CZ20032736A3 - Hydraulic liquids exhibiting enhanced protection against corrosion - Google Patents
Hydraulic liquids exhibiting enhanced protection against corrosion Download PDFInfo
- Publication number
- CZ20032736A3 CZ20032736A3 CZ20032736A CZ20032736A CZ20032736A3 CZ 20032736 A3 CZ20032736 A3 CZ 20032736A3 CZ 20032736 A CZ20032736 A CZ 20032736A CZ 20032736 A CZ20032736 A CZ 20032736A CZ 20032736 A3 CZ20032736 A3 CZ 20032736A3
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- weight
- triazole
- corrosion
- fluids
- hydraulic
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M133/44—Five-membered ring containing nitrogen and carbon only
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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
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- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
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- 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
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- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/106—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four carbon atoms only
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- 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
- 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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- C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
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- C10M2209/109—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
- C10M2227/062—Cyclic esters
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
- C10M2227/062—Cyclic esters
- C10M2227/0625—Cyclic esters used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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Abstract
Description
Hydraulické kapaliny majíc! zlepšenou ochranu proti koroziHydraulic fluids having! Improved corrosion protection
Oblast technikyTechnical field
Přítomný vynález se týká hydraulických kapalin, zvláště brzdových kapalin pro motorová vozidla, které mají zlepšenou ochranu proti korozi a které obsahujíThe present invention relates to hydraulic fluids, in particular brake fluids for motor vehicles, which have improved corrosion protection and which comprise
a) od 0,005 do 0,125 % hmotnostního 1H-1,2,4-triazolu, a(a) from 0.005 to 0.125% by weight of 1H-1,2,4-triazole, and
b) od 0 do 10 % hmotnostních jednoho nebo více dalších inhibitorů koroze, kde při průvodním použití 1H-1,2,3-benztriazolu a/nebo 1H-1,2,3-tolutriazolu a/nebo jejich derivátů, hmotnostní poměr mezi 1H-1,2,4-tríazolem a uvedenými 1H-1,2,3-triazoly musí být větší než 4:1.b) from 0 to 10% by weight of one or more other corrosion inhibitors, wherein, when used concomitantly with 1H-1,2,3-benztriazole and / or 1H-1,2,3-tolutriazole and / or derivatives thereof, the weight ratio between 1H -1,2,4-triazole and said 1H-1,2,3-triazoles must be greater than 4: 1.
Dosavadní stav technikyBACKGROUND OF THE INVENTION
Hydraulické kapaliny a zvláště brzdové kapaliny pro motorová vozidla jsou předmětem velmi vysokých požadavků s ohledem na jejich chemické a fyzické vlastnosti. V souladu s existujícími standardy a specifikacemi pro brzdové kapaliny z ministerstva dopravy USA (US Department of Transportation) ve federálním standardu pro bezpečnost motorových vozidel FMVSS č. 116 (Federal Motor Vehicle Safety Standard FMVSS-No. 116) a normě SAE J 1704 publikovaným společností automobilových inženýrů (Society of Automotive Engineers), moderní brzdové kapaliny mají na jedné straně mít vysoké teploty varu ve vysoce bezvodém stavu (rovnovážné teploty varu pod zpětným ghladičem „ERBP) a vysoké teploty varu ve vlhkém stavu („vlhké ERBP), ale na druhé straně mají také mít viskozitu, která se v širokém teplotním rozmezí mění pouze mírně.Hydraulic fluids and especially brake fluids for motor vehicles are subject to very high requirements with regard to their chemical and physical properties. In accordance with existing US Department of Transportation standards and specifications for brake fluids in the Federal Motor Vehicle Safety Standard FMVSS No. 116 and SAE J 1704 published by automotive engineers (Society of Automotive Engineers), modern brake fluids are supposed to have high boiling points in the highly anhydrous state (equilibrium reflux temperature "ERBP") and high boiling points in the wet state ("wet ERBP") on the one hand, but They should also have a viscosity that varies only slightly over a wide temperature range.
Kromě toho existují ze, strany automobilového průmyslu přísnější požadavky na zlepšenou ochranu proti korozi v případě kovů a neželežných kovů. Inhibitory koroze v brzdových kapalinách mají za pracovní úkol zabránit destrukci kovových materiálů způsobené korozí.In addition, there are stricter requirements from the automotive industry for improved corrosion protection for metals and non-ferrous metals. Corrosion inhibitors in brake fluids are designed to prevent corrosion of metallic materials.
Použití 1H-1,2,3-triazolů, jako je 1H-1,2,3-benztriazol nebo 1H-1,2,3-tolutriazol, jako inhibitorů koroze v hydraulických kapalinách nebo brzdových kapalinách je po určitou dobu známé, například z EP-A 028 789 (1) aThe use of 1H-1,2,3-triazoles, such as 1H-1,2,3-benztriazole or 1H-1,2,3-tolutriazole, as corrosion inhibitors in hydraulic or brake fluids has been known for some time, e.g. EP-A-028,789 (1) a
EP-A 454 110 (2).EP-A-454,110 (2).
WO 00/46325 (3) doporučuje hydraulické kapaliny, které obsahují kombinaci 1H-1,2,3-benztriazolu nebo jeho derivátů, jako jsou 1H-1,2,3-tolutriazol a 1H-1,2,4-triazol nebo jejich deriváty v poměru hmotnostním od 1 : 4 do 4 : 1, jako inhibitorový systém proti korozi. Pro účely srovnání, tabulky 1 až 4 v publikaci (3) také ukazují hydraulické kapaliny, které obsahují samotný 1H-1,2,4-triazol v koncentracích o 0,15 % hmotnostního, avšak jeho korozi inhibující působení je přijatelné pouze v případě mědi.WO 00/46325 (3) recommends hydraulic fluids containing a combination of 1H-1,2,3-benztriazole or derivatives thereof such as 1H-1,2,3-tolutriazole and 1H-1,2,4-triazole or their derivatives in a weight ratio of from 1: 4 to 4: 1, as a corrosion inhibitor system. For purposes of comparison, Tables 1 to 4 of publication (3) also show hydraulic fluids which contain 1H-1,2,4-triazole alone in concentrations of 0.15% by weight, but its corrosion inhibiting action is acceptable only in the case of copper .
Hydraulické a brzdové kapaliny pro motorová vozidla, které jsou známé z dosavadního stavu techniky, jsou však stále neuspokojivé s ohledem na jejich vlastnosti a zvláště jejich ochranu proti korozi. Je proto předmětem přítomného vynálezu poskytnout hydraulické kapaliny, které zvláště uspokojují výše uvedené požadavky na zlepšenou ochranu proti korozi v případě kovů a neželezných kovů.However, hydraulic and brake fluids for motor vehicles known from the prior art are still unsatisfactory with regard to their properties and in particular their corrosion protection. It is therefore an object of the present invention to provide hydraulic fluids which particularly satisfy the above requirements for improved corrosion protection for metals and non-ferrous metals.
Podstata vynálezuSUMMARY OF THE INVENTION
Původci zjistili, že tohoto předmětu je dosaženo hydraulickými nebo sílu přenášejícími kapalinami definovanými v úvodu.We have found that this object is achieved by the hydraulic or force transfer fluids defined in the introduction.
Hydraulické kapaliny, zvláště brzdové kapaliny pro motorová vozidla podle tohoto vynálezu výhodně obsahují od 0, 005 do 0,10 % hmotnostního, výhodně od 0,005 do 0,08 % hmotnostního, zvláště od 0,005 do 0,06 % hmotnostního, složky (a) .Hydraulic fluids, in particular brake fluids for motor vehicles according to the invention preferably comprise from 0.005 to 0.10% by weight, preferably from 0.005 to 0.08% by weight, in particular from 0.005 to 0.06% by weight, of component (a).
Ve výhodném ztělesnění hydraulické kapaliny, zvláště brzdové kapaliny pro motorová vozidla, podle tohoto vynálezu obsahují složku (a) jako jediný na triazolu založený inhibitor koroze. To znamená, že triazoly, jako jsou 1H-1,2,3-benztriazol, 1H-1,2,3-tolutriazol nebo hydrogenovaný 1H-1,2,3-tolutriazol, jsou zde vyloučeny, ale mohou být přítomné anorganické a/nebo organické inhibitory koroze, které mají odlišnou strukturu.In a preferred embodiment of the hydraulic fluid, in particular the brake fluid for motor vehicles, according to the invention, component (a) is the only triazole-based corrosion inhibitor. That is, triazoles such as 1H-1,2,3-benztriazole, 1H-1,2,3-tolutriazole or hydrogenated 1H-1,2,3-tolutriazole are excluded, but inorganic and / or or organic corrosion inhibitors having a different structure.
V jiném výhodném ztělesnění hydraulické kapaliny, zvláště brzdové kapaliny pro motorová vozidla, podle tohoto vynálezu také obsahují až do 10 % hmotnostních, zvláště až do 5 % hmotnostních, jednoho nebo více dalších inhibitorů koroze (b), kde v případě průvodního použití 1H-1,2,3-benztriazolu a/nebo 1H-1,2,3-tolutriazolu a/nebo jejich derivátů, poměr hmotnostní mezi 1H-1,2,4-triazolem a uvedenými 1H-1,2,3-triazoly musí být větší než 4:1.In another preferred embodiment of a hydraulic fluid, in particular a brake fluid for motor vehicles, 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), wherein in case of concomitant use 1H-1 2,3-benztriazole and / or 1H-1,2,3-tolutriazole and / or derivatives thereof, the ratio by weight between 1H-1,2,4-triazole and said 1H-1,2,3-triazoles must be greater than 4: 1.
Další vhodné inhibitory koroze alkalické soli kyseliny fosforečné mastné kyseliny, (b) jsou zde zvláště a kyseliny fosforité, laurová, jako jsou kyseliny kaprylová • · isononylamin, amin diisopropylamin nebo palmitová, stearová nebo olejová a jejich soli s alkalickými kovy, estery kyseliny fosforečné a kyseliny fosforité, jako jsou ethyl-fosfát, dimethyl-fosfát, isopropyl-fosfát, diisopropyl-fosfát, butyl-fosfit nebo dimethyl-fosfit, substituované nebo nesubstituované ethoxylované mono- a dialkylaminy a jejich soli s minerálními kyselinami a mastnými kyselinami, například butylamin, hexylamin, oktylamin, kyseliny olejové, dipropylamin, dibutylamin, substituované nebo nesubstituované ethoxylované alkanolaminy, například mono-, di- nebo triethanolamin, N,Ν'-di-n-butyl-aminoethanol nebo 1,1'-iminodipropan-2-ol, cyklohexylamin, benzimidazol a hydrogenovaný tolutriazol, a nitroaromatické sloučeniny, například 3-nitrobenzaldehyd.Other suitable corrosion inhibitors of the alkali metal salt of phosphoric acid, (b) are particularly and phosphorous, lauric acids such as caprylic acid isononylamine, amine diisopropylamine or palmitic, stearic or oleic acids and their alkali metal salts, phosphoric acid esters and phosphorous acids such as ethyl phosphate, dimethyl phosphate, isopropyl phosphate, diisopropyl phosphate, butyl phosphite or dimethyl phosphite, substituted or unsubstituted ethoxylated mono- and dialkylamines and their salts with mineral acids and fatty acids, for example butylamine, hexylamine, octylamine, oleic acid, dipropylamine, dibutylamine, substituted or unsubstituted ethoxylated alkanolamines, for example mono-, di- or triethanolamine, N, Ν'-di-n-butyl-aminoethanol or 1,1'-iminodipropan-2-ol, cyclohexylamine, benzimidazole and hydrogenated tolutriazole, and nitroaromatic compounds such as 3-nitrobenzaldehyde.
Uvedené inhibitory koroze (b) jsou výhodně přítomné v hydraulických kapalinách, zvláště brzdových kapalinách pro motorová vozidla, podle tohoto vynálezu v množstvích od 0,001 do 10 % hmotnostních, zvláště od 0,001 do 5 % hmotnostních.Said corrosion inhibitors (b) are preferably present in the hydraulic fluids, in particular the brake fluids for motor vehicles, according to the invention in amounts of from 0.001 to 10% by weight, in particular from 0.001 to 5% by weight.
Ve zvláště výhodném ztělesnění obsahují hydraulické kapaliny, zvláště brzdové kapaliny pro motorová vozidla, podle tohoto vynálezu, kromě 1H-1,2,4-triazolu (a), od 0,001 do 5 % hmotnostních, zvláště od 0,001 do 0,5 % hmotnostního, jedné nebo více sloučenin ze skupiny, která se skládá z benzimidazolu, hydrogenovaného 1H-1,2,3-tolutriazolu, purinu, adeninu, 6-chlorpurinu, 2,6-dichlorpurinu, 6-methoxypurinu, 1H-1,2,3-triazolo[4,5-b]pyridinu, 6-histaminopurinu a 6-furfurylaminopurinu a, je-li to žádoucí, další inhibitory koroze jiné než (a) jako přídavné inhibitory koroze (b). Uvedené deriváty purinu jsou popsány v německé patentové přihlášce P 100 26 010.1 jako inhibitory koroze neželezných kovů určené pro hydraulické kapaliny nebo brzdové kapaliny.In a particularly preferred embodiment, the hydraulic fluids, in particular the brake fluids for motor vehicles according to the invention, in addition to 1H-1,2,4-triazole (a), comprise from 0.001 to 5% by weight, in particular from 0.001 to 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, if desired, other corrosion inhibitors other than (a) as additional corrosion inhibitors (b). Said purine derivatives are described in German patent application P 100 26 010.1 as corrosion inhibitors of non-ferrous metals for hydraulic fluids or brake fluids.
• «• «
Všechny údaje v procentech hmotnostních uvedené dříve a dále se v každém případě vztahují k celkovému množství hydraulické nebo brzdové kapaliny, pokud není uvedeno jinak. Součet všech dříve a dále uvedených složek u hydraulické nebo brzdové kapaliny podle tohoto vynálezu se v každém případě sčítá až do 100 % hmotnostních.All percentages by weight given above and in any case refer to the total amount of hydraulic or brake fluid unless otherwise stated. The sum of all the components mentioned above for the hydraulic or brake fluid according to the invention in any case adds up to 100% by weight.
Přítomný vynález se zvláště týká brzdových kapalin pro motorová vozidla, která jako inhibitory koroze obsahují uvedené složky (a) a je-li to žádoucí složky (b).In particular, the present invention relates to brake fluids for motor vehicles which contain as components corrosion inhibitors (a) and, if desired, components (b).
Ve výhodném ztělesnění brzdové kapaliny pro motorová vozidla podle tohoto vynálezu mimoto obsahují, navíc k složkám (a), a, je-li to žádoucí k složkám (b) , od 0,1 do 97 % hmotnostních, zvláště od 30 do 97 % hmotnostních, obzvláště od 50 do 97 % hmotnostních, jednoho nebo více polyglykoletherů a/nebo jejich borátů.In a preferred embodiment of the brake fluid for motor vehicles according to the present invention, they additionally comprise, in addition to components (a) and, if desired, components (b), from 0.1 to 97% by weight, in particular from 30 to 97% by weight. %, in particular from 50 to 97% by weight, of one or more polyglycol ethers and / or borates thereof.
Vhodnými polyglykolethery zde jsou zvláště ethylenglykolmonoalkylethery, které obsahují až 6 ethylenoxidových skupin a v alkylovém radikálu obsahují až 4 atomy uhlíku, například diethylenglykolmonomethylether, triethylenglykolmonomethylether, triethylenglykolmonobutylether nebo tetraethylenglykolmonomethylether. Také vhodné jsou ethylenglykoldialkylethery a propylenglykoldialkylethery, které obsahují až 6 alkylenoxidových skupin a obsahují až 4 atomy uhlíku v každém z alkylových radikálů, například triethylenglykoldimethylether, tetraethylenglykoldimethylether, diethylenglykol-di-terc-butylether, diethylenglykoldibutylether, diethylenglykol-dí-terc-butylether nebo dipropylglykoldimethylether.Suitable polyglycol ethers herein are in particular ethylene glycol monoalkyl ethers containing up to 6 ethylene oxide groups and containing up to 4 carbon atoms in the alkyl radical, for example diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether or tetraethylene glycol monomethyl ether. Also suitable are ethylene glycol dialkyl ethers and propylene glycol dialkyl ethers containing up to 6 alkylene oxide groups and containing up to 4 carbon atoms in each of the alkyl radicals, for example triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol di-tert-butyl ether, diethylene glycol ether, diethylene glycol ether.
Vhodné estery kyseliny borité uvedených nebo jiných polyglykoletherů jsou popsány zvláště v publikacích EP-B 013 925 (cyklické estery kyseliny diborité), DE-C 28 04 535 (estery kyseliny borité obsahující dusík), DE-A 24 38 038 (estery kyseliny borité s alkylenglykolmonoalkyletherem) a DE-B 17 68 933 (trisalkoxyalkylestery kyseliny borité).Suitable boronic esters of said or other polyglycol ethers are described in particular in EP-B 013 925 (cyclic diboric acid esters), DE-C 28 04 535 (nitrogen-containing boric esters), DE-A 24 38 038 (boronic esters with alkylene glycol monoalkyl ether) and DE-B 17 68 933 (trisalkoxyalkylesters of boric acid).
Místo uvedených polyglykoletherů a/nebo jejich esterů s kyselinou boritou, brzdové kapaliny pro motorová vozidla podle tohoto vynálezu mohou také obsahovat, jako základní pložku, složky založené na esterech karboxylových kyselin, ropných nebo silikonových olejích.Instead of said polyglycol ethers and / or their boronic esters, the brake fluids for motor vehicles according to the invention may also contain, as a base component, components based on carboxylic acid esters, petroleum or silicone oils.
V dalším výhodném ztělesnění, brzdové kapaliny pro motorová vozidla podle tohoto vynálezu dále obsahují, kromě složek (a) a, je-li to žádoucí, (b) , od 0,1 do 50 % hmotnostních, zvláště od 1 do 40 % hmotnostních, zejména od 5 do 30 % hmotnostních, jednoho nebo více polyglykolů.In a further preferred embodiment, the brake fluids for motor vehicles according to the invention further comprise, in addition to components (a) and, if desired, (b), from 0.1 to 50% by weight, in particular from 1 to 40% by weight, in particular from 5 to 30% by weight, of one or more polyglycols.
Vhodnými polyglykoly zde jsou zvláště relativně vysoko vroucí produkty reakce ethylepoxidu a/nebo propylenoxidu a/nebo butylenoxidu s vodou nebo dioly, zvláště odpovídající produkty ze směsí ethylenoxidu a propylenoxidu s vodou. Počet alkylenoxidových skupin v polyglykolech tohoto typu je normálně od 2 do 10.Suitable polyglycols here are particularly the relatively high-boiling products of the reaction of ethylepoxide and / or propylene oxide and / or butylene oxide with water or diols, especially the corresponding products from mixtures of ethylene oxide and propylene oxide with water. The number of alkylene oxide groups in polyglycols of this type is normally from 2 to 10.
Působení těchto vysoko vroucích polyglykolů je působením mazadla, které je schopné přispívat podstatně k zlepšení v teplotním/viskozitním chování. Tyto polyglykoly poskytují nízko viskozitní polyglykolethery s dostatečnou viskozitou při vysokých teplotách a tak zajišťují odpovídající mazání. Odpovídající mazání je ve složkách brzdového systému motorových vozidel potřeba, jelikož kaučuk nebo elastomeryThe action of these high-boiling polyglycols is the action of a lubricant which is capable of contributing substantially to an improvement in temperature / viscosity behavior. These polyglycols provide low viscosity polyglycol ethers with sufficient viscosity at high temperatures and thus provide adequate lubrication. Adequate lubrication is needed in the components of the brake system of motor vehicles, since rubber or elastomers
být běžné antioxidanty, například fenothiazin a/nebo takové, které jsou založené na fenolu, a běžná odpěňovadla.be conventional antioxidants, for example phenothiazine and / or phenol-based ones, and conventional antifoams.
Navíc brzdové kapaliny podle tohoto vynálezu mohou obsahovat deriváty cyklických karboxylových kyselin zmíněné ve WO 00/65001, které jsou vhodné jako složky pro snížení viskózity při nízké teplotě za přítomnosti vody.In addition, the brake fluids of the present invention may comprise the cyclic carboxylic acid derivatives mentioned in WO 00/65001 which are useful as components for lowering the low temperature viscosity in the presence of water.
Přítomnost uvedeného malého množství 1H-1,2,4-triazolu zajišťuje znamenitým způsobem, že hydraulické kapaliny nebo brzdové kapaliny pro motorová vozidla podle tohoto vynálezu splňují požadavky uvedené v úvodu a že je dosaženo zvláště korozního chování, které je obecně dobře srovnatelné s dosavadním stavem techniky, tj . zlepšené ochrany proti korozi v případě kovů, jako jsou železo, ocel, pocínované plechy, litina (šedá litina), olovo, cín, chrom, zinek, hliník, hořčík a jejich slitiny, a v případě pájecích kovů, například pájecího cínu, a v případě neželezných kovů, jako je měď a její slitiny, například mosazi.The presence of said small amount of 1H-1,2,4-triazole ensures in an excellent manner that the hydraulic fluids or brake fluids for motor vehicles according to the present invention meet the requirements set out in the introduction and that particularly corrosion behavior is achieved which is generally well comparable to the prior art. techniques, ie. improved corrosion protection for metals such as iron, steel, tinplate, cast iron (lead), lead, tin, chromium, zinc, aluminum, magnesium and their alloys, and for solder metals such as solder tin, and in the case of non-ferrous metals such as copper and its alloys such as brass.
Dalšími výhodami hydraulických kapalin nebo brzdových kapalin pro motorová vozidla podle tohoto vynálezu jsou jejich výhodná viskozita při nízké teplotě, dobrá snášenlivost s vodou, mírné pH, dobrá stabilita při nízké teplotě, vysoké teplotě a oxidaci a dobrá chemická stabilita, výhodné chování (tj. dobrá snášenlivost) s materiály jako jsou kaučuky, plastické hmoty, lepidla, vlákna, těsnění z elastomerů a kaučuků a podobné materiály, stejně jako dobré mazací chování.Further advantages of hydraulic fluids or brake fluids for motor vehicles according to the present invention are their advantageous low temperature viscosity, good water compatibility, moderate pH, good low temperature, high temperature and oxidation stability and good chemical stability, advantageous behavior (i.e. good compatibility with materials such as rubbers, plastics, adhesives, fibers, elastomer and rubber seals and the like, as well as good lubricating behavior.
V neposlední řadě pQužití pouze malého množství 1H-1,2,4-triazolu v hydraulických kapalinách nebo brzdových kapalinách pro motorová vozidla podle tohoto vynálezu je výhodné jak v ekonomických tak v ekologických podmínkách.Last but not least, the use of only a small amount of 1H-1,2,4-triazole in hydraulic or brake fluids for motor vehicles according to the present invention is advantageous in both economic and environmental conditions.
Dále uváděné příklady jsou zamýšleny jako vysvětlení přítomného vynálezu bez toho, že by představovaly omezeni.The following examples are intended to illustrate the present invention without being a limitation.
Příklady provedení vynálezuDETAILED DESCRIPTION OF THE INVENTION
Brzdové kapaliny BF la, BF lb, BF lc a BF 2a podle tohoto vynálezu se zkoušejí ve srovnání s BF 1 (rovnovážná teplota varu pod zpětným chladičem (ERBP): 267 °C, rovnovážná teplota varu pod zpětným chladičem ve vlhkém stavu (vlhká ERBP): 173 °C, kinematická viskozita při -40 °C: 676xl0”6 m2.s_1 (676 cSt) ) a BF 2 (rovnovážná teplota varu pod zpětným chladičem (ERBP): 263 ?C, rovnovážná teplota varu pod zpětným chladičem ve vlhkém stavu (vlhká ERBP): 181 °C, kinematická viskozita při -40 QC: 850xl06 m2.s_1 (850 cSt) ) , z nichý každá obsahuje 0,05 % hmotnostního 1H-1,2,3-tolutriazolu jako inhibitoru koroze neželezných kovů, přičemž BF 1 a BF 2 jsou na bázi průmyslově dostupné brzdové kapaliny DOT 4 nebo DOT 5.1.The brake fluids BF 1a, BF 1b, BF 1c and BF 2a of the present invention are tested in comparison to BF 1 (equilibrium reflux temperature (ERBP): 267 ° C, equilibrium reflux temperature in the wet state (wet ERBP) ): 173 ° C, kinematic viscosity at -40 ° C 676xl0 "6 m 2 .s _1 (676 cSt)) and BF 2 (equilibrium temperature of reflux (ERBP): 263? C, the equilibrium temperature of the reflux condenser in a wet state (wet ERBP): 181 ° C, kinematic viscosity at -40 Q C 850xl0 6 m 2 .s _1 (850 cSt)), each containing 0.05% by weight of 1H-1,2,3 -tolutriazole as a non-ferrous metal corrosion inhibitor, wherein BF 1 and BF 2 are based on commercially available brake fluid DOT 4 or DOT 5.1.
Používané brzdové následující složení:Used brake composition as follows:
kapaliny pro motorová vozidla majíLiquids for motor vehicles have
BF 1:BF 1:
55,00 % hmotnostních55.00% by weight
43,44 % hmotnostních esteru kyseliny borité s triethylenglykolméthyletherem, směs triethylenglykolmonoethyletheru, tetraethylenglykolmonomethyletheru, triethylenglykolmonobutylětheru a diethylenglykolmonómethyletheru, • · směsi 1,1'-iminodipropan-2-olu, fenothiazinu a esteru kyseliny fosforečné, lH-^-l, 2,3-tolutriazolu43.44% by weight of a boronic ester with triethylene glycol methyl ether, a mixture of triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, triethylene glycol monobutyl ether and diethylene glycol monomethyl ether, a mixture of 1,1'-iminodipropan-2-ol, phosphorothiazin-2-ol, phenothiazole-2-ol, tolutriazole
1,51 % hmotnostních1.51% by weight
0,05 % hmotnostního0.05% by weight
BF 2:BF 2:
68,00 % hmotnostních68.00% by weight
28,84 % hmotnostních28.84% by weight
3,11 % hmotnostních3.11% by weight
0,05 % hmotnostního esteru kyseliny borité s triethylenglykolmethyletherem, směs triethylenglykolmonoethyletheru, diethylenglykolmonomethyletheru, diethylenglykolmonobutyletheru a diethylenglykolu, směsi 1,1'-iminodipropan-2-olu, fenothiazinu a derivátu kyseliny fosfonové,0.05% by weight of boric ester with triethylene glycol methyl ether, a mixture of triethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether and diethylene glycol, a mixture of 1,1'-iminodipropan-2-ol, phenothiazine and a phosphonic acid derivative,
1H-1,2,3-tolutriazolu.1H-1,2,3-tolutriazole.
Brzdové kapaliny BF la a BF 2a podle tohoto vynálezu se liší od BF 1 a BF 2 pouze v tom, že 0,05 % hmotnostních 1H-1,2,3-tolutriazolu se nahradí stejným množstvím 1H-1,2,4— -triazolu; brzdová kapalina BF lb obsahuje 0,04 % hmotnostního 1H-1,2,4-triazolu a 0,01 % hmotnostního adeninu místo 0,05 % hmotnostního 1H-1,2,3-tolutriazolu; brzdová kapalina BF lc podle tohoto vynálezu obsahuje 0,07 % hmotnostního 1H-1,2,4-triazolu (ale pouze 54,98 % hmotnostních esteru kyseliny borité s triethylenglykolmonomethyletherem) místo 0,05 % hmotnostního 1H-1,2,3-tolutriazolu.The brake fluids BF 1a and BF 2a of the present invention differ from BF 1 and BF 2 only in that 0.05% by weight of 1H-1,2,3-tolutriazole is replaced by 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% adenine instead of 0.05 wt% 1H-1,2,3-tolutriazole; the BF 1c brake fluid of the present invention contains 0.07 wt% 1H-1,2,4-triazole (but only 54.98 wt% boric ester with triethylene glycol monomethyl ether) instead of 0.05 wt% 1H-1,2,3- tolutriazole.
Aplikační studie se provádějí podle zkoušky na korozi mědi PSA Peugeot-Citroěn D 53 5387 ve verzi 2000. Při zkoušce se nejprve měděný plech, který se předtím očistí v acetonu, s celkovou plochou povrchu 1000 cm2 (rozměry: 71,4 cm x 7 cm x 0,05 cm) svine do formy kruhového válce takovým způsobem, že povrch kovu ve vnitřku se navzájem nedotýká. Měděný plech se umístí do směsi 294 ml brzdové kapaliny obsahující 6 ml destilované vody a zahřívá se na 100 °C po 100 hodin, přičemž skrz kapalinu prochází 10 litrů za hodinu vzduchu, který se předtím nechal projít destilovanou vodou ochlazenou na 2 °C. Po zkoušce se vizuálně vyhodnocuje vzhled nesvinutého měděného plechu a vzhled kapaliny a stanoví se obsah mědi v kapalině.Application studies are carried out according to the copper corrosion test PSA Peugeot Citroen D 53 5387 version 2000. In the test, the copper sheet, which has been previously cleaned in acetone, is first coated with a total surface area of 1000 cm 2 (dimensions: 71.4 cm x 7) cm x 0.05 cm) is wound into a circular cylinder in such a way that the metal surface in the interior does not touch each other. The copper plate is placed in a mixture of 294 ml of brake fluid containing 6 ml of distilled water and heated to 100 ° C for 100 hours, passing through the fluid at 10 liters per hour of air previously passed through distilled water cooled to 2 ° C. After the test, the appearance of the unwound copper plate and the appearance of the liquid are visually evaluated and the copper content of the liquid is determined.
Výsledky z popsané zkoušky jsou uvedeny v tabulce 1 dále.The results of the described assay are shown in Table 1 below.
Tabulka 1Table 1
Můžeme pozorovat, že formulace podle tohoto vynálezu, v protikladu k běžným brzdovým kapalinám, jako jsou BF 1 a BF • · · · · ·It can be observed that the formulations of the invention, as opposed to conventional brake fluids such as BF 1 and BF
2, nenabízejí pouze velihi dobrou ochranu proti korozi mědi s nízkým obsahem mědi ve zkušební kapalině, ale navíc také vytvářejí povrch kovu bez povlaku a v brzdové kapalině se nevytvářejí žádné sedliny.2, they not only offer a very good corrosion protection of low copper copper in the test fluid, but also provide a metal surface without coating and no sediment is formed in the brake fluid.
Výsledky uvedené dále pro zkoušku koroze podle SAE J 1704 (leden 1997) také potvrzují, že brzdové kapaliny podle tohoto vynálezu, jako je BF 2a, která má nízký obsah 1H-1,2,4-triazolu, nabízejí výhody proti formulacím, které nejsou podle tohoto vynálezu, jako je BF ld, která má vysoký obsah 1H-1,2,4-triazolu, jelikož vykazují lepší výsledky v oblasti koroze v případě mědi (BF ld odpovídá BF 1, ale obsahuje 0,20 % hmotnostního 1H-1,2,4-triazolu místo 1H-1,2,3-tolutriazolu a obsahuje pouze 54,85 % hmotnostních esteru kyseliny borité s triethylenglykolmonomethyletherem).The results presented below for the corrosion test of SAE J 1704 (January 1997) also confirm that the brake fluids of the present invention, such as BF 2a, which has a low 1H-1,2,4-triazole content, offer advantages over formulations that are not according to the invention, such as BF 1d, which has a high content of 1H-1,2,4-triazole, since they show better corrosion results in the case of copper (BF 1d corresponds to BF 1 but contains 0.20 wt% 1H-1 2,4-triazole instead of 1H-1,2,3-tolutriazole and contains only 54.85% by weight of boric ester with triethylene glycol monomethyl ether).
Výsledky ze zkoušky koroze podle SAE J 1704 (leden 1997) jsou uvedeny v tabulce 2 dále.The results from the corrosion test according to SAE J 1704 (January 1997) are shown in Table 2 below.
Tabulka 2Table 2
·· · · · ·· · • * · ··· · · · ·
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US20070093395A1 (en) * | 2005-10-21 | 2007-04-26 | Habeeb Jacob J | Antiwear inhibiting and load enhancing additive combinations for lubricating oils |
US7535673B2 (en) * | 2006-01-23 | 2009-05-19 | Hitachi Global Storage Technologies Netherlands B.V. | Fluid dynamic bearing comprising a lubricating fluid having tolutriazole |
WO2008142795A1 (en) | 2007-05-24 | 2008-11-27 | Chiyoda Chemical Co., Ltd. | Functional fluid |
US10669503B2 (en) | 2014-02-25 | 2020-06-02 | Jon A. Petty | Corrosion inhibiting hydraulic fluid additive |
US9593289B2 (en) * | 2014-02-25 | 2017-03-14 | Jon A. Petty | Corrosion inhibiting hydraulic fluid additive |
CN107557121A (en) * | 2017-08-15 | 2018-01-09 | 杭州天汇精细化工有限公司 | A kind of motor vehicle brake fluid and its production method |
CN111676082A (en) * | 2020-05-11 | 2020-09-18 | 江苏龙蟠科技股份有限公司 | Brake fluid for ESP (electronic stability program) automobile control system and preparation method thereof |
US12018224B2 (en) | 2021-07-28 | 2024-06-25 | Afton Chemical Corporation | Hydraulic fluid |
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DE4013243A1 (en) * | 1990-04-26 | 1991-10-31 | Hoechst Ag | AGAINST METAL CORROSION INHIBITED BRAKE FLUIDS BASED ON GLYCOL COMPOUNDS |
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ATE178953T1 (en) * | 1994-12-23 | 1999-04-15 | Cookson Group Plc | METHOD FOR CORROSION INHIBITION OF COPPER AND COPPER ALLOYS |
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