EP0071167A1 - Water-soluble lubricant - Google Patents

Water-soluble lubricant Download PDF

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Publication number
EP0071167A1
EP0071167A1 EP82106564A EP82106564A EP0071167A1 EP 0071167 A1 EP0071167 A1 EP 0071167A1 EP 82106564 A EP82106564 A EP 82106564A EP 82106564 A EP82106564 A EP 82106564A EP 0071167 A1 EP0071167 A1 EP 0071167A1
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EP
European Patent Office
Prior art keywords
water
alkyl
acid
alkenyl
ethylene oxide
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EP82106564A
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German (de)
French (fr)
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EP0071167B1 (en
Inventor
Max Dr. Grossmann
Rainer Dr. Helwerth
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Hoechst AG
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Hoechst AG
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Classifications

    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
    • 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
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles

Definitions

  • oils or aqueous emulsions of mineral oils or fatty oils which contain anionic or nonionic emulsifiers or mixtures of such emulsifiers are generally used as coolants and lubricants.
  • these oil emulsions can contain more or less large amounts of substances that improve the lubricity. These are mostly chlorine, phosphorus or sulfur-containing compounds. Nevertheless, these oil emulsions often do not meet the requirements placed on such metalworking agents.
  • the emulsions often have insufficient physical stability and, due to particle enlargement under operating conditions, often tend to separate into an oil and a water phase. As a result, the emulsion becomes unusable for the application mentioned and no longer has the optimum properties of such metalworking fluids.
  • the purpose of the invention is therefore to provide water-soluble lubricants which are suitable for high-performance operations such as punching, tapping, tapping and the like, and not only for the machining of ferrous metals such as steel and steel alloys, but also for the machining of non-ferrous metals such as copper, aluminum, Brass, bronze and the like are suitable.
  • the invention relates to water-soluble lubricants which contain one or more compounds of the formula contain, wherein R is hydrogen, C 1 -C 12 alkyl or C 1 -C 12 alkenyl, R 1 C 1 -C 18 alkyl or C 2 -C 18 alkenyl, A is a group of the formulas X means a number from 0 to 15 and the numerical values for m and n are selected so that the total content of ethylene oxide and / or propylene oxide in the molecule is 10 to 800 alkylene oxide units.
  • Preferred compounds of the above formula are those in which R is hydrogen or C 1 -C 4 alkyl, R 1 C 6 -C 18 alkyl or C 6 - C 18 alkenyl, A is a group of the formula - (CH 2 CH 2 O ) m -X is a number from 1 to 9 and the numerical value for m is chosen so that the total content of ethylene oxide in the molecule is 40 to 200 ethylene oxide units.
  • the compounds described above are prepared by known processes. For example, phenol or alkylphenols or their mixtures with formaldehyde or paraformaldehyde are first condensed to linear or cyclic novolaks, as described in Hultzsch, Chemie der Phenolharze, 1950, page 114 or in U.S. Patent 4032514 or in J. Org. Chem. Vol. 43 , No. 25, 1978, 4905-4906. These novolaks are then reacted with alkylene oxides in a known manner to give the novolak oxethylates and the latter are converted into carboxylic acid esters.
  • phenol or alkylphenols which are bifunctional to formaldehyde and have straight-chain or branched alkyl radicals from C 1 to C 12 or mixtures thereof.
  • the water of reaction occurring during the formation of novolak must be removed. This can optionally be carried out azeotropically, during or after the reaction with aldehydes or by applying a vacuum.
  • acids such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid can be used as the catalyst, and sodium hydroxide, potassium hydroxide, sodium methylate or potassium tert-butoxide are preferably used as alkaline catalysts.
  • the manufacture of the novolaks produces either open-chain or cyclic products.
  • the two free valences in the above formulas are each saturated with hydrogen atoms, while in the case of cyclic novolaks the two free valences close the ring together.
  • the linear novolaks are brittle to soft resins, the cyclic white or yellowish solids that melt above 300 ° C. Both types are mixtures of multi-chain phenols or alkylphenols linked by methylene bridges.
  • the oxyalkylation of the linear novolaks is carried out by known processes with alkylene oxides in the presence of alkaline catalysts at about 100-210 ° C., preferably 140-180 ° C.
  • Alkaline catalysts which are particularly suitable are alkali metal hydroxides such as potassium hydroxide or preferably sodium hydroxide or alkali metal alcoholates such as sodium methylate or potassium tert-butoxide.
  • concentration of these alkaline catalysts should preferably be 0.05 to 1.0% by weight, based on the novolak resin.
  • the oxyalkylation can be carried out without pressure or in pressure vessels, and the alkylene oxide can be supplied in gaseous or liquid form.
  • the amount of the alkylene oxide is such that an average of 10-50 alkylene oxide residues are introduced into each phenolic hydroxyl group of the novolak resin.
  • the oxyalkylation of the high-melting cvcli- see novolaks can be carried out in xylene suspension according to US Pat. No. 4,032,514, Example 13C. After the oxyalkylation, the xylene can remain as a water entrainer in the esterification in the oxyalkylate.
