ES2235077T3 - HYDRAULIC LIQUIDS WITH IMPROVED ANTI-CORROSION PROTECTION. - Google Patents

HYDRAULIC LIQUIDS WITH IMPROVED ANTI-CORROSION PROTECTION.

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Publication number
ES2235077T3
ES2235077T3 ES02759789T ES02759789T ES2235077T3 ES 2235077 T3 ES2235077 T3 ES 2235077T3 ES 02759789 T ES02759789 T ES 02759789T ES 02759789 T ES02759789 T ES 02759789T ES 2235077 T3 ES2235077 T3 ES 2235077T3
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ES
Spain
Prior art keywords
weight
motor vehicles
brake fluids
triazole
tolutriazole
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
ES02759789T
Other languages
Spanish (es)
Inventor
Bernd Wenderoth
Michael Roida
Bayram Aydin
Uwe Fidorra
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BASF SE
Original Assignee
BASF SE
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Publication date
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Publication of ES2235077T3 publication Critical patent/ES2235077T3/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
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    • 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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    • C10M2223/10—Phosphatides, e.g. lecithin, cephalin
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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

Líquidos de freno para vehículos automóviles con protección anticorrosión mejorada, que contienen: (a) un 0, 005 a un 0, 125 % en peso de 1H-1, 2, 4-triazol, y (b) un 0 a un 10 % en peso de uno o varios inhibidores de corrosión adicionales, debiendo ser la proporción ponderal de 1H-1, 2, 4-triazol respecto a los citados 1H- 1, 2, 3-triazoles mayor que 4:1 en el caso de empleo concomitante de 1H-1, 2, 3-benzotriazol y/o 1H-1, 2, 3- tolutriazol, y/o sus derivados, así como, además, un 0, 1 a un 97 % en peso de uno o varios éteres de poliglicol y/o sus boratos.Brake fluids for motor vehicles with improved corrosion protection, containing: (a) 0.005 to 0.125% by weight of 1H-1, 2, 4-triazole, and (b) 0 to 10% by weight of one or more additional corrosion inhibitors, the weight ratio of 1H-1, 2, 4-triazole with respect to the aforementioned 1H-1, 2, 3-triazoles must be greater than 4: 1 in the case of concomitant use of 1H-1, 2, 3-benzotriazole and / or 1H-1, 2, 3- tolutriazole, and / or its derivatives, as well as, in addition, 0.1 to 97% by weight of one or more ethers of polyglycol and / or its borates.

Description

Líquidos hidráulicos con protección anticorrosión mejorada.Hydraulic fluids with corrosion protection improved

La presente invención se refiere a líquidos de freno para vehículos automóviles con protección anticorrosión mejorada, que contienenThe present invention relates to liquids of brake for motor vehicles with corrosion protection enhanced, which contain

(a)(to)
un 0,005 a un 0,125% en peso de 1H-1,2,4-triazol, ya 0.005 to 0.125% by weight of 1H-1,2,4-triazole, and

(b)(b)
un 0 a un 10% en peso de uno o varios inhibidores de corrosión adicionales, debiendo ser la proporción ponderal de 1H-1,2,4-triazol respecto a los citados 1H-1,2,3-triazoles mayor que 4:1 en el caso de empleo concomitante de 1H-1,2,3-benzotriazol y/o 1H-1,2,3-tolutriazol, y/o sus derivados,a 0 at 10% by weight of one or more corrosion inhibitors additional, must be the weight ratio of 1H-1,2,4-triazole with respect to cited 1H-1,2,3-triazoles major that 4: 1 in the case of concomitant employment of 1H-1,2,3-benzotriazole and / or 1H-1,2,3-tolutriazole, and / or its derivatives,

así como, además, un 0,1 a un 97% en peso de uno o varios éteres de poliglicol y/o sus boratos.as well as 0.1 to 97% by weight of one or more polyglycol ethers and / or their borates

Los líquidos de freno para vehículos automóviles están sujetos a requisitos muy elevados respecto a sus propiedades químicas y físicas. Correspondientemente a las normas y especificaciones existentes para líquidos de frenos del US-Department of Transportation im Federal Motor Vehicle Safety Standard FMVSS-Nr. 116 y de la norma evitada por la Society of Automotive Engineers SAE J 1704, los líquidos de freno modernos deben disponer por una parte de puntos de ebullición en seco elevados (puntos de ebullición a reflujo) en seco [Equilibrium reflux boiling point, "ERBP"]), así como puntos de ebullición en húmedo (puntos de ebullición a reflujo, en húmedo ["wet ERBP"]), pero por otra parte deben presentar también una viscosidad que no se modifique apenas dentro de un intervalo de temperatura amplio.Brake fluids for motor vehicles they are subject to very high requirements regarding their properties Chemical and physical Corresponding to the rules and Existing specifications for brake fluids US-Department of Transportation im Federal Motor Vehicle Safety Standard FMVSS-Nr. 116 and of the norm avoided by the Society of Automotive Engineers SAE J 1704, the Modern brake fluids must have a part high dry boiling (reflux boiling points) in dry [Equilibrium reflux boiling point, "ERBP"]), as well as wet boiling points (reflux boiling points, in wet ["wet ERBP"]), but on the other hand must present also a viscosity that does not change just within a wide temperature range.

Además, existen requisitos amplios del sector de la industria automovilística en el sentido de una protección anticorrosiva mejorada en el caso de metales y metales no ferrosos. Los inhibidores de corrosión en líquidos de freno tienen el cometido de impedir la destrucción de materiales metálicos ocasionada por corrosión.In addition, there are broad requirements of the sector of the car industry in the sense of protection Improved anticorrosive in the case of metals and non-ferrous metals. Corrosion inhibitors in brake fluids have the committed to prevent the destruction of metallic materials caused by corrosion.

El empleo de 1H-1,2,3-triazoles, como 1H-1,2,3-benzotriazol o 1H-1,2,3-tolutriazol como inhibidores de corrosión en líquidos hidráulicos, o bien líquidos de freno, es conocido desde hace tiempo, a modo de ejemplo por la EP-A 028 789 (1) y la EP-A 454 110 (2).The employment of 1H-1,2,3-triazoles, as 1H-1,2,3-benzotriazole or 1H-1,2,3-tolutriazole as corrosion inhibitors in hydraulic liquids, or liquids brake, it has long been known, by way of example for the EP-A 028 789 (1) and EP-A 454 110 (2).

En la WO 00/46325 (3) se recomiendan líquidos hidráulicos que contienen una combinación de 1H-1,2,3-benzotriazol o sus derivados, como 1H-1,2,3-tolutriazol y 1H-1,2,4-triazol, o sus derivados en proporción ponderal de 1:4 a 4:1 como sistema inhibidor de corrosión. Con fines comparativos, en las tablas 1 a 4 de (3) se indican también líquidos hidráulicos, que contienen 1H-1,2,4-triazol por separado en concentraciones de un 0,15% en peso; no obstante, su acción inhibidora de corrosión es aceptable solo en el caso de cobre.In WO 00/46325 (3) liquids are recommended hydraulics that contain 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 in a weight ratio of 1: 4 to 4: 1 as an inhibitor system corrosion. For comparative purposes, tables 1 to 4 of (3) show also indicate hydraulic liquids, which contain 1H-1,2,4-triazole separately in concentrations of 0.15% by weight; nevertheless its action Corrosion inhibitor is acceptable only in the case of copper.

No obstante, los líquidos de freno para vehículos automóviles conocidos en el estado de la técnica requieren aún mejora con respecto a sus propiedades, y en especial a la protección anticorrosiva. Por lo tanto, existía la tarea de poner a disposición líquidos hidráulicos que cumplieran especialmente los requisitos citados anteriormente en el sentido de una protección dicorrosiva mejorada en metales y metales no ferrosos.However, brake fluids for vehicles cars known in the state of the art still require improvement with respect to its properties, and especially to the corrosion protection. Therefore, there was the task of putting disposal of hydraulic liquids that especially met the requirements cited above in the sense of protection Improved dichorrosive in metals and non-ferrous metals.

Por consiguiente se encontraron los líquidos hidráulicos o transmisores de fuerza definidos inicialmente.Therefore the liquids were found hydraulic or force transmitters defined initially.

Los líquidos de freno según la invención para vehículos automóviles contienen preferentemente un 0,005 a un 0,10% en peso, preferentemente un 0,005 a un 0,08% en peso, en especial un 0,005 a un 0,06% en peso del componente (a).Brake fluids according to the invention for motor vehicles preferably contain 0.005 to 0.10% by weight, preferably 0.005 to 0.08% by weight, especially 0.005 to 0.06% by weight of component (a).

Los líquidos de freno según la invención para vehículos automóviles, contienen el componente (a) como único inhibidor de corrosión a base de triazol en una forma de ejecución preferente. Con ello se indica que los triazoles, como 1H-1,2,3-benzotriazol, 1H-1,2,3-tolutriazol, o 1H-1,2,3-tolutriazol hidrogenado, se excluyen en este caso, pero pueden estar presentes inhibidores de corrosión inorgánicos y/u orgánicos de otra estructura.Brake fluids according to the invention for motor vehicles, contain component (a) as unique triazole based corrosion inhibitor in one embodiment preferential. This indicates that triazoles, such as 1H-1,2,3-benzotriazole, 1H-1,2,3-tolutriazole, or 1H-1,2,3-hydrogenated tolutriazole, are excluded in this case, but inhibitors of inorganic and / or organic corrosion of another structure.

En otra forma de ejecución preferente, los líquidos de freno según la invención para vehículos automóviles contienen aún hasta un 10% en peso, en especial hasta un 5% en peso, de uno o varios inhibidores de corrosión adicionales (b) debiendo ser la proporción ponderal de 1H-1,2,4-triazol respecto a los citados 1H-1,2,3-triazoles mayor que 4:1 en el caso de empleo concomitante de 1H-1,2,3-benzotriazol y/o 1H-1,2,3-tolutriazol, y/o sus derivados.In another preferred embodiment, the brake fluids according to the invention for motor vehicles they still contain up to 10% by weight, especially up to 5% in weight, of one or more additional corrosion inhibitors (b) must be the weight ratio of 1H-1,2,4-triazole with respect to cited 1H-1,2,3-triazoles major that 4: 1 in the case of concomitant employment of 1H-1,2,3-benzotriazole and / or 1H-1,2,3-tolutriazole, and / or its derivatives.

Como inhibidores de corrosión adicionales (b), en este caso entran en consideración sobre todo sales metálicas alcalinas de ácido fosfórico y ácido fosforoso, ácidos grasos, como ácido caprílico, láurico, palmítico, esteárico u oléico, así como sus sales metálicas alcalinas, ésteres de ácido fosfórico y de ácido fosforoso, como fosfato de etilo, fosfato de dimetilo, fosfato de isopropilo, fosfato de diisopropilo, fosfito de butilo o fosfito de dimetilo, mono- y dialquilaminas, en caso dado etoxiladas, y sus sales con ácidos minerales y grasos, por ejemplo butilamina, hexilamina, octilamina, isononilamina, oleilamina, dipropilamina, diisopropilamina o dibutilamina, alcanolaminas, en caso dado etoxiladas, por ejemplo mono-, di- o trietanolamina, N,N'-di-n-butilaminoetanol o 1,1'-iminodipropan-2-ol, ciclohexilamina, bencimidazol y tolutriazol hidrogenado, así como compuestos nitroaromáticos, por ejemplo 3-nitrobenzaldehído.As additional corrosion inhibitors (b), in this case comes into consideration especially metal salts phosphoric acid and phosphorous acid alkalines, fatty acids, such as caprylic, lauric, palmitic, stearic or oleic acid, as well as its alkali metal salts, phosphoric acid esters and phosphorous acid, such as ethyl phosphate, dimethyl phosphate, phosphate of isopropyl, diisopropyl phosphate, butyl phosphite or phosphite of dimethyl, mono- and dialkylamines, if appropriate ethoxylated, and their salts with mineral and fatty acids, for example butylamine, hexylamine, octylamine, isonylamine, oxylamine, dipropylamine, diisopropylamine or dibutylamine, alkanolamine, if appropriate ethoxylates, for example mono-, di- or triethanolamine, N, N'-di-n-butylaminoethanol or 1,1'-iminodipropan-2-ol, cyclohexylamine, benzimidazole and hydrogenated tolutriazole, as well as nitroaromatic compounds, for example 3-nitrobenzaldehyde.

Los citados inhibidores de corrosión (b) se presentan preferentemente en cantidades de un 0,001 a un 10% en peso, en especial un 0,001 a un 5% en peso, en los líquidos hidráulicos según la invención, en especial líquidos de freno para vehículos automóviles.The said corrosion inhibitors (b) are preferably present in amounts of 0.001 to 10% in weight, especially 0.001 to 5% by weight, in liquids hydraulics according to the invention, especially brake fluids for motor vehicles

En una forma de ejecución especialmente preferente, los líquidos de freno para vehículos automóviles según la invención, además de 1H-1,2,4-triazol (a), contienen como inhibidores de corrosión adicionales (b) un 0,001 a un 5% en peso, y en especial un 0,001 a un 0,5% en peso, de uno o varios compuestos del grupo bencimidazol, 1H-1,2,3-tolutriazol hidrogenado, purina, adenina, 6-cloropurina, 2,6-dicloropurina, 6-metoxipurina, 1H-1,2,3-triazolo(4,5B)piridina, 6-histaminopurina y 6-furfurilaminopurina, y en caso dado otros inhibidores de corrosión diferentes a (a). Los citados derivados de purina se describen como inhibidores de corrosión de metales no ferrosos para líquidos hidráulicos, o bien líquidos de freno, en la solicitud de patente alemana Az. P 100 26 010.1.In a way of execution especially Preferably, brake fluids for motor vehicles according to the invention in addition to 1H-1,2,4-triazole (a), contain as additional corrosion inhibitors (b) 0.001 to 5% in weight, and especially 0.001 to 0.5% by weight, of one or more benzimidazole group compounds, 1H-1,2,3-hydrogenated tolutriazole, purine, adenine, 6-chloropurine, 2,6-dichloropurine, 6-methoxypurine, 1H-1,2,3-triazolo (4,5B) pyridine, 6-histaminopurine and 6-furfurylaminopurine, and if necessary others corrosion inhibitors other than (a). The aforementioned derivatives of purine are described as non-metal corrosion inhibitors ferrous for hydraulic fluids, or brake fluids, in the German patent application Az. P 100 26 010.1.

Todos los anteriores y siguientes datos de % en peso se refieren respectivamente a la cantidad total de líquido de freno, en tanto no se indique lo contrario. La suma de todos los componentes indicados anteriormente y a continuación para los líquidos hidráulicos, o bien líquidos de freno según la invención, se suma respectivamente para dar un 100% en peso.All previous and following% data in weight refer respectively to the total amount of liquid from brake, as long as the opposite is not indicated. The sum of all components indicated above and below for hydraulic fluids, or brake fluids according to the invention, It is added respectively to give 100% by weight.

Son objeto de la presente invención líquidos de freno para vehículos automóviles, que contienen como inhibidores de corrosión los citados componentes (a), y en caso dado (b).Liquids of the present invention are subject to brake for motor vehicles, which contain as inhibitors of corrosion of said components (a), and if necessary (b).

En una forma de ejecución preferente, los líquidos de freno para vehículos automóviles según la invención contienen, además de los componentes (a), y en caso dado (b), un 0,1 a un 97% en peso, en especial un 30 a un 97% en peso, sobre todo un 50 a un 97% en peso, de uno o varios poliglicoléteres y/o sus boratos.In a preferred embodiment, the brake fluids for motor vehicles according to the invention contain, in addition to the components (a), and if necessary (b), a 0.1 to 97% by weight, especially 30 to 97% by weight, about 50 to 97% by weight, of one or more polyglycol ethers and / or your borates

En este caso, los poliglicoléteres apropiados son, sobre todo, monoalquiléter de etilenglicol con hasta 6 unidades óxido de etileno y con hasta 4 átomos de carbono en el resto alquilo, como por ejemplo metildiglicol, metiltriglicol, butiltriglicol o metiltetraglicol. Además entran en consideración dialquiléteres de etilenglicol o propilenglicol con hasta 6 unidades óxido de alquileno, y respectivamente hasta 4 átomos de carbono en los restos alquilo, como por ejemplo dimetiléter de trietilenglicol, dimetiléter de tetraetilenglicol, di-terc-butiléter de dietilenglicol, dibutiléter de dietilenglicol, terc-butiléter de butildiglicol o dimetiléter de dipropilenglicol.In this case, the appropriate polyglycol ethers They are, above all, ethylene glycol monoalkyl ether with up to 6 units ethylene oxide and with up to 4 carbon atoms in the rest alkyl, such as methyldiglycol, methyltriglycol, butyltriglycol or methyltetraglycol. They also come into consideration dialkyl ethers of ethylene glycol or propylene glycol with up to 6 alkylene oxide units, and respectively up to 4 atoms of carbon in the alkyl moieties, such as dimethyl ether of triethylene glycol, tetraethylene glycol dimethyl ether, diethylene glycol di-tert-butyl ether, diethylene glycol dibutyl ether, tert-butyl ether butyldiglycol or dipropylene glycol dimethyl ether.

Los boratos apropiados de los citados u otros poliglicoléteres se describen especialmente en los documentos EP-B 013 925 (bis-boratos cíclicos), DE-C 28 04 535 (boratos nitrogenados), DE-A 24 38 038 (monoalquiléter-éster de ácido bórico-alquilenglicol) y DE-B 17 68 933 (borato de tris-alcoxialquilo).Appropriate borates of those cited or others polyglycol ethers are especially described in the documents EP-B 013 925 (cyclic bis-borates),  DE-C 28 04 535 (nitrogen borates), DE-A 24 38 038 (monoalkyl ether-acid ester boric-alkylene glycol) and DE-B 17 68 933 (tris-alkoxyalkyl borate).

En lugar de los poliglicoléteres citados y/o sus boratos, los líquidos de freno para vehículos automóviles según la invención pueden contener como componente principal también aquellos a base de carboxilatos, aceites minerales o aceites de silicona.Instead of the polyglycol ethers mentioned and / or their borates, brake fluids for motor vehicles according to invention may contain as main component also those based on carboxylates, mineral oils or oils of silicone.

En otra forma de ejecución preferente, los líquidos de freno para vehículos automóviles según la invención contienen, además de los componentes (a), y en caso dado (b), además un 0,1 a un 50% en peso, en especial un 1 a un 40% en peso, sobre todo un 5 a un 30% en peso, de uno o varios poliglicoles.In another preferred embodiment, the brake fluids for motor vehicles according to the invention contain, in addition to the components (a), and if necessary (b), in addition 0.1 to 50% by weight, especially 1 to 40% by weight, especially 5 to 30% by weight, of one or more polyglycols.

En este caso, los poliglicoles apropiados son sobre todo productos de reacción de punto de ebullición elevado de óxido de etileno y/u óxido de propileno y/u óxido de butileno con agua o dioles, en especial encuentran empleo los correspondientes productos de reacción de mezclas de óxido de etileno y óxido de propileno con agua. El número de unidades óxido de alquileno en tales poliglicoles asciende normalmente a 2 hasta 10.In this case, the appropriate polyglycols are especially high boiling reaction products of ethylene oxide and / or propylene oxide and / or butylene oxide with water or diols, especially the corresponding ones find employment reaction products of mixtures of ethylene oxide and propylene with water. The number of alkylene oxide units in such polyglycols normally amounts to 2 to 10.

La acción de estos poliglicoles de punto de ebullición elevado es la de un agente lubricante, que se puede atribuir esencialmente a una mejora del comportamiento de temperatura-viscosidad. Los poliglicoles conceden viscosidad suficiente a los poliglicoléteres muy fluidos a temperaturas elevadas, y proporcionan con ello un lubricado suficiente. Por consiguiente, un lubricado suficiente es necesario en los elementos de un sistema de freno de un vehículo automóvil, ya que en este se deben deslizar el menor desgaste posible gomas o elastómeros sobre metal.The action of these point polyglycols of high boiling is that of a lubricating agent, which can be essentially attribute to an improvement in the behavior of viscosity temperature. Polyglycols grant sufficient viscosity to very fluid polyglycol ethers at high temperatures, and thus provide a lubricated enough. Therefore, sufficient lubrication is necessary in the elements of a brake system of a motor vehicle, since in this one you should slide the least possible wear rubber or elastomers on metal.

Otros componentes y agentes auxiliares en los líquidos de freno para vehículos automóviles según la invención pueden ser agentes antioxidantes habituales, como por ejemplo fenotiazina y/o aquellos a base de fenol, y antiespumantes habituales.Other components and auxiliary agents in brake fluids for motor vehicles according to the invention they can be usual antioxidant agents, such as phenothiazine and / or those based on phenol, and antifoams usual.

Además, los líquidos de freno según la invención pueden contener los derivados de ácido carboxílico cíclicos indicados en la WO 00/65001, que son apropiados como componentes para la reducción de la viscosidad a baja temperatura en presencia de agua.In addition, brake fluids according to the invention may contain cyclic carboxylic acid derivatives indicated in WO 00/65001, which are suitable as components for the reduction of viscosity at low temperature in the presence of water.

La presencia de las citadas cantidades reducidas de 1H-1,2,4-triazol procura de manera extraordinaria que los líquidos de freno para vehículos automóviles según la invención cumplan los requisitos citados anteriormente, y que ocasionen especialmente un comportamiento de corrosión generalmente bueno frente al estado de la técnica, es decir, una protección anticorrosiva mejorada en el caso de metales, como hierro, acero, hojalata, hierro fundido (fundición gris), plomo, estaño, cromo, cinc, aluminio, magnesio, y sus aleaciones, y en el caso de metales de soldadura, a modo de ejemplo estaño de soldadura, así como en el caso de metales no ferrosos, como cobre o sus aleaciones, a modo de ejemplo latón.The presence of the aforementioned reduced amounts of 1H-1,2,4-triazole seeks extraordinary way that brake fluids for vehicles cars according to the invention meet the requirements cited above, and that especially cause a behavior of corrosion generally good against the state of the art, is that is, an improved corrosion protection in the case of metals, such as iron, steel, tinplate, cast iron (gray cast iron), lead, tin, chromium, zinc, aluminum, magnesium, and their alloys, and in the case of welding metals, by way of example tin of welding, as well as in the case of non-ferrous metals, such as copper or its alloys, by way of example brass.

Otras ventajas de los líquidos de freno para vehículos automóviles según la invención son su conveniente viscosidad a baja temperatura, una buena compatibilidad con agua, un valor de pH suave, una buena estabilidad al frío, temperatura elevada y oxidación, así como una buena estabilidad química, un comportamiento conveniente (es decir, una buena compatibilidad) frente a materiales como cauchos, materiales sintéticos, juntas coladas, juntas de fibra, elastómeros y goma, y materiales similares, así como un buen comportamiento de lubricado.Other advantages of brake fluids for motor vehicles according to the invention are its convenient low temperature viscosity, good water compatibility, a soft pH value, good cold stability, temperature high and oxidation, as well as good chemical stability, a convenient behavior (i.e. good compatibility) against materials such as rubbers, synthetic materials, joints castings, fiber gaskets, elastomers and rubber, and materials similar, as well as good lubricating behavior.

No en último término es ventajoso tanto desde el punto de vista económico, como también desde el punto de vista ecológico, el empleo de una cantidad apenas reducida de 1H-1,2,4-triazol en los líquidos de freno para vehículos automóviles según la invención.Not ultimately it is advantageous both since economic point of view, as well as from the point of view ecological, the use of a barely reduced amount of 1H-1,2,4-triazole in the liquids of brake for motor vehicles according to the invention.

Los siguientes compuestos explicarán la presente invención sin limitarla.The following compounds will explain the present invention without limiting it.

Ejemplos técnicos de aplicaciónTechnical examples of application

Basándose en los líquidos de freno comerciales DOT 4- o bien DOT 5, BF 1 (ERBP: 267ºC, wet ERBP: 173ºC, viscosidad cinemática a -40ºC: 676 cSt), y BF 2 (ERBP: 263ºC, wet ERBP: 181ºC, viscosidad cinemática a -40ºC: 850 cSt) respectivamente con un 0,05% en peso de 1H-1,2,3-tolutriazol como inhibidor de corrosión de metales no ferrosos, se analizaron los líquidos de freno BF 1a, BF 1b, BF 1c y BF 2a según la invención en comparación con los mismos.Based on commercial brake fluids DOT 4- or DOT 5, BF 1 (ERBP: 267ºC, wet ERBP: 173ºC, viscosity kinematic at -40 ° C: 676 cSt), and BF 2 (ERBP: 263 ° C, wet ERBP: 181 ° C, kinematic viscosity at -40 ° C: 850 cSt) respectively with 0.05% by weight of 1H-1,2,3-tolutriazole as corrosion inhibitor of non-ferrous metals, the brake fluids BF 1a, BF 1b, BF 1c and BF 2a according to the invention in comparison with them.

Los líquidos de freno para vehículos automóviles empleados tenían las siguientes composiciones:Brake fluids for motor vehicles Employees had the following compositions:

BF 1BF one

un 55,00% en peso 55.00% by weight
de borato de metiltriglicol,of methyltriglycol borate,

un 43,44% en peso 43.44% by weight
de mezcla de metiltriglicol, metiltetraglicol, butiltriglicol y metildiglicol,of methyltriglycol mixture, methyltetraglycol, butyltriglycol and methyldiglycol,

un 1,51 1% en peso 1.51 1% by weight
de mezcla de 1,1'-iminodipropan-2-ol, fenotiazina y un fosfato,of mixing 1,1'-iminodipropan-2-ol, phenothiazine and a phosphate,

un 0,05% en peso 0.05% by weight
de 1H-1,2,3-tolutriazol.from 1H-1,2,3-tolutriazole.

BF 2BF 2

un 68,00% en peso 68.00% by weight
de borato de metiltriglicolof methyltriglycol borate

un 28,84% en peso 28.84% by weight
de mezcla de metiltriglicol, metildiglicol, butildiglicol y diglicol,of methyltriglycol mixture, methyldiglycol, butyldiglycol and diglycol,

un 3,11% en peso 3.11% by weight
de mezcla de 1,1'-iminodipropan-2-ol, hidroxianisol y un derivado de ácido fosfónico,of mixing 1,1'-iminodipropan-2-ol, hydroxyanisole and a phosphonic acid derivative,

un 0,05% en peso 0.05% by weight
de 1H-1,2,3-tolutriazol.from 1H-1,2,3-tolutriazole.

Los líquidos de freno BF 1ª y BF 2a según la invención se diferencian de BF 1 y BF 2 solo porque, en lugar de un 0,05% en peso de 1H-1,2,3-tolutriazol, contenían la misma cantidad de 1H-1,2,4-triazol; el líquido de freno BF 1b según la invención contenía, en lugar de un 0,05% en peso de 1H-1,2,3-tolutriazol, un 0,04% en peso de 1H-1,2,4-triazol, y un 0,01% en peso de adenina; el líquido de freno BF 1c según la invención contenía, en lugar de un 0,05% en peso de 1H-1,2,3-tolutriazol, un 0,07% en peso de 1H-1,2,4-triazol (pero a tal efecto solo un 54,98% en peso de borato de metiltriglicol).The brake fluids BF 1st and BF 2nd according to the invention differ from BF 1 and BF 2 just because, instead of a 0.05% by weight of 1H-1,2,3-tolutriazole, contained the same amount of 1H-1,2,4-triazole; the brake fluid BF 1b according to the invention contained, instead of 0.05% by weight of 1H-1,2,3-tolutriazole, 0.04% in weight of 1H-1,2,4-triazole, and 0.01% by weight of adenine; the brake fluid BF 1c according to the invention it contained, instead of 0.05% by weight of 1H-1,2,3-tolutriazole, 0.07% in weight of 1H-1,2,4-triazole (but as such effect only 54.98% by weight of methyltriglycol borate).

Las investigaciones técnicas de aplicación se llevaron a cabo según el ensayo de corrosión de cobre PSA D 53 5387 en la versión del año 2000 de la firma PSA Peugeot-Citroën. En este caso se arrolla en forma de espiral en primer lugar una chapa de cobre, depurada previamente en acetona, con una superficie total de 1.000 cm^{2} (dimensiones: 71,4 cm x 7 cm x 0,05 cm) en forma de un cilindro circular, de modo que la superficie metálica no se tocaba en el interior. La chapa de cobre se coloca en una mezcla de 294 ml de líquido de freno con 6 ml de agua destilada, y se calienta a 100ºC durante 100 horas; a través del líquido se condujeron por hora 10 litros de aire, que se condujo previamente a través de agua destilada enfriada a 2ºC. Tras el test se valora ópticamente la apariencia de la chapa de cobre arrollada de nuevo y la apariencia del líquido, y se determina el contenido en cobre del líquido.The technical application investigations are carried out according to the PSA D 53 5387 copper corrosion test in the 2000 version of the PSA firm Peugeot-Citroën. In this case it is rolled in the form of spiral first a copper plate, previously purified in acetone, with a total area of 1,000 cm2 (dimensions: 71.4 cm x 7 cm x 0.05 cm) in the form of a circular cylinder, so that the metal surface did not touch inside. The sheet of Copper is placed in a mixture of 294 ml of brake fluid with 6 ml of distilled water, and heated at 100 ° C for 100 hours; to 10 liters of air were conducted per hour through the liquid, which previously conducted through distilled water cooled to 2 ° C. After the test optically assesses the appearance of the copper plate rolled again and the appearance of the liquid, and the Copper content of the liquid.

Los resultados según el ensayo descrito se pueden extraer de la siguiente tabla 1.The results according to the described assay can be extract from the following table 1.

TABLA 1TABLE 1

1one

Se desprende que las formulaciones según la invención, en contrapartida a líquidos de freno convencionales, como BF 1 y BF 2, no solo ofrecen una protección contra la corrosión de cobre muy conveniente con contenido en Cu reducido en el líquido de ensayo, sino que ocasionan adicionalmente también una superficie metálica exenta de depósito, y no ocasionan una formación de sedimento en el líquido de freno.It follows that the formulations according to invention, in contrast to conventional brake fluids, like BF 1 and BF 2, they not only offer protection against Very convenient copper corrosion with reduced Cu content in the test liquid, but also additionally cause a metal surface free of deposit, and do not cause formation of sediment in the brake fluid.

Los resultados indicados a continuación en el ensayo de corrosión según SAE J 1704 (Enero 97) demuestran además que los líquidos de freno según la invención, como BF 2a, con un contenido en 1H-1,2,4-triazol reducido, ofrecen ventajas en comparación con formulaciones no correspondientes a la invención, como BF 1d, con un contenido elevado en 1H-1,2,4-triazol, ya que estas muestran un mejor resultado de corrosión en el caso de cobre (BF 1d correspondía a BF 1, pero contenía, en lugar de 1H-1,2,3-tolutriazol, un 0,20% en peso de 1H-1,2,4-triazol, y solo un 54,85% en peso de borato de metiltriglicol):The results indicated below in the corrosion test according to SAE J 1704 (January 97) further demonstrate that the brake fluids according to the invention, such as BF 2a, with a 1H-1,2,4-triazole content reduced, offer advantages compared to non-formulations corresponding to the invention, as BF 1d, with a content elevated in 1H-1,2,4-triazole, since these show a better corrosion result in the case of copper (BF 1d corresponded to BF 1, but contained, instead of 1H-1,2,3-tolutriazole, 0.20% in weight of 1H-1,2,4-triazole, and only one 54.85% by weight of methyltriglycol borate):

Los resultados conforme al ensayo de corrosión según SAE J 1704 (Enero 97) se pueden extraer de la siguiente tabla 2.The results according to the corrosion test according to SAE J 1704 (January 97) can be extracted from the following table 2.

TABLA 2TABLE 2

22

Claims (5)

1. Líquidos de freno para vehículos automóviles con protección anticorrosión mejorada, que contienen1. Brake fluids for motor vehicles with improved corrosion protection, containing
(a)(to)
un 0,005 a un 0,125% en peso de 1H-1,2,4-triazol, ya 0.005 to 0.125% by weight of 1H-1,2,4-triazole, and
(b)(b)
un 0 a un 10% en peso de uno o varios inhibidores de corrosión adicionales, debiendo ser la proporción ponderal de 1H-1,2,4-triazol respecto a los citados 1H-1,2,3-triazoles mayor que 4:1 en el caso de empleo concomitante de 1H-1,2,3-benzotriazol y/o 1H-1,2,3-tolutriazol, y/o sus derivados,a 0 at 10% by weight of one or more corrosion inhibitors additional, must be the weight ratio of 1H-1,2,4-triazole with respect to cited 1H-1,2,3-triazoles major that 4: 1 in the case of concomitant employment of 1H-1,2,3-benzotriazole and / or 1H-1,2,3-tolutriazole, and / or its derivatives,
así como, además, un 0,1 a un 97% en peso de uno o varios éteres de poliglicol y/o sus boratos.as well as 0.1 to 97% by weight of one or more polyglycol ethers and / or their borates 2. Líquidos de freno para vehículos automóviles según la reivindicación 1, que contienen un 0,005 a un 0,08% en peso de componente (a).2. Brake fluids for motor vehicles according to claim 1, containing 0.005 to 0.08% by weight of component (a). 3. Líquidos de freno para vehículos automóviles según la reivindicación 1 o 2, que contienen el componente (a) como único inhibidor de corrosión a base de triazol.3. Brake fluids for motor vehicles according to claim 1 or 2, which contain component (a) as unique corrosion inhibitor based on triazole. 4. Líquidos de freno para vehículos automóviles según la reivindicación 1 o 2, que contienen como componente (b) un 0,001 a un 0,5%en peso de uno o varios compuestos del grupo bencimidazol, 1H-1,2,3-tolutriazol hidrogenado, purina, adenina, 6-cloropurina, 2,6-dicloropurina, 6-metoxipurina, 1H-1,2,3-triazolo(4,5B)piridina, 6-histaminopurina y 6-furfurilaminopurina, y en caso dado otros inhibidores de corrosión diferentes a (a).4. Brake fluids for motor vehicles according to claim 1 or 2, which contain as component (b) a 0.001 to 0.5% by weight of one or more compounds of the group benzimidazole, 1H-1,2,3-tolutriazole hydrogenated, purine, adenine, 6-chloropurine, 2,6-dichloropurine, 6-methoxypurine, 1H-1,2,3-triazolo (4,5B) pyridine, 6-histaminopurine and 6-furfurylaminopurine, and if necessary others corrosion inhibitors other than (a). 5. Líquidos de freno para vehículos automóviles según las reivindicaciones 1 a 4, que contienen, además de los componentes (a), y en caso dado (b), además un 0,1 a un 50% en peso de uno o varios poliglicoles.5. Brake fluids for motor vehicles according to claims 1 to 4, which contain, in addition to the components (a), and if necessary (b), in addition 0.1 to 50% by weight of one or more polyglycols.
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