EP0275351B1 - Fluide hydraulique lubrifiant, notamment liquide de freins, sa méthode de fabrication et son utilisation - Google Patents

Fluide hydraulique lubrifiant, notamment liquide de freins, sa méthode de fabrication et son utilisation Download PDF

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Publication number
EP0275351B1
EP0275351B1 EP87109206A EP87109206A EP0275351B1 EP 0275351 B1 EP0275351 B1 EP 0275351B1 EP 87109206 A EP87109206 A EP 87109206A EP 87109206 A EP87109206 A EP 87109206A EP 0275351 B1 EP0275351 B1 EP 0275351B1
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Prior art keywords
hydraulic fluid
lubricating
metal
brake fluid
nickel
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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EP87109206A
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German (de)
English (en)
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EP0275351A1 (fr
Inventor
Erasmus Dr. Froeschmann
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MAX GRILL GES.MBH
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Max Grill Gesmbh
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Priority to AT87109206T priority Critical patent/ATE101411T1/de
Publication of EP0275351A1 publication Critical patent/EP0275351A1/fr
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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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/78—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing boron
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • C10M107/34—Polyoxyalkylenes
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    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/52—Lubricating compositions characterised by the base-material being a macromolecular compound containing boron
    • C—CHEMISTRY; METALLURGY
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    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
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    • 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
    • C10M137/10—Thio derivatives
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    • C10M169/04—Mixtures of base-materials and additives
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    • C10M2205/026—Butene
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    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
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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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/08—Groups 4 or 14
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/10—Groups 5 or 15
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/14—Group 7
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/16—Groups 8, 9, or 10
    • 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
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Definitions