  • the novolak oxalkylates are esterified by known methods with carboxylic acids without or in the presence of azeotropic drag compounds with carboxylic acid derivatives, such as carboxylic acid halides, anhydrides or by transesterification with C 1 to C 4 alkyl esters of the carboxylic acids.
  • Preferred carboxylic acids are saturated monocarboxylic acids with 2 to 20, in particular with G to 18 carbon atoms or their Mixtures in question. Examples are: so-called pre-fatty acids, 2-ethyl-hexanoic acid, i-nonanoic acid, dodecanoic acid, i-tridecanoic acid, stearic acid, i-stearic acid or oleic acid.
  • carboxylic acids can be partially substituted by carboxylic acids with 2-5 carbon atoms, e.g. Acetic acid to be replaced.
  • the properties of the compounds described above depend on the length of the radicals R and R 1 , on the size. of the value for X and the degree of oxyalkylation, expressed by the indices m and n.
  • the water solubility decreases with increasing size of the radicals R and R 1 and with decreasing degree of oxalkylation.
  • the desired solubility in water can be achieved in any case by suitable variations of these substituents.
  • the cloud points, measured in 1% strength aqueous solution, should be above 25 ° C., preferably above 30 ° C.
  • the alkylphenol is placed together with a catalytically effective amount of p-toluenesulfonic acid in a flask and heated.
  • a 35% formaldehyde solution is then slowly added dropwise, the amount of formaldehyde being determined by the size of the respective value for X in the table.
  • the mixture is heated under reflux for about 16 hours.
  • the water is then completely distilled off at 120-140 ° C., first under normal pressure and then under reduced pressure. After the cold, the novolak al brittle, almost colorless resin.
  • the novolak thus obtained is introduced into an autoclave together with 1.1 g of sodium hydroxide.
  • the air is displaced by nitrogen and it is heated to 150 - 170 ° C.
  • liquid ethylene oxide or a mixture of ethylene oxide and propylene oxide is introduced until the weight increase in the autoclave has reached the total molar amount indicated under A in the table. Then it is stirred for another hour.
  • a mixture of the oxyalkylated novolak, a catalytically effective amount of p-toluenesulfonic acid and the amount of acid of the formula R 1 -CCOH required in each case are introduced into a stirred vessel equipped with a stirrer and cooler and the mixture is stirred at a temperature of about 170 for as long as possible ° C heated until no more water distilled off and the acid number has dropped to a value below 3.
  • the esterification product is thus obtained in the form of a brown substance with an oily to waxy consistency.
  • the M invention for producing etallbearbeitungs- medium required amounts of esterified oxyalkylated novolaks may vary within wide limits.
  • An application concentration of less than 10% by weight is generally sufficient for the usual metalworking operations. It is an advantage of the metalworking agents according to the invention that they are effective even at low concentrations. With the new metal processing agents, a satisfactory effect can still be achieved at concentrations of about 0.5% by weight.
  • the - application concentration of the metalworking agent depends above all on the type of processing of the workpieces. In usual processes, the application concentration of the new metalworking agents is in the range of about one to eight percent by weight. In special cases, however, the values given above can also be exceeded or fallen short of. In the case of particularly heavy metalworking processes, it may be appropriate to use solutions with a content of esterified oxyalkylated novolaks of up to about 25% by weight.
  • the water-soluble lubricants can also contain other additives such as Contain amines and conventional corrosion inhibitors from the carboxylic acid series and / or fatty acid-amine condensation products and / or boric acid alkanolamides.
  • the results of comparative tests reported below show that the metalworking fluids according to the invention are able to withstand very high loads and that they have significantly better load and wear resistance properties than the known preparations.
  • the metalworking fluids according to the invention are due to their very good lubricating and cooling properties both for fast metalworking gears such as turning, milling, drilling, grinding, etc., which usually only place a relatively low load on the lubricant, as well as for heavy-duty operations, such as thread cutting, in which the lubricant is exposed to a large load, are equally suitable .
  • the friction wear balance according to Reichert was used.
  • This device essentially consists of two interchangeable steel friction partners of different hardness, one of which, a slip ring, is movable and the other, a test roller, is rigidly arranged.
  • the slip ring and test roller are pressed axially crossed on each other using a double lifting system with a defined force.
  • the slip ring is partially immersed in the metalworking fluid to be examined and at the same time executes a rotary movement, with constant lubricant transport to the wear zone between the test roller and the test ring being guaranteed.
  • the rotary movement creates a more or less large elliptical wear mark depending on the pressure absorption capacity of the respective lubricant on the test roller.
  • a numerical value obtained with the dimension / kp / cm 2 / known as "specific surface pressure” is referred to, and as M ate for the carrying capacity of lubricating films is used.
  • the lubricants according to the invention are therefore not only very suitable as auxiliaries for normal metalworking operations such as turning, drilling, grinding and the like, which generally involve a comparatively low load on the lubricant, but they are also advantageous for very heavy machining operations such as e.g. Use thread cutting.

