EP0569366A1 - Low-foam scouring powder. - Google Patents

Low-foam scouring powder.

Info

Publication number
EP0569366A1
EP0569366A1 EP92900845A EP92900845A EP0569366A1 EP 0569366 A1 EP0569366 A1 EP 0569366A1 EP 92900845 A EP92900845 A EP 92900845A EP 92900845 A EP92900845 A EP 92900845A EP 0569366 A1 EP0569366 A1 EP 0569366A1
Authority
EP
European Patent Office
Prior art keywords
scouring
alkyl
surfactant
weight
surfactants
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP92900845A
Other languages
German (de)
French (fr)
Other versions
EP0569366B1 (en
Inventor
Eva Kiewert
Lothar Pioch
Wolfgang Seiter
Winfried Wichelhaus
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0569366A1 publication Critical patent/EP0569366A1/en
Application granted granted Critical
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Anticipated expiration legal-status Critical
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures

Definitions

  • the invention relates to scouring powders which at the same time offer a good cleaning action, in particular with regard to greasy soiling, and develop only a little foam when used.
  • Scouring powder is one of the oldest and still indispensable cleaning agents that are used in households and businesses to remove stubborn dirt.
  • the basic constituents of scouring powders form, on the one hand, the abrasive particles required for the mechanical loosening of stubborn dirt and, on the other hand, surfactants as surface-active substances, which are essential for the removal of greasy or greasy dirt.
  • the scouring powders currently on the market contain almost exclusively alkylbenzenesulfonates as surfactants, as well as occasionally other active ingredients and auxiliaries such as. B. bleach and disinfectants, zeolites and alkaline salts.
  • German patent applications DE 2539733 AI and DE 2739776 AI describe liquid and powdered abrasives with an abrasive content of pearlite in an amount of up to 65%. These applications essentially focus on this special abrasive. Alkyl sulfates and alkylbenzenesulfonates are specified here as surfactants for the powdery compositions.
  • Canadian Patent 1,048,365 (Procter & Gamble) describes abrasive powders with a high surfactant content of 20-35% and an abrasive content of 5-20%, which are recommended as both abrasive powder and dishwashing detergent.
  • Alkyl sulfates, alkylbenzenesulfonates and fatty alcohol ethoxylates are mentioned as surfactants.
  • the common known and currently commercially available scouring powders have a good cleaning ability as a common feature Z greasy and fatty dirt, but foams to an undesirably high degree when used. In order to avoid foaming, an attempt was even made to offer pure abrasives without any surfactant addition.
  • the object of the invention was therefore to provide the desired agents which combine the two product effects: good dirt removal and low foaming tendency.
  • this object was achieved by adding alkyl glycosides with a degree of oligomerization from 1.2 to 1.4 or surfactant combinations containing these alkyl glycosides to the scouring powders, which scouring powders may also contain conventional ingredients.
  • the invention therefore relates to low-foaming scouring powders with a content of abrasives, other customary constituents and, if appropriate, other surfactants, which are characterized in that they contain an addition of alkyl glycosides with a degree of oligomerization of 1.2 to 1.4.
  • Alkyl glycosides are known to be degradable surfactants of native origin.
  • the alkyl glycosides which can be used here as surfactants can be represented by the structural formula R0 (G) x , where R is an aliphatic radical having at least 4 carbon atoms, in particular the remainder of a primary alcohol and very particularly a fatty alkyl or fatty alkenyl radical 8 to 22, preferably 12 to 18 carbon atoms.
  • R is an aliphatic radical having at least 4 carbon atoms, in particular the remainder of a primary alcohol and very particularly a fatty alkyl or fatty alkenyl radical 8 to 22, preferably 12 to 18 carbon atoms.
  • the symbol (G) in the formula stands for a glycose unit, glucose being preferred because of the technical availability on the one hand and the good reactivity on the other hand.
  • the index number x is any number between 1.2 and 1.4, which means the so-called degree of oligomerization, ie the distribution of monoglycosides and oligoglycosides is specified.
  • the alkyl glycosides are represented by the formula R0 (G) x , the percentage of fatty alcohol is neglected. In principle, this fatty alcohol portion can largely be controlled by gentle distillