PL197796B1 - Hydraulic fluids with improved anti-corrosion properties - Google Patents

Hydraulic fluids with improved anti-corrosion properties

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Publication number
PL197796B1
PL197796B1 PL367159A PL36715902A PL197796B1 PL 197796 B1 PL197796 B1 PL 197796B1 PL 367159 A PL367159 A PL 367159A PL 36715902 A PL36715902 A PL 36715902A PL 197796 B1 PL197796 B1 PL 197796B1
Authority
PL
Poland
Prior art keywords
weight
triazole
fluids
brake
tolutriazole
Prior art date
Application number
PL367159A
Other languages
Polish (pl)
Other versions
PL367159A1 (en
Inventor
Bernd Wenderoth
Michael Roida
Bayram Aydin
Uwe Fidorra
Original Assignee
Basf Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Ag filed Critical Basf Ag
Publication of PL367159A1 publication Critical patent/PL367159A1/en
Publication of PL197796B1 publication Critical patent/PL197796B1/en

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    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
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    • 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
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    • 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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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
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    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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    • C10M2209/106—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four carbon atoms only
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    • C10M2209/1075—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106 used as base material
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    • 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
    • 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
    • C10M2227/0615—Esters derived from boron used as base material
    • 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
    • C10M2227/062—Cyclic 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
    • 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
    • C10M2227/062—Cyclic esters
    • C10M2227/0625—Cyclic esters used as base material
    • 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

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Braking Arrangements (AREA)

Abstract

The invention relates to hydraulic fluids, in particular brake fluids for motor vehicles, with improved anti-corrosion properties, containing (a) between 0.005 and 0.125 wt. % 1H-1,2,4-triazole and (b) between 0 and 10 wt. % of one or more corrosion inhibitors, whereby with the co-use of 1H-1,2,3-benzotriazole and/or 1H-1,2,3-tolyltriazole and/or their derivatives, the weight ratio of 1H-1,2,4-triazole to the aforementioned 1H-1,2,3-triazoles must be greater than 4:1.

Description

Opis wynalazkuDescription of the invention

Przedmiotem wynalazku jest płyn hamulcowy do pojazdów mechanicznych.The present invention relates to a brake fluid for motor vehicles.

Płyny hydrauliczne, a zwłaszcza płyny hamulcowe do pojazdów mechanicznych, muszą spełniać bardzo ostre wymagania co do ich właściwości chemicznych i fizycznych. Zgodnie z obowiązującymi normami i wymaganiami dotyczącymi płynów hamulcowych, ustalonymi przez US Department of Transportation w Federal Motor Vehicle Safety Standard FMVSS-Nr 116, oraz normą SAE J 1704 opublikowaną przez Society of Automotive Engineers nowoczesne płyny hamulcowe powinny mieć wysoką „temperaturę wrzenia w stanie suchym (oznaczaną w stanie równowagi przy ogrzewaniu w temperaturze wrzenia w warunkach powrotu skroplin - ERPB) oraz wysoką temperaturę wrzenia w stanie wilgotnym („wilgotna ERPB), a także lepkość nieznacznie zmieniającą się w szerokim zakresie temperatury.Hydraulic fluids, and in particular brake fluids for motor vehicles, must meet very stringent requirements as to their chemical and physical properties. According to the applicable standards and requirements for brake fluids, established by the US Department of Transportation in Federal Motor Vehicle Safety Standard FMVSS-No. 116, and the SAE J 1704 standard published by the Society of Automotive Engineers, modern brake fluids should have a high "boiling point when dry" (determined at equilibrium on reflux - ERPB) and high wet boiling point ("wet ERPB), and viscosity varies slightly over a wide temperature range.

Ponadto przemysł samochodowy narzuca ściślejsze wymagania co do lepszej ochrony przeciwkorozyjnej metali i metali nieżelaznych. Zadaniem inhibitorów korozji dodawanych do płynów hamulcowych jest zapobieganie powodowanemu przez korozję niszczeniu części metalowych.In addition, the car industry imposes stricter requirements for better corrosion protection for metals and non-ferrous metals. When added to brake fluids, corrosion inhibitors are designed to prevent corrosion damage to metal parts.

Zastosowanie pochodnych 1H-1,2,3-triazolu, takich jak 1H-1,2,3-benzotriazol lub 1H-1,2,3-tolutriazol, jako inhibitorów korozji w płynach hydraulicznych lub hamulcowych jest znane od dawna, np. z EP-A 028789 (1) i EP-A 454110 (2).The use of 1H-1,2,3-triazole derivatives such as 1H-1,2,3-benzotriazole or 1H-1,2,3-tolutriazole as corrosion inhibitors in hydraulic or brake fluids has been known for a long time, e.g. EP-A 028789 (1) and EP-A 454110 (2).

W WO 00/46325 (3) zalecano płyny hydrauliczne zawierające połączenie 1H-1,2,3-benzotriazolu lub jego pochodnych, takich jak 1H-1,2,3-tolutriazol, oraz 1H-1,2,4-triazolu lub jego pochodnych, w stosunku wagowym od 1:4 do 4:1, do stosowania jako układ inhibitorów korozji. Dla porównania w tabelach 1 - 4 w (3) podano również właściwości płynów hydraulicznych zawierających tylko 1H-1,2,4-triazol w stężeniu 0,15% wagowych; jednak jego działanie antykorozyjne można uznać za wystarczające tylko w przypadku miedzi.WO 00/46325 (3) recommends hydraulic fluids containing a combination of 1H-1,2,3-benzotriazole or its derivatives, such as 1H-1,2,3-tolutriazole, and 1H-1,2,4-triazole or its derivatives derivatives in a weight ratio of 1: 4 to 4: 1 for use as a corrosion inhibitor system. For comparison, Tables 1-4 in (3) also show the properties of hydraulic fluids containing only 1H-1,2,4-triazole at a concentration of 0.15% by weight; however, its anti-corrosion effect can only be considered sufficient for copper.

Znane ze stanu techniki płyny hydrauliczne i płyny hamulcowe do pojazdów mechanicznych nie wykazują zadowalających właściwości, w szczególności działania antykorozyjnego. Zatem istniało zapotrzebowanie na płyny hydrauliczne, a zwłaszcza płyny hamulcowe, spełniające w szczególności powyższe wymagania co do lepszej ochrony antykorozyjnej metali i metali nieżelaznych.The prior art hydraulic fluids and brake fluids for motor vehicles do not show satisfactory properties, in particular anti-corrosion effect. Thus, there was a need for hydraulic fluids, and in particular brake fluids, meeting in particular the above requirements for improved corrosion protection for metals and non-ferrous metals.

Nieoczekiwanie stwierdzono, że takie wymagania spełnia płyn hamulcowy o odpowiednim składzie podanym poniżej.It has surprisingly been found that a brake fluid having the appropriate composition given below meets these requirements.

Wynalazek dotyczy płynu hamulcowego do pojazdów mechanicznych charakteryzującego się tym, że zawiera:The invention relates to a brake fluid for motor vehicles, characterized in that it comprises:

(a) 0,005 - 0,125% wagowych 1H-1,2,4-triazolu i (b) 0 - 10% wagowych jednego lub większej liczby dodatkowych inhibitorów korozji, przy czym przy jednoczesnym stosowaniu 1H-1,2,3-benzotriazolu i/lub 1H-1,2,3-tolutriazolu i/lub ich pochodnych stosunek wagowy 1H-1,2,4-triazolu do tych 1H-1,2,3-triazoli jest wyższy niż 4:1, a ponadto 0,1 - 97% wagowych jednego lub większej liczby eterów poliglikoli i/lub ich estrów z kwasem borowym.(a) 0.005-0.125% by weight of 1H-1,2,4-triazole and (b) 0-10% by weight of one or more additional corrosion inhibitors, whereby 1H-1,2,3-benzotriazole and / or 1H-1,2,3-tolutriazole and / or derivatives thereof, the weight ratio of the 1H-1,2,4-triazole to the 1H-1,2,3-triazoles is greater than 4: 1 and furthermore 0.1 - 97% by weight of one or more polyglycol ethers and / or their esters with boric acid.

Korzystnie płyn hamulcowy zawiera 0,005 - 0,08% wagowych składnika (a).Preferably, the brake fluid contains 0.005-0.08% by weight of component (a).

Korzystnie płyn hamulcowy zawiera składnik (a) jako jedyny inhibitor korozji na bazie triazolu.Preferably, the brake fluid comprises component (a) as the sole triazole-based corrosion inhibitor.

Korzystnie płyn hamulcowy zawiera jako składnik (b) 0,001 - 0,5% wagowych jednego lub większej liczby związków z grupy obejmującej benzimidazol, uwodorniony 1H-1,2,3-tolutriazol, purynę, adeninę, 6-chloropurynę, 2,6-dichloropurynę, 6-metoksypurynę, 1H-1,2,3-triazolo[4,5-b]pirydynę, 6-histaminopurynę i 6-furfuryloaminopurynę oraz ewentualnie dodatkowe inhibitory korozji inne niż (a).Preferably, the brake fluid comprises as component (b) 0.001-0.5% by weight of one or more compounds from the group consisting of benzimidazole, hydrogenated 1H-1,2,3-tolutriazole, purine, adenine, 6-chloropurine, 2,6-dichloropurine , 6-methoxypurine, 1H-1,2,3-triazolo [4,5-b] pyridine, 6-histaminopurine and 6-furfurylaminopurine, and optionally additional corrosion inhibitors other than (a).

Korzystnie płyn hamulcowy zawiera ponadto oprócz składników (a) i ewentualnie (b), 0,1 - 50% wagowych jednego lub większej liczby poliglikoli.Preferably, the brake fluid further comprises, in addition to components (a) and optionally (b), 0.1-50% by weight of one or more polyglycols.

Płyny hamulcowe według wynalazku zawierają korzystnie 0,005 - 0,10% wagowych, korzystniej 0,005 - 0,08% wagowych, a zwłaszcza 0,005 - 0,06% wagowych, składnika (a).The brake fluids according to the invention preferably contain 0.005-0.10% by weight, more preferably 0.005-0.08% by weight, more preferably 0.005-0.06% by weight, of component (a).

Płyny hamulcowe według wynalazku korzystnie zawierają składnik (a) jako jedyny inhibitor korozji na bazie triazolu. Oznacza to, że nie zawierają one pochodnych triazolu, takich jak 1H-1,2,3-benzotriazol, 1H-1,2,3-tolutriazol lub uwodorniony 1H-1,2,3-tolutriazol, ale mogą zawierać nieorganiczne i/lub organiczne inhibitory korozji o innej budowie.The brake fluids of the invention preferably contain component (a) as the sole triazole-based corrosion inhibitor. This means that they do not contain triazole derivatives such as 1H-1,2,3-benzotriazole, 1H-1,2,3-tolutriazole or hydrogenated 1H-1,2,3-tolutriazole, but may contain inorganic and / or organic corrosion inhibitors of a different structure.

Płyny hamulcowe według wynalazku również zawierają do 10% wagowych, a zwłaszcza do 5% wagowych, jednego lub większej liczby dodatkowych inhibitorów korozji (b), z tym że przy jednoczesnym stosowaniu 1H-1,2,3-benzotriazolu i/lub 1H-1,2,3-tolutriazolu i/lub ich pochodnych stosunek wagowy 1H-1,2,4-triazolu do tych 1H-1,2,3-triazoli musi być wyższy niż 4:1.The brake fluids according to the invention also contain up to 10% by weight, in particular up to 5% by weight, of one or more additional corrosion inhibitors (b), provided that when 1H-1,2,3-benzotriazole and / or 1H-1 are used simultaneously , 2,3-tolutriazole and / or derivatives thereof, the weight ratio of 1H-1,2,4-triazole to these 1H-1,2,3-triazoles must be greater than 4: 1.

PL 197 796 B1PL 197 796 B1

Odpowiednie dodatkowe inhibitory korozji (b) stanowią sole metali alkalicznych i kwasu fosforowego i fosforawego; kwasy tłuszczowe, takie jak kwas oktanowy, laurynowy, palmitynowy, stearynowy lub oleinowy i ich sole z metalami alkalicznymi; estry kwasu fosforowego i fosforawego, takie jak fosforan etylu, fosforan dimetylu, fosforan izopropylu, fosforan diizopropylu, fosforyn butylu lub fosforyn dimetylu; ewentualnie podstawione oksyetylenowane mono- i dialkiloaminy oraz ich sole z kwasami mineralnymi i z kwasami tłuszczowymi, np. butyloamina, heksyloamina, oktyloamina, izononyloamina, oleiloamina, dipropyloamina, diizopropyloamina lub dibutyloamina; ewentualnie podstawione oksyetylenowane alkanoloaminy, np. mono-, di- lub trietanoloamina, N,N'-di-n-butyloaminoetanol lub 1,1'-iminodipropan-2-ol, cykloheksyloamina, benzimidazol i uwodorniony tolutriazol; oraz związki nitroaromatyczne, np. aldehyd 3-nitrobenzoesowy.Suitable additional corrosion inhibitors (b) are the alkali metal salts of phosphoric and phosphorous acid; fatty acids such as octanoic, lauric, palmitic, stearic or oleic acid and their alkali metal salts; phosphoric and phosphorous acid esters such as ethyl phosphate, dimethyl phosphate, isopropyl phosphate, diisopropyl phosphate, butyl phosphite or dimethyl phosphite; optionally substituted ethoxylated mono- and dialkylamines and their mineral acid and fatty acid salts, e.g., butylamine, hexylamine, octylamine, isononylamine, oleylamine, dipropylamine, diisopropylamine or dibutylamine; optionally substituted ethoxylated alkanolamines, e.g. mono-, di- or triethanolamine, N, N'-di-n-butylaminoethanol or 1,1'-iminodipropan-2-ol, cyclohexylamine, benzimidazole and hydrogenated tolutriazole; and nitroaromatics, e.g. 3-nitrobenzaldehyde.

Inhibitory korozji (b) stosuje się w płynach hamulcowych według wynalazku korzystnie w ilości 0,001 - 10% wagowych, a zwłaszcza 0,001 - 5% wagowych.The corrosion inhibitors (b) are preferably used in the brake fluids according to the invention in an amount of 0.001-10% by weight, in particular 0.001-5% by weight.

Płyny hamulcowe według wynalazku zawierają oprócz 1H-1,2,4-triazolu (a) korzystnie 0,001 - 5% wagowych, a zwłaszcza 0,001 - 0,5% wagowych, jednego lub większej liczby związków wybranych z grupy obejmującej benzimidazol, uwodorniony 1H-1,2,3-tolutriazol, purynę, adeninę, 6-chloropurynę, 2,6-dichloropurynę, 6-meto-ksypurynę, 1H-1,2,3-triazolo[4,5-b]pirydynę, 6-histaminopurynę i 6-furfuryloaminopurynę, oraz ewentualnie dodatkowe inhibitory korozji inne niż (a) jako dodatkowe inhibitory korozji (b). Wyżej wymienione pochodne puryny opisano w niemieckim zgłoszeniu patentowym P 10026010.1 jako inhibitory korozji metali nieżelaznych do stosowania w płynach hydraulicznych lub płynach hamulcowych.The brake fluids according to the invention contain in addition to 1H-1,2,4-triazole (a) preferably 0.001-5% by weight, in particular 0.001-0.5% by weight, one or more compounds selected from the group consisting of benzimidazole, hydrogenated 1H-1 , 2,3-tolutriazole, purine, adenine, 6-chloropurine, 2,6-dichloropurine, 6-methoxypurine, 1H-1,2,3-triazolo [4,5-b] pyridine, 6-histaminopurine and 6 -furfurylaminopurine, and optionally additional corrosion inhibitors other than (a) as additional corrosion inhibitors (b). The aforementioned purine derivatives are described in the German patent application P 10026010.1 as corrosion inhibitors of non-ferrous metals for use in hydraulic fluids or brake fluids.

O ile nie podano inaczej, wszystkie dane dotyczące składu podanego w % wagowych odnoszą się w każdym przypadku do całkowitej ilości płynu hamulcowego. Łączna ilość wszystkich składników występujących w płynach hamulcowych według wynalazku w każdym przypadku wynosi 100% wagowych.Unless otherwise stated, all% by weight data are based on the total amount of brake fluid in each case. The total amount of all components present in the brake fluids according to the invention is in each case 100% by weight.

W szczególności płyny hamulcowe według wynalazku zawierają jako inhibitory korozji wyżej opisane składniki (a) i ewentualnie (b).In particular, the brake fluids according to the invention contain the above-described components (a) and, if appropriate, (b) as corrosion inhibitors.

Płyny hamulcowe według wynalazku zawierają dodatkowo oprócz składników (a) i ewentualnie (b), 0,1 - 97% wagowych, korzystnie 30 - 97% wagowych, a zwłaszcza 50 - 97% wagowych, jednego lub większej liczby eterów poliglikoli i/lub ich boranów.The brake fluids according to the invention contain, in addition to components (a) and, if appropriate, (b), 0.1 to 97% by weight, preferably 30 to 97% by weight, in particular 50 to 97% by weight, of one or more polyglycol ethers and / or their borates.

Odpowiednie etery poliglikoli to w szczególności etery monoalkilowe glikolu etylenowego zawierające do 6 jednostek tlenku etylenu oraz do 4 atomów węgla w grupie alkilowej, jak np. eter monometylowy glikolu dietylenowego, eter monometylowy glikolu trietylenowego, eter monobutylowy glikolu trietylenowego lub eter monometylowy glikolu tetraetylenowego. Można również stosować etery dialkilowe glikolu etylenowego i etery dialkilowe glikolu propylenowego zawierające do 6 jednostek tlenku alkilenu oraz do 4 atomów węgla w każdej z grup alkilowych, jak np. eter dimetylowy glikolu trietylenowego, eter dimetylowy glikolu tetraetylenowego, eter di-tert-butylowy glikolu dietylenowego, eter dibutylowy glikolu dietylenowego, eter di-tert-butylowy glikolu dietylenowego lub eter dimetylowy glikolu dipropylenowego.Suitable polyglycol ethers are, in particular, ethylene glycol monoalkyl ethers with up to 6 ethylene oxide units and up to 4 carbon atoms in the alkyl group, such as, for example, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether or tetraethylene glycol monomethyl ether. Ethylene glycol dialkyl ethers and propylene glycol dialkyl ethers with up to 6 alkylene oxide units and up to 4 carbon atoms in each alkyl group may also be used, such as e.g. triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol di-tert-butyl ether , diethylene glycol dibutyl ether, diethylene glycol di-tert-butyl ether or dipropylene glycol dimethyl ether.

Odpowiednie estry kwasu borowego powyższych i innych eterów poliglikoli opisano w EP-B 013925 (cykliczne estry kwasu bisborowego), w DE-C 2804535 (estry kwasu borowego zawierające atom azotu), DE-A 2438038 (estry eteru monoalkilowego glikolu alkilenowego i kwasu borowego) oraz w DE-B 1768933 (estry trialkoksyalkilowe kwasu borowego).Suitable boric acid esters of the above and other polyglycol ethers are described in EP-B 013925 (cyclic bisboric acid esters), DE-C 2804535 (nitrogen-containing boric acid esters), DE-A 2438038 (alkylene glycol monoalkyl ether esters of boric acid) and in DE-B 1768933 (boric acid trialkoxyalkyl esters).

Zamiast opisanych powyżej eterów poliglikoli i/lub ich estrów z kwasem borowym, płyny hamulcowe według wynalazku mogą również zawierać jako główny składnik estry kwasów karboksylowych, oleje mineralne lub oleje silikonowe.Instead of the polyglycol ethers and / or their esters with boric acid described above, the brake fluids according to the invention may also contain carboxylic acid esters, mineral oils or silicone oils as their main constituent.

Korzystnie płyny hamulcowe według wynalazku zawierają dodatkowo, oprócz składników (a) i ewentualnie (b), 0,1 - 50% wagowych, szczególnie 1 - 40% wagowych, a wyjątkowo korzystnie 5 - 30% wagowych, jednego lub większej liczby poliglikoli.Preferably, the brake fluids according to the invention contain, in addition to components (a) and, if appropriate, (b), 0.1-50% by weight, particularly 1-40% by weight, particularly preferably 5-30% by weight, of one or more polyglycols.

Odpowiednie poliglikole to w szczególności produkty reakcji tlenku etylenu i/lub tlenku propylenu i/lub tlenku butylenu z wodą lub diolami, a zwłaszcza odpowiednie produkty reakcji mieszanin tlenku etylenu i tlenku propylenu z wodą; wszystkie te związki mają stosunkowo wysoką temperaturę wrzenia. Liczba jednostek tlenku alkilenu w poliglikolach tego typu wynosi zazwyczaj 2-10.Suitable polyglycols are in particular the reaction products of ethylene oxide and / or propylene oxide and / or butylene oxide with water or diols, in particular suitable reaction products of mixtures of ethylene oxide and propylene oxide with water; all of these compounds have a relatively high boiling point. The number of alkylene oxide units in polyglycols of this type is usually 2-10.

Opisane powyżej poliglikole o wysokiej temperaturze wrzenia pełnią rolę środka smarującego, co wiąże się zasadniczo z poprawą działania w zależności od temperatury i lepkości. Obecność poliglikoli nadaje eterom poliglikoli o niskiej lepkości wystarczająco wysoką lepkość w wysokiej temperaturze, co zapewnia odpowiednie smarowanie. Takie smarowanie jest konieczne w układzie hamulco4The high boiling point polyglycols described above act as a lubricant which essentially improves performance with temperature and viscosity. The presence of polyglycols gives the low viscosity polyglycol ethers a sufficiently high viscosity at high temperature to provide adequate lubrication. This lubrication is essential in the brake system4

PL 197 796 B1 wym pojazdu mechanicznego ze względu na to, że guma lub elastomery ślizgające się na metalowych częściach muszą wykazywać bardzo niski stopień zużycia.Due to the fact that the rubber or elastomers sliding on metal parts must show a very low degree of wear.

Dalsze składniki i środki pomocnicze w płynach hamulcowych według wynalazku mogą stanowić znane przeciwutleniacze, jak np. fenotiazyna i/lub środki na bazie fenolu, oraz znane środki przeciwpieniące.Further ingredients and adjuvants in the brake fluids according to the invention may be known antioxidants, such as, for example, phenothiazine and / or phenol-based agents, and known antifoams.

Ponadto płyny hamulcowe według wynalazku mogą zawierać pochodne cyklicznych kwasów karboksylowych wymienione w WO 00/65001, stosowane jako składniki zmniejszające lepkość w niskiej temperaturze w obecności wody.In addition, the brake fluids of the invention may contain the cyclic carboxylic acid derivatives mentioned in WO 00/65001, used as low temperature viscosity reducing components in the presence of water.

Obecność wyżej podanej niewielkiej ilości 1H-1,2,4-triazolu powoduje, że płyny hamulcowe według wynalazku spełniają stawiane im wymagania i w szczególności wykazują działanie antykorozyjne lepsze niż płyny znane ze stanu techniki, to jest zapewniają zwiększoną ochronę antykorozyjną metali, takich jak żelazo, stal, blacha ocynowana, żeliwo (żeliwo szare), ołów, cyna, chrom, cynk, aluminium, magnez i ich stopy, jak również metali lutowniczych, jak np. cyna do lutowania, a także metali nieżelaznych, takich jak miedź i jej stopy, np. mosiądz.The presence of the above-mentioned small amount of 1H-1,2,4-triazole makes the brake fluids according to the invention meet the requirements set for them and, in particular, show an anti-corrosion effect better than the fluids known from the state of the art, i.e. they provide increased corrosion protection for metals such as iron, steel, tinplate, cast iron (gray cast iron), lead, tin, chrome, zinc, aluminum, magnesium and their alloys, as well as soldering metals such as soldering tin, and non-ferrous metals such as copper and its alloys e.g. brass.

Dalsze korzystne zalety płynów płynów hamulcowych według wynalazku to korzystna lepkość w niskiej temperaturze, dobra mieszalność z wodą, umiarkowana wartość pH, trwałość w niskiej i wysokiej temperaturze, odporność na utlenianie oraz trwałość chemiczna, korzystne zachowanie (czyli zgodność) wobec takich materiałów jak gumy, tworzywa sztuczne, kleje, włókna, uszczelki z elastomerów i z gumy oraz podobnych materiałów, jak również dobre właściwości smarujące.Further advantageous advantages of the brake fluids according to the invention are favorable low temperature viscosity, good miscibility with water, moderate pH value, low and high temperature stability, resistance to oxidation and chemical stability, favorable behavior (i.e. compatibility) with materials such as rubbers, plastics, adhesives, fibers, gaskets of elastomers and rubber and similar materials, as well as good lubricating properties.

Co niemniej ważne, zastosowanie nawet niewielkich ilości 1H-1,2,4-triazolu w płynach płynach hamulcowych według wynalazku jest korzystne zarówno z ekonomicznego, jak i ekologicznego punktu widzenia.Last but not least, the use of even small amounts of 1H-1,2,4-triazole in the brake fluids of the invention is advantageous both from an economic and an ecological point of view.

Wynalazek ilustrują poniższe przykłady.The following examples illustrate the invention.

Przykłady zastosowaniaApplication examples

W oparciu o dostępne w handlu płyny hamulcowe DOT 4 lub DOT 5.1 poddano badaniom płyny BF 1 (ERBP: 267°C, wilgotna ERBP: 173°C, lepkość kinematyczna w temperaturze -40°C: 676 cSt) i BF 2 (ERBP: 263°C, mokra ERBP: 181°C, lepkość kinematyczna w temperaturze -40°C: 850 cSt), z których każdy zawierał 0,05% wag. 1H-1,2,3-tolutriazolu jako inhibitora korozji metali nieżelaznych, oraz porównano je z płynami hamulcowymi BF 1a, BF 1b, BF 1c i BF 2a według wynalazku.Based on commercially available DOT 4 or DOT 5.1 brake fluids, BF 1 fluids (ERBP: 267 ° C, wet ERBP: 173 ° C, kinematic viscosity at -40 ° C: 676 cSt) and BF 2 (ERBP:: 263 ° C, wet ERBP: 181 ° C, kinematic viscosity at -40 ° C: 850 cSt) each containing 0.05 wt. 1H-1,2,3-tolutriazole as a corrosion inhibitor of non-ferrous metals and compared with the brake fluids BF 1a, BF 1b, BF 1c and BF 2a according to the invention.

Stosowane płyny hamulcowe do pojazdów mechanicznych miały następujący skład.The brake fluids used for motor vehicles had the following composition.

BF 1BF 1

55,00% wag. boranu eteru metylowego glikolu trietylenowego,55.00 wt.% triethylene glycol methyl ether borate,

43,44% wag. mieszaniny eteru monometylowego glikolu trietylenowego, eteru monometylowego glikolu tetraetylenowego, eteru monobutylowego glikolu trietylenowego i eteru monometylowego glikolu dietylenowego,43.44 wt.% mixtures of triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, triethylene glycol monobutyl ether and diethylene glycol monomethyl ether,

1,51% wag. mieszaniny 1,1'-iminodipropan-2-olu, fenotiazyny i estru kwasu fosforowego1.51 wt.% mixtures of 1,1'-iminodipropan-2-ol, phenothiazine and an ester of phosphoric acid

0,05% wag. 1H-1,2,3-tolutriazolu.0.05 wt.% 1H-1,2,3-tolutriazole.

BF 2BF 2

68,00% wag. boranu eteru metylowego glikolu trietylenowego,68.00 wt.% triethylene glycol methyl ether borate,

28,84% wag. mieszaniny eteru monometylowego glikolu trietylenowego, eteru monometylowego glikolu dietylenowego, eteru monobutylowego glikolu dietylenowego i glikolu dietylenowego,28.84 wt.% mixtures of triethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether and diethylene glycol,

3,11% wag. mieszaniny 1,1'-iminodipropan-2-olu, fenotiazyny i pochodnej kwasu fosfonowego3.11 wt.% mixtures of 1,1'-iminodipropan-2-ol, phenothiazine and a phosphonic acid derivative

0,05% wag. 1H-1,2,3-tolutriazolu.0.05 wt.% 1H-1,2,3-tolutriazole.

Płyny hamulcowe BF 1a i BF 2a według wynalazku różnią się od BF 1 i BF 2 tylko tym, że 1H-1,2,3-tolutriazol w ilości 0,05% wag. zastąpiono taką samą ilością 1H-1,2,4-triazolu; płyn hamulcowy BF 1b zawiera 0,04% wag. 1H-1,2,4-triazolu i 0,01% wag. adeniny zamiast 0,05% wag. 1H-1,2,3-tolutriazolu; płyn hamulcowy BF 1c według wynalazku zawiera 0,07% wag. 1H-1,2,4-triazolu (ale tylko 54,98% wag. boranu eteru monometylowego glikolu trietylenowego) zamiast 0,05% wag. 1H-1,2,3-tolutriazolu.The brake fluids BF 1a and BF 2a according to the invention differ from BF 1 and BF 2 only in that 1H-1,2,3-tolutriazole in an amount of 0.05% by weight. replaced with the same amount of 1H-1,2,4-triazole; the brake fluid BF 1b contains 0.04 wt. 1H-1,2,4-triazole and 0.01 wt. of adenine instead of 0.05 wt.%. 1H-1,2,3-tolutriazole; The brake fluid BF 1c according to the invention contains 0.07 wt. 1H-1,2,4-triazole (but only 54.98 wt.% Of triethylene glycol monomethyl ether borate) instead of 0.05 wt.%. 1H-1,2,3-tolutriazole.

Badania przeprowadzono zgodnie z testem na korozję miedzi stosowanym przez PSA PeugeotCitroen D 53 5387 w wersji 2000. Zgodnie z tym testem blachę miedzianą oczyszczoną uprzednio w acetonie, o powierzchni całkowitej 1000 cm2 (o wymiarach 71,4 cm x 7 cm x 0,05 cm) zwinięto najpierw w kształt cylindra w taki sposób, aby wewnętrzne powierzchnie metalu nie stykały się ze sobą. Blachę miedzianą następnie umieszczono w mieszaninie 294 ml płynu hamulcowego i 6 ml wody destylowanej i ogrzewano w temperaturze 100°C przez 100 godzin; przez płyn z szybkością 10 litrów na godzinę przepuszczano powietrze przepuszczone uprzednio przez wodę destylowaną ochłodzoną doThe tests were carried out in accordance with the copper corrosion test used by PSA Peugeot Citroen D 53 5387 version 2000. According to this test, a copper sheet previously cleaned in acetone, with a total area of 1000 cm 2 (dimensions 71.4 cm x 7 cm x 0.05 cm) was first rolled into a cylinder shape in such a way that the internal surfaces of the metal do not touch each other. The copper sheet was then placed in a mixture of 294 ml of brake fluid and 6 ml of distilled water and heated at 100 ° C for 100 hours; air was passed through the liquid at a rate of 10 liters per hour through distilled water cooled to

PL 197 796 B1 temperatury 2°C. Po zakończeniu badań oceniano wizualnie wygląd blachy miedzianej po odwinięciu oraz wygląd płynu i oznaczano w nim zawartość miedzi.Temperature of 2 ° C. After completion of the tests, the appearance of the copper sheet after unwinding and the appearance of the liquid were visually assessed, and its copper content was determined.

Wyniki badań podano w tabeli 1.The test results are given in Table 1.

T a b e l a 1T a b e l a 1

Zawartość Cu [m9/k9] Cu content [m 9 / k 9 ] Wygląd blachy miedzianej The appearance of the copper sheet Wygląd płynu The appearance of the fluid pH pH BF 1 (porównawczy) BF 1 (comparative) 24 24 Gruba powłoka Thick coating Mętny, z osadem Cloudy, with sediment 7,4 7.4 BF 1a BF 1a 29 29 Błyszcząca, bez powłoki Glossy, no coating Barwa bursztynowa, przejrzysty Amber, transparent 7,6 7.6 BF 1b BF 1b 34 34 Błyszcząca, bez powłoki Glossy, no coating Barwa bursztynowa, przejrzysty Amber, transparent 7,6 7.6 BF 1c BF 1c 18 18 Błyszcząca, bez powłoki Glossy, no coating Barwa bursztynowa, przejrzysty Amber, transparent 7,5 7.5 BF 2 (porównawczy) BF 2 (comparative) 10 10 Gruba powłoka Thick coating Mętny, z osadem Cloudy, with sediment 7,6 7.6 BF 2a BF 2a 30 thirty Błyszcząca, bez powłoki Glossy, no coating Barwa bursztynowa, przejrzysty Amber, transparent 7,7 7.7

Jak wynika z powyższych danych, w przeciwieństwie do znanych płynów hamulcowych, takich jak BF 1 i BF 2, płyny według wynalazku nie tylko zapewniają bardzo dobrą ochronę antykorozyjną miedzi oraz małą zawartość Cu w badanym płynie, ale dodatkowo powierzchnia metalu nie pokrywa się nalotem, a w płynie hamulcowym nie wytrąca się osad.As can be seen from the above data, in contrast to known brake fluids, such as BF 1 and BF 2, the fluids according to the invention not only provide very good corrosion protection for copper and a low Cu content in the tested fluid, but also the metal surface is not tarnished, and in the brake fluid, no precipitate forms.

Przedstawione poniżej wyniki badań korozyjnych przeprowadzonych zgodnie z normą SAE J 1704 (styczeń 97) również potwierdzają lepsze działanie płynów hamulcowych według wynalazku, takich jak BF 2a, o małej zawartości 1H-1,2,4-triazolu, w porównaniu z innymi płynami, takimi jak BF 1d o dużej zawartości 1H-1,2,4-triazolu, gdyż uzyskano lepsze wyniki testu korozyjnego w przypadku miedzi (BF 1d jest odpowiednikiem BF 1, ale zawiera 0,20% wag. 1H-1,2,4-triazolu zamiast 1H-1,2,3-toluotriazlu i zawiera tylko 54,85% wag. boranu eteru monometylowego glikolu trietylenowego).The following corrosion test results according to SAE J 1704 (January 97) also confirm the superior performance of the brake fluids of the invention, such as BF 2a, with a low 1H-1,2,4-triazole content, compared to other fluids such as as BF 1d with a high content of 1H-1,2,4-triazole, as better corrosion test results were obtained for copper (BF 1d is equivalent to BF 1, but contains 0.20 wt.% of 1H-1,2,4-triazole instead of 1H-1,2,3-toluotriazl and contains only 54.85 wt.% of triethylene glycol monomethyl ether borate).

Wyniki testu korozyjnego przeprowadzonego zgodnie z normą SAE J 1704 (styczeń 97) podano w tabeli 2.The corrosion test results according to SAE J 1704 (January 97) are shown in Table 2.

T a b e l a 2T a b e l a 2

Metal Metal BF 2a Zmiana masy [mg/cm2]BF 2a Mass change [mg / cm 2 ] BF 1d (porównawczy) Zmiana masy [mg/cirr] BF 1d (comparative) Mass change [mg / cirr] Blacha ocynowana Tinned sheet 0,00 0.00 -0,01 -0.01 Stal steel +0,03 +0.03 0,00 0.00 Aluminium Aluminum 0,00 0.00 0,00 0.00 Żeliwo Cast iron +0,05 +0.05 +0,02 +0.02 Mosiądz Brass 0,00 0.00 0,00 0.00 Miedź Copper -0,05 -0.05 -0,11 -0.11 Cynk Zinc +0,05 +0.05 +0,04 +0.04

Zastrzeżenia patentowePatent claims

Claims (5)

1. Płyn hamulcowy do pojazdów mechanicznych, znamienny tym, że zawiera:1. Brake fluid for motor vehicles, characterized in that it contains: (a) 0,005 - 0,125% wagowych 1H-1,2,4-triazolu i (b) 0 - 10% wagowych jednego lub większej liczby dodatkowych inhibitorów korozji, przy czym przy jednoczesnym stosowaniu 1H-1,2,3-benzotriazolu i/lub 1H-1,2,3-tolutriazolu i/lub ich pochodnych stosunek wagowy 1H-1,2,4-triazolu do tych 1H-1,2,3-triazoli jest wyższy niż 4:1, a ponadto 0,1 - 97% wagowych jednego lub większej liczby eterów poliglikoli i/lub ich estrów z kwasem borowym.(a) 0.005-0.125% by weight of 1H-1,2,4-triazole and (b) 0-10% by weight of one or more additional corrosion inhibitors, whereby 1H-1,2,3-benzotriazole and / or 1H-1,2,3-tolutriazole and / or derivatives thereof, the weight ratio of 1H-1,2,4-triazole to these 1H-1,2,3-triazoles is greater than 4: 1, and furthermore 0.1 - 97% by weight of one or more polyglycol ethers and / or their esters with boric acid. 2. Płyn hydrauliczny według zastrz. 1, znamienny tym, że zawiera 0,005 - 0,08% wagowych składnika (a).2. A hydraulic fluid according to claim 1 The method of claim 1, comprising 0.005-0.08% by weight of component (a). PL 197 796 B1PL 197 796 B1 3. Płyn hamulcowy według zastrz. 1 albo 2, znamienny tym, że zawiera składnik (a) jako jedyny inhibitor korozji na bazie triazolu.3. The brake fluid according to claim 1 The process of claim 1 or 2, wherein component (a) is the sole triazole-based corrosion inhibitor. 4. Płyn hamulcowy według zastrz. 1 albo 2, znamienny tym, że zawiera jako składnik (b) 0,001 - 0,5% wagowych jednego lub większej liczby związków z grupy obejmującej benzimidazol, uwodorniony 1H-1,2,3-tolutriazol, purynę, adeninę, 6-chloropurynę, 2,6-dichloropurynę, 6-metoksypurynę, 1H-1,2,3-triazolo[4,5-b]pirydynę, 6-histaminopurynę i 6-furfuryloaminopurynę oraz ewentualnie dodatkowe inhibitory korozji inne niż (a).4. The brake fluid according to claim 1 A method as claimed in claim 1 or 2, characterized in that it contains as component (b) 0.001 - 0.5% by weight of one or more compounds from the group consisting of benzimidazole, hydrogenated 1H-1,2,3-tolutriazole, purine, adenine, 6-chloropurine, 2,6-dichloropurine, 6-methoxypurine, 1H-1,2,3-triazolo [4,5-b] pyridine, 6-histaminopurine and 6-furfurylaminopurine, and optionally additional corrosion inhibitors other than (a). 5. Płyn hamulcowy według zastrz. 1 albo 2, znamienny tym, że zawiera ponadto oprócz składników (a) i ewentualnie (b), 0,1 - 50% wagowych jednego lub większej liczby poliglikoli.The brake fluid according to claim 1 The process of claim 1 or 2, further comprising, in addition to components (a) and optionally (b), 0.1-50% by weight of one or more polyglycols.
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