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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)

Abstract

Wasserlösliche Schmiermittel gekennzeichnet durch einen Gehalt an Verbindungen der Formel 1 <IMAGE> wobei R Wasserstoff, C1-C12-Alkyl oder C1-C12-Alkenyl, R1 C1-C18-Alkyl oder C2-C18-Alkenyl, A eine Gruppe der Formeln -(CH2CH2O)m- und (C3H6O)n- X eine Zahl von 0 bis 15 bedeutet und die Zahlenwerte für m und n so gewählt sind, daß der Gesamtgehalt an Ethylenoxid und/oder Propylenoxid im Molekül 10 bis 800 Alkylenoxid-Einheiten beträgt.Water-soluble lubricants characterized by a content of compounds of the formula 1 <IMAGE> where R is hydrogen, C1-C12-alkyl or C1-C12-alkenyl, R1 C1-C18-alkyl or C2-C18-alkenyl, A is a group of the formulas - ( CH2CH2O) m- and (C3H6O) n- X is a number from 0 to 15 and the numerical values for m and n are chosen such that the total content of ethylene oxide and / or propylene oxide in the molecule is 10 to 800 alkylene oxide units.

Description

Bei verformenden und spangebenden Metallbearbeitungen werden als Kühl- und Schmiermittel im allgemeinen öle oder wäßrige Emulsionen von Mineralölen oder fetten Ölen eingesetzt, die anionische oder nichtionogene Emulgatoren oder Mischungen solcher Emulgatoren enthalten. Diese Ölemulsionen können zur Verbesserung ihrer Gebrauchswerteigenschaften mehr oder weniger große Mengen an Stoffen enthalten, die die Schmierfähigkeit verbessern. Hierbei handelt es sich meist um chlor-, phosphor- oder schwefelhaltige Verbindungen. Trotzdem genügen diese Ölemulsionen oftmaals nicht den an solche Metallbearbeitungsmittel gestellten Anforderungen.In the case of shaping and machining metalworking, oils or aqueous emulsions of mineral oils or fatty oils which contain anionic or nonionic emulsifiers or mixtures of such emulsifiers are generally used as coolants and lubricants. To improve their performance properties, these oil emulsions can contain more or less large amounts of substances that improve the lubricity. These are mostly chlorine, phosphorus or sulfur-containing compounds. Nevertheless, these oil emulsions often do not meet the requirements placed on such metalworking agents.

Als Mehrphasensysteme besitzen die Emulsionen aber oft eine nicht ausreichende physikalische Stabilität und neigen durch Teilchenvergrößerung unter Betriebsbedingungen häufig zur Trennung in eine öl-und eine Wasserphase. Die Emulsion wird dadurch für den genannten Anwendungszweck unbrauchbar und besitzt nicht mehr die optimalen Eigenschaften solcher Metallbearbeitungsflüssigkeiten.However, as multi-phase systems, the emulsions often have insufficient physical stability and, due to particle enlargement under operating conditions, often tend to separate into an oil and a water phase. As a result, the emulsion becomes unusable for the application mentioned and no longer has the optimum properties of such metalworking fluids.

Es besteht daher ein Bedarf an Metallbearbeitungsflüssigkeiten, die einerseits eine ausreichende Schmierwirkung besitzen, andererseits eine ausreichende Stabilität aufweisen.There is therefore a need for metalworking fluids which on the one hand have a sufficient lubricating effect and on the other hand have an adequate stability.

Neuere Entwicklungen nutzen deshalb die Tatsache, daß wäßrige Einphasensysteme, wie sie beispielsweise in klaren Lösungen schmierwirksamer, wassermischbarer Polymerkörper auf Basis von Ethylonoxid und Propylenoxid vorliegen, derartigen nachteiligen Veränderungen nicht unterliegen und deshalb eine vielfach höhere Lebensdauer im praktischen Betrieb aufweisen als die Emulsionen.Recent developments therefore take advantage of the fact that aqueous single-phase systems, such as those present in clear solutions of lubricating, water-miscible polymer bodies based on ethylene oxide and propylene oxide, are not subject to such disadvantageous changes and therefore have a service life that is many times longer in practical operation than the emulsions.

So ist bekannt, daß wasserlösliche Vertreter aus der Substanzklasse der Polyalkylenoxide, beispielsweise geradkettige oder verzweigtkettige Ethylen-Propylen-Blockpolymerisate für diesen Zweck Verwendung finden. (Vgl. Th. Mang u. u.a.' in "Kontakt und Studium 1980" Bd. 61, Seite 35. Expert Verlag)It is known, for example, that water-soluble representatives from the substance class of polyalkylene oxides are straight chain or branched chain ethylene-propylene block polymers are used for this purpose. (See Th. Mang uua 'in "Kontakt und Studium 1980" Vol. 61, page 35. Expert Verlag)

Die Praxis hat jedoch gezeigt, daß die Schmierwirkung dieser Substanzklasse in vielen Fällen nicht ausreicht, auch schwerere schnellaufende Bearbeitungsvorgänge im Bereich der spanenden Fertigung von Eisen- und Nichteisenmetallen wie Fräsen oder Bohren bzw. Schneiden von Gewinden, durchzuführen.Practice has shown, however, that in many cases the lubricating effect of this class of substances is not sufficient to carry out even heavier, high-speed machining operations in the field of machining ferrous and non-ferrous metals, such as milling or drilling or cutting threads.

Zweck der Erfindung ist daher die Bereitstellung von wasserlöslichen Schmiermitteln, die für Hochleistungsarbeitsgänge wie Lochen, Gewindeschneiden, Gewindebohren und dgl. geeignet sind und nicht nur für die Bearbeitung von Eisenmetallen wie Stahl und Stahllegierungen, sondern auch für die Bearbeitung von Nichteisenmetallen wie Kupfer, Aluminium, Messing, Bronze und dgl. geeignet sind.The purpose of the invention is therefore to provide water-soluble lubricants which are suitable for high-performance operations such as punching, tapping, tapping and the like, and not only for the machining of ferrous metals such as steel and steel alloys, but also for the machining of non-ferrous metals such as copper, aluminum, Brass, bronze and the like are suitable.

Gegenstand der Erfindung sind wasserlösliche Schmiermittel, die eine oder mehrere Verbindungen der Formel

Figure imgb0001
enthalten, wobei R Wasserstoff, C1-C12-Alkyl oder C1-C12-Alkenyl, R1 C1-C18-Alkyl oder C2-C18-Alkenyl, A eine Gruppe der Formeln
Figure imgb0002
X eine Zahl von 0 bis 15 bedeutet und die Zahlenwerte für m und n so gewählt sind, daß der Gesamtgehalt an Ethylenoxid und/oder Propylenoxid im Molekül 10 bis 800 AlkylenoxidEinheiten beträgt.The invention relates to water-soluble lubricants which contain one or more compounds of the formula
Figure imgb0001
 contain, wherein R is hydrogen, C 1 -C 12 alkyl or C 1 -C 12 alkenyl, R 1 C 1 -C 18 alkyl or C 2 -C 18 alkenyl, A is a group of the formulas
Figure imgb0002
 X means a number from 0 to 15 and the numerical values for m and n are selected so that the total content of ethylene oxide and / or propylene oxide in the molecule is 10 to 800 alkylene oxide units.

Bevorzugt sind solche Verbindungen der obigen Formel, worin R Wasserstoff oder C1-C4-Alkyl, R 1 C6-C18-Alkyl oder C 6-C 18-Alkenyl, A eine Gruppe der Formel -(CH2CH2O)m-X eine Zahl von 1 bis 9 bedeutet und der Zahlenwert für m so gewählt ist, daß der Gesamtgehalt an Ethylenoxid im Molekül 40 bis 200 Ethylenoxid-Einheiten beträgt.Preferred compounds of the above formula are those in which R is hydrogen or C 1 -C 4 alkyl, R 1 C 6 -C 18 alkyl or C 6 - C 18 alkenyl, A is a group of the formula - (CH 2 CH 2 O ) m -X is a number from 1 to 9 and the numerical value for m is chosen so that the total content of ethylene oxide in the molecule is 40 to 200 ethylene oxide units.

Die Herstellung der oben beschriebenen Verbindungen erfolgt nach bekannten Verfahren. So werden zunächst Phenol oder Alkylphenole oder deren Mischungen mit Formaldehyd oder Paraformaldehyd zu linearen oder cyclischen Novolaken kondensiert, wie es in Hultzsch, Chemie der Phenolharze, 1950, Seite 114 oder im US-Patent 4032514 oder in J. Org. Chem. Vol. 43, No. 25, 1978, 4905-4906 beschrieben ist. Diese Novolake werden dann mit Alkylenoxiden in bekannter Weise zu den Novolak-Oxethylaten umgesetzt und letztere in Carbonsäureester überführt. Zur Herstellung der linearen oder cyclischen Novolake können Phenol oder gegenüber Formaldehyd bifunktionelle Alkylphenole mit geradkettigen oder verzweigten Alkylresten von C1 bis C12 oder deren Mischungen eingesetzt werden. Das bei der Novolakbildung auftretende Reaktionswasser muß entfernt werden. Dies kann gegebenenfalls azeotrop, während oder nach der Reaktion mit Aldehyden oder durch Anlegen von Vakuum erfolgen. Als Katalysator können beispielsweise Säuren wie Salzsäure, Schwefelsäure, p-Toluolsulfonsäure, Oxalsäure, als alkalische Katalysatorer bevorzugt Natriumhydroxid, Kaliumhydroxid, Natriummethylat oder Kalium-tert.-butylat eingesetzt werden.The compounds described above are prepared by known processes. For example, phenol or alkylphenols or their mixtures with formaldehyde or paraformaldehyde are first condensed to linear or cyclic novolaks, as described in Hultzsch, Chemie der Phenolharze, 1950, page 114 or in U.S. Patent 4032514 or in J. Org. Chem. Vol. 43 , No. 25, 1978, 4905-4906. These novolaks are then reacted with alkylene oxides in a known manner to give the novolak oxethylates and the latter are converted into carboxylic acid esters. To prepare the linear or cyclic novolaks it is possible to use phenol or alkylphenols which are bifunctional to formaldehyde and have straight-chain or branched alkyl radicals from C 1 to C 12 or mixtures thereof. The water of reaction occurring during the formation of novolak must be removed. This can optionally be carried out azeotropically, during or after the reaction with aldehydes or by applying a vacuum. For example, acids such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid can be used as the catalyst, and sodium hydroxide, potassium hydroxide, sodium methylate or potassium tert-butoxide are preferably used as alkaline catalysts.

Bei der Herstellung der Novolake entstehen entweder offenkettige oder cyclischc Produkte. Im Falle der offenkettigen Novolake sind die beiden freien Valenzen in den obigen Formeln jeweils durch Wasserstoffatome abgesättigt, während im Falle der cyclischen Novolake die beiden freien Valenzen zusammen den Ring schließen. Die linearen Novolake sind spröde bis weiche Harze, die cyclischen weiße oder gelbstichige, über 300°C schmelzende Feststoffe. Beide Typen stellen Gemische von mehrkettigen, durch Methylenbrücken verknüpfte Phenole oder Alkylphenole dar.The manufacture of the novolaks produces either open-chain or cyclic products. In the case of open chain Novolaks, the two free valences in the above formulas are each saturated with hydrogen atoms, while in the case of cyclic novolaks the two free valences close the ring together. The linear novolaks are brittle to soft resins, the cyclic white or yellowish solids that melt above 300 ° C. Both types are mixtures of multi-chain phenols or alkylphenols linked by methylene bridges.

Die Oxalkylierung der linearen Novolake wird nach bekannten Verfahren mit Alkylenoxiden in Gegenwart von alkalischen Katalysatoren bei etwa 100 - 210°C, bevorzugt 140 - 180°C, vorgenommen. Als alkalische Katalysatoren kommen vor allem Alkalihydroxide wie Kaliumhydroxid oder bevorzugt Natriumhydroxid oder Alkalialkoholate, wie Natriummethylat oder Kalium-tert.-butylat in Betracht. Die Konzentration dieser alkalischen Katalysatoren soll bevorzugt 0,05 bis 1,0 Gew.-%, bezogen auf das Novolakharz, betragen. Die Oxalkylierung kann drucklos oder in Druckgefäßen durchgeführt werden, wobei das Alkylenoxid gasförmig oder flüssig zugeführt werden kann. Die Menge des Alkylenoxids wird so bemessen, daß im Durchschnitt auf jede phenolische Hydroxygruppe des Novolakharzes 10 - 50 Alkylenoxidreste eingeführt werden. Die Oxalkylierung der hochschmelzenden cvcli- sehen Novolake kann nach US-Patent 4 032 514, Beispiel 13C in Xylol-Suspension erfolgen. Das Xylol kann nach der Oxalkylierung als Wasser-Schleppmittel bei der Veresterung im Oxalkylat verbleiben.The oxyalkylation of the linear novolaks is carried out by known processes with alkylene oxides in the presence of alkaline catalysts at about 100-210 ° C., preferably 140-180 ° C. Alkaline catalysts which are particularly suitable are alkali metal hydroxides such as potassium hydroxide or preferably sodium hydroxide or alkali metal alcoholates such as sodium methylate or potassium tert-butoxide. The concentration of these alkaline catalysts should preferably be 0.05 to 1.0% by weight, based on the novolak resin. The oxyalkylation can be carried out without pressure or in pressure vessels, and the alkylene oxide can be supplied in gaseous or liquid form. The amount of the alkylene oxide is such that an average of 10-50 alkylene oxide residues are introduced into each phenolic hydroxyl group of the novolak resin. The oxyalkylation of the high-melting cvcli- see novolaks can be carried out in xylene suspension according to US Pat. No. 4,032,514, Example 13C. After the oxyalkylation, the xylene can remain as a water entrainer in the esterification in the oxyalkylate.

Die Veresterung der Novolak-Oxalkylate erfolgt nach bekannten Methoden mit Carbonsäuren ohne oder in Anwesenheit von Azeotrop-Schleppnitteln mit Carbonsäurederivaten, wie Carbonsäurehalogeniden, -anhydriden oder durch Umesterung mit C1 bis C4-Alkylestern der Carbonsäuren. Als Carbonsäuren kommen bevorzugt gesättigte Monocarbonsäuren mit 2 bis 20, insbesondere mit G bis 18 Kohlenstoffatomen oder deren Mischungen in Frage. Als Beispiele seien angeführt: sogenannte Vorlauffettsäuren, 2-Ethyl-hexansäure, i-Nonansäure, Dodecansäure, i-Tridecansäure, Stearinsäure, i-Stearinsäure oder Ölsäure.The novolak oxalkylates are esterified by known methods with carboxylic acids without or in the presence of azeotropic drag compounds with carboxylic acid derivatives, such as carboxylic acid halides, anhydrides or by transesterification with C 1 to C 4 alkyl esters of the carboxylic acids. Preferred carboxylic acids are saturated monocarboxylic acids with 2 to 20, in particular with G to 18 carbon atoms or their Mixtures in question. Examples are: so-called pre-fatty acids, 2-ethyl-hexanoic acid, i-nonanoic acid, dodecanoic acid, i-tridecanoic acid, stearic acid, i-stearic acid or oleic acid.

Diese Carbonsäuren können teilweise durch Carbonsäuren mit 2 - 5 Kohlenstoffatomen, z.B. Essigsäure ersetzt werden.These carboxylic acids can be partially substituted by carboxylic acids with 2-5 carbon atoms, e.g. Acetic acid to be replaced.

Die Eigenschaften der oben beschriebenen Verbindungen, insbe sondere die Wasserlöslichkeit und das Schaumverhalten, werden von der Länge der Reste R und R1, von der Größe . des Wertes für X und vom Oxalkylierungsgrad, ausgedrückt durch die Indizes m und n, beeinflußt. Allgemein ist zu sagen, daß die Waserlöslichkeit abnimmt mit zunehmender Größe der Reste R und R1 und mit abnehmendem Oxalkylierungsgrad. Durch geeignete Variationen dieser Substituenten läßt sich in jedem Fall die gewünschte Löslichkeit in Wasser erreichen. Die Trübungspunkte, gemessen in 1 %iger wäßriger Lösung sollen oberhalb 25°C, bevorzugt oberhalb 30°C liegenThe properties of the compounds described above, in particular the water solubility and the foaming behavior, depend on the length of the radicals R and R 1 , on the size. of the value for X and the degree of oxyalkylation, expressed by the indices m and n. In general it can be said that the water solubility decreases with increasing size of the radicals R and R 1 and with decreasing degree of oxalkylation. The desired solubility in water can be achieved in any case by suitable variations of these substituents. The cloud points, measured in 1% strength aqueous solution, should be above 25 ° C., preferably above 30 ° C.

Allgemeine HerstellvorschriftGeneral manufacturing instructions

In der folgenden Tabelle A sind eine Reihe von erfindungsge mäß zu verwendenden veresterten Novolak-Harzen dargestellt. Man erhält diese Verbindungen nach folgender Vorschrift.The following Table A shows a number of esterified novolak resins to be used according to the invention. These compounds are obtained according to the following regulation.

Das Alkylphenol wird zusammen mit einer katalytisch wirksamen Menge an p-Toluolsulfonsäure in einem Kolben vorgelegt und erwärmt. Dann tropft man langsam eine 35 %ige Formaldehydlösung zu, wobei die Menge an Formaldehyd durch die Größe des jeweiligen Wertes für X in der Tabelle bestimmt wird. Nach Abklingen der exotherm verlaufenden Reaktion heizt man noch ca. 16 Stunden unter Rückfluß nach Anschließend wird bei 120 - 140°C zunächst unter Normaldruck, dann unter vermindertem Druck das Wasser vollständi abdestilliert. Nach dem Erkälien erhält man den Novolak al sprödes fast farbloses Harz.The alkylphenol is placed together with a catalytically effective amount of p-toluenesulfonic acid in a flask and heated. A 35% formaldehyde solution is then slowly added dropwise, the amount of formaldehyde being determined by the size of the respective value for X in the table. After the exothermic reaction has subsided, the mixture is heated under reflux for about 16 hours. The water is then completely distilled off at 120-140 ° C., first under normal pressure and then under reduced pressure. After the cold, the novolak al brittle, almost colorless resin.

Der so erhaltene Novolak wird zusammen mit 1,1 g Natriumhydroxid in einen Autoklaven eingefüllt. Die Luft wird durch Stickstoff verdrängt und es wird auf 150 - 170°C aufgeheizt. Bei dieser Temperatur wird flüssiges Ethylenoxid bzw. ein Gemisch von Ethylenoxid und Propylenoxid eingeleitet bis die Gewichtszunahme im Autoklaven die jeweils unter A in der Tabelle angegebene Gesamt-Molmenge erreicht hat. Anschließend wird noch eine Stunde nachgerührt.The novolak thus obtained is introduced into an autoclave together with 1.1 g of sodium hydroxide. The air is displaced by nitrogen and it is heated to 150 - 170 ° C. At this temperature, liquid ethylene oxide or a mixture of ethylene oxide and propylene oxide is introduced until the weight increase in the autoclave has reached the total molar amount indicated under A in the table. Then it is stirred for another hour.

In einem Rührgefäß, versehen mit Rührer und Kühler wird eine Mischung des oxalkylierten Novolaks, eine katalytisch wirksame Menge an p-Toluolsulfonsäure und die jeweils erforderliche Menge der Säure der Formel R1-CCOH eingefüllt und so lange unter Rühren auf eine Temperatur von ca. 170°C erhitzt, bis kein Wasser mehr abdestilliert und die Säurezahl auf einen Wert unter 3 abgesunken ist. Man erhält so das Veresterungsprodukt in Form einer braunen Substanz mit öliger bis wachsartiger Konsistenz.A mixture of the oxyalkylated novolak, a catalytically effective amount of p-toluenesulfonic acid and the amount of acid of the formula R 1 -CCOH required in each case are introduced into a stirred vessel equipped with a stirrer and cooler and the mixture is stirred at a temperature of about 170 for as long as possible ° C heated until no more water distilled off and the acid number has dropped to a value below 3. The esterification product is thus obtained in the form of a brown substance with an oily to waxy consistency.

Figure imgb0003
Figure imgb0003

Die zur Herstellung der erfindungsgemäßen Metallbearbeitungs- mittel benötigten Mengen an veresterten oxalkylierten Novolacken können in weiten Grenzen variieren.The M invention for producing etallbearbeitungs- medium required amounts of esterified oxyalkylated novolaks may vary within wide limits.

Für die üblichen Metallbearbeitungsvorgänge reicht im allgemeinen eine Anwendungskonzentration von unter 10 Gew.-% aus. Es stellt ein Vorteil der erfindungsgemäßen Metallbearbeitungsmittel dar, daß sie bereits bei geringen Konzentrationen eine gute Wirksamkeit aufweisen. So kann mit den neuen Metallbearbeitungsmitteln eine befriedigende Wirkung noch bei Konzentrationen von etwa 0,5 Gew.-% erreicht werden. Die - Anwendungskonzentration der Metallbearbeitungsmittel richtet sich, wie auch bei bekannten Mitteln, vor allem nach der Art des Bearbeitungsganges der Werkstücke. Bei üblichen Vorgängen liegt die Anwendungskonzentration der neuen Metallbearbeitungsmittel im Bereich von etwa ein bis acht Gew.-%. In besonders gelagerten Fällen können die obenangegebchen Werte jedoch auch unter- bzw. überschritten werden. So ist es bei besonders schweren Metallbearbeitungsvorgängen unter Umständen angebracht, Lösungen mit einem Gehalt an veresterten oxalkylierten Novolaken bis zu etwa 25 Gew.-% einzusetzen.An application concentration of less than 10% by weight is generally sufficient for the usual metalworking operations. It is an advantage of the metalworking agents according to the invention that they are effective even at low concentrations. With the new metal processing agents, a satisfactory effect can still be achieved at concentrations of about 0.5% by weight. The - application concentration of the metalworking agent, as with known agents, depends above all on the type of processing of the workpieces. In usual processes, the application concentration of the new metalworking agents is in the range of about one to eight percent by weight. In special cases, however, the values given above can also be exceeded or fallen short of. In the case of particularly heavy metalworking processes, it may be appropriate to use solutions with a content of esterified oxyalkylated novolaks of up to about 25% by weight.

Die wasserlöslichen Schmiermittel können noch weitere Zusätze wie z.B. Amine und übliche Korrosionsinhibitoren aus der Carbonsäurereihe und/oder Fettsäure-Amin-Kondensationsprodukte und/oder Bohrsäurealkanolamide enthalten.The water-soluble lubricants can also contain other additives such as Contain amines and conventional corrosion inhibitors from the carboxylic acid series and / or fatty acid-amine condensation products and / or boric acid alkanolamides.

Die weiter unten mitgeteilten Ergebnisse von vergleichenden Prüfungen zeigen, daß die erfindungsgemäßen Metallbearbeitungsflüssigkeiten sehr starke Belastungen auszuhalten vermögen und daß sie deutlich bessere Belastungs- und Verschleißfestigkeitseigenschaften besitzen als die bekannten Zubereitungen. Die erfindungsgemäßen Metallbearbeitungsflüssigkeiten sind aufgrund ihrer sehr guten Schmier- und Kühleigenschaften sowohl für schnelle Metallbearbeitungsgänge wie Drehen, Fräsen, Bohren, Schleifen usw., die meist nur eine relativ geringe Belastung des Schmiermittels mit sich bringen, als auch für schwere Arbeitsgänge, wie z.B. Gewindeschneiden, bei denen das Schmiermittel einer großen Belastung ausgesetzt ist, in gleicher Weise gut geeignet.The results of comparative tests reported below show that the metalworking fluids according to the invention are able to withstand very high loads and that they have significantly better load and wear resistance properties than the known preparations. The metalworking fluids according to the invention are due to their very good lubricating and cooling properties both for fast metalworking gears such as turning, milling, drilling, grinding, etc., which usually only place a relatively low load on the lubricant, as well as for heavy-duty operations, such as thread cutting, in which the lubricant is exposed to a large load, are equally suitable .

In den nachfolgenden Beispielen bedeuten, sofern es nicht ausdrücklich anders vermerkt ist, die Teile Gewichtsteile und die Prozentangaben Gewichtsprozente.In the following examples, the parts by weight and the percentages mean percentages by weight, unless expressly stated otherwise.

Zur Qualitätsbeurteilung der Metallbearbeitungsmittel gemäß der Erfindung und zum Vergleich mit wäßrigen Lösungen bekannter Schmierstoffkomponenten wurde die Reibverschleißwaage nach Reichert herangezogen. Diese Vorrichtung besteht im wesentlichen aus zwei auswechselbaren Reibpartnern aus Stahl von unterschiedlicher Härte, wovon der eine, ein Schleifring, beweglich und der andere, eine Prüfrolle, starr angeordnet ist. Während der Prüfung werden Schleifring und Prüfrolle über ein Doppelhebesystem mit einer definierten Kraft axial gekreuzt aufeinander gepreßt. Der Schleifring taucht dabei teilweise in die zu untersuchende Metallbearbeitungsflüssigkeit ein und führt gleichzeitig eine Drehbewegung aus, wobei ein ständiger Schmiermitteltransport zur Reibverschleißzone zwischen Prüfrolle und Prüfring gewährleistet ist.For the quality assessment of the metalworking agents according to the invention and for comparison with aqueous solutions of known lubricant components, the friction wear balance according to Reichert was used. This device essentially consists of two interchangeable steel friction partners of different hardness, one of which, a slip ring, is movable and the other, a test roller, is rigidly arranged. During the test, the slip ring and test roller are pressed axially crossed on each other using a double lifting system with a defined force. The slip ring is partially immersed in the metalworking fluid to be examined and at the same time executes a rotary movement, with constant lubricant transport to the wear zone between the test roller and the test ring being guaranteed.

Durch die Drehbewegung entsteht in Abhängigkeit von der Druckaufnahmefähigkeit der jeweiligen Schmierflüssigkeit auf der Prüfrolle eine mehr oder minder große elliptische Verschleißmarke. Auf dieser, nach einer bestimmten Laufzeit entstandenen Abriebfläche und der jeweiligen Anpreßkraft ergibt sich ein Zahlwert mit der Dimension /kp/cm2/, der als "spezifische Flächenpressung" bezeichnet wird und als Maß für die Tragfähigkeit von Schmierfilmen Verwendung findet. (Vgl. Zeitschrift "Mineralöl-Technik" 3 (1958) Nr. 2, Seiten 1 - 17).The rotary movement creates a more or less large elliptical wear mark depending on the pressure absorption capacity of the respective lubricant on the test roller. In this, after a certain running time incurred wear surface and the respective contact pressure, a numerical value obtained with the dimension / kp / cm 2 / known as "specific surface pressure" is referred to, and as M ate for the carrying capacity of lubricating films is used. (See magazine "Mineralöl-Technik" 3 (1958) No. 2, pages 1-17).

Die Prüfungen wurden an wäßrigen Lösungen mit steigenden Gehalten an Wirksubstanz veresterter oxethylierter Novcl bzw. EO/PO-Blockpolymerevon 1, 2 und 5 Gew.-% durchgefüh ;The tests were carried out on aqueous solutions with increasing active substance contents of esterified, ethoxylated Novcl or EO / PO block polymers of 1, 2 and 5% by weight;

Die Metallbearbeitungsflüssigkeiten wurden durch Lösen d Wirksubstanzen in Trinkwasser von 20° dH hergestellt.

  • Beispiel 1: Verbindung A 1 aus Tabelle A
  • Beispiel 2: Verbindung A 2 aus Tabelle A
  • Beispiel 3: Verbindung A 4 aus Tabelle A
  • Beispiel 4: Verbindung A 7 aus Tabelle A
  • Beispiel 5: Verbindung A 12 aus Tabelle A
  • Beispiel 6: Verbindung B . 1 aus Tabelle A
The metalworking fluids were produced by dissolving the active substances in drinking water at 20 ° dH.
  • Example 1: Compound A 1 from Table A
  • Example 2: Compound A 2 from Table A
  • Example 3: Compound A 4 from Table A
  • Example 4: Compound A 7 from Table A
  • Example 5: Compound A 12 from Table A
  • Example 6: Compound B. 1 from Table A

Vergleichs-

  • produkt I : Verzweigtkettiges EO/PO-Blockpolymer. Reaktionsprodukt aus Ethylendiamin + 30 Ethylenoxid ÷ 30 Propylenoxid
Comparative
  • product I: branched-chain EO / PO block polymer. Reaction product from ethylenediamine + 30 ethylene oxide ÷ 30 propylene oxide

Vergleichs-

  • produkt II: Verzweigtkettiges EO/PO-Blockpolymer. Reaktionsprodukt aus Ethylendiamin + 30 Ethylenoxid + 60 Propylenoxid
Comparative
  • product II: branched chain EO / PO block polymer. Reaction product from ethylenediamine + 30 ethylene oxide + 60 propylene oxide

Die Ergebnisse der vergleichenden Prüfungen sind in der nachfolgenden Tabelle zusammengestellt.

