EP0217597B1 - Water-miscible metalworking lubricants - Google Patents
Water-miscible metalworking lubricants Download PDFInfo
- Publication number
- EP0217597B1 EP0217597B1 EP86307185A EP86307185A EP0217597B1 EP 0217597 B1 EP0217597 B1 EP 0217597B1 EP 86307185 A EP86307185 A EP 86307185A EP 86307185 A EP86307185 A EP 86307185A EP 0217597 B1 EP0217597 B1 EP 0217597B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- phosphoric acid
- biocide
- acid esters
- miscible
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000314 lubricant Substances 0.000 title claims abstract description 27
- 238000005555 metalworking Methods 0.000 title claims abstract description 26
- 239000003139 biocide Substances 0.000 claims abstract description 30
- 150000003014 phosphoric acid esters Chemical class 0.000 claims abstract description 21
- 239000000839 emulsion Substances 0.000 claims abstract description 20
- 230000003115 biocidal effect Effects 0.000 claims abstract description 18
- 230000002378 acidificating effect Effects 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 230000007797 corrosion Effects 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 12
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 239000012895 dilution Substances 0.000 abstract 1
- 238000010790 dilution Methods 0.000 abstract 1
- 239000012141 concentrate Substances 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 10
- 230000000813 microbial effect Effects 0.000 description 7
- 244000005700 microbiome Species 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 241000238634 Libellulidae Species 0.000 description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 230000002110 toxicologic effect Effects 0.000 description 3
- 231100000027 toxicology Toxicity 0.000 description 3
- 206010061217 Infestation Diseases 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000009897 systematic effect Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000005068 cooling lubricant Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- -1 isoalkyl Chemical group 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012009 microbiological test Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001575 pathological effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
Classifications
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- 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
-
- 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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/24—Aldehydes; Ketones
-
- 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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
-
- 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
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/046—Hydroxy ethers
-
- 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
- C10M2207/08—Aldehydes; Ketones
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/286—Esters of 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
- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2211/08—Halogenated waxes
-
- 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
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
-
- 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
- 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
- C10M2223/041—Triaryl phosphates
-
- 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
- C10M2223/042—Metal salts thereof
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- 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
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
-
- 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
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/02—Macromolecular compounds from phosphorus-containg monomers, obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- 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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
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- 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
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- 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 water-miscible or aqueous metalworking lubricants.
- Aqueous metalworking lubricants are excellent culture media for microorganisms, and as emulsions and solutions must therefore be protected against microbial attack or they will lose their utility and toxicological problems may arise owing to infection of the aqueous metalworking lubricant.
- a biocide incorporated as an ingredient in the metalworking lubricant concentrate.
- a microbial infestation of an emulsion can cause considerable toxicological problems (rapid multiplication of microorganisms, occurrence of coliformic germs with the risk of human pathological infections), it results in a drop of the pH-value (increased corrosivity of the aqueous metalworking lubricant) and incomplete breaking of the emulsion (which in turn necessitates not only replacement of existing emulsion and loss of broken emulsion, but also inadequate machining efficiency and reduced tool service life).
- the speed of decomposition of the biocide depends upon the respective composition of the metalworking lubricant.
- the present invention seeks to solve this problem by improving metalworking lubricants of this type in respect of their microbial stability to prevent or hinder decomposition of the biocide during storage of the metalworking lubricant concentrate.
- a water-miscible metalworking lubricant containing mineral oil, emulsifier, solubilizer, corrosion inhibitor biocide and acidic components, characterized in that the acidic component comprises an acidic organic phosphoric acid ester in an amount of preferably 3 to 12% by weight of the composition and that the biocide comprises a formaldehyde liberating compound.
- Such a composition may have a composition in percentage by weight:
- compositions according to the invention provide prolonged inhibition of biocide decomposition by virtue of using instead of the conventional carboxylic acids (in particular fatty acids), acidic organic phosphoric acid esters. This markedly retarded biocide decomposition results in a considerably better microbial resistivity of the metalworking lubricants of the invention after storage as compared with conventional compositions.
- compositions contain no or only very minor amounts of carboxylic acids (in particular fatty acids), and instead, acidic organic phosphoric acid esters.
- Conventional water-miscible metalworking lubricants for metal machining contain biocides, predominantly formaldehyde liberating biocides, in the concentrate for protection against microbial attack of the working emulsions or solutions.
- These water-miscible metalworking lubricants contain also inter alia alkaline components (for example alkanolamines) as well as carboxylic acids (predominantly fatty acids), which perform a neutralizing, lubricating, and partly an emulsifying and corrosion inhibiting function.
- biocides which in most cases are selected by microbiological tests, impart to the working emulsions and solutions a good or at least adequate resistance to microorganisms provided that the emulsions or solutions are prepared from concentrates which are freshly prepared or stored for short periods only.
- the biostability of the working emulsions and solutions is, however, often unsatisfactory or at least no longer completely sufficient since due to decay of the biocide during storage the biocide concentration necessary for microbial protection in the working solution or emulsion (minimum restraint concentration) is no longer available.
- skimmers often containing silicon.
- skimmers often become ineffective even after brief use (since they become adsorbed and discharged or altered in their particle structure). There is therefore a need for metalworking lubricant formulations which do not froth per ge and do not require the use of skimmers.
- biocides have also been investigated in which the effective mechanism does not reside in the release of anti-microbially acting formaldehyde.
- formaldehyde-free biocides either do not have the necessary broad spectrum activity (against all bacteria, fungi and yeasts usually occurring in machining emulsions) or have doubtful toxicological or ecological effects. Moreoever, these formaldehyde-free biocides often cannot be incorporated into concentrates.
- the decomposition rate of the biocides during storage of the concentrate can, to a specific extent, be influenced by the chemical composition of the concentrates.
- the presence or absence of certain components can favorably or unfavorably affect the decomposition speed.
- Cooling lubricant formulations of this kind do not have a frothing tendency (as emulsions or solutions) in laboratory tests or under practical conditions (even in complex situations, for example high emulsion concentrations and under unfavorable conditions, for example in drilling a deep blind hole) compared with conventional products.
- Acidic organic phosphoric acid esters are sometimes used as components for corrosion reduction (extreme pressure components) in metalworking lubricants.
- the stabilizing effect of acidic organic phosphoric acid esters on formaldehyde liberating biocides was not previously known.
- carboxylic acids especially fatty acids
- acidic organic phosphoric acid esters are at least substantially replaced by acidic organic phosphoric acid esters.
- Particularly suitable acid phosphoric acid esters for use in the compositions of the invention are monoalkyl phosphoric acid esters, dialkyl phosphoric acid esters, monoisoalkyl phosphoric acid esters, diisoalkyl phosphoric acid esters, monoalkenyl phosphoric acid esters, dialkenyl phophoric acid esters, mono(alkylphenyl) phophoric acid esters, di(alkylphenyl) phosphoric acid esters, mono (iso- alkylphenyl) phosphoric acid esters, di(isoalkyl- phenyl) phosphoric acid esters as well as mono and dipolyether phosphoric acid esters, the polyether group comprising, if desired, as terminal group alkyl, isoalkyl, phenyl, alkylphenyl and isoalkylphe- nyl and hydrogen.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Metal Extraction Processes (AREA)
Abstract
Description
- This invention relates to water-miscible or aqueous metalworking lubricants.
- Aqueous metalworking lubricants are excellent culture media for microorganisms, and as emulsions and solutions must therefore be protected against microbial attack or they will lose their utility and toxicological problems may arise owing to infection of the aqueous metalworking lubricant. For protection against microbial infestation, there is normally employed a biocide incorporated as an ingredient in the metalworking lubricant concentrate.
- The so-called formaldehyde liberating biocides are widely used in this respect since they have broad antimicrobial activity at low concentrations. However, they have the disadvantage that their stability upon storage of the metalworking lubricant concentrates is insufficient so that upon preparation of the emulsion or solution, only a fraction of the original biocide is available.
- The resulting underdosage of the biocide results in the biostability of the emulsion or solution being inadequate. The stability of such emulsions and solutions against microorganisms is, however, a decisive factor for their utility and service life. A microbial infestation of an emulsion can cause considerable toxicological problems (rapid multiplication of microorganisms, occurrence of coliformic germs with the risk of human pathological infections), it results in a drop of the pH-value (increased corrosivity of the aqueous metalworking lubricant) and incomplete breaking of the emulsion (which in turn necessitates not only replacement of existing emulsion and loss of broken emulsion, but also inadequate machining efficiency and reduced tool service life).
- The speed of decomposition of the biocide depends upon the respective composition of the metalworking lubricant.
- The present invention seeks to solve this problem by improving metalworking lubricants of this type in respect of their microbial stability to prevent or hinder decomposition of the biocide during storage of the metalworking lubricant concentrate.
- In accordance with the invention, there is provided a water-miscible metalworking lubricant containing mineral oil, emulsifier, solubilizer, corrosion inhibitor biocide and acidic components, characterized in that the acidic component comprises an acidic organic phosphoric acid ester in an amount of preferably 3 to 12% by weight of the composition and that the biocide comprises a formaldehyde liberating compound.
-
- The compositions according to the invention provide prolonged inhibition of biocide decomposition by virtue of using instead of the conventional carboxylic acids (in particular fatty acids), acidic organic phosphoric acid esters. This markedly retarded biocide decomposition results in a considerably better microbial resistivity of the metalworking lubricants of the invention after storage as compared with conventional compositions.
- It has been possible to demonstrate that such a composition of the metalworking lubricants displays a considerably improved frothing behavior for emulsions and solutions. For this aspect also, it is important that the compositions contain no or only very minor amounts of carboxylic acids (in particular fatty acids), and instead, acidic organic phosphoric acid esters.
- Conventional water-miscible metalworking lubricants for metal machining contain biocides, predominantly formaldehyde liberating biocides, in the concentrate for protection against microbial attack of the working emulsions or solutions. These water-miscible metalworking lubricants contain also inter alia alkaline components (for example alkanolamines) as well as carboxylic acids (predominantly fatty acids), which perform a neutralizing, lubricating, and partly an emulsifying and corrosion inhibiting function.
- The biocides, which in most cases are selected by microbiological tests, impart to the working emulsions and solutions a good or at least adequate resistance to microorganisms provided that the emulsions or solutions are prepared from concentrates which are freshly prepared or stored for short periods only.
- Owing to the decomposition of the biocides upon prolonged storage of the concentrate, the biostability of the working emulsions and solutions is, however, often unsatisfactory or at least no longer completely sufficient since due to decay of the biocide during storage the biocide concentration necessary for microbial protection in the working solution or emulsion (minimum restraint concentration) is no longer available.
- The resulting underdosage of the biocide results in the disadvantages and problems described above.
- As regards the frothing tendency of conventional formulations (containing carboxylic acids), attempts have been made to suppress frothing by using skimmers (often containing silicon). However, such skimmers often become ineffective even after brief use (since they become adsorbed and discharged or altered in their particle structure). There is therefore a need for metalworking lubricant formulations which do not froth per ge and do not require the use of skimmers.
- In developing the compositions of the invention, biocides have also been investigated in which the effective mechanism does not reside in the release of anti-microbially acting formaldehyde. However, it has been found that these so-called formaldehyde-free biocides either do not have the necessary broad spectrum activity (against all bacteria, fungi and yeasts usually occurring in machining emulsions) or have doubtful toxicological or ecological effects. Moreoever, these formaldehyde-free biocides often cannot be incorporated into concentrates.
- Attempts were therefore made to determine by systematic variation of the composition of the concentrates whether the presence or absence of certain components influences the decomposition rate of the biocides concerned.
- By systematic variation of the composition of the concentrates, it was possible to show that the decomposition rate of the biocides during storage of the concentrate can, to a specific extent, be influenced by the chemical composition of the concentrates. The presence or absence of certain components can favorably or unfavorably affect the decomposition speed.
- It was in particular found that the incorporation of acidic organic phosphoric acid esters in metalworking lubricant formulations, while no carboxylic acid was present, resulted according to the invention in a marked hinderance of the biocide decay.
- Moreover, it was possible to prove that the complete or at least extensive replacement of carboxylic acids (especially fatty acids) by acidic organic phosphoric acid esters leads to a considerably reduced frothing of emulsions and solutions.
- Cooling lubricant formulations of this kind do not have a frothing tendency (as emulsions or solutions) in laboratory tests or under practical conditions (even in complex situations, for example high emulsion concentrations and under unfavorable conditions, for example in drilling a deep blind hole) compared with conventional products.
- Acidic organic phosphoric acid esters are sometimes used as components for corrosion reduction (extreme pressure components) in metalworking lubricants. However, the stabilizing effect of acidic organic phosphoric acid esters on formaldehyde liberating biocides (restriction of biocide decomposition during storage of the concentrate) was not previously known. On the contrary, it was assumed that no phosphoric acid compounds should be present in view of the growth of microorganisms (and accordingly they were considered to be a drawback for the biostability of lubricants), since phosphorus belongs to the group of elements which are necessary for the metabolism of microorganisms.
- The considerable reduction of frothing of water-miscible metalworking lubricants is also unexpected.
- For the improved frothing property of the products described here, it is of importance that carboxylic acids (especially fatty acids) normally contained in conventional compositions are at least substantially replaced by acidic organic phosphoric acid esters.
- In order to ensure that the improvements in accordance with the invention (biostability/inhibition of biocide decomposition during storage/frothing property) are achieved, it is not sufficent merely to add a certain amount of acid organic phosphoric acid ester to a conventional composition.
- Particularly suitable acid phosphoric acid esters for use in the compositions of the invention, are monoalkyl phosphoric acid esters, dialkyl phosphoric acid esters, monoisoalkyl phosphoric acid esters, diisoalkyl phosphoric acid esters, monoalkenyl phosphoric acid esters, dialkenyl phophoric acid esters, mono(alkylphenyl) phophoric acid esters, di(alkylphenyl) phosphoric acid esters, mono (iso- alkylphenyl) phosphoric acid esters, di(isoalkyl- phenyl) phosphoric acid esters as well as mono and dipolyether phosphoric acid esters, the polyether group comprising, if desired, as terminal group alkyl, isoalkyl, phenyl, alkylphenyl and isoalkylphe- nyl and hydrogen.
Claims (6)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT86307185T ATE56745T1 (en) | 1985-09-26 | 1986-09-18 | WATER-MISCIBLE METALWORKING LUBRICANTS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3534226 | 1985-09-26 | ||
DE3534226A DE3534226C1 (en) | 1985-09-26 | 1985-09-26 | Water-miscible coolant |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0217597A2 EP0217597A2 (en) | 1987-04-08 |
EP0217597A3 EP0217597A3 (en) | 1988-06-08 |
EP0217597B1 true EP0217597B1 (en) | 1990-09-19 |
Family
ID=6281922
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86307185A Expired - Lifetime EP0217597B1 (en) | 1985-09-26 | 1986-09-18 | Water-miscible metalworking lubricants |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0217597B1 (en) |
JP (1) | JPS62104898A (en) |
AT (1) | ATE56745T1 (en) |
DE (2) | DE3534226C1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0753916B2 (en) * | 1990-03-19 | 1995-06-07 | 住友金属工業株式会社 | Oily scale inhibitor for hot rolling and hot rolling method |
DE19620084A1 (en) * | 1996-05-20 | 1997-11-27 | Schenk Filterbau Gmbh | Use of depth filters for the treatment of cooling lubricants |
US5716917A (en) * | 1996-09-24 | 1998-02-10 | Cincinnati Milacron Inc. | Machining fluid composition and method of machining |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4371447A (en) * | 1981-07-06 | 1983-02-01 | Standard Oil Company | Low viscosity water-in-oil microemulsions |
EP0147760B1 (en) * | 1983-12-19 | 1991-04-03 | Hitachi, Ltd. | Emulsion type liquid lubricant for metal forming, process for preparing the lubricant and process for metal forming with the lubricant |
-
1985
- 1985-09-26 DE DE3534226A patent/DE3534226C1/en not_active Expired
-
1986
- 1986-09-17 JP JP61219089A patent/JPS62104898A/en active Pending
- 1986-09-18 DE DE8686307185T patent/DE3674315D1/en not_active Expired - Fee Related
- 1986-09-18 EP EP86307185A patent/EP0217597B1/en not_active Expired - Lifetime
- 1986-09-18 AT AT86307185T patent/ATE56745T1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
JPS62104898A (en) | 1987-05-15 |
DE3674315D1 (en) | 1990-10-25 |
ATE56745T1 (en) | 1990-10-15 |
EP0217597A3 (en) | 1988-06-08 |
DE3534226C1 (en) | 1987-04-23 |
EP0217597A2 (en) | 1987-04-08 |
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