EP0712436B1 - Low-foaming washing or cleaning agents - Google Patents

Low-foaming washing or cleaning agents Download PDF

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Publication number
EP0712436B1
EP0712436B1 EP94925395A EP94925395A EP0712436B1 EP 0712436 B1 EP0712436 B1 EP 0712436B1 EP 94925395 A EP94925395 A EP 94925395A EP 94925395 A EP94925395 A EP 94925395A EP 0712436 B1 EP0712436 B1 EP 0712436B1
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EP
European Patent Office
Prior art keywords
alkyl
weight
fatty acid
detergent
cleaning formulation
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
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EP94925395A
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German (de)
French (fr)
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EP0712436A1 (en
Inventor
Udo Hees
Eva Kiewert
Ansgar Behler
Astrid Haferkamp
Kerstin Link
Amerigo Pastura
Nada Volf
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols

Definitions

  • the invention relates to low-foaming detergents or cleaning agents, with liquid detergents and cleaning agents for hard surfaces being preferred. All non-textile surfaces occurring in the household and commercial sector, with the exception of dishes, are to be understood as cleaning agents for hard surfaces.
  • the term general-purpose cleaner has become established for this type of cleaning agent. Low-foaming all-purpose cleaners are those that develop a low volume of foam when used manually, which significantly reduces within a few minutes.
  • All-purpose cleaners have been known for a long time. These are essentially aqueous surfactant solutions of various types with or without the addition of builders and with or without the addition of water-soluble solvents or solubilizers.
  • a disadvantage of manual application in practice has been its high foaming power. Although the consumer wants to perceive a certain amount of foam in the application solution at the beginning of his cleaning work to prove its effectiveness, the foam should then collapse as quickly as possible, so that once cleaned surfaces do not have to be wiped down.
  • Liquid detergents also tend to have a high foaming capacity, which affects their applicability in washing machines.
  • alkyl polyglycosides are known to be highly foaming surfactants; They are therefore used for products with the desired high foaming capacity, So recommended for manual dishwashing detergents or for washing hair.
  • EP 0 070 074 B1 and 0 070 076 B2 describe such high-foaming washing and cleaning agents based on various APG-containing surfactant combinations. Consequently, these combinations are not recommended for the area of all-purpose cleaners.
  • German published patent application DE 42 27 046 describes detergent mixtures based on fatty acid alkyl ester alkoxylates.
  • WO-A-91 14 760 discloses low-foaming surfactant mixtures consisting of alkyl polyglycosides and fatty alcohol alkoxylates etherified with alkyl radicals.
  • the object of the present invention was to provide washing or cleaning agents which at the same time have good cleaning properties, good biodegradability and a pronouncedly low foaming power.
  • the criterion should be that initially formed foam visibly reduces within 2 minutes.
  • the invention relates to water-containing washing or cleaning agents containing 0.1 to 50% by weight, preferably 1 to 20% by weight, of at least one alkyl polyglycoside of the formula I, R 1 -O- [Z] x (I), where R 1 is a branched or straight-chain, saturated or unsaturated alkyl group having 8 to 18 carbon atoms, Z is a sugar residue, preferably a glucose or Xylose radical and x represents integers from 1 to 10, and 0.05 to 50% by weight, preferably 1 to 20% by weight, of at least one fatty acid alkyl ester alkoxylate of the formula II, R 2 -CO 2 - (AO) y -R 3 (II), where R 2 is a branched or straight-chain, saturated or unsaturated alkyl group having 5 to 21 C atoms, AO is a C 2 -C 4 alkylene oxide unit, y is a number from 1 to 30 and R 3 represents a straight-chain or branched alkyl group
  • the alkyl polyglycosides used in the agents according to the invention are known substances which can be obtained by the relevant methods of preparative organic chemistry; as a representative, reference is made to the documents EP 0 301 298 A1 and WO 90/3977.
  • the alkyl polyglycosides can be from sugars or sugar residues, i.e. Derive aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose and xylose.
  • the preferred alkyl polyglycosides are thus alkyl polyglucosides and alkyl polyxylosides.
  • the alkyl radical R 1 in the formula (I) can be derived from primary branched and unbranched alcohols having 8 to 18 carbon atoms. Typical examples are myristyl alcohol, cetyl alcohol and their technical mixtures. However, preference is given to using alkylpolyglycosides of the formula (I) in which R 1 represents a carbon radical having 8 to 12, in particular 8 to 10, carbon atoms. In addition to lauryl alcohol, typical examples are, in particular, caprylic alcohol and capric alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the fatty acid alkyl ester alkoxylates of the formula (II) used in the agents according to the invention can be prepared by conventional methods, such as, for example, by esterification of fatty acid derivatives with alkoxylated methanol.
  • this process has some disadvantages, it has two stages, the esterification takes a very long time and the products are colored by the high reaction temperatures.
  • fatty acid methyl ester alkoxylates produced in this way often have relatively high OH numbers after the esterification, which can be problematic for some applications.
  • the fatty acid alkyl ester alkoxylates of the formula (II) are preferably prepared by heterogeneously catalyzed direct alkoxylation of fatty acid alkyl esters with alkylene oxide, in particular ethylene oxide. This synthesis method is described in detail in WO 90/13533 and WO 91/15441. The resulting products are characterized by a low OH number, the reaction is carried out in one step and light-colored products are obtained. Those fatty acid alkyl ester alkoxylates of the formula (II) which are formed by ethoxylation of fatty acid methyl esters, ie in which A0 in the formula (II) is an ethylene oxide unit and R 3 is a methyl group, are preferably used.
  • the fatty acid methyl esters used as starting materials can be obtained from natural oils and fats as well as produced synthetically.
  • Fatty acid alkyl ester alkoxylates are preferably used in the all-purpose cleaners according to the invention, where y is a number from 5 to 25, in particular from 9 to 18.
  • fatty acid alkyl ester alkoxylates are preferably used in the liquid detergents according to the invention, where R 2 is a branched or straight-chain, saturated alkyl group having 12 to 18 carbon atoms and y is a number from 3 to 15.
  • liquid detergents and general-purpose cleaners according to the invention are to be used to remove lipophilic soiling, fatty acid alkyl ester alkoxylates with a low degree of ethoxylation in the range according to the invention are selected; if hydrophilic soiling is to be removed, the use of fatty acid alkyl ester ethoxylates with a higher degree of ethoxylation in the range according to the invention is expedient.
  • the above-mentioned liquid detergents and all-purpose cleaners additionally contain an anionic surfactant selected from the group of the C 6 -C 18 alkylbenzenesulfonates, C 6 -C 18 alkanesulfonates, C 6 -C 18 alkyl sulfates, C 6 -C 18 - Alkyl polyglycol ether sulfates, ⁇ -olefin sulfonates, C 6 -C 18 alkyl polyglycol ether sulfonates, glycerol ether sulfonates, glycerin ether sulfates, hydroxymixed ether sulfates, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, soaps, amide soaps, C 6 -C 6 fatty acid alkamides, C 6 -C 18 carboxylate alkoxide s
  • an anionic surfactant
  • liquid detergent or all-purpose cleaners additionally contain a further nonionic surfactant selected from the group of C 6 -C 18 -alkyl polyglycol ether, Zuckerester, C 6 -C 18 -Fettklarepolyglykolether, sorbitan fatty acid esters, C 6 -C 18 fatty acid partial glycerides as well as their Mixtures in a total amount of up to 30 wt .-%, based on the total amount of liquid detergent or all-purpose cleaner.
  • a further nonionic surfactant selected from the group of C 6 -C 18 -alkyl polyglycol ether, Zuckerester, C 6 -C 18 -Fettkladilicates, sorbitan fatty acid esters, C 6 -C 18 fatty acid partial glycerides as well as their Mixtures in a total amount of up to 30 wt .-%, based on the total amount of liquid detergent or all-purpose cleaner.
  • Particularly preferred embodiments contain anionic surfactants selected from the group of the C 6 -C 18 alkyl sulfates, the C 6 -C 18 alkyl polyglycol ether sulfates, the soaps and the C 6 -C 18 alkane sulfonates and their mixtures or nonionic surfactants selected from the group of the C 6 -C 18 alkyl polyglycol ether.
  • the soaps to be used according to the invention are alkali, ammonium or alkanolammonium salts of saturated or unsaturated fatty acids with 8-22, preferably 10-18, carbon atoms.
  • the soaps can either be added as such or, after the addition of appropriate fatty acids, can be formed by salt formation with bases such as NaOH, KOH, NH 3 , amines or alkanolamines.
  • bases such as NaOH, KOH, NH 3 , amines or alkanolamines.
  • the soaps are either completely neutralized or partly also in free form as fatty acids.
  • the C 6 -C 18 alkyl ether sulfates are primarily addition products of 2-15 moles of ethylene oxide with C 6 -C 18 fatty alcohols, which are then sulfated.
  • the C 6 -C 18 alkyl polyglycol ethers used as nonionic surfactants are primarily adducts of 2-10 mol ethylene oxide with C 6 -C 18 fatty alcohols.
  • Auxiliaries customary in liquid detergents or all-purpose cleaners can optionally be added; these substances are builders, e.g. Glutaric acid, succinic acid, adipic acid, tartaric acid, benzene hexacarboxylic acid, gluconic acid, trisodium citrate; Solvents, e.g. Acetone, ethanol or glycerin, hydrotropes e.g. Cumene sulfonate, octyl sulfate, butyl glucoside, butylene glycol; Cleaning booster; Viscosity regulators, e.g. synthetic polymers such as polyacrylates; pH regulators, e.g. Citric acid, triethanolamine or NaOH; Preservatives, e.g. Glutaraldehyde; Dyes, fragrances and opacifiers.
  • builders e.g. Glutaric acid, succinic acid, adipic acid, tartaric acid, benzene
  • the pH of the all-purpose cleaners according to the invention is usually between 4 and 8.5, preferably between 6 and 8. However, a range between 7.0 and 7.5 is particularly preferred.
  • the pH value at an application concentration of 10 g / l is preferably 7.3-7.8.
  • the agents according to the invention are particularly suitable for cleaning hard surfaces such as e.g. Enamel, glass, PVC, linoleum, stone floors, e.g. Marble, terrazzo, unglazed clinker, ceramic tiles or sealed wooden floors, e.g. Parquet or floorboards.
  • hard surfaces such as e.g. Enamel, glass, PVC, linoleum, stone floors, e.g. Marble, terrazzo, unglazed clinker, ceramic tiles or sealed wooden floors, e.g. Parquet or floorboards.
  • the pH of the liquid detergents according to the invention is usually between 6.0 and 10.0, preferably between 7.0 and 9.0.
  • the liquid detergents are suitable both for use in washing machines and for use in hand basins for washing high-quality textiles made of wool or silk.
  • the test method described below according to "Seifen- ⁇ le-Fette-Wwachs", 112 , 371, (1986) was used to test the cleaning ability and provides very reproducible results.
  • the cleaning agent to be tested was then placed in the form of a 1% by weight aqueous solution (10 g / l) on an artificially soiled plastic surface.
  • a mixture of carbon black, machine oil, triglyceride, saturated fatty acids and low-boiling aliphatic hydrocarbon was used as artificial soiling for the dilute use of the cleaning agent.
  • the test area of 26 x 28 cm was evenly coated with 2 g of the artificial soiling with the aid of a surface coater.
  • a plastic sponge was impregnated with 10 ml of the 1% detergent solution to be tested and moved mechanically on the dirt-coated test surface, to which 10 ml of the 1% detergent solution to be tested was also applied. After 10 wiping movements, the cleaned test area was kept under running water and the loose dirt was removed.
  • the cleaning effect of the plastic surface cleaned in this way was determined with the aid of a "Microcolor" remission color measuring device (Dr. B. Lange).
  • the measurand is the degree of whiteness.
  • the clean white plastic surface served as the white standard; the whiteness of the clean, white plastic surface corresponds to 100% RV (cleaning ability).
  • the whiteness of a soiled and then cleaned plastic surface corresponds to a value between 0% and 100% RV.
  • The% RV values represent mean values from triplicate determinations.
  • the foaming behavior of the all-purpose cleaners according to the invention was tested as follows: The test product was placed in a large-volume serving glass. Then the amount of tap water was allowed to flow in freely from a height of 30 cm, which, together with the amount of product presented, gave an application concentration of the product of 10 g / l. The foam height in the beaker was read off immediately after the addition of water had ended.
  • compositions were prepared by mixing the components together and then adjusting the desired pH. All percentages relate to percent by weight of active substance.
  • Compositions 1 to 9 are shown in Table 1.
  • Composition 1 (V) is not according to the invention and is used for comparison.
  • the fatty acid alkyl ester alkoxylates are given in Table 1 in the following notation:
  • Example: C 12 FSEO 15 Me stands for C 11 H 23 CO 2 (CH 2 CH 2 O) 15 CH 3 , methyl ester of C 12 fatty acid ethoxylated with 15 ethylene oxide units.
  • EO stands for ethylene oxide
  • PO stands for propylene oxide.
  • the degrees of alkoxylation represent mean values.
  • compositions 2 to 9 according to the invention are clearly superior to comparative composition 1 (V) in terms of cleaning ability and foam disintegration.
  • Example 10 represents an all-purpose cleaner high concentrate, which is used in 0.1% solution.
  • the agent had excellent foam properties (low foam values).
  • an agent V was tested which had a C 13 -C 15 alcohol x 5 E0 instead of the fatty acid methyl ester.