Figure imgb0004
Die Meßergebnisse zeigen die deutlich überlegene Schmiereigenschaften der erfindungsgemäßen Metallbearbeitungshilfsmittel. Es hat sich gezeigt, daß die neuen Schmierstoffe gemäß der Erfindung sehr starke Belastungen auszuhalten vermögen und daß-sie eine deutlich bessere Belastu festigkeit und bessere Verschleißeigenschaften besitzen a wäßrige Lösungen bereits bekannter Schmierstoffe.The results of the comparative tests are summarized in the table below.
Figure imgb0004
 The measurement results show the clearly superior lubricating properties of the metalworking aids according to the invention. It has been shown that the new lubricants according to the invention are able to withstand very high loads and that they have a significantly better strength and better wear properties than aqueous solutions of already known lubricants.

Die erfindungsgemäßen Schmierstoffe sind daher nicht nur sehr gut geeignet als Hilfsmittel für normale Metallbearbeitungsvorgänge wie Drehen, Bohren, Schleifen und dergleichen, die im allgemeinen eine vergleichsweise nur geringe Belastung des Schmiermittels mit sich bringen, sond sie sind mit Vorteil auch für sehr schwere Bearbeitungsvc gänge wie z.B. Gewindeschneiden einzusetzen.The lubricants according to the invention are therefore not only very suitable as auxiliaries for normal metalworking operations such as turning, drilling, grinding and the like, which generally involve a comparatively low load on the lubricant, but they are also advantageous for very heavy machining operations such as e.g. Use thread cutting.

Claims (2)

1. Wasserlösliche Schmiermittel gekennzeichnet durch einen Gehalt an Verbindungen der Formel 1
Figure imgb0005
wobei R Wasserstoff, C1-C12-Alkyl oder C1-C12-Alkenyl, R1 C1-C18 Alkyl oder C2-C18-Alkenyl, A eine Gruppe der Formeln
Figure imgb0006
X eine Zahl von 0 bis 15 bedeutet und die Zahlenwerte für m und n so gewählt sind, daß der Gesamtgehalt an Ethylenoxid und/oder Propylenoxid im Molekül 10 bis 800 Alkylenoxid-Einheiten beträgt.1. Water-soluble lubricants characterized by a content of compounds of formula 1
Figure imgb0005
 where R is hydrogen, C 1 -C 12 alkyl or C 1 -C 12 alkenyl, R 1 C 1 -C 18 alkyl or C 2 -C 18 alkenyl, A is a group of the formulas
Figure imgb0006
 X denotes a number from 0 to 15 and the numerical values for m and n are chosen such that the total content of ethylene oxide and / or propylene oxide in the molecule is 10 to 800 alkylene oxide units. 2. Wasserlösliche Schmiermittel nach Anspruch 1 gekennzeichnet durch einen Gehalt an Verbindungen der Formel 1, wobei R Wasserstoff oder C1-C4-Alkyl, R1 C6-C18 Alkyl oder C6-C18-Alkenyl, A eine Gruppe der Formel
Figure imgb0007
X eine Zahl von 1 bis 9 bedeutet und der Zahlenwert für m und n so gewählt ist, daß der Gesamtgehalt an Ethylenoxid im Molekül 40 bis 200 Ethylenoxideinheiten beträgt.2. Water-soluble lubricant according to claim 1, characterized in that it contains compounds of the formula 1, where R is hydrogen or C 1 -C 4 alkyl, R 1 C 6 -C 18 alkyl or C 6 -C 18 alkenyl, A is a group of formula
Figure imgb0007
 X denotes a number from 1 to 9 and the numerical value for m and n is chosen such that the total content of ethylene oxide in the molecule is 40 to 200 ethylene oxide units.
EP82106564A 1981-07-24 1982-07-21 Water-soluble lubricant Expired EP0071167B1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5100989A (en) * 1987-09-04 1992-03-31 Hoechst Aktiengesellschaft Resin acid esters based on novolak oxyalkylates, their preparation and their use
US6293665B1 (en) 1998-09-10 2001-09-25 Hewlett-Packard Company Dual capillarity ink accumulator for ink-jet

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CA1260868A (en) * 1984-04-11 1989-09-26 Izaak Lindhout Process for calcining green coke
JP2571100B2 (en) * 1988-05-30 1997-01-16 日清製油株式会社 Lubricant
WO1996001301A1 (en) * 1994-07-06 1996-01-18 Mitsui Petrochemical Industries, Ltd. Lubricating oil containing aromatic ether compound

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2692859A (en) * 1951-07-18 1954-10-26 Shell Dev Metal-working lubricant
DE2104202A1 (en) * 1971-01-29 1972-08-10
EP0041688A1 (en) * 1980-06-10 1981-12-16 Hoechst Aktiengesellschaft Use of esterified oxyalkylates of hydroxy-aromatic compounds to prepare dyeing agents, and the corresponding dyestuff preparations

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Publication number Priority date Publication date Assignee Title
JPS6026864B2 (en) * 1978-05-30 1985-06-26 花王株式会社 Lubricating agent for synthetic fibers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2692859A (en) * 1951-07-18 1954-10-26 Shell Dev Metal-working lubricant
DE2104202A1 (en) * 1971-01-29 1972-08-10
EP0041688A1 (en) * 1980-06-10 1981-12-16 Hoechst Aktiengesellschaft Use of esterified oxyalkylates of hydroxy-aromatic compounds to prepare dyeing agents, and the corresponding dyestuff preparations

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5100989A (en) * 1987-09-04 1992-03-31 Hoechst Aktiengesellschaft Resin acid esters based on novolak oxyalkylates, their preparation and their use
US6293665B1 (en) 1998-09-10 2001-09-25 Hewlett-Packard Company Dual capillarity ink accumulator for ink-jet

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