EP1356857B1 - Method for producing and applying of emulsifier free oil-in-water dispersions as a release agent or cooling lubricant - Google Patents
Method for producing and applying of emulsifier free oil-in-water dispersions as a release agent or cooling lubricant Download PDFInfo
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- EP1356857B1 EP1356857B1 EP02008174A EP02008174A EP1356857B1 EP 1356857 B1 EP1356857 B1 EP 1356857B1 EP 02008174 A EP02008174 A EP 02008174A EP 02008174 A EP02008174 A EP 02008174A EP 1356857 B1 EP1356857 B1 EP 1356857B1
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Classifications
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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
- C10M173/00—Lubricating compositions containing more than 10% water
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/40—Mixing liquids with liquids; Emulsifying
- B01F23/41—Emulsifying
- B01F23/4105—Methods of emulsifying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/40—Mixing liquids with liquids; Emulsifying
- B01F23/41—Emulsifying
- B01F23/411—Emulsifying using electrical or magnetic fields, heat or vibrations
- B01F23/4111—Emulsifying using electrical or magnetic fields, heat or vibrations using vibrations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B7/00—Moulds; Cores; Mandrels
- B28B7/38—Treating surfaces of moulds, cores, or mandrels to prevent sticking
- B28B7/384—Treating agents
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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
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
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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
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
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- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
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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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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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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- 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
- C10N2040/20—Metal working
- C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
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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
- C10N2040/36—Release agents or mold release agents
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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
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/01—Emulsions, colloids, or micelles
- C10N2050/011—Oil-in-water
Definitions
- the present invention relates to a process for the preparation and application of emulsifier-free, medium and low viscosity oil-in-water dispersions.
- Oil-in-water dispersions are used in many industrial areas, e.g. as release agents in the construction industry e.g. for demoulding of cast concrete, in the metal industry in die casting, in forging or in the pharmaceutical industry, in the manufacture of tablets and dragees, as a cutting fluid in metal cutting operations, i. when drilling, turning, milling or the like.
- Release agents and coolants are formulated predominantly in the form of oil-in-water emulsions
- dispersants are added to the dispersions, which reduce the interfacial tension between the individual phases, in order to avoid segregation of the phases over a relatively long period of time, and thus maintain microscopic microdissection of the dispersed phase (s) in the continuous phase over an extended period of time receive.
- the proportion of emulsifiers depends on the specific application and is up to 30 wt .-% in commercial concrete release agents and coolants.
- emulsifiers have application disadvantages, which can often only be partially compensated even by the addition of suitable auxiliaries.
- emulsifiers due to their high interfacial affinity and interfacial activity cause at least partial emulsification of the interface release agent / concrete body, whereby a part of the release agent penetrates into the concrete surface and leads to a correspondingly reduced surface quality of the concrete body after curing.
- a considerable development effort for the selection and testing of suitable auxiliaries is necessary.
- emulsifiers ensure a reliable and long enough stabilization only within a very narrow concentration and temperature range.
- Exceeding or undershooting the critical concentration limit values for example by evaporation or by incorporation of foreign substances as a result of improper storage such as dilution of the dispersion with condensation or rainwater, as well as corresponding temperature jumps, in particular those below the freezing point (freeze-thaw change), to an irreversible instability of the dispersion or emulsion. Unless the instability is recognized and the dispersion is used in this form, this inevitably leads to the loss of the processed products.
- the emulsifiers due to the high proportion in the dispersions and last but not least, because only selected, often specially synthesized for the application emulsifiers can be used for the respective applications, a significant cost factor.
- a mold release agent for concrete which as an oil component, optionally in addition to other substances, a water-immiscible and liquid at temperatures between 5 and 15 ° C monofunctional C6 to C30 alcohol component, preferably one unsaturated C12 to C22 fatty alcohol, C16 to C28 guebertic alcohol, C8 to C15 oxo alcohol or a saturated C6 to C10 alcohol.
- Emulsifiers used are preferably fatty acid monoglycerol esters or ethoxylates of fatty alcohols, of alkylphenols or of fatty acids, and particularly preferably sodium or potassium soaps of saturated and unsaturated C 12 to C 22 fatty acids.
- DE 199 11 777 A1 discloses a process for producing highly viscous cosmetic or pharmaceutical formulations in which two or more liquid components are mixed with one another directly from the use of the formulation from separate storage chambers by passing them through a micromixer.
- a micromixer By using the micromixer, a homogeneous distribution of all ingredients in extremely high-viscosity formulations with a viscosity of 67,000 mPa.s without the addition of emulsifiers should be achieved.
- this method also envisages adding compositions with a viscosity of less than 50,000 mPa.s depending on the viscosity of 2 to 50 wt .-% of emulsifiers, wherein, in accordance with the physical principle, after which the separation of immiscible phases with decreasing Viscosity is faster, with decreasing viscosity more emulsifier must be added.
- the object of the present invention is to provide a process by which medium to low viscosity oil-in-water dispersions can be prepared for use as release agents or coolants without the addition of emulsifiers, compared to known dispersions of the same type Have at least comparable, preferably better performance properties.
- emulsifier-free, medium-viscosity and low-viscosity oil-in-water dispersions can be obtained solely by correspondingly intensive mixing of the phases, which emulsions have the same composition as the dispersions previously known for the individual applications, except for the emulsifier have sufficient homogeneity and sufficient stability for the respective application.
- the stability duration of the semistable dispersion according to the invention depends essentially on the quality and the degree of energy input during the mixing and must be optimized for the respective application.
- the corresponding energy input parameters must be set during mixing so that the oil-in-water emulsion has a stability of ⁇ 10 seconds, corresponding to the time required for spreading and bleeding of the release agent in the mold.
- the dispersions are prepared immediately prior to use. This ensures that the dispersion has the greatest possible homogeneity in the application.
- emulsifier-free dispersions are obtained with the process according to the invention, it is usually possible to dispense with the addition of the previously known oil-in-water dispersions to compensate for the adjuvants which have been added with adverse effect on the application technology.
- Another advantage of the method according to the invention is that only the organic phase has to be stored before use, since water is usually available at the point of use from water pipes. Further, since the water and oil phases are brought together immediately before use in defined volume ratios, exceeding or falling below the critical concentration limits due to improper storage, for example by ingestion of foreign substances or uneven evaporation of individual phases, no longer occur.
- the inventive method to the hitherto in oil-in-water dispersions to prevent the growth of Microorganisms mandatory addition of biocides or other preservatives can be largely or even completely dispensed with, because only one possibly stored before use aqueous phase or an aqueous concentrate which is diluted with tap water immediately prior to preparation, but not organic phase, in the an increase of microorganisms does not take place anyway, are treated accordingly.
- the method according to the invention makes it possible to flexibly adapt the ratio of the oil and water phase to the specific conditions on site immediately before use, whereas in the previously known dispersions the corresponding ratio is inevitably predetermined by the emulsion.
- the mixing of the at least two phases can be carried out in any manner known to the person skilled in the art for this purpose, for example by injecting a phase into the at least other phase, by turbulent mixing, by application of vibrations and cavitation, such as ultrasound, by means of homogenizers or others commercially available mixing devices.
- static micromixers e.g. in DE 199 28 123 A1, which is hereby introduced as a reference and thus applies as part of the disclosure.
- these static micromixers allow a very high energy input during mixing, whereby semi-stable oil-in-water emulsions of comparatively long stability can be obtained.
- these mixers ensure a uniform energy input, which leads to a high reproducibility with regard to the homogeneity, the particle size distribution and the stability of the dispersions thus prepared.
- the size distribution of the emulsified phase forming droplets can be adjusted by the flow rate of the individual phases targeted to a suitable value for the specific application.
- the mixing of the at least two phases by membrane emulsification has been particularly suitable for the production of oil-in-solution. Water emulsions proved to be practicable.
- the at least one phase to be dispersed through a microporous membrane, for example.
- the droplet size of the dispersed phase and the droplet size distribution depend in particular on the pretreatment of the membrane and the pressure with which the phase to be dispersed is forced through the membrane, whereby even droplets with a smaller diameter than the membrane pores can be formed.
- the addition of emulsifiers, as previously provided, is dispensed with.
- micromixers are particularly suitable for the mixing of the at least two phases.
- the fragmentation of the at least one phase during the merging of the liquid lamellae is additionally assisted by mechanical vibrations.
- the size distribution of the droplets forming the emulsified phase can be adjusted to a value suitable for the particular application by the flow rate of the individual phases, the frequency and intensity of the mechanical vibrations.
- Such a cycle process is particularly suitable for cooling and lubrication in metal cutting machining, in which the oil-in-water emulsion comes into contact with the product to be processed only for a short time and the impurities caused by the application in the form of chips very easy to separate can be. Any liquid losses of the individual phases occurring during the cooling lubrication can then be easily compensated before mixing by appropriate metering. Biocides or other preservatives need only be added to the aqueous phase since the growth of microorganisms in the organic phase is in any case inhibited. In case of disposal, only the organic Phase to treat as hazardous chemical waste, since the most weakly organically contaminated water phase can be eliminated in conventional treatment plants. Thus, significant cost savings can be achieved in comparison to the previously used stable emulsions.
- Such a continuous process can also be used, for example, for release agents, in particular in the pharmaceutical sector in the production of tablets and dragees.
- a continuous process is not limited to medium and low viscosity oil-in-water dispersions, but is feasible with any type of dispersant-free dispersions. Further examples are the production of cakes, candies, pralines or gummi bears.
- the oil-in-water dispersions prepared according to the invention can have the same composition with regard to the contents and the proportions of the ingredients as the hitherto known stable oil-in-water dispersions of the same type.
- the additives added in many known oil-in-water dispersions to compensate for the negative performance effects of the dispersants can be dispensed with.
- an addition of biocides or preservatives is only required if the aqueous phase or a corresponding concentrate is stored for a long period of time before the preparation of the semi-stable dispersion or if the semi-stable dispersion is to be used repeatedly over a longer period of time.
- the release agents prepared according to the invention may contain as oil phase, for example, mineral oils, white oils, waxes, triglycerides, esters of aliphatic carboxylic acids and monohydric or polyhydric alcohols, alcohols or ethers or a mixture of two or more substances from one or more of the abovementioned groups.
- the ratio of the aqueous phase to the organic phase is preferably between 20: 1 and 1: 1.
- the release agents according to the invention contain as oil phase a mixture of 90 to 98 wt .-% of a base oil, 0 to 10 wt .-% of a release component, 0.2 to 1 wt .-% of a corrosion protection additive and 0.2 to 5 Wt .-% of a wetting agent.
- Suitable base oils are, in particular, hydrocarbons, triglyceride mixtures, esters, very particularly preferably esters of a carboxylic acid having more than 16 carbon atoms and an alcohol component having more than 8 carbon atoms, fatty alcohols and a mixture of two or more substances from one or more of the abovementioned groups.
- Separating components are mixtures of fatty and resin acids, triglyceride mixtures, esters and polyolo-alcohol derivatives and mixtures thereof.
- anticorrosive additive are merely, for example, succinic acid esters, amine phosphates, sulfonate / carboxylate mixtures, imidazole derivatives, N-oleylsarcosine and phosphoric acid esters mentioned, which can be used both alone and in combination with each other.
- Suitable wetting agents are fatty acid polyethylene glycol esters, Na diisooctyl sulfosuccinate, sorbitan trioleate, glycerol monooleate, glycerol dioleate, alcohol derivatives, ester derivatives and silicone additives, which may be used both alone and in combination.
- Cooling lubricants according to the present invention may e.g. as the organic phase, a mixture of 5 to 80 wt .-% base oil, 5 to 20 wt .-% corrosion inhibiting additives and metal inhibitors, optionally preservatives and other conventional additives.
- Suitable base oils are ester oils, paraffinic or naphthenic hydrocarbons, alcohols, ethers, polyisobutenes, polyalkylene glycols and mixtures of two or more substances from one or more of the groups listed above.
- Suitable corrosion protection additives are, in particular, phosphoric esters, triazoles, thiadiazoles, reaction products of boric acid with primary or tertiary alkanolamines, fatty acids, fatty acid alkanolamines or mixtures of two or more substances from one or more of the groups listed above.
- oil phase alkyl succinimides, Castoroilethoxylate, petroleum sulfonates, solid lubricants, Toluyltriazole, defoamers and / or Antinebelzu accounts as other common additives.
- the proportion of the oil phase in the novel cooling lubricant can be between 2 and 25% by weight.
- an oil phase was first prepared from the following components: 90% by weight spindle oil 5% by weight rapeseed oil 3% by weight oleic acid 0.5% by weight BernsteinTexreester 0.5% by weight FettTexrepolyethylenglykolester Subsequently, the oil phase was mixed with water via a static micromixer, as described in Example 1 of DE 199 28 123 A1, to form an oil-in-water emulsion with an oil content of 5.5% by weight.
- an oil phase was first prepared from the following components: 98% by weight rapeseed oil 1% by weight AdditinRC 4820 (commercial product) 1% by weight Isooctylsulfosuccinat Subsequently, the oil phase was mixed as described in Example 1 with water to an oil-in-water emulsion with an oil content of 13.3 wt .-%.
- an oil phase was first prepared from the following components: 91.2% by weight Isooctyloleat 5% by weight oleic acid 0.8% by weight Additin RC 4220 (commercial product 9 3% by weight glycerol oleate
- Example 1 the oil phase was mixed with water as described in Example 1 to one to an oil-in-water emulsion with an oil content of 24.4 wt .-%.
- the viscosity of the oil phase, the viscosity of the emulsion and the average diameter of the oil droplets are shown in Table 1.
- example 1 2 3 Viscosity (20 ° C) oil phase (mm 2 / s) 17.1 15.0 39.7 Viscosity (20 ° C) emulsion (mm 2 / s) 7.1 3.1 2.4 Particle Size Distribution / Volume Distribution Mean Diameter ( ⁇ m) 6.67 7.62 6.74
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Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung und Aufbringung von emulgatorfreien, mittel- und niedrigviskoser Öl-in-Wasser-Dispersionen.The present invention relates to a process for the preparation and application of emulsifier-free, medium and low viscosity oil-in-water dispersions.