  • the invention relates to a novel lubricable hydraulic fluid, in particular brake fluid, based on polyglycol ether and containing at least one metal dialkyldithiocarbamate and metal dialkyldithiophosphate, a process for its production and its use as a working fluid for central hydraulics, in particular as a brake fluid, for power steering, central locking.
  • Fan hydraulics, the level control and suspension hydraulics in motor vehicles and generally as hydraulic fluid in other land, water and aircraft and engines.
  • Hydraulic fluids are important structural elements for the operation of the brakes, the steering, the opening and closing of the doors as well as other auxiliary units and the suspension on vehicles, in particular motor vehicles. Of particular importance is the brake fluid, the properties of which are essential for the design of the brake system Meaning.
  • the invention is explained below on the basis of its use as a brake fluid for motor vehicles, but the same or similar considerations also apply to its use as a different hydraulic fluid, in particular as a working fluid for the central hydraulics, the power steering, the fan hydraulics, the central locking and the suspension hydraulics, and generally as Hydraulic fluid in other land, water and aircraft, especially motor vehicles, and engines.
  • brake fluids are those based on polyglycol ether and mineral oil.
  • glycol ethers are also used, which are derived from propylene glycol.
  • ether is mostly used, which are not composed of a single building block, but represent a certain mixed form.
  • the following empirical formula can be given for these substances: HO- (CH2-CH2-O) x - (CH ⁇ CH3-CH2-O) y -H where the indices x and y lie between 0 and 25, whereby the sum of x and y does not usually exceed the value 25.
  • the distribution of the building blocks can be irregular, which is why these compounds are referred to as "statistical copolymers".
  • polyglycol ethers of the following type are formed: RO- (CH2-CH2-O) x - (CH-CH3-CH2-O) y -H wherein R is CH3 or C2H5 or i- or n-C3H7 or n- or i- or t-C4H9.
  • X + y 2 to 4, mainly 3.
  • Brake fluids containing a third type of polyglycol ether have also been on the market for some years. These include in particular the DOT 4 brake fluids. They arise from the fact that the polyglycol ethers described above are subjected to a further modification to form their borate esters.
  • the reactive OH group still present is esterified with boric acid H3BO3, so that compounds of the following type are formed: wherein RH or CH3, R1, R2, R3 CH3 or C2H5, C3H7, C4H9 (all isomers), x, y and z represent a number from 2 to 4, preferably 3.
  • This class of compounds is contained in a proportion of approximately 40% by weight in the brake fluids according to DOT 4.
  • the brake fluids on the market (such as Hydraulan H 407® from BASF and DOT 4 + TSA® from Hoechst) consist of a balanced mixture of the three classes of compounds described above.
  • the compounds and mixing ratios are modified in order to take the end product into account to optimize for certain properties.
  • a general disadvantage of these brake fluids based on polyglycol ethers is that their lubricity is limited, i.e. the pressure generators, in particular the feed pumps, cylinders and the like.
  • the hydraulic systems containing them must be lubricated separately, which entails a considerable technical outlay.
  • Another type of usable brake fluids are those based on mineral oil / synthetic oil. Due to the diverse requirements placed on brake fluids, only highly refined mineral oil fractions from selected crude oils can be considered for this purpose.
  • the boiling cut must be based on the boiling point requirements on the one hand and the viscosity requirements on the other hand, whereby the use of viscosity index improvers (VI) in higher concentrations must be used.
  • VI viscosity index improvers
  • Oligonucleotides of propene, n-butene-1, n-pentene-1 and n-decene-1 are often used either alone or as a mixture with one another or with mineral oil-based components.
  • additives commonly used in the mineral oil industry are available for property-improving additives, e.g. Antioxidants, wear inhibitors, metal deactivators, detergents, dispersants, antifoams, viscosity index improvers and the like.
  • the commercial brake fluids usually contain about 5% additives, VI improvers are added up to 15%.
  • a lubricating oil for gasoline and diesel engines which contains an oil-soluble zinc dialkyldithiophosphate (ZDDP) as a lubricant additive in a mixture with an oil-soluble molybdenum (II) bis (dialkyldithiocarbamate) (column 1, lines 48-63 ).
  • ZDDP oil-soluble zinc dialkyldithiophosphate
  • II oil-soluble molybdenum
  • high-pressure lubricants based on polyglycol ether which contain a metal dialkyldithiophosphate in a lubricating oil or grease base, for example the corresponding zinc (II) or antimony (III) salt in combination with a metal dialkyldithiocarbamate, for example the corresponding zinc (II) or lead (II) salt.
  • metal dialkyldithiophosphate in a lubricating oil or grease base
  • a metal dialkyldithiocarbamate for example the corresponding zinc (II) or lead (II) salt.
  • the object of the invention was therefore to develop a hydraulic fluid, in particular brake fluid, which offers the advantages of the fluids based on polyglycol ether, but is significantly improved with regard to their lubricity and wear protection.
  • a lubricating additive in a quantity of 0.1 to 5% by weight to a commercially available hydraulic fluid, in particular brake fluid, based on polyglycol ether, which additive comprises a combination of at least one specific metal dialkyldithiophosphate of the formula given below and at least two specific dialkyldithocarbamates of the formula given below, one of which is a bordialkyldithocarbamate, in a specific weight ratio.
  • the present invention relates to a method for producing the lubricating hydraulic fluid, in particular brake fluid, described above, which is characterized in that the submitted commercially available hydraulic fluid, in particular brake fluid, which optionally contains customary additives, optionally heated to 100 to 120 ° C.
  • the first dialkyldithiocarbamate is added with stirring within 5 to 60 minutes, preferably 10 minutes, then with further stirring at a temperature below 100 ° C, preferably at about 90 ° C, within 2 to 20 minutes, preferably 5 to 10 minutes, the second dialkyldithiocarbamate is added and with further stirring at a temperature of about 90 ° C within 2 to 20 minutes, preferably 5 to 10 minutes, the metal dialkyldithiophosphate is added.
  • the present invention relates to the use of the above-described lubricable hydraulic fluid, in particular brake fluid, as a working fluid for the central hydraulics, in particular as a brake fluid, for the power steering, the central locking, the suspension hydraulics and the level control and fan hydraulics in motor vehicles.
  • the hydraulic fluid according to the invention in particular brake fluid, has an unprecedented lubricating capacity and an unprecedented wear protection, so that additional, structurally separate lubrication of the components coming into contact with the hydraulic fluid, in particular brake cylinders, pressure generator pumps, feed pumps and the like; is no longer required.
  • the wear protection achievable with the hydraulic fluid according to the invention, in particular brake fluid is higher than with the commercial brake fluids without the additive according to the invention. They are in the order of magnitude of a good to very good gear oil.
  • the hydraulic fluid according to the invention is therefore not only suitable as an excellent brake fluid, but can also be used to operate the power steering, suspension, central locking and as operating fluid for other hydraulic units in motor vehicles, but also in other land, water and aircraft vehicles and engines.
  • An essential feature of the lubricating hydraulic fluid, in particular brake fluid, claimed here is its content of an lubricating additive which consists of a combination of at least two metal dialkyldithiocarbamates and at least one metal dialkyldithiophosphate.
  • the lubricating additive generally makes up 0.1 to 5% by weight, preferably 0.5 to 2.5% by weight, of the total weight of the lubricating hydraulic fluid, in particular brake fluid.
  • the first metal dialkyldithiocarbamate and the second metal dialkyldithiocarbamate lie in component (a) of the lubricating additive used according to the invention generally in a weight ratio of 5: 1 to 1: 1, preferably 2.5: 1 to 1: 1, to each other.
  • Component (b) of the lubricating additive is two or more dialkyldithiocarbamates of boron and of metals in the mixed oxidation states from the group boron (B), titanium (Ti), zirconium (Zr), tin (Sn), Lead (Pb); Vanadium (V), tantalum (Ta), antimony (Sb); Chromium (Cr), molybdenum (Mo), tungsten (W); Manganese (Mn); Cobalt (Co) and nickel (Ni), the dialkyldithiocarbamates of boron (B), nickel (Ni), cobalt (Co) and molybdenum (Mo) being particularly preferred.
  • metal dialkyldithiocarbamates used according to the invention can be represented by the general formula where Me is B or one of the above metals and alkyl has the meanings given below.
  • Examples of metal dialkyldithiocarbamates which can be used with particular advantage according to the invention are as follows: Boron trisdialkyldithiocarbamates and titanium, zirconium, tin and lead tetrakisdialkyldithiocarbarates and tin and lead bisdialkyldithiocarbamates; Antimony, vanadium and tantalum dialkyldithiocarbamates, tetrekis and pentakisdialkyldithiocarbamates, ie the dialkyldithiocarbamates in which these metals are present in mixed oxidation states; Chromium, Chromium, Chromium tetrakis and chromium hexakis dialkyldithiocarbamates, molybdenum and tungsten
