SK286828B6 - Hydraulic fluids with improved anti-corrosion properties - Google Patents
Hydraulic fluids with improved anti-corrosion properties Download PDFInfo
- Publication number
- SK286828B6 SK286828B6 SK1192-2003A SK11922003A SK286828B6 SK 286828 B6 SK286828 B6 SK 286828B6 SK 11922003 A SK11922003 A SK 11922003A SK 286828 B6 SK286828 B6 SK 286828B6
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- SK
- Slovakia
- Prior art keywords
- weight
- triazole
- fluids
- corrosion
- tolyltriazole
- Prior art date
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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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- C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C10M107/34—Polyoxyalkylenes
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- 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
Oblasť technikyTechnical field
Predložený vynález sa týka hydraulických kvapalín, predovšetkým brzdových kvapalín pre motorové vozidlá, so zlepšenými protikoróznymi vlastnosťami, ktoré obsahujú ako zložku (a) lH-l,2,4-triazol a ako zložku (b) jeden alebo viaceré inhibítory korózie.The present invention relates to hydraulic fluids, in particular brake fluids for motor vehicles, with improved anti-corrosion properties, comprising as component (a) 1H-1,2,4-triazole and as component (b) one or more corrosion inhibitors.
Podstata vynálezuSUMMARY OF THE INVENTION
Predložený vynález sa týka hydraulických, predovšetkým brzdových kvapalín pre motorové vozidlá, poskytujúcich zlepšenú ochranu proti korózii, ktoré obsahujúThe present invention relates to hydraulic, in particular brake fluids for motor vehicles, providing improved corrosion protection comprising:
a) od 0,005 do 0,125 % hmotnostných lH-l,2,4-triazolu a(a) from 0.005 to 0.125% by weight of 1H-1,2,4-triazole; and
b) do 10 % hmotnostných jedného alebo viacerých ďalších inhibítorov korózie, kde pri súčasnom použití lH-l,2,3-benzotriazolu a/alebo lH-l,2,3-tolyltriazolu, a/alebo ich derivátov hmotnostný pomer medzi 1H-1,2,4-triazolom a uvedenými lH-l,2,3-triazolmi musí byť vyšší ako 4:1.(b) up to 10% by weight of one or more other corrosion inhibitors, wherein the simultaneous use of 1H-1,2,3-benzotriazole and / or 1H-1,2,3-tolyltriazole, and / or derivatives thereof, a weight ratio between 1H-1 The 2,4-triazole and said 1H-1,2,3-triazoles must be greater than 4: 1.
Hydraulické kvapaliny a predovšetkým brzdové kvapaliny pre motorové vozidlá sú vystavené veľmi vysokým požiadavkám, pokiaľ ide o ich chemické a fyzikálne vlastnosti. Podľa jestvujúcich noriem a technických predpisov pre brzdové kvapaliny amerického úradu US Department of Transportation in Federal Motor Vehicle Safety Štandard FMVSS-No. 116 a podľa SAE J 1704 noriem publikovaných spoločnosťou Society of Automotive Engineers, moderné brzdové kvapaliny by na jednej strane mali mať vysoké suché teploty varu (rovnovážne refluxné teploty varu (equilibrium reflux boiling points, „ERBP“)) a vysoké mokré teploty varu (mokré ERBP („wet ERBP“)), ale na druhej strane by mali tiež mať viskozitu, ktorá sa v rámci širokého teplotného rozsahu mení len nepatrne.Hydraulic fluids, and in particular brake fluids for motor vehicles, are subject to very high requirements regarding their chemical and physical properties. According to existing standards and technical regulations for brake fluids of the US Department of Transportation in Federal Motor Vehicle Safety Standard FMVSS-No. 116 and according to SAE J 1704 standards published by the Society of Automotive Engineers, modern brake fluids on the one hand should have high dry boiling points (equilibrium reflux boiling points ("ERBP")) and high wet boiling points (wet ERBP (wet ERBP), but on the other hand, should also have a viscosity that varies only slightly over a wide temperature range.
Okrem toho tu jestvujú viaceré exaktné požiadavky z oblasti automobilového priemyslu na zlepšenie ochrany pred koróziou v prípade kovov a neželezných kovov. Inhibítory korózie v brzdových kvapalinách majú za úlohu brániť deštrukcii kovových materiálov, spôsobenej koróziou.In addition, there are several exacting requirements from the automotive industry to improve corrosion protection for metals and non-ferrous metals. Corrosion inhibitors in brake fluids are intended to prevent the destruction of metal materials caused by corrosion.
Použitie lH-l,2,3-triazolov, ako je lH-l,2,3-benzotriazol alebo lH-l,2,3-tolyltriazol, ako inhibítorov korózie v hydraulických kvapalinách alebo v brzdových kvapalinách je už istý čas známe, napríklad z európskych patentových prihlášok EP-A 028 789 (1) a EP-A 454 110 (2).The use of 1H-1,2,3-triazoles such as 1H-1,2,3-benzotriazole or 1H-1,2,3-tolyltriazole as corrosion inhibitors in hydraulic fluids or brake fluids has been known for some time, e.g. European Patent Applications EP-A 028 789 (1) and EP-A 454 110 (2).
Medzinárodný patentový dokument WO 00/46325 (3) odporúča hydraulické kvapaliny, ktoré obsahujú kombináciu lH-l,2,3-benzotriazolu alebo jeho derivátov, ako je lH-l,2,3-tolyltriazol, a lH-l,2,4-triazolu alebo jeho derivátov, v hmotnostnom pomere od 1 : 4 do 4 : 1, ako systém inhibítorov korózie. Na účely porovnania sa v tabuľkách 1 až 4 v (3) uvádzajú tiež hydraulické kvapaliny, ktoré obsahujú samotný 1H-1,2,4-triazol v koncentráciách 0,15 % hmotnostných; ale jeho koróziu inhibujúci účinok je akceptovateľný len v prípade medi.International patent document 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-tolyltriazole, and 1H-1,2,4 -triazole or derivatives thereof, in a weight ratio of from 1: 4 to 4: 1, as a corrosion inhibitor system. For purposes of comparison, Tables 1-4 in (3) also disclose hydraulic fluids which contain 1H-1,2,4-triazole alone in concentrations of 0.15% by weight; but its corrosion inhibiting effect is acceptable only in the case of copper.
Hydraulické kvapaliny a brzdové kvapaliny pre motorové vozidlá, ktoré sú známe z doterajšieho stavu techniky, sú však ešte stále nepostačujúce, pokiaľ ide o ich vlastnosti a predovšetkým o ich ochranu pred koróziou. Úlohou predloženého vynálezu je preto poskytnúť hydraulické kvapaliny, ktoré predovšetkým uspokoja uvedené požiadavky na zlepšenie ochrany pred koróziou v prípade kovov a neželezných kovov.However, hydraulic fluids and brake fluids for motor vehicles known from the prior art are still insufficient in terms of their properties and, in particular, their protection against corrosion. It is therefore an object of the present invention to provide hydraulic fluids which in particular satisfy the aforementioned requirements for improving corrosion protection for metals and non-ferrous metals.
Prekvapujúco sme zistili, že tento cieľ sa dá dosiahnuť pomocou hydraulických alebo energiu prenášajúcich kvapalín, definovaných v úvode.We have surprisingly found that this objective can be achieved by the hydraulic or energy-transferring fluids defined in the introduction.
Hydraulické kvapaliny, predovšetkým brzdové kvapaliny pre motorové vozidlá, podľa predloženého vynálezu vhodne obsahujú od 0,005 do 0,10 % hmotnostných, výhodne od 0,005 do 0,08 % hmotnostných, predovšetkým výhodne od 0,005 do 0,06 % hmotnostných, zložky (a).Hydraulic fluids, in particular brake fluids for motor vehicles, according to the present invention suitably comprise from 0.005 to 0.10% by weight, preferably from 0.005 to 0.08% by weight, particularly preferably from 0.005 to 0.06% by weight, of component (a).
Vo výhodnom uskutočnení hydraulické kvapaliny, predovšetkým brzdové kvapaliny pre motorové vozidlá, podľa predloženého vynálezu obsahujú zložku (a) ako inhibítor korózie, ktorý je len na báze triazolu. Toto je potrebné chápať tak, že triazoly, ako je lH-l,2,3-benzotriazol, lH-l,2,3-tolyltriazol alebo hydrogenovaný lH-l,2,3-tolyltriazol, sú tu vylúčené, ale anorganické a/alebo organické inhibítory korózie, ktoré majú odlišnú štruktúru, môžu byť prítomné.In a preferred embodiment, hydraulic fluids, in particular brake fluids for motor vehicles, according to the present invention comprise component (a) as a triazole-based corrosion inhibitor. This is understood to mean that triazoles such as 1H-1,2,3-benzotriazole, 1H-1,2,3-tolyltriazole or hydrogenated 1H-1,2,3-tolyltriazole are excluded, but inorganic and / or or organic corrosion inhibitors having a different structure may be present.
V ďalšom výhodnom uskutočnení môžu hydraulické kvapaliny podľa predloženého vynálezu, predovšetkým brzdové kvapaliny pre motorové vozidlá, tiež obsahovať až do 10 % hmotnostných, predovšetkým až so 5 % hmotnostných, jedného alebo viacerých ďalších inhibítorov korózie (b), kde v prípade súčasného použitia lH-l,2,3-benzotriazolu a/alebo lH-l,2,3-tolyltriazolu, a/alebo ich derivátov hmotnostný pomer medzi lH-l,2,4-triazolom a uvedenými lH-l,2,3-triazolmi musí byť vyšší ako 4:1.In a further preferred embodiment, the hydraulic fluids according to the present invention, in particular motor vehicle brake fluids, may also contain up to 10% by weight, in particular up to 5% by weight, of one or more further corrosion inhibitors (b). the 1,2,3-benzotriazole and / or 1H-1,2,3-tolyltriazole, and / or derivatives thereof, the weight ratio between 1H-1,2,4-triazole and said 1H-1,2,3-triazoles must be higher than 4: 1.
Vhodnými ďalšími inhibítormi korózie (b) sú predovšetkým alkalické kovové soli kyseliny fosforečnej a kyseliny fosforitej, mastné kyseliny, ako je kyselina kaprylová, kyselina laurová, kyselina palmitová, kyselina stearová alebo kyselina olejová, a ich soli alkalických kovov, estery kyseliny fosforečnej a kyseliny fosforitej, ako je etylester kyseliny fosforečnej, dimetylester kyseliny fosforečnej, izopropylester kyseliny fosforečnej, diizopropylester kyseliny fosforečnej, butylester kyseliny fosforitej alebo dimetylester kyseliny fosforitej, substituované alebo nesubstituované etoxylované mono- a dialkylamíny a ich soli s minerálnymi kyse linami a mastnými kyselinami, napríklad butylamín, hexylamín, oktylamín, izononylamín, oleylamín, dipropylamin, diizopropylamín alebo dibutylamín, substituované alebo nesubstituované etoxylované alkanolamíny, napríklad mono-, di- alebo trietanolamín, N,N'-di-n-butylaminoetanol alebo l,ľ-iminodipropan-2-ol, cyklohexylamin, benzimidazol a hydrogenovaný tolyltriazol, a nitroaromatické zlúčeniny, napríklad 3-nitrobenzaldehyd.Suitable further corrosion inhibitors (b) are, in particular, alkali metal salts of phosphoric acid and phosphoric acid, fatty acids such as caprylic acid, lauric acid, palmitic acid, stearic acid or oleic acid, and their alkali metal salts, phosphoric acid esters and phosphoric acid such as ethyl phosphate, dimethyl phosphate, isopropyl phosphate, diisopropyl phosphate, butyl phosphate or dimethyl phosphate, substituted or unsubstituted ethoxylated mono- and dialkylamines and their salts with mineral acids and fatty acids, for example butylamines, fatty acids, for example butylamines , octylamine, isononylamine, oleylamine, dipropylamine, diisopropylamine or dibutylamine, substituted or unsubstituted ethoxylated alkanolamines, for example mono-, di- or triethanolamine, N, N'-di-n-butylaminoethanol or 1,1'-iminodipropan-2-ol, cyclohexylamine, benzimidazole and hydrogenated tolyltriazole, and nitroaromatic compounds such as 3-nitrobenzaldehyde.
Uvedené inhibítory korózie (b) sú podľa predloženého vynálezu výhodne prítomné v hydraulických kvapalinách, predovšetkým v brzdových kvapalinách pre motorové vozidlá, v množstvách od 0,001 do 10 % hmotnostných, výhodne od 0,001 do 5 % hmotnostných.Said corrosion inhibitors (b) according to the present invention are preferably present in hydraulic fluids, in particular in brake fluids for motor vehicles, in amounts of from 0.001 to 10% by weight, preferably from 0.001 to 5% by weight.
Predovšetkým vo výhodnom uskutočnení hydraulické kvapaliny, predovšetkým brzdové kvapaliny pre motorové vozidlá, podľa predloženého vynálezu obsahujú, okrem lH-l,2,4-triazolu (a), od 0,001 do 5 % hmotnostných, výhodne od 0,001 do 0,5 % hmotnostných, jednej alebo viacerých zlúčenín zo skupiny zahrnujúcej benzimidazol, hydrogenovaný lH-l,2,3-tolyltriazol, purín, adenín, 6-chlórpurín, 2,6-dichlórpurín, 6-metoxypurín, lH-l,2,3-triazolo(4,5-ó)pyridín, 6-histaminopurín a 6-furfurylaminopurín a prípadne ďalšie inhibítory korózie, iné ako (a), ako prídavné inhibítory korózie (b). Uvedené purínové deriváty sú opísané v nemeckej patentovej prihláške P 100 26 010.1 ako inhibítory korózie neželezných kovov pre hydraulické kvapaliny alebo pre brzdové kvapaliny.In a particularly preferred embodiment, hydraulic fluids, in particular motor vehicle brake fluids, according to the present invention contain, in addition to 1H-1,2,4-triazole (a), from 0.001 to 5% by weight, preferably from 0.001 to 0.5% by weight, one or more of benzimidazole, hydrogenated 1H-1,2,3-tolyltriazole, purine, adenine, 6-chloropurine, 2,6-dichloropurine, 6-methoxypurine, 1H-1,2,3-triazolo 5-a) pyridine, 6-histaminopurine and 6-furfurylaminopurine and optionally 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 for brake fluids.
Všetky uvedené a hmotnostné percentá sú v každom prípade vztiahnuté na celkové množstvo hydraulickej kvapaliny alebo brzdovej kvapaliny, pokiaľ nie je uvedené inak. Suma všetkých uvedených zložiek pre hydraulické kvapaliny alebo pre brzdové kvapaliny podľa predloženého vynálezu v každom prípade predstavuje až do 100 % hmotnostných.All percentages and weight percentages are in each case based on the total amount of hydraulic fluid or brake fluid, unless otherwise indicated. In any case, the sum of the above-mentioned components for the hydraulic or brake fluids of the present invention is up to 100% by weight.
Predložený vynález sa predovšetkým týka brzdových kvapalín pre motorové vozidlá, ktoré, ako inhibítory korózie, obsahujú uvedené zložky (a) a prípadne zložky (b).In particular, the present invention relates to brake fluids for motor vehicles comprising, as corrosion inhibitors, said components (a) and optionally components (b).
Vo výhodnom uskutočnení brzdové kvapaliny pre motorové vozidlá podľa predloženého vynálezu ďalej obsahujú, okrem zložiek (a) a prípadne (b), od 0,1 do 97 % hmotnostných, výhodne od 30 do 97 % hmotnostných, predovšetkým výhodne od 50 do 97 % hmotnostných, jedného alebo viacerých polyglykoléterov a/alebo ich borátov.In a preferred embodiment, the brake fluids for motor vehicles according to the present invention further comprise, in addition to components (a) and optionally (b), from 0.1 to 97% by weight, preferably from 30 to 97% by weight, particularly preferably from 50 to 97% by weight. , one or more polyglycol ethers and / or borates thereof.
Vhodnými polyglykolétermi sú predovšetkým etylénglykolmonoalkylétery, ktoré obsahujú až do 6 etylénoxidových jednotiek a obsahujú až 4 atómy uhlíka v alkylovom zvyšku, ako je napríklad dietylénglykolmonometyléter, trietylénglykolmonometyléter, trietylénglykolmonobutyléter alebo tetraetylénglykolmonometyléter. Vhodnými sú taktiež etylénglykoldialkylétery a propylénglykoldialkylétery, ktoré obsahujú až do 6 alkylénoxidových jednotiek a obsahujú až do 4 atómov uhlíka v každom z alkylových zvyškov, ako je napríklad trietylénglykoldimetyléter, tetraetylénglykoldimetyléter, dietylénglykoldi-Zerc-butyléter, dietylénglykoldibutyléter, dietylénglykoldi-terc-butyléter alebo dipropylénglykoldimetyléter.Suitable polyglycol ethers are, in particular, ethylene glycol monoalkyl ethers which contain up to 6 ethylene oxide units and contain up to 4 carbon atoms in the alkyl moiety, such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether or tetraethylene glycol ether. Also suitable are ethylene glycol dialkyl ethers and propylene glycol dialkyl ethers which contain up to 6 alkylene oxide units and contain up to 4 carbon atoms in each of the alkyl radicals, such as triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether.
Vhodné estery kyseliny boritej uvedených alebo iných polyglykoléterov sú opísané najmä v patentových dokumentoch EP-B 013 925 (cyklické estery kyseliny bisboritej), DE-C 28 04 535 (dusík obsahujúce estery kyseliny boritej), DE-A 24 38 038 (alkylénglykolmonoalkyléterestery kyseliny boritej) a DE-B 17 68 933 (trisalkoxyalkylestery kyseliny boritej).Suitable boronic esters of the aforementioned or other polyglycol ethers are described, in particular, in EP-B 013 925 (cyclic bisboric acid esters), DE-C 28 04 535 (nitrogen-containing boronic esters), DE-A 24 38 038 (alkylene glycol monoalkyl ether esters of boric acid) ) and DE-B 17 68 933 (trisalkoxyalkylesters of boric acid).
Namiesto uvedených polyglykoléterov a/alebo ich esterov kyseliny boritej brzdové kvapaliny pre motorové vozidlá podľa predloženého vynálezu môžu tiež ako základnú zložku obsahovať zlúčeniny na báze esterov karboxylových kyselín, minerálnych olejov alebo silikónových olejov.Instead of the aforementioned polyglycol ethers and / or their boronic acid esters, the brake fluids for motor vehicles according to the present invention may also contain as base component compounds based on carboxylic acid esters, mineral oils or silicone oils.
V ďalšom výhodnom uskutočnení brzdové kvapaliny pre motorové vozidlá podľa predloženého vynálezu ďalej okrem zložiek (a) a prípadne (b) obsahujú od 0,1 do 50 % hmotnostných, výhodne od 1 do 40 % hmotnostných, predovšetkým výhodne od 5 do 30 % hmotnostných, jedného alebo viacerých polyglykolov.In another preferred embodiment, the brake fluids for motor vehicles of the present invention further comprise, in addition to components (a) and optionally (b), from 0.1 to 50% by weight, preferably from 1 to 40% by weight, particularly preferably from 5 to 30% by weight, % of one or more polyglycols.
Vhodnými polyglykolmi sú najmä produkty reakcie etylénoxidu a/alebo propylénoxidu, a/alebo butylénoxidu s vodou alebo s diolmi, ktoré majú relatívne vysokú teplotu varu, predovšetkým príslušné produkty zmesí etylénoxidu a propylénoxidu s vodou. Počet alkylénoxidových v polyglykoloch tohto typu je zvyčajne od 2 do 10.Suitable polyglycols are in particular products of the reaction of ethylene oxide and / or propylene oxide, and / or butylene oxide with water or diols having a relatively high boiling point, in particular the corresponding products of mixtures of ethylene oxide and propylene oxide with water. The number of alkylene oxide in polyglycols of this type is usually from 2 to 10.
Účinok týchto polyglykolov s vysokou teplotou varuje taký, že pôsobia ako mastivo, ktoré podstatne prispieva k zlepšeniu vlastnosti teplota/viskozita. Polyglykoly poskytujú polyglykolétery s nízkou viskozitou postačujúcu viskozitu pri vysokých teplotách a tým zabezpečujú primerané mastenie. Primerané mastenie je potrebné v zložkách brzdového systému motorových vozidiel, pretože v týchto systémoch guma alebo elastoméry sa musia na kove kĺzať s veľmi nízkym opotrebovaním.The effect of these high temperature polyglycols warns that they act as a lubricant, which substantially contributes to improving the temperature / viscosity property. The polyglycols provide low viscosity polyglycol ethers sufficient for high temperature viscosity to provide adequate lubrication. Adequate lubrication is needed in the components of the braking system of motor vehicles, since in these systems rubber or elastomers must slide on the metal with very low wear.
Ďalšími zložkami a pomocnými látkami v brzdových kvapalinách motorových vozidiel podľa predloženého vynálezu môžu byť konvenčné antioxidanty, napríklad fenotiazín a/alebo zlúčeniny na báze fenolu, a konvenčné odpeňovacie činidlá.The other components and excipients in the brake fluids of motor vehicles according to the present invention may be conventional antioxidants, for example phenothiazine and / or phenol-based compounds, and conventional antifoams.
Navyše, brzdové kvapaliny podľa predloženého vynálezu môžu obsahovať deriváty cyklických karboxylových kyselín uvedené v medzinárodnom patentovom dokumente WO 00/65001, ktoré sú vhodné ako zložky na redukciu viskozity pri nízkych teplotách v prítomnosti vody.In addition, the brake fluids of the present invention may comprise cyclic carboxylic acid derivatives disclosed in WO 00/65001, which are useful as components for reducing low temperature viscosity in the presence of water.
Prítomnosť uvedeného malého množstva lH-l,2,4-triazolu vynikajúcim spôsobom zabezpečuje, že hydraulické kvapaliny alebo brzdové kvapaliny pre motorové vozidlá podľa predloženého vynálezu spĺňajú po žiadavky uvedené v úvode a najmä, že sú ovplyvnené vlastnosti korózie, ktoré sú vo všeobecnosti dobre porovnateľné s doterajším stavom techniky, t. j. zlepšenie ochrany pred koróziou v prípade kovov, ako je železo, oceľ, cínová platňa, liatina, olovo, cín, chróm, zinok, hliník, horčík a ich zliatiny, a v prípade spájkových kovov napríklad spájkový cín, a v prípade neželezných kovov, ako je meď a jej zliatiny, napríklad mosadz.The presence of said small amount of 1H-1,2,4-triazole in an excellent manner ensures that the hydraulic or brake fluids for motor vehicles according to the present invention meet the requirements set out in the introduction and in particular that the corrosion properties which are generally well comparable are affected. with the prior art, i. j. improving corrosion protection for metals such as iron, steel, tinplate, cast iron, lead, tin, chromium, zinc, aluminum, magnesium and their alloys, and solder metals such as solder tin and non-ferrous metals such as copper and alloys thereof such as brass.
Ďalšími výhodami hydraulických kvapalín alebo brzdových kvapalín pre motorové vozidlá podľa predloženého vynálezu je ich vynikajúca viskozita pri nízkych teplotách, dobrá kompatibilita s vodou, mierne hodnoty pH, dobrá stabilita pri nízkych a vysokých teplotách a dobrá stabilita proti oxidácii ako aj dobrá chemická stabilita, vynikajúce vlastnosti (t. j. dobrá kompatibilita) s materiálmi, ako sú gumy, plastické materiály, vrstvy lepidiel, vlákna, elastoméry a gumové tesnenia a podobné materiály, ako aj dobré mastiace vlastnosti.Further advantages of hydraulic fluids or brake fluids for motor vehicles according to the present invention are their excellent low temperature viscosity, good water compatibility, moderate pH values, good low and high temperature stability and good oxidation stability as well as good chemical stability, excellent properties (ie, good compatibility) with materials such as rubbers, plastics, adhesive layers, fibers, elastomers and rubber seals and the like, as well as good lubricating properties.
Nie na poslednom mieste použitie len malého množstva lH-l,2,4-triazolu v hydraulických kvapalinách alebo v brzdových kvapalinách pre motorové vozidlá podľa predloženého vynálezu je výhodné tak z ekonomického ako aj z ekologického hľadiska.Not lastly, the use of only a small amount of 1H-1,2,4-triazole in hydraulic fluids or brake fluids for motor vehicles according to the present invention is advantageous both economically and environmentally.
Uvedené príklady podrobnejšie opisujú predložený vynález bez toho, aby ho v akomkoľvek zmysle obmedzovali.The examples described in more detail describe the present invention without limiting it in any sense.
Príklady uskutočnenia vynálezuDETAILED DESCRIPTION OF THE INVENTION
Príklady použitiaExamples of use
Na báze komerčne dostupných DOT 4 alebo DOT 5.1 brzdových kvapalín BF 1 (ERBP: 267 °C, mokré ERBP: 173 °C, kinematická viskozita pri teplote -40 °C: 676 cSt) a BF 2 (ERBP: 263 °C, mokré ERBP: 181 °C, kinematická viskozita pri teplote -40 °C: 850 cSt) v každom prípade s obsahom 0,05 % hmotnostných lH-l,2,3-tolyltriazolu ako inhibítora korózie neželezného kovu sa v porovnaní s nimi testovali brzdové kvapaliny BF la, BF lb, BF lc a BF 2a podľa predloženého vynálezu.Based on commercially available DOT 4 or DOT 5.1 brake fluids BF 1 (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) in each case containing 0.05% by weight of 1H-1,2,3-tolyltriazole as a non-ferrous metal corrosion inhibitor, brake fluids were tested against them BF 1a, BF 1b, BF 1c and BF 2a according to the present invention.
Použité brzdové kvapaliny pre motorové vozidlá mali nasledujúce zloženia:The brake fluid used for motor vehicles had the following compositions:
BF 1:BF 1:
55,00 % hmotnostných55.00% by weight
43,44 % hmotnostných43.44% by weight
1,51 % hmotnostných1.51% by weight
0,05 % hmotnostných trietylénglykolmetyléterborátu, zmesi trietylénglykolmonometyléteru, tetraetylénglykolmonometyléteru, trietylénglykolmonobutyléteru a dietylénglykolmonometyléteru, zmesi l,l'-iminodipropan-2-olu, fenotiazinu a esteru kyseliny fosforečnej,0.05% by weight of triethylene glycol methyl ether borate, a mixture of triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, triethylene glycol monobutyl ether and diethylene glycol monomethyl ether, a mixture of 1,1'-iminodipropan-2-ol, phosphorothiazine and a phosphorothiazine ester
H-1,2,3 -tolyltriazoluH-1,2,3-tolyltriazole
BF2:BF2:
68,00 % hmotnostných68.00% by weight
28,84 % hmotnostných28.84% by weight
3,11 % hmotnostných3.11% by weight
0,05 % hmotnostných trietylénglykolmetyléterborátu, zmesi trietylénglykolmonometyléteru, dietylénglykolmono-metyléteru, dietylénglykolmonobutyléteru a dietylén-glykolu, zmesi l,ľ-iminodipropan-2-olu, fenotiazinu a derivátu kyseliny fosforitej, lH-l,2,3-tolyltriazolu.0.05% by weight of triethylene glycol methyl ether borate, a mixture of triethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether and diethylene glycol, a mixture of 1,1'-iminodipropan-2-ol, phenothiazine, 1-phospholithic acid derivative.
Brzdové kvapaliny BF la a BF 2a podľa predloženého vynálezu sa odlišujú od BF 1 a BF 2 len v tom, že 0,05 % hmotnostných lH-l,2,3-tolyltriazolu sa nahradilo s rovnakým množstvom lH-l,2,4-triazolu; brzdová kvapalina BF lb obsahuje 0,04 % hmotnostných lH-l,2,4-triazolu a 0,01 % hmotnostných adenínu namiesto 0,05 % hmotnostných lH-l,2,3-tolyltriazolu; brzdová kvapalina BF lc podľa vynálezu obsahuje 0,07 % hmotnostných lH-l,2,4-triazolu (ale len 54,98 % hmotnostných trietylénglykol-monometyléterborátu) namiesto 0,05 % hmotnostných 1 H-l,2,3-tolyltriazolu.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-tolyltriazole has been 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% adenine instead of 0.05 wt% 1H-1,2,3-tolyltriazole; The BF 1c brake fluid of the present invention contains 0.07 wt% 1H-1,2,4-triazole (but only 54.98 wt% triethylene glycol monomethyl ether borate) instead of 0.05 wt% 1H-1,2,3-tolyltriazole.
Štúdie použitia sa uskutočnili v súlade s PSA Peugeot-Citroen D 53 5387 testom korózie medi vo verzii 2000. V tomto teste sa najskôr medená platňa, ktorá sa vopred vyčistila v acetóne a mala celkovú plochu povrchu 1 000 cm2 (rozmery: 71,4 cm x 7 cm x 0,05 cm) zvinula do formy kruhového valca takým spôsobom, aby kovový povrch vnútornej časti nebol vo vzájomnom kontakte. Medená platňa sa umiestnila v zmesi 294 ml brzdovej kvapaliny obsahujúcej 6 ml destilovanej vody a zahrievala sa pri teplote 100 °C počas 100 hodín; cez kvapalinu sa nechalo prechádzať 10 litrov vzduchu za hodinu, pričom tento vzduch sa nechal vopred prejsť cez destilovanú vodu ochladenú na teplotu 2 °C. Po ukončení testu sa vzhľad nezvinutej medenej platne a vzhľad kvapaliny vyhodnotili vizuálne a stanovil sa obsah medi v kvapaline.The use studies were conducted in accordance with the PSA Peugeot-Citroen D 53 5387 copper corrosion test version 2000. In this test, a copper plate that had been pre-cleaned in acetone and had a total surface area of 1,000 cm 2 (dimensions: 71.4) cm x 7 cm x 0.05 cm) is rolled into a circular cylinder in such a way that the metal surface of the inner part is not in contact with each other. The copper plate was placed in a mixture of 294 ml brake fluid containing 6 ml distilled water and heated at 100 ° C for 100 hours; 10 liters of air per hour were passed through the liquid, and the air was previously passed through distilled water cooled to 2 ° C. At the end of the test, the appearance of the unwound copper plate and the appearance of the liquid were evaluated visually and the copper content of the liquid was determined.
