EP1075506B1 - Bleaching and disinfecting agents - Google Patents

Bleaching and disinfecting agents Download PDF

Info

Publication number
EP1075506B1
EP1075506B1 EP99923494A EP99923494A EP1075506B1 EP 1075506 B1 EP1075506 B1 EP 1075506B1 EP 99923494 A EP99923494 A EP 99923494A EP 99923494 A EP99923494 A EP 99923494A EP 1075506 B1 EP1075506 B1 EP 1075506B1
Authority
EP
European Patent Office
Prior art keywords
weight
alkali metal
alkyl ether
formulation according
carbon atoms
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.)
Revoked
Application number
EP99923494A
Other languages
German (de)
French (fr)
Other versions
EP1075506A1 (en
Inventor
Jaume Josa
Clement K. Choy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=22187088&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1075506(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1075506A1 publication Critical patent/EP1075506A1/en
Application granted granted Critical
Publication of EP1075506B1 publication Critical patent/EP1075506B1/en
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions

Definitions

  • the invention relates to new aqueous bleaches and disinfectants containing alkali metal hypochlorites, Surfactants, electrolyte salts and tetrahydromyrcenol in defined proportions.
  • EP-A 0079102, EP-A 0137551 and EP-A 0447261 disclose the use of amine oxides with soap or sarcosinate and other anionic surfactants, for example alkyl sulfates, alkyl ether sulfates, secondary alkane sulfonates or alkylbenzenesulfonates, as thickening components.
  • EP-A 0156438 reports on the use of alkylarylsulfonates as thickeners in aqueous bleaches which contain certain stilbene dyes as optical brighteners.
  • ES-A 8801389 Henkel Ibérica
  • aqueous hypochlorite solutions which, as surfactant components, contain predominantly alkyl ether sulfates and also small amounts of amine oxides.
  • Aqueous bleaching agent compositions containing sodium hypochlorite and anionic surfactants are also known from EP-A1 0447261.
  • the hypochlorite concentration of these agents is 0.1 to 8 and preferably 0.5 to 5% by weight of active chlorine.
  • European patent application EP-A-622451 describes perfumed hypochlorite bleaching agents, tetrahydromyrcenol being mentioned as a bleach-stable perfume. It is not disclosed that this increases the viscosity of agents which contain alkyl ether sulfates or their mixtures with amine oxides.
  • the European patent application EP-A-129980 describes hypochlorite-containing bleaching agents with quaternary alkoxysilanes and amine oxides, the viscosity of which can be increased by adding secondary and tertiary alcohols. This document also contains no indication that tetrahydromyrcenol could increase the viscosity of agents with other surfactant compositions.
  • the object of the invention was thus to provide new aqueous bleaching and disinfecting agents which, with a low active chlorine content, are characterized by a sufficiently high and stable viscosity. Finally, an additional task was to develop thickening agents for hypochlorite bleaching agents, which can take on additional tasks in the formulations.
  • Alkali metal hypochlorites are to be understood as meaning lithium, potassium and, in particular, sodium hypochlorite.
  • the hypochlorites can preferably be used in amounts of 2 to 4% by weight, based on the agent - be used.
  • Alkyl ether sulfates are known anionic surfactants which are obtained by sulfating nonionic surfactants of the alkyl polyglycol ether type and subsequent neutralization.
  • the alkyl ether sulfates in the context of the agents according to the invention follow the formula (I), R 1 O- (CH 2 CH 2 O) n SO 3 X in which R 1 is an alkyl radical having 12 to 18 carbon atoms, n is numbers 2 to 5 and X is sodium or potassium.
  • Typical examples are the sodium salts of sulfates of the C 12/14 coconut alcohol-2, 2,3- and -3-EO adduct.
  • the alkyl ether sulfates can have a conventional or narrow homolog distribution.
  • the alkyl ether sulfates are preferably used in amounts of 2 to 4% by weight, based on the agent.
  • Amine oxides are also known substances that are occasionally classified as cationic, but usually classified as nonionic surfactants. They are prepared from tertiary fatty amines, which usually have either one long and two short or two long and one short alkyl radical, and they are oxidized in the presence of hydrogen peroxide.
  • the amine oxides which are suitable for the purposes of the invention follow the formula (II), in which R 2 represents a linear or branched alkyl radical having 12 to 18 carbon atoms and R 3 and R 4 independently of one another represent R 2 or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms.
  • amine oxides of the formula (II) in which R 2 and R 3 are C 12/14 or C 12/18 coconut alkyl radicals and R 4 is a methyl or a hydroxyethyl radical.
  • R 2 and R 3 are C 12/14 or C 12/18 coconut alkyl radicals and R 4 is a methyl or a hydroxyethyl radical.
  • amine oxides of the formula (II) in which R 2 represents a C 12/14 or C 12/18 coconut alkyl radical and R 3 and R 4 represent a methyl or hydroxyethyl radical.
  • the amine oxides are preferably used in amounts of 1.5 to 3% by weight, based on the agent.
  • potassium hydroxide and especially sodium hydroxide come into consideration, which are preferably used in amounts of 1.5 to 2% by weight, based on the agent, and serve to adjust the pH of the agents to an optimal value of 12.5 to 14.
  • Suitable electrolyte salts are the alkali and alkaline earth carbonates, chlorides, Silicates, phosphates and phosphonates and their mixtures.
  • An additional advantage is its low price and light weight Incorporability.
  • the electrolyte salts are preferably used in amounts of 1 to 2% by weight on the means - used.
  • Tetrahydromyrcenol follows the formula (IV).
  • the terpene is obtained by hydrogenating myrcenol, which is a precursor to the production of geraniol and citronellol.
  • the preferred amounts used are 0.1 to 0.5% by weight, based on the agent.
  • the agents according to the invention can contain fatty acid salts of the formula (III) as further constituents, R 5 CO-OX in which R 5 CO is an acyl radical having 12 to 22 carbon atoms and X is an alkali metal.
  • R 5 CO is an acyl radical having 12 to 22 carbon atoms and X is an alkali metal.
  • Typical examples are the sodium and / or potassium salts of lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, eleostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid, as well as their technical mixtures the pressure splitting of technical fats and oils arise.
  • Salts of technical coconut or tallow fatty acids are preferably used. Since the formulations according to the invention are made strongly alkaline, the fatty acids which are neutralized in situ when they are added to the mixture can also be used instead of the salts.
  • the fatty acid salts are preferably used in amounts of 0.5 to 2% by weight, based on the agent.
  • the agents according to the invention have a viscosity above 500 mPas - measured at 20 ° C in a Brookfield viscometer - are storage-stable, against the consumption of chlorine stable and are characterized by excellent dispersibility for dye pigments the end.
  • the invention also relates to the use of tetrahydromyrcenol As a chlorine-stable fragrance and thickener in hypochlorite-containing bleaches and disinfectants.
  • Auxiliaries and additives that the preparations can also contain include, for example other chlorine-stable surfactants or hydrotropes such as alkyl sulfates, alkyl sulfonates, alkylbenzenesulfonates, Xylene sulfonates, sarcosinates, taurides, isethionates, sulfosuccinates, betaines, sugar esters, Fatty alcohol polyglycol ethers and alkyl oligoglycosides.
  • the sum of these makes up additional surfactants from a maximum of 10 wt .-% of the total amount of surfactants in the formulation.
  • alkyl sulfates in amounts of 0.5 to 3% by weight is particularly preferred.
  • the agents can contain other active chlorine-stable fragrances, optical brighteners, dyes and Pigments in total amounts of 0.01 to 0.5 wt .-% - based on the agent - contain.
  • active chlorine include, for example, monocyclic and bicyclic ones Monoterpene alcohols and their esters with acetic or propionic acid (e.g. isoborneal, dihydroterpene oil, Isobornyl acetate, dihydroterpenyl acetate).
  • the optical brighteners can be, for example act the potash salt of 4,4'-bis- (1,2,3-triazolyl) - (2 -) - stilbine-2,2-sulfonic acid, which is sold under the trademark Phorwite® BHC 766 is sold.
  • Color pigments include green chlorophthalocyanines (Pigmosol® Green, Hostaphine® Green) or yellow Solar Yellow® BG 300 (Sandoz) are possible.
  • Sequestering agents can also be polyacrylates, amine oxide phosphonic acids and lignosulfonates and their mixtures in amounts of 0.1 to 2 and preferably 0.5 to 1 wt .-% - based on the Means - be included.
  • the agents according to the invention are produced by stirring. Possibly the product obtained can be used to separate foreign bodies and / or agglomerates decanted or filtered.
  • the viscosity was determined at 20 ° C. using a Brookfield viscometer (model RVT, spindle # 1 or # 2, 200 rpm). To determine the chlorine stability, the test mixtures were stored in a colorless plastic bottle under the influence of daylight and the active chlorine content was determined.
  • the formulations 1 to 7 are according to the invention, the formulations V1 to V3 are used for comparison.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to new bleaching and disinfecting agents which contain, in relation to the agents, (a) between 1 and 6 weight % alkali metal hypochlorites, (b) between 0.5 and 5 weight % alkylether sulfates and/or amino oxides, (c) between 0.5 and 2 weight % alkali metal hydroxides, (d) between 0.5 and 3 weight % electrolyte salts, (e) between 0.01 and 1 weight % tetrahydromyrcenol, and (f) between 0 and 4 weight % fatty acid salts, provided that the above quantities are completed to 100 weight % by the addition of water and possibly other aids and additives. These preparations have a sufficiently high viscosity as well as a very good storage stability, dispersing power for colour pigments and stability in chlorine.