  • Particularly preferred among these compounds are the boron trisdialkyldithiocarbamates, the nickeltrisdialkyldithiocarbamates and the molybdenum tetrakis and molybdenum oxytetrakisdialkyldithiocarbamates.
  • Component (a) of the lubricating additive used according to the invention is one or more dialkyldithiophosphates of metals in mixed oxidation states from the group titanium (Ti), zirconium (Zr), tin (Sn), lead (Pb); Vanadium (V), tantalum (Ta), antimony (Sb); Chromium (Cr), molybdenum (Mo), tungsten (W); Manganese (Mn); Cobalt (Co) and nickel (Ni), among which the dialkyldithiophosphates of nickel, titanium, vanadium, molybdenum, tungsten and manganese are particularly preferred.
  • dialkyldithiophosphates of metals in mixed oxidation states from the group titanium (Ti), zirconium (Zr), tin (Sn), lead (Pb); Vanadium (V), tantalum (Ta), antimony (Sb); Chromium (Cr), molybdenum (Mo), tungsten
  • the metal dialkyldithiophosphates used according to the invention can be represented by the general formula: wherein Me represents one of the above metals and alkyl has the meaning given below.
  • Metal dialkyldithiophosphates which can be used according to the invention are the dialkyldithiophosphates of the same metals in the same oxidation states as those above for the metal dialkyldithiocarbamates have been enumerated.
  • Nickel bis and tris dialkyl dithiophosphates, titanium and vanadium tetrakis dialkyl dithiophosphates, molybdenum and tungsten tetrakis dialkyl dithiophosphates and molybdenum and tungsten oxytetrakisdialkyl dithiophosphates are very particularly advantageous.
  • alkyl group in the above-mentioned metal dialkyldithiocarbamates and metal dialkyldithiophosphates each contains 4 to 8 carbon atoms, so that the metal salts mentioned are still soluble in the commercially available brake fluid
  • examples of particularly advantageous alkyl groups include the n-, i- and tert-butyl groups; the n- and i-amyl group; the n- and i-pentyl group; the n- and i-hexyl group; the n- and i-heptyl group; and the 2-ethylhexyl group.
  • the i-butyl group, the n-amyl group and the 2-ethylhexyl group are very particularly preferred.
  • metal dialkyldithiocarbamates used according to the invention are: Boron trisdiisobutyldithiocarbamate, bortrisdi-2-ethylhexyldithiocarbamate, nickel trisdiisobutyldithiocarbamate, nickel trisdiamyldithiocarbamate, nickel trisdi-2-ethylhexyldithiocarbamate and molybdenum trakisdi-2-ethylhexyldithiodibodiobyldithiobiobithdibioblithiobioblithdibiobiethyldibioblithiobioblithiobiethyldibiobioblithioblodioblodioblb
  • metal dialkyldithiophosphates used according to the invention are nickel bis- and trisdi-2-ethylhexyl dithiophosphate, titanium and vanadium tetrakisdi 2-ethylhexyl dithiophosphate as well as molybdenum and tungsten tetrakis and molybdenum oxyphosphate and tungsten oxytetrakisdi-2-ethylhexyl dyophosphate.
  • the invention further relates to a method for producing the lubricating hydraulic fluid, in particular brake fluid, described above, which is characterized in that the commercially available brake fluid, which optionally contains customary additives, is initially introduced, optionally under pressure, heated to 100 to 120 ° C. and with stirring within 5 to 60 min, preferably within 10 min, the first metal dialkyldithiocarbamate is added, then with further stirring at a temperature below 100 ° C, preferably at about 90 ° C, within 2 to 20 min, preferably within 5 to 10 minutes, the second metal dialkyldithiocarbamate is added and the metal dialkyldithiophosphate is added with further stirring at a temperature of about 90 ° C. within 2 to 20 minutes, preferably within 5 to 10 minutes. The mixture obtained is then allowed to cool and is filled into suitable containers in which it can be stored, preferably in the absence of air.
  • the commercially available brake fluid which optionally contains customary additives
  • the first metal dialkyldithiocarbamate used is preferably nickel trisdiisobutyldithiocarbanate, nickel trisdi-n-amyldithiocarbamate and / or nickel trisdi-2-ethylhexyldithiocarbamate.
  • Bortrisdiisobutyldithiocarbamate and / or Bortrisdi-2-ethylhexyldithiocarbamate are preferably used as the second metal dialkyldithiocarbamate.
  • Nickel trisdi-2-ethylhexyldithiophosphate is preferably used as the metal dialkyldithiophosphate, Titanium tetrakisdi-2-ethylhexyldithiophosphate, vanadium tetrakisdi-2-ethylhexyldithiophosphate, molybdenum tetrakis or molybdenum oxytetrakisdi-2-ethylhexyldithiophosphate, tungsten tetrakis and / or tungsten oxytetrakisdi-2-ethylhexyldithiophosphate. Molybdenum oxytetrakisdi-2-ethylhexyldithiophosphate and nickel trisdi-2-ethylhexyldithiophosphate are particularly preferred.