Výsledky z opísaného testu sú zosumarizované v nasledujúcej tabuľke 1.The results of the described assay are summarized in Table 1 below.
Tabuľka 1Table 1
Z uvedeného vidieť, že prípravky podľa predloženého vynálezu, na rozdiel od konvenčných brzdových kvapalín, ako je BF 1 a BF 2, nielenže poskytujú veľmi dobrú ochranu medi pred koróziou s nízkym obsa5 hom Cu v testovanej kvapaline, ale navyše tiež poskytujú povrch kovu bez povlaku a nevytvárajú sediment v brzdovej kvapaline.From the above, it can be seen that the formulations of the present invention, in contrast to conventional brake fluids such as BF 1 and BF 2, not only provide very good copper protection against corrosion with low Cu content in the test fluid, but additionally also provide uncoated metal surface and do not form sediment in the brake fluid.
Uvedené výsledky pre test korózie podľa SAE J 1704 (Jan. 97) taktiež potvrdzujú, že brzdové kvapaliny podľa predloženého vynálezu, ako je BF 2a, ktoré majú nízky obsah lH-l,2,4-triazolu, poskytujú výhody v porovnaní s prípravkami, ktoré nie sú predmetom vynálezu, ako je BF ld, s vysokým obsahom 1 H-1,2,410 -triazolu, pretože majú lepšie výsledky korózie v prípade medi (BF ld zodpovedá BF 1, ale obsahuje 0,20 % hmotnostných lH-l,2,4-triazolu, namiesto lH-l,2,3-tolyltriazolu a pozostáva len z 54,85 % hmotnostných trietylénglykolmonometyl-éterborátu).The results for the corrosion test of SAE J 1704 (Jan. 97) also confirm that the brake fluids of the present invention, such as BF 2a, having a low 1H-1,2,4-triazole content, provide advantages over the formulations, which are not the subject of the invention, such as BF 1d, having a high content of 1H-1,2,410-triazole, because they have better corrosion results in the case of copper (BF 1d corresponds to BF 1 but contains 0.20% by weight of 1H-1,2) 4-triazole, instead of 1H-1,2,3-tolyltriazole and consists only of 54.85% by weight of triethylene glycol monomethyl etherborate).
Výsledky testov korózie podľa SAE J 1704 (Jan. 97) sú zosumarizované v nasledujúcej tabuľke 2.The results of the corrosion tests according to SAE J 1704 (Jan. 97) are summarized in the following Table 2.
Tabuľka 2Table 2
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DE10117647A DE10117647A1 (en) | 2001-04-09 | 2001-04-09 | Hydraulic fluids with improved corrosion protection |
PCT/EP2002/003671 WO2002081604A1 (en) | 2001-04-09 | 2002-04-03 | Hydraulic fluids with improved anti-corrosion properties |
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JP2009507938A (en) * | 2005-07-01 | 2009-02-26 | ダウ グローバル テクノロジーズ インコーポレイティド | Low viscosity functional fluid |
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 |
GB2272000B (en) * | 1992-10-30 | 1997-03-26 | Castrol Ltd | A method of inhibiting corrosion |
ATE178953T1 (en) * | 1994-12-23 | 1999-04-15 | Cookson Group Plc | METHOD FOR CORROSION INHIBITION OF COPPER AND COPPER ALLOYS |
FR2733509B1 (en) * | 1995-04-28 | 1997-07-04 | Bp Chemicals Snc | ANTIFREEZE COMPOSITION AND AQUEOUS FLUID COMPRISING THE COMPOSITION |
US6074992A (en) * | 1999-02-02 | 2000-06-13 | Union Carbide Chemicals & Plastics Technology Corporation | Functional fluid compositions |
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DE10026010A1 (en) * | 2000-05-25 | 2001-11-29 | Basf Ag | Hydraulic liquid, useful as a brake fluid and having improved corrosion protection for bright metals, contains 0.005-0.5 wt.% of at least one heterocyclic compound |
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