Description

Gebiet der ErfindungField of invention

Die Erfindung betrifft neue wäßrige Bleich- und Desinfektionsmittel, enthaltend Alkalimetallhypochlorite, Tenside, Elektrolytsalze und Tetrahydromyrcenol in definierten Mengenverhältnissen.The invention relates to new aqueous bleaches and disinfectants containing alkali metal hypochlorites, Surfactants, electrolyte salts and tetrahydromyrcenol in defined proportions.

Stand der TechnikState of the art

In der Vergangenheit haben sich in den Bereichen Hygiene und Desinfektion, aber auch in der Textilbehandlung, solche Bleichmittel auf der Grundlage von Alkalimetallhypochloriten bewährt, die über eine bemerkenswerte Viskosität verfügen und sich daher sowohl für die Behandlung horizontaler als auch geneigter und vor allem vertikaler Oberflächen eignen. Die Viskosität dieser Mittel bewirkt, daß die Kontaktzeit zwischen diesen und den zu behandelnden Oberflächen wesentlich größer ist als bei handelsüblichen Flüssigprodukten, die rasch von der Oberfläche abfließen.In the past, hygiene and disinfection, but also in the Textile treatment, such bleaching agents based on alkali metal hypochlorites that have proven successful have a remarkable viscosity and are therefore suitable for both horizontal treatment as well as inclined and especially vertical surfaces. The viscosity of these agents causes the contact time between these and the surfaces to be treated is much longer than with commercially available liquid products that drain quickly from the surface.

In der Vergangenheit hat es nicht an Versuchen gemangelt, derartig viskose Bleich- und Desinfektionsmittel bereitzustellen. So wurde beispielsweise gefunden, daß bestimmte Tenside oder Tensidgemische eine verdickende Wirkung auf wäßrige Hypochforitlösungen ausüben. In der EP-A 0274885 (ICI) wird beispielsweise der Einsatz von Mischungen linearer und verzweigter Aminoxide empfohlen. Gemäß der Lehre der EP-A 0145084 (Unilever) können für diesen Zweck auch Mischungen von Aminoxiden mit Seifen, Sarkosinaten, Tauriden oder Zuckerestem eingesetzt werden. Aus den Schriften EP-A 0079102, EP-A 0137551 und EP-A 0447261 (Unilever) ist der Einsatz von Aminoxiden mit Seife oder Sarkosinat und weiteren anionischen Tensiden, beispielsweise Alkylsulfaten, Alkylethersulfaten, sekundären Alkansulfonaten oder Alkylbenzolsulfonaten als verdickende Komponente bekannt. Über die Verwendung von Alkylarylsulfonaten als Verdickungsmitteln in wäßrigen Bleichmitteln, die bestimmte Stilbenfarbstoffe als optische Aufheller enthalten, wird in der EP-A 0156438 berichtet. Gegenstand der ES-A 8801389 (Henkel Ibérica) sind Bleichmittel auf Basis von wäßrigen Hypochloritlösungen, die als Tensidkomponente überwiegend Alkylethersulfate und daneben kleine Anteile an Aminoxiden enthalten. Aus der EP-A1 0447261 sind weiterhin wäßrige Bleichmittelzusammensetzungen mit einem Gehalt an Natriumhypochlorit und anionischen Tensiden bekannt. Die Hypochloritkonzentration dieser Mittel liegt jedoch bei 0,1 bis 8 und vorzugsweise 0,5 bis 5 Gew.-% Aktivchlor. Im Deutschen Patent DE-C1 4333100 hat die Anmelderin bereits stabile und ausreichend viskose wäßrige Bleich- und Reinigungsmittel auf Basis von Hypochloriten, Fettalkoholethersulfaten und Aminoxiden vorgeschlagen, die als zwingende Komponente Aminoxidphosphonsäuren enthalten. Diese tragen zwar entscheidend zur Verdickung der Mittel bei, können jedoch den Aktivchlorgehalt nicht stabilisieren. Aus der Schrift US 4,588,514 (Lever) sind schließlich alkalische Hypochloritbleichmittel bekannt, die zur Viskositätseinstellung Aminoxide sowie geringe Mengen an Alkyfethersulfaten und Seifen enthalten. Die Zubereitungen weisen jedoch einen hohen Hypochloritanteil von 7 Gew.-% auf. Bei Übertragung der Lehre auf modeme Bleichmittel mit niedrigem Aktivchloranteil werden weder ausreichend verdickte noch lagerstabile Produkte erhalten. Des weiteren sei auf die intemationale Patentanmeldung WO 93/08247 (Clorox) verwiesen, die alkalische Reiniger mit einem Gehalt an Alkylethersulfaten und Terpenderivaten betrifft sowie auf die europäische Offenlegungsschrift EP-A2 0651051 (Clorox), die gelförmige Hypochloritzubereitungen offenbart, welche ein temäres Verdickungsmittelsystem bestehend aus Seife, Aminoxid oder Betain und Terpenderivaten enthalten. Die europäische Patentanmeldung EP-A-622451 beschreibt parfümierte Hypochlorit-Bleichmittel, wobei Tetrahydromyrcenol als bleichstabiles Parfüm genannt wird. Daß dieses die Viskosität von Mitteln erhöht, die Alkylethersulfate oder deren Mischungen mit Aminoxiden enthalten, ist nicht offenbart. Die europäische Patentanmeldung EP-A-129980 beschreibt hypochlorithaltige Bleichmittel mit quaternären Alkoxysilanen und Aminoxiden, deren Viskosität durch die Zugabe von sekundären und tertiären Alkoholen erhöht werden kann. Auch diese Schrift enthält keinen Hinweis darauf, daß Tetrahydromyrcenol die Viskosität von Mitteln mit anderen Tensidzusammensetzungen erhöhen könnte.
Die Aufgabe der Erfindung hat somit darin bestanden, neue wäßrige Bleich- und Desinfektionsmittel zur Verfügung zu stellen, die sich bei niedrigem Aktivchlorgehalt durch eine ausreichend hohe und stabile Viskosität auszeichnen. Eine zusätzliche Aufgabe hat schließlich darin bestanden, Verdickungsmittel für Hypochloritbleichmittel zu entwickeln, die in den Rezepturen noch weitere Aufgaben übernehmen können.In the past there has been no shortage of attempts to provide such viscous bleaches and disinfectants. For example, it has been found that certain surfactants or surfactant mixtures have a thickening effect on aqueous hypochlorite solutions. In EP-A 0274885 (ICI), for example, the use of mixtures of linear and branched amine oxides is recommended. According to the teaching of EP-A 0145084 (Unilever), mixtures of amine oxides with soaps, sarcosinates, taurides or sugar esters can also be used for this purpose. The documents EP-A 0079102, EP-A 0137551 and EP-A 0447261 (Unilever) disclose the use of amine oxides with soap or sarcosinate and other anionic surfactants, for example alkyl sulfates, alkyl ether sulfates, secondary alkane sulfonates or alkylbenzenesulfonates, as thickening components. EP-A 0156438 reports on the use of alkylarylsulfonates as thickeners in aqueous bleaches which contain certain stilbene dyes as optical brighteners. The subject of ES-A 8801389 (Henkel Ibérica) is bleaching agents based on aqueous hypochlorite solutions which, as surfactant components, contain predominantly alkyl ether sulfates and also small amounts of amine oxides. Aqueous bleaching agent compositions containing sodium hypochlorite and anionic surfactants are also known from EP-A1 0447261. However, the hypochlorite concentration of these agents is 0.1 to 8 and preferably 0.5 to 5% by weight of active chlorine. In the German patent DE-C1 4333100, the applicant has already proposed stable and sufficiently viscous aqueous bleaching and cleaning agents based on hypochlorites, fatty alcohol ether sulfates and amine oxides, which contain amine oxide phosphonic acids as a mandatory component. Although these contribute decisively to thickening the agent, they cannot stabilize the active chlorine content. Finally, from US Pat. No. 4,588,514 (Lever), alkaline hypochlorite bleaches are known which contain amine oxides and small amounts of alkyl ether sulfates and soaps to adjust the viscosity. However, the preparations have a high hypochlorite content of 7% by weight. If the teaching is applied to modern bleaching agents with a low active chlorine content, neither sufficiently thickened nor storage-stable products are obtained. Furthermore, reference is made to the international patent application WO 93/08247 (Clorox), which relates to alkaline cleaners with a content of alkyl ether sulfates and terpene derivatives, and to the European patent application EP-A2 0651051 (Clorox), which discloses gel-like hypochlorite preparations which consist of a system of ternary thickeners from soap, amine oxide or betaine and terpene derivatives. European patent application EP-A-622451 describes perfumed hypochlorite bleaching agents, tetrahydromyrcenol being mentioned as a bleach-stable perfume. It is not disclosed that this increases the viscosity of agents which contain alkyl ether sulfates or their mixtures with amine oxides. The European patent application EP-A-129980 describes hypochlorite-containing bleaching agents with quaternary alkoxysilanes and amine oxides, the viscosity of which can be increased by adding secondary and tertiary alcohols. This document also contains no indication that tetrahydromyrcenol could increase the viscosity of agents with other surfactant compositions.
The object of the invention was thus to provide new aqueous bleaching and disinfecting agents which, with a low active chlorine content, are characterized by a sufficiently high and stable viscosity. Finally, an additional task was to develop thickening agents for hypochlorite bleaching agents, which can take on additional tasks in the formulations.

Beschreibung der ErfindungDescription of the invention

Gegenstand der Erfindung sind Bleich- und Desinfektionsmittel, enthaltend - bezogen auf die Mittel -

  • (a) 1 bis 6 Gew.-% Alkalimetallhypochlorite,
  • (b) 0,5 bis 5 Gew.-% unten näher definierte Alkylethersulfate oder Alkylethersulfate und Aminoxide,
  • (c) 0,5 bis 2 Gew.-% Alkalimetallhydroxide,
  • (d) 0,5 bis 3 Gew.-% Elektrolytsalze,
  • (e) 0,01 bis 1 Gew.-% Tetrahydromyrcenol und
  • (f) 0 bis 4 Gew.-% Fettsäuresalze,
    • mit der Maßgabe, daß sich die Mengenangaben mit Wasser sowie gegebenenfalls weiteren Hilfs- und Zusatzstoffen zu 100 Gew.-% ergänzen.
    Überraschenderweise wurde gefunden, daß Bleich- und Desinfektionsmittel der angegebenen Zusammensetzung nicht nur chlorstabil sind, sondern durch den Zusatz von Tetrahydromyrcenol auch eine ausreichend hohe und konstante Viskosität erhalten. Die Erfindung schließt dabei die Erkenntnis ein, daß das Tetrahydromyrcenol nicht nur einen verdickenden Effekt bewirkt, sondern selbst auch als aktivchlorstabiler Duftstoff wirkt, was zu einer Vereinfachung der Rezeptur und damit zu einem wirtschaftlichen Vorteil führen kann, da andere, in der Regel deutlich teurere Parfümstoffe nicht noch zusätzlich eingearbeitet werden müssen.The invention relates to bleaching agents and disinfectants containing - based on the agent -
  • (a) 1 to 6% by weight alkali metal hypochlorites,
  • (b) 0.5 to 5% by weight of alkyl ether sulfates or alkyl ether sulfates and amine oxides defined in more detail below,
  • (c) 0.5 to 2% by weight alkali metal hydroxides,
  • (d) 0.5 to 3% by weight of electrolyte salts,
  • (e) 0.01 to 1 weight percent tetrahydromyrcenol and
  • (f) 0 to 4% by weight of fatty acid salts,
    •  with the proviso that the quantitative data with water and optionally other auxiliaries and additives add up to 100% by weight.
    Surprisingly, it has been found that bleaching agents and disinfectants of the specified composition are not only stable to chlorine, but also obtain a sufficiently high and constant viscosity through the addition of tetrahydromyrcenol. The invention includes the knowledge that the tetrahydromyrcenol not only has a thickening effect, but also acts as an active chlorine-stable fragrance, which can lead to a simplification of the recipe and thus to an economic advantage, since other, usually much more expensive perfumes do not have to be additionally incorporated.

    AlkalimetallhypochloriteAlkali metal hypochlorites

    Unter Alkalimetallhypochloriten sind Lithium-, Kalium- und insbesondere Natriumhypochlorit zu verstehen. Die Hypochlorite können vorzugsweise in Mengen von 2 bis 4 Gew.-% - bezogen auf die Mittel - eingesetzt werden.Alkali metal hypochlorites are to be understood as meaning lithium, potassium and, in particular, sodium hypochlorite. The hypochlorites can preferably be used in amounts of 2 to 4% by weight, based on the agent - be used.

    AlkylethersulfateAlkyl ether sulfates

    Alkylethersulfate stellen bekannte anionische Tenside dar, die durch Sulfatierung von nichtionischen Tensiden vom Typ der Alkylpolyglycolether und nachfolgende Neutralisation erhalten werden. Die im Sinne der erfindungsgemäßen Mittel in Betracht kommenden Alkylethersulfate folgen der Formel (I), R 1 O-(CH 2 CH 2 O) n SO 3 X in der R1 für einen Alkylrest mit 12 bis 18 Kohlenstoffatomen, n für Zahlen 2 bis 5 und X für Natrium oder Kalium steht. Typische Beispiele sind die Natriumsalze von Sulfaten des C12/14-Kokosalkohol-2, - 2,3- und -3-EO-Adduktes. Die Alkylethersulfate können eine konventionelle oder eingeengte Homologenverteilung aufweisen. Vorzugsweise werden die Alkylethersulfate in Mengen von 2 bis 4 Gew.-% - bezogen auf die Mittel - eingesetzt.Alkyl ether sulfates are known anionic surfactants which are obtained by sulfating nonionic surfactants of the alkyl polyglycol ether type and subsequent neutralization. The alkyl ether sulfates in the context of the agents according to the invention follow the formula (I), R 1 O- (CH 2 CH 2 O) n SO 3 X in which R 1 is an alkyl radical having 12 to 18 carbon atoms, n is numbers 2 to 5 and X is sodium or potassium. Typical examples are the sodium salts of sulfates of the C 12/14 coconut alcohol-2, 2,3- and -3-EO adduct. The alkyl ether sulfates can have a conventional or narrow homolog distribution. The alkyl ether sulfates are preferably used in amounts of 2 to 4% by weight, based on the agent.

    AminoxideAmine oxides

    Auch Aminoxide stellen bekannte Stoffe dar, die gelegentlich den kationischen, in der Regel jedoch den nichtionischen Tensiden zugerechnet werden. Zu ihrer Herstellung geht man von tertiären Fettaminen aus, die üblicherweise entweder einen langen und zwei kurze oder zwei lange und einen kurzen Alkylrest aufweisen, und oxidiert sie in Gegenwart von Wasserstoffperoxid. Die im Sinne der Erfindung in Betracht kommenden Aminoxide folgen der Formel (II),

    Figure 00040001
    in der R2 für einen linearen oder verzweigten Alkylrest mit 12 bis 18 Kohlenstoffatomen sowie R3 und R4 unabhängig voneinander für R2 oder einen gegebenenfalls hydroxysubstituierten Alkylrest mit 1 bis 4 Kohlenstoffatomen stehen. Vorzugsweise werden Aminoxide der Formel (II) eingesetzt, in der R2 und R3 für C12/14- bzw. C12/18-Kokosalkylreste stehen und R4 einen Methyl- oder einen Hydroxyethylrest bedeutet. Ebenfalls bevorzugt sind Aminoxide der Formel (II), in denen R2 für einen C12/14- bzw. C12/18-Kokosalkylrest steht und R3 und R4 die Bedeutung eines Methyl- oder Hydroxyethylrestes haben. Vorzugsweise werden die Aminoxide in Mengen von 1,5 bis 3 Gew.-% - bezogen auf die Mittel - eingesetzt.Amine oxides are also known substances that are occasionally classified as cationic, but usually classified as nonionic surfactants. They are prepared from tertiary fatty amines, which usually have either one long and two short or two long and one short alkyl radical, and they are oxidized in the presence of hydrogen peroxide. The amine oxides which are suitable for the purposes of the invention follow the formula (II),
    Figure 00040001
    in which R 2 represents a linear or branched alkyl radical having 12 to 18 carbon atoms and R 3 and R 4 independently of one another represent R 2 or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms. Preference is given to using amine oxides of the formula (II) in which R 2 and R 3 are C 12/14 or C 12/18 coconut alkyl radicals and R 4 is a methyl or a hydroxyethyl radical. Also preferred are amine oxides of the formula (II) in which R 2 represents a C 12/14 or C 12/18 coconut alkyl radical and R 3 and R 4 represent a methyl or hydroxyethyl radical. The amine oxides are preferably used in amounts of 1.5 to 3% by weight, based on the agent.

    AlkalimetallhydroxideAlkali metal hydroxides

    Als Alkalimetallhydroxide kommen Kaliumhydroxid und insbesondere Natriumhydroxid in Betracht, welche vorzugsweise in Mengen von 1,5 bis 2 Gew.-% - bezogen auf die Mittel - eingesetzt werden und dazu dienen, den pH-Wert der Mittel auf einen optimalen Wert von 12,5 bis 14 einzustellen.As alkali metal hydroxides, potassium hydroxide and especially sodium hydroxide come into consideration, which are preferably used in amounts of 1.5 to 2% by weight, based on the agent, and serve to adjust the pH of the agents to an optimal value of 12.5 to 14.

    ElektrolytsalzeElectrolyte salts

    Typische Beispiele für geeignete Elektrolytsalze sind die Alkali- und Erdalkalicarbonate, -chloride, - silicate, -phosphate und -phosphonate sowie deren Gemische. Vorzugsweise werden Natrium- oder Kaliumcarbonat bzw. -chlorid eingesetzt, die nicht nur die gewünschten Pufferung der Zubereitung bewirken, sondern zusätzlich auch noch eine Sequestrierung von Metall-, insbesondere von Schwermetallionen leisten. Ein zusätzlicher Vorteil besteht weiterhin in ihrem niedrigen Preis und der leichten Einarbeitbarkeit. Vorzugsweise werden die Elektrolytsalze in Mengen von 1 bis 2 Gew.-% - bezogen auf die Mittel - eingesetzt.Typical examples of suitable electrolyte salts are the alkali and alkaline earth carbonates, chlorides, Silicates, phosphates and phosphonates and their mixtures. Preferably sodium or Potassium carbonate or chloride used, which not only provides the desired buffering of the preparation cause, but also a sequestration of metal, especially heavy metal ions Afford. An additional advantage is its low price and light weight Incorporability. The electrolyte salts are preferably used in amounts of 1 to 2% by weight on the means - used.

    TetrahydromyrcenolTetrahydromyrcenol

    Tetrahydromyrcenol folgt der Formel (IV). Das Terpen wird durch Hydrierung von Myrcenol gewonnen, welches eine Vorstufe zur Herstellung von Geraniol und Citronellol darstellt.

    Figure 00050001
    Tetrahydromyrcenol follows the formula (IV). The terpene is obtained by hydrogenating myrcenol, which is a precursor to the production of geraniol and citronellol.
    Figure 00050001

    Die bevorzugten Einsatzmengen liegen bei 0,1 bis 0,5 Gew.-% - bezogen auf die Mittel.The preferred amounts used are 0.1 to 0.5% by weight, based on the agent.

    FettsäuresalzeFatty acid salts

    Als weitere Bestandteile können die erfindungsgemäßen Mittel Fettsäuresalze der Formel (III) enthalten, R 5 CO-OX in der R5CO für einen Acylrest mit 12 bis 22 Kohlenstoffatomen und X für ein Alkalimetall steht. Typische Beispiele sind die Natrium- und/oder Kaliumsalze der Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, wie sie bei der Druckspaltung technischer Fette und Öle anfallen. Vorzugsweise werden Salze technischer Kokos- oder Talgfettsäuren eingesetzt. Da die erfindungsgemäßen Rezepturen stark alkalisch eingestellt sind, können anstelle der Salze auch die Fettsäuren eingesetzt werden, die beim Eintragen in die Mischung in situ neutralisiert werden. Vorzugsweise werden die Fettsäuresalze in Mengen von 0,5 bis 2 Gew.-% - bezogen auf die Mittel - eingesetzt.The agents according to the invention can contain fatty acid salts of the formula (III) as further constituents, R 5 CO-OX in which R 5 CO is an acyl radical having 12 to 22 carbon atoms and X is an alkali metal. Typical examples are the sodium and / or potassium salts of lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, eleostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid, as well as their technical mixtures the pressure splitting of technical fats and oils arise. Salts of technical coconut or tallow fatty acids are preferably used. Since the formulations according to the invention are made strongly alkaline, the fatty acids which are neutralized in situ when they are added to the mixture can also be used instead of the salts. The fatty acid salts are preferably used in amounts of 0.5 to 2% by weight, based on the agent.

    Gewerbliche AnwendbarkeitCommercial applicability

    Die erfindungsgemäßen Mittel weisen unmittelbar nach der Herstellung eine Viskosität oberhalb von 500 mPas - gemessen bei 20°C in einem Brookfield-Viskosimeter - auf, sind lagerstabil, gegen Chlorzehrung beständig und zeichnen sich durch ein ausgezeichnetes Dispergiervermögen für Farbstoffpigmente aus. Ein weiterer Gegenstand der Erfindung betrifft die Verwendung von Tetrahydromyrcenol als chlorstabiler Duftstoff und Verdickungsmittel in hypochlorithaltigen Bleich- und Desinfektionsmitteln.Immediately after production, the agents according to the invention have a viscosity above 500 mPas - measured at 20 ° C in a Brookfield viscometer - are storage-stable, against the consumption of chlorine stable and are characterized by excellent dispersibility for dye pigments the end. The invention also relates to the use of tetrahydromyrcenol As a chlorine-stable fragrance and thickener in hypochlorite-containing bleaches and disinfectants.

    Als Hilfs- und Zusatzstoffe, die die Zubereitungen weiterhin enthalten können, kommen beispielsweise weitere chlorstabile Tenside bzw. Hydrotrope in Betracht, wie etwa Alkylsulfate, Alkylsulfonate, Alkylbenzolsulfonate, Xylolsulfonate, Sarkosinate, Tauride, Isethionate, Sulfosuccinate, Betaine, Zuckerester, Fettalkoholpolyglycolether und Alkyloligoglykoside. Vorzugsweise macht die Summe dieser zusätzlichen Tenside höchstens 10 Gew.-% der Gesamtmenge an Tensiden in der Rezeptur aus. Die Mitverwendung von Alkylsulfaten in Mengen von 0,5 bis 3 Gew.-% ist dabei besonders bevorzugt. Darüberhinaus können die Mittel weitere aktivchlorstabile Duftstoffe, optische Aufheller, Farbstoffe und Pigmente in Mengen von insgesamt 0,01 bis 0,5 Gew.-% - bezogen auf die Mittel - enthalten. Zu den als aktivchlorbeständig bekannten Duftstoffen zählen beispielsweise monocyclische und bicyclische Monoterpenalkohole sowie deren Ester mit Essig- oder Propionsäure (z.B. Isoborneal, Dihydroterpenöl, Isobornylacetat, Dihydroterpenylacetat). Bei den optischen Aufhellern kann es sich beispielsweise um das Kalisalz der 4,4'-bis-(1,2,3-Triazolyl)-(2-)-Stilbin-2,2-sulfonsäure handeln, das unter der Marke Phorwite® BHC 766 vertrieben wird. Als Farbpigmente kommen u.a. grüne Chlorophthalocyanine (Pigmosol® Green, Hostaphine® Green) oder gelbes Solar Yellow® BG 300 (Sandoz) in Frage. Als Sequestriermittel können des weiteren Polyacrylate, Aminoxidphosphonsäuren und Ligninsulfonate sowie deren Gemische in Mengen von 0,1 bis 2 und vorzugsweise 0,5 bis 1 Gew.-% - bezogen auf die Mittel - enthalten sein. Die Herstellung der erfindungsgemäßen Mittel erfolgt mittels Umrühren. Gegebenenfalls kann das erhaltene Produkt zur Abtrennung von Fremdkörpern und/oder Agglomeraten dekantiert oder filtriert werden. Auxiliaries and additives that the preparations can also contain include, for example other chlorine-stable surfactants or hydrotropes such as alkyl sulfates, alkyl sulfonates, alkylbenzenesulfonates, Xylene sulfonates, sarcosinates, taurides, isethionates, sulfosuccinates, betaines, sugar esters, Fatty alcohol polyglycol ethers and alkyl oligoglycosides. Preferably the sum of these makes up additional surfactants from a maximum of 10 wt .-% of the total amount of surfactants in the formulation. the The use of alkyl sulfates in amounts of 0.5 to 3% by weight is particularly preferred. In addition, the agents can contain other active chlorine-stable fragrances, optical brighteners, dyes and Pigments in total amounts of 0.01 to 0.5 wt .-% - based on the agent - contain. To the Fragrances known to be resistant to active chlorine include, for example, monocyclic and bicyclic ones Monoterpene alcohols and their esters with acetic or propionic acid (e.g. isoborneal, dihydroterpene oil, Isobornyl acetate, dihydroterpenyl acetate). The optical brighteners can be, for example act the potash salt of 4,4'-bis- (1,2,3-triazolyl) - (2 -) - stilbine-2,2-sulfonic acid, which is sold under the trademark Phorwite® BHC 766 is sold. Color pigments include green chlorophthalocyanines (Pigmosol® Green, Hostaphine® Green) or yellow Solar Yellow® BG 300 (Sandoz) are possible. as Sequestering agents can also be polyacrylates, amine oxide phosphonic acids and lignosulfonates and their mixtures in amounts of 0.1 to 2 and preferably 0.5 to 1 wt .-% - based on the Means - be included. The agents according to the invention are produced by stirring. Possibly the product obtained can be used to separate foreign bodies and / or agglomerates decanted or filtered.

    BeispieleExamples

    Die Viskosität wurde bei 20°C mit Hilfe eines Brookfield-Viskosimeters (Modell RVT, Spindel Nr.1 oder Nr.2, 200 Upm) bestimmt. Zur Bestimmung der Chlorstabilität wurden die Testmischungen unter dem Einfluß von Tageslicht in einer farblosen Kunststoffflasche gelagert und der Aktivchlorgehalt bestimmt. Die Rezepturen 1 bis 7 sind erfindungsgemäß, die Rezepturen V1 bis V3 dienen zum Vergleich. Die Ergebnisse sind in Tabelle 1 zusammengefaßt (Mengenangaben als Gew.-%) Viskosität, Lagerstabilität, Chlorzehrung und Reinigungsvermögen Komponenten 1 2 3 4 5 6 7 V1 V2 V3 Natriumhypochlorit 2,0 2,0 2,0 2,0 2,0 2,0 4,0 2,0 2,0 2,0 Kokosfettalkohol+2EO-sulfat-Natriumsalz 2,6 2,0 2,0 2,0 2,0 2,0 2,0 2,0 2,0 2,0 Dimethylkokosalkylaminoxid - - - - - - - - - - Natriumhydroxid 0,9 0,9 0,9 0,9 0,4 0,4 0,9 0,4 0,4 0,9 Natriumcarbonat 1,0 1,0 1,0 1,5 1,5 2,0 1,5 1,5 2,0 1,0 Natriumchlorid - - 0,5 - - - - - - - Tetrahydromyrcenol 0,05 0,1 0,1 0,1 0,1 0,1 0,1 - - - Laurinsäure-Natriumsalz - - - - - 0,1 - - - - Natriumsilicat - - - - - 0,5 - - - - Aminoxidphosphonsäure - - - 0,05 - - - - - - Polyacrylat - - - - 0,05 - - - - - Wasser ad 100 Viskosität [mPas] - nach 24 Stunden 250 620 590 585 520 610 600 15 25 25 - nach 2 Wochen 220 610 570 545 485 590 580 10 10 10 - nach 4 Wochen 190 580 550 510 415 550 550 10 10 10 Aktivchlorgehalt [%- rel ] - sofort 100 100 100 100 100 100 100 100 100 100 - nach 4 Wochen 81 83 85 85 85 86 85 79 78 76 The viscosity was determined at 20 ° C. using a Brookfield viscometer (model RVT, spindle # 1 or # 2, 200 rpm). To determine the chlorine stability, the test mixtures were stored in a colorless plastic bottle under the influence of daylight and the active chlorine content was determined. The formulations 1 to 7 are according to the invention, the formulations V1 to V3 are used for comparison. The results are summarized in Table 1 (quantitative data as% by weight) Viscosity, storage stability, chlorine consumption and cleaning power Components 1 2 3 4th 5 6th 7th V1 V2 V3 Sodium hypochlorite 2.0 2.0 2.0 2.0 2.0 2.0 4.0 2.0 2.0 2.0 Coconut fatty alcohol + 2EO sulfate sodium salt 2.6 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Dimethyl coconut alkyl amine oxide - - - - - - - - - - Sodium hydroxide 0.9 0.9 0.9 0.9 0.4 0.4 0.9 0.4 0.4 0.9 sodium 1.0 1.0 1.0 1.5 1.5 2.0 1.5 1.5 2.0 1.0 Sodium chloride - - 0.5 - - - - - - - Tetrahydromyrcenol 0.05 0.1 0.1 0.1 0.1 0.1 0.1 - - - Lauric acid sodium salt - - - - - 0.1 - - - - Sodium silicate - - - - - 0.5 - - - - Amine oxide phosphonic acid - - - 0.05 - - - - - - Polyacrylate - - - - 0.05 - - - - - water ad 100 Viscosity [mPas] - after 24 hours 250 620 590 585 520 610 600 15th 25th 25th - after 2 weeks 220 610 570 545 485 590 580 10 10 10 - after 4 weeks 190 580 550 510 415 550 550 10 10 10 Active chlorine content [% - rel ] - immediately 100 100 100 100 100 100 100 100 100 100 - after 4 weeks 81 83 85 85 85 86 85 79 78 76

    Claims (8)

    1. Bleaching and disinfectant formulation comprising - based on the formulation -
      (a) 1 to 6% by weight of alkali metal hypochlorites,
      (b) 0.5 to 5% by weight of alkyl ether sulphates or alkyl ether sulphates and amine oxides,
      where the alkyl ether sulphates correspond to the formula (I) R1O-(CH2CH2O)nSO3X in which R1 is an alkyl radical having 12 to 18 carbon atoms, n is 2 to 5 and X is sodium or potassium, and the amine oxides to the formula (II)
      Figure 00100001
      in which R2 is a linear or branched alkyl radical having 12 to 18 carbon atoms, and R3 and R4 are each independently R2 or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms,
      (c) 0.5 to 2% by weight of alkali metal hydroxides,
      (d) 0.5 to 3% by weight of electrolyte salts,
      (e) 0.01 to 1% by weight of tetrahydromyrcenol and
      (f) 0 to 4% by weight of fatty acid salts,
      with the proviso that the quantities mentioned above add up to 100% by weight with water and any other auxiliaries and additives present.
    2. Formulation according to Claim 1, characterized in that it comprises sodium hypochlorite.
    3. Formulation according to Claim 1 or 2, characterized in that it comprises sodium hydroxide.
    4. Formulation according to one of Claims 1 to 3, characterized in that it comprises electrolyte salts selected from the group consisting of alkali metal and/or alkaline earth metal carbonates, chlorides, silicates, phosphates and phosphonates.
    5. Formulation according to one of Claims 1 to 4, characterized in that it comprises fatty acid salts of the formula (III) R6CO-OX in which R6CO is an acyl radical having 12 to 22 carbon atoms and X is an alkali metal.
    6. Formulation according to one of Claims 1 to 5, characterized in that it comprises sequestering agents selected from the group consisting of polyacrylates, amine oxide phosphonic acids and lignin sulphonates.
    7. Formulation according to one of Claims 1 to 6, characterized in that, immediately after production, they have a viscosity above 500 mPas, as measured at 20°C in a Brookfield viscometer.
    8. The use of tetrahydromyrcenol as a chlorine-free fragrance and thickener in hypochlorite-containing bleaching and disinfectant formulations, comprising alkyl ether sulphates or alkyl ether sulphates and amine oxides.
    EP99923494A 1998-05-08 1999-04-29 Bleaching and disinfecting agents Revoked EP1075506B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    US8476798P 1998-05-08 1998-05-08
    US84767P 1998-05-08
    PCT/EP1999/002903 WO1999058635A1 (en) 1998-05-08 1999-04-29 Bleaching and disinfecting agents

    Publications (2)

    Publication Number Publication Date
    EP1075506A1 EP1075506A1 (en) 2001-02-14
    EP1075506B1 true EP1075506B1 (en) 2005-06-15

    Family

    ID=22187088

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP99923494A Revoked EP1075506B1 (en) 1998-05-08 1999-04-29 Bleaching and disinfecting agents

    Country Status (6)

    Country Link
    EP (1) EP1075506B1 (en)
    CN (1) CN1299405A (en)
    AT (1) ATE297978T1 (en)
    DE (1) DE59912187D1 (en)
    ES (1) ES2244196T3 (en)
    WO (1) WO1999058635A1 (en)

    Families Citing this family (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    CA2432642A1 (en) 2000-12-21 2002-08-08 Subhash P. Khanapure Substituted aryl compounds as novel cyclooxygenase-2 selective inhibitors, compositions and methods of use
    CN102234597B (en) * 2010-04-26 2015-05-27 东友精细化工有限公司 Cleaning composition
    WO2016200343A1 (en) * 2015-06-09 2016-12-15 Hayat Kimya Sanayi Anonim Sirketi Aqueous, thickened and transparent bleaching compositions
    CN107319694B (en) * 2017-07-07 2020-10-09 浙江伟星实业发展股份有限公司 Silver edge filament-shaped wrapping button and preparation method thereof

    Family Cites Families (5)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    GB8314500D0 (en) * 1983-05-25 1983-06-29 Procter & Gamble Ltd Cleaning compositions
    EP0622451B1 (en) * 1993-04-26 1998-12-02 The Procter & Gamble Company Perfumed hypochlorite bleaching compositions
    DE4333100C1 (en) * 1993-09-29 1994-10-06 Henkel Kgaa Bleaching and disinfecting compositions
    DE19621048C2 (en) * 1996-05-24 2000-06-21 Henkel Kgaa Aqueous bleach and disinfectant
    DE19626906C1 (en) * 1996-07-04 1998-03-12 Henkel Kgaa Means for cleaning hard surfaces

    Also Published As

    Publication number Publication date
    ES2244196T3 (en) 2005-12-01
    EP1075506A1 (en) 2001-02-14
    WO1999058635A1 (en) 1999-11-18
    CN1299405A (en) 2001-06-13
    ATE297978T1 (en) 2005-07-15
    DE59912187D1 (en) 2005-07-21

    Similar Documents

    Publication Publication Date Title
    EP0966514A1 (en) Aqueous bleaching agents
    EP0721496B1 (en) Bleaches and disinfectants
    EP1075506B1 (en) Bleaching and disinfecting agents
    EP0703973B1 (en) Aqueous bleaching agents
    WO1999038943A2 (en) Bleaching agents and disinfectants
    EP0925351B1 (en) Agent for cleaning hard surfaces
    DE69633113T2 (en) Detergent compositions
    EP0912696B1 (en) Aqueous bleach and disinfectant
    DE69727567T2 (en) CLEANING SUPPLIES
    DE4243468A1 (en) Neutral liquid detergent (I)
    DE19623571C2 (en) Thickener for aqueous hydrogen peroxide solutions
    EP1185605A1 (en) Bleaching and disinfecting agents
    WO1999036502A1 (en) Aqueous bleaching agents in the form of a microemulsion
    EP1957621B1 (en) Stability improvement of liquid hypochlorite-containing washing and cleaning compositions
    DE4243477A1 (en) Neutral liquid detergent (II)
    DE19902904A1 (en) Bleach and disinfectant
    DE19838104C1 (en) Thickened aqueous peroxide bleach, especially useful for pretreating textile
    DE10124288A1 (en) Aqueous hard surface cleaning composition, especially for tiles, containing alkali metal hypochlorite, carbonate and hydroxide, surfactant and hydrotrope, plus amine oxide phosphonic acid to improve gloss after cleaning
    DE10136207A1 (en) Hypochlorite-containing aqueous liquid detergents or cleaning agents are stabilized especially against sunlight by use of a yellow container and optionally also an alkali salt of an aromatic sulfonic acid
    DE10124304A1 (en) Aqueous hard surface cleaning composition, especially for tiles, comprises alkali metal hypochlorite and hydroxide, surfactant, hydrotrope and amine oxide phosphonic acid
    DE10136209A1 (en) Hypochlorite-containing aqueous liquid detergents or cleaning agents, useful in cleaning compositions, e.g. for tiles, are stabilized against sunlight by addition of alkali salts of aromatic sulfonic acids

    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

    17P Request for examination filed

    Effective date: 20001031

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): AT BE DE ES FR GB IT NL

    17Q First examination report despatched

    Effective date: 20040212

    GRAP Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOSNIGR1

    GRAS Grant fee paid

    Free format text: ORIGINAL CODE: EPIDOSNIGR3

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): AT BE DE ES FR GB IT NL

    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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050615

    Ref country code: IT

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

    Effective date: 20050615

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050615

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    Free format text: NOT ENGLISH

    REF Corresponds to:

    Ref document number: 59912187

    Country of ref document: DE

    Date of ref document: 20050721

    Kind code of ref document: P

    NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FG2A

    Ref document number: 2244196

    Country of ref document: ES

    Kind code of ref document: T3

    GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]

    Effective date: 20050615

    PLBI Opposition filed

    Free format text: ORIGINAL CODE: 0009260

    ET Fr: translation filed
    PLAX Notice of opposition and request to file observation + time limit sent

    Free format text: ORIGINAL CODE: EPIDOSNOBS2

    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: 20060429

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: BE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20060430

    26 Opposition filed

    Opponent name: THE PROCTER & GAMBLE COMPANY

    Effective date: 20060314

    Opponent name: UNILEVER PLC/ UNILEVER NV

    Effective date: 20060310

    PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

    Free format text: ORIGINAL CODE: EPIDOSCOBS2

    PLBB Reply of patent proprietor to notice(s) of opposition received

    Free format text: ORIGINAL CODE: EPIDOSNOBS3

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DE

    Payment date: 20070426

    Year of fee payment: 9

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: ES

    Payment date: 20070521

    Year of fee payment: 9

    RDAF Communication despatched that patent is revoked

    Free format text: ORIGINAL CODE: EPIDOSNREV1

    BERE Be: lapsed

    Owner name: HENKEL K.G.A.A.

    Effective date: 20060430

    RDAG Patent revoked

    Free format text: ORIGINAL CODE: 0009271

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: PATENT REVOKED

    27W Patent revoked

    Effective date: 20071108

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: FR

    Payment date: 20070411

    Year of fee payment: 9

    PLAB Opposition data, opponent's data or that of the opponent's representative modified

    Free format text: ORIGINAL CODE: 0009299OPPO