EP1213340B1 - Urea containing functional fluid for automotive vehicles - Google Patents
Urea containing functional fluid for automotive vehicles Download PDFInfo
- Publication number
- EP1213340B1 EP1213340B1 EP01403164A EP01403164A EP1213340B1 EP 1213340 B1 EP1213340 B1 EP 1213340B1 EP 01403164 A EP01403164 A EP 01403164A EP 01403164 A EP01403164 A EP 01403164A EP 1213340 B1 EP1213340 B1 EP 1213340B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fluid
- functional fluid
- urea
- fluids
- weight
- 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
Links
Classifications
-
- 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
- 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
-
- 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
- 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
-
- 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
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/20—Compounds containing nitrogen
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/061—Carbides; Hydrides; Nitrides
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/082—Inorganic acids or salts thereof containing nitrogen
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/082—Inorganic acids or salts thereof containing nitrogen
- C10M2201/083—Inorganic acids or salts thereof containing nitrogen nitrites
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/16—Carbon dioxide
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/18—Ammonia
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
- C10M2209/1013—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/102—Polyesters
- C10M2209/1023—Polyesters 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- 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
-
- 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
- C10N2040/25—Internal-combustion engines
-
- 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
- C10N2040/25—Internal-combustion engines
- C10N2040/251—Alcohol fueled engines
-
- 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
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
-
- 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
- C10N2040/25—Internal-combustion engines
- C10N2040/255—Gasoline engines
- C10N2040/28—Rotary engines
Definitions
- the invention relates to functional fluids for motor vehicles and more particularly to functional fluids allowing a lasting lubrication of the engines.
- Each motor vehicle currently contains a variety of fluids that perform various functions such as engine and / or gear lubricating oils, hydraulic oils such as power steering oils, brake fluid or damper fluid, and coolant. .
- GB-A-348 642 relates to improvements in lubricating fluids and for hydraulic applications.
- Oxalic acid is a crystalline acid that deposits on parts of the engine whose temperature is below its decomposition temperature (of the order of 189 ° C) and fouls them.
- polyesters The presence of maleic, malonic and oxalic acid also stimulates an esterification reaction with the polyalkylene glycols (diols).
- the polyalkylene glycol chains contain terminal hydroxyl groups which are capable of reacting by esterification with a dicarboxylic acid to form water and polyesters.
- the formation of polyesters is manifested by a volatile loss of the base lubricating oil and an increase in the total acid number and the viscosity of the lubricating fluid thus degrading the qualities of the latter.
- antioxidants such as phenols and amines have been used as additives (see US 4,701,273 and DE 28 06 133 ).
- these products are not always satisfactory from the point of view of their efficiency and from the point of view of their ecotoxicity or their biodegradability.
- the Applicant has now surprisingly found that it is possible to overcome the problems of thermal and oxidative stability in functional fluids by introducing a reducing agent therein.
- the fluid is a motor lubricant
- the addition of this reducing additive ensures a long-term lubrication of the engine.
- reducing agents present directly in the functional fluid has been found to be particularly effective in ensuring the thermal and oxidative stability of lubricating fluids comprising as base fluids polyalkylene glycols.
- agent or reducing additive is meant a compound capable of reducing the nitrogen oxides emitted during combustion, the nitric and nitrous acids present in the engine under the normal operating conditions of the latter.
- the use of such reducing agents has the additional advantage, when lubricating fluid containing them arrives in the combustion chamber, to reduce at the source the nitrogen oxides emitted by combustion or by the valve guides, in order to reduce the concentration of these harmful oxides in the exhaust gas.
- the invention relates to the use of a reducing agent for reducing, limiting and / or eliminating oxidation in the functional fluids of motor vehicles.
- the functional fluid comprises, as base fluid, at least one polyalkylene glycol and / or a polyalkylene glycol ether such as those described in the patent applications. EP 0570 121 and EP 0 355 977 . More particularly, the functional fluid may be a motor lubricant.
- urea as reducing agent.
- urea Another advantage of urea is its solubility in PAGs.
- urea in polyalkylene glycol fluids contributes, because of its biodegradability and low toxicity (LD 50 of about 8,500 mg / kg, administered orally to rats), the efforts in terms of ecotoxicity that led to the use of polyalkylene glycols as base fluids.
- the invention will be more particularly described in the context of a motor lubricating fluid and more particularly of a motor lubricating fluid using base of the polyalkylene glycols.
- the polyalkylene glycols used as base fluid for the manufacture of functional fluids and more particularly motor lubricants are generally random copolymers containing from 30 to 90% by weight of ethylene oxide unit and from 70 to 10% by weight of ethylene oxide.
- Propylene oxide-derived unit weight having a weight average molecular weight between 300 and 1200.
- the lubricating fluid is supplemented with a reducing agent capable of reducing the nitrogen oxides emitted during combustion, and nitrous acid and nitric acid dissolved in the lubricating fluid under normal operating conditions of the engine.
- the reducing action of the additive thus makes it possible to overcome the oxidation reaction by the nitric and nitrous acids of the PAGs which leads to the formation of crystalline oxalic acid responsible for the fouling or deposits observed on the "cold" parts "whose temperature does not exceed that of decomposition of oxalic acid.
- this reducing agent also makes it possible to overcome the esterification reaction initiated by the dicarboxylic acids on the hydroxyl end groups of the polyalkylene glycol chains. This esterification reaction was responsible for thickening of the lubricating fluid.
- urea is more particularly preferred to use urea as an antioxidant especially because of a selective reducing action.
- urea is a natural, biodegradable and low toxicity substance (urea is classified in Germany as a low pollutant ie in pollution class 1 ( Wassergefährdungstrain 1 )) and is not corrosive to aluminum alloys or gray cast irons.
- the lubricant may comprise, in addition to the base fluid, a mixture of very varied additives.
- urea mixed with the lubricant, reacts preferably with nitrogen oxides, nitrous acid and nitric acid by converting them into water, carbon dioxide and nitrogen.
- urea reacts selectively with the compounds responsible for the oxidative degradation of the lubricating fluid and thus acts as a consumer of free radicals.
- Urea is generally used in concentrations of less than or equal to 10% by weight relative to the total weight of the lubricant. More particularly, urea is present in the lubricating fluid in lower concentrations of between 0.01 and 5% by weight relative to the total weight of the lubricant, even more particularly between 0.5 and 2% by weight relative to the total weight of the lubricant.
- the functional fluid according to the invention when it is a lubricant, allows a long-term lubrication of the engine, because even a small amount of urea considerably slows the phenomena of fouling and increase of the viscosity of the lubricating fluid.
- the functional fluid produced by adding reducing agents to base fluids such as polyalkylene glycols can be, for example, motor oil, gear oil, automatic transmission oil, power steering oil. , a hydraulic fluid for dampers, a brake fluid or a coolant.
- additives may be added to the final functional fluid depending on the nature of the functional fluid. These are usual additives, preferably biodegradable and of low toxicity.
Landscapes
- 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)
- Inorganic Chemistry (AREA)
- Lubricants (AREA)
- Exhaust Gas After Treatment (AREA)
- Detergent Compositions (AREA)
Abstract
Description
L'objet du présent brevet est défini dans le libellé de la revendication indépendante 1. Les revendications dépendantes 2 à 5 concernent des caractéristiques optatives de l'invention.The subject matter of this patent is defined in the wording of the independent claim 1. Dependent claims 2 to 5 relate to optative features of the invention.
L'invention concerne des fluides fonctionnels pour véhicules automobiles et plus particulièrement des fluides fonctionnels permettant une lubrification durable des moteurs.The invention relates to functional fluids for motor vehicles and more particularly to functional fluids allowing a lasting lubrication of the engines.
Chaque véhicule automobile contient actuellement une variété de fluides remplissant différentes fonctions comme les huiles lubrifiantes de moteur et/ou d'engrenage, les huiles hydrauliques comme les huiles pour direction assistée, le liquide de frein ou le fluide d'amortisseur et le liquide de refroidissement.Each motor vehicle currently contains a variety of fluids that perform various functions such as engine and / or gear lubricating oils, hydraulic oils such as power steering oils, brake fluid or damper fluid, and coolant. .
Tous ces fluides présentent une instabilité thermique et oxydative à l'usage. Cette instabilité entraîne une modification de leurs propriétés physiques et chimiques. Les fluides ne remplissent plus leur rôle de manière satisfaisante, ce qui peut être à l'origine de dysfonctionnements mécaniques graves du véhicule. Ces fluides doivent alors être retirés et mis en décharge, ce qui pose des problèmes d'ordre financier et environnemental.All these fluids have a thermal and oxidative instability in use. This instability leads to a modification of their physical and chemical properties. Fluids no longer perform their role satisfactorily, which can be the cause of serious mechanical malfunctions of the vehicle. These fluids must then be removed and disposed of, which poses financial and environmental problems.
Parmi ces fluides fonctionnels, le plus problématique est sans doute le lubrifiant de moteur. Les vidanges fréquentes de ces huiles de moteur dégradées, actuellement majoritairement à base d'huiles minérales ou synthétiques, peu ou pas biodégradables et toxiques, sont à l'origine d'une pollution non négligeable liée au stockage et à la non maîtrise du recyclage de ces huiles.Among these functional fluids, the most problematic is probably the engine lubricant. The frequent emptying of these degraded motor oils, currently mostly based on mineral or synthetic oils, with little or no biodegradability and toxicity, are at the origin of a significant pollution related to the storage and non control of these oils.
On a proposé alors d'utiliser des fluides de base non toxiques et rapidement biodégradables comme les polyalkylèneglycols (ultérieurement PAG dans le texte), obtenus notamment à partir d'oxyde d'éthylène et d'oxyde de propylène (
Or, il s'avère que le phénomène de dégradation thermique et oxydative des lubrifiants comprenant des PAG comme fluides de base est particulièrement important.However, it turns out that the phenomenon of thermal and oxidative degradation of lubricants comprising PAG as base fluids is particularly important.
En effet, on a observé, en utilisant des PAG comme fluides de base dans des lubrifiants de moteur la formation de dépôts et/ou d'encrassement autour de pièces comme les segments racleurs et/ou les bossages des pistons.Indeed, it has been observed, using PAGs as base fluids in engine lubricants the formation of deposits and / or fouling around parts such as scraper rings and / or piston bosses.
Les moteurs à combustion interne actuels produisent notamment des oxydes d'azote NOx. Ces oxydes d'azote qui se forment pendant la combustion peuvent se dissoudre dans le film lubrifiant PAG existant sur la chemise. En effet, le PAG contient par nature ou attire une certaine quantité d'eau, qui peut augmenter pendant le fonctionnement du moteur. Ainsi, les acides azotés, formés par dissolution des oxydes d'azote, oxydent l'éthylèneglycol et le propylèneglycol des PAG pour former de l'acide oxalique, puis, à un stade ultérieur, des acides dicarboxyliques comme l'acide maléique ou malonique.Current internal combustion engines produce nitrogen oxides NO x . These nitrogen oxides that form during combustion can dissolve in the existing PAG lubricant film on the jacket. Indeed, the PAG contains by nature or attracts a certain amount of water, which can increase during the operation of the engine. Thus, nitrogenous acids, formed by dissolution of the nitrogen oxides, oxidize the ethylene glycol and propylene glycol PAG to form oxalic acid, and then, at a later stage, dicarboxylic acids such as maleic or malonic acid.
L'acide oxalique est un acide cristallin qui se dépose sur les parties du moteur dont la température est inférieure à sa température de décomposition (de l'ordre de 189°C) et les encrasse.Oxalic acid is a crystalline acid that deposits on parts of the engine whose temperature is below its decomposition temperature (of the order of 189 ° C) and fouls them.
La présence d'acide maléique, malonique et oxalique stimule par ailleurs une réaction d'estérification avec les polyalkylèneglycols (diols). Les chaînes de polyalkylèneglycol contiennent des groupes hydroxyles terminaux qui sont susceptibles de réagir par estérification avec un acide dicarboxylique en formant de l'eau et des polyesters. La formation de polyesters se manifeste par une perte volatile de l'huile lubrifiante de base et une augmentation de l'indice d'acide total et de la viscosité du fluide lubrifiant dégradant ainsi les qualités de ce dernier.The presence of maleic, malonic and oxalic acid also stimulates an esterification reaction with the polyalkylene glycols (diols). The polyalkylene glycol chains contain terminal hydroxyl groups which are capable of reacting by esterification with a dicarboxylic acid to form water and polyesters. The formation of polyesters is manifested by a volatile loss of the base lubricating oil and an increase in the total acid number and the viscosity of the lubricating fluid thus degrading the qualities of the latter.
Jusqu'à présent, afin de limiter autant que se peut l'oxydation dans les fluides fonctionnels, on a utilisé comme additifs des agents antioxydants tels que les phénols et les amines (voir
Il existe donc un besoin de limiter davantage ou plus efficacement ces phénomènes d'oxydation dans les fluides fonctionnels, notamment accrus avec l'utilisation de PAG comme huile de base, afin de garantir une stabilité thermique et oxydative à ces fluides.There is therefore a need to further limit or more effectively these oxidation phenomena in functional fluids, in particular increased with the use of PAG as oil basic, to ensure thermal and oxidative stability to these fluids.
Il existe également un besoin de fournir un fluide fonctionnel de véhicule automobile qui permette une lubrification durable du moteur.There is also a need to provide a motor vehicle functional fluid that allows for durable lubrication of the engine.
En outre, il apparaît de plus en plus incontournable de devoir fournir un fluide fonctionnel de véhicule automobile qui surmonte également les problèmes liés à l'écotoxicité et au recyclage des fluides fonctionnels et notamment des lubrifiants de moteur.In addition, it appears more and more essential to provide a functional fluid of a motor vehicle that also overcomes the problems related to the ecotoxicity and recycling of functional fluids and in particular engine lubricants.
La demanderesse a découvert à présent d'une manière surprenante qu'il était possible de surmonter les problèmes liés à la stabilité thermique et oxydative dans les fluides fonctionnels en introduisant dans ceux-ci un agent réducteur. Lorsque le fluide est un lubrifiant de moteur, l'adjonction de cet additif réducteur permet d'assurer une lubrification à long terme du moteur.The Applicant has now surprisingly found that it is possible to overcome the problems of thermal and oxidative stability in functional fluids by introducing a reducing agent therein. When the fluid is a motor lubricant, the addition of this reducing additive ensures a long-term lubrication of the engine.
L'utilisation d'agents réducteurs présents directement dans le fluide fonctionnel s'est avérée particulièrement efficace pour garantir la stabilité thermique et oxydative de fluides lubrifiants comprenant comme fluides de base des polyalkylèneglycols.The use of reducing agents present directly in the functional fluid has been found to be particularly effective in ensuring the thermal and oxidative stability of lubricating fluids comprising as base fluids polyalkylene glycols.
On entend par agent ou additif réducteur un composé capable de réduire les oxydes d'azote émis lors de la combustion, les acides nitrique et nitreux présents dans le moteur dans les conditions de fonctionnement normal de ce dernier.By agent or reducing additive is meant a compound capable of reducing the nitrogen oxides emitted during combustion, the nitric and nitrous acids present in the engine under the normal operating conditions of the latter.
Par ailleurs, l'utilisation de tels agents réducteurs présente l'avantage supplémentaire, lorsque du fluide lubrifiant les contenant parvient dans la chambre de combustion, de réduire à la source les oxydes d'azote émis par la combustion ou par les guides de soupapes, de manière à diminuer la concentration de ces oxydes nocifs dans les gaz d'échappement.Furthermore, the use of such reducing agents has the additional advantage, when lubricating fluid containing them arrives in the combustion chamber, to reduce at the source the nitrogen oxides emitted by combustion or by the valve guides, in order to reduce the concentration of these harmful oxides in the exhaust gas.
L'invention a pour objet l'utilisation d'un agent réducteur pour diminuer, limiter et/ou supprimer l'oxydation dans les fluides fonctionnels de véhicules automobiles.The invention relates to the use of a reducing agent for reducing, limiting and / or eliminating oxidation in the functional fluids of motor vehicles.
Selon une mise en oeuvre avantageuse de l'invention, le fluide fonctionnel comprend, comme fluide de base, au moins un polyalkylèneglycol et/ou un éther de polyalkylèneglycol tel que ceux décrits dans les demandes de brevets
Selon une mise en oeuvre préférentielle de l'invention, on préfère utiliser l'urée comme agent réducteur.According to a preferred embodiment of the invention, it is preferred to use urea as reducing agent.
En effet, il a été constaté que l'utilisation d'urée comme agent réducteur donnait d'excellents résultats notamment sur la diminution de l'oxydation des fluides lubrifiants comprenant des polyalkylèneglycols comme fluides de base.Indeed, it has been found that the use of urea as reducing agent gave excellent results, in particular on the reduction of the oxidation of lubricating fluids comprising polyalkylene glycols as base fluids.
Un autre avantage de l'urée est sa solubilité dans les PAG.Another advantage of urea is its solubility in PAGs.
En outre, l'utilisation d'urée dans des fluides à base de polyalkylèneglycol contribue, du fait de sa biodégradabilité et de sa faible toxicité (DL50 d'environ 8.500 mg/kg, administration par voie orale à des rats), aux efforts en matière d'écotoxicité qui ont mené à l'utilisation de polyalkylèneglycols comme fluides de base.In addition, the use of urea in polyalkylene glycol fluids contributes, because of its biodegradability and low toxicity (LD 50 of about 8,500 mg / kg, administered orally to rats), the efforts in terms of ecotoxicity that led to the use of polyalkylene glycols as base fluids.
Bien que pouvant s'appliquer de façon générale à tout type de fluides fonctionnels pour véhicules automobiles, l'invention sera plus particulièrement décrite dans le cadre d'un fluide lubrifiant de moteur et plus particulièrement d'un fluide lubrifiant de moteur utilisant comme fluide de base des polyalkylèneglycols.Although generally applicable to all types of functional fluids for motor vehicles, the invention will be more particularly described in the context of a motor lubricating fluid and more particularly of a motor lubricating fluid using base of the polyalkylene glycols.
Les polyalkylèneglycols utilisés comme fluide de base pour la fabrication de fluides fonctionnels et plus particulièrement de lubrifiants de moteur, sont généralement des copolymères statistiques contenant de 30 à 90 % en poids de motif dérivés d'oxyde d'éthylène et de 70 à 10 % en poids de motif dérivés d'oxyde de propylène, ayant une masse moléculaire moyenne en poids comprise entre 300 et1200.The polyalkylene glycols used as base fluid for the manufacture of functional fluids and more particularly motor lubricants, are generally random copolymers containing from 30 to 90% by weight of ethylene oxide unit and from 70 to 10% by weight of ethylene oxide. Propylene oxide-derived unit weight having a weight average molecular weight between 300 and 1200.
Selon la présente invention, le fluide lubrifiant est additionné d'un agent réducteur capable de réduire les oxydes d'azote émis lors de la combustion, et l'acide nitreux et l'acide nitrique dissous dans le fluide lubrifiant dans des conditions normales de fonctionnement du moteur.According to the present invention, the lubricating fluid is supplemented with a reducing agent capable of reducing the nitrogen oxides emitted during combustion, and nitrous acid and nitric acid dissolved in the lubricating fluid under normal operating conditions of the engine.
L'action réductrice de l'additif permet ainsi de palier à la réaction d'oxydation par les acides nitriques et nitreux des PAG qui conduit à la formation d'acide oxalique cristallin responsable de l'encrassement ou des dépôts observés sur les pièces "froides", dont la température n'excède pas celle de décomposition de l'acide oxalique.The reducing action of the additive thus makes it possible to overcome the oxidation reaction by the nitric and nitrous acids of the PAGs which leads to the formation of crystalline oxalic acid responsible for the fouling or deposits observed on the "cold" parts "whose temperature does not exceed that of decomposition of oxalic acid.
L'utilisation de cet agent réducteur permet également de palier à la réaction d'estérification initiée par les acides dicarboxylique sur les groupes terminaux hydroxyles des chaînes de polyalkylèneglycols. Cette réaction d'estérification était responsable d'un épaississement du fluide lubrifiant.The use of this reducing agent also makes it possible to overcome the esterification reaction initiated by the dicarboxylic acids on the hydroxyl end groups of the polyalkylene glycol chains. This esterification reaction was responsible for thickening of the lubricating fluid.
On préfère plus particulièrement utiliser l'urée comme agent antioxydant notamment du fait d'une action réductrice sélective.It is more particularly preferred to use urea as an antioxidant especially because of a selective reducing action.
En outre, l'utilisation d'urée comme agent réducteur présente les avantages supplémentaires que l'urée est une substance naturelle, biodégradable et de faible toxicité (l'urée est classée en Allemagne en tant que composé à faible pouvoir polluant, c'est-à-dire dans la classe de pollution 1 (Wassergefährdungsklasse 1)) et n'est pas corrosive envers les alliages en aluminium ou les fontes grises.In addition, the use of urea as a reducing agent has the additional advantages that urea is a natural, biodegradable and low toxicity substance (urea is classified in Germany as a low pollutant ie in pollution class 1 ( Wassergefährdungsklasse 1 )) and is not corrosive to aluminum alloys or gray cast irons.
En effet, le lubrifiant peut comprendre outre le fluide de base, un mélange d'additifs très variés. Or l'urée, mélangée au lubrifiant, réagit de préférence avec les oxydes d'azote, l'acide nitreux et l'acide nitrique en les transformant en eau, gaz carbonique et azote. En d'autres termes, l'urée réagit de sélectivement avec les composés responsables de la dégradation oxydative du fluide lubrifiant et agit ainsi comme un consommateur de radicaux libres.Indeed, the lubricant may comprise, in addition to the base fluid, a mixture of very varied additives. However, urea, mixed with the lubricant, reacts preferably with nitrogen oxides, nitrous acid and nitric acid by converting them into water, carbon dioxide and nitrogen. In other words, urea reacts selectively with the compounds responsible for the oxidative degradation of the lubricating fluid and thus acts as a consumer of free radicals.
On utilise généralement l'urée dans des concentrations inférieures ou égales à 10 % en poids par rapport au poids total du lubrifiant. Plus particulièrement, l'urée est présente dans le fluide lubrifiant dans des concentrations inférieures comprises entre 0,01 et 5 % en poids par rapport au poids total du lubrifiant, encore plus particulièrement entre 0,5 et 2 % en poids par rapport au poids total du lubrifiant.Urea is generally used in concentrations of less than or equal to 10% by weight relative to the total weight of the lubricant. More particularly, urea is present in the lubricating fluid in lower concentrations of between 0.01 and 5% by weight relative to the total weight of the lubricant, even more particularly between 0.5 and 2% by weight relative to the total weight of the lubricant.
Il s'avère que l'utilisation de l'urée, même en faible quantité, dans des lubrifiants de la présente invention à base de polyalkylèneglycols, garantit une stabilité thermique et oxydative du lubrifiant sur une distance parcourue par le véhicule automobile qui équivaut environ au triple de celle parcourue en n'utilisant pas d'agent réducteur dans le fluide lubrifiant.It has been found that the use of urea, even in small amounts, in lubricants of the present invention based on polyalkylene glycols, ensures a thermal and oxidative stability of the lubricant over a distance traveled by the motor vehicle which is approximately equivalent to triple of that traveled by not using a reducing agent in the lubricating fluid.
Le fluide fonctionnel selon l'invention, lorsqu'il est un lubrifiant, permet une lubrification à long terme du moteur, car même une faible quantité d'urée ralentit considérablement les phénomènes d'encrassement et d'augmentation de la viscosité du fluide lubrifiant.The functional fluid according to the invention, when it is a lubricant, allows a long-term lubrication of the engine, because even a small amount of urea considerably slows the phenomena of fouling and increase of the viscosity of the lubricating fluid.
De manière générale, le fluide fonctionnel fabriqué par adjonction d'agents réducteurs à des fluides de base tels que les polyalkylèneglycols peut être par exemple, une huile de moteur, une huile d'engrenage, une huile pour transmission automatique, une huile pour direction assistée, un fluide hydraulique pour amortisseurs, un liquide de freins ou un liquide de refroidissement.In general, the functional fluid produced by adding reducing agents to base fluids such as polyalkylene glycols can be, for example, motor oil, gear oil, automatic transmission oil, power steering oil. , a hydraulic fluid for dampers, a brake fluid or a coolant.
D'autres additifs peuvent être ajoutés au fluide fonctionnel final suivant la nature du fluide fonctionnel. Il s'agit d'additifs usuels de préférence biodégradables et de faible toxicité.Other additives may be added to the final functional fluid depending on the nature of the functional fluid. These are usual additives, preferably biodegradable and of low toxicity.
Claims (5)
- Use of a reducing agent for limiting or eliminating oxidation by nitrogen oxides, nitric acid and nitrous acid in a functional fluid of a motor vehicle comprising, as base fluid, at least one polyalkylene glycol and/or one polyalkylene glycol ether.
- Use according to Claim 1, characterized in that the base fluid is a copolymer of ethylene oxide (EO) and of propylene oxide (PO) with an EO/PO weight ratio between 30/70 and 90/10 and having a weight-average molecular weight between 300 and 1200.
- Use according to one of the preceding claims, characterized in that the reducing agent is urea.
- Use according to Claim 3, characterized in that the amount of urea is between 0.01 and 5% by weight relative to the total weight of functional fluid, and preferably between 0.5 and 2% by weight relative to the total weight of functional fluid.
- Use according to one of the preceding claims, characterized in that the functional fluid is an engine lubricant.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0015956 | 2000-12-08 | ||
FR0015956A FR2817874B1 (en) | 2000-12-08 | 2000-12-08 | FUNCTIONAL FLUID FOR MOTOR VEHICLES COMPRISING UREA |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1213340A1 EP1213340A1 (en) | 2002-06-12 |
EP1213340B1 true EP1213340B1 (en) | 2010-11-17 |
Family
ID=8857398
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01403164A Expired - Lifetime EP1213340B1 (en) | 2000-12-08 | 2001-12-07 | Urea containing functional fluid for automotive vehicles |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1213340B1 (en) |
AT (1) | ATE488563T1 (en) |
DE (1) | DE60143467D1 (en) |
ES (1) | ES2353954T3 (en) |
FR (1) | FR2817874B1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8357644B2 (en) | 2008-04-28 | 2013-01-22 | Dow Global Technologies Llc | Polyalkylene glycol lubricant composition |
FR2968011B1 (en) | 2010-11-26 | 2014-02-21 | Total Raffinage Marketing | LUBRICATING COMPOSITION FOR ENGINE |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL31017C (en) * | 1930-02-10 | |||
GB802941A (en) * | 1956-07-10 | 1958-10-15 | Exxon Research Engineering Co | Lubricating composition |
US3164553A (en) * | 1960-12-16 | 1965-01-05 | Union Carbide Corp | Process of treating synthetic lubricating oils with urea |
-
2000
- 2000-12-08 FR FR0015956A patent/FR2817874B1/en not_active Expired - Fee Related
-
2001
- 2001-12-07 ES ES01403164T patent/ES2353954T3/en not_active Expired - Lifetime
- 2001-12-07 AT AT01403164T patent/ATE488563T1/en not_active IP Right Cessation
- 2001-12-07 EP EP01403164A patent/EP1213340B1/en not_active Expired - Lifetime
- 2001-12-07 DE DE60143467T patent/DE60143467D1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
ATE488563T1 (en) | 2010-12-15 |
FR2817874A1 (en) | 2002-06-14 |
EP1213340A1 (en) | 2002-06-12 |
FR2817874B1 (en) | 2005-02-11 |
ES2353954T3 (en) | 2011-03-08 |
DE60143467D1 (en) | 2010-12-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1310547B1 (en) | Fuel with low sulphur content for diesel engines | |
EP0213027B1 (en) | Dispersant additive compositions for lubricating oils, and their preparation | |
EP3174960B1 (en) | Lubricating compositions for motor vehicles | |
EP2513273A1 (en) | Additive composition for engine oil | |
EP3274432A1 (en) | Lubricating composition | |
FR2894592A1 (en) | ADDITIVES IN THE FORM OF NANOSPHERES, LUBRICANT FORMULATIONS CONTAINING SAME, AND PROCESS FOR THEIR USE | |
FR2905704A1 (en) | COMPOSITION OF LUBRICATING OILS INTENDED TO INHIBIT CLOSURE OF OIL FILTERS INDUCED BY COOLING FLUIDS | |
EP1213340B1 (en) | Urea containing functional fluid for automotive vehicles | |
FR2839315A1 (en) | ADDITIVE FOR IMPROVING THERMAL STABILITY OF HYDROCARBON COMPOSITIONS | |
FR2706469A1 (en) | Polyfunctional polyisobutenes, their preparation, formulation and use | |
WO2014128104A1 (en) | Lubricating composition based on aminated compounds | |
FR2910023A1 (en) | LUBRICANT FORMULATIONS AND METHODS FOR THEIR USE | |
FR2510597A1 (en) | COMPOSITION BASED ON FUEL AND LUBRICANT FOR TWO-STROKE ENGINE | |
FR2650289A1 (en) | Additive compound for fuels intended for internal combustion engines | |
EP3529341B1 (en) | Lubricant composition | |
EP1046699A1 (en) | Non-toxic, biodegradable functional fluids for motor vehicles | |
FR3124800A1 (en) | Aqueous lubricating composition for metal working | |
FR2632319A1 (en) | ALUMINUM OXIDE POWDER-CONTAINING LUBRICANT FOR LUBRICATING OIL BASES FOR LUBRICATING AND / OR SLIDING SURFACES AND PROCESS FOR PREPARING THE SAME | |
EP0882115A1 (en) | Synthetic lubricant composition and use thereof in internal combustion engines | |
EP0873385B1 (en) | Vegetable oil-based lubricants for internal combustion engines | |
FR2792325A1 (en) | Non-toxic and biodegradable fluids for multi-functional applications in automobiles are based on ethylene oxide/propylene oxide copolymers or esters of neopolyols | |
EP3277738A1 (en) | Star copolymer and use thereof as a viscosity improver | |
JP3804248B2 (en) | 2-cycle engine base oil | |
FR3127953A1 (en) | Spiro compound as a detergent additive in lubricants for engine systems | |
FR3124802A1 (en) | Aqueous lubricating composition for metal working |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: RENAULT S.A.S. |
|
AKX | Designation fees paid | ||
REG | Reference to a national code |
Ref country code: DE Ref legal event code: 8566 |
|
17P | Request for examination filed |
Effective date: 20021212 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
GRAJ | Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR1 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: C10M 169/04 20060101ALI20100127BHEP Ipc: C10M 125/20 20060101AFI20100127BHEP |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 60143467 Country of ref document: DE Date of ref document: 20101230 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Effective date: 20110224 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20101117 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20101221 Year of fee payment: 10 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101117 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101117 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101117 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101117 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110317 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101117 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
BERE | Be: lapsed |
Owner name: RENAULT S.A.S. Effective date: 20101231 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20110218 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101231 Ref country code: IE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101117 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101117 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101231 |
|
26N | No opposition filed |
Effective date: 20110818 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101231 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101231 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 60143467 Country of ref document: DE Effective date: 20110818 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20120105 Year of fee payment: 11 Ref country code: ES Payment date: 20111227 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20111222 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20111228 Year of fee payment: 11 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101207 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20101117 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20121207 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20130830 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60143467 Country of ref document: DE Effective date: 20130702 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130702 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130102 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20121207 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20121207 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20140307 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20121208 |