  • Hydraulic H 407 (a commercial product available from BASF) or DOT 4 Plus (a commercial product from Hoechst AG) are preferably used as the commercially available brake fluid.
  • the invention also relates to the use of the lubricating hydraulic fluid described above as a working fluid for the central hydraulics, in particular as a brake fluid, for the power steering, the central locking, the level control, the suspension hydraulics, the fan hydraulics and other hydraulic auxiliary units for land, water and aircraft , especially motor vehicles and engines.
  • a working fluid for the central hydraulics in particular as a brake fluid, for the power steering, the central locking, the level control, the suspension hydraulics, the fan hydraulics and other hydraulic auxiliary units for land, water and aircraft , especially motor vehicles and engines.
  • a lubricious brake fluid according to the invention is produced from the following components: 97.2 g Hydraulan H 407 (commercially available brake fluid from BASF) 1.2 g of nickel trisdiisobutyldithiocarbamate (first metal dialkyldithiocarbamate in mixed oxidation stages 1.0 g boron trisdi-2-ethylhexyldithiocarbamate (second dialkyldithiocarbamate) 0.6 g molybdenum oxytetrakisdi-2-ethylhexyldithiophosphate (metal dialkyldithiophosphate in mixed oxidation states)
  • the commercially available brake fluid is introduced and heated to 100 ° C., then 1.2 g of the first metal dialkyldithiocarbamate are added with stirring over the course of 40 minutes at normal pressure and at a temperature of 100 ° C., and the mixture obtained is
  • the brake fluid according to the invention (sample A) thus produced is examined with the commercially available hydraulic fluid Hydraulan H 407 without the lubricating additive used according to the invention (sample A ') for its lubricating properties, in particular its wear protection properties.
  • 98 g of commercially available brake fluid (DOT 4 Plus from Hoechst AG) are heated to 108 ° C.
  • the following components are added: 1 g of nickel trisdi-n-amyldithiocarbamate (first metal dialkyldithiocarbamate in mixed oxidation states) 0.4 g boron trisdi-2-ethylhexyldithiocarbamate (second metal dialkyldithiocarbamate) 0.6 g molybdenum oxytetrakisdi-2-ethylhexyldithiophosphate (metal dialkyldithiophosphate in mixed oxidation states) 1 g of the first metal dialkyldithiocarbamate is added to the commercially available brake fluid heated to 108 ° C.
  • the brake fluid sample B according to the invention is subjected to the comparative test described below with the commercially available brake fluid DOT 4 Plus without the lubricating additive (sample B ') used according to the invention under the same test conditions.
  • a circular disk was used to carry out the tests made of stainless steel with a diameter of 23 mm and a thickness of 10 mm, on the surface of which a drop of the brake fluid to be examined was applied.
  • a spot made of the same stainless steel with a diameter of 10 mm was applied to the spot where the drop of brake fluid was located, which exerted pressure on the surface of the metal disc due to its loading.
  • the metal ball was reciprocated at a frequency of 50 Hz over an amplitude of 1 mm for 90 minutes under load on the surface of the metal disc, the load being within the range of 50 to 150 N and the temperature within the range of during the experiment 50 to 150 ° C was varied (SRV (vibration-friction-wear) device, which is sold worldwide by Optimol GmbH).
  • the wear profile transverse to the direction of oscillation of the ball due to the friction between the loaded ball and the surface of the metal disc within the test period was recorded by means of a suitable recording device, whereby the diagrams given below were obtained, in which the wear height as the difference between the highest was obtained on the ordinate and the lowest point of the surface profile of the metal disk is shown as a function of the scanning distance of the surface of the metal disk on the abscissa.
  • a profile depth on the ordinate of 1 cm corresponds to a real profile depth in the surface of the metal disc of 1 ⁇ m
  • the scanning device was damped so that a profile depth of 1 cm in Diagram corresponds to a real profile depth in the surface of the pane of 2.5 ⁇ m.
  • Diagrams A and A ' were otherwise identical Conditions recorded (load on the ball 50 to 122 N, friction frequency 50 Hz, temperature 50 to 150 ° C, friction amplitude 1 mm, test duration 90 min). Diagrams A and A 'show the measurement results when using the brake fluid sample A according to the invention or the commercially available comparison sample A'.
  • Diagrams B and B ' were also recorded under identical test conditions (load on the ball 50 to 112 N, test temperature 50 to 100 ° C, friction frequency 50 Hz, friction amplitude 1 mm, test duration 90 min).

