EP0675933B1 - Sweeping powder - Google Patents

Sweeping powder Download PDF

Info

Publication number
EP0675933B1
EP0675933B1 EP94902749A EP94902749A EP0675933B1 EP 0675933 B1 EP0675933 B1 EP 0675933B1 EP 94902749 A EP94902749 A EP 94902749A EP 94902749 A EP94902749 A EP 94902749A EP 0675933 B1 EP0675933 B1 EP 0675933B1
Authority
EP
European Patent Office
Prior art keywords
weight
diglycol
sweeping
powder
alcohol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94902749A
Other languages
German (de)
French (fr)
Other versions
EP0675933A1 (en
Inventor
Birgit Skodell
Rainer Osberghaus
Karl-Heinz Rogmann
Heiko Faubel
Harald Bossek
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.)
Ecolab GmbH and Co oHG
Original Assignee
Henkel Ecolab GmbH and Co KG
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
Application filed by Henkel Ecolab GmbH and Co KG filed Critical Henkel Ecolab GmbH and Co KG
Publication of EP0675933A1 publication Critical patent/EP0675933A1/en
Application granted granted Critical
Publication of EP0675933B1 publication Critical patent/EP0675933B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/40—Products in which the composition is not well defined
    • C11D7/44—Vegetable products
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols

Definitions

  • the present invention relates to scatterable aids which are used in the manual cleaning of larger areas with the aid of brooms. Such agents are also referred to as dust or dust.
  • sweeping dust is sprinkled on the floor before sweeping.
  • They are granular products that consist of an absorbent carrier, usually sawdust, and an adsorbed mixture of water and caring or cleaning agents.
  • the slightly sticky flours are pushed before the broom when sweeping and bind the dust before it can be whirled up in the air.
  • some of the active ingredients contained in the sweeping flours are released to the surface during transport across the surface, so that, in addition to the dust binding, a certain care effect is also achieved.
  • sweeping flours with a mineral oil content are particularly suitable for cement floors; Sweeping flours containing a solution of wax in organic solvents are particularly suitable for wood, stone wood and linoleum flooring, while sweeping flours containing wax as an aqueous emulsion are almost universally applicable.
  • the dust-binding effect of the sweeping flour is sufficient in almost all cases, the release of active ingredients to the floors is often uneven. Especially if the uneven distribution of the care substances can also be perceived optically, this phenomenon is considered a defect. To remedy this was one of the objects of the present invention.
  • the invention relates to a dust on the basis of sawdust, which are impregnated with a mixture of water and one or more active ingredients, which additionally contains an alcohol from the group consisting of benzyl alcohol, 2-phenylethanol, 2-phenoxyethanol, methyl diglycol, ethyl diglycol, propyl diglycol, butyl diglycol and contains their mixtures.
  • the addition of the alcohols used according to the invention largely independently of the other active ingredients of the sweeping flours, makes it easier to distribute and spread, and a more uniform release of the active ingredients to the soil than with conventional agents. In many cases, a higher cleaning performance was also observed with the agents according to the invention. Finally, it was also found that, especially when using the diethylene glycol monoalkyl ether, the sweepings are stable against microbial attack during storage, so that the addition of conventional preservatives can be dispensed with.
  • Sawdust is primarily used as the carrier material in the sweepings according to the invention. They can be used as the only carrier material or together with other carrier materials, for example fine sand.
  • the grain size of the sawdust is preferably chosen so that according to sieve analysis between 10 and 70 wt .-% of the material have a grain size between 0.315 and 0.8 mm.
  • the sawdust content in the agents is preferably 20 to 80% by weight, in particular 20 to 50% by weight.
  • Other carrier materials can also be used in amounts of up to 50% by weight, preferably between 1 and 20% by weight.
  • the active ingredients used in the agent according to the invention preferably come from the group of mineral oil, wax, surfactant and mixtures of these substances.
  • the mineral oils are usually high-boiling fractions from petroleum distillation, which are also referred to as paraffin oils.
  • the boiling ranges are above about 280 ° C, preferably above 300 ° C.
  • Waxes are primarily synthetic and semi-synthetic waxes. Hydrocarbon waxes (paraffin waxes) and montan waxes are particularly suitable. Of course, all other common waxes, such as polyethylene waxes, oxidized polyethylene waxes, microcrystalline paraffin waxes and naturally occurring washes, can also be used.
  • the waxes can be incorporated into the sweeping flours in the form of a dispersion in water, which can be prepared using conventional wax emulsifiers, or as a solution in hydrophobic solvents.
  • Hydrophobic solvents are those that practically do not dissolve in water, but have good solvent power for waxes.
  • Gasoline fractions with boiling points between 100 and 250 ° C., preferably 150 to 200 ° C., which are traded for example as white spirit or crystal oil, are preferred.
  • Aromatic-free gasolines are particularly preferred. These solvents can make up to 50% by weight of the finished sweeping flour, the proportion preferably being between 1 and 25% by weight.
  • Suitable surfactants for the agents according to the invention are, in addition to conventional soaps, in particular synthetic surfactants from the classes of anionic and nonionic surfactants.
  • particularly suitable surfactants are sodium alkane sulfonates and ethoxylated fatty alcohols.
  • the above-mentioned active ingredients are contained in the sweeping flours in amounts of at least 1% by weight.
  • the upper limit of their content in the case of mineral oils is 50% by weight, this active ingredient group is preferably contained in an amount between 10 and 25% by weight.
  • the upper limit is preferably 25% by weight. Contents of between 2 and 8% by weight are particularly preferred for these two classes of active ingredients.
  • the sweeping flours according to the invention contain certain alcohols as a characteristic constituent. These are the aromatic alcohols Benzyl alcohol, 2-phenylethanol and 2-phenoxyethanol and also the ether alcohols from the group of diethylene glycol monoalkyl ethers with 1 to 4 carbon atoms in the alkyl part. Of the latter, methyl diglycol, ethyl diglycol and n-butyl diglycol are particularly preferred.
  • the abovementioned alcohols can be present in the compositions individually or as a mixture of several of these alcohols. The minimum content for a noticeable effect is about 1% by weight. The upper limit of the content is not least determined by the price of these alcohols and is generally not more than 11% by weight.
  • the alcohols are preferably used in the compositions in amounts of between 2 and 8% by weight.
  • the sweepings contain more or less water.
  • the content can be freely selected within wide limits, but in most cases is between about 35 and about 75% by weight.
  • the sweeping flours according to the invention can be produced by simultaneously mixing all of the components in suitable dry mixing units. In individual cases, however, it may be more expedient to first dissolve the waxes in the solvent before mixing in, or to process them into a dispersion with water and to introduce them into the mixing unit in this form.
  • Sweeping flours 1 to 5 were produced by mixing the components listed in Table 1. Unless otherwise stated, the contents, as in the examples below, are listed as percentages by weight and are always based on the active substance content of the raw materials.
  • Table 1 example 1 2nd 3rd 4th 5 Glyoxal 0.3 - - - - - Sawdust (spruce) 25.0 25.0 25.0 25.0 25.0 Quartz sand 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 White oil (flash point 155 ° C) 4.0 4.0 4.0 4.0 4.0 4.0 dye 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Perfume 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Diethylene glycol mono-n-butyl ether - 10.0 - - - 2-phenoxyethanol - - 2.0 - - 2-phenylethanol - - - 1.00 - Benzyl alcohol - - - - 1.0 water
  • Both the comparative example 1 and examples 2 to 4 according to the invention determined the care effect and cleaning performance by the following methods:
  • Table 3 shows the composition of the products.
  • Table 3 example 6 7 8th 9 10th Glyoxal 0.3 - - - - - sawdust 34.0 34.0 34.0 34.0 34.0 Hydrocarbon wax (dropping point 75 ° C) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Paraffin (dropping point 54 ° C) 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Crystal oil (boiling range 145-200 ° C) 12th 12th 12th 12th 12th dye 0.2 0.2 0.2 0.2 0.2 Perfume 0.1 0.1 0.1 0.1 0.1 0.1 Diethylene glycol mono-n-butyl ether - 10.0 - - - 2-phenoxyethanol - - 2.0 - - 2-phenylethanol - - - 1.0 - Benzyl alcohol - - - - 1.0 water to 100 to 100

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Detergent Compositions (AREA)
  • Fats And Perfumes (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention concerns a sweeping powder made from sawdust impregnated with a mixture of water and one or more active substances. The sweeping powder also contains an alcohol selected from the group comprising benzyl alcohol, 2-phenylethanol, 2-phenoxyethanol, methyldiglycol, ethyldiglycol, propyldiglycol, butyldiglycol and mixtures thereof. The sweeping powder ensures particularly uniform cleaning.

Description

Die vorliegende Erfindung betrifft streubare Hilfsmittel, die bei der manuellen Reinigung größerer Flächen mit Hilfe von Besen eingesetzt werden. Derartige Mittel werden auch als Kehrspäne oder Kehrmehle bezeichnet.The present invention relates to scatterable aids which are used in the manual cleaning of larger areas with the aid of brooms. Such agents are also referred to as dust or dust.

Um zu verhindern, daß beim Kehren trockener Flächen Staub aufgewirbelt wird, streut man vor dem Kehren sogenannte Kehrmehle auf den Boden. Es handelt sich um körnige Produkte, die aus einem saugfähigen Trägerstoff, meist Sägespänen, und einer daran adsorbierten Mischung von Wasser und pflegenden oder reinigenden Wirkstoffen bestehen. Die leicht klebrigen Mehle werden beim Kehren vor dem Besen hergeschoben und binden den Staub, bevor er in die Luft aufgewirbelt werden kann. Gleichzeitig wird beim Transport über die Fläche ein Teil der in den Kehrmehlen enthaltenen Wirkstoffe an die Oberfläche abgegeben, so daß neben der Staubbindung auch eine gewisse Pflegewirkung erreicht wird. Je nach Art der zu reinigenden Flächen werden unterschiedliche Wirkstoffe in die Kehrmehle eingearbeitet: So eignen sich beispielsweise Kehrmehle mit einem Gehalt an Mineralöl vor allem für Zementfußböden; Kehrmehle, die eine Lösung von Wachs in organischen Lösungsmitteln enthalten, sind besonders für Holz, Steinholz und Linoleumbeläge geeignet, während sich Kehrmehle, die Wachs als wäßrige Emulsion enthalten, nahezu universell anwendbar sind. Während die staubbindende Wirkung der Kehrmehle in fast allen Fällen ausreicht, ist die Abgabe von Wirkstoffen an die Fußböden häufig ungleichmäßig. Vor allem dann, wenn die ungleichmäßige Verteilung der Pflegestoffe auch optisch wahrgenommen werden kann, wird diese Erscheinung als Mangel angesehen. Hier eine Abhilfe zu schaffen, war eine der Aufgaben der vorliegenden Erfindung.In order to prevent dust from being whirled up when sweeping dry surfaces, so-called sweeping dust is sprinkled on the floor before sweeping. They are granular products that consist of an absorbent carrier, usually sawdust, and an adsorbed mixture of water and caring or cleaning agents. The slightly sticky flours are pushed before the broom when sweeping and bind the dust before it can be whirled up in the air. At the same time, some of the active ingredients contained in the sweeping flours are released to the surface during transport across the surface, so that, in addition to the dust binding, a certain care effect is also achieved. Depending on the type of surfaces to be cleaned, different active ingredients are incorporated into the sweeping flours: For example, sweeping flours with a mineral oil content are particularly suitable for cement floors; Sweeping flours containing a solution of wax in organic solvents are particularly suitable for wood, stone wood and linoleum flooring, while sweeping flours containing wax as an aqueous emulsion are almost universally applicable. While the dust-binding effect of the sweeping flour is sufficient in almost all cases, the release of active ingredients to the floors is often uneven. Especially if the uneven distribution of the care substances can also be perceived optically, this phenomenon is considered a defect. To remedy this was one of the objects of the present invention.

Es wurde gefunden, daß der vorstehend beschriebene Mangel durch die Einarbeitung bestimmter organischer Lösungsmittel in die Kehrmehle weitgehend gemindert werden kann.It has been found that the deficiency described above can be largely reduced by incorporating certain organic solvents into the dust.

Gegenstand der Erfindung ist ein Kehrmehl auf Basis von Sägespänen, die mit einer Mischung aus Wasser und einem oder mehreren Wirkstoffen getränkt sind, das zusätzlich einen Alkohol aus der Gruppe Benzylalkohol, 2-Phenylethanol, 2-Phenoxyethanol, Methyldiglykol, Ethyldiglykol, Propyldiglykol, Butyldiglykol und deren Mischungen enthält.The invention relates to a dust on the basis of sawdust, which are impregnated with a mixture of water and one or more active ingredients, which additionally contains an alcohol from the group consisting of benzyl alcohol, 2-phenylethanol, 2-phenoxyethanol, methyl diglycol, ethyl diglycol, propyl diglycol, butyl diglycol and contains their mixtures.

Überraschenderweise wird durch den Zusatz der erfindungsgemäß verwendeten Alkohole, weitgehend unabhängig von den sonstigen Wirkstoffen der Kehrmehle, eine leichtere Verteilbarkeit und Streubarkeit sowie eine wesentlich gleichmäßigere Abgabe der Wirkstoffe an den Boden erreicht als bei herkömmlichen Mitteln. In vielen Fällen wurde außerdem auch eine höhere Reinigungsleistung bei den erfindungsgemäßen Mitteln beobachtet. Schließlich konnte auch festgestellt werden, daß insbesondere bei Verwendung der Diethylenglykolmonoalkylether die Kehrmehle stabil gegen mikrobiellen Befall während der Lagerung sind, so daß auf den Zusatz herkömmlicher Konservierungsmittel verzichtet werden kann.Surprisingly, the addition of the alcohols used according to the invention, largely independently of the other active ingredients of the sweeping flours, makes it easier to distribute and spread, and a more uniform release of the active ingredients to the soil than with conventional agents. In many cases, a higher cleaning performance was also observed with the agents according to the invention. Finally, it was also found that, especially when using the diethylene glycol monoalkyl ether, the sweepings are stable against microbial attack during storage, so that the addition of conventional preservatives can be dispensed with.

Es folgt eine Beschreibung der einzelnen Inhaltsstoffe der erfindungsgemäßen Mittel.A description of the individual ingredients of the agents according to the invention follows.

Als Trägermaterial werden in den erfindungsgemäßen Kehrmehlen in erster Linie Sägespäne eingesetzt. Sie können als einziges Trägermaterial oder aber zusammen mit weiteren Trägermaterialien, beispielsweise feinem Sand, verwendet werden. Die Korngröße des Sägemehls wird vorzugsweise so gewählt, daß nach Siebanalyse zwischen 10 und 70 Gew.-% des Materials eine Korngröße zwischen 0,315 und 0,8 mm aufweisen. Der Gehalt an Sägespänen in den Mitteln beträgt vorzugsweise 20 bis 80 Gew.-%, insbesondere 20 bis 50 Gew.-%. Andere Trägermaterialien können daneben in Mengen bis zu 50 Gew.-%, vorzugsweise zwischen 1 und 20 Gew.-% eingesetzt werden.Sawdust is primarily used as the carrier material in the sweepings according to the invention. They can be used as the only carrier material or together with other carrier materials, for example fine sand. The grain size of the sawdust is preferably chosen so that according to sieve analysis between 10 and 70 wt .-% of the material have a grain size between 0.315 and 0.8 mm. The sawdust content in the agents is preferably 20 to 80% by weight, in particular 20 to 50% by weight. Other carrier materials can also be used in amounts of up to 50% by weight, preferably between 1 and 20% by weight.

Die in dem erfindungsgemäßen Mittel eingesetzten Wirkstoffe stammen vorzugsweise aus der Gruppe Mineralöl, Wachs, Tensid und Mischungen dieser Stoffe.The active ingredients used in the agent according to the invention preferably come from the group of mineral oil, wax, surfactant and mixtures of these substances.

Bei den Mineralölen handelt es sich in der Regel um hochsiedende Fraktionen aus der Erdöldestillation, die auch als Paraffinöle bezeichnet werden. Die Siedebereiche liegen oberhalb von etwa 280 °C, vorzugsweise oberhalb von 300 °C.The mineral oils are usually high-boiling fractions from petroleum distillation, which are also referred to as paraffin oils. The boiling ranges are above about 280 ° C, preferably above 300 ° C.

Als Wachse kommen in erster Linie synthetische und teilsynthetische Wachse in Betracht. Besonders geeignet sind Kohlenwasserstoffwachse (Paraffinwachse) und Montanwachse. Selbstverständlich können aber auch alle anderen gebräuchlichen Wachse, wie Polyethylenwachse, oxidierte Polyethylenwachse, mikrokristalline Paraffinwachse und natürlich vorkommende Waschse eingesetzt werden.Waxes are primarily synthetic and semi-synthetic waxes. Hydrocarbon waxes (paraffin waxes) and montan waxes are particularly suitable. Of course, all other common waxes, such as polyethylene waxes, oxidized polyethylene waxes, microcrystalline paraffin waxes and naturally occurring washes, can also be used.

Die Wachse können in die Kehrmehle in Form einer Dispersion in Wasser, die mit Hilfe üblicher Wachsemulgatoren hergestellt werden kann, oder als Lösung in hydrophoben Lösungsmitteln eingearbeitet werden. Hydrophobe Lösungsmittel sind solche, die sich in Wasser praktisch nicht lösen, aber ein gutes Lösevermögen für Wachse besitzen. Bevorzugt werden Benzinfraktionen mit Siedepunkten zwischen 100 und 250 °C, vorzugsweise 150 bis 200 °C, die beispielsweise als Testbenzin oder Kristallöl gehandelt werden. Besonders bevorzugt werden aromatenfreie Benzine. Diese Lösungsmittel können bis zu 50 Gew.-% des fertigen Kehrmehls ausmachen, vorzugsweise liegt der Anteil zwischen 1 und 25 Gew.-%.The waxes can be incorporated into the sweeping flours in the form of a dispersion in water, which can be prepared using conventional wax emulsifiers, or as a solution in hydrophobic solvents. Hydrophobic solvents are those that practically do not dissolve in water, but have good solvent power for waxes. Gasoline fractions with boiling points between 100 and 250 ° C., preferably 150 to 200 ° C., which are traded for example as white spirit or crystal oil, are preferred. Aromatic-free gasolines are particularly preferred. These solvents can make up to 50% by weight of the finished sweeping flour, the proportion preferably being between 1 and 25% by weight.

Als Tenside eignen sich für die erfindungsgemäßen Mittel neben üblichen Seifen insbesondere synthetische Tenside aus den Klassen der anionischen und der nichtionischen Tenside. Beispiele besonders geeigneter Tenside sind Natriumalkansulfonate und ethoxylierte Fettalkohole.Suitable surfactants for the agents according to the invention are, in addition to conventional soaps, in particular synthetic surfactants from the classes of anionic and nonionic surfactants. Examples of particularly suitable surfactants are sodium alkane sulfonates and ethoxylated fatty alcohols.

Die vorstehend genannten Wirkstoffe sind in den Kehrmehlen in Mengen von wenigstens 1 Gew.-% enthalten. Die Obergrenze ihres Gehalts liegt im Falle der Mineralöle bei 50 Gew.-%, vorzugsweise ist diese Wirkstoffgruppe in einer Menge zwischen 10 und 25 Gew.-% enthalten. Für Wachse und Tenside liegt die Obergrenze vorzugsweise bei jeweils 25 Gew.-%. Besonders bevorzugt werden für diese beiden Wirkstoffklassen Gehalte zwischen 2 und 8 Gew.-%.The above-mentioned active ingredients are contained in the sweeping flours in amounts of at least 1% by weight. The upper limit of their content in the case of mineral oils is 50% by weight, this active ingredient group is preferably contained in an amount between 10 and 25% by weight. For waxes and surfactants, the upper limit is preferably 25% by weight. Contents of between 2 and 8% by weight are particularly preferred for these two classes of active ingredients.

Als kennzeichnenden Bestandteil enthalten die erfindungsgemäßen Kehrmehle bestimmte Alkohole. Es handelt sich dabei um die aromatischen Alkohole Benzylalkohol, 2-Phenylethanol und 2-Phenoxyethanol sowie um die Etheralkohole aus der Gruppe der Diethylenglykolmonoalkylether mit 1 bis 4 C-Atomen im Alkylteil. Von den letzteren werden Methyldiglykol, Ethyldiglykol und n-Butyldiglykol besonders bevorzugt. Die vorstehend genannten Alkohole können in den Mitteln einzeln aber auch als Gemisch mehrerer dieser Alkohole enthalten sein. Als Mindestgehalt für eine merkliche Wirkung sind etwa 1 Gew.-% anzusehen. Die Obergrenze des Gehalts wird nicht zuletzt durch den Preis dieser Alkohole bestimmt und liegt im allgemeinen nicht über 11 Gew.-%. Vorzugsweise werden die Alkohole in Mengen zwischen 2 und 8 Gew.-% in den Mitteln verwendet.The sweeping flours according to the invention contain certain alcohols as a characteristic constituent. These are the aromatic alcohols Benzyl alcohol, 2-phenylethanol and 2-phenoxyethanol and also the ether alcohols from the group of diethylene glycol monoalkyl ethers with 1 to 4 carbon atoms in the alkyl part. Of the latter, methyl diglycol, ethyl diglycol and n-butyl diglycol are particularly preferred. The abovementioned alcohols can be present in the compositions individually or as a mixture of several of these alcohols. The minimum content for a noticeable effect is about 1% by weight. The upper limit of the content is not least determined by the price of these alcohols and is generally not more than 11% by weight. The alcohols are preferably used in the compositions in amounts of between 2 and 8% by weight.

Je nach Art der verwendeten Wirkstoffe enthalten die Kehrmehle mehr oder weniger Wasser. Der Gehalt kann, solange die Streufähigkeit der Mittel gewährleistet ist, in weiten Grenzen frei gewählt werden, liegt in den meisten Fällen aber zwischen etwa 35 und etwa 75 Gew.-%.Depending on the type of active ingredients used, the sweepings contain more or less water. As long as the dispersibility of the agents is guaranteed, the content can be freely selected within wide limits, but in most cases is between about 35 and about 75% by weight.

Neben den bereits genannten Inhaltsstoffen können in den Mitteln weitere Wirk- und Zusatzstoffe enthalten sein. Hier sind in erster Linie Farbstoffe zur Kennzeichnung des Kehrmehltyps und, soweit nötig, Konservierungsmittel zu nennen. Daneben sind Parfümöle, sowie, in Einzelfällen, filmbildende Polymere und Netzharze zu erwähnen. Der Gehalt an derartigen Hilfs- und Zusatzstoffen liegt im allgemeinen nicht über 10 Gew.-%, meist erheblich darunter.In addition to the ingredients already mentioned, other active ingredients and additives may be contained in the agents. First of all, there are dyes to identify the type of sweepings and, if necessary, preservatives. In addition, perfume oils and, in individual cases, film-forming polymers and wetting resins should be mentioned. The content of such auxiliaries and additives is generally not more than 10% by weight, mostly considerably less.

Im folgenden sind eine Reihe von typischen Rahmenrezepturen für erfindungsgemäße Kehrmehle angegeben. Die erfindungsgemäß enthaltenen Alkohole aus der Gruppe Benzylakohol, 2-Phenylethanol, 2-Phenoxyethanol, Methyldiglykol, Ethyldiglykol, Propyldiglykol, Butyldiglykol und deren Mischungen sind dabei der Einfachheit halber als "wirksame Alkohole" bezeichnet worden.

Figure imgb0001
Figure imgb0002
 Kehrmehl auf Basis von Wachs Sägespäne 20 bis 80 Gew.-% Wachse 1 bis 25 Gew.-% hydrophobe Lösungsmittel 0 bis 50 Gew.-% Wachsemulgator 0 bis 3 Gew.-% wirksame Alkohole 1 bis 11 Gew.-% filmbildende Polymere 0 bis 10 Gew.-% Netzharze 0 bis 10 Gew.-% Konservierungsmittel 0 bis 10 Gew.-% Farbstoffe 0 bis 1 Gew.-% Parfümöle 0 bis 2 Gew.-% Wasser und weitere Hilfsstoffe zu 100 Gew.-% Kehrmehl auf Basis Tensid Sägespäne 20 bis 80 Gew.-% feiner Quarzsand 1 bis 50 Gew.-% synthetische Tenside 1 bis 25 Gew.-% wirksame Alkohole 1 bis 11 Gew.-% Seife 1 bis 20 Gew.-% Konservierungsmittel 0 bis 10 Gew.-% Farbstoffe 0 bis 1 Gew.-% Parfümöle 0 bis 2 Gew.-% Wasser und weitere Hilfsstoffe zu 100 Gew.-% A number of typical frame formulations for sweepings according to the invention are given below. The alcohols according to the invention from the group of benzyl alcohol, 2-phenylethanol, 2-phenoxyethanol, methyl diglycol, ethyl diglycol, propyl diglycol, butyl diglycol and mixtures thereof have been referred to as "effective alcohols" for the sake of simplicity.
Figure imgb0001
Figure imgb0002
 Dust based on wax Sawdust 20 to 80% by weight Waxes 1 to 25% by weight hydrophobic solvents 0 to 50% by weight Wax emulsifier 0 to 3% by weight effective alcohols 1 to 11% by weight film-forming polymers 0 to 10% by weight Mesh resins 0 to 10% by weight Preservative 0 to 10% by weight Dyes 0 to 1% by weight Perfume oils 0 to 2% by weight Water and other additives 100% by weight Sweeping flour based on surfactant Sawdust 20 to 80% by weight fine quartz sand 1 to 50% by weight synthetic surfactants 1 to 25% by weight effective alcohols 1 to 11% by weight Soap 1 to 20% by weight Preservative 0 to 10% by weight Dyes 0 to 1% by weight Perfume oils 0 to 2% by weight Water and other additives 100% by weight

Die Herstellung der erfindungsgemäßen Kehrmehle kann im einfachsten Falle durch gleichzeitiges Vermischen aller Komponenten in geeigneten Trockenmischaggregaten erfolgen. In Einzelfällen kann es allerdings zweckmäßiger sein, die Wachse vor dem Einmischen zunächst im Lösungsmittel aufzulösen oder mit Wasser zu einer Dispersion zu verarbeiten und sie in dieser Form in das Mischaggregat einzuführen.In the simplest case, the sweeping flours according to the invention can be produced by simultaneously mixing all of the components in suitable dry mixing units. In individual cases, however, it may be more expedient to first dissolve the waxes in the solvent before mixing in, or to process them into a dispersion with water and to introduce them into the mixing unit in this form.

BeispieleExamples Kehrmehle auf Basis MineralölSweeping flours based on mineral oil

Durch Vermischen der in Tabelle 1 angegebenen Komponenten wurden die Kehrmehle 1 bis 5 hergestellt. Die Gehalte sind in der Tabelle, wie auch in den folgenden Beispielen, soweit nichts anderes angegeben wird, als Gewichtsprozent aufgeführt und immer auf den Wirkstoffgehalt der Rohstoffe bezogen. Tabelle 1 Beispiel 1 2 3 4 5 Glyoxal 0,3 - - - - Sägemehl (Fichte) 25,0 25,0 25,0 25,0 25,0 Quarzsand 20,0 20,0 20,0 20,0 20,0 Weißöl (Flammpunkt 155 °C) 4,0 4,0 4,0 4,0 4,0 Farbstoff 0,2 0,2 0,2 0,2 0,2 Parfüm 0,1 0,1 0,1 0,1 0,1 Diethylenglykol-mono-n-butylether - 10,0 - - - 2-Phenoxyethanol - - 2,0 - - 2-Phenylethanol - - - 1,00 - Benzylalkohol - - - - 1,0 Wasser zu 100 zu 100 zu 100 zu 100 zu 100 Sweeping flours 1 to 5 were produced by mixing the components listed in Table 1. Unless otherwise stated, the contents, as in the examples below, are listed as percentages by weight and are always based on the active substance content of the raw materials. Table 1 example 1 2nd 3rd 4th 5 Glyoxal 0.3 - - - - Sawdust (spruce) 25.0 25.0 25.0 25.0 25.0 Quartz sand 20.0 20.0 20.0 20.0 20.0 White oil (flash point 155 ° C) 4.0 4.0 4.0 4.0 4.0 dye 0.2 0.2 0.2 0.2 0.2 Perfume 0.1 0.1 0.1 0.1 0.1 Diethylene glycol mono-n-butyl ether - 10.0 - - - 2-phenoxyethanol - - 2.0 - - 2-phenylethanol - - - 1.00 - Benzyl alcohol - - - - 1.0 water to 100 to 100 to 100 to 100 to 100

Sowohl vom Vergleichsbeispiel 1 als auch von den erfindungsgemäßen Beispielen 2 bis 4 wurden Pflegeeffekt und Reinigungsleistung nach folgenden Verfahren bestimmt:Both the comparative example 1 and examples 2 to 4 according to the invention determined the care effect and cleaning performance by the following methods:

Prüfung der StreufähigkeitScatterability test

Für die Anwendung von Kehrmehlen ist eine klumpenfreie Streufähigkeit wichtig. Das Produkt wird dazu manuell auf den Boden verteilt und visuell beurteilt. Spätestens beim Kehren sollten vorhandene Produktklumpen auseinanderfallen.

  • 0 keine Klumpenbildung, Produkt ist fein verteilbar
  • 1 wenig Klumpen, die beim Kehren sofort auseinanderfallen
  • 2 Klumpenbildung; die Klumpen fallen beim Kehren überwiegend auseinander
  • 3 starke Klumpenbildung; die Klumpen fallen beim Kehren zu ca. 50 % auseinander
  • 4 sehr starke Klumpenbildung; die Klumpen fallen auch beim Kehren nicht auseinander
A lump-free spreadability is important for the use of sweeping flours. The product is manually spread on the floor and assessed visually. At the latest when sweeping existing clumps of product should fall apart.
  • 0 no clumping, product is finely distributed
  • 1 little lump that immediately falls apart when sweeping
  • 2 lump formation; the lumps mostly fall apart when sweeping
  • 3 strong clumping; about 50% of the lumps fall apart when sweeping
  • 4 very strong lump formation; the lumps do not fall apart when sweeping

Prüfung des PflegeeffektsChecking the care effect

Um für den Labortest einen schnellen Filmaufbau zu erreichen, wurde ein unbeschichteter, dunkler Fußbodenbelag sehr dicht mit Kehrmehl bestreut und dieses manuell leicht verrieben. Dann wurde das Kehrmehl abgekehrt und der verbliebene Rückstand mit einen unbehandelten Belagstück verglichen. Bei wachshaltigen Kehrmehlen wird zusätzlich der entstandene Pflegefilm mit dem Handblocker poliert und das Polierverhalten geprüft. Die Beurteilung erfolgt nach folgender Skala:

  • 0 gleichmäßiger, ggf. leicht polierbarer Rückstand
  • 1 sichtbarer, ggf. polierbarer Rückstand
  • 2 sichtbarer, aber ungleichmäßiger Rückstand
  • 3 geringer, aber ungleichmäßiger Rückstand
  • 4 kein Rückstand
In order to achieve a quick film build-up for the laboratory test, an uncoated, dark floor covering was very densely sprinkled with sweeping flour and lightly rubbed in manually. Then the dust was swept and the remaining residue compared to an untreated piece of topping. In the case of wax-containing sweeping flours, the resulting care film is additionally polished with the hand blocker and the polishing behavior is checked. The assessment is based on the following scale:
  • 0 even residue, which can be easily polished if necessary
  • 1 visible, possibly polishable residue
  • 2 visible but uneven residue
  • 3 small but uneven residue
  • 4 no backlog

Aus den Ergebnissen in Tabelle 2 wird das bessere Ergebnis mit den erfindungsgemäßen Mitteln deutlich Tabelle 2 Beispiel 1 2 3 4 5 Pflegeeffekt 2 0 0 0 0 Streufähigkeit 2 0 0 0 0 The better result with the agents according to the invention is clear from the results in Table 2 Table 2 example 1 2nd 3rd 4th 5 Care effect 2nd 0 0 0 0 Scatterability 2nd 0 0 0 0

Kehrmehle auf Basis Wachs/LösungsmittelSweeping flours based on wax / solvent

Bei der Herstellung dieser Kehrmehle wurden zunächst die Wachse in Benzin gelöst, und dann in dieser Form mit den übrigen Komponenten vermischt. Tabelle 3 gibt die Zusammensetzung der Produkte wieder. Tabelle 3 Beispiel 6 7 8 9 10 Glyoxal 0,3 - - - - Sägemehl 34,0 34,0 34,0 34,0 34,0 Kohlenwasserstoffwachs (Tropfpunkt 75 °C) 0,1 0,1 0,1 0,1 0,1 Paraffin (Tropfpunkt 54 °C) 3,5 3,5 3,5 3,5 3,5 Kristallöl (Siedebereich 145 -200 °C) 12 12 12 12 12 Farbstoff 0,2 0,2 0,2 0,2 0,2 Parfüm 0,1 0,1 0,1 0,1 0,1 Diethylenglykol-mono-n-butylether - 10,0 - - - 2-Phenoxyethanol - - 2,0 - - 2-Phenylethanol - - - 1,0 - Benzylakohol - - - - 1,0 Wasser zu 100 zu 100 zu 100 zu 100 zu 100 In the manufacture of these sweepings, the waxes were first dissolved in petrol and then mixed in this form with the other components. Table 3 shows the composition of the products. Table 3 example 6 7 8th 9 10th Glyoxal 0.3 - - - - sawdust 34.0 34.0 34.0 34.0 34.0 Hydrocarbon wax (dropping point 75 ° C) 0.1 0.1 0.1 0.1 0.1 Paraffin (dropping point 54 ° C) 3.5 3.5 3.5 3.5 3.5 Crystal oil (boiling range 145-200 ° C) 12th 12th 12th 12th 12th dye 0.2 0.2 0.2 0.2 0.2 Perfume 0.1 0.1 0.1 0.1 0.1 Diethylene glycol mono-n-butyl ether - 10.0 - - - 2-phenoxyethanol - - 2.0 - - 2-phenylethanol - - - 1.0 - Benzyl alcohol - - - - 1.0 water to 100 to 100 to 100 to 100 to 100

Die Prüfung erfolgte wie bei den Beispielen 1 bis 5 und lieferte die in Tabelle 4 aufgeführten Ergebnisse. Auch hier wirkt sich der erfindungsgemäße Alkoholzusatz in den Mitteln 7 bis 10 deutlich vorteilhaft aus. Tabelle 4 Beispiel 6 7 8 9 10 Pflegeeffekt 2 0 0 0 0 Streufähigkeit 2 0 0 0 0 The test was carried out as in Examples 1 to 5 and gave the results listed in Table 4. Here, too, the alcohol additive according to the invention has a significantly advantageous effect in means 7 to 10. Table 4 example 6 7 8th 9 10th Care effect 2nd 0 0 0 0 Scatterability 2nd 0 0 0 0

Kehrmehle auf Basis einer WachsemulsionSweeping flours based on a wax emulsion

Bei den folgenden Beispielen wurde zunächst auf üblichem Wege mit Hilfe von Amin und Wachsemulgator eine 24 %ige Emulsion der Wachse in Wasser hergestellt und diese dann mit den übrigen Bestandteilen der Mittel vermischt. Die genaue Zusammensetzung der Produkte enthält Tabelle 5. Tabelle 5 Beispiel 11 12 13 14 15 Na-Benzoat 0,01 - - - - Chloracetamid 0,02 - - - - Glyoxal 0,3 - - - - teilverseiftes Montanwachs (Tropfpunkt 105 °C) 1,0 1,0 1,0 1,0 1,0 Montanwachs (Tropfpunkt 82 °C) 1,0 1,0 1,0 1,0 1,0 Kohlenwasserstoffwachs (Tropfpunkt 62 °C) 1,0 1,0 1,0 1,0 1,0 Oleylcetylalkohol + 23 EO 0,2 0,2 0,2 0,2 0,2 Diethylethanolamin 0,05 0,05 0,05 0,05 0,05 Sägemehl 25 25 25 25 25 Quarzsand 20 20 20 20 20 Farbstoff 0,2 0,2 0,2 0,2 0,2 Parfüm 0,1 0,1 0,1 0,1 0,1 Diethylenglykol-mono-n-butylether - 10,0 - - - Phenoxyethanol - - 3,0 - - Phenylethanol - - - 2,0 - Benzylalkohol - - - - 3,0 Wasser zu 100 zu 100 zu 100 zu 100 zu 100 In the following examples, a 24% emulsion of the waxes in water was first prepared in the usual way with the aid of amine and wax emulsifier and this was then mixed with the other constituents of the compositions. The exact composition of the products is shown in Table 5. Table 5 example 11 12th 13 14 15 Na benzoate 0.01 - - - - Chloroacetamide 0.02 - - - - Glyoxal 0.3 - - - - partially saponified montan wax (drop point 105 ° C) 1.0 1.0 1.0 1.0 1.0 Montan wax (dropping point 82 ° C) 1.0 1.0 1.0 1.0 1.0 Hydrocarbon wax (dropping point 62 ° C) 1.0 1.0 1.0 1.0 1.0 Oleyl acetyl alcohol + 23 EO 0.2 0.2 0.2 0.2 0.2 Diethylethanolamine 0.05 0.05 0.05 0.05 0.05 sawdust 25th 25th 25th 25th 25th Quartz sand 20th 20th 20th 20th 20th dye 0.2 0.2 0.2 0.2 0.2 Perfume 0.1 0.1 0.1 0.1 0.1 Diethylene glycol mono-n-butyl ether - 10.0 - - - Phenoxyethanol - - 3.0 - - Phenylethanol - - - 2.0 - Benzyl alcohol - - - - 3.0 water to 100 to 100 to 100 to 100 to 100

Die Prüfung der Kehlmehle erfolgte wie in den Beispielen 1 bis 5. Tabelle 6 gibt die Ergebnisse wieder. Auch in diesen Fällen sind die erfindungsgemäßen Mittel 12 bis 15 dem Vergleichsbeispiel überlegen. Tabelle 6 Beispiele 11 12 13 14 15 Pflegeeffekt 2 0 0 0 0 Streufähigkeit 2 0 0 0 0 The throat flours were tested as in Examples 1 to 5. Table 6 shows the results. In these cases as well, agents 12 to 15 according to the invention are superior to the comparative example. Table 6 Examples 11 12th 13 14 15 Care effect 2nd 0 0 0 0 Scatterability 2nd 0 0 0 0

Claims (6)

  1. A powder-form sweeping aid based on sawdust impregnated with a mixture of water and one or more active substances, characterized in that it additionally contains an alcohol from the group consisting of benzyl alcohol, 2-phenyl ethanol, 2-phenoxy ethanol, methyl diglycol, ethyl diglycol, propyl diglycol, butyl diglycol and mixtures thereof.
  2. A powder-form sweeping aid as claimed in claim 1, in which the active substance is selected from the group consisting of mineral oil, wax, surfactant and mixtures thereof.
  3. A powder-form sweeping aid as claimed in claim 1 or 2, in which the content of alcohol from the group consisting of benzyl alcohol, 2-phenyl ethanol, 2-phenoxy ethanol, methyl diglycol, ethyl diglycol, propyl diglycol, butyl diglycol and mixtures thereof is 1 to 11 % by weight and preferably 2 to 8% by weight.
  4. A powder-form sweeping aid as claimed in any of claims 1 to 3 containing 20 to 80% by weight of sawdust, 1 to 50% by weight of mineral oil, 1 to 11 % by weight of alcohol from the group consisting of benzyl alcohol, 2-phenyl ethanol, 2-phenoxy ethanol, methyl diglycol, ethyl diglycol, propyl diglycol, butyl diglycol and mixtures thereof.
  5. A powder-form sweeping aid as claimed in any of claims 1 to 3 containing
    Figure imgb0003
    Figure imgb0004
  6. A powder-form sweeping aid as claimed in any of claims 1 to 3 containing 20 to 80% by weight of sawdust, 1 to 50% by weight of sand, 1 to 25% by weight of surfactant, 1 to 11% by weight of alcohol from the group consisting of benzyl alcohol, 2-phenyl ethanol, 2-phenoxy ethanol, methyl diglycol, ethyl diglycol, propyl diglycol, butyl diglycol and mixtures thereof.
EP94902749A 1992-12-22 1993-12-10 Sweeping powder Expired - Lifetime EP0675933B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4243474 1992-12-22
DE4243474A DE4243474A1 (en) 1992-12-22 1992-12-22 sweeping flour
PCT/EP1993/003489 WO1994014916A1 (en) 1992-12-22 1993-12-10 Sweeping powder

Publications (2)

Publication Number Publication Date
EP0675933A1 EP0675933A1 (en) 1995-10-11
EP0675933B1 true EP0675933B1 (en) 1997-09-03

Family

ID=6476112

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94902749A Expired - Lifetime EP0675933B1 (en) 1992-12-22 1993-12-10 Sweeping powder

Country Status (4)

Country Link
EP (1) EP0675933B1 (en)
DE (2) DE4243474A1 (en)
ES (1) ES2105615T3 (en)
WO (1) WO1994014916A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19731573C2 (en) * 1997-07-23 2001-05-17 Bayer Ag Cleaning process

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR544437A (en) * 1921-12-12 1922-09-22 Manufacturing processes for hygienic products intended for washing and sweeping, as well as for saturation of dust by dry sweeping
FR547638A (en) * 1922-02-20 1922-12-20 Siliceous product, intended for sweeping, washing and dry cleaning, without dust, of any solid body
FR690323A (en) * 1930-02-20 1930-09-18 Cleaning products and manufacturing process
FR796186A (en) * 1935-09-16 1936-03-31 Maintenance product for floors, tiles, furniture, etc.
FR2233810A5 (en) * 1973-06-18 1975-01-10 Skirde Gerhard Surfaces, partic. of vehicles cleaned with expanded particles - which shrink with evapn. of swelling agent to granulate particles with the dirt
FR2428070A1 (en) * 1978-06-09 1980-01-04 Ernst Marc Cleaning industrial floors using tacky fibrous compsn. - which is spread and then swept to avoid dust ingress in interstices or duct dispersion in atmosphere
DE3437629A1 (en) * 1984-10-13 1986-04-17 Henkel KGaA, 4000 Düsseldorf CARPET CLEANER
DE3444959A1 (en) * 1984-12-10 1986-06-12 Henkel KGaA, 4000 Düsseldorf CARPET CLEANER
EP0379544A1 (en) * 1988-06-21 1990-08-01 Vax Appliances Limited Fabric cleaning and sanitizing compositions

Also Published As

Publication number Publication date
DE4243474A1 (en) 1994-06-23
WO1994014916A1 (en) 1994-07-07
DE59307286D1 (en) 1997-10-09
ES2105615T3 (en) 1997-10-16
EP0675933A1 (en) 1995-10-11

Similar Documents

Publication Publication Date Title
DE69412080T2 (en) IMPROVED FLOOR SEALING COMPOSITION AND METHOD
DE3437629A1 (en) CARPET CLEANER
EP0187257A2 (en) Carpet cleaning agent
DE3855381T2 (en) Water-based composition for removing coatings
DE2838089A1 (en) POWDERED CARE PRODUCT FOR CARPETS
WO2008107453A2 (en) Skin cleansing agent with particles containing hydrogenated castor oil
EP0393072B1 (en) Anhydrous personal washing agent and use thereof
EP1180362B1 (en) Cleansing compositions for the skin
DE69217486T2 (en) METHOD FOR CLEANING COATED HARD SURFACES WITH CLEANING AGENTS THAT CONTAIN LESS VOLATILE ORGANIC COMPOUNDS
EP0675933B1 (en) Sweeping powder
EP0753040B1 (en) Carpet cleaning agent
EP0085163A2 (en) Paint remover for lacquers and dispersion paints
DE2056565A1 (en) cleaning supplies
DE4243472A1 (en) Neutral self-gloss emulsion for the care of floors (III)
EP0263959A1 (en) Floor polish
EP0675945B1 (en) Neutral cleaning agents (i)
EP0688355B1 (en) Floor-care agents
EP0627479A1 (en) Cleaning agent
DE202015008508U1 (en) Composition for commercial maintenance cleaning
EP0130371B1 (en) Audio disc polish
DE3331995C2 (en)
EP0317897A1 (en) Process for cleaning and polishing furniture
DE2114843B2 (en) Floor care products
DE3834416A1 (en) Aerosol cleaner for textile areas, in particular for cleaning textile upholstery areas
WO1994014943A1 (en) Neutral cleaning agents (ii)

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: 19950620

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI NL SE

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19961029

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

REF Corresponds to:

Ref document number: 59307286

Country of ref document: DE

Date of ref document: 19971009

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2105615

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19971201

Year of fee payment: 5

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

Ref country code: FR

Payment date: 19971209

Year of fee payment: 5

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

Ref country code: DE

Payment date: 19971222

Year of fee payment: 5

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

Ref country code: NL

Payment date: 19971223

Year of fee payment: 5

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19971201

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

Ref country code: ES

Payment date: 19971230

Year of fee payment: 5

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

Ref country code: GB

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

Effective date: 19981210

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: 19990701

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19981210

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

Ref country code: FR

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

Effective date: 19990831

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19990701

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

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

Ref country code: DE

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

Effective date: 19991001

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

Ref country code: ES

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

Effective date: 19991211

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20000114

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

Ref country code: IT

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

Effective date: 20051210