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Abstract

The invention concerns low-foaming liquid detergents and all-purpose cleaners containing C8-C18 alkyl polyglycosides and fatty acid alkyl ester alkoxylates, especially fatty acid methyl ester ethoxylates.

Description

Die Erfindung betrifft schwach schäumende Wasch- oder Reinigungsmittel, wobei Flüssigwaschmittel und Reinigungsmittel für harte Oberflächen bevorzugt sind. Als Reinigungsmittel für harte Oberflächen sind alle im Haushalt- und Gewerbesektor auftretenden, nicht textilen Oberflächen, ausgenommen Geschirr, zu verstehen. Für diese Art von Reinigungsmitteln hat sich der Begriff Allzweckreiniger eingebürgert. Schwach schäumende Allzweckreiniger sind solche, die bei manueller Anwendung ein geringes Schaumvolumen entwickeln, das sich innerhalb weniger Minuten signifikant weiter verringert.The invention relates to low-foaming detergents or cleaning agents, with liquid detergents and cleaning agents for hard surfaces being preferred. All non-textile surfaces occurring in the household and commercial sector, with the exception of dishes, are to be understood as cleaning agents for hard surfaces. The term general-purpose cleaner has become established for this type of cleaning agent. Low-foaming all-purpose cleaners are those that develop a low volume of foam when used manually, which significantly reduces within a few minutes.

Allzweckreiniger sind seit langem bekannt. Es handelt sich dabei im wesentlichen um wäßrige Tensidlösungen unterschiedlichster Art mit oder ohne Zusatz an Buildern sowie mit oder ohne Zusatz an wasserlöslichen Lösungsmitteln oder Lösungsvermittlern. Nachteilig hat sich bei der manuellen Anwendung in der Praxis zunehmend deren hohes Schaumvermögen gezeigt. Der Verbraucher möchte zwar zum Nachweis der Wirksamkeit bei Beginn seiner Reinigungsarbeit ein gewisses Schäumen der Anwendungslösung wahrnehmen, der Schaum soll dann jedoch anschließend möglichst rasch zusammenfallen, damit einmal gereinigte Flächen nicht nachgewischt werden müssen.All-purpose cleaners have been known for a long time. These are essentially aqueous surfactant solutions of various types with or without the addition of builders and with or without the addition of water-soluble solvents or solubilizers. A disadvantage of manual application in practice has been its high foaming power. Although the consumer wants to perceive a certain amount of foam in the application solution at the beginning of his cleaning work to prove its effectiveness, the foam should then collapse as quickly as possible, so that once cleaned surfaces do not have to be wiped down.

Flüssigwaschmittel neigen häufig ebenfalls zu hohem Schaumvermögen, wodurch ihre Anwendbarkeit in Waschmaschinen beeinträchtigt wird.Liquid detergents also tend to have a high foaming capacity, which affects their applicability in washing machines.

Um diesem vermehrten Wunsch nach geringerem Schaumvermögen nachzukommen, sind einige Hersteller von Allzweckreinigern dazu übergegangen, den Tensidgehalt ihrer Produkte deutlich zu senken, was jedoch naturgemäß wiederum zu erheblichem Verlust an Reinigungsleistung führt. Der Anwender solcher Produkte muß die verringerte Reinigungswirkung durch vermehrten Aufwand an mechanischer Wischarbeit ausgleichen.In order to meet this increased desire for lower foaming power, some manufacturers of all-purpose cleaners have started to significantly reduce the surfactant content of their products, which in turn naturally leads to a considerable loss in cleaning performance. The user of such products must compensate for the reduced cleaning effect through increased mechanical wiping work.

