EP0256354A1 - Cleaning agent - Google Patents
Cleaning agent Download PDFInfo
- Publication number
- EP0256354A1 EP0256354A1 EP87110749A EP87110749A EP0256354A1 EP 0256354 A1 EP0256354 A1 EP 0256354A1 EP 87110749 A EP87110749 A EP 87110749A EP 87110749 A EP87110749 A EP 87110749A EP 0256354 A1 EP0256354 A1 EP 0256354A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alcohol
- cleaning agent
- agent according
- carbon atoms
- fatty
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2093—Esters; Carbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/42—Amino alcohols or amino ethers
- C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- the invention relates to cleaning agents which are particularly suitable as laundry pretreatment and detaching agents and contain no halogenated hydrocarbons.
- HKW halogenated hydrocarbons
- stain treatment agents do not meet the requirements because of their content of non-biodegradable alkylphenol ethoxylates and their relatively high content of chlorinated hydrocarbons.
- Liquid cleaning agents containing water and organic solvents are known from German patent specification 1,792,066. Mixtures of various nonionic alcohol alkoxylates are used as surfactants, the main constituent of which is an ethylene oxide / propylene oxide block polymer which is not sufficiently biodegradable. Due to their water content, the agents are not suitable for filling in spray cans susceptible to corrosion and not painted on the inside. They are also largely ineffective against some types of soiling.
- European patent specification 0 026 422 discloses cleaning agents which are intended for spraying and which contain blowing agents and which, in addition to ethoxylated alcohols and hydrocarbon mixtures of different degrees, contain chlorinated hydrocarbons. Some other known products are flammable due to their composition.
- the object of the present invention is therefore to provide a cleaning agent which on the one hand does not contain any CHP and is also not considered to be combustible. Further requirements placed on such a product are: - The surfactants used must be sufficiently biodegradable; - the product must be easy to rinse; - The product must be easy to scent.
- ethoxylated fatty alcohols Both saturated and unsaturated fatty alcohols can serve as the starting material.
- Oxo alcohols are synthetically produced alcohols with different proportions of 2-methyl branched alcohols.
- it can be useful to optimize properties of the cleaning agents according to the invention be to use combinations of fatty alcohol and / or oxo alcohol ethoxylates which have a different number of carbon atoms in the fatty alcohol component and / or different degrees of ethoxylation. By selecting the components, cleaning agents with different performance focuses and characteristics can be produced.
- preferred cleaning agents additionally contain water in amounts of 0.1 to 50% by weight; other, likewise preferred embodiments contain, in addition to the alcohol ethoxylate and the fatty acid ester, 1 to 50% by weight of a monohydric alcohol having 1 to 4 carbon atoms.
- Products that contain 3 to 15% by weight of a monohydric alcohol with 1 to 4 carbon atoms and 0.5 to 40% by weight water in addition to the two obligatory components have particularly valuable properties.
- mixtures of different alcohol ethoxylates are used, combinations of 2 to 30% by weight alcohol ethoxylate with 5 to 10 mol ethylene oxide and 2 to 10% by weight alcohol ethoxylate with 1 to 4 mol ethylene oxide are used particularly interesting in view of a balanced high level of performance.
- the low-ethoxylated alcohol can also be replaced in whole or in part by a fatty amine having 10 to 20 carbon atoms and 1 to 4 moles of ethylene oxide.
- the fatty acid ester or the fatty acid ester mixture can be replaced by aliphatic, straight-chain and / or branched liquid hydrocarbons having 6 to 40 carbon atoms or mixtures thereof. Such a measure also enables an optimal adaptation of the cleaning agent according to the invention to the desired combination of properties.
- ethyl alcohol and / or isopropyl alcohol are particularly preferred.
- the alcohol and liquid hydrocarbon content influences the consistency, the flammability and the cleaning performance.
- particularly preferred cleaning agents contain a more or less large proportion of the components mentioned.
- cleaning agents with particularly well-balanced properties contain 5 to 20% by weight fatty alcohols and / or oxo alcohol with 10 to 20 carbon atoms, on the 5 to 10, both against pigment soiling and oil or grease-like soiling on different types of fabric Mol ethylene oxide are attached.
- a cleaning agent with a content of 3 to 7% by weight of fatty alcohol and / or oxo alcohol with 10 to 20 carbon atoms, to which 1 to 4 mol of ethylene oxide are attached also has excellent properties.
- particularly effective cleaning agents contain both higher and lower ethoxylated alcohols of the above type and amount.
- the agent can additionally or instead of the lower ethoxy gated alcohol also contain fatty amine with 10 to 20 carbon atoms and with 1 to 4 moles of ethylene oxide, which increases the cleaning effect. Fragrances can also be added to the agents.
- the agent according to the invention can be sprayed with or without propellant gas, such as carbon dioxide or butane or propane, onto the soiled textiles or by application in liquid or pasty or gel-like Apply shape.
- propellant gas such as carbon dioxide or butane or propane
- washing tests were carried out on white PES / BW 50:50 pieces of tissue.
- a commercially available product in a concentration of 16.1 g / l at a temperature of 60 ° C. was used as the detergent.
- the tissue was placed on a filter sheet and three drops of soiling applied. After an exposure time of 30 seconds, the tissue was placed in a screw-top glass jar.
- the evaluation was carried out by visual assessment of the stain removal in comparison to a patch which had not been pretreated with cleaning agent.
- Cleaning agents of the following general composition were produced: 7.5% C 14/15 oxo alcohol + 7 EO 5% C 18/13 cocosamine + 2 EO 30% ethanol, anhydrous and 57.5% fatty acid esters.
- the formulations of the comparative examples show significantly poorer cleaning action than those of Examples 1 (a) to (d).
- a formulation according to Example 4 was used using 10% ethanol, 99.9% and 27.5 isoparaffin mixture, boiling range 207 to 251 ° C produced.
- the cleaning agents of Examples 4 and 5 had a very good effect on removing dirt from used motor oil.
