EP1517980B1 - Floor cleaning and/or floor care product - Google Patents

Floor cleaning and/or floor care product Download PDF

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Publication number
EP1517980B1
EP1517980B1 EP03761476A EP03761476A EP1517980B1 EP 1517980 B1 EP1517980 B1 EP 1517980B1 EP 03761476 A EP03761476 A EP 03761476A EP 03761476 A EP03761476 A EP 03761476A EP 1517980 B1 EP1517980 B1 EP 1517980B1
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Prior art keywords
agent
weight
atoms
nonionic surfactant
formula
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German (de)
French (fr)
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EP1517980A1 (en
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Karl-Heinz Rogmann
Nicola Kriens
Heiko Faubel
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Ecolab Inc
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Ecolab Inc
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D2111/14—

Definitions

  • the present invention relates to aqueous floor cleaning and / or floor care compositions comprising one or more specific nonionic surfactants and the use of these agents for cleaning and / or care of soils.
  • Floor coverings can be factory-equipped with polymer films, treated with polymer-based care products afterwards or left untreated. All of these surfaces may be prone to staining, even if they are glossy surfaces. It can impurities, dusts, but also residues of the drying drying fleet made more visible and an unsightly overall picture can be generated. To solve the problem one tries to remove dusts and easily adhering soiling from these surfaces. This is usually achieved by cleaning in the so-called wet mopping process with mist-moist textile covers or fleeces, without any impairment of the surface occurs. In practice, however, other contaminants occur, which adhere more strongly or are also registered, for example, in bad weather. Such soiling can only be removed by wet wiping with cleaning textiles using cleaning agents.
  • the cleaning agent wets the surface and emulsifies or disperses the dirt.
  • a sufficient amount of cleaning liquor on the floor ensures the correct removal of the emulsified or dispersed dirt.
  • a larger amount of residual moisture also remains on the floor covering. This can, depending on the chosen cleaning agent, lead to visible residues on the surfaces. Accordingly, care should be taken when selecting cleaning agents that when used according to the Dry if possible no / few visible residues left on the floor surfaces.
  • Another criterion in choosing the appropriate cleaning agent is the wettability of surfaces.
  • the floor covering which, as explained at the outset, may be provided with polymer films, treated with polymer-containing care products in retrospect or may also be untreated, but also depending on the polishing effect, the surfaces have different surface properties.
  • EP 0 916 717 A1 describes an aqueous floor cleaner containing a nonionic surfactant from the group C 8 -C 22 -fatty alcohol-EO-PO adducts.
  • WO 96/10069 A1 describes a disinfecting cleaning agent for hard surfaces. This contains to reinforce the disinfecting effect, a mixture of alkyl or Alkylenpolyglykosiden and C 8 -C 18 alkyl ether.
  • US 5 858 956 describes an all-purpose cleaner containing anionic and nonionic surfactants.
  • the detergents currently available on the market for manual cleaning contain as surfactant base usually combinations of anionic and / or nonionic surfactants and possibly combinations with amphoteric surfactants.
  • the surfactant-based formulating agent preferably uses, if not exclusively, surfactants from the group of nonionic surfactants.
  • the main reason is that the candidate anionic surfactants used in the manual application formulations are out of the question due to their strong foaming properties. As a result, the formulator must inevitably resort to less foaming nonionic surfactants.
  • the developer was forced to accept other application-related deficiencies, in particular with regard to the cleaning performance.
  • the present invention has the object to develop floor cleaning and / or care products that can be used both manually and in cleaning machines equally problematic, with their cleaning performance should be comparable to that of the known anionic surfactant-based.
  • the agent according to the invention contains, based on the total agent, less than 3% by weight, preferably less than 1% by weight, of anionic surfactants, it being particularly preferred if substantially no anionic surfactant is present at all.
  • anionic surfactants are not intentionally added in the formulation of appropriate agents. It can not be ruled out that small quantities of anionic surfactants may nevertheless be introduced into the composition according to the invention as a result of other raw materials or impurities.
  • Bu in formula II is to be understood as meaning butyl, for example in a form such as is present in commercially available products, for example Plurafac® LF 221, which is available from BASF.
  • compositions according to the invention which comprise a nonionic surfactant according to formula II, with the proviso that R 6 is hydrogen and m is 0.
  • a further preferred embodiment of the agent according to the invention consists in that in the agent said nonionic surfactant of the formula I is at least one third and at most twice the weight of the further nonionic surfactant preferably present according to the invention. It is very particularly preferred if in the composition according to the invention, the amount by weight of said nonionic surfactant of the formula I is at least half as large, but not greater than the amount by weight of further nonionic surfactant preferably contained according to the invention.
  • the total amount of said nonionic surfactant of the formula I and, if present, the further nonionic surfactant preferably present according to the invention be from 5 to 35% by weight, preferably from 7 to 20% by weight. % is.
  • amine oxide derivatives are amine oxide derivatives, it being particularly preferred that the amine oxide derivative is a trialkylamine oxide having an alkyl group containing 8 to 20 carbon atoms and two alkyl groups having a smaller number of carbon atoms in the alkyl chain, the two shorter alkyl groups being the same or different, it being most preferred that the amine oxide derivative is tallow fatty bis (2-hydroxyethyl) amine oxide, oleyl bis (2-hydroxyethyl) amine oxide, coconut bis (2-hydroxyethyl) amine oxide, tetradecyldimethylamine oxide and / or alkyl dimethyl amine oxide having 12 to 18 carbon atoms in the alkyl chain.
  • Additional preferred surface active components are selected from the groups of cationic, nonionic, amphoteric surfactants, protein hydrolysates, silicone compounds and phosphoric acid esters and their salts.
  • alkylpolyglucosides which are usually commercially available by condensation of fatty alcohols with glucose or polyglucose and commercially available in various variants may be used in the compositions according to the invention.
  • alkylpolyglucosides that are suitable for use in the invention, the products Glukopon ® 600 Henkel and Triton ® BG10 made by Rohm & Haas.
  • Nonionic surfactants which may additionally be present in the agents according to the invention are further alkoxylated alkyl alcohols which do not fall under the compounds defined in formulas I and II.
  • Further surface-active compounds which are preferably contained in the agents according to the invention are those from the class of phosphoric esters, among which preferably at least one salt of a phosphoric acid partial ester is present, more preferably at least one alkali metal salt of a phosphoric acid partial ester of alkoxylated alkylphenol being present.
  • the phosphoric acid esters are surface-active substances which are preferably derived from long-chain aliphatic or araliphatic alcohols.
  • the salts of the phosphoric acid partial esters and here in particular those of alkoxylated alkylphenols have proved to be particularly suitable.
  • the alkali salts used are preferably the sodium and potassium salts, of which in turn the potassium salts are particularly preferred.
  • Surfactant phosphoric acid partial esters, which are preferably used according to the invention, are commercially available.
  • An example of an active ingredient of this type which is particularly useful according to the invention is the product Triton® H 66 (Röhm & Haas).
  • the inventive composition contains as additional component of polyethylene glycol and / or polypropylene glycol, said polyethyleneglycol and / or polypropylene glycol preferably has a molecular weight in the range of 200 to 2000. It has been found to be particularly advantageous if said polyethylene glycol and / or polypropylene glycol from 0.01 to 5 wt .-%, particularly preferably 0.05 to 1 wt .-%, based on the total agent, makes up.
  • Another object of the present invention is the use of an agent according to the invention for cleaning and / or care of soils that are uncoated or equipped with a polymer layer.
  • said agent is diluted with water by a dilution factor of 5 to 5,000, in particular 50 to 3,500.
  • the agents according to the invention are distinguished by the fact that their use achieves the same or better cleaning activity as with agents which contain more than 3% by weight of anionic surfactants.
  • the agents according to the invention have a very good wetting behavior, which is otherwise also observed only with agents containing more than 3% by weight of anionic surfactants.
  • the residue behavior and the desired foam profile in the compositions according to the invention is rated equal to or better than those currently marketed on the basis of pure nonionic surfactant basis.
  • Table 1a and Table 1b are given to an artificially soiled white PVC strip the detergent to be tested and machine a sponge back and forth. After a certain number of wiping cycles, the whiteness of the thus cleaned test strip is measured with a photoelectronic colorimeter.
  • test soil is generated as shown in Table 2 below: ⁇ b> Table 2: Generation of Test Debris ⁇ / b> raw material Wt .-% method Myritol 318 17.0 Mix oil and gasoline and add special black while stirring. Stir another eight hours. Stir again after three days. After 14 days the test soil is ready for use. 1 hour stirring time is required before each use. Gasoline 80/110 36.0 Telura 310 40.0 special Black 7.0
  • test strips 7 hard PVC strips are laid close to each other, resulting in an area of 280 * 554 mm.
  • the strips are provided with pressure-sensitive adhesive and allowed to dry overnight.
  • the white PVC film painted with the slightly smoother roll outside up is placed on the PVC strips, smoothed and pressed with the rubber roller, so that a uniform, bubble and wrinkle-free surface is formed.
  • Table 1a and Table 1b applied to a dilution factor of 500 prepared application solutions also laboratory tests for wetting and residue behavior (after drying).
  • specimens were prepared as described in Tables 4a and 4b. Thereafter, the specimens were wiped with eight-wiper textiles soaked in application solution. Lint-free, pre-washed wiping textiles were used, which had an area of about 15 ⁇ 15 cm. Before the wiping process, the wiping textiles were soaked in the respective application solution and expressed so manually that it no longer dripped.
  • Table 4a Performance properties of aqueous 0.2% detergents (see Table 1) with respect to different evaluation criteria ⁇ / b> E1 E2 * E3 E4 Cleaning power (Gardner in% RV) 59 62 55 57 network behavior A) 0 0 0 0 B) -0.1 -0.1 -0.3 -0.4 C) -0.2 -0.2 -0.3 -0.3 D) -0.4 -0.4 -0.6 -0.6 residue behavior e) -0.5 -1.0 -1.0 0 F) -1 -1.5 -1.5 0 G) -0.5 -1.0 -1.0 -0.5 H) -0.5 -1.5 -1.5 -0.5 D) -1.5 -2.0 -2.0 -1.0 * Comparative Example V1 V2 V3 V4 V5 V6 V7 V8 V9 Cleaning power (Gardner in% RV) 62 51 53 56 44 48 41 44 55 network behavior A)

Abstract

Aqueous floor cleaning and/or care composition, containing, based on the total composition, at least 3% by weight of a nonionic surfactant of formula I: wherein R1 represents hydrogen or an alkyl radical having 1 to 18 C atoms, and R2, independently of R1, represents hydrogen or an alkyl radical having 1 to 18 C atoms, and the sum of the C atoms present overall in R1 and R2 is between 6 and 18, and R3 represents an alkyl radical having 4 to 18 C atoms, and R4 hydrogen or an alkyl radical having 1 to 6 C atoms and n is a number from 1 to 30 and m a number from 0 to 5.

Description

Gegenstand der vorliegenden Erfindung sind wässerige Bodenreinigungs- und/oder Bodenpflegemittel, umfassend ein oder mehrere spezielle nichtionische Tenside sowie die Verwendung dieser Mittel zur Reinigung und/oder Pflege von Böden.The present invention relates to aqueous floor cleaning and / or floor care compositions comprising one or more specific nonionic surfactants and the use of these agents for cleaning and / or care of soils.

Fussbodenbeläge können werksseitig mit Polymerfilmen ausgestattet, durch den Einsatz polymerhaltiger Pflegemittel im nachhinein behandelt oder aber unbehandelt belassen werden.
All diese Oberflächen können verschmutzungsanfällig sein, auch und besonders wenn es sich um glänzende Oberflächen handelt. Es können Verunreinigungen, Stäube, aber auch Rückstände der antrocknenden Reinigungsflotte verstärkt sichtbar gemacht und ein unansehnliches Gesamtbild erzeugt werden.
Zur Lösung des Problems versucht man Stäube und leicht anhaftende Verschmutzungen von diesen Oberflächen zu entfernen. Dies gelingt üblicherweise durch Reinigung im sogenannten Feuchtwisch-Verfahren mit nebelfeuchten Textilbezügen oder Vliesen, ohne dass eine Beeinträchtigung der Oberfläche eintritt.
In der Praxis treten aber auch andere Verschmutzungen auf, die stärker haften oder aber auch zum Beispiel bei schlechtem Wetter eingetragen werden. Solche Verschmutzungen lassen sich nur durch nasses Wischen mit Reinigungstextilien unter Verwendung von Reinigungsmitteln entfernen. Durch die Reinigungsmittel wird die Oberfläche benetzt und der Schmutz emulgiert bzw. dispergiert.
Eine ausreichende Reinigungsflottenmenge auf dem Fußboden sorgt für den richtigen Abtransport des emulgierten bzw. dispergierten Schmutzes. Beim nassen Wischen verbleibt aber auch eine größere Menge Restfeuchte auf dem Bodenbelag zurück.
Dies kann, in Abhängigkeit von dem gewählten Reinigungsmittel, zu sichtbaren Rückständen auf den Oberflächen führen. Dementsprechend ist bei der Auswahl von Reinigungsmitteln darauf zu achten, dass bei deren Verwendung nach dem Trocknen möglichst keine/wenige sichtbare Rückstände auf den Bodenoberflächen zurückbleiben.Floor coverings can be factory-equipped with polymer films, treated with polymer-based care products afterwards or left untreated.
All of these surfaces may be prone to staining, even if they are glossy surfaces. It can impurities, dusts, but also residues of the drying drying fleet made more visible and an unsightly overall picture can be generated.
To solve the problem one tries to remove dusts and easily adhering soiling from these surfaces. This is usually achieved by cleaning in the so-called wet mopping process with mist-moist textile covers or fleeces, without any impairment of the surface occurs.
In practice, however, other contaminants occur, which adhere more strongly or are also registered, for example, in bad weather. Such soiling can only be removed by wet wiping with cleaning textiles using cleaning agents. The cleaning agent wets the surface and emulsifies or disperses the dirt.
A sufficient amount of cleaning liquor on the floor ensures the correct removal of the emulsified or dispersed dirt. During wet wiping, however, a larger amount of residual moisture also remains on the floor covering.
This can, depending on the chosen cleaning agent, lead to visible residues on the surfaces. Accordingly, care should be taken when selecting cleaning agents that when used according to the Dry if possible no / few visible residues left on the floor surfaces.

Ein weiteres Kriterium bei der Auswahl des geeigneten Reinigungsmittels ist die Benetzungsfähigkeit von Oberflächen. Je nach Fußbodenbelag, der wie eingangs erläutert mit Polymerfilmen ausgestattet, mit polymerhaltigen Pflegemitteln im nachhinein behandelt oder aber auch unbehandelt sein kann, aber auch je nach Poliereffekt weisen die Oberflächen unterschiedliche Oberflächeneigenschaften auf.Another criterion in choosing the appropriate cleaning agent is the wettability of surfaces. Depending on the floor covering, which, as explained at the outset, may be provided with polymer films, treated with polymer-containing care products in retrospect or may also be untreated, but also depending on the polishing effect, the surfaces have different surface properties.

Bei einer praxisüblichen Dosierung von 0,5 bis 1 g Tensid pro Liter Reinigungsflotte ist bei vielen marktüblichen Reinigungsmitteln die Benetzungsfähigkeit nicht zufriedenstellend. Werden derartige Reinigungsmittel eingesetzt, beobachtet man häufig, daß der Flüssigkeitsfilm aufreißt und auf der Bodenoberfläche Flüssigkeitsinseln mit unterschiedlich hoher Flüssigkeitsschichtdicke gebildet werden. Nach dem Abtrocknen werden meist genau diese Inseln aufgrund der zurückbleibenden Reinigungsmittelinhaltsstoffe sichtbar. Das resultierende fleckige Aussehen der Oberfläche wird in der Praxis als deutlicher Nachteil der entsprechenden Reinigungsmittel gewertet.In a practice usual dosage of 0.5 to 1 g of surfactant per liter of cleaning liquor wettability is not satisfactory in many commercially available cleaning agents. If such detergents are used, it is frequently observed that the liquid film ruptures and liquid islands of different high liquid layer thickness are formed on the bottom surface. After drying, these islands are usually visible due to the remaining detergent ingredients. The resulting spotty appearance of the surface is considered in practice to be a significant disadvantage of the corresponding cleaning agents.

Aufgrund der dargestellten Praxis-Probleme sind wesentliche Kriterien bei der Bewertung der Qualität von Bodenreinigungs- und/oder Bodenpflegemittel die Reinigungsleistung, die Benetzungsfähigkeit sowie (bei glänzenden Oberflächen) die Beeinträchtigung des Glanzes nach dem Abtrocknen.Due to the practical problems presented, essential criteria in the assessment of the quality of floor cleaning and / or floor care products are the cleaning performance, the wettability and (in the case of glossy surfaces) the impairment of the gloss after drying.

Als weitere Anforderung kommt bei Verwendung der wässerigen Bodenreinigungs- und/oder Bodenpflegemittel in sogenannten Scheuersaugmaschinen oder Reinigungsautomaten hinzu, dass die Mittel eine geringe Schaumstabilität und ein niedriges Schaumniveau aufweisen müssen, da sonst der Reinigungsvorgang durch Abschalten des Gerätes unterbrochen wird.
Zur Erläuterung sei hierzu gesagt: aufgrund des Einsatzes stark schäumender Reinigungsmittel bildet sich im Schmutzwassertank ein Schaumpolster. Dadurch wird der Schwimmer im Schmutzwassertank über das tatsächliche Flüssigkeitsniveau angehoben. Je nach Schaumstärke kann das dazu führen, dass der Abschaltmechanismus betätigt wird.As a further requirement when using the aqueous floor cleaning and / or floor care products in so-called scrubber or cleaning machines added that the means must have a low foam stability and a low foam level, otherwise the cleaning process is interrupted by switching off the device.
To explain this, it should be said: due to the use of strong foaming detergent forms a foam pad in the waste water tank. Thereby the float in the waste water tank is raised above the actual liquid level. Depending on the foam thickness, this can lead to the shut-off mechanism being actuated.

EP 0 916 717 A1 beschreibt einen wässrigen Fußbodenreiniger enthaltend ein nichtionisches Tensid aus der Gruppe C8-C22-Feltalkohol-EO-PO-Addukte.EP 0 916 717 A1 describes an aqueous floor cleaner containing a nonionic surfactant from the group C 8 -C 22 -fatty alcohol-EO-PO adducts.

WO 96/10069 A1 beschreibt ein desinfizierendes Reinigungsmittel für harte Oberflächen. Dieses enthält zur Verstärkung der desinfizierenden Wirkung eine Mischung aus Alkyl bzw. Alkylenpolyglykosiden und C8-C18-Alkylether.WO 96/10069 A1 describes a disinfecting cleaning agent for hard surfaces. This contains to reinforce the disinfecting effect, a mixture of alkyl or Alkylenpolyglykosiden and C 8 -C 18 alkyl ether.

US 5 858 956 beschreibt einen Allzweckreiniger, der anionische und nicht ionische Tenside enthält.US 5 858 956 describes an all-purpose cleaner containing anionic and nonionic surfactants.

Die derzeit im Markt verfügbaren Mittel für die manuelle Reinigung enthalten als tensidische Basis meist Kombinationen aus anionischen und/oder nichtionischen Tensiden sowie evtl. Kombinationen mit amphoteren Tensiden.
Bei der Anwendung in den oben genannten Reinigungsautomaten verwendet der Formulierer von Reinigungsmitteln als tensidische Basis vorzugsweise, wenn nicht sogar ausschließlich oberflächenaktive Verbindungen aus der Gruppe der nichtionischen Tenside. Der Grund besteht hauptsächlich darin, dass die in Frage kommenden Aniontenside, die in den Formulierungen für die manuelle Anwendung eingesetzt werden, aufgrund ihrer starken schaumbildenden Eigenschaften nicht in Frage kommen. Demzufolge muss der Formulierer notgedrungen auf weniger schäumende nichtionische Tenside ausweichen. Dabei war der Entwickler in der Vergangenheit gezwungen, andere anwendungstechnische Mängel insbesondere im Hinblick auf die Reinigungsleistung in Kauf zu nehmen.The detergents currently available on the market for manual cleaning contain as surfactant base usually combinations of anionic and / or nonionic surfactants and possibly combinations with amphoteric surfactants.
When used in the above-mentioned cleaning machines, the surfactant-based formulating agent preferably uses, if not exclusively, surfactants from the group of nonionic surfactants. The main reason is that the candidate anionic surfactants used in the manual application formulations are out of the question due to their strong foaming properties. As a result, the formulator must inevitably resort to less foaming nonionic surfactants. In the past, the developer was forced to accept other application-related deficiencies, in particular with regard to the cleaning performance.

Dementsprechend lag der vorliegenden Erfindung die Aufgabe zugrunde, Bodenreinigungs- und/oder -pflegemittel zu entwickeln, die sowohl manuell als auch in Reinigungsautomaten gleichermaßen unproblematisch eingesetzt werden können, wobei deren Reinigungsleistung mit der der bekannten Mittel auf Aniontensid-Basis vergleichbar sein soll.Accordingly, the present invention has the object to develop floor cleaning and / or care products that can be used both manually and in cleaning machines equally problematic, with their cleaning performance should be comparable to that of the known anionic surfactant-based.

Dementsprechend sind Gegenstand der vorliegenden Erfindung wässerige Bodenreinigungs- und/oder Bodenpflegemittel, enthaltend bezogen auf das gesamte Mittel wenigstens 3 Gew.-% eines nichtionischen Tensids der Formel I

Figure imgb0001
wobei R1 für Wasserstoff steht und R2 einen Alkylrest mit 6 bis 18 C-Atomen bedeutet, oder

  • R1 für einen Alkylrest mit 6 bis 18 C-Atomen steht, und R2 Wasserstoff bedeutet, oder
  • R1 für einen Alkylrest mit 1 bis 18 C-Atomen steht, und R2 unabhängig von R1 einen Alkylrest mit 1 bis 18 C-Atomen bedeutet, und die Summe der in R1 und R2 insgesamt vorliegenden C-Atome zwischen 6 und 18 liegt, und
  • R3 einen Alkylrest mit 4 bis 18 C-Atomen, und R4 Wasserstoff oder einen Alkylrest mit 1 bis 6 C-Atomen darstellt und n eine Zahl von 1 bis 30 und m eine Zahl von 0 bis 5 ist und, dass das Mittel mindestens ein weiteres nichtionisches Tensid umfaßt, das nicht unter die Formel I fällt, wobei dass das genannte weitere nichtionische Tensid ausgewählt ist aus den Verbindungen der Formel II

            R5-CH2-CH2-(OCH2-CH2)n-(OCH(CH3)-CH2]m,-[OBu]l-OR6     (II)

wobei R5 für einen Alkylrest mit 6 bis 18 C-Atomen steht, und R6 Wasserstoff oder einen Alkylrest mit 1 bis 6 C-Atomen darstellt, und der mittlere Ethoxlierungsgrad n eine Zahl von 1 bis 30, der mittlere Propoxylierungsgrad m eine Zahl von 0 bis 5, sowie der mittlere Butoxylierungsgrad I eine Zahl von, 1 bis 4 ist.Accordingly, the subject of the present invention aqueous floor cleaning and / or floor care compositions containing, based on the total agent, at least 3% by weight of a nonionic surfactant of the formula I.
Figure imgb0001
 wherein R 1 is hydrogen and R 2 is an alkyl radical having 6 to 18 carbon atoms, or
  • R 1 is an alkyl radical having 6 to 18 C atoms, and R 2 is hydrogen, or
  • R 1 is an alkyl radical having 1 to 18 carbon atoms, and R 2 is independently of R 1 is an alkyl radical having 1 to 18 carbon atoms, and the sum of the total in R 1 and R 2 present C atoms between 6 and 18 lies, and
  • R 3 is an alkyl radical having 4 to 18 C atoms, and R 4 is hydrogen or an alkyl radical having 1 to 6 C atoms and n is a number from 1 to 30 and m is a number from 0 to 5 and that the agent is at least another nonionic surfactant which does not fall under the formula I, wherein said further nonionic surfactant is selected from the compounds of formula II

    R 5 -CH 2 -CH 2 - (OCH 2 -CH 2 ) n - (OCH (CH 3 ) -CH 2 ] m , - [OBu] l -OR 6 (II)

where R 5 is an alkyl radical having 6 to 18 C atoms, and R 6 is hydrogen or an alkyl radical having 1 to 6 C atoms, and the average degree of ethoxylation n is a number from 1 to 30, the average degree of propoxylation m is a number of 0 to 5, and the average Butoxylierungsgrad I is a number from, 1 to 4.

In einer bevorzugten Ausführungsform enthält das erfindungsgemäße Mittel bezogen auf das gesamte Mittel, weniger als 3 Gew.-%, vorzugsweise weniger als 1 Gew.% Anion-Tenside, wobei es besonders bevorzugt ist, wenn im wesentlichen überhaupt kein Anion-Tensid vorliegt. Die Abwesenheit von Anion-Tensid ist im Sinne der vorliegenden Erfindung so zu verstehen, dass bei der Formulierung entsprechender Mittel nicht absichtlich Aniontenside zugegeben werden. Es kann nicht ausgeschlossen werden, dass durch andere Rohstoffe oder Verunreinigungen dennoch Aniontenside in geringen Mengen in das erfindungsgemäße Mittel gelangen.In a preferred embodiment, the agent according to the invention contains, based on the total agent, less than 3% by weight, preferably less than 1% by weight, of anionic surfactants, it being particularly preferred if substantially no anionic surfactant is present at all. For the purposes of the present invention, the absence of anionic surfactant is to be understood as meaning that anionic surfactants are not intentionally added in the formulation of appropriate agents. It can not be ruled out that small quantities of anionic surfactants may nevertheless be introduced into the composition according to the invention as a result of other raw materials or impurities.

Unter Bu in Formel II ist im Sinne der vorliegenden Erfindung Butyl zu verstehen, und zwar beispielsweise in einer Form wie es in marktüblichen Produkten, beispielsweise Plurafac® LF 221, das von der BASF erhältlich ist, vorliegt.
Ganz besonders bevorzugt sind erfindungsgemäße Mittel, die ein nichtionisches Tensid gemäß Formel II enthalten, mit der Auflage, dass R6 gleich Wasserstoff und m gleich 0 ist.For the purposes of the present invention, Bu in formula II is to be understood as meaning butyl, for example in a form such as is present in commercially available products, for example Plurafac® LF 221, which is available from BASF.
Very particular preference is given to compositions according to the invention which comprise a nonionic surfactant according to formula II, with the proviso that R 6 is hydrogen and m is 0.

Eine weitere bevorzugte Ausführungsform des erfindungsgemäßen Mittels besteht darin, dass in dem Mittel das genannte nichtionische Tensid der Formel I wenigstens ein Drittel und höchstens das Zweifache des Gewichts des weiteren erfindungsgemäß bevorzugt enthaltenen nichtionischen Tensids beträgt.
Dabei ist es ganz besonders bevorzugt, wenn in dem erfindungsgemäßen Mittel die Gewichtsmenge des genannten nichtionischen Tensids der Formel I wenigstens halb so groß, aber nicht größer als die Gewichtsmenge des weiteren erfindungsgemäß bevorzugt enthaltenen nichtionischen Tensids ist.A further preferred embodiment of the agent according to the invention consists in that in the agent said nonionic surfactant of the formula I is at least one third and at most twice the weight of the further nonionic surfactant preferably present according to the invention.
It is very particularly preferred if in the composition according to the invention, the amount by weight of said nonionic surfactant of the formula I is at least half as large, but not greater than the amount by weight of further nonionic surfactant preferably contained according to the invention.

Es ist weiterhin bevorzugt, dass, bezogen auf das gesamte Mittel, die Gesamtmenge an genanntem nichtionischen Tensid der Formel I und, sofern vorhanden, dem weiteren erfindungsgemäß bevorzugt enthaltenen nichtionischen Tensid, 5 bis 35 Gew.-%, vorzugsweise 7 bis 20 Gew.-% beträgt.It is furthermore preferred that, based on the total agent, the total amount of said nonionic surfactant of the formula I and, if present, the further nonionic surfactant preferably present according to the invention, be from 5 to 35% by weight, preferably from 7 to 20% by weight. % is.

Weitere bevorzugte oberflächenaktive Komponenten sind Aminoxidderivate, wobei besonders bevorzugt ist, dass das Aminoxidderivat ein Trialkylaminoxid mit einer 8 bis 20 Kohlenstoffatome enthaltenden Alkylgruppe und zwei Alkylgruppen mit einer geringeren Anzahl an Kohlenstoffatomen in der Alkylkette darstellt, wobei die beiden kürzeren Alkylgruppen gleich oder verschieden sein können, wobei es ganz besonders bevorzugt ist, dass das Aminoxidderivat Talgfett-bis-(2-hydroxyethyl)-aminoxid, Oleyl-bis-(2-hydroxyethyl-)-aminoxid, Kokos-bis-(2-hydroxyethyl)-aminoxid, Tetradecyldimethyl-aminoxid und/oder Alkyldimethyl-aminoxid, das 12 bis 18 Kohlenstoffatome in der Alkylkette aufweist, ist.Further preferred surface active components are amine oxide derivatives, it being particularly preferred that the amine oxide derivative is a trialkylamine oxide having an alkyl group containing 8 to 20 carbon atoms and two alkyl groups having a smaller number of carbon atoms in the alkyl chain, the two shorter alkyl groups being the same or different, it being most preferred that the amine oxide derivative is tallow fatty bis (2-hydroxyethyl) amine oxide, oleyl bis (2-hydroxyethyl) amine oxide, coconut bis (2-hydroxyethyl) amine oxide, tetradecyldimethylamine oxide and / or alkyl dimethyl amine oxide having 12 to 18 carbon atoms in the alkyl chain.

Zusätzliche bevorzugte oberflächenaktive Komponenten sind ausgewählt aus den Gruppen der kationischen, nichtionischen, amphoteren Tenside, Eiweißhydrolysate, der Silikonverbindungen und der Phosphorsäureester und deren Salzen. Als zusätzliche nichtionische Tenside können in den erfindungsgemäßen Mitteln Alkylpolyglukoside, die üblicherweise durch Kondensation von Fettalkoholen mit Glukose oder Polyglukose großtechnisch zugänglich und in verschiedenen Varianten im Handel erhältlich sind, eingesetzt werden. Beispiele von Alkylpolyglukosiden, die sich für den erfindungsgemäßen Einsatz eignen, sind die Produkte Glukopon® 600 der Firma Henkel und Triton® BG10 der Firma Röhm & Haas. Als nichtionische Tenside können in den erfindungsgemäßen Mitteln zusätzlich weitere alkoxylierte Alkylalkohole enthalten sein, die nicht unter die in Formel I und II definierten Verbindungen fallen.Additional preferred surface active components are selected from the groups of cationic, nonionic, amphoteric surfactants, protein hydrolysates, silicone compounds and phosphoric acid esters and their salts. As additional nonionic surfactants, alkylpolyglucosides which are usually commercially available by condensation of fatty alcohols with glucose or polyglucose and commercially available in various variants may be used in the compositions according to the invention. Examples of alkylpolyglucosides that are suitable for use in the invention, the products Glukopon ® 600 Henkel and Triton ® BG10 made by Rohm & Haas. Nonionic surfactants which may additionally be present in the agents according to the invention are further alkoxylated alkyl alcohols which do not fall under the compounds defined in formulas I and II.

Weitere in den erfindungsgemäßen Mitteln bevorzugt enthaltene tensidische Verbindungen sind solche aus der Klasse der Phosphorsäureester, worunter sich vorzugsweise zumindest ein Salz eines Phosphorsäurepartialesters befindet, wobei besonders bevorzugt wenigstens ein Alkalisalz eines Phosphorsäurepartialesters von alkoxyliertem Alkylphenol vorliegt.Further surface-active compounds which are preferably contained in the agents according to the invention are those from the class of phosphoric esters, among which preferably at least one salt of a phosphoric acid partial ester is present, more preferably at least one alkali metal salt of a phosphoric acid partial ester of alkoxylated alkylphenol being present.

Bei den Phosphorsäureestern handelt es sich um tensidische Substanzen, die sich vorzugsweise von langkettigen aliphatischen oder araliphatischen Alkoholen ableiten. Als besonders geeignet haben sich die Salze der Phosphorsäurepartialester und hier insbesondere die von alkoxylierten Alkylphenolen erwiesen. Vorzugsweise werden als Alkalisalze die Natrium- und Kaliumsalze verwendet, von denen wiederum die Kaliumsalze besonders bevorzugt werden. Tensidisch wirksame Phosphorsäurepartialester, wie sie bevorzugt erfindungsgemäß verwendet werden, sind im Handel erhältlich. Ein Beispiel eines erfindungsgemäß besonders gut brauchbaren Wirkstoffs dieser Art ist das Produkt Triton® H 66 (Röhm & Haas).The phosphoric acid esters are surface-active substances which are preferably derived from long-chain aliphatic or araliphatic alcohols. The salts of the phosphoric acid partial esters and here in particular those of alkoxylated alkylphenols have proved to be particularly suitable. The alkali salts used are preferably the sodium and potassium salts, of which in turn the potassium salts are particularly preferred. Surfactant phosphoric acid partial esters, which are preferably used according to the invention, are commercially available. An example of an active ingredient of this type which is particularly useful according to the invention is the product Triton® H 66 (Röhm & Haas).

Vorzugsweise enthält das erfindungsgemäße Mittel als zusätzliche Komponente Polyethylenglykol und/oder Polypropylenglykol, wobei das genannte Polyethylenglykol und/oder Polypropylenglykol bevorzugt ein Molekulargewicht im Bereich von 200 bis 2000 aufweist.
Dabei hat es sich als besonders vorteilhaft herausgestellt, wenn das genannte Polyethylenglykol und/oder Polypropylenglykol 0,01 bis 5 Gew.-%, besonders bevorzugt 0,05 bis 1 Gew.-%, bezogen auf das gesamte Mittel, ausmacht.Preferably, the inventive composition contains as additional component of polyethylene glycol and / or polypropylene glycol, said polyethyleneglycol and / or polypropylene glycol preferably has a molecular weight in the range of 200 to 2000.
It has been found to be particularly advantageous if said polyethylene glycol and / or polypropylene glycol from 0.01 to 5 wt .-%, particularly preferably 0.05 to 1 wt .-%, based on the total agent, makes up.

Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung eines erfindungsgemäßen Mittels zur Reinigung und/oder Pflege von Böden, die unbeschichtet oder mit einer Polymerschicht ausgerüstet sind.Another object of the present invention is the use of an agent according to the invention for cleaning and / or care of soils that are uncoated or equipped with a polymer layer.

Vorzugsweise wird vor der erfindungsgemäßen Verwendung für die Reinigung und/oder Pflege das genannte Mittel mit Wasser um einen Verdünnungsfaktor von 5 bis 5000, insbesondere 50 bis 3500 verdünnt.Preferably, before use according to the invention for cleaning and / or care, said agent is diluted with water by a dilution factor of 5 to 5,000, in particular 50 to 3,500.

Die erfindungsgemäßen Mittel zeichnen sich dadurch aus, dass durch ihren Einsatz gleiche oder bessere Reinigungsaktivität erreichbar ist wie mit Mitteln, die mehr als 3 Gew.-% an Aniontensiden enthalten. Darüber hinaus beobachtet man mit den erfindungsgemäßen Mitteln ein sehr gutes Benetzungsverhalten, wie es ansonsten ebenfalls nur mit Mitteln beobachtet wird, die mehr als 3 Gew.-% an Aniontensiden enthalten.
Außerdem sei gesagt, dass das Rückstandverhalten und das gewünschte Schaumprofil bei den erfindungsgemäßen Mitteln gleich oder besser bewertet wird wie bei den derzeit im Markt befindlichen Mitteln, die auf reiner Niotensid-Basis formuliert sind.The agents according to the invention are distinguished by the fact that their use achieves the same or better cleaning activity as with agents which contain more than 3% by weight of anionic surfactants. In addition, the agents according to the invention have a very good wetting behavior, which is otherwise also observed only with agents containing more than 3% by weight of anionic surfactants.
In addition, it should be noted that the residue behavior and the desired foam profile in the compositions according to the invention is rated equal to or better than those currently marketed on the basis of pure nonionic surfactant basis.

BEISPIELEEXAMPLES 1. Herstellung von Testlösungen1. Preparation of test solutions

Durch einfaches Zusammenfügen verschiedener Einzelbestandteile, vorzugsweise unter Rühren, wurden die erfindungsgemäßen Reinigungsmittel E1 bis E4 gemäß Tabelle 1a sowie die zum Vergleich herangezogenen Reinigungsmittel V1 bis V9 gemäß Tabelle 1b hergestellt. Tabelle 1a: Wässerige erfindungsgemäße Reinigungsmittel mit unterschiedlichen Inhaltsstoffen (in Gew.-%) Rohstoffe E1 E2* E3 E4 Fettalkohol C12-C18 EO/BuO-Addukt 10,0 - 20,0 15,0 Alkohol C8-C10-1PO-22EO Hydroxydecylether 20,0 30,0 10,0 15,0 Glykolether 0-10 Komplexbildner 0,1-1 Hilfsstoffe 0-1 Farbstoffe 0-0,1 Andere Hilfsstoffe 0-8 Wasser Ad100 * Vergleichsbeispiel Tabelle 1b: Wässerige Vergleichs-Reinigungsmittel mit unterschiedlichen Inhaltsstoffen (in Gew.-%) Rohstoffe V1 V2 V3 V4 V5 V6 V7 V8 V9 C15-Alkansulfonat-Na 15,0 10,0 5,0 - - - - - - C12-C14Laurylethersulfat 15,0 - 15,0 15,0 - - - - Fettalkohol C8-C10 Glucosid - 10.0 - - - - - - - Fettalkohol C12-C18 + 10EO - 10,0 - - 16,0 - 10,0 10,0 - Fettalkohol C12-C14 + 4EO - - - - 4,0 - - - - Fettalkohol C12-C14 + 5 EO + 4PO - - - 15,0 - - - - - Fettalkohol C12-C18 Polyglykolether - - 10,0 - 10,0 - - - - Fettalkohol C12-C15 + 10EO - - - - - - 10,0 - Isotridecylalkohol + 8 EO - - - - - - 10,0 - 12,0 Oxoalkohol C12-C15 + 8EO - - - - - 12,0 - - - Dimethylalkyl C12-C14 Aminoxid - - - - - 6,0 - - 6,0 Oxoalkohol C13-C15 + 6EO + 2BuO Methyl-endgruppenverschlossen - - - - - 12,0 - - 12,0 Fettalkohol C12-C18 EO/BuO-Addukt - - - - - - - 20,0 - Alkohol C8-C10-1PO-22EO Hydroxydecylether - - - - - - - - - Glykolether 0-10 Komplexbildner 0,1-1 Hilfsstoffe 0-1 Farbstoffe 0,01 Andere Hilfsstoffe 0-8 Wasser ad 100 By simply combining various individual constituents, preferably while stirring, the inventive cleaning compositions E1 to E4 according to Table 1a and the cleaning agents V1 to V9 used for comparison were prepared according to Table 1b. <b> Table 1a: </ b> Aqueous cleaning agents according to the invention with different ingredients (in% by weight) raw materials E1 E2 * E3 E4 Fatty alcohol C 12 -C 18 EO / BuO adduct 10.0 - 20.0 15.0 Alcohol C 8 -C 10 -1PO-22EO hydroxydecyl ether 20.0 30.0 10.0 15.0 glycol ethers 0-10 complexing 0.1-1 excipients 0-1 dyes 0-0.1 Other adjuvants 0-8 water ad100 * Comparative Example raw materials V1 V2 V3 V4 V5 V6 V7 V8 V9 C 15 alkanesulfonate Na 15.0 10.0 5.0 - - - - - - C 12 -C 14 lauryl ether sulfate 15.0 - 15.0 15.0 - - - - Fatty alcohol C 8 -C 10 glucoside - 10.0 - - - - - - - Fatty alcohol C 12 -C 18 + 10EO - 10.0 - - 16.0 - 10.0 10.0 - Fatty alcohol C 12 -C 14 + 4EO - - - - 4.0 - - - - Fatty alcohol C 12 -C 14 + 5 EO + 4PO - - - 15.0 - - - - - Fatty alcohol C 12 -C 18 polyglycol ether - - 10.0 - 10.0 - - - - Fatty alcohol C 12 -C 15 + 10EO - - - - - - 10.0 - Isotridecyl alcohol + 8 EO - - - - - - 10.0 - 12.0 Oxoalcohol C 12 -C 15 + 8EO - - - - - 12,0 - - - Dimethylalkyl C 12 -C 14 amine oxide - - - - - 6.0 - - 6.0 Oxo alcohol C 13 -C 15 + 6EO + 2BuO methyl end-capped - - - - - 12,0 - - 12.0 Fatty alcohol C 12 -C 18 EO / BuO adduct - - - - - - - 20.0 - Alcohol C 8 -C 10 -1PO-22EO hydroxydecyl ether - - - - - - - - - glycol ethers 0-10 complexing 0.1-1 excipients 0-1 dyes 0.01 Other adjuvants 0-8 water ad 100

Für die Untersuchungen in Labortests wurden aus den Reinigungsmitteln gemäß Tabelle 1a und Tabelle 1b durch Verdünnen mit Wasser um einen Verdünnungsfaktor von 500 je 500 ml Anwendungslösung hergestellt und in 1000 ml Bechergläser mit weiter Form gefüllt.For laboratory testing, 500 ml of 500 ml solution of each of the detergents shown in Table 1a and Table 1b was prepared by dilution with water and filled into 1,000 ml wide mouth beakers.

Reinigungsverhalten nach Gardner:Cleaning behavior according to Gardner:

Für die Durchführung der Versuche zum Reinigungsverhalten der verdünnten Reinigungsmittel gem. Tabelle 1a und Tabelle 1b gibt man auf einen künstlich angeschmutzten weißen PVC Streifen das zu prüfende Reinigungsmittel und bewegt maschinell einen Schwamm hin und her. Nach einer bestimmten Anzahl von Wischzyklen wird der Weißgrad des so gereinigten Teststreifens mit einem photoelektronischen Farbmessgerät gemessen.For carrying out the experiments on the cleaning behavior of the diluted detergent gem. Table 1a and Table 1b are given to an artificially soiled white PVC strip the detergent to be tested and machine a sponge back and forth. After a certain number of wiping cycles, the whiteness of the thus cleaned test strip is measured with a photoelectronic colorimeter.

Als Gerätschaften für die Durchführung der Versuche sind folgende Gegenstände zu nennen:

  1. 1. Gardner-Waschbarkeits- und Scheuerprüfgerät Modell 494 (DIN ASTM-515) Lieferant: Erichson GmbH & Co. KG
  2. 2. Dr. Lange Farbdifferenzmessgerät "Micro Colour LM" Lieferant: Dr. Lange GmbH
  3. 3. Schwammpresse
  4. 4. Weißer PVC-Film, Benova Nr. 2211180
  5. 5. Hart-PVC-Streifen der Abmessung 40*554*3 mm als Träger
  6. 6. Haftkleber J 6251 der Firma Henkel (1:1 mit Ethylacetat verdünnt)
  7. 7. Schablone aus Hart-PVC
  8. 8. Polyesterschwämme, 30*45*90 mm, Typ Europor B, Porenzahl: 40 ppi (pores per inch), Stauchkante: 2,6 kPa (DIN 53577) Lieferant: Europlastic Pahl & Pahl & Co.
  9. 9. Lackierflachpinsel mit Naturborsten, ca. 55 mm breit zum Auftragen des Testschmutzes
  10. 10. Uhrgläser, ca. 12 cm Durchmesser, zum Abwiegen des Testschmutzes
  11. 11. Gummiroller, glatt, 150 mm breit
  12. 12. Teppichmesser
  13. 13. Einwegspritzen
  14. 14. Magnetrührer
  15. 15. Laborwaage, Bereich 2000 g, Messgenauigkeit 0,01 g
As equipment for carrying out the experiments, the following items should be mentioned:
  1. 1. Gardner Washability and Abrasion Tester Model 494 (DIN ASTM-515) Supplier: Erichson GmbH & Co. KG
  2. 2. Dr. Long Color Difference Meter "Micro Color LM" Supplier: Dr. med. Lange GmbH
  3. 3. sponge press
  4. 4. White PVC film, Benova No. 2211180
  5. 5. Hard PVC strip measuring 40 * 554 * 3 mm as a carrier
  6. 6. Pressure-sensitive adhesive J 6251 from Henkel (diluted 1: 1 with ethyl acetate)
  7. 7. Stencil made of hard PVC
  8. 8. Polyester sponges, 30 * 45 * 90 mm, Europor B type, porosity: 40 ppi (pores per inch), upset edge: 2.6 kPa (DIN 53577) Supplier: Europlastic Pahl & Pahl & Co.
  9. 9. Varnishing flat brush with natural bristles, approx. 55 mm wide for applying the test dirt
  10. 10. Watch glasses, about 12 cm in diameter, to weigh the test dirt
  11. 11. Rubber roller, smooth, 150 mm wide
  12. 12. Carpet knife
  13. 13. Disposable syringes
  14. 14. Magnetic stirrer
  15. 15. Laboratory balance, 2000 g range, measuring accuracy 0.01 g

Die Testanschmutzung wird wie in nachstehender Tabelle 2 dargestellt, erzeugt: Tabelle 2: Erzeugung der Testanschmutzung Rohstoff Gew.-% Verfahren Myritol 318 17,0 Öl und Benzin mischen und unter Rühren Spezialschwarz zugeben. Weitere acht Stunden rühren. Nach drei Tagen nochmals rühren. Nach 14 Tagen ist der Testschmutz gebrauchsfertig. Vor jedem Gebrauch ist 1 Stunde Rührzeit erforderlich. Benzin 80/110 36,0 Telura 310 40,0 Spezialschwarz 7,0 The test soil is generated as shown in Table 2 below: <b> Table 2: Generation of Test Debris </ b> raw material Wt .-% method Myritol 318 17.0 Mix oil and gasoline and add special black while stirring. Stir another eight hours. Stir again after three days. After 14 days the test soil is ready for use. 1 hour stirring time is required before each use. Gasoline 80/110 36.0 Telura 310 40.0 special Black 7.0

Zur Vorbereitung der Teststreifen werden 7 Hart-PVC-Streifen dicht nebeneinander gelegt, so dass sich eine Fläche von 280*554 mm ergibt. Die Streifen werden mit Haftkleber versehen und über Nacht trocknen gelassen.
Die weiße PVC-Folie gestrichen mit der etwas glatteren Rollenaußenseite nach oben wird auf die PVC-Streifen gelegt, glattgestrichen und mit dem Gummiroller aufgepresst, so dass eine einheitliche, blasen- und faltenfreie Oberfläche entsteht.To prepare the test strips, 7 hard PVC strips are laid close to each other, resulting in an area of 280 * 554 mm. The strips are provided with pressure-sensitive adhesive and allowed to dry overnight.
The white PVC film painted with the slightly smoother roll outside up is placed on the PVC strips, smoothed and pressed with the rubber roller, so that a uniform, bubble and wrinkle-free surface is formed.

Beim Auftragen des Testschmutzes wird wie folgt verfahren:

  1. 1. die PVC-Schablone über die Folie und die Streifen legen.
  2. 2. Auf einem Uhrglas 2 g Testschmutz abwiegen.
  3. 3. Mit dem Flachpinsel den Schmutz auf der weißen PVC-Folie, innerhalb der Schablone, auftragen. Zuerst mit horizontalen und dann mit vertikalen Pinselstrichen. Den Vorgang mehrmals wiederholen, wobei der letzte Auftrag quer zur Scheuerbewegung erfolgen soll.
  4. 4. Den Schmutz-mindestens eine Stunde trocknen lassen.
  5. 5. Mit dem Teppichmesser die PVC-Folie entlang der untenliegenden Hart-PVC-Streifen schneiden.
When applying the test dirt proceed as follows:
  1. 1. Lay the PVC stencil over the foil and the strips.
  2. 2. Weigh 2 g of test dirt on a watch glass.
  3. 3. Use the flat brush to apply the dirt on the white PVC foil inside the template. First with horizontal and then with vertical brushstrokes. Repeat the process several times, the last job being done across the rubbing motion.
  4. 4. Allow the dirt to dry for at least one hour.
  5. 5. Use the utility knife to cut the PVC film along the hard PVC strips underneath.

Bei der Bestimmung des Reinigungsvermögens (RV-Wert) geht man wie folgt vor: Die für den Test benötigte Anzahl Polyersterschwämme über Nacht in Leitungswasser wässern.

  1. 1. Einen Schwamm aus dem Eimer nehmen und abtropfen lassen.
  2. 2. Den Schwamm in der Auspressvorrichtung 10 Sekunden lang auspressen.
  3. 3. Den Schwamm in die Halterung der Gardner-Apparatur einsetzten.
  4. 4. Einen angeschmutzten Teststreifen in die Führungsschiene des Gardnergeräts legen.
  5. 5. Die Führungsschiene unter dem Schwammhalter anbringen und den Schwamm aufsetzen.
  6. 6. Mit einem Messbecher die benötigte Menge an Reinigungslösung aufbringen. Bei konzentrierten Produkten 6 ml und bei verdünnten Produkten 12 ml auf den Teststreifen geben.
  7. 7. Die automatische Zählvorrichtung des Gerätes auf 10 Wischzyklen einstellen und das Gardnergerät einschalten.
  8. 8. Nach Beendigung der Wischzyklen den Schwamm entnehmen und wegwerfen (nicht wiederverwenden)
  9. 9. Den Teststreifen aus dem Gerät entnehmen, unter fließendem Wasser abspülen und trocknen lassen.
  10. 10. Pro Testlösung sechs angeschmutzte Teststreifen nach dieser Methode reinigen.
  11. 11. Der 7. Teststreifen wird zum Vergleich nur mit Wasser gereinigt.
When determining the cleaning power (RV value), proceed as follows: Water the number of polyester sponges required for the test overnight in tap water.
  1. 1. Remove a sponge from the bucket and drain.
  2. 2. Press out the sponge in the squeezer for 10 seconds.
  3. 3. Insert the sponge into the holder of the Gardner apparatus.
  4. 4. Place a soiled test strip in the guide rail of the Gardner device.
  5. 5. Install the guide rail under the sponge holder and place the sponge.
  6. 6. Using a measuring cup, apply the required amount of cleaning solution. For concentrated products add 6 ml and for diluted products 12 ml to the test strip.
  7. 7. Set the automatic counting device of the device to 10 wiping cycles and switch on the Gardner device.
  8. 8. After completing the wiping cycles, remove the sponge and discard it (do not reuse it)
  9. 9. Remove the test strip from the device, rinse under running water and allow to dry.
  10. 10. Clean six soiled test strips per test solution using this method.
  11. 11. The 7th test strip is only cleaned with water for comparison.

Nach Durchführung dieser Versuchsfolge wird der Weißgrad (% RV) wie folgt gemessen:

  1. 1. Das Farbmessgerät mit einem unbehandelten Stück der weißen PVC-Folie kalibrieren. Die Reflektion wird gleich 100 % gesetzt.
  2. 2. Von jedem der 6 Teststreifen an sieben verschiedenen Punkten die Reflektion messen. Der Mittelwert der gefundenen Werte gibt das Reinigungsvermögen in % an.
After performing this test, the whiteness (% RV) is measured as follows:
  1. 1. Calibrate the colorimeter with an untreated piece of white PVC film. The reflection is set equal to 100%.
  2. 2. Measure the reflection from each of the 6 test strips at seven different points. The mean value of the values found indicates the cleaning capacity in%.

Einzelne stark abweichende Werte werden bei der Berechnung nicht berücksichtigt.Individual strongly deviating values are not taken into account in the calculation.

Danach werden für die zu untersuchenden Lösungen die Mittelwerte aus allen Messungen bestimmt: X ‾ = Σ x N

Figure imgb0002

  • N = Zahl der Messwerte (7*7 = 49)
  • X̅ = Mittlere Reinigungsleistung
Then the mean values of all measurements are determined for the solutions to be investigated: X ~ = Σ x N
Figure imgb0002
  • N = number of measured values (7 * 7 = 49)
  • X̅ = average cleaning performance

Die auf diese Weise ermittelten Ergebnisse sind in den Tabellen 4a und 4b enthalten.The results obtained in this way are shown in Tables 4a and 4b.

Benetzungs- und Rückstandsverhalten:Wetting and residue behavior:

Neben dem Reinigungsverhalten wurden mit den durch Verdünnen der Reinigungsmittel gem. Tabelle 1a und Tabelle 1b um einen Verdünnungsfaktor von 500 hergestellten Anwendungslösungen auch Laborversuche zum Benetzungs- und Rückstandsverhalten (nach Trocknen) durchgeführt.
Hierfür wurden Prüflinge, wie im Anschluß an die Tabellen 4a und 4b beschrieben, vorbereitet.
Danach wurden die Prüflinge mit in Anwendungslösung getränkten Wischtextilien in Achterschleifen gewischt.
Dabei wurden flusenfreie, vorgewaschene Wischtextilien verwendet, die eine Fläche von etwa 15 X 15 cm aufwiesen.
Vor dem Wischvorgang wurden die Wischtextilien in der jeweiligen Anwendungslösung getränkt und so sehr manuell ausgedrückt, dass es nicht mehr tropfte.In addition to the cleaning behavior were mixed with the by diluting the detergent. Table 1a and Table 1b applied to a dilution factor of 500 prepared application solutions also laboratory tests for wetting and residue behavior (after drying).
For this purpose, specimens were prepared as described in Tables 4a and 4b.
Thereafter, the specimens were wiped with eight-wiper textiles soaked in application solution.
Lint-free, pre-washed wiping textiles were used, which had an area of about 15 × 15 cm.
Before the wiping process, the wiping textiles were soaked in the respective application solution and expressed so manually that it no longer dripped.

Zur Bewertung der Ergebnisse nach Durchführung der Wischversuche wurden die Oberflächen unter Heranziehen der Bewertungsmaßstäbe aus Tabelle 3 begutachtet. Die Ergebnisse sind in den Tabellen 4a und 4b wiedergegeben.In order to evaluate the results after the wiping tests were carried out, the surfaces were evaluated using the evaluation scales from Table 3. The results are shown in Tables 4a and 4b.

Hinsichtlich des Netzverhaltens wurde der Mittelwert aus fünf Wischzyklen genommen und als Ergebnis in die Tabellen 4a und 4b übernommen.With regard to the network behavior, the mean value was taken from five wipe cycles and taken over as the result in Tables 4a and 4b.

Bei der Auswertung des Rückstandsverhaltens ist zu beachten, daß die Oberflächen nach 10, 20 und 30 Wischzyklen begutachtet wurden und die in den Tabellen 4a und 4b angegebenen Werte den Mittelwert aus den drei Werten darstellen. Tabelle 3: Bewertungsmaßstäbe für das Benetzungs- und Rückstandsverhaltens nach dem Wischen von Oberflächen Benetzungsverhalten Rückstandsverhalten Optimale Benetzung auch kritischer Oberflächen wie z.B. Glas 0 Einheitliches Abtrocknen, keine optische Beeinträchtigung der Oberflächen (selbst bei Glas) Gute Benetzung von Standardoberflächen PVC, Linoleum, Gummi, jedoch sichtbare Netzprobleme, insbesondere im Randbereich bei hydrophoberen Materialien -1 Fast einheitliches Abtrocknen mit einigen geringen Beeinträchtigungen besonders auf hochglänzenden Materialien Leichte Benetzungsmängel auf den Standardbelägen PVC, Linoleum, Gummi -2 Leichte Schleierbildung insbesondere im Bereich der Zonen mit Benetzungsdefekten auf hochglänzenden Oberflächen Benetzungsmangel auf den Standardbelägen PVC, Linoleum, Gummi Aufreissen des Flüssigkeitsfilms auf hydrophoberen Materialien -3 Leichte Beeinträchtigung der Gesamtoptik durch Schleier mit punktuellen Störungen im Bereich der Zonen mit Benetzungsproblemen auf allen Belägen Deutlicher Benetzungsmangel auf den Standardbelägen PVC, Linoleum, Gummi -4 Sichtbare Schleierbildung, Beeinträchtigung der Gesamtoptik, insbesondere auf glänzenden Oberflächen Schlechte Benetzung, flächige Insel- und Tröpfchenbildung -5 Fleckiges Aussehen mit sichtbaren mattierten Zonen im Bereich der Insel- und Tröpfchenbildung Extreme Benetzungsprobleme, spontanes Aufreißen des Flüssigkeitsfilms; Bildung von Inseln/Tropfen -6 Unbefriedigendes Aussehen, starke Fleckenbildung matter und glänzenderer Zonen When evaluating the residue behavior, it should be noted that the surfaces were inspected after 10, 20 and 30 wiping cycles and the values given in Tables 4a and 4b represent the average of the three values. <b> Table 3: </ b> Evaluation standards for wetting and residue behavior after wiping surfaces Wetting behavior residue behavior Optimum wetting of critical surfaces such as glass 0 Uniform drying, no visual impairment of the surfaces (even with glass) Good wetting of standard surfaces PVC, linoleum, rubber, but visible mesh problems, especially in the edge area of more hydrophobic materials -1 Almost uniform drying with some minor damage especially on high gloss materials Slight wetting defects on the standard coverings PVC, linoleum, rubber -2 Slight fogging especially in the zone of wetting defects on high-gloss surfaces Wetting deficiency on the standard coverings PVC, linoleum, rubber Tearing of the liquid film on more hydrophobic materials -3 Slight deterioration of the overall appearance due to fog with occasional disturbances in the zone of wetting problems on all coverings Significant wetting deficiency on the standard coverings PVC, linoleum, rubber -4 Visible fogging, impairment of overall appearance, especially on glossy surfaces Bad wetting, flat island and droplet formation -5 Spotty appearance with visible frosted zones in the area of island and droplet formation Extreme wetting problems, spontaneous tearing of the liquid film; Formation of islands / drops -6 Unsatisfactory appearance, severe staining of dull and shiny areas

Die Ergebnisse aus den Versuchen zum Reinigungs- Benetzungs- und Rückstandsverhalten sind in den nachstehenden Tabellen 4a und 4b enthalten. Tabelle 4a: Anwendungstechnische Eigenschaften von wässerigen 0,2 %igen Reinigungsmitteln (siehe Tabelle 1) hinsichtlich unterschiedlicher Bewertungskriterien E1 E2* E3 E4 Reinigungsvermögen (Gardner in %RV) 59 62 55 57 Netzverhalten A) 0 0 0 0 B) -0,1 -0,1 -0,3 -0,4 C) -0,2 -0,2 -0,3 -0,3 D) -0,4 -0,4 -0,6 -0,6 Rückstandsverhalten E) -0,5 -1,0 -1,0 0 F) -1 -1,5 -1,5 0 G) -0,5 -1,0 -1,0 -0,5 H) -0,5 -1,5 -1,5 -0,5 D) -1,5 -2,0 -2,0 -1,0 * Vergleichsbeispiel Tabelle 4b: Anwendungstechnische Eigenschaften von wässerigen 0,2 %igen Reinigungsmitteln (siehe Tabelle 1) hinsichtlich unterschiedlicher Bewertungskriterien V1 V2 V3 V4 V5 V6 V7 V8 V9 Reinigungsvermögen (Gardner in %RV) 62 51 53 56 44 48 41 44 55 Netzverhalten A) -1,5 -2,3 -2,2 -2,1 -3,8 -3,5 -4,6 -3,7 -1,8 B) -1,6 -2,7 -2,8 -2,6 -4,2 -3,9 -4,8 -4,0 -1,9 C) -1,9 -2,9 -3,0 -2,9 -4,8 -4,6 -5,1 -4,7 -2,1 D) -2,0 -3,0 -3,5 -3,0 -5,0 -4,5 -6,0 -5,0 2,3 Rückstandsverhalten E) -3,0 -3,0 -3,0 -3,0 -3,5 -3,0 -3,5 -3,0 -2,0 F) -3,5 -4,0 -3,5 -3,5 -4,0 -3,5 -4,0 -3,5 -2,0 G) -4,0 -3,0 -3,0 -3,0 -3,5 -3,0 -3,5 -3,0 -2,5 H) -4,5 -4,0 -4,0 -4,0 -4,0 -3,5 -4,0 -3,5 -2,5 D) -5,0 -5,0 -4,5 -5,0 -4,5 -4,0 -4,5 -4,0 -2,5 The results of the cleaning wetting and residue behavior tests are shown in Tables 4a and 4b below. <b> Table 4a: Performance properties of aqueous 0.2% detergents (see Table 1) with respect to different evaluation criteria </ b> E1 E2 * E3 E4 Cleaning power (Gardner in% RV) 59 62 55 57 network behavior A) 0 0 0 0 B) -0.1 -0.1 -0.3 -0.4 C) -0.2 -0.2 -0.3 -0.3 D) -0.4 -0.4 -0.6 -0.6 residue behavior e) -0.5 -1.0 -1.0 0 F) -1 -1.5 -1.5 0 G) -0.5 -1.0 -1.0 -0.5 H) -0.5 -1.5 -1.5 -0.5 D) -1.5 -2.0 -2.0 -1.0 * Comparative Example V1 V2 V3 V4 V5 V6 V7 V8 V9 Cleaning power (Gardner in% RV) 62 51 53 56 44 48 41 44 55 network behavior A) -1.5 -2.3 -2.2 -2.1 -3.8 -3.5 -4.6 -3.7 -1.8 B) -1.6 -2.7 -2.8 -2.6 -4.2 -3.9 -4.8 -4.0 -1.9 C) -1.9 -2.9 -3.0 -2.9 -4.8 -4.6 -5.1 -4.7 -2.1 D) -2.0 -3.0 -3.5 -3.0 -5.0 -4.5 -6.0 -5.0 2.3 residue behavior e) -3.0 -3.0 -3.0 -3.0 -3.5 -3.0 -3.5 -3.0 -2.0 F) -3.5 -4.0 -3.5 -3.5 -4.0 -3.5 -4.0 -3.5 -2.0 G) -4.0 -3.0 -3.0 -3.0 -3.5 -3.0 -3.5 -3.0 -2.5 H) -4.5 -4.0 -4.0 -4.0 -4.0 -3.5 -4.0 -3.5 -2.5 D) -5.0 -5.0 -4.5 -5.0 -4.5 -4.0 -4.5 -4.0 -2.5

Prüflinge für die Versuche zum Benetzungs- und Rückstandsverhalten:Test specimens for the tests on wetting and residue behavior:

Als Grundmaterial für die Prüflinge wurde PVC, Linoleum und Gummi verwendet, wie sie bei üblichen Bodenbelägen vorkommen. Für die Versuchsdurchführung wurden Prüflinge mit einer Fläche von 30 X 60 cm verwendet.
Sofern gemäß Versuchsplan erforderlich, wurden die Prüflinge vor der Untersuchung mit Polymerpflegemitteln eingepflegt und gegebenenfalls High-Speed poliert. In diesen Fällen wurden die Prüflinge aus Bahnen von 80 X 200 cm hergestellt: nach der gewünschten Ausrüstung und gegebenenfalls Behandlung mit der Poliermaschine wurden aus den Bahnen die Prüflinge mit 30 X 60 cm hergeschnitten.
Wie gesagt wurden zur Untersuchung des Benetzungs- und Rückstandsverhaltens unterschiedliche Oberflächen ausgewählt.
Die Ergebnisse in Tabelle 4a und Tabelle 4b sind dementsprechend den unterschiedlichen untersuchten Bodenoberflächen A bis H zugeordnet. Zur Erläuterung sei gesagt, was unter den Bodenoberflächen A bis H zu verstehen ist:

  • A: Die Versuche wurden jeweils auf unbeschichteten Prüflingen aus PVC, Linoleum und Gummi durchgeführt. Das Ergebnis in den Tabellen 4a und 4b ist ein Mittelwert aus den jeweiligen Einzelbewertungen.
  • B: Die Versuche wurden auf Prüflingen aus PVC, Linoleum und Gummi, die jeweils mit zwei Filmen Polyacrylatdispersion eingepflegt worden sind, durchgeführt. Das Ergebnis ist wie bei A ein Mittelwert.
  • C: Die Versuche wurden auf Prüflingen aus PVC, Linoleum und Gummi, die jeweils mit 3 Pflegefilmen Polyacrylatdispersion eingepflegt und zweimal High-Speed poliert worden sind, durchgeführt. Das Ergebnis entspricht wie bei A und B einem Mittelwert der beobachteten Resultate.
  • D: Die Versuche wurden auf einer entsprechenden unbehandelten Glas-Fläche durchgeführt.
  • E: Die Versuche wurden auf unbeschichteten Prüflingen aus PVC durchgeführt.
  • F: Die Versuche wurden auf unbeschichteten Prüflingen aus Gummi durchgeführt.
  • G: Die Versuche wurden auf Prüflingen aus Linoleum, die mit 2 Pflegefilmen Polyacrylatdispersion eingepflegt worden sind, durchgeführt.
  • H: Die Versuche wurden auf Prüflingen aus PVC, die mit 3 Pflegefilmen Polyacrylatdispersion eingepflegt und zweimal High-Speed poliert worden sind, durchgeführt.
The basic material used for the test specimens was PVC, linoleum and rubber, as found on common floor coverings. For the experiment, specimens with an area of 30 × 60 cm were used.
If required in accordance with the test plan, the specimens were incorporated with polymer care agents before the examination and optionally polished at high speed. In these cases, the specimens were made of sheets of 80 X 200 cm: after the desired equipment and, if necessary, treatment with the polishing machine, the specimens were cut from the webs with 30 X 60 cm.
As mentioned, different surfaces were selected to study the wetting and residue behavior.
The results in Table 4a and Table 4b are accordingly assigned to the different examined soil surfaces A to H. For explanation, what is meant by the floor surfaces A to H:
  • A: The tests were carried out on uncoated test specimens made of PVC, linoleum and rubber. The result in Tables 4a and 4b is an average of the respective individual ratings.
  • B: The tests were carried out on test specimens made of PVC, linoleum and rubber, each of which had been incorporated with two films of polyacrylate dispersion. The result is an average, as in A.
  • C: The tests were carried out on test specimens made of PVC, linoleum and rubber, each of which was treated with 3 care films of polyacrylate dispersion and twice high-speed polished. The result, as with A and B, is an average of the observed results.
  • D: The experiments were carried out on a corresponding untreated glass surface.
  • E: The experiments were carried out on uncoated test specimens made of PVC.
  • F: The experiments were carried out on uncoated rubber specimens.
  • G: The tests were carried out on test specimens made of linoleum, which had been incorporated with 2 care films, polyacrylate dispersion.
  • H: The experiments were carried out on test specimens made of PVC, which were incorporated with 3 care films polyacrylate dispersion and twice high-speed polishing.

Claims (13)

  1. An aqueous floor cleaning and/or floor care agent, containing, based on the total agent, at least 3% by weight of a nonionic surfactant of formula I
    Figure imgb0004
     wherein R1 represents hydrogen, and R2 represents an alkyl residue having 6 to 18 C atoms, or
    R1 represents an alkyl residue having 6 to 18 C atoms, and R2 represents hydrogen, or
    R1 represents an alkyl residue having 1 to 18 C atoms, and R2, independently of R1, represents an alkyl residue having 1 to 18 C atoms, and the sum of total C atoms present in R1 and R2 is between 6 and 18, and
    R3 represents an alkyl residue having 4 to 18 C atoms, and R4 represents hydrogen or an alkyl residue having 1 to 6 C atoms, n is a number from 1 to 30, and m is a number from 0 to 5,
    said agent including at least one additional nonionic surfactant which does not come under formula I, said above-mentioned additional nonionic surfactant being selected from the compounds of formula II

            R5-CH2-CH2-(OCH2-CH2)n-[OCH(CH3)-CH2]m-[OBu]1-OR6     (II)

    wherein R5 represents an alkyl residue having 6 to 18 C atoms, and R6 represents hydrogen or an alkyl residue having 1 to 6 C atoms, and the mean degree of ethoxylation n is a number from 1 to 30, the mean degree of propoxylation m is a number from 0 to 5, and the mean degree of butoxylation I is a number from 1 to 4, and Bu is butyl.
  2. The agent according to claim 1, characterized in that, based on the total agent, less than 3% by weight, preferably less than 1.5% by weight, of anionic surfactants are included.
  3. The agent according to claim 2, characterized in that substantially no anionic surfactant is present.
  4. The agent according to any of claims 1 to 3, characterized in that in the above-mentioned nonionic surfactant according to formula II, R6 is hydrogen and m is 0.
  5. The agent according to any of claims 1 to 4, characterized in that in said agent, the weight of the above-mentioned nonionic surfactant of formula I is at least one third and at most twice the weight of the additional nonionic surfactant of formula II included according to any of claims 1 and 4.
  6. The agent according to claim 5, characterized in that in said agent, the amount by weight of said nonionic surfactant of formula I is at least half as great, but not greater than the amount by weight of the additional nonionic surfactant of formula II included according to any of claims 1 and 4.
  7. The agent according to one or more of claims 1 to 6, characterized in that, based on the overall agent, the total amount by weight of the above-mentioned nonionic surfactant of formula I and, if present, of the additional nonionic surfactant of formula II included according to any of claims 1 and 4 is 5 to 35% by weight, preferably 7 to 20% by weight.
  8. The agent according to one or more of claims 1 to 7, characterized in that the agent includes polyethylene glycol and/or polypropylene glycol as additional component.
  9. The agent according to claim 8, characterized in that the above-mentioned polyethylene glycol and/or polypropylene glycol has a molecular weight ranging from 200 to 2000.
  10. The agent according to any of claims 8 or 9, characterized in that the above-mentioned polyethylene glycol and/or polypropylene glycol makes up 0.01 to 5% by weight, based on the overall agent.
  11. Use of an agent as claimed in one or more of claims 1 to 10 in floor cleaning and/or care.
  12. The use according to claim 11, characterized in that, prior to use in cleaning and/or care, the above-mentioned agent is diluted with water using a dilution factor of 5 to 5000.
  13. The use according to any of claims 11 or 12, characterized in that the floors to be treated are uncoated or finished with a polymer layer.
EP03761476A 2002-06-29 2003-06-20 Floor cleaning and/or floor care product Expired - Lifetime EP1517980B1 (en)

Applications Claiming Priority (3)

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DE10229421 2002-06-29
DE10229421A DE10229421A1 (en) 2002-06-29 2002-06-29 Floor cleaning and / or care products
PCT/EP2003/006497 WO2004003122A1 (en) 2002-06-29 2003-06-20 Floor cleaning and/or floor care product

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DE10229421A1 (en) * 2002-06-29 2004-01-29 Ecolab Gmbh & Co. Ohg Floor cleaning and / or care products
DE102004015392A1 (en) * 2004-03-26 2005-10-20 Henkel Kgaa Machine dishwashing detergent
JP5243522B2 (en) * 2007-04-13 2013-07-24 イーコラブ インコーポレイティド Floor cleaning composition with reduced foaming properties
GB0822323D0 (en) * 2008-12-08 2009-01-14 Reckitt Benckiser Nv Drying aid composition
CN108137459B (en) 2015-10-07 2021-06-18 海名斯精细化工公司 Wetting and antifoam agents
AU2017286154B2 (en) 2016-06-16 2021-04-01 Dow Global Technologies Llc Automatic dishwashing compositions with spot prevention surfactant
CN113943611A (en) * 2021-10-20 2022-01-18 安徽克菱保健科技有限公司 Fragrant floor scrubber effervescent cleaning tablet with sterilization effect

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GB8802106D0 (en) * 1988-01-30 1988-02-24 Procter & Gamble Hard-surface cleaning compositions
JPH0756038B2 (en) 1989-08-22 1995-06-14 花王株式会社 Hard surface liquid detergent composition
DE4404199A1 (en) 1994-02-10 1995-08-17 Henkel Kgaa Detergent for hard surfaces
US5576284A (en) 1994-09-26 1996-11-19 Henkel Kommanditgesellschaft Auf Aktien Disinfecting cleanser for hard surfaces
DE19517814A1 (en) 1995-05-18 1996-11-21 Henkel Ecolab Gmbh & Co Ohg Highly concentrated water-based basic cleaner
US5858956A (en) 1997-12-03 1999-01-12 Colgate-Palmolive Company All purpose liquid cleaning compositions comprising anionic, EO nonionic and EO-BO nonionic surfactants
DE19750456A1 (en) 1997-11-14 1999-05-27 Henkel Ecolab Gmbh & Co Ohg Means for cleaning hard surfaces
DE19751859A1 (en) * 1997-11-22 1999-07-29 Henkel Ecolab Gmbh & Co Ohg Means for cleaning hard surfaces
DE19856727A1 (en) * 1998-12-09 2000-06-15 Cognis Deutschland Gmbh All-purpose cleaner
DK1149143T3 (en) * 1999-02-02 2003-01-06 Ecolab Gmbh & Co Ohg Means for cleaning hard surfaces
US6268330B1 (en) * 1999-05-21 2001-07-31 Colgate-Palmolive Company Clear microemulsion acidic light duty liquid cleaning compositions
DE10229421A1 (en) * 2002-06-29 2004-01-29 Ecolab Gmbh & Co. Ohg Floor cleaning and / or care products

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DE10229421A1 (en) 2004-01-29
DE50306858D1 (en) 2007-05-03
US20080188389A1 (en) 2008-08-07
US7563759B2 (en) 2009-07-21
WO2004003122A1 (en) 2004-01-08

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