Mittel- und niedrigviskose Öl-in-Wasser-Dispersionen finden in vielen industriellen Bereichen Anwendung, z.B. als Trennmittel in der Bauindustrie z.B. zum Entschalen von gegossenem Beton, in der Metallindustrie beim Druckgussverfahren, beim Schmieden oder der pharmazeutischen Industrie, bei der Herstellung von Tabletten und Dragees, als Kühlschmierstoff bei der spanenden Metallbearbeitung, d.h. beim Bohren, Drehen, Fräsen oder dergleichen. Trennmittel und Kühlschmierstoffe sind vorwiegend in Form von Öl-in-Wasser-Emulsionen formuliertMedium and low viscosity oil-in-water dispersions are used in many industrial areas, e.g. as release agents in the construction industry e.g. for demoulding of cast concrete, in the metal industry in die casting, in forging or in the pharmaceutical industry, in the manufacture of tablets and dragees, as a cutting fluid in metal cutting operations, i. when drilling, turning, milling or the like. Release agents and coolants are formulated predominantly in the form of oil-in-water emulsions
Zur Stabilisierung werden den Dispersionen Dispergiermittel zugesetzt, welche die Grenzflächenspannung zwischen den einzelnen Phasen herabsetzen, um eine Entmischung der Phasen über einen längeren Zeitraum zu vermeiden und so eine mikroskopische Feinstverteilung der dispergierten Phase(n) in der kontinuierlichen Phase auch über einen längeren Zeitraum aufrecht zu erhalten. Der Anteil an Emulgatoren hängt von der speziellen Anwendung ab und beträgt in handelsüblichen Betontrennmitteln und Kühlschmierstoffen bis zu 30 Gew.-%.For stabilization, dispersants are added to the dispersions, which reduce the interfacial tension between the individual phases, in order to avoid segregation of the phases over a relatively long period of time, and thus maintain microscopic microdissection of the dispersed phase (s) in the continuous phase over an extended period of time receive. The proportion of emulsifiers depends on the specific application and is up to 30 wt .-% in commercial concrete release agents and coolants.
Die bisher für erforderlich gehaltenen Emulgatoren weisen anwendungstechnische Nachteile auf, welche selbst durch den Zusatz geeigneter Hilfsstoffe oftmals lediglich teilweise kompensiert werden können. Bei der Anwendung von Betontrennmitteln bspw. können Emulgatoren aufgrund deren hohen Grenzflächenaffinität und Grenzflächenaktivität eine zumindest partielle Emulgierung der Grenzfläche Trennmittel/Betonkörper bewirken, wodurch ein Teil des Trennmittels in die Betonoberfläche eindringt und nach Aushärtung zu einer entsprechend verminderten Oberflächenqualität des Betonkörpers führt. Um diese anwendungstechnischen Nachteile zumindest teilweise zu kompensieren ist ein erheblicher Entwicklungsaufwand für die Auswahl und Testung geeigneter Hilfsstoffe notwendig.The previously considered necessary emulsifiers have application disadvantages, which can often only be partially compensated even by the addition of suitable auxiliaries. In the application of concrete release agents, for example, emulsifiers due to their high interfacial affinity and interfacial activity cause at least partial emulsification of the interface release agent / concrete body, whereby a part of the release agent penetrates into the concrete surface and leads to a correspondingly reduced surface quality of the concrete body after curing. To compensate for these application disadvantages at least partially, a considerable development effort for the selection and testing of suitable auxiliaries is necessary.
Ein weiterer Nachteil der Emulgatoren besteht darin, dass diese eine zuverlässige und ausreichend lange Stabilisierung nur innerhalb eines sehr engen Konzentrations- und Temperaturbereichs gewährleisten. Ein Über- oder Unterschreiten der kritischen Konzentrationsgrenzwerte bspw. durch Verdunsten oder durch Aufnahme von Fremdsubstanzen infolge unsachgemässer Lagerung wie etwa Verdünnung der Dispersion mit Kondens- oder Regenwasser, führt ebenso wie entsprechende Temperatursprünge, insbesondere solche unterhalb des Gefrierpunkts (Frost-Tau-Wechsel), zu einer irreversiblen Instabilisierung der Dispersion bzw. Emulsion. Sofern die Instabilität nicht erkannt und die Dispersion in dieser Form verwendet wird, führt dies zwangsläufig zum Verlust der damit bearbeiteten Produkte.Another disadvantage of the emulsifiers is that they ensure a reliable and long enough stabilization only within a very narrow concentration and temperature range. Exceeding or undershooting the critical concentration limit values, for example by evaporation or by incorporation of foreign substances as a result of improper storage such as dilution of the dispersion with condensation or rainwater, as well as corresponding temperature jumps, in particular those below the freezing point (freeze-thaw change), to an irreversible instability of the dispersion or emulsion. Unless the instability is recognized and the dispersion is used in this form, this inevitably leads to the loss of the processed products.
Ferner stellen die Emulgatoren aufgrund des hohen Mengenanteils in den Dispersionen und nicht zuletzt auch deshalb, weil für die jeweiligen Anwendungen nur ausgewählte, häufig speziell für die Anwendung synthetisierte Emulgatoren eingesetzt werden können, einen erheblichen Kostenfaktor dar.Furthermore, the emulsifiers due to the high proportion in the dispersions and last but not least, because only selected, often specially synthesized for the application emulsifiers can be used for the respective applications, a significant cost factor.
Es hat daher in der Vergangenheit nicht an Versuchen gefehlt, den Anteil an Emulgatoren in Dispersionen bzw. Emulsionen zu reduzieren.There has therefore been no lack of attempts in the past to reduce the proportion of emulsifiers in dispersions or emulsions.
Aus der DE 44 00 272 A1 ist ein Formtrennmittel für Beton bekannt, welches als Ölkomponente, ggf. neben anderen Substanzen, eine mit Wasser nicht mischbare und bei Temperaturen zwischen 5 und 15°C flüssige, monofunktionelle C6- bis C30-Alkoholkomponente, vorzugsweise einen ungesättigten C12- bis C22- Fettalkohol, C16- bis C28- Guebertalkohol, C8- bis C15- Oxo-Alkohol oder einen gesättigten C6- bis C10-Alkohol, enthält. Als Emulgatoren werden vorzugsweise Fettsäuremonoglycerinester oder Ethoxylate von Fettalkoholen, von Alkylphenolen oder von Fettsäuren, und besonders bevorzugt Natrium- oder Kaliumseifen von gesättigten und ungesättigten C12-bis C22-Fettsäuren, eingesetzt. Aufgrund der stark emulgierenden Wirkung dieser Alkohole sollen schon durch den Zusatz vergleichsweise geringer Emulgatormengen stabile Emulsionen erhalten werden. Allerdings weisen auch diese Betontrennmittel wegen der Verwendung von Emulgatoren die oben beschriebenen Nachteile auf.From DE 44 00 272 A1 discloses a mold release agent for concrete is known which as an oil component, optionally in addition to other substances, a water-immiscible and liquid at temperatures between 5 and 15 ° C monofunctional C6 to C30 alcohol component, preferably one unsaturated C12 to C22 fatty alcohol, C16 to C28 guebertic alcohol, C8 to C15 oxo alcohol or a saturated C6 to C10 alcohol. Emulsifiers used are preferably fatty acid monoglycerol esters or ethoxylates of fatty alcohols, of alkylphenols or of fatty acids, and particularly preferably sodium or potassium soaps of saturated and unsaturated C 12 to C 22 fatty acids. Due to the strong emulsifying effect of these alcohols stable emulsions should be obtained even by the addition of comparatively small amounts of emulsifier. However, these concrete release agents also have the disadvantages described above because of the use of emulsifiers.