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  • Lubricants (AREA)

Claims (9)

  1. Un fluide hydraulique lubrifiant, en particulier un fluide de frein, à base d'un polyglycolether comportant au moins un dialkyldithiocarbamate de métal et un dialkyldithiophosphate de métal, caracterisé en ce qu'il contient comme l'additive lubrifiant de 0,1 à 5 % en poids, par rapport au poids total du fluide hydraulique, d'une combinaison de
    (a) au moins un dialkyldithiophosphate de métal ayant la formule générale
    Figure imgb0011
     dans laquelle
    Me   représente un métal qui est présent en degrés d'oxydation mixtes choisi parmi le groupe titane (Ti), zirconium (Zr), étain (Sn), plomb (Pb); vanadium (V), tantale (Ta), antimoine (Sb); chrome (Cr), moybdène (Mo), tungstène (W); manganèse (Mn); cobalt (Co) et nickel (Ni), et
    Alk   représente un groupe alkyle en C₄ à C₈ et
    (b) au moins deux dialkyldithiocarbamates ayant la formule générale suivante, un parmi eux étant un dialkyldithiocarbamate de bore,
    Figure imgb0012
     dans laquelle
    Me   représente B et un métal, respectivement, le métal étant présent en degrés d'oxydation mixtes, choisi parmi le groupe titane (Ti), Zirconium (Zr), étain (Sn), plomb (Pb); vanadium (V), tantale (Ta), antimoine (Sb); chrome (Cr), moybdène (Mo), tungstène (W); manganèse (Mn); cobalt (Co) et nickel (Ni), et
    Alk   représente un groupe alkyle en C₄ à C₈ et
    dans lequel les constituents (a) et (b) sont présents en une proportion en poids de 1:1 à 1:4.
  2. Le fluide hydraulique lubrifiant selon la revendication 1, caracterisé en ce qu'il contient l'additive lubrifiant en une quantité de 0,1 à 2,5 % en poids, par rapport au poids total du fluide hydraulique lubrifiant.
  3. Le fluide hydraulique lubrifiant selon la revendication 1 ou 2, caracterisé en ce que les constituents (a) et (b) sont présents dans l'additive lubrifiant en une proportion en poids de 1:1 à 3:7.
  4. Le fluide hydraulique lubriflant selon l'une quelconque des revendications 1 à 3, caracterisé en ce que le groupe alkyle représenté par Alk est un groupe isobutyle, tert-butyle, n- et iso-amyle, n- et iso-hexyle, n- et iso-heptyle ou 2-ethylhexyle.
  5. Le fluide hydraulique lubrifiant selon l'une quelconque des revendications 1 à 4, caracterisé en ce qu'il contient comme constituent (b) de l'additive lubrifiant le trisdiisobutyldithiocarbamate de bore et/ou le tris-di-2-ethylhexyldithiocarbamate de bore combiné avec le trisdiisobutyldithiocarbamate de nickel, le tris-diamyldithiocarbamate de nickel et/ou le tris-di-2-ethylhexyldithiocarbamate de nickel.
  6. Le fluide hydraulique lubrifiant selon l'une quelconque des revendications 1 à 5, caracterisé en ce qu'il contient comme constituent (a) de l'additive lubrifiant le tris-di-2-ethylhexyldithiophosphate de nickel, le tetrakis-di-2-ethylhexyldithiophosphate de titane, le tetrakis-di-2-ethylhexyldithiophosphate de vanadium, le tetrakis- ou oxytetrakis-di-2-ethylhexyldithophosphate de molybdène et/ou le tetrakis- ou oxytetrakis-di-2-ethylhexyldithiophosphate de tungstène.
  7. Le fluide hydraulique lubrifiant selon l'une quelconque des revendications 1 à 6, caracterisé en ce qu'il contient comme additive un ou plusieurs agents d'antioxydation, agents de désactivation de métaux, detergents, dispersants et agents antimousses.
  8. Procédé pour la production du fluide hydraulique lubrifiant, en particulier du fluide de frein, selon l'une quelconque des revendications 1 à 7, caracterisé en ce que le fluide hydraulique commercial, en particulier le fluide de frein, contenant en cas échéant des additives usuels, est chauffé, en cas échéant sous pression, à une température de 100 à 120°C, et le premier dialkyldithiocarbamate est ajouté en agitant et en 5 à 60 minutes, de préférence en 10 minutes, ensuite le deuxième dialkyldithiocarbamate est ajouté en agitant à une température inferieur à 100°C, de préférence à 90°C environ, en 2 à 20 minutes, de préférence en 5 à 10 minutes, et alors le dialkyldithiophosphate de métal est ajouté en agitant à une température de 90°C environ en 2 à 20 minutes, de préférence en 5 à 10 minutes.
  9. Utilisation du fluide hydraulique lubrifiant selon l'une quelconque des revendications 1 à 7 comme fluide operatoire pour la hydraulique centrale, en particulier comme fluide de frein, pour la servodirection, pour le verrouillage central des portes et pour les hydrauliques de suspension à ressort, de correction d'assiette et ventilateur des automobiles.
EP87109206A 1987-01-22 1987-06-26 Fluide hydraulique lubrifiant, notamment liquide de freins, sa méthode de fabrication et son utilisation Expired - Lifetime EP0275351B1 (fr)

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AT87109206T ATE101411T1 (de) 1987-01-22 1987-06-26 Schmierfaehige hydraulikfluessigkeit, insbesondere bremsfluessigkeit, verfahren zu ihrer herstellung und ihre verwendung.

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DE3701780 1987-01-22
DE19873701780 DE3701780A1 (de) 1987-01-22 1987-01-22 Schmierfaehige hydraulikfluessigkeit, insbesondere bremsfluessigkeit, verfahren zu ihrer herstellung und ihre verwendung

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EP0275351B1 true EP0275351B1 (fr) 1994-02-09

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EP (1) EP0275351B1 (fr)
JP (1) JPH01501947A (fr)
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WO1988005460A1 (fr) 1988-07-28
ATE101411T1 (de) 1994-02-15
DE3701780C2 (fr) 1993-02-25
JPH01501947A (ja) 1989-07-06
DE3701780A1 (de) 1988-12-01
DE3789055D1 (de) 1994-03-24
EP0275351A1 (fr) 1988-07-27

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