- the detergents with the compositions according to Examples 6 and 7 had an excellent cleaning effect.
Abstract
Description
Die Erfindung betrifft Reinigungsmittel, die insbesondere als Wäschevorbehandlungs- und Detachurmittel geeignet sind und keine Halogenkohlenwasserstoffe enthalten.The invention relates to cleaning agents which are particularly suitable as laundry pretreatment and detaching agents and contain no halogenated hydrocarbons.
Massive lokale Verschmutzungen lassen sich nicht immer durch Waschen in einer Waschmaschine in zufriedenstellendem Maße aus Textilien auswaschen. Der Grund liegt insbesondere darin, daß immer mehr pflegeleichte waschbare Textilien auf den Markt gekommen sind, die zur Erhaltung ihrer Eigenschaften nur bei niedrigen Waschtemperaturen, wie z.B. 60°C oder nur 30°C, gewaschen werden dürfen. Mit zu den problematischsten Flecken im Haushalt gehören gerade bei niedrigen Waschtemperaturen Verschmutzungen wie Öl, insbesondere benutztes Motorenöl, Pigmentschmutz und Gemische davon. In manchen Fällen ist es daher erforderlich, besonders stark verschmutzte Stellen der Textilien mit einem Reinigungsmittel vor dem Waschen vorzubehandeln. Bei bekannten, markgängigen Wäschevorbehandlungsmitteln beruht die Wirkung im wesentlichen auf einem hohen Gehalt an Halogenkohlenwasserstoffen (HKW), wie etwa Methylenchlorid oder Perchlorethylen oder Fluorkohlenwasserstoffen. HKW müssen aber ihrer Auswirkungen auf die Umwelt durch umweltverträgliche Rohstoffe ersetzt werden.Massive local soiling cannot always be washed out of textiles to a satisfactory degree by washing in a washing machine. The reason lies in particular in the fact that more and more easy-care washable textiles have come onto the market which, in order to maintain their properties, may only be washed at low washing temperatures, such as 60 ° C. or only 30 ° C. One of the most problematic stains in the household is dirt, such as oil, especially used motor oil, pigment dirt and mixtures thereof, especially at low washing temperatures. In some cases, it is therefore necessary to pretreat particularly heavily soiled areas of the textiles with a cleaning agent before washing. In known, marketable laundry pretreatment agents, the effect is based essentially on a high content of halogenated hydrocarbons (HKW), such as methylene chloride or perchlorethylene or fluorocarbons. However, HKW's effects on the environment must be replaced by environmentally compatible raw materials.
Bekannte Fleckenbehandlungsmittel entsprechen wegen ihres Gehalts an biologisch nicht abbaufähigen Alkylphenolethoxylaten und ihres verhältnismäßig hohen Gehalts an Chlorkohlenwasserstoffen nicht den gestellten Anforderungen.Known stain treatment agents do not meet the requirements because of their content of non-biodegradable alkylphenol ethoxylates and their relatively high content of chlorinated hydrocarbons.
Aus der deutschen Patentschrift 1 792 066 sind flüssige, Wasser sowie organische Lösungsmittel enthaltende Reinigungsmittel bekannt. Als Tenside dienen Mischungen verschiedener nichtionischer Alkoholalkoxylate, deren Hauptbestandteil ein biologisch nicht genügend abbaufähiges Ethylenoxid/Propylenoxid-Blockpolymerisat ist. Aufgrund ihres Wassergehaltes eignen sich die Mittel nicht zum Abfüllen in korrosionsanfälligen, innen nicht lackierten Sprühdosen. Gegenüber manchen Verschmutzungen sind sie außerdem weitgehend wirkungslos.Liquid cleaning agents containing water and organic solvents are known from German patent specification 1,792,066. Mixtures of various nonionic alcohol alkoxylates are used as surfactants, the main constituent of which is an ethylene oxide / propylene oxide block polymer which is not sufficiently biodegradable. Due to their water content, the agents are not suitable for filling in spray cans susceptible to corrosion and not painted on the inside. They are also largely ineffective against some types of soiling.
Aus der europäischen Patentschrift 0 026 422 sind zum Aufsprühen vorgesehene, Treibmittel enthaltende Reinigungsmittel bekannt, die neben unterschiedlich hoch ethoxylierten Alkoholen und Kohlenwasserstoffgemischen Chlorkohlenwasserstoffe enthalten. Manche andere bekannte Produkte sind auf Grund ihrer Zusammensetzung brennbar.European patent specification 0 026 422 discloses cleaning agents which are intended for spraying and which contain blowing agents and which, in addition to ethoxylated alcohols and hydrocarbon mixtures of different degrees, contain chlorinated hydrocarbons. Some other known products are flammable due to their composition.
Aufgabe der vorliegenden Erfindung ist es daher, ein Reinigungsmittel zur Verfügung zu stellen, das einerseits keine HKW enthält und zudem nicht als brennbar gilt. Weitere Anforderungen, die an ein derartiges Produkt gestellt werden, sind:
- die eingesetzten Tenside müssen ausreichend biologisch abbauber sein;
- das Produkt muß gut ausspülbar sein;
- das Produkt muß gut parfümierbar sein.The object of the present invention is therefore to provide a cleaning agent which on the one hand does not contain any CHP and is also not considered to be combustible. Further requirements placed on such a product are:
- The surfactants used must be sufficiently biodegradable;
- the product must be easy to rinse;
- The product must be easy to scent.
Es wurde nun überraschend gefunden, daß Reinigungsmittel, die bestimmte Fettsäureester in Kombination mit bestimmten nichtionischen Tensiden enthalten, die geforderten Voraussetzungen erfüllen.It has now surprisingly been found that cleaning agents which contain certain fatty acid esters in combination with certain nonionic surfactants meet the required requirements.