Wegen ihrer ökologisch guten Eigenschaften erfreut sich der Einsatz von Alkylpolyglycosiden (APG's) in Wasch- und Reinigungsmittel wachsender Beliebtheit. Alkylpolyglycoside sind aber als stark schäumende Tenside bekannt; sie werden deshalb für Produkte mit wunschgemäß hohem Schaumvermögen, also z.B. für manuell anzuwendende Geschirrspülmittel oder für die Haarwäsche empfohlen. EP 0 070 074 B1 und 0 070 076 B2 beschreiben derartige hochschäumende Wasch- und Reinigungsmittel auf Basis verschiedener APG-haltiger Tensidkombinationen. Folgerichtig werden diese Kombinationen auch nicht für das Gebiet der Allzweckreiniger empfohlen.Because of their ecologically good properties, the use of alkyl polyglycosides (APG's) in washing and cleaning agents is becoming increasingly popular. However, alkyl polyglycosides are known to be highly foaming surfactants; They are therefore used for products with the desired high foaming capacity, So recommended for manual dishwashing detergents or for washing hair. EP 0 070 074 B1 and 0 070 076 B2 describe such high-foaming washing and cleaning agents based on various APG-containing surfactant combinations. Consequently, these combinations are not recommended for the area of all-purpose cleaners.

Auch spezielle kurzkettige C8-C10-Alkylglucoside (z.B. Triton(R)CG-110 von Rohm & Haas) sind seit langem als gut schäumende und schaumstabile nichtionische Tenside bekannt. Schwach schäumende Reinigungsmittel mit einem Gehalt an Alkypolyglucosiden für maschinelle Reinigungsarbeiten, insbesondere Geschirrspülen, werden in WO 88/09369 beschrieben. Die Schaumarmut wird in diesen Mitteln durch Mitverwendung von konventionellen, schwachschäumenden Fettalkoholalkoxylaten, die einen HLB-Wert von etwa 10 oder weniger aufweisen und Propylenoxideinheiten enthalten können, erreicht.Special short-chain C 8 -C 10 alkyl glucosides (eg Triton ( R ) CG-110 from Rohm & Haas) have also been known for a long time as good foaming and foam-stable nonionic surfactants. Low-foaming cleaning agents containing alkypolyglucosides for machine cleaning work, in particular dishwashing, are described in WO 88/09369. In these agents, low-foaming is achieved by using conventional, low-foaming fatty alcohol alkoxylates, which have an HLB value of about 10 or less and can contain propylene oxide units.

In der deutschen Offenlegungsschrift DE 42 27 046 werden Detergens-Mischungen auf Basis von Fettsäurealkylesteralkoxylaten beschrieben.German published patent application DE 42 27 046 describes detergent mixtures based on fatty acid alkyl ester alkoxylates.

WO-A-91 14 760 offenbart schwachschäumende Tensidgemische bestehend aus Alkylpolyglycosiden und mit Alkylresten veretherten Fettalkoholalkoxylaten.WO-A-91 14 760 discloses low-foaming surfactant mixtures consisting of alkyl polyglycosides and fatty alcohol alkoxylates etherified with alkyl radicals.

Aufgabe der vorliegenden Erfindung war es, Wasch- oder Reinigungsmittel zu schaffen, welche zugleich ein gutes Reinigungsvermögen, gute biologische Abbaubarkeit und ein ausgeprägt schwaches Schäumvermögen besitzen. Bei der Verwendung zur manuellen Reinigung von harten Oberflächen soll als Kriterium gelten, daß sich anfänglich gebildeter Schaum innerhalb von 2 Minuten sichtbar verringert.The object of the present invention was to provide washing or cleaning agents which at the same time have good cleaning properties, good biodegradability and a pronouncedly low foaming power. When used for the manual cleaning of hard surfaces, the criterion should be that initially formed foam visibly reduces within 2 minutes.

Überraschenderweise wurde nun gefunden, daß mit Hilfe von Kombinationen bestimmter als stark schäumend bekannter C8-C18-Alkylpolyglycoside mit bestimmten Fettsäurealkylesteralkoxylaten Flüssigwaschmittel und Allzweckreiniger mit hohem Reinigungsvermögen und extrem schwachem Schaumverhalten bereitgestellt werden können.Surprisingly, it has now been found that with the aid of combinations of certain C 8 -C 18 alkyl polyglycosides known to be highly foaming with certain fatty acid alkyl ester alkoxylates, liquid detergents and all-purpose cleaners with high cleaning power and extremely low foaming behavior can be provided.

Gegenstand der Erfindung sind wasserhaltige Wasch- oder Reinigungsmittel, enthaltend 0,1 bis 50 Gew.-%, vorzugsweise 1 bis 20 Gew.-%, mindestens eines Alkylpolyglycosids der Formel I, R1-O-[Z]x (I), wobei R1 eine verzweigte oder geradkettige, gesättigte oder ungesättigte Alkylgruppe mit 8 bis 18 C-Atomen, Z einen Zuckerrest, vorzugsweise einen Glucose- oder Xylose-Rest und x ganze Zahlen von 1 bis 10, darstellt und 0,05 bis 50 Gew.-%, vorzugsweise 1 bis 20 Gew.-%, mindestens eines Fettsäurealkylesteralkoxylats der Formel II, R2-CO2-(AO)y-R3 (II), wobei R2 für eine verzweigte oder geradkettige, gesättigte oder ungesättigte Alkylgruppe mit 5 bis 21 C-Atomen, AO für eine C2-C4-Alkylenoxideinheit, y für eine Zahl von 1 bis 30 und R3 für eine geradkettige oder verzweigte Alkylgruppe mit 1 bis 6 C-Atomen steht.The invention relates to water-containing washing or cleaning agents containing 0.1 to 50% by weight, preferably 1 to 20% by weight, of at least one alkyl polyglycoside of the formula I, R 1 -O- [Z] x (I), where R 1 is a branched or straight-chain, saturated or unsaturated alkyl group having 8 to 18 carbon atoms, Z is a sugar residue, preferably a glucose or Xylose radical and x represents integers from 1 to 10, and 0.05 to 50% by weight, preferably 1 to 20% by weight, of at least one fatty acid alkyl ester alkoxylate of the formula II, R 2 -CO 2 - (AO) y -R 3 (II), where R 2 is a branched or straight-chain, saturated or unsaturated alkyl group having 5 to 21 C atoms, AO is a C 2 -C 4 alkylene oxide unit, y is a number from 1 to 30 and R 3 represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms.

Die in den erfindungsgemäßen Mitteln eingesetzten Alkylpolyglycoside stellen bekannte Stoffe dar, die nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden können; stellvertretend sei hier auf die Schriften EP 0 301 298 Al und WO 90/3977 verwiesen. Die Alkylpolyglycoside können sich von Zuckern bzw. Zuckerresten, d.h. Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose und der Xylose ableiten. Die bevorzugten Alkylpolyglycoside sind somit Alkylpolyglucoside und Alkylpolyxyloside.The alkyl polyglycosides used in the agents according to the invention are known substances which can be obtained by the relevant methods of preparative organic chemistry; as a representative, reference is made to the documents EP 0 301 298 A1 and WO 90/3977. The alkyl polyglycosides can be from sugars or sugar residues, i.e. Derive aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose and xylose. The preferred alkyl polyglycosides are thus alkyl polyglucosides and alkyl polyxylosides.

Der Index x in der Formel (I) gibt den Oligomerisierungsgrad (DP-Grad), d.h. die Verteilung von Mono- und Oligoglycosiden an und steht für eine Zahl zwischen 1 und 10. Während x in einer gegebenen Verbindung stets ganzzahlig sein muß und hier vor allem die Werte x = 1 bis 6 annehmen kann, ist der Wert x für ein bestimmtes Alkylpolyglycosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkylpolyglycoside mit einem mittleren Oligomerisierungsgrad von 1,1 bis 3,0, vorzugsweise 1,1 bis 1,7 eingesetzt.The index x in formula (I) indicates the degree of oligomerization (DP degree), i.e. the distribution of mono- and oligoglycosides is present and stands for a number between 1 and 10. While x must always be an integer in a given compound and here can assume the values x = 1 to 6, the value x is for a certain alkyl polyglycoside an analytically calculated quantity, which usually represents a fractional number. Alkyl polyglycosides with an average degree of oligomerization of 1.1 to 3.0, preferably 1.1 to 1.7, are preferably used.

Der Alkylrest R1 in der Formel (I) kann sich von primären verzweigten und unverzweigten Alkoholen mit 8 bis 18 Kohlenstoffatomen ableiten. Typische Beispiele sind Myristylalkohol, Cetylalkohol sowie deren technische Gemische. Vorzugsweise werden jedoch Alkylpolyglycoside der Formel (I) eingesetzt, in denen R1 einen Kohlenstoffrest mit 8 bis 12, insbesondere 8 bis 10 Kohlenstoffatomen, darstellt. Typische Beispiele sind neben Laurylalkohol insbesondere Caprylalkohol und Caprinalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelen'schen-Oxosynthese anfallen.The alkyl radical R 1 in the formula (I) can be derived from primary branched and unbranched alcohols having 8 to 18 carbon atoms. Typical examples are myristyl alcohol, cetyl alcohol and their technical mixtures. However, preference is given to using alkylpolyglycosides of the formula (I) in which R 1 represents a carbon radical having 8 to 12, in particular 8 to 10, carbon atoms. In addition to lauryl alcohol, typical examples are, in particular, caprylic alcohol and capric alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.

Die in den erfindungsgemäßen Mitteln eingesetzten Fettsäurealkylesteralkoxylate der Formel (II) können durch konventionelle Methoden hergestellt werden, wie z.B. durch Veresterung von Fettsäurederivaten mit alkoxyliertem Methanol. Dieses Verfahren ist jedoch mit einigen Nachteilen verbunden, es verläuft zweistufig, die Veresterung dauert sehr lange und die Produkte sind durch die hohen Reaktionstemperaturen gefärbt. Außerdem besitzen solchermaßen hergestellte Fettsäuremethylesteralkoxylate häufig nach der Veresterung relativ hohe OH-Zahlen, was für manche Anwendungen problematisch sein kann. Vorzugsweise werden die Fettsäurealkylesteralkoxylate der Formel (II) durch eine heterogen katalysierte Direktalkoxylierung von Fettsäurealkylester mit Alkylenoxid, insbesondere Ethylenoxid, hergestellt. Dieses Syntheseverfahren ist in WO 90/13533 und WO 91/15441 ausführlich beschrieben. Die dabei entstehenden Produkte zeichnen sich durch eine niedrige OH-Zahl aus, die Reaktion wird einstufig durchgeführt und man erhält hellfarbige Produkte. Vorzugsweise werden solche Fettsäurealkylesteralkoxylate der Formel (II) eingesetzt, die durch Ethoxylierung von Fettsäuremethylester entstehen, d.h. in denen A0 in der Formel (II) für eine Ethylenoxideinheit und R3 für eine Methylgruppe steht. Die als Ausgangsstoffe dienenden Fettsäuremethylester können sowohl aus natürlichen Ölen und Fetten gewonnen als auch auf synthetischem Wege hergestellt werden.The fatty acid alkyl ester alkoxylates of the formula (II) used in the agents according to the invention can be prepared by conventional methods, such as, for example, by esterification of fatty acid derivatives with alkoxylated methanol. However, this process has some disadvantages, it has two stages, the esterification takes a very long time and the products are colored by the high reaction temperatures. In addition, fatty acid methyl ester alkoxylates produced in this way often have relatively high OH numbers after the esterification, which can be problematic for some applications. The fatty acid alkyl ester alkoxylates of the formula (II) are preferably prepared by heterogeneously catalyzed direct alkoxylation of fatty acid alkyl esters with alkylene oxide, in particular ethylene oxide. This synthesis method is described in detail in WO 90/13533 and WO 91/15441. The resulting products are characterized by a low OH number, the reaction is carried out in one step and light-colored products are obtained. Those fatty acid alkyl ester alkoxylates of the formula (II) which are formed by ethoxylation of fatty acid methyl esters, ie in which A0 in the formula (II) is an ethylene oxide unit and R 3 is a methyl group, are preferably used. The fatty acid methyl esters used as starting materials can be obtained from natural oils and fats as well as produced synthetically.

In den erfindungsgemäßen Allzweckreinigern werden vorzugsweise Fettsäurealkylesteralkoxylate verwendet, wobei y für eine Zahl von 5 bis 25, insbesondere von 9 bis 18 steht. In den erfindungsgemäßen Flüssigwaschmitteln hingegen werden vorzugsweise Fettsäurealkylesteralkoxylate verwendet, wobei R2 für eine verzweigte oder geradkettige, gesättigte Alkylgruppe mit 12 bis 18 C-Atomen und y für eine Zahl von 3 bis 15 steht.Fatty acid alkyl ester alkoxylates are preferably used in the all-purpose cleaners according to the invention, where y is a number from 5 to 25, in particular from 9 to 18. In contrast, fatty acid alkyl ester alkoxylates are preferably used in the liquid detergents according to the invention, where R 2 is a branched or straight-chain, saturated alkyl group having 12 to 18 carbon atoms and y is a number from 3 to 15.

Sollen die erfindungsgemäßen Flüssigwaschmittel und Allzweckreiniger zur Entfernung lipophiler Anschmutzungen verwendet werden, wählt man Fettsäurealkylesteralkoxylate mit im erfindungsgemäßen Bereich liegendem niedrigen Ethoxylierungsgrad; sollen hydrophile Anschmutzungen entfernt werden, ist der Einsatz von Fettsäurealkyesterethoxylaten mit im erfindungsgemäßen Bereich liegenden höheren Ethoxylierungsgrad zweckmäßig.If the liquid detergents and general-purpose cleaners according to the invention are to be used to remove lipophilic soiling, fatty acid alkyl ester alkoxylates with a low degree of ethoxylation in the range according to the invention are selected; if hydrophilic soiling is to be removed, the use of fatty acid alkyl ester ethoxylates with a higher degree of ethoxylation in the range according to the invention is expedient.

In einer bevorzugten Ausführungsform der Erfindung beinhalten obengenannte Flüssigwaschmittel und Allzweckreiniger zusätzlich ein anionisches Tensid ausgewählt aus der Gruppe der C6-C18-Alkylbenzolsulfonate, C6-C18-Alkansulfonate, C6-C18-Alkylsulfate, C6-C18-Alkylpolyglykolethersulfate, α-Olefinsulfonate, C6-C18-Alkylpolyglykolethersulfonate, Glycerinethersulfonate, Glycerinethersulfate, Hydroxymischethersulfate, Monoglyceridsulfate, Sulfosuccinate, Sulfotriglyceride, Seifen, Amidseifen, C6-C18-Fettsäureamid-ethersulfate, C6-C18-Alkylcarboxylate, Fettsäureisethionate, N-C6-C18-Acyl-Sarcosinate, N-C6-C18-Acyl-Tauride, C6-C18-Alkyloligoglucosidsulfate, C6-C18-Alkyl-phosphate sowie deren Mischungen in einer Gesamtmenge von bis zu 40 Gew.-% bezogen auf das Gesamtgewicht des Flüssigwaschmittels oder Allzweckreinigers.In a preferred embodiment of the invention, the above-mentioned liquid detergents and all-purpose cleaners additionally contain an anionic surfactant selected from the group of the C 6 -C 18 alkylbenzenesulfonates, C 6 -C 18 alkanesulfonates, C 6 -C 18 alkyl sulfates, C 6 -C 18 - Alkyl polyglycol ether sulfates, α-olefin sulfonates, C 6 -C 18 alkyl polyglycol ether sulfonates, glycerol ether sulfonates, glycerin ether sulfates, hydroxymixed ether sulfates, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, soaps, amide soaps, C 6 -C 6 fatty acid alkamides, C 6 -C 18 carboxylate alkoxide sulfate NC 6 -C 18 acyl sarcosinates, NC 6 -C 18 acyl taurides, C 6 -C 18 alkyl oligoglucoside sulfates, C 6 -C 18 alkyl phosphates and mixtures thereof in a total amount of up to 40% by weight. % based on the total weight of the liquid detergent or all-purpose cleaner.

In einer weiteren bevorzugten Ausführungsform enthalten die erfindungsgemäßen Flüssigwaschmittel oder Allzweckreiniger zusätzlich ein weiteres nichtionisches Tensid ausgewählt aus der Gruppe der C6-C18-Alkylpolyglykolether, Zuckerester, C6-C18-Fettsäurepolyglykolether, Sorbitanfettsäureester, C6-C18-Fettsäurepartialglyceride sowie deren Mischungen in einer Gesamtmenge von bis zu 30 Gew.-%, bezogen auf die Gesamtmenge des Flüssigwaschmittels oder Allzweckreinigers.In a further preferred embodiment of the present invention liquid detergent or all-purpose cleaners additionally contain a further nonionic surfactant selected from the group of C 6 -C 18 -alkyl polyglycol ether, Zuckerester, C 6 -C 18 -Fettsäurepolyglykolether, sorbitan fatty acid esters, C 6 -C 18 fatty acid partial glycerides as well as their Mixtures in a total amount of up to 30 wt .-%, based on the total amount of liquid detergent or all-purpose cleaner.

Besonders bevorzugte Ausführungsformen enthalten Aniontenside ausgewählt aus der Gruppe der C6-C18-Alkylsulfate, der C6-C18-Alkylpolyglykolethersulfate, der Seifen und der C6-C18-Alkansulfonate sowie deren Mischungen bzw. nichtionische Tenside ausgewählt aus der Gruppe der C6-C18-Alkylpolyglycolether.Particularly preferred embodiments contain anionic surfactants selected from the group of the C 6 -C 18 alkyl sulfates, the C 6 -C 18 alkyl polyglycol ether sulfates, the soaps and the C 6 -C 18 alkane sulfonates and their mixtures or nonionic surfactants selected from the group of the C 6 -C 18 alkyl polyglycol ether.

Bei den erfindungsgemäß einzusetzenden Seifen handelt es sich um Alkali-, Ammonium- oder Alkanolammoniumsalze von gesättigten oder ungesättigten Fettsäuren mit 8 - 22, vorzugsweise 10 - 18 C-Atomen. Die Seifen können entweder als solche zugegeben werden oder nach Zugabe von entsprechenden Fettsäuren durch Salzbildung mit Basen wie z.B. NaOH, KOH, NH3, Aminen oder Alkanolaminen gebildet werden. In Abhängigkeit des eingestellten pH-Werts der erfindungsgemäßen Mittel liegen die Seifen entweder vollständig neutralisiert oder teilweise auch in freier Form als Fettsäure vor.The soaps to be used according to the invention are alkali, ammonium or alkanolammonium salts of saturated or unsaturated fatty acids with 8-22, preferably 10-18, carbon atoms. The soaps can either be added as such or, after the addition of appropriate fatty acids, can be formed by salt formation with bases such as NaOH, KOH, NH 3 , amines or alkanolamines. Depending on the adjusted pH of the agents according to the invention, the soaps are either completely neutralized or partly also in free form as fatty acids.

Bei den C6-C18-Alkylethersulfaten handelt es sich in erster Linie um Anlagerungsprodukte von 2 - 15 Mol Ethylenoxid an C6-C18-Fettalkohole, welche anschließend sulfatiert werden. Bei den als nichtionische Tenside eingesetzten C6-C18-Alkylpolyglykolethern handelt es sich in erster Linie um Anlagerungsprodukte von 2 - 10 Mol Ethylenoxid an C6-C18-Fettalkohole.The C 6 -C 18 alkyl ether sulfates are primarily addition products of 2-15 moles of ethylene oxide with C 6 -C 18 fatty alcohols, which are then sulfated. The C 6 -C 18 alkyl polyglycol ethers used as nonionic surfactants are primarily adducts of 2-10 mol ethylene oxide with C 6 -C 18 fatty alcohols.

Fakultativ können weiterhin in Flüssigwaschmitteln oder Allzweckreinigern übliche Hilfsstoffe zugesetzt werden; bei diesen Stoffen handelt es sich um Builder, z.B. Glutarsäure, Bernsteinsäure, Adipinsäure, Weinsäure, Benzolhexacarbonsäure, Gluconsäure, Trinatriumcitrat; Lösungsmittel, z.B. Aceton, Ethanol oder Glycerin, Hydrotrope, z.B. Cumolsulfonat, Octylsulfat, Butylglucosid, Butylenglykol; Reinigungsverstärker; Viskositätsregler, z.B. synthetische Polymere wie Polyacrylate; pH-Regulatoren, z.B. Zitronensäure, Triethanolamin oder NaOH; Konservierungsmittel, z.B. Glutaraldehyd; Farb- und Duftstoffe sowie Trübungsmittel.Auxiliaries customary in liquid detergents or all-purpose cleaners can optionally be added; these substances are builders, e.g. Glutaric acid, succinic acid, adipic acid, tartaric acid, benzene hexacarboxylic acid, gluconic acid, trisodium citrate; Solvents, e.g. Acetone, ethanol or glycerin, hydrotropes e.g. Cumene sulfonate, octyl sulfate, butyl glucoside, butylene glycol; Cleaning booster; Viscosity regulators, e.g. synthetic polymers such as polyacrylates; pH regulators, e.g. Citric acid, triethanolamine or NaOH; Preservatives, e.g. Glutaraldehyde; Dyes, fragrances and opacifiers.

Der pH-Wert der erfindungsgemäBen Allzweckreiniger liegt üblicherweise zwischen 4 und 8,5, vorzugsweise zwischen 6 und 8. Besonders bevorzugt ist jedoch ein Bereich zwischen 7,0 und 7,5. Der pH-Wert bei einer Anwendungskonzentration von 10 g/l liegt vorzugsweise bei 7,3 - 7,8.The pH of the all-purpose cleaners according to the invention is usually between 4 and 8.5, preferably between 6 and 8. However, a range between 7.0 and 7.5 is particularly preferred. The pH value at an application concentration of 10 g / l is preferably 7.3-7.8.

Die erfindungsgemäßen Mittel eignen sich besonders zum Reinigen von harten Oberflächen wie z.B. Emaille, Glas, PVC, Linoleum, Steinböden, wie z.B. Marmor, Terrazzo, nicht glasierten Klinker, Keramik-Fliesen oder versiegelten Holzfußböden, wie z.B. Parkett oder Dielen.The agents according to the invention are particularly suitable for cleaning hard surfaces such as e.g. Enamel, glass, PVC, linoleum, stone floors, e.g. Marble, terrazzo, unglazed clinker, ceramic tiles or sealed wooden floors, e.g. Parquet or floorboards.

Der pH-Wert der erfindungsgemäßen Flüssigwaschmittel liegt üblicherweise zwischen 6,0 und 10,0, vorzugsweise zwischen 7,0 und 9,0.The pH of the liquid detergents according to the invention is usually between 6.0 and 10.0, preferably between 7.0 and 9.0.

Die Flüssigwaschmittel eignen sich sowohl für den Einsatz in Waschmaschinen als auch für den Einsatz im Handwaschbecken zum Waschen von hochwertigen Textilien aus Wolle oder Seide.The liquid detergents are suitable both for use in washing machines and for use in hand basins for washing high-quality textiles made of wool or silk.

BeispieleExamples

Zum Nachweis der Vorteile der erfindungsgemäßen Allzweckreiniger gegenüber bekannten Allzweckreinigern für harte Oberflächen wurden Vergleichsversuche hinsichtlich des Reinigungsvermögens und des Schaumzerfalls angestellt.To demonstrate the advantages of the all-purpose cleaners according to the invention over known all-purpose cleaners for hard surfaces, comparative tests were carried out with regard to the cleaning ability and the foam breakdown.

Reinigungsvermögen:Cleaning ability:

Zur Prüfung des Reinigungsvermögens diente die unten nach "Seifen-Öle-Fette-Wachse", 112, 371, (1986) beschriebene Testmethode, die sehr gut reproduzierbare Ergebnisse liefert. Danach wurde das zu prüfende Reinigungsmittel in Form einer 1 Gew.-%igen wäßrigen Lösung (10 g/l) auf eine künstlich angeschmutzte Kunststoffoberfläche gegeben. Als künstliche Anschmutzung für die verdünnte Anwendung des Reinigungmittels wurde ein Gemisch aus Ruß, Maschinenöl, Triglycerid gesättigter Fettsäuren und niedersiedendem aliphatischen Kohlenwasserstoff verwendet. Die Testfläche von 26 x 28 cm wurde mit Hilfe eines Flächenstreichers gleichmäßig mit 2 g der künstlichen Anschmutzung beschichtet.The test method described below according to "Seifen-Öle-Fette-Wwachs", 112 , 371, (1986) was used to test the cleaning ability and provides very reproducible results. The cleaning agent to be tested was then placed in the form of a 1% by weight aqueous solution (10 g / l) on an artificially soiled plastic surface. A mixture of carbon black, machine oil, triglyceride, saturated fatty acids and low-boiling aliphatic hydrocarbon was used as artificial soiling for the dilute use of the cleaning agent. The test area of 26 x 28 cm was evenly coated with 2 g of the artificial soiling with the aid of a surface coater.

Ein Kunststoffschwamm wurde jeweils mit 10 ml der zu prüfenden 1 %igen Reinigungsmittellösung getränkt und mechanisch auf der schmutzbeschichteten Testfläche bewegt, auf die ebenfalls 10 ml der zu prüfenden, 1 %igen Reinigungsmittellösung aufgebracht waren. Nach 10 Wischbewegungen wurde die gereinigte Testfläche unter fließendes Wasser gehalten und der lose sitzende Schmutz entfernt. Die Reinigungswirkung der so gereinigten Kunststoffoberfläche wurde mit Hilfe eines Remissionsfarbmeßgerätes "Microcolor" (Dr. B. Lange) ermittelt. Die Meßgröße ist dabei der Weißgrad. Als Weiß-Standard diente die saubere weiße Kunststoffoberfläche; der Weißgrad der sauberen, weißen Kunststoffoberfläche entspricht 100 % RV (Reinigungsvermögen). Der Weißgrad einer angeschmutzten und anschließend gereinigten Kunststoffoberfläche entspricht demgemäß einem Wert zwischen 0 % und 100 % RV. Die % RV-Werte stellen jeweils Mittelwerte aus Dreifachbestimmungen dar.A plastic sponge was impregnated with 10 ml of the 1% detergent solution to be tested and moved mechanically on the dirt-coated test surface, to which 10 ml of the 1% detergent solution to be tested was also applied. After 10 wiping movements, the cleaned test area was kept under running water and the loose dirt was removed. The cleaning effect of the plastic surface cleaned in this way was determined with the aid of a "Microcolor" remission color measuring device (Dr. B. Lange). The measurand is the degree of whiteness. The clean white plastic surface served as the white standard; the whiteness of the clean, white plastic surface corresponds to 100% RV (cleaning ability). The whiteness of a soiled and then cleaned plastic surface corresponds to a value between 0% and 100% RV. The% RV values represent mean values from triplicate determinations.

Die Meßwerte wurden in Relation zum Reinigungsergebnis eines als Standard benutzten leistungsstarken Allzweckreinigers gesetzt. Meßwerte der Probe · 100 Meßwert des Standards = % RV relativ

Figure imgb0001
The measured values were set in relation to the cleaning result of a high-performance all-purpose cleaner used as standard. Measured values of the sample · 100 Reading of the standard =% RV relative
Figure imgb0001

Die als Standard benutzte leistungsstarke Formulierung hatte die Zusammensetzung:

8 %
Alkylbenzolsulfonat-Na-Salz
2 %
Addukt von C12-C14-Alkylepoxid + Ethylenglykol + 10 Mol Ethylenoxid
2 %
Na-gluconat
0,1 %
Polyethylenglykol mit einem Molgewicht von ca. 600000 (Polyox WSR 205 der Fa. UCC)
The powerful formulation used as standard had the composition:
8th %
Alkylbenzenesulfonate Na salt
2%
Adduct of C 12 -C 14 alkyl epoxide + ethylene glycol + 10 moles of ethylene oxide
2%
Na gluconate
0.1%
Polyethylene glycol with a molecular weight of approx. 600,000 (Polyox WSR 205 from UCC)

Schaumverhalten:Foam behavior:

Das Schaumverhalten der erfindungsgemäßen Allzweckreiniger wurde folgendermaßen geprüft: Das Prüfprodukt wurde in ein weitlumiges Becfierglas vorgelegt. Sodann wurde darauf aus 30 cm Höhe im freien Fall die Menge an Leitungswasser zuflieBen gelassen, die mit der Menge an vorgelegtem Produkt eine Anwendungskonzentration des Produkts von 10 g/l ergibt. Die Schaumhöhe im Becherglas wurde unmittelbar nach Beendigung der Wasserzugabe abgelesen.The foaming behavior of the all-purpose cleaners according to the invention was tested as follows: The test product was placed in a large-volume serving glass. Then the amount of tap water was allowed to flow in freely from a height of 30 cm, which, together with the amount of product presented, gave an application concentration of the product of 10 g / l. The foam height in the beaker was read off immediately after the addition of water had ended.

Die folgenden Zusammensetzungen wurden durch Zusammenmischen der Komponenten und anschließende Einstellung des gewünschten pH-Wertes hergestellt. Alle Prozentangaben beziehen sich auf Gewichtsprozent Aktivsubstanz.The following compositions were prepared by mixing the components together and then adjusting the desired pH. All percentages relate to percent by weight of active substance.

Die Zusammensetzungen 1 bis 9 sind Tabelle 1 zu entnehmen. Die Zusammensetzung 1 (V) ist nicht erfindungsgemäß und dient zum Vergleich.Compositions 1 to 9 are shown in Table 1. Composition 1 (V) is not according to the invention and is used for comparison.

Die Fettsäurealkylesteralkoxylate werden in Tabelle 1 in folgender Schreibweise wiedergegeben:
Beispiel: C12FSEO15Me steht für
   C11H23CO2(CH2CH2O)15CH3, Methylester der mit 15 Ethylenoxideinheiten ethoxylierten C12-Fettsäure.
EO steht für Ethylenoxid, PO steht für Propylenoxid. Die Alkoxylierungsgrade stellen dabei Mittelwerte dar. Tabelle 1 Zahlenangaben in Gew.% 1(V) 2 3 4 5 6 7 8 9 Octanol x 4 EO (Dehydol 04 DEO, Fa. Henkel) 2 - - - - - - - - C12FSEO15Me - 2 - - - - - - - C6-10FSEO10,6Me - - 2 - - - - - - C12FSEO12ME - - - 2 - - 2 2 2 C6-10FSEO6Me - - - - 2 - - - - C12FSEO6Me - - - - - 2 - - - APG 225 (C8-10-Alkylpolyglucosid, Fa. Henkel, DP = 1,6) 3,5 3,5 3,5 3,5 3,5 3,5 - - - C8-Alkylpolyglucosid, (DP = 1,6) - - - - - - 3,5 - - C8-Alkylpolyxylosid, (DP = 1,4) - - - - - - - 3,5 - C10-Alkylpolyxylosid, (DP = 1,4) - - - - - - - - 3,5 C12-18-Fettsäure (Edenor K12/18, Fa. Henkel) 0,6 0,6 0,6 0,6 0,6 0,6 0,6 0,6 0,6 Bernstein-, Glutar-, Adipinsäuregem. (Sokalan DCS, BASF) 2 2 2 2 2 2 2 2 2 NaOH 1,2 1,2 1,2 1,2 1,2 1,2 1,2 1,2 1,2 pH 7,0-7,5 7,0-7,5 7,0-7,5 7,0-7,5 7,0-7,5 7,0-7,5 7,0-7,5 7,0-7,5 7,0-7,5 Reinigungsvermögen (%) 61 74 66 74 68 64 66 69 67 Schaumhöhe (cm) unmittelbar n. Wasserzugabe: 2 1,3 2 1,2 1 2,3 2,1 1,8 1,7 Aufreißen der Schaumdecke (in Min.) 2,5 0,5 1 0,5 0,5 1 1 0,5 0,5 The fatty acid alkyl ester alkoxylates are given in Table 1 in the following notation:
Example: C 12 FSEO 15 Me stands for
C 11 H 23 CO 2 (CH 2 CH 2 O) 15 CH 3 , methyl ester of C 12 fatty acid ethoxylated with 15 ethylene oxide units.
EO stands for ethylene oxide, PO stands for propylene oxide. The degrees of alkoxylation represent mean values. Table 1 Figures in% by weight 1 (V) 2nd 3rd 4th 5 6 7 8th 9 Octanol x 4 EO (Dehydol 04 DEO, Henkel) 2nd - - - - - - - - C 12 FSEO 15 Me - 2nd - - - - - - - C 6-10 FSEO 10.6 me - - 2nd - - - - - - C 12 FSEO 12 ME - - - 2nd - - 2nd 2nd 2nd C 6-10 FSEO 6Me - - - - 2nd - - - - C 12 FSEO 6 me - - - - - 2nd - - - APG 225 (C 8-10 alkyl polyglucoside, from Henkel, DP = 1.6) 3.5 3.5 3.5 3.5 3.5 3.5 - - - C 8 alkyl polyglucoside, (DP = 1.6) - - - - - - 3.5 - - C 8 alkyl polyxyloside, (DP = 1.4) - - - - - - - 3.5 - C 10 alkyl polyxyloside, (DP = 1.4) - - - - - - - - 3.5 C 12-18 fatty acid (Edenor K12 / 18, from Henkel) 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Amber, glutaric, adipic acid gem. (Sokalan DCS, BASF) 2nd 2nd 2nd 2nd 2nd 2nd 2nd 2nd 2nd NaOH 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 pH 7.0-7.5 7.0-7.5 7.0-7.5 7.0-7.5 7.0-7.5 7.0-7.5 7.0-7.5 7.0-7.5 7.0-7.5 Cleaning ability (%) 61 74 66 74 68 64 66 69 67 Foam height (cm) immediately after adding water: 2nd 1.3 2nd 1.2 1 2.3 2.1 1.8 1.7 Tear open the foam blanket (in min.) 2.5 0.5 1 0.5 0.5 1 1 0.5 0.5

Es zeigt sich, daß die erfindungsgemäßen Zusammensetzungen 2 bis 9 gegenüber der Vergleichszusammensetzung 1 (V) hinsichtlich Reinigungsvermögen und Schaumzerfall eine deutliche Überlegenheit aufweisen.It can be seen that compositions 2 to 9 according to the invention are clearly superior to comparative composition 1 (V) in terms of cleaning ability and foam disintegration.

Die folgenden Beispiele zeigen weitere bevorzugte Formulierungen und Einsatzmöglichkeiten für die beanspruchten Allzweckreiniger.The following examples show further preferred formulations and possible uses for the claimed general-purpose cleaners.

Beispiel 10Example 10

45,0 Gew.-%45.0% by weight
C8 - C10-Alkylpolyglucosid, DP = 1,6C 8 -C 10 alkyl polyglucoside, DP = 1.6
20,0 Gew.-%20.0% by weight
C12-Fettsäuremethylester x 13 EOC 12 fatty acid methyl ester x 13 EO
5,0 Gew.-%5.0% by weight
PalmkernfettsäurePalm kernel fatty acid
1,0 Gew.-%1.0% by weight
Zitronensäurecitric acid
10,0 Gew.-%10.0% by weight
Cumolsulfonat
Kalilauge zur Einstellung des pH-Wertes des Fertigproduktes auf pH 8 Farb- und DuftstoffeCumene sulfonate
Potash lye to adjust the pH of the finished product to pH 8 colors and fragrances
ad 100,0 Gew.-%ad 100.0% by weight
Wasserwater

Das Beispiel 10 stellt ein Allzweckreiniger-Hochkonzentrat dar, welches in 0,1 %iger Lösung zur Anwendung kommt.Example 10 represents an all-purpose cleaner high concentrate, which is used in 0.1% solution.

Beispiel 11Example 11

3,0 Gew.-%3.0% by weight
C8 - C10-Alkylpolyglucosid, DP = 1,6C 8 -C 10 alkyl polyglucoside, DP = 1.6
1 Gew.-%1% by weight
ButylpolyglucosidButyl polyglucoside
1 Gew.-%1% by weight
C12-Fettsäuremethylester x 12 E0C 12 fatty acid methyl ester x 12 E0
0,5 Gew.-%0.5% by weight
PalmkernfettsäurePalm kernel fatty acid
2,0 Gew.-%2.0% by weight
Methacrylsäure-(Stearylalkohol-20 EO-ester)ester/Acrylsäure-Copolymer (Acrysol ICS-1 der Fa. Rohm & Haas)Methacrylic acid (stearyl alcohol-20 EO-ester) ester / acrylic acid copolymer (Acrysol ICS-1 from Rohm & Haas)
0,05 Gew.-%0.05% by weight
Polyethylenoxid, MG 600000Polyethylene oxide, MW 600000
2,0 Gew.-%2.0% by weight
Butylglykol
Natronlauge zur Einstellung auf pH 8 Farb- und Duftstoffe, KonservierungsmittelButyl glycol
Sodium hydroxide solution for adjustment to pH 8 colors and fragrances, preservative
ad 100,0 Gew.-%ad 100.0% by weight
Wasserwater
Beispiel 12Example 12

0,2 Gew.-%0.2% by weight
C10-Alkylpolyglucosid, DP = 1,6C 10 alkyl polyglucoside, DP = 1.6
0,05 Gew.-%0.05% by weight
C10-C12-Fettsäuremethylester x 17 E0C 10 -C 12 fatty acid methyl ester x 17 E0
7,0 Gew.-%7.0% by weight
Ethanol
Ammoniak zur Einstellung auf pH 8,3Ethanol
Ammonia to adjust to pH 8.3
ad 100,0 Gew.-%ad 100.0% by weight
Wasserwater

Es handelt sich hierbei um einen Allzwecksprühreiniger, der unverdünnt mittels Handsprühpumpe appliziert wird. Bei dieser Angebotsform erfolgt die Bestimmung des Schaumzerfalls durch visuelle Abmusterung des Sprühvorganges: die zu reinigende angesprühte Fläche zeigte unmittelbar nach Applikation des Sprühreinigers keine Schaumbläschen.It is an all-purpose spray cleaner that is applied undiluted using a hand spray pump. In this form of offer, foam decay is determined by visual sampling of the spraying process: the sprayed surface to be cleaned showed no foam bubbles immediately after application of the spray cleaner.

Beispiel 13Example 13

5 Gew.-%5% by weight
C10-Alkylpolyglucosid, DP = 1,6C 10 alkyl polyglucoside, DP = 1.6
4 Gew.-%4% by weight
C12-Fettsäuremethylester x 6 E0C 12 fatty acid methyl ester x 6 E0
2 Gew.-%2% by weight
OctylsulfatOctyl sulfate
5 Gew.-%5% by weight
EthanolEthanol
3 Gew.-%3% by weight
Trinatriumcitrat
Zitronensäure zur Einstellung auf pH 5,5Trisodium citrate
Citric acid to adjust to pH 5.5
ad 100,0 Gew.-%ad 100.0% by weight
Wasserwater
Beispiel 14Example 14

12 Gew.-%12% by weight
C10-Alkylpolyxylosid, DP = 1,4C 10 alkyl polyxyloside, DP = 1.4
8 Gew.-%8% by weight
C12-Fettsäuremethylester x 11 E0C 12 fatty acid methyl ester x 11 E0
2 Gew.-%2% by weight
C12-FettalkoholsulfatC 12 fatty alcohol sulfate
5 Gew.-%5% by weight
Ethanol
Kalilauge zur Einstellung auf pH 7-7,5Ethanol
Potash lye to adjust to pH 7-7.5
ad 100,0 Gew.-%ad 100.0% by weight
Wasserwater
Beispiel 15Example 15

6 Gew.-%6% by weight
C10-Alkylpolyxylosid, DP = 1,4C 10 alkyl polyxyloside, DP = 1.4
8 Gew.-%8% by weight
C12-Fettsäuremethylester x 11 EOC 12 fatty acid methyl ester x 11 EO
6 Gew.-%6% by weight
C12-C14-Fettalkoholether(2 EO) sulfatC 12 -C 14 fatty alcohol ether (2 EO) sulfate
5 Gew.-%5% by weight
Ethanol
NaOH zur Einstellung auf pH 7-7,5Ethanol
NaOH to adjust to pH 7-7.5
ad 100,0 Gew.-%ad 100.0% by weight
Wasserwater
Beispiel 16Example 16

10 Gew.-%10% by weight
C8-Alkylpolyxylosid, DP = 1,4C 8 alkyl polyxyloside, DP = 1.4
8 Gew.-%8% by weight
C12-Fettsäuremethylester x 11 EOC 12 fatty acid methyl ester x 11 EO
2 Gew.-%2% by weight
Decanol x 3 EODecanol x 3 EO
1,5 Gew.-%1.5% by weight
KokosfettsäureCoconut fatty acid
5 Gew.-%5% by weight
Ethanol
NaOH zur Einstellung auf pH 7-7,5Ethanol
NaOH to adjust to pH 7-7.5
ad 100,0 Gew.-%ad 100.0% by weight
Wasserwater
Beispiel 17Example 17

10 Gew.-%10% by weight
C8-C10-Alkylpolyglucosid, DP = 1,6C 8 -C 10 alkyl polyglucoside, DP = 1.6
8 Gew.-%8% by weight
C8-C16-Fettsäuremethylester x 18 POC 8 -C 16 fatty acid methyl ester x 18 PO
2 Gew.-%2% by weight
C13-C18-sec-Alkansulfonat, Na-Salz Hostapur SAS 60 der Fa. HoechstC 13 -C 18 -sec-alkanesulfonate, Na salt Hostapur SAS 60 from Hoechst
3 Gew.-%3% by weight
CumolsulfonatCumene sulfonate
1,5 Gew.-%1.5% by weight
KokosfettsäureCoconut fatty acid
5 Gew.-%5% by weight
Ethanol
NaOH zur Einstellung auf pH 7-7,5Ethanol
NaOH to adjust to pH 7-7.5
ad 100,0 Gew.-%ad 100.0% by weight
Wasserwater
Beispiel 18Example 18

1,5 Gew.-%1.5% by weight
APG 600 (C12-C14-Alkylpolyglucosid der Fa. Henkel, DP = 1,4)APG 600 (C 12 -C 14 alkyl polyglucoside from Henkel, DP = 1.4)
1,5 Gew.-%1.5% by weight
C12-Fettsäuremethylester x 15 EOC 12 fatty acid methyl ester x 15 EO
1 Gew.-%1% by weight
Methacrylsäure-(Stearylalkohol-20 EO-ester)ester/Acrylsäure-Copolymer (Acrysol ICS-1 der Fa. Rohm + Haas)Methacrylic acid (stearyl alcohol-20 EO-ester) ester / acrylic acid copolymer (Acrysol ICS-1 from Rohm + Haas)
50 Gew.-%50% by weight
Quarzmehl
Triethanolamin zur Einstellung auf pH 8Quartz flour
Triethanolamine to adjust to pH 8
ad 100,0 Gew.-%ad 100.0% by weight
Wasserwater
Beispiel 19Example 19

4,0 Gew.-%4.0% by weight
C10-Alkylpolyglucosid, DP = 1,6C 10 alkyl polyglucoside, DP = 1.6
5,0 Gew.-%5.0% by weight
C12-Fettsäuremethylester x 17 EOC 12 fatty acid methyl ester x 17 EO
1,0 Gew.-%1.0% by weight
OctylsulfatOctyl sulfate
4,0 Gew.-%4.0% by weight
EthanolEthanol
2,0 Gew.-%2.0% by weight
Tri-Natrium-Citrat
Citronensäure zur Einstellung des pH's auf 4,8Tri-sodium citrate
Citric acid to adjust the pH to 4.8
ad 100,0 Gew.-%ad 100.0% by weight
Wasserwater
Beispiel 20Example 20

Wäßriges Flüssigwaschmittel M1 mit geringer Schaumneigung:

8,0 Gew.-%
C12-C14-Alkylpolyglucosid, DP=1,4
10,0 Gew.-%
C12-C18-Fettsäuremethylester x 3 EO
5,0 Gew.-%
C12-Alkylbenzolsulfonat
5,0 Gew.-%
Ethanol
8,0 Gew.-%
Glycerin
0,5 Gew.-%
Protease
5,0 Gew.-%
Tri-Natrium-Citrat
0,1 Gew.-%
Farb- und Duftstoffe
ad 100,0 Gew.-%
Wasser
Aqueous liquid detergent M1 with low tendency to foam:
8.0% by weight
C 12 -C 14 alkyl polyglucoside, DP = 1.4
10.0% by weight
C 12 -C 18 fatty acid methyl ester x 3 EO
5.0% by weight
C 12 alkyl benzene sulfonate
5.0% by weight
Ethanol
8.0% by weight
Glycerin
0.5% by weight
Protease
5.0% by weight
Tri-sodium citrate
0.1% by weight
Dyes and fragrances
ad 100.0% by weight
water

Das Mittel besaß hervorragende Schaumeigenschaften (niedrige Schaumwerte).The agent had excellent foam properties (low foam values).

Beispiel 21Example 21

Wäßriges Flüssigwaschmittel M2 mit geringer Schaumneigung:

9,0 Gew.-%
C12-C14-Alkylpolyglucosid, DP=1,4
9,0 Gew.-%
C12-C18-Fettsäuremethylester x 5 EO
6,0 Gew.-%
Ethanol
5,0 Gew.-%
Glycerin
0,5 Gew.-%
Tri-Natrium-Citrat
ad 100,0 Gew.-%
Wasser
Aqueous liquid detergent M2 with low foaming tendency:
9.0% by weight
C 12 -C 14 alkyl polyglucoside, DP = 1.4
9.0% by weight
C 12 -C 18 fatty acid methyl ester x 5 EO
6.0% by weight
Ethanol
5.0% by weight
Glycerin
0.5% by weight
Tri-sodium citrate
ad 100.0% by weight
water

Schaumbestimmung in der Trommelwaschmaschine:Foam determination in the drum washing machine:

WasserhärteWater hardness
: 16 °d: 16 ° d
Dosierungdosage
: 0,8 g/l: 0.8 g / l
Temperaturtemperature
: 60 °C: 60 ° C
SchaumnotenFoam notes
:
0  bedeutet, daß kein Schaum am unteren Rand des Bullauges der Waschmaschine zu sehen ist.
3  bedeutet, daß die Schaumhöhe die Hälfte des Bullauges erreicht hat.
5  bedeutet, daß das gesamte Bullauge mit Schaum bedeckt ist.:
0 means that there is no foam at the bottom of the washing machine's porthole.
3 means that the foam height has reached half of the porthole.
5 means that the entire porthole is covered with foam.

Als Vergleichsbeispiel wurde ein Mittel V getestet, das anstatt des Fettsäuremethylesters einen C13-C15-Alkohol x 5 E0 aufwies.

Figure imgb0002
As a comparative example, an agent V was tested which had a C 13 -C 15 alcohol x 5 E0 instead of the fatty acid methyl ester.
Figure imgb0002

Claims (8)

  1. A water-containing detergent or cleaning formulation containing
    0.1 to 50% by weight and preferably 1 to 20% by weight of at least one alkyl polyglycoside corresponding to formula (I): R1-O-[Z]x (I), where R1 is a linear or branched, saturated or unsaturated alkyl group containing 8 to 18 carbon atoms, Z is a sugar unit, preferably a glucose or xylose unit, and x is an integer of 1 to 10, and
    0.05 to 50% by weight and preferably 1 to 20% by weight of at least one fatty acid alkyl ester alkoxylate corresponding to formula (II): R2CO2-(AO)y-R3 (II), where R2 is a branched or linear, saturated or unsaturated alkyl group containing 5 to 21 carbon atoms, AO is a C2-4 alkylene oxide unit, y is a number of 1 to 30 and R3 is a linear or branched alkyl group containing 1 to 6 carbon atoms.
  2. A detergent or cleaning formulation as claimed in claim 1, characterized in that, in the alkyl polyglycoside corresponding to formula I, R1 is an alkyl group containing 8 to 12 carbon atoms and in the fatty acid alkyl ester alkoxylate corresponding to formula II, AO is an ethylene oxide unit and R3 is a methyl group.
  3. A detergent or cleaning formulation as claimed in claims 1 and 2, characterized in that it contains an anionic surfactant selected from the group consisting of C6-18 alkyl benzene sulfonates, C6-18 alkane sulfonates, C6-18 alkyl sulfates, C6-18 alkyl polglycol ether sulfates, α-olefin sulfonates, C6-18 alkyl polyglycol ether sulfonates, glycerol ether sulfonates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, soaps, amide soaps, C6-18 fatty acid amide ether sulfates, C6-18 alkyl carboxylates, fatty acid isethionates, N-C6-18-acyl sarcosinates, N-C6-18-acyl taurides, C6-18 alkyl oligoglucoside sulfates, C6-18 alkyl phosphates and mixtures thereof in a total quantity of up to 40% by weight, based on the detergent/ cleaning formulation as a whole.
  4. A detergent or cleaning formulation as claimed in claims 1 to 3, characterized in that it contains another nonionic surfactant selected from the group consisting of C6-18 alkyl polyglycol ethers, sugar esters, C6-18 fatty acid polyglycol ethers, sorbitan fatty acid esters, C6-18 fatty acid partial glycerides and mixtures thereof in a total quantity of up to 30% by weight, based on the detergent/ cleaning formulation as a whole.
  5. A detergent or cleaning formulation as claimed in claim 3, characterized in that the anionic surfactant is selected from the group of C6-18 alkyl sulfates, C6-18 alkyl polyglycol ether sulfates, soaps and C6-18 alkane sulfonates and mixtures thereof.
  6. A detergent as claimed in claim 4, characterized in that the nonionic surfactant is selected from the group of C6-18 alkyl polyglycol ethers.
  7. The use of the detergent or cleaning formulation claimed in any of claims 1 to 6, as a multipurpose cleaner for cleaning hard surfaces, a fatty acid alkyl ester alkoxylate in which y is a number of 5 to 25 and, more particularly, 9 to 18 preferably being used.
  8. The use of the detergent or cleaning formulation claimed in any of claims 1 to 6 as a liquid detergent, a fatty acid alkyl ester alkoxylate in which R2 is a linear or branched, saturated alkyl group containing 12 to 18 carbon atoms and y is a number of 3 to 15, preferably being used.
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WO1995004803A1 (en) 1995-02-16
US5753606A (en) 1998-05-19
DE4326112A1 (en) 1995-02-09
JPH09501195A (en) 1997-02-04
EP0712436A1 (en) 1996-05-22
ES2099628T3 (en) 1997-05-16

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