In der DE 199 11 777 A1 ist ein Verfahren zum Herstellen von hochviskosen kosmetischen oder pharmazeutischen Formulierungen offenbart, bei dem zwei oder mehrere flüssige Komponenten unmittelbar vor der Verwendung der Formulierung aus getrennten Vorratskammern miteinander vermischt werden, indem sie durch einen Mikromischer geführt werden. Durch die Verwendung des Mikromischers soll eine homogene Verteilung aller Inhaltsstoffe bei extrem hochviskosen Formulierungen mit einer Viskosität von 67.000 mPa.s ohne Zusatz von Emulgatoren erreicht werden können. Allerdings sieht auch dieses Verfahren vor, Zusammensetzungen mit einer Viskosität von weniger als 50.000 mPa.s in Abhängigkeit von der Viskosität 2 bis 50 Gew.-% an Emulgatoren zuzusetzen, wobei, im Einklang mit dem physikalischen Prinzip, wonach die Entmischung nichtmischbarer Phasen mit abnehmender Viskosität schneller vonstatten geht, mit abnehmender Viskosität mehr Emulgator zugesetzt werden muss.DE 199 11 777 A1 discloses a process for producing highly viscous cosmetic or pharmaceutical formulations in which two or more liquid components are mixed with one another directly from the use of the formulation from separate storage chambers by passing them through a micromixer. By using the micromixer, a homogeneous distribution of all ingredients in extremely high-viscosity formulations with a viscosity of 67,000 mPa.s without the addition of emulsifiers should be achieved. However, this method also envisages adding compositions with a viscosity of less than 50,000 mPa.s depending on the viscosity of 2 to 50 wt .-% of emulsifiers, wherein, in accordance with the physical principle, after which the separation of immiscible phases with decreasing Viscosity is faster, with decreasing viscosity more emulsifier must be added.
Aufgabe der vorliegenden Erfindung ist es, ein Verfahren zur Verfügung zu stellen, mit dem Öl-in-Wasser-Dispersionen mittlerer bis niedriger Viskosität zur Verwendung als Trennmittel oder Kühlschmierstoffe ohne Zusatz an Emulgatoren hergestellt werden können, welche, verglichen mit den bekannten Dispersionen gleichen Typs, zumindest vergleichbare, vorzugsweise bessere anwendungstechnische Eigenschaften aufweisen.The object of the present invention is to provide a process by which medium to low viscosity oil-in-water dispersions can be prepared for use as release agents or coolants without the addition of emulsifiers, compared to known dispersions of the same type Have at least comparable, preferably better performance properties.
Diese Aufgabe wird erfindungsgemäß durch das Verfahren gemäß Patentanspruch 1 gelöst.This object is achieved by the method according to claim 1.
Überraschenderweise wurde gefunden, dass allein durch eine entsprechend intensive Vermischung der Phasen emulgatorfreie mittel- und niedrigviskose Öl-in-Wasser-Dispersionen erhalten werden können, welche selbst bei - abgesehen von dem Emulgator - gleicher Zusammensetzung wie die bisher für die einzelnen Anwendungen bekannten Dispersionen eine für die jeweilige Anwendung ausreichende Homogenität und zudem hinreichende Stabilität aufweisen. Die Stabilitätsdauer der erfindungsgemässen semistabilen Dispersion hängt im Wesentlichen von der Qualität und dem Grad des Energieeintrags bei der Durchmischung ab und muss für die jeweilige Anwendung optimiert werden. Sowohl für Kühlschmierstoffe bei der spanenden Bearbeitung als auch für die Herstellung von Betontrennmitteln müssen die entsprechenden Energieeintragparameter bei der Durchmischung so eingestellt werden, dass die Öl-in-Wasser-Emulsion eine Stabilität von < 10 Sekunden, entsprechend der benötigten Zeitspanne für das Verteilen und Verlaufen des Trennmittels in der Form, aufweist.Surprisingly, it has been found that emulsifier-free, medium-viscosity and low-viscosity oil-in-water dispersions can be obtained solely by correspondingly intensive mixing of the phases, which emulsions have the same composition as the dispersions previously known for the individual applications, except for the emulsifier have sufficient homogeneity and sufficient stability for the respective application. The stability duration of the semistable dispersion according to the invention depends essentially on the quality and the degree of energy input during the mixing and must be optimized for the respective application. For both cutting fluids used in machining and for the production of concrete release agents, the corresponding energy input parameters must be set during mixing so that the oil-in-water emulsion has a stability of <10 seconds, corresponding to the time required for spreading and bleeding of the release agent in the mold.
Vorzugsweise werden die Dispersionen unmittelbar vor der Verwendung hergestellt. So wird gewährleistet, dass die Dispersion bei der Anwendung die größtmögliche Homogenität aufweist.Preferably, the dispersions are prepared immediately prior to use. This ensures that the dispersion has the greatest possible homogeneity in the application.
Da mit dem erfindungsgemäßen Verfahren emulgatorfreie Dispersionen erhalten werden, kann auf den Zusatz der den bisher bekannten Öl-in-Wasser-Dispersionen üblicherweise zur Kompensation der anwendungstechnisch nachteiligen Nebeneffekte der Emulgatoren zugefügten Hilfsstoffe verzichtet werden. Ein weiterer Vorteil des erfindungsgemäßen Verfahrens liegt darin, dass nur noch die organische Phase vor der Anwendung gelagert werden muss, da in der Regel am Verwendungsort Wasser aus Wasserleitungen zur Verfügung steht. Da ferner die Wasser- und Ölphasen unmittelbar vor der Verwendung in definierten Volumenverhältnissen zusammengeführt werden, kann ein Über- oder Unterschreiten der kritischen Konzentrationsgrenzwerte infolge unsachgemässer Lagerung, bspw. durch Aufnahme von Fremdsubstanzen oder durch ungleichmässige Verdunstung einzelner Phasen, nicht mehr auftreten. Ferner kann bei dem erfindungsgemäßen Verfahren auf den bisher bei Öl-in-Wasser-Dispersionen zur Vermeidung des Wachstums von Mikroorganismen zwingend erforderlichen Zusatz von Bioziden oder sonstigen Konservierungsstoffen größtenteils oder sogar ganz verzichtet werden kann, weil nur noch eine etwaig vor der Anwendung gelagerte wässrige Phase oder ein wässriges Konzentrat, welches unmittelbar vor der Herstellung mit Leitungswasser verdünnt wird, nicht jedoch organische Phase, in der eine Vermehrung von Mikroorganismen ohnehin nicht stattfindet, entsprechend zu behandeln sind. Schließlich erlaubt das erfindungsgemäße Verfahren, das Verhältnis der Öl- und Wasserphase unmittelbar vor der Verwendung den speziellen Gegebenheiten vor Ort flexibel anzupassen, wohingegen bei den bisher bekannten Dispersionen das entsprechende Verhältnis durch die Emulsion zwangsläufig vorgegeben ist.Since emulsifier-free dispersions are obtained with the process according to the invention, it is usually possible to dispense with the addition of the previously known oil-in-water dispersions to compensate for the adjuvants which have been added with adverse effect on the application technology. Another advantage of the method according to the invention is that only the organic phase has to be stored before use, since water is usually available at the point of use from water pipes. Further, since the water and oil phases are brought together immediately before use in defined volume ratios, exceeding or falling below the critical concentration limits due to improper storage, for example by ingestion of foreign substances or uneven evaporation of individual phases, no longer occur. Furthermore, in the inventive method to the hitherto in oil-in-water dispersions to prevent the growth of Microorganisms mandatory addition of biocides or other preservatives can be largely or even completely dispensed with, because only one possibly stored before use aqueous phase or an aqueous concentrate which is diluted with tap water immediately prior to preparation, but not organic phase, in the an increase of microorganisms does not take place anyway, are treated accordingly. Finally, the method according to the invention makes it possible to flexibly adapt the ratio of the oil and water phase to the specific conditions on site immediately before use, whereas in the previously known dispersions the corresponding ratio is inevitably predetermined by the emulsion.
Die Durchmischung der wenigstens zwei Phasen kann auf jede dem Fachmann zu diesem Zweck bekannte Weise durchgeführt werden, bspw. durch Einspritzen einer Phase in die wenigstens andere Phase, durch turbulentes Mischen, durch Anwendung von Schwingungen und Kavitation, wie etwa Ultraschall, mittels Homogenisatoren oder anderer handelsüblicher Mischeinrichtungen.The mixing of the at least two phases can be carried out in any manner known to the person skilled in the art for this purpose, for example by injecting a phase into the at least other phase, by turbulent mixing, by application of vibrations and cavitation, such as ultrasound, by means of homogenizers or others commercially available mixing devices.
Als besonders geeignet für diesen Zweck, insbesondere zur Herstellung von Öl-in-Wasser-Emulsionen, haben sich statische Mikromischer erwiesen, wie sie z.B. in der DE 199 28 123 A1 beschrieben sind, die hiermit als Referenz eingeführt wird und somit als Teil der Offenbarung gilt. Bei diesen statischen Mikromischern werden die einzelnen Phasen durch einzelne Führungskanäle definierter Ausmaße geführt und in eine Vielzahl von Flüssigkeitslamellen aufgeteilt, bevor die einzelnen Flüssigkeitslamellen unter Fragmentation wenigstens einer der Phasen zusammengeführt werden. Diese statischen Mikromischer ermöglichen einen sehr hohen Energieeintrag während der Vermischung, wodurch semistabile Öl-in-Wasser-Emulsionen vergleichsweise langer Stabilität erhalten werden können. Zum anderen gewährleisten diese Mischer einen gleichmäßigen Energieeintrag, was zu einer hohen Reproduzierbarkeit hinsichtlich der Homogenität, der Teilchengrössenverteilung und der Stabilität der so hergestellten Dispersionen führt. Die Größenverteilung der die emulgierte Phase bildenden Tröpfchen kann durch die Strömungsgeschwindigkeit der einzelnen Phasen gezielt auf einen für die spezielle Anwendung geeigneten Wert eingestellt werden.Particularly suitable for this purpose, especially for the preparation of oil-in-water emulsions, have been found to be static micromixers, e.g. in DE 199 28 123 A1, which is hereby introduced as a reference and thus applies as part of the disclosure. In these static micromixers, the individual phases are guided through individual guide channels of defined dimensions and subdivided into a multiplicity of liquid lamellae before the individual lamellae are brought together under fragmentation of at least one of the phases. These static micromixers allow a very high energy input during mixing, whereby semi-stable oil-in-water emulsions of comparatively long stability can be obtained. On the other hand, these mixers ensure a uniform energy input, which leads to a high reproducibility with regard to the homogeneity, the particle size distribution and the stability of the dispersions thus prepared. The size distribution of the emulsified phase forming droplets can be adjusted by the flow rate of the individual phases targeted to a suitable value for the specific application.
Auch die Durchmischung der wenigstens zwei Phasen durch Membranemulgierung, wie sie bspw. von Vladisavljevic, Goran T.; Tesch, Sabine und Schubert, Helmar in Chemical Engineering and Processing 2002, 41 (3), S. 231-238 beschrieben wurde, die hiermit als Referenz eingeführt und somit als Teil der Offenbarung gilt, hat sich insbesondere zur Herstellung von Öl-in-Wasser-Emulsionen als praktikabel erwiesen. Bei der Membranemulgierung wird die wenigstens eine zu dispergierende Phase durch eine mikroporöse Membran, bspw. eine Polypropylenmembran mit einer Porengrösse von 0,4 mu m, in die kontinuierliche Phase gepresst. Die Tröpfchengröße der dispergierten Phase sowie die Tröpfchengrößenverteilung hängt insbesondere von der Vorbehandlung der Membran und dem Druck, mit welchem die zu dispergierende Phase durch die Membran gepresst wird, ab, wobei sogar Tröpfchen mit einem geringeren Durchmesser als dem der Membranporen gebildet werden können. Erfindungsgemäß wird hierbei auf die Zugabe von Emulgatoren, wie sie bisher vorgesehen war, verzichtet.Also, the mixing of the at least two phases by membrane emulsification, such as, for example, by Vladisavljevic, Goran T .; Tesch, Sabine and Schubert, Helmar in Chemical Engineering and Processing 2002, 41 (3), pp. 231-238, which is hereby incorporated by reference and thus part of the disclosure, has been particularly suitable for the production of oil-in-solution. Water emulsions proved to be practicable. In the Membrane emulsification, the at least one phase to be dispersed through a microporous membrane, for example. A polypropylene membrane with a pore size of 0.4 .mu.m, pressed into the continuous phase. The droplet size of the dispersed phase and the droplet size distribution depend in particular on the pretreatment of the membrane and the pressure with which the phase to be dispersed is forced through the membrane, whereby even droplets with a smaller diameter than the membrane pores can be formed. According to the invention, the addition of emulsifiers, as previously provided, is dispensed with.
Ebenfalls als besonders geeignet für die Durchmischung der wenigstens zwei Phasen haben sich dynamische Mikromischer erwiesen, wie sie z.B. in der DE 199 17 148 A1 beschrieben sind, die hiermit als Referenz eingeführt wird und somit als Teil der Offenbarung gilt. Bei diesen Mikromischern wird die Fragmentation der wenigstens einen Phase beim Zusammenführen der Flüssigkeitslamellen zusätzlich durch mechanische Schwingungen unterstützt. Mit derartigen Mikromischern kann die Größenverteilung der die emulgierte Phase bildenden Tröpfchen durch die Strömungsgeschwindigkeit der einzelnen Phasen, die Frequenz sowie Intensität der mechanischen Schwingungen gezielt auf einen für die spezielle Anwendung geeigneten Wert eingestellt werden.Also particularly suitable for the mixing of the at least two phases have been found to be dynamic micromixers, as e.g. in DE 199 17 148 A1, which is hereby introduced as a reference and thus applies as part of the disclosure. In these micromixers, the fragmentation of the at least one phase during the merging of the liquid lamellae is additionally assisted by mechanical vibrations. With such micromixers, the size distribution of the droplets forming the emulsified phase can be adjusted to a value suitable for the particular application by the flow rate of the individual phases, the frequency and intensity of the mechanical vibrations.
In Weiterbildung des Erfindungsgedankens wird vorgeschlagen, das erfindungsgemässe Verfahren in Form eines Kreislaufprozesses durchzuführen. Zunächst werden wie zuvor beschrieben, semistabile Öl-in-Wasser-Dispersionen hergestellt und der Verwendung zugeführt. Anschließend werden die Dispersionen aufgefangen und zwecks Separation der einzelnen Phasen bspw. in einem Scheidetrichter inkubiert, bevor die wenigstens zwei Phasen ggf. nach Abtrennung von aus der Anwendung resultierenden Verunreinigungen sowie ggf. nach Ausgleich etwaiger Flüssigkeitsverluste mittels Dosierpumpen erneut der Mischvorrichtung zugeführt werden, in der die Phasen miteinander zu semistabilen Dispersionen vermischt werden.In a further development of the inventive concept, it is proposed to carry out the method according to the invention in the form of a circulation process. First, as previously described, semi-stable oil-in-water dispersions are prepared and supplied for use. Subsequently, the dispersions are collected and incubated in a separating funnel for the purpose of separating the individual phases before the at least two phases are again fed to the mixing device after separation of impurities resulting from the application and, if necessary, to compensate for any liquid losses by means of metering pumps the phases are mixed together to semistable dispersions.
Ein solcher Kreislaufprozess eignet sich insbesondere für die Kühlung und Schmierung bei der spanenden Metallbearbeitung, bei der die Öl-in-Wasser-Emulsion nur kurzzeitig mit dem zu bearbeitenden Produkt in Berührung kommt und die durch die Anwendung verursachten Verunreinigungen in Form von Spänen besonders einfach abgetrennt werden können. Etwaig bei der Kühlschmierung auftretende Flüssigkeitsverluste der einzelnen Phasen können dann vor der Vermischung durch entsprechende Zudosierung einfach ausgeglichen werden. Biozide oder sonstige Konservierungsstoffe müssen nur der wässrigen Phase zugefügt werden, da das Wachstum von Mikroorganismen in der organischen Phase ohnehin gehemmt ist. Im Falle einer Entsorgung ist nur die organische Phase als chemischer Sondermüll zu behandeln, da die allenfalls schwach organisch belastete Wasserphase in herkömmlichen Kläranlagen beseitigt werden kann. So können im Vergleich zu den bisher verwendeten stabilen Emulsionen erhebliche Kosteneinsparungen erzielt werden.Such a cycle process is particularly suitable for cooling and lubrication in metal cutting machining, in which the oil-in-water emulsion comes into contact with the product to be processed only for a short time and the impurities caused by the application in the form of chips very easy to separate can be. Any liquid losses of the individual phases occurring during the cooling lubrication can then be easily compensated before mixing by appropriate metering. Biocides or other preservatives need only be added to the aqueous phase since the growth of microorganisms in the organic phase is in any case inhibited. In case of disposal, only the organic Phase to treat as hazardous chemical waste, since the most weakly organically contaminated water phase can be eliminated in conventional treatment plants. Thus, significant cost savings can be achieved in comparison to the previously used stable emulsions.
Ein solches kontinuierliches Verfahren lässt sich bspw. auch für Trennmittel, insbesondere im pharmazeutischen Bereich bei der Herstellung von Tabletten und Dragees, anwenden. Der Fachmann erkennt sofort, dass ein solches kontinuierliches Verfahren nicht auf Öl-in-Wasser-Dispersionen mittlerer und niedriger Viskosität beschränkt ist, sondern mit jeder Art von dispergiermittelfreier Dispersionen durchführbar ist. Weitere Beispiele sind die Herstellung von Kuchen, Bonbons, Pralinen oder Gummibären.Such a continuous process can also be used, for example, for release agents, in particular in the pharmaceutical sector in the production of tablets and dragees. One skilled in the art will readily recognize that such a continuous process is not limited to medium and low viscosity oil-in-water dispersions, but is feasible with any type of dispersant-free dispersions. Further examples are the production of cakes, candies, pralines or gummi bears.
Abgesehen von den Dispergiermitteln können die erfindungsgemäß hergestellten Öl-in-Wasser-Dispersionen hinsichtlich der Inhaltsstoffe und der Mengenanteile der Inhaltsstoffe dieselbe Zusammensetzung aufweisen wie die bisher bekannten stabilen Öl-in-Wasser-Dispersionen gleichen Typs. Allerdings kann auf die in vielen bekannten Öl-in-Wasser-Dispersionen zur Kompensation der negativen anwendungstechnischen Effekte der Dispergiermittel zugesetzten Hilfsstoffe verzichtet werden. Des weiteren ist ein Zusatz an Bioziden oder Konservierungsstoffen nur dann erforderlich, wenn die wässrige Phase oder ein entsprechendes Konzentrat vor der Herstellung der semistabilen Dispersion über einen längeren Zeitraum gelagert wird oder sofern die semistabile Dispersion über einen längeren Zeitraum mehrfach verwendet werden soll.Apart from the dispersants, the oil-in-water dispersions prepared according to the invention can have the same composition with regard to the contents and the proportions of the ingredients as the hitherto known stable oil-in-water dispersions of the same type. However, the additives added in many known oil-in-water dispersions to compensate for the negative performance effects of the dispersants can be dispensed with. Furthermore, an addition of biocides or preservatives is only required if the aqueous phase or a corresponding concentrate is stored for a long period of time before the preparation of the semi-stable dispersion or if the semi-stable dispersion is to be used repeatedly over a longer period of time.
Die erfindungsgemäß hergestellten Trennmittel können als Ölphase bspw. Mineralöle, Weissöle, Wachse, Triglyceride, Ester aus aliphatischen Carbonsäuren und ein- oder mehrwertigen Alkoholen, Alkohole oder Ether oder eine Mischung aus zwei oder mehreren Substanzen aus einer oder mehreren der zuvor genannten Gruppen enthalten. Das Verhältnis der wässrigen zu der organischen Phase beträgt vorzugsweise zwischen 20:1 und 1:1.The release agents prepared according to the invention may contain as oil phase, for example, mineral oils, white oils, waxes, triglycerides, esters of aliphatic carboxylic acids and monohydric or polyhydric alcohols, alcohols or ethers or a mixture of two or more substances from one or more of the abovementioned groups. The ratio of the aqueous phase to the organic phase is preferably between 20: 1 and 1: 1.
Besonders bevorzugt enthalten die erfindungsgemäß hergestellten Trennmittel als Ölphase eine Mischung aus 90 bis 98 Gew.-% eines Grundöls, 0 bis 10 Gew.-% einer trennwirksamen Komponente, 0,2 bis 1 Gew.-% eines Korrosionsschutzadditivs sowie 0,2 bis 5 Gew.-% eines Netzmittels. Als Grundöl eignen sich insbesondere Kohlenwasserstoffe, Triglyceridgemische, Ester, ganz besonders bevorzugt Ester aus einer Carbonsäure mit mehr als 16 Kohlenstoffatomen und einer Alkoholkomponente mit mehr als 8 Kohlenstoffatomen, Fettalkohole sowie eine Mischung aus zwei oder mehreren Substanzen aus einer oder mehreren der zuvor genannten Gruppen. Beispiele für trennwirksame Komponenten sind Mischungen aus Fett und Harzsäuren, Triglyceridgemische, Ester und Polyolakoholderivate sowie deren Mischungen. Als Korrosionsschutzadditiv seien lediglich bspw. Bernsteinsäureester, Aminphosphate, Sulfonat/Carboxylat-Mischungen, Imidazol-Derivate, N-Oleylsarkosin sowie Phosporsäureester genannt, die sowohl alleine als auch in Kombination miteinander eingesetzt werden können. Geeignete Netzmittel sind Fettsäurepolyethylenglycolester, Na-Diisooctylsulfosuccinat, Sorbitantrioleat, Glycerinmonooleat, Glycerindioleat, Alkoholderivate, Esterderivate und Silikonadditive, welche sowohl alleine als auch in Kombination miteinander eingesetzt werden können.Particularly preferably, the release agents according to the invention contain as oil phase a mixture of 90 to 98 wt .-% of a base oil, 0 to 10 wt .-% of a release component, 0.2 to 1 wt .-% of a corrosion protection additive and 0.2 to 5 Wt .-% of a wetting agent. Suitable base oils are, in particular, hydrocarbons, triglyceride mixtures, esters, very particularly preferably esters of a carboxylic acid having more than 16 carbon atoms and an alcohol component having more than 8 carbon atoms, fatty alcohols and a mixture of two or more substances from one or more of the abovementioned groups. examples for Separating components are mixtures of fatty and resin acids, triglyceride mixtures, esters and polyolo-alcohol derivatives and mixtures thereof. As anticorrosive additive are merely, for example, succinic acid esters, amine phosphates, sulfonate / carboxylate mixtures, imidazole derivatives, N-oleylsarcosine and phosphoric acid esters mentioned, which can be used both alone and in combination with each other. Suitable wetting agents are fatty acid polyethylene glycol esters, Na diisooctyl sulfosuccinate, sorbitan trioleate, glycerol monooleate, glycerol dioleate, alcohol derivatives, ester derivatives and silicone additives, which may be used both alone and in combination.
Kühlschmierstoffe gemäß der vorliegenden Erfindung können z.B. als organische Phase eine Mischung aus 5 bis 80 Gew.-% Grundöl, 5 bis 20 Gew.-% Korrosionsschutzadditiven sowie Metallinhibitoren, ggf. Konservierungsstoffe und andere gängige Additive enthalten. Als Grundöl eignen sich Esteröle, paraffinische oder naphthenische Kohlenwasserstoffe, Alkohole, Ether, Polyisobutene, Polyalkylenglykole sowie Mischungen aus zwei oder mehreren Substanzen aus einer oder mehreren der vorstehend aufgeführten Gruppen. Als Korrosionsschutzadditive kommen insbesondere Phosphorsäureester, Triazole, Thiadiazole, Umsetzungsprodukte von Borsäure mit primären oder tertiären Alkanolaminen, Fettsäuren, Fettsäurealkanolamine oder Mischungen aus zwei oder mehreren Substanzen aus einer oder mehreren der vorstehend aufgeführten Gruppen in Betracht. Ferner kann die Ölphase Alkylbernsteinsäureimide, Castoroilethoxylate, Petrolsulfonate, Festschmierstoffe, Toluyltriazole, Entschäumer und/oder Antinebelzusätze als weitere, gängige Additive enthalten. Der Anteil der Ölphase kann in dem erfindungsgemässen Kühlschmierstoff zwischen 2 und 25 Gew.-% betragen.Cooling lubricants according to the present invention may e.g. as the organic phase, a mixture of 5 to 80 wt .-% base oil, 5 to 20 wt .-% corrosion inhibiting additives and metal inhibitors, optionally preservatives and other conventional additives. Suitable base oils are ester oils, paraffinic or naphthenic hydrocarbons, alcohols, ethers, polyisobutenes, polyalkylene glycols and mixtures of two or more substances from one or more of the groups listed above. Suitable corrosion protection additives are, in particular, phosphoric esters, triazoles, thiadiazoles, reaction products of boric acid with primary or tertiary alkanolamines, fatty acids, fatty acid alkanolamines or mixtures of two or more substances from one or more of the groups listed above. Furthermore, the oil phase alkyl succinimides, Castoroilethoxylate, petroleum sulfonates, solid lubricants, Toluyltriazole, defoamers and / or Antinebelzusätze as other common additives. The proportion of the oil phase in the novel cooling lubricant can be between 2 and 25% by weight.
Bevorzugte Anwendungen der erfindungsgemäß hergestellten Öl-in-Wasser-Dispersionen sind:
- a) Die Verwendung des erfindungsgemäßen Trennmittels für das Formtrennen eines hydraulischen Bindemittels, bspw. Beton,
- b) die Verwendung des erfindungsgemäßen Kühlschmierstoffs bei der spanenden Bearbeitung von Metallen,
- c) die Verwendung der erfindungsgemäßen Öl-in-Wasser-Dispersion als Trennmittel beim Schmieden,
- d) die Verwendung der erfindungsgemäßen Öl-in-Wasser-Dispersion in der Nahrungs- und Genussmittelindustrie, bspw. zur Herstellung von Kuchen, Bonbons, Pralinen, Gummibären oder dergl.,
- e) die Verwendung der erfindungsgemäßen Öl-in-Wasser-Dispersion bei der Herstellung von Autoreifen, von Polymeren oder polymerhaltigen Zusammensetzungen, bspw. von Gleitlacken und Gleitfilmen.
- a) The use of the release agent according to the invention for the mold cutting of a hydraulic binder, for example concrete,
- b) the use of the inventive cooling lubricant in the machining of metals,
- c) the use of the oil-in-water dispersion according to the invention as a release agent in forging,
- d) the use of the oil-in-water dispersion according to the invention in the food and beverage industry, for example for the production of cakes, candies, pralines, gummi bears or the like,
- e) the use of the oil-in-water dispersion according to the invention in the production of car tires, of polymers or polymer-containing compositions, for example of bonded coatings and sliding films.
Im Folgenden wird die Erfindung anhand der Beispiele 1 bis 3 erläutert. Diese Erläuterungen sind lediglich beispielhaft und schränken den allgemeinen Erfindungsgedanken nicht ein.The invention will be explained below with reference to Examples 1 to 3. These explanations are merely exemplary and do not limit the general inventive concept.
Zur Herstellung einer erfindungsgemäßen Betontrennmittelformulierung in Form einer Öl-in-Wasser-Emulsionen wurde zunächst eine Ölphase aus den folgenden Komponenten hergestellt:
Die Viskosität der Ölphase, die Viskosität der Emulsion sowie der mittlere Durchmesser der Öltröpfchen ist in der Tabelle 1 wiedergegeben.The viscosity of the oil phase, the viscosity of the emulsion and the average diameter of the oil droplets are shown in Table 1.
Zur Herstellung einer erfindungsgemäßen Betontrennmittelformulierung in Form einer Öl-in-Wasser-Emulsionen wurde zunächst eine Ölphase aus den folgenden Komponenten hergestellt:
Die Viskosität der Ölphase, die Viskosität der Emulsion sowie der mittlere Durchmesser der Öltröpfchen ist in der Tabelle 1 wiedergegeben.The viscosity of the oil phase, the viscosity of the emulsion and the average diameter of the oil droplets are shown in Table 1.
Zur Herstellung einer erfindungsgemässen Betontrennmittelformulierung in Form einer Öl-in-Wasser-Emulsionen wurde zunächst eine Ölphase aus den folgenden Komponenten hergestellt:
Anschließend wurde die Ölphase wie in Beispiel 1 beschrieben mit Wasser zu einer zu einer Öl-in-Wasser-Emulsion mit einem Ölanteil von 24,4 Gew.-% vermischt. Die Viskosität der Ölphase, die Viskosität der Emulsion sowie der mittlere Durchmesser der Öltröpfchen ist in der Tabelle 1 wiedergegeben.
Alle vorstehenden Öl-in-Wasser-Emulsionen wurden erfolgreich als Trennmittel bei der Entschalung von Betonkörpern eingesetzt. Alle Emulsionen wiesen eine ausreichend lange Stabilitätsdauer und hervorragende anwendungstechnische Eigenschaften auf.All of the above oil-in-water emulsions have been successfully used as release agents in the deconstruction of concrete bodies. All emulsions had a sufficiently long stability time and excellent performance properties.
Claims (15)
- Method for manufacturing and applying a release agent or a cooling lubricant, wherein the release agent or cooling lubricant is an emulsifier-free oil-in-water dispersion with a viscosity of less than 10,000 mPa.s, preferably less than 5,000 mPa.s., and in particular preference less than 1,000 mPa.s, and wherein the oil-in-water dispersion consists of(a) at least a first essentially aqueous phase and(b) at least a further phase immiscible with the first phase
and the method comprises the following steps:- combining the components forming the phases and- intensive mixing with the admission of energy, and without the addition of an emulsifier, so that a dispersion is obtained that is stable for at least 5 seconds, and- immediate application of the thus intensively mixed semi-stable dispersion to the mould or working surface, wherein(b.1) for the manufacture of the release agent, at least one phase (b) not miscible with the first phase is an oil phase, manufactured using a composition comprising a mixture of the components:90 to 98% by weightof a base oil,0 to 10% by weight of an active parting component,0.2 to 1% by weight of a corrosion protection additive and0.2 to 5% by weight of a wetting agent, or(b.2) for the manufacture of the cooling lubricant, at least one phase (b) not miscible with the first phase is an organic phase, manufactured using a composition comprising a mixture of the components:5 to 80% by weight of a base oil and5 to 20% by weight of a corrosion protective additive and metal inhibitors, and optional preservatives and other additives. - Method according to any of the preceding claims, characterised in that the aqueous phase(a) is manufactured by diluting a concentrate with water before mixing it with at least one further phase (b).
- Method according to any of the preceding claims, characterised in that the at least two phases are mixed by injecting one phase into at least the other phase, by turbulent mixing, applying vibrations and cavitation, such as by ultrasound, or by means of bomogenisers.
- Method according to any of the preceding claims, characterised in that the at last two phases are mixed by means of a static or dynamic micro-mixer.
- Method for the manufacture of an emulsifier-free oil-in-water dispersion according to any of the preceding claims, characterised in that the at least two phases are mixed by means of a micro-mixer, wherein the individual phases are guided through individual guide channels of defined dimensions and are divided into a plurality of liquid lamellae before the individual liquid lamellae are combined by fragmentation of at least one of the phases.
- Method according to Claim 5, characterised in that the fragmentation of at least one phase, when combining the liquid lamellae, is additionally supported by mechanical vibrations.
- Method for the continuous manufacture of an emulsifier-free dispersion according to any of the preceding claims, characterised in that the dispersion is collected, after it has been supplied for application, and for separating the individual phases incubated in a separatory funnel for example, before the at least two phases are again mixed together to form semi-stable dispersions.
- Method according to Claim 7, characterised in that contaminations resulting from the application are separated from the dispersion or from the separated phases of the dispersion after the dispersion is collected and before re-mixing the at least two phases.
- Method according to Claim 7 or 8, characterised in that after collection of the dispersion and before re-mixing of the at least two phases the liquid losses suffered as a result of the application are compensated by additional dosing.
- Method according to any of the preceding claims, characterised in that the method consists in the application as a release agent and in that the ratio of the aqueous phase to the oil phase is, in particular, between 20:1 and 1:1.
- Method according to Claim 10, characterised in that the method consists in the application as a release agent for the mould separation of an hydraulic bonding agent material.
- Method according to Claim 10, characterised in that the method consists in the application as a release agent for the mould separation of concrete.
- Method according to Claim 10, characterised in that the method consists in the application as a release agent in the manufacture of cakes, sweets, pralines or jelly bears.
- Method according to any one of Claims 1 to 9, characterised in that the application consists in the application as a cooling lubricant when cutting metal.
- Method according to either of Claims 12 or 14, characterised in that the oil-in-water emulsion has a stability of less than 10 seconds, corresponding to the time required for dividing and dispersing the release agent in the mould or the cooling lubricant on the machining surface.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE50207291T DE50207291D1 (en) | 2002-04-16 | 2002-04-16 | Process for the preparation and application of emulsifier-free oil-in-water dispersions as release agent or cooling lubricant |
EP02008174A EP1356857B1 (en) | 2002-04-16 | 2002-04-16 | Method for producing and applying of emulsifier free oil-in-water dispersions as a release agent or cooling lubricant |
AT02008174T ATE330697T1 (en) | 2002-04-16 | 2002-04-16 | METHOD FOR THE PRODUCTION AND APPLICATION OF EMULSIFIER-FREE OIL-IN-WATER DISPERSIONS AS A RELEASE AGENT OR COOLING LUBRICANT |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02008174A EP1356857B1 (en) | 2002-04-16 | 2002-04-16 | Method for producing and applying of emulsifier free oil-in-water dispersions as a release agent or cooling lubricant |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1356857A1 EP1356857A1 (en) | 2003-10-29 |
EP1356857B1 true EP1356857B1 (en) | 2006-06-21 |
Family
ID=28685853
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02008174A Expired - Lifetime EP1356857B1 (en) | 2002-04-16 | 2002-04-16 | Method for producing and applying of emulsifier free oil-in-water dispersions as a release agent or cooling lubricant |
Country Status (3)
Country | Link |
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EP (1) | EP1356857B1 (en) |
AT (1) | ATE330697T1 (en) |
DE (1) | DE50207291D1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102005028989A1 (en) * | 2005-06-21 | 2007-01-04 | Basf Ag | Process for the preparation of an aqueous polymer dispersion |
WO2013098673A1 (en) * | 2011-12-26 | 2013-07-04 | Koninklijke Philips Electronics N.V. | Device and method for generating emulsion |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE957474C (en) * | 1943-11-05 | 1957-02-07 | Siemens Ag | Process for the preparation of emulsions, e.g. from oil and water |
AT398078B (en) * | 1990-09-17 | 1994-09-26 | Nolz Ges M B H & Co Kg | Release agent for concrete shuttering |
DE4400272A1 (en) * | 1994-01-10 | 1995-07-13 | Henkel Kgaa | Release agent for hydraulic binder, esp. concrete or shell mould |
DE19515258A1 (en) * | 1995-04-26 | 1996-10-31 | Paul Jaerke | Liquid separating, lubricating and cooling agent, esp. for die casting |
DE19911777A1 (en) * | 1999-03-17 | 2000-09-21 | Merck Patent Gmbh | Process for the preparation of cosmetic formulations |
DE19917148C2 (en) * | 1999-04-16 | 2002-01-10 | Inst Mikrotechnik Mainz Gmbh | Process and micromixer for producing a dispersion |
DE19928123A1 (en) * | 1999-06-19 | 2000-12-28 | Karlsruhe Forschzent | Static micromixer has a mixing chamber and a guiding component for guiding fluids to be mixed or dispersed with slit-like channels that widen in the direction of the inlet side |
DE10031917B4 (en) * | 2000-06-07 | 2005-08-04 | H. Hiendl Gmbh & Co. Kg | Use of a water-in-oil emulsion as a concrete release agent |
-
2002
- 2002-04-16 EP EP02008174A patent/EP1356857B1/en not_active Expired - Lifetime
- 2002-04-16 AT AT02008174T patent/ATE330697T1/en active
- 2002-04-16 DE DE50207291T patent/DE50207291D1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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ATE330697T1 (en) | 2006-07-15 |
EP1356857A1 (en) | 2003-10-29 |
DE50207291D1 (en) | 2006-08-03 |
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