Bei dem erfindungsgemäßen Reinigungsmittel handelt es sich um Reinigungsmittel auf Basis von Anlagerungsprodukten von Ethylenoxid an Fettalkohole und/order Oxoalkohole, das dadurch gekennzeichnet ist, daß es
- (a) 2 bis 40 Gew.-% wenigstens eines Fettalkohols und/oder Oxoalkohols mit 10 bis 20 C-Atomen und 1 bis 10 Mol Ethylenoxid,
- (b) 10 bis 90 Gew.-% wenigstens eines Fettsäureesters, ausgewählt aus der aus Isopropylmyristat, Isopropylpalmitat, Isopropylstearat, Oleyloleat, Hexyllaurat, Di-n-butyladipat, Capryl- oder Caprinsäureester von gesättigten Fettalkoholen mit 12 bis 18 C-Atomen, Ester von verzweigtkettigen Fettsäuren mit 8 bis 12 C-Atomen mit Fettalkoholen mit 14 bis 20 C-Atomen, Decyloleat, Isooctylstearat, Glycerintrioleat und i-Butyloleat bestehenden Gruppe
- (a) 2 to 40% by weight of at least one fatty alcohol and / or oxo alcohol with 10 to 20 C atoms and 1 to 10 mol ethylene oxide,
- (b) 10 to 90% by weight of at least one fatty acid ester selected from the group consisting of isopropyl myristate, isopropyl palmitate, isopropyl stearate, oleyl oleate, hexyl laurate, di-n-butyl adipate, caprylic or capric acid esters of saturated fatty alcohols with 12 to 18 carbon atoms, esters of branched-chain fatty acids with 8 to 12 carbon atoms with fatty alcohols with 14 to 20 carbon atoms, decyl oleate, isooctyl stearate, glycerol trioleate and i-butyl oleate
Als ethoxylierte Fettalkohole kommen von synthetischen oder insbesondere natürlichen Alkoholen bzw. Alkoholgemischen abgeleitete Verbindungen in Frage. Dabei können sowohl gesättigte als auch ungesättigte Fettalkohole als Ausgangsmaterial dienen. Oxoalkohole sind synthetisch hergestellte Alkohole mit unterschiedlich hohen Anteilen an 2-methylverzweigten Alkoholen. In manchen Fällen kann es zur Optimierung von Eigenschaften der erfindungsgemäßen Reinigungsmittel zweckmäßig sein, Kombinationen von Fettalkohol- und/oder Oxoalkohol-Ethoxylaten einzusetzen, die eine unterschiedliche Anzahl von Kohlenstoffatomen in der Fettalkohol-Komponente und/oder unterschiedlich hohe Ethoxylierungsgrade haben. Durch die Auswahl der Komponenten lassen sich Reinigungsmittel mit unterschiedlich ausgeprägten Leistungsschwerpunkten und Eigenschaftsmerkmalen herstellen.Compounds derived from synthetic or, in particular, natural alcohols or alcohol mixtures are suitable as ethoxylated fatty alcohols. Both saturated and unsaturated fatty alcohols can serve as the starting material. Oxo alcohols are synthetically produced alcohols with different proportions of 2-methyl branched alcohols. In some cases it can be useful to optimize properties of the cleaning agents according to the invention be to use combinations of fatty alcohol and / or oxo alcohol ethoxylates which have a different number of carbon atoms in the fatty alcohol component and / or different degrees of ethoxylation. By selecting the components, cleaning agents with different performance focuses and characteristics can be produced.
Bevorzugte Reinigungsmittel enthalten neben dem Alkohol-Ethoxylat und dem Fettsäureester zusätzlich Wasser in Mengen von 0,1 bis 50 Gew.-%; andere, ebenfalls bevorzugte Ausführungsformen enthalten zusätzlich zu dem Alkohol-Ethoxylat und dem Fettsäureester 1 bis 50 Gew.-% eines einwertigen Alkohols mit 1 bis 4 C-Atomen.In addition to the alcohol ethoxylate and the fatty acid ester, preferred cleaning agents additionally contain water in amounts of 0.1 to 50% by weight; other, likewise preferred embodiments contain, in addition to the alcohol ethoxylate and the fatty acid ester, 1 to 50% by weight of a monohydric alcohol having 1 to 4 carbon atoms.
Besonders wertvolle Eigenschaften haben Produkte, die neben den beiden obligatoreischen Bestandteilen 3 bis 15 Gew.-% eines einwertigen Alkohols mit 1 bis 4 Kohlenstoffatomen und 0,5 bis 40 Gew.-% Wasser enthalten.Products that contain 3 to 15% by weight of a monohydric alcohol with 1 to 4 carbon atoms and 0.5 to 40% by weight water in addition to the two obligatory components have particularly valuable properties.
Setzt man, wie bereits erwähnt, Gemische verschiedener Alkohol-Ethoxylate ein, sind Kombinationen von 2 bis 30 Gew.-% Alkohol-Ethoxylat mit 5 bis 10 Mol Ethylenoxid und 2 bis 10 Gew.-% Alkohol-Ethoxylat mit 1 bis 4 Mol Ethylenoxid im Hinblick auf ein ausgeglichen hohes Leistungsniveau besonders interessant. Dabei kann der niedrig ethoxylierte Alkohol auch ganz oder teilweise durch ein Fettamin mit 10 bis 20 Kohlenstoffatomen und 1 bis 4 Mol Ethylenoxid ersetzt werden.If, as already mentioned, mixtures of different alcohol ethoxylates are used, combinations of 2 to 30% by weight alcohol ethoxylate with 5 to 10 mol ethylene oxide and 2 to 10% by weight alcohol ethoxylate with 1 to 4 mol ethylene oxide are used particularly interesting in view of a balanced high level of performance. The low-ethoxylated alcohol can also be replaced in whole or in part by a fatty amine having 10 to 20 carbon atoms and 1 to 4 moles of ethylene oxide.
Der Fettsäureester oder das Fettsäureester-Gemisch kann bis zu 90 % seines Gewichts durch aliphatische, geradkettige und/oder verzweigte flüssige Kohlenwasserstoffe mit 6 bis 40 C-Atomen oder deren Gemische ersetzt werden. Auch durch eine derartige Maßnahme ist eine optimale Anpassung des erfindungsgemäßen Reinigungsmittels an die gewünschte Eigenschaftskombination möglich.Up to 90% of its weight, the fatty acid ester or the fatty acid ester mixture can be replaced by aliphatic, straight-chain and / or branched liquid hydrocarbons having 6 to 40 carbon atoms or mixtures thereof. Such a measure also enables an optimal adaptation of the cleaning agent according to the invention to the desired combination of properties.
Von den Frage kommenden einwertigen Alkoholen, die Bestandteil des erfindungsgemäßen Reinigungsmittels sein können, sind Ethylalkohol und/oder Isopropylalkohol besonders bevorzugt. Der Gehalt an Alkohol und an flüssigen Kohlenwasserstoffen hat Einfluß auf die Konsistenz die Brennbarkeit und die Reinigungsleistung. Je nach dem Anforderungsprofil enthalten besonders bevorzugte Reinigungsmittel einen mehr oder weniger großen Anteil der genannten Komponenten.Of the question of monohydric alcohols which can be part of the cleaning agent according to the invention, ethyl alcohol and / or isopropyl alcohol are particularly preferred. The alcohol and liquid hydrocarbon content influences the consistency, the flammability and the cleaning performance. Depending on the requirement profile, particularly preferred cleaning agents contain a more or less large proportion of the components mentioned.
Im allgemeinen enthalten Reinigungsmittel mit besonders ausgewogenen Eigenschaften hinsichltich ihrer Reinigungswirkung sowohl gegenüber Pigmentverschmutzungen als auch gegenüber öl- oder fettartigen Verschmutzungen auf unterschiedlichen Gewebearten 5 bis 20 Gew.-% Fettalkohole und/oder Oxoalkohol mit 10 bis 20 C-Atomen, an den 5 bis 10 Mol Ethylenoxid angelagert sind. Ebenfalls ausgezeichnete Eigenschaften hat ein Reinigungsmittel mit einem Gehalt an 3 bis 7 Gew.-% Fettalkohol und/oder Oxoalkohol mit 10 bis 20 C-Atomen, an den 1 bis 4 Mol Ethylenoxid angelagert sind. In manchen Fällen enthalten besonders wirksame Reinigungsmittel sowohl höher als auch niedriger ethoxylierte Alkohole der o.g. Art und Menge. Dabei kann das Mittel zusätzlich oder anstelle des niedriger ethoxy lierten Alkohols auch Fettamin mit 10 bis 20 C-Atomen und mit 1 bis 4 Mol Ethylenoxid enthalten, wodurch die Reinigungswirkung verstärkt wird. Den Mitteln können außerdem Duftstoffe zugesetzt werden.In general, cleaning agents with particularly well-balanced properties contain 5 to 20% by weight fatty alcohols and / or oxo alcohol with 10 to 20 carbon atoms, on the 5 to 10, both against pigment soiling and oil or grease-like soiling on different types of fabric Mol ethylene oxide are attached. A cleaning agent with a content of 3 to 7% by weight of fatty alcohol and / or oxo alcohol with 10 to 20 carbon atoms, to which 1 to 4 mol of ethylene oxide are attached, also has excellent properties. In some cases, particularly effective cleaning agents contain both higher and lower ethoxylated alcohols of the above type and amount. The agent can additionally or instead of the lower ethoxy gated alcohol also contain fatty amine with 10 to 20 carbon atoms and with 1 to 4 moles of ethylene oxide, which increases the cleaning effect. Fragrances can also be added to the agents.
Je nach der Konsistenz, die über die genannten Bestandteile in weiten Grenzen variierbar ist, läßt sich das erfindungsgemäße Mittel durch Versprühen mit oder ohne Treibgas, wie z.B. Kohlendioxid oder Butan bzw. Propan, auf die verschmutzten Textilien oder durch Auftragen in flüssiger oder pastöser oder gelartiger Form applizieren. Die Verwendung des genannten Reinigungsmittels in den genannten Applikationsformen zur Vorbehandlung stark verschmutzter Textilien ist daher ein weiterer Gegenstand der vorliegenden Erfindung.Depending on the consistency, which can be varied within wide limits via the constituents mentioned, the agent according to the invention can be sprayed with or without propellant gas, such as carbon dioxide or butane or propane, onto the soiled textiles or by application in liquid or pasty or gel-like Apply shape. The use of the cleaning agent mentioned in the application forms mentioned for pretreating heavily soiled textiles is therefore a further subject of the present invention.
Die folgenden Ausführungsbeispiele beschreiben die Wirkungsweise unterschiedlich zusammengesetzter erfindungsgemäßer Reinigungsmittel. In den folgenden Beispielen steht "EO" für angelagertes Ethylenoxid. Die Prozentangaben bedeuten Gewichtsprozent.The following exemplary embodiments describe the mode of action of differently composed cleaning agents according to the invention. In the following examples, "EO" stands for attached ethylene oxide. The percentages mean percent by weight.
An weißen PES/BW 50:50 Gewebestücken wurden Waschversuche durchgeführt. Als Waschmittel wurde ein marktgängiges Produkt in einer Konzentration von 16,1 g/l bei einer Temperatur von 60°C verwendet.Washing tests were carried out on white PES / BW 50:50 pieces of tissue. A commercially available product in a concentration of 16.1 g / l at a temperature of 60 ° C. was used as the detergent.
Die Anschmutzungen erfolgten durch
- (1) Olivenöl mit Sudanrot,
- (2) gebrauchtes Motorenöl,
- (3) Pigment-Schmutz-Dispersion.
- (1) olive oil with Sudan red,
- (2) used motor oil,
- (3) pigment-dirt dispersion.
Das Gewebe wurde auf einen Filterbogen gelegt und drei Tropfen einer Anschmutzung aufgetragen. Nach einer Einwirkungszeit von 30 sec wurde das Gewebe in ein Schraubdeckelglas gegeben.The tissue was placed on a filter sheet and three drops of soiling applied. After an exposure time of 30 seconds, the tissue was placed in a screw-top glass jar.
2 g eines der weiter unten beschriebenen Reinigungsmittel wurden auf das Läppchen getropft und 5 min einwirken gelassen. Dann wurden 75 ml Waschmittellösung dazugegeben und 10mal geschüttelt. Anschließend wurde das Läppchen herausgenommen, in 500 ml Stadtwasser ausgespült (10mal umrühren) und auf einem Filterbogen getrocknet.2 g of one of the cleaning agents described below were dropped onto the lobule and left to act for 5 minutes. Then 75 ml of detergent solution were added and shaken 10 times. The lobule was then removed, rinsed in 500 ml of city water (stirred 10 times) and dried on a filter sheet.
Die Auswertung erfolgte durch visuelle Beurteilung der Fleckenentfernung im Vergleich zu einem nicht mit Reinigungsmittel vorbehandelten Läppchen.The evaluation was carried out by visual assessment of the stain removal in comparison to a patch which had not been pretreated with cleaning agent.
Es wurden Reinigungsmittel der folgenden allgemeinen Zusammensetzung hergestellt:
7,5 % C14/15-Oxoalkohol + 7 EO
5 % C18/13-Kokosamin + 2 EO
30 % Ethanol, wasserfrei und
57,5 % Fettsäüreester.Cleaning agents of the following general composition were produced:
7.5% C 14/15 oxo alcohol + 7 EO
5% C 18/13 cocosamine + 2 EO
30% ethanol, anhydrous and
57.5% fatty acid esters.
In den Ausführungsbeispielen wurde als Fettsäureester verwendet:
- (a) Decyloleat,
- (b) Ester von Isononansäure mit Fettalkoholen mit 14 bis 20 C-Atomen,
- (c) Isopropylmyristat,
- (d) Isopropylstearat.
- (a) decyl oleate,
- (b) esters of isononanoic acid with fatty alcohols with 14 to 20 C atoms,
- (c) isopropyl myristate,
- (d) Isopropyl stearate.
Als Fettsäureester gemäß der Rezeptur des Beispiels 1 wurde
- (a) Polyolfettsäureester und
- (b) Glycerin-monooleat
- (a) polyol fatty acid esters and
- (b) Glycerol monooleate
Die Rezepturen der Vergleichsbeispiele zeigen deutlich schlechtere Reinigungswirkung als die der Beispiele 1 (a) bis (d).The formulations of the comparative examples show significantly poorer cleaning action than those of Examples 1 (a) to (d).
Rezepturen wie in Beispielen 1 (a) bis (d) unter Verwendung von
40 % Ethanol, wasserfrei und
47,5 % Fettsäureester.Formulations as in Examples 1 (a) to (d) using
40% ethanol, anhydrous and
47.5% fatty acid ester.
Rezeptur wie in Beispiel 2 unter Verwendung der Fettsäureester gemäß Vergleichsbeispiel 1.Recipe as in Example 2 using the fatty acid esters according to Comparative Example 1.
Die Ergebnisse der Waschtests entsprechen denen des Beispiels 1 und des Vergleichsbeispiels 1.The results of the washing tests correspond to those of Example 1 and Comparative Example 1.
Rezepturen wie in Beispielen 1 (a) bis (d) unter Verwendung von
37,5 % Ethanol, wasserfrei, und
50 % Fettsäureester.Formulations as in Examples 1 (a) to (d) using
37.5% ethanol, anhydrous, and
50% fatty acid ester.
Auch mit diesen Reinigungsmitteln wurden gegenüber entsprechend zusammengesetzten Vergleichsprodukten bessere Ergebnisse erhalten.With these cleaning agents, too, better results were obtained compared to correspondingly composed comparison products.
Es wurden Reinigungsmittel der folgenden Zusammensetzung hergestellt:
7,5 % C₁₄/₁₅-Oxoalkohol + 7 EO
5 % C8/13-Kokosamin + 2 EO
5 % Ethanol, 99,9%
32,5 % C12/14-Isoparaffingemisch, Siedebereich 207 bis 251°C
48,7 % Fettsäureester
0,5 % Parfum und
0,8 % Wasser.Cleaning agents with the following composition were produced:
7.5% C ₁₄ / ₁₅ oxo alcohol + 7 EO
5% C 8/13 cocosamine + 2 EO
5% ethanol, 99.9%
32.5% C 12/14 isoparaffin mixture, boiling range 207 to 251 ° C
48.7% fatty acid ester
0.5% perfume and
0.8% water.
In den Ausführungsbeispielen wurde als Fettsäure verwendet:
- (a) Isooctylstearat,
- (b) Decyloleat,
- (c) Ester aus Isononansäure und C₁₄-C₂₀-Fettalkoholen
- (d) Laurinsäurehexylester und
- (e) Isopropylmyristat.
- (a) isooctyl stearate,
- (b) decyl oleate,
- (c) esters of isononanoic acid and C₁₄-C₂₀ fatty alcohols
- (d) hexyl laurate and
- (e) Isopropyl myristate.
Es wurde eine Rezeptur gemäß Beispiel 4 unter Verwendung von
10 % Ethanol, 99,9 % und
27,5 Isoparaffingemisch, Siedebereich 207 bis 251°C
hergestellt.A formulation according to Example 4 was used using
10% ethanol, 99.9% and
27.5 isoparaffin mixture, boiling range 207 to 251 ° C
produced.
Die Reinigungsmittel der Beispiele 4 und 5 zeigten eine sehr gute Wirkung bei der Entfernung von Verschmutzungen aus gebrauchtem Motoröl.The cleaning agents of Examples 4 and 5 had a very good effect on removing dirt from used motor oil.
Es wurde ein Reinigungsmittel mit einer Rezeptur wie Beispiel 1(a) bis 1(d) unter Verwendung von
- (a) 7,5 % C12/18-Fettalkohol + 5 EO und
- (b) 7,5 % eines Fettalkoholgemischs
- (a) 7.5% C 12/18 fatty alcohol + 5 EO and
- (b) 7.5% of a fatty alcohol mixture
Es wurde ein Reinigungsmittel mit einer Rezeptur wie Beispiele 1(a) bis 1(d) unter Verwendung von
- (a) 5 % Oleylcetylalkohol + 5 EO
- (b) 5 % C12/14-Alkohol + 3 EO
- (c) C12/18-Alkohol + 4 EO
- (a) 5% oleyl cetyl alcohol + 5 EO
- (b) 5% C 12/14 alcohol + 3 EO
- (c) C 12/18 alcohol + 4 EO
Die Reinigungsmittel mit den Zusammensetzungen nach den Beispielen 6 und 7 hatten eine ausgezeichnete Reinigungswirkung.The detergents with the compositions according to Examples 6 and 7 had an excellent cleaning effect.
Claims (15)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT87110749T ATE67241T1 (en) | 1986-08-02 | 1987-07-24 | CLEANING SUPPLIES. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3626224 | 1986-08-02 | ||
| DE19863626224 DE3626224A1 (en) | 1986-08-02 | 1986-08-02 | CLEANING SUPPLIES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0256354A1 true EP0256354A1 (en) | 1988-02-24 |
| EP0256354B1 EP0256354B1 (en) | 1991-09-11 |
Family
ID=6306573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87110749A Expired - Lifetime EP0256354B1 (en) | 1986-08-02 | 1987-07-24 | Cleaning agent |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4877556A (en) |
| EP (1) | EP0256354B1 (en) |
| JP (1) | JPS6341599A (en) |
| AT (1) | ATE67241T1 (en) |
| DE (2) | DE3626224A1 (en) |
| ES (1) | ES2024460B3 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991000331A1 (en) * | 1989-06-26 | 1991-01-10 | Unilever N.V. | Liquid detergent composition |
| WO1991005906A1 (en) * | 1989-10-19 | 1991-05-02 | Chemische Fabrik Grünau Gmbh | Aqueous dispersions containing carboxylic and/or resin acids for de-inking printed waste paper |
| WO1991005905A1 (en) * | 1989-10-19 | 1991-05-02 | Chemische Fabrik Grünau Gmbh | Aqueous dispersions containing alkaline earth soaps and/or alkaline earth resin soaps for de-inking printed waste paper |
| EP0559777A1 (en) * | 1990-11-29 | 1993-09-15 | Petroferm Inc. | A process and composition for cleaning contaminants with terpene and monobasic ester |
| WO1994010274A1 (en) * | 1992-10-26 | 1994-05-11 | Henkel Kommanditgesellschaft Auf Aktien | Liquid detergent |
| GB2353288A (en) * | 1999-06-23 | 2001-02-21 | Reckitt Benckiser Inc | Spot cleaning compositions useful for cleaning garments and textiles |
| WO2003066797A1 (en) * | 2002-02-07 | 2003-08-14 | Henkel Kommanditgesellschaft Auf Aktien | Cleaning paste |
| WO2016202572A1 (en) | 2015-06-19 | 2016-12-22 | Unilever N.V. | Laundry pretreatment composition |
| WO2017198419A1 (en) | 2016-05-16 | 2017-11-23 | Unilever N.V. | Pre-treatment composition for fabric stains |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5276204A (en) * | 1988-11-09 | 1994-01-04 | Henkel Kommanditgesellschaft Auf Aktien | Fatty alcohol mixtures and ethoxylates thereof showing improved low-temperature behavior |
| US5725730A (en) * | 1989-10-19 | 1998-03-10 | Gruenau Illertissen | Aqueous dispersions containing carboxylic acids and/or resinic acids for deinking printed wastepaper |
| JP2789046B2 (en) * | 1989-11-08 | 1998-08-20 | 荒川化学工業株式会社 | Cleaning agent for rosin solder flux |
| GB9101850D0 (en) * | 1991-01-29 | 1991-03-13 | Du Pont Howson Ltd | Improvements in or relating to printing |
| US5298195A (en) * | 1992-03-09 | 1994-03-29 | Amway Corporation | Liquid dishwashing detergent |
| US5264045A (en) * | 1992-06-04 | 1993-11-23 | Alfred Zofchak | Method for cleaning mechanical surfaces covered with grease, oil and other sticky materials |
| US5340493A (en) * | 1992-08-20 | 1994-08-23 | Principato Richard J | Low-volatility cleaning compositions for printing inks |
| US5464477A (en) * | 1992-09-18 | 1995-11-07 | Crest Ultrasonics Corporation | Process for cleaning and drying ferrous surfaces without causing flash rusting |
| US5397397A (en) * | 1992-09-18 | 1995-03-14 | Crestek, Inc. | Method for cleaning and drying of metallic and nonmetallic surfaces |
| CA2120375A1 (en) * | 1993-04-02 | 1994-10-03 | John Klier | A laundry pretreater having enhanced oily soil removal |
| US5340495A (en) * | 1993-04-30 | 1994-08-23 | Siebert, Inc. | Compositions for cleaning ink from a printing press and methods thereof |
| US5454969A (en) * | 1993-06-18 | 1995-10-03 | Fields; Paul B. | Cleaning fluids |
| US5435936A (en) * | 1993-09-01 | 1995-07-25 | Colgate Palmolive Co. | Nonaqueous liquid microemulsion compositions |
| EP0753557B1 (en) * | 1995-07-13 | 1998-04-15 | The Procter & Gamble Company | Packaged foaming composition |
| ATE252146T1 (en) * | 1995-07-13 | 2003-11-15 | Procter & Gamble | PACKAGED FOAMING COMPOSITION |
| US6021926A (en) * | 1995-07-13 | 2000-02-08 | The Procter & Gamble Company | Packaged foaming composition |
| US5925608A (en) * | 1995-07-13 | 1999-07-20 | The Procter & Gamble Company | Packaged foaming composition |
| CA2185308C (en) * | 1995-10-05 | 2009-08-11 | Charles J. Good | Ester-based cleaning compositions |
| US6087312A (en) * | 1996-09-13 | 2000-07-11 | The Procter & Gamble Company | Laundry bleaching processes and compositions |
| US5780415A (en) * | 1997-02-10 | 1998-07-14 | Colgate-Palmolive Company | Stable microemulsion cleaning composition |
| US6043209A (en) * | 1998-01-06 | 2000-03-28 | Playtex Products, Inc. | Stable compositions for removing stains from fabrics and carpets and inhibiting the resoiling of same |
| US6204233B1 (en) * | 1998-10-07 | 2001-03-20 | Ecolab Inc | Laundry pre-treatment or pre-spotting compositions used to improve aqueous laundry processing |
| US6180592B1 (en) * | 1999-03-24 | 2001-01-30 | Ecolab Inc. | Hydrophobic and particulate soil removal composition and method for removal of hydrophobic and particulate soil |
| WO2001006053A1 (en) | 1999-07-20 | 2001-01-25 | Micell Technologies, Inc. | Pre-treatment methods and compositions for carbon dioxide dry cleaning |
| US6407051B1 (en) | 2000-02-07 | 2002-06-18 | Ecolab Inc. | Microemulsion detergent composition and method for removing hydrophobic soil from an article |
| FR2816965B1 (en) * | 2000-11-23 | 2003-09-05 | Inst Francais Du Petrole | CLEANING PRODUCTS BASED ON FATTY ACID ESTERS TO ENSURE THE DETACHMENT OF SOILED TEXTILES BY HYDROCARBON RESIDUES |
| US6767881B1 (en) | 2003-03-19 | 2004-07-27 | Ecolab, Inc. | Cleaning concentrate |
| CN103748202A (en) * | 2011-08-29 | 2014-04-23 | 罗门哈斯公司 | Biorenewable solvents and cleaning methods |
| GB2547685A (en) * | 2016-02-26 | 2017-08-30 | Reckitt Benckiser Laundry Detergents | Composition |
| GB201604901D0 (en) * | 2016-03-23 | 2016-05-04 | Reckitt Benckiser Laundry Detergents | Composition |
| GB201604902D0 (en) * | 2016-03-23 | 2016-05-04 | Reckitt Benckiser Laundry Detergents | Composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2867585A (en) * | 1957-09-06 | 1959-01-06 | Colgate Palmolive Co | Detergent composition |
| DE1792066A1 (en) * | 1968-07-18 | 1971-10-14 | Henkel & Cie Gmbh | Low-foaming stain treatment agent for textiles |
| DE2358822A1 (en) * | 1973-11-26 | 1975-06-05 | Henkel & Cie Gmbh | LIQUID DETERGENT CONCENTRATE WITH FATTY PROPERTIES |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1617119A1 (en) * | 1966-11-18 | 1971-02-18 | Henkel & Cie Gmbh | Low-foaming stain treatment agent for textiles |
| DK128786C (en) * | 1967-12-28 | |||
| GB1518676A (en) * | 1975-10-30 | 1978-07-19 | Procter & Gamble Ltd | Detergent compositions |
| DE2939810A1 (en) * | 1979-10-01 | 1981-04-16 | Henkel KGaA, 4000 Düsseldorf | SPRAY CLEANER SUITABLE FOR TEXTILE TREATMENT |
| US4457857A (en) * | 1980-10-20 | 1984-07-03 | Lever Brothers Company | Pretreatment composition for stain removal |
| US4530781A (en) * | 1983-10-12 | 1985-07-23 | S. C. Johnson & Son, Inc. | Metastable prespotting composition |
| US4801544A (en) * | 1984-09-12 | 1989-01-31 | The Clorox Company | Method of improving the storage life of liquid compositions containing enzymes |
| DE3514364A1 (en) * | 1985-04-20 | 1986-10-23 | Henkel KGaA, 4000 Düsseldorf | GRINNY DETERGENT WITH IMPROVED CLEANING CAPACITY |
-
1986
- 1986-08-02 DE DE19863626224 patent/DE3626224A1/en not_active Withdrawn
-
1987
- 1987-07-24 AT AT87110749T patent/ATE67241T1/en not_active IP Right Cessation
- 1987-07-24 EP EP87110749A patent/EP0256354B1/en not_active Expired - Lifetime
- 1987-07-24 DE DE8787110749T patent/DE3772899D1/en not_active Expired - Lifetime
- 1987-07-24 ES ES87110749T patent/ES2024460B3/en not_active Expired - Lifetime
- 1987-08-03 JP JP62194290A patent/JPS6341599A/en active Pending
-
1988
- 1988-11-15 US US07/274,634 patent/US4877556A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2867585A (en) * | 1957-09-06 | 1959-01-06 | Colgate Palmolive Co | Detergent composition |
| DE1792066A1 (en) * | 1968-07-18 | 1971-10-14 | Henkel & Cie Gmbh | Low-foaming stain treatment agent for textiles |
| DE2358822A1 (en) * | 1973-11-26 | 1975-06-05 | Henkel & Cie Gmbh | LIQUID DETERGENT CONCENTRATE WITH FATTY PROPERTIES |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991000331A1 (en) * | 1989-06-26 | 1991-01-10 | Unilever N.V. | Liquid detergent composition |
| WO1991005906A1 (en) * | 1989-10-19 | 1991-05-02 | Chemische Fabrik Grünau Gmbh | Aqueous dispersions containing carboxylic and/or resin acids for de-inking printed waste paper |
| WO1991005905A1 (en) * | 1989-10-19 | 1991-05-02 | Chemische Fabrik Grünau Gmbh | Aqueous dispersions containing alkaline earth soaps and/or alkaline earth resin soaps for de-inking printed waste paper |
| TR25424A (en) * | 1989-10-19 | 1993-03-01 | Du Pont | REMOVING THE ORIGIN FROM THE PRINTED PAPER-OPTICALLY REMOVING THE ORIGIN FROM THE PAPERS- NEMAHSUS, HYDRAULIC, CARBONIC ACIDS OR RECINE RECINE WHAT RECIPE, AQUATIC, CARBONIC ACID. DISPERSIONS WHICH LOSE ACIDS |
| AU638069B2 (en) * | 1989-10-19 | 1993-06-17 | Chemische Fabrik Grunau Gmbh | Aqueous dispersions containing carboxylic and/or resin acids for de-inking printed waste paper |
| EP0559777A4 (en) * | 1990-11-29 | 1994-08-17 | Petroferm Inc | A process and composition for cleaning contaminants with terpene and monobasic ester |
| EP0559777A1 (en) * | 1990-11-29 | 1993-09-15 | Petroferm Inc. | A process and composition for cleaning contaminants with terpene and monobasic ester |
| WO1994010274A1 (en) * | 1992-10-26 | 1994-05-11 | Henkel Kommanditgesellschaft Auf Aktien | Liquid detergent |
| GB2353288A (en) * | 1999-06-23 | 2001-02-21 | Reckitt Benckiser Inc | Spot cleaning compositions useful for cleaning garments and textiles |
| WO2003066797A1 (en) * | 2002-02-07 | 2003-08-14 | Henkel Kommanditgesellschaft Auf Aktien | Cleaning paste |
| WO2016202572A1 (en) | 2015-06-19 | 2016-12-22 | Unilever N.V. | Laundry pretreatment composition |
| CN107787356A (en) * | 2015-06-19 | 2018-03-09 | 荷兰联合利华有限公司 | Laundry pretreatment compositions |
| CN107787356B (en) * | 2015-06-19 | 2020-10-16 | 荷兰联合利华有限公司 | Laundry pretreatment compositions |
| WO2017198419A1 (en) | 2016-05-16 | 2017-11-23 | Unilever N.V. | Pre-treatment composition for fabric stains |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0256354B1 (en) | 1991-09-11 |
| DE3772899D1 (en) | 1991-10-17 |
| DE3626224A1 (en) | 1988-02-04 |
| ES2024460B3 (en) | 1992-03-01 |
| JPS6341599A (en) | 1988-02-22 |
| ATE67241T1 (en) | 1991-09-15 |
| US4877556A (en) | 1989-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0256354B1 (en) | Cleaning agent | |
| DE69631549T3 (en) | CLEANING SOUR CLEANERS FOR HARD SURFACES | |
| DE2511854C3 (en) | Aerosol detergents | |
| DE60211552T2 (en) | LIQUID DISHWASHER CONTAINING HYDROGEN PEROXIDE | |
| EP0633927B1 (en) | Detergents for hard surfaces | |
| DE3707409A1 (en) | METHOD FOR REMOVING TEXTILES | |
| EP0521899A1 (en) | Liquid hand-cleansing agent | |
| DE2701727B2 (en) | laundry detergent | |
| DE2922345A1 (en) | LIQUID DETERGENT MIXTURE | |
| EP0197434A2 (en) | Rinsing agents for use in mechanical dish washing | |
| EP0026422B1 (en) | A spray cleaning agent suited for the treatment of textiles | |
| EP0288858A1 (en) | Laundry prespotting agent for oil and fatty greases | |
| DE2642398B2 (en) | Dry cleaning compositions | |
| DE102012200673A1 (en) | Washing, cleaning or pretreatment agent with increased cleaning power | |
| DE102012209827A1 (en) | Washing, cleaning or pretreatment agent with increased cleaning power II | |
| WO1991009926A1 (en) | Liquid cleaning material for hard surfaces | |
| WO2000039270A1 (en) | Aqueous multi-phase cleaning agent | |
| DE2918255A1 (en) | LIQUID DETERGENT COMPOUND | |
| DE60123830T2 (en) | ANTIMICROBIAL WIPES | |
| WO2007036497A1 (en) | Detergents containing short-chain alcohol ethoxylates and solvents | |
| DE1792066A1 (en) | Low-foaming stain treatment agent for textiles | |
| DE102012202043A1 (en) | Washing or cleaning agent with cellulose or a cellulose derivative | |
| DE2323246A1 (en) | LOW-FOAMING DETERGENT AND CLEANING AGENTS | |
| DE102013210271A1 (en) | Washing, cleaning or pretreatment agent with increased cleaning power III | |
| AT256289B (en) | Detergents for glass surfaces |
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 DE ES FR GB IT LI NL SE |
|
| 17P | Request for examination filed |
Effective date: 19880718 |
|
| 17Q | First examination report despatched |
Effective date: 19890616 |
|
| RBV | Designated contracting states (corrected) |
Designated state(s): AT BE CH DE ES FR GB IT LI NL |
|
| 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 DE ES FR GB IT LI NL |
|
| REF | Corresponds to: |
Ref document number: 67241 Country of ref document: AT Date of ref document: 19910915 Kind code of ref document: T |
|
| ET | Fr: translation filed | ||
| REF | Corresponds to: |
Ref document number: 3772899 Country of ref document: DE Date of ref document: 19911017 |
|
| ITF | It: translation for a ep patent filed |
Owner name: STUDIO JAUMANN |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) | ||
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2024460 Country of ref document: ES Kind code of ref document: B3 |
|
| 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 |
|
| 26N | No opposition filed | ||
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19930713 Year of fee payment: 7 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19940724 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19940724 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20010711 Year of fee payment: 15 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20010730 Year of fee payment: 15 Ref country code: CH Payment date: 20010730 Year of fee payment: 15 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20010918 Year of fee payment: 15 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020724 |
|
| 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: 20020731 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020731 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020731 |
|
| BERE | Be: lapsed |
Owner name: *HENKEL K.G.A.A. Effective date: 20020731 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030201 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20030201 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20060719 Year of fee payment: 20 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20060720 Year of fee payment: 20 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20060731 Year of fee payment: 20 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20060825 Year of fee payment: 20 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20070725 |
|
| 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 EXPIRATION OF PROTECTION Effective date: 20070725 |