 2 to about 4 carbon atoms.
  • Examples of useful compounds include those compounds made by reacting P 2 0 5 with UCON Lubricant 50-HB-100 which is a product of Union Carbide identified as a polyalkylene glycol monobutyl ether.
  • the concentration of this ester in the acid-containing composition (A) may range from up to about 99 percent by weight based on the weight of the composition (A), and in one embodiment about 0.2 to about 60 percent by weight, and in one embodiment from about 0.5 to about 30 percent by weight.
  • the acid-containing composition (A) may further comprise at least one compound represented by the formula R 2
  • R 1 and R 2 independently may contain 1 to about 10 carbon atoms, and in one embodiment 1 to about 8 carbon atoms.
  • R 1 and R 2 may independently be straight chain or branched chain groups.
  • R 1 is a phenyl group or an alkyl (e.g., methyl) substituted phenyl group
  • R 2 is hydrogen.
  • R 3 may contain 1 to about 10 carbon atoms, and in one embodiment, 1 to about 8 carbon atoms.
  • R 3 may be a straight chain alkylene group, or it may have hydrocarbyl (e.g., alkyl) groups attached to it.
  • An example of a useful compound is 6[[(4-methyl- phenyl) sulfonyl] amino] hexanoic acid.
  • the concentration of this acid in the acid-containing composition (A) may range up to about 50 percent by weight based on the weight of the acid-containing composition (A), and in one embodiment from about 10 to about 40 percent by weight.
  • the acid containing composition (A) may further comprise at least one compound represented by the formula
  • R 1 , R 3 and R 5 are independently hydrogen or hydrocarbyl groups, and R 2 , R 4 and R 6 are independently alkylene groups.
  • R 1 , R 3 and R 5 independently may be hydrogen or hydrocarbyl groups containing 1 to about 10 carbon atoms, and in one embodiment 1 to about 8 carbon atoms.
  • R 1 , R 3 and R 5 are each hydrogen.
  • R 2 , R 4 and R 6 may independently contain 1 to about 10 carbon atoms, and in one embodiment, 1 to about 8 carbon atoms.
  • Examples of useful compounds include hexanoic acid-6,6 1 ,6"-(1 ,3,5-triazin-2,4,6- triyltriim).
  • concentration of this acid in the acid-containing composition (A) may range up to about 10 percent by weight based on the weight of the acid-containing composition (A), and in one embodiment from about 0.5 to about 5 percent by weight.
  • the alkanol amine (B) may be a primary, secondary or tertiary alkanol amine, or mixture thereof.
  • the alkanol amine may be an ether amine. These amines may be represented by the formulae:
  • R 1 is an alkylene group
  • R 2 and R 3 are independently hydrogen or hydrocarbyl groups.
  • R 1 may contain 2 to about 18 carbon atoms, and in one embodiment 2 to about 8 carbon atoms, and in one embodiment 2 to about 4 carbon atoms.
  • R 1 and R 2 may independently be hydrocarbyl groups of 1 to about 8 carbon atoms or hydroxyl-substituted hydrocarbyl groups of 2 to about 8 carbon atoms, x may be a number in the range of 2 to about 15.
  • alkanolamines examples include mono-, di-, and triethanol amine, dimethethanol amine, diethylethanol amine, di-(3- hydroxyl propyl) amine, N-(3-hydroxyl butyl) amine, N-(4-hydroxyl butyl) amine, N,N-di-(2-hydroxyl propyl) amine, N-(2-hydroxyl ethyl) morpholine, N-(2- hydroxyl ethyl) cyclohexyl amine, N-3-hydroxyl cyclopentyl amine, o-, m- and p- aminophenol, N-(hydroxyl ethyl) piperazine, N,N'-di(hydroxyl ethyl) piperazine, and the like.
  • the alkanol amine (B) is comprised of a mixture of monoethanolamine and triethanolamine.
  • the weight ratio of monoethanolamine to triethanolamine may range from about 1 :100 to about 20:100, and in one embodiment about 3:100 to about 15:100, and in one embodiment about 5:100 to about 10:100, and in one embodiment about 5:65.
  • all parts and percentages are by weight, and all temperatures are in degrees Celsius.
  • Neodecanoic acid 25.4%
  • step (A) (30 parts) is mixed with triethanolamine (65 parts) and monoethanolamine (5 parts) and heated with agitation to a temperature in the range of 110 F (43.3 m C) to 120 m F (48.9 C) until a clear liquid is formed.
  • the resulting mixture is cooled to room temperature to provide the desired product.
  • Step (B) The product from step (A) (30 parts) is mixed with triethanolamine (65 parts) and monoethanolamine (5 parts) and heated with agitation to a temperature in the range of 110 m F (43.3 m C) to 120 m F (48.9 m C) until a clear liquid is formed. The resulting mixture is cooled to room temperature to provide the desired product.
  • Example 3 A partially neutralized acid mixture is prepared by mixing isononanic acid
  • step (A) The product from step (A) (54.5 parts) is mixed with triethanolamine (42.0 parts) and monoethanolamine (3.5 parts) and heated with agitation to a temperature in the range of 110 m F (43.3 C) to 120 m F (48.9 m C) until a clear liquid is formed. The resulting mixture is cooled to room temperature to provide the desired product.
  • the products from Examples 1-3 are tested for their anti-corrosion properties using three known anti-corrosion tests, namely DIN51 360, IP287 and IP125. The results of these tests are indicated below.
  • the results for the DIN51 360 test are reported in terms of the concentration of product from each example required to achieve no staining.
  • the results for the IP 287 and IP125 tests are expressed in terms of the concentration of product from each example required to reach the break point, that is, the point at which there is a significant increase in the area stained.
  • Product DIN 51 360 IP287 IP125 Example 1 2.50% 1.25% 0.50%
  • inventive salt compositions may be employed in the inventive metal working fluids at a concentration in the range of about .001 to about 50 percent by weight, and in one embodiment about 0.01 to about 30 percent by weight, and in one embodiment about 0.03 to about 10 percent by weight, and in one embodiment about 0.05 to about 5 percent by weight, and in one embodiment about 0.05 to about 2 percent by weight.
  • the inventive metal working fluids are water-based metal working fluids which may include other conventional additives commonly employed in water- based metal working fluids. These other additives include lubricity additives, dispersants, surfactants, additives for adjusting the pH of the fluid, shear stabilizing agents, bactericides, dyes, water-softeners, odor masking agents, anti-foam agents, and the like. When used, each of these additives is typically employed in the metal working fluids at concentrations of up to about 5% by weight, and in one embodiment up to about 1 % by weight.
  • the concentrates are analogous to the metal working fluids except that they contain less water and proportionately more of the other ingredients. Typically, the concentrates contain from about 10% to about 90% by weight of the inventive salt compositions.
  • the concentrates can be converted to metal working fluids by dilution with water. This dilution is usually done by standard mixing techniques. This is often a convenient procedure since the concentrate can be shipped to the point of use before additional water is added. Thus, the cost of shipping a substantial amount of the water in the final metal working fluid is saved. Only the water necessary to formulate the concentrate (which is determined primarily by ease of handling and convenience factor), need be shipped. Generally these metal working fluids are made by diluting the concentrates with water, wherein the ratio of water to concentrate is in the range of about 10:1 to about 40:1 by weight.
  • UCON EPML-X product of Union Carbide identified as poly- alkalkylene glycol lubricity additive
  • metal working fluids are prepared by adding water to the foregoing concentrates (all numerical values being in percent by weight): Metal Working Fluid Concentrate %Concentrate %Added Water

Abstract

This invention relates to to a composition, comprising: a salt derived from (A) an acid-containing composition comprising at least one carboxylic acid represented by the formula wherein in formula (A-1), R?1 and R2¿ are independently hydrocarbyl groups, R3 is an alkylene group, and the total number of carbon atoms in R?1 , R?2 and R3¿ is from about 3 to about 20 carbon atoms, and (B) at least one alkanolamine. The invention also relates to concentrates and metal working fluids containing the foregoing composition.

Description

TITLE: CORROSION INHIBITING SALTS, CONCENTRATES AND
METAL WORKING FLUIDS CONTAINING SAME
Technical Field
This invention relates to corrosion inhibiting salts for metal working fluids, and to concentrates and metal working fluids containing such corrosion inhibiting salts.
Background of the Invention Metal working operations, for example, rolling, forging, hot-pressing, blanking, bending, stamping, drawing, cutting, punching, spinning and the like generally employ a lubricant to facilitate the same. Metal working fluids (e.g., lubricants, cutting fluids, and the like) greatly improve these operations in that they can reduce the power required for the operation, prevent sticking and decrease wear of dies, cutting bits and the like. In addition, they frequently provide rust inhibiting properties to the metal being treated. These metal working fluids are often oil-based, but for many applications there is a desire to replace such oil-based metal working fluids with water-based metal working fluids.
A problem with many water-based metal working fluids is that they often contain trace amounts of nitrites. These may be contributed to the fluid by additives used to inhibit corrosion. The presence of such nitrites can lead to the formation of nitrosamines which are carcinogenic and can present a problem for the individuals working with such fluids. The problem therefore is to provide a water-based metal working fluid that is nitrite free. The present invention provides a solution to this problem by providing a corrosion inhibitor for metal working fluids which is nitrite free. Summary of the Invention
This invention relates to a composition, comprising: a salt derived from
(A) an acid-containing composition comprising at least one carboxylic acid represented by the formula
R1-C-R3-COOH (A-l)
R2 wherein in formula (A-l): R1 and R2 are independently hydrocarbyl groups; R3 is an alkylene group; and the total number of carbon atoms in R1 , R2 and R3 is from about 3 to about 20 carbon atoms, and
(B) at least one alkanol amine.
The invention also relates to concentrates and metal working fluids containing the foregoing composition. Detailed Description of the Invention
The term "hydrocarbyl" refers to groups attached to a molecule having a purely hydrocarbon or predominantly hydrocarbon character within the context of this invention. Such groups include the following:
(1) Purely hydrocarbon groups; that is, aliphatic, alicyclic, aromatic, aliphatic- and alicyclic-substituted aromatic, aromatic-substituted aliphatic and alicyclic groups, and the like, as well as cyclic groups wherein the ring is completed through another portion of the molecule (that is, any two indicated substituents may together form an alicyclic group). Examples include methyl, octyl, cyclohexyl, phenyl, etc. (2) Substituted hydrocarbon groups; that is, groups containing non-hydrocarbon substituents which do not alter the predominantly hydrocarbon character of the group. Examples include hydroxy, nitro, cyano, alkoxy, acyl, sulfinyl, sulfonyl, etc.
(3) Hetero groups; that is, groups which, while predominantly hydrocarbon in character, contain atoms other than carbon in a chain or ring otherwise composed of carbon atoms. Examples include nitrogen, oxygen and sulfur. In general, no more than about three substituents or hetero atoms, and in one embodiment no more than one, will be present for each 10 carbon atoms in the hydrocarbyl group.
The term "lower" as used herein in conjunction with terms such as hydrocarbyl, alkyl, alkenyl, alkoxy, and the like, is intended to describe such groups which contain a total of up to 7 carbon atoms.
The term "water-soluble" refers to materials that are soluble in water to the extent of at least 0.5 gram per 100 milliliters of water at 25mC.
The inventive salt compositions are made by reacting (A) an acid- containing composition with (B) at least one alkanol amine. These salt compositions are water-soluble. The weight ratio of (A) to (B) may range from about 1 :1 to about 10:1 , and in one embodiment about 1 :1 to about 5:1.
Typically, the salt compositions are formed by mixing (A) and (B) together, heating the mixture with agitation at a temperature of about 30mC to about 60mC, and in one embodiment about 40 C to about 50mC, until a clear liquid is formed. The reaction mixture is then cooled to room temperature to provide the inventive salt composition. These salt compositions are useful as corrosion inhibiting additives for water-based metal working fluids. In one embodiment, these salt compositions are also useful as lubricity additives. An advantage of these salt compositions is that they are nitrite free. Another advantage is that they are boron free.
The acid-containing composition (A) is comprised of at least one carboxylic acid represented by the formula
R1-C-R3-COOH (A-l)
F wherein in formula (A-l), R1 and R2 are independently hydrocarbyl groups; R3 is an alkylene group; and the total number of carbon atoms in R1, R2 and R3 is from about 3 to about 20 carbon atoms. R1 and R2 independently may contain 1 to about 8 carbon atoms, and in one embodiment 1 to about 4 carbon atoms. R1 and R2 may independently be straight chain or branched chain groups. R1 and R2 may together form a cyclic group. In one embodiment, R1 and R2 are each alkyl groups. In one embodiment, R1 and R2 are methyl groups. R3 may contain 1 to about 10 carbon atoms, and in one embodiment, 1 to about 8 carbon atoms. R3 may be a straight chain alkylene group, or it may have hydrocarbyl (e.g., alkyl) groups attached to it. Examples of useful compounds include isnonanoic acid, neodecanoic acid, and the like. The concentration of this acid in the acid-containing composition (A) may range from about 1 to about 99 percent by weight based on the weight of the acid-containing composition (A), and in one embodiment about 5 to about 70 percent by weight, and in one embodiment from about 10 to about 40 percent by weight.
The acid-containing composition (A) may further comprise at least one phosphate ester. The phosphate ester may be a compound represented by the formulae
R10(R20)
Figure imgf000005_0001
(A-llla) (A-lllb) wherein in formulae (A-llla) and (A-lllb): R1 is a hydrocarbyl group; R2 is an alkylene group; and n is a number in the range of about 1 to about 10, and in one embodiment about 2 to about 6. R1 may contain 1 to about 10 carbon atoms, and in one embodiment 1 to about 8 carbon atoms. R1 may be a straight chain or branched chain group. In one embodiment, R1 is an alkyl group. R2 may contain 1 to about 10 carbon atoms, and in one embodiment about 2 to about 4 carbon atoms. Examples of useful compounds include those compounds made by reacting P205 with UCON Lubricant 50-HB-100 which is a product of Union Carbide identified as a polyalkylene glycol monobutyl ether. The concentration of this ester in the acid-containing composition (A) may range from up to about 99 percent by weight based on the weight of the composition (A), and in one embodiment about 0.2 to about 60 percent by weight, and in one embodiment from about 0.5 to about 30 percent by weight.
The acid-containing composition (A) may further comprise at least one compound represented by the formula R2
R1-S02— N I-R 33-COOH (A-lll) wherein in formula (A-lll): R1 is a hydrocarbyl group;R2 is hydrogen or a hydrocarbyl group; and R3 is an alkylene group. R1 and R2 independently may contain 1 to about 10 carbon atoms, and in one embodiment 1 to about 8 carbon atoms. R1 and R2 may independently be straight chain or branched chain groups. In one embodiment, R1 is a phenyl group or an alkyl (e.g., methyl) substituted phenyl group, and R2 is hydrogen. R3 may contain 1 to about 10 carbon atoms, and in one embodiment, 1 to about 8 carbon atoms. R3 may be a straight chain alkylene group, or it may have hydrocarbyl (e.g., alkyl) groups attached to it. An example of a useful compound is 6[[(4-methyl- phenyl) sulfonyl] amino] hexanoic acid. The concentration of this acid in the acid-containing composition (A) may range up to about 50 percent by weight based on the weight of the acid-containing composition (A), and in one embodiment from about 10 to about 40 percent by weight.
The acid containing composition (A) may further comprise at least one compound represented by the formula
Figure imgf000006_0001
N-R4-COOH l 3 R3 wherein in formula (A-IV), R1, R3 and R5 are independently hydrogen or hydrocarbyl groups, and R2, R4 and R6 are independently alkylene groups. R1, R3 and R5 independently may be hydrogen or hydrocarbyl groups containing 1 to about 10 carbon atoms, and in one embodiment 1 to about 8 carbon atoms. In one embodiment, R1, R3 and R5 are each hydrogen. R2, R4 and R6 may independently contain 1 to about 10 carbon atoms, and in one embodiment, 1 to about 8 carbon atoms. Examples of useful compounds include hexanoic acid-6,61 ,6"-(1 ,3,5-triazin-2,4,6- triyltriim). The concentration of this acid in the acid-containing composition (A) may range up to about 10 percent by weight based on the weight of the acid-containing composition (A), and in one embodiment from about 0.5 to about 5 percent by weight. The alkanol amine (B) may be a primary, secondary or tertiary alkanol amine, or mixture thereof. The alkanol amine may be an ether amine. These amines may be represented by the formulae:
R3-N-R1OH R3-N-(R10)χH
I or | R2 R2
(B-l) (B-ll) wherein in formulae (B-l) and (B-ll), R1 is an alkylene group, and R2 and R3 are independently hydrogen or hydrocarbyl groups. R1 may contain 2 to about 18 carbon atoms, and in one embodiment 2 to about 8 carbon atoms, and in one embodiment 2 to about 4 carbon atoms. R1 and R2 may independently be hydrocarbyl groups of 1 to about 8 carbon atoms or hydroxyl-substituted hydrocarbyl groups of 2 to about 8 carbon atoms, x may be a number in the range of 2 to about 15. Examples of the alkanolamines that may be used include mono-, di-, and triethanol amine, dimethethanol amine, diethylethanol amine, di-(3- hydroxyl propyl) amine, N-(3-hydroxyl butyl) amine, N-(4-hydroxyl butyl) amine, N,N-di-(2-hydroxyl propyl) amine, N-(2-hydroxyl ethyl) morpholine, N-(2- hydroxyl ethyl) cyclohexyl amine, N-3-hydroxyl cyclopentyl amine, o-, m- and p- aminophenol, N-(hydroxyl ethyl) piperazine, N,N'-di(hydroxyl ethyl) piperazine, and the like.
In one embodiment, the alkanol amine (B) is comprised of a mixture of monoethanolamine and triethanolamine. The weight ratio of monoethanolamine to triethanolamine may range from about 1 :100 to about 20:100, and in one embodiment about 3:100 to about 15:100, and in one embodiment about 5:100 to about 10:100, and in one embodiment about 5:65. In the following examples as well as throughout the entire specification and the claims, unless otherwise indicated, all parts and percentages are by weight, and all temperatures are in degrees Celsius.
Example 1 Step (A)
The following mixture of acids is prepared:
Isononanoic acid 59.4%
Neodecanoic acid 25.4%
6[[(4-methyl-phenyl) sulfonyl] amino] hexanoic acid 1.0%
Polyalkylene glycol monobutylether phosphate ester derived from P205 (8-10%) and
UCON Lubricant 50-HB-100 (product of Union Carbide identified as a polyalkylene glycol monobutyl ether)
(90-92%) 14.2% Step (B)
The product from step (A) (30 parts) is mixed with triethanolamine (65 parts) and monoethanolamine (5 parts) and heated with agitation to a temperature in the range of 110 F (43.3mC) to 120mF (48.9 C) until a clear liquid is formed. The resulting mixture is cooled to room temperature to provide the desired product.
Example 2
Step (A)
The following mixture of acids is prepared:
Isononanoic acid 69.3% Neodecanoic acid 29.7%
6[[4-methyl-phenyl) sulfonyl] amino] hexanoic acid 1.0%
Step (B) The product from step (A) (30 parts) is mixed with triethanolamine (65 parts) and monoethanolamine (5 parts) and heated with agitation to a temperature in the range of 110mF (43.3mC) to 120mF (48.9mC) until a clear liquid is formed. The resulting mixture is cooled to room temperature to provide the desired product.
Example 3 Step A A partially neutralized acid mixture is prepared by mixing isononanic acid
(11.0 parts), hexanoic acid-6,61,6"-(1 ,3,5-triazin-2,4,6- triyltriim) (44.0 parts), triethanolamine (41.8 parts) and monoethanolamine (3.2 parts) with agitation at a temperature in the range of 110mF (43.3mC) to 120mF (48.9mC) until a clear liquid is formed. The resulting mixture is cooled to room temperature. Step B
The product from step (A) (54.5 parts) is mixed with triethanolamine (42.0 parts) and monoethanolamine (3.5 parts) and heated with agitation to a temperature in the range of 110mF (43.3 C) to 120mF (48.9mC) until a clear liquid is formed. The resulting mixture is cooled to room temperature to provide the desired product.
The products from Examples 1-3 are tested for their anti-corrosion properties using three known anti-corrosion tests, namely DIN51 360, IP287 and IP125. The results of these tests are indicated below. The results for the DIN51 360 test are reported in terms of the concentration of product from each example required to achieve no staining. The results for the IP 287 and IP125 tests are expressed in terms of the concentration of product from each example required to reach the break point, that is, the point at which there is a significant increase in the area stained. Product DIN 51 360 IP287 IP125 Example 1 2.50% 1.25% 0.50%
Example 2 2.50% 1.25% 0.50%
Example 3 2.75% 1.00% 0.80%
The inventive salt compositions may be employed in the inventive metal working fluids at a concentration in the range of about .001 to about 50 percent by weight, and in one embodiment about 0.01 to about 30 percent by weight, and in one embodiment about 0.03 to about 10 percent by weight, and in one embodiment about 0.05 to about 5 percent by weight, and in one embodiment about 0.05 to about 2 percent by weight.
The inventive metal working fluids are water-based metal working fluids which may include other conventional additives commonly employed in water- based metal working fluids. These other additives include lubricity additives, dispersants, surfactants, additives for adjusting the pH of the fluid, shear stabilizing agents, bactericides, dyes, water-softeners, odor masking agents, anti-foam agents, and the like. When used, each of these additives is typically employed in the metal working fluids at concentrations of up to about 5% by weight, and in one embodiment up to about 1 % by weight.
The concentrates are analogous to the metal working fluids except that they contain less water and proportionately more of the other ingredients. Typically, the concentrates contain from about 10% to about 90% by weight of the inventive salt compositions. The concentrates can be converted to metal working fluids by dilution with water. This dilution is usually done by standard mixing techniques. This is often a convenient procedure since the concentrate can be shipped to the point of use before additional water is added. Thus, the cost of shipping a substantial amount of the water in the final metal working fluid is saved. Only the water necessary to formulate the concentrate (which is determined primarily by ease of handling and convenience factor), need be shipped. Generally these metal working fluids are made by diluting the concentrates with water, wherein the ratio of water to concentrate is in the range of about 10:1 to about 40:1 by weight.
The following concentrates are prepared using the inventive salt compositions (all numerical values being in percent by weight):
Inαredient A B C D E F
Product of Example 1 20 - - 15 - -
Product of Example 2 - 20 - - 30 -
Product of Example 3 - - 20 - - 25
UCON EPML-X (product of Union Carbide identified as poly- alkalkylene glycol lubricity additive) 20 20 20 30 20 30
Triethanolamine 10 10 10 7 20 15
Biocide 1 2 1 0 3 0
Water 49 48 49 48 27 30
The following metal working fluids are prepared by adding water to the foregoing concentrates (all numerical values being in percent by weight): Metal Working Fluid Concentrate %Concentrate %Added Water
I A 10 90
II A 5 95
III B 2.5 97.5
IV B 5 95
V B 7 93
VI C 2 98
VII D 8 92
VIII E 1 99
IX E 4 96
X F 3 97
While the invention has been explained in relation to specific embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification.
Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Claims

3142BClaims
1. A composition, comprising: a salt derived from
(A) an acid-containing composition comprising at least one carboxylic acid represented by the formula R1-C-R3-COOH (A-l)
R2 wherein in formula (A-l), R1 and R2 are independently hydrocarbyl groups; R3 is an alkylene group; and the total number of carbon atoms in R1, R2 and R3 is from about 3 to about 20 carbon atoms, and
(B) at least one alkanol amine.
2. The composition of claim 1 wherein (A) further comprises at least one phosphate ester.
3. The composition of claim 1 wherein (A) further comprises at least one compound represented by the formula
R2
R1-S02-N 1 -R 33-COOH (A-lll)
wherein in formula (A-lll), R1 is a hydrocarbyl group, R2 is hydrogen or a hydrocarbyl group, and R3 is an alkylene group.
4. The composition of claim 1 wherein (A) further comprises at least one compound represented by the formula
Figure imgf000013_0001
N-R4-COOH
wherein in formula (A-IV), Ft1, R3 and R5 are independently hydrogen or hydrocarbyl groups, and R2, R4 and R6 are independently alkylene groups.
5. The composition of claim 1 wherein (B) is one or more compounds represented by the formulae:
R3N-R1OH
(B-l)
R or
Figure imgf000013_0002
wherein in formulae (B-l) and (B-ll), R1 is an alkylene group, and R2 and R3 are independently hydrogen or hydrocarbyl groups, and x is a number in the range of 2 to about 15.
6. A composition, comprising: a salt derived from
(A) an acid-containing mixture comprising isononanoic acid, neodecanoic acid, 6-[[(4-methyl-phenyl)sulfonyl]amino]hexanoic acid, and a polyalkylene glycol monobutyl ether phosphate ester; and
(B) a mixture of monoethanolamine and triethanolamine.
7. A composition, comprising: a salt derived from
(A) an acid-containing mixture comprising isononanoic acid, neodecanoic acid, and 6-[[(4-methyl-phenyl)sulfonyl]amino]hexanoic acid; and (B) a mixture of monoethanolamine and triethanolamine.
8. A composition, comprising: a salt derived from
(A) an acid-containing mixture comprising isononanoic acid and hexanoic acid-6,6 ,6 "-(1 ,3,5 triazin— 2,4,6-triyltriim); and
(B) a mixture of monoethanolamine and triethanolamine.
9. A composition, comprising: a salt derived from (A) an acid-containing composition comprising isononanoic acid; and
(B) a mixture of monoethanolamine and triethanolamine, the weight ratio of monoethanolamine to triethanolamine ranging from about 1 :100 to about 20:100.
10. A concentrate comprising water and about 10 to about 90% by weight of the composition of claim 1.
11. A metal working fluid comprising water and about 0.001 to about 50% by weight of the composition of claim 1.
PCT/US2003/008245 2002-03-18 2003-03-13 Corrosion inhibiting salts, concentrates and metal working fluids containing same WO2003080895A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003220376A AU2003220376A1 (en) 2002-03-18 2003-03-13 Corrosion inhibiting salts, concentrates and metal working fluids containing same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US36561002P 2002-03-18 2002-03-18
US60/365,610 2002-03-18

Publications (1)

Publication Number Publication Date
WO2003080895A1 true WO2003080895A1 (en) 2003-10-02

Family

ID=28454686

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/008245 WO2003080895A1 (en) 2002-03-18 2003-03-13 Corrosion inhibiting salts, concentrates and metal working fluids containing same

Country Status (2)

Country Link
AU (1) AU2003220376A1 (en)
WO (1) WO2003080895A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007016167A (en) * 2005-07-08 2007-01-25 Taiyu Kk Water soluble metal-working oil agent
WO2013099891A1 (en) * 2011-12-27 2013-07-04 出光興産株式会社 Water-based detergent
EP3130654A1 (en) * 2015-08-14 2017-02-15 Sasol Performance Chemicals GmbH Composition comprising 2-alkyl carboxylic acid salts and use thereof as anti-corrosion additive

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2160100A1 (en) * 1971-12-03 1973-06-07 Bantleon Hermann Gmbh Anticorrosion agent for aq system - contg reaction prodt of branched aliphatic carboxylic acid and base
EP0095312A1 (en) * 1982-05-17 1983-11-30 Amchem Products, Inc. Process for removal of sealants from surfaces
EP0124851A2 (en) * 1983-05-07 1984-11-14 Henkel Kommanditgesellschaft auf Aktien Composition and process for metal cleaning and passivation by spraying
JPS61117288A (en) * 1984-04-04 1986-06-04 Chiyoda Kagaku Kenkyusho:Kk Corrosion inhibitor for iron and iron alloy
EP0206144A1 (en) * 1985-06-20 1986-12-30 Henkel Kommanditgesellschaft auf Aktien Aqueous compositions for the Hilite and flux process, and their use
GB2194782A (en) * 1985-11-09 1988-03-16 Ciba Geigy Ag Additives for aqueous functional fluids
EP0553962A1 (en) * 1992-01-18 1993-08-04 Ciba-Geigy Ag Corrosion inhibiting compositions
EP0922753A2 (en) * 1997-12-05 1999-06-16 The Lubrizol Corporation Polyethoxylated alcohol-based phosphonates for metal working lubricants
WO2000014190A1 (en) * 1998-09-07 2000-03-16 Skoeld Rolf A method for mechanical working in the presence of a cobalt-containing metal
EP1041174A1 (en) * 1999-03-30 2000-10-04 Stefan Graichen Melamine containing corrosion inhibiting composition
FR2795432A1 (en) * 1999-06-28 2000-12-29 Atofina Corrosion inhibiting compositions for heat transfer fluids comprise unsaturated carboxylic acid, saturated mono- or di-carboxylic acid, 1,3,5-triazine carboxylic acid and azole compound
DE19959588A1 (en) * 1999-12-10 2001-06-13 Henkel Kgaa Metal treatment liquid for the neutral pH range

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2160100A1 (en) * 1971-12-03 1973-06-07 Bantleon Hermann Gmbh Anticorrosion agent for aq system - contg reaction prodt of branched aliphatic carboxylic acid and base
EP0095312A1 (en) * 1982-05-17 1983-11-30 Amchem Products, Inc. Process for removal of sealants from surfaces
EP0124851A2 (en) * 1983-05-07 1984-11-14 Henkel Kommanditgesellschaft auf Aktien Composition and process for metal cleaning and passivation by spraying
JPS61117288A (en) * 1984-04-04 1986-06-04 Chiyoda Kagaku Kenkyusho:Kk Corrosion inhibitor for iron and iron alloy
EP0206144A1 (en) * 1985-06-20 1986-12-30 Henkel Kommanditgesellschaft auf Aktien Aqueous compositions for the Hilite and flux process, and their use
GB2194782A (en) * 1985-11-09 1988-03-16 Ciba Geigy Ag Additives for aqueous functional fluids
EP0553962A1 (en) * 1992-01-18 1993-08-04 Ciba-Geigy Ag Corrosion inhibiting compositions
EP0922753A2 (en) * 1997-12-05 1999-06-16 The Lubrizol Corporation Polyethoxylated alcohol-based phosphonates for metal working lubricants
WO2000014190A1 (en) * 1998-09-07 2000-03-16 Skoeld Rolf A method for mechanical working in the presence of a cobalt-containing metal
EP1041174A1 (en) * 1999-03-30 2000-10-04 Stefan Graichen Melamine containing corrosion inhibiting composition
FR2795432A1 (en) * 1999-06-28 2000-12-29 Atofina Corrosion inhibiting compositions for heat transfer fluids comprise unsaturated carboxylic acid, saturated mono- or di-carboxylic acid, 1,3,5-triazine carboxylic acid and azole compound
DE19959588A1 (en) * 1999-12-10 2001-06-13 Henkel Kgaa Metal treatment liquid for the neutral pH range

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 010, no. 303 (C - 378) 16 October 1986 (1986-10-16) *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007016167A (en) * 2005-07-08 2007-01-25 Taiyu Kk Water soluble metal-working oil agent
WO2013099891A1 (en) * 2011-12-27 2013-07-04 出光興産株式会社 Water-based detergent
CN104024390A (en) * 2011-12-27 2014-09-03 出光兴产株式会社 Aqueous detergent
EP3130654A1 (en) * 2015-08-14 2017-02-15 Sasol Performance Chemicals GmbH Composition comprising 2-alkyl carboxylic acid salts and use thereof as anti-corrosion additive
WO2017028947A1 (en) * 2015-08-14 2017-02-23 Sasol Performance Chemicals Gmbh Composition comprising 2-alkyl carboxylic acid salts and use thereof as anti-corrosion additive

Also Published As

Publication number Publication date
AU2003220376A1 (en) 2003-10-08

Similar Documents

Publication Publication Date Title
CN101044230B (en) Corrosion-inhibiting agent for functional fluids, water-miscible lubricating concentrate and its use
US4151099A (en) Water-based hydraulic fluid and metalworking lubricant
EP0206833B1 (en) Aqueous fluids
EP0061693B1 (en) Water-based hydraulic fluids having improved lubricity and corrosion inhibiting properties
US8969270B2 (en) Water-soluble metal working fluid, and coolant for metal working
EP2928992B1 (en) Additive compositions and industrial process fluids
CN104073333B (en) Water-ethylene glycol nonflame hydraulic fluid and preparation method thereof
JP6283552B2 (en) Water-soluble metalworking oil and coolant for metalworking
EP0052751B1 (en) Water-based hydraulic fluid containing an alkyl dialkanolamide
CN101437929A (en) Metalworking fluids comprising neutralized fatty acids
US11292981B2 (en) Emulsifier for lubricating oil concentrate
JP6009378B2 (en) Water-soluble metalworking fluid and metalworking coolant
CN101802154A (en) Water-glycol hydraulic fluid compositions
CA1294511C (en) Aqueous fluids
KR930007896B1 (en) Metal working fluid composition
CS207675B2 (en) Means against the corrosion
BR102015020543A2 (en) boron free corrosion inhibitors for metalworking fluids
EP3124584A1 (en) Water-soluble metalworking oil, and metalworking coolant
CA2867413C (en) Corrosion-protection system for treating metal surfaces
WO2003080895A1 (en) Corrosion inhibiting salts, concentrates and metal working fluids containing same
US4683081A (en) Aqueous corrosion inhibitor compositions of a half-amide and a dicarboxylic acid amine salt
JPH0617268A (en) Anticorrosive agent
JPH08302379A (en) Bacteristat and water-base or emulsion-base metal processing composition containing same
US4722767A (en) Alkyl polyoxyalkylene sulfides and alkyl polyoxyalkylene sulfoxides as lubricating additives
DE3416857A1 (en) Phenoxyalkanecarboxylic acid alkanolamine salts as water-soluble corrosion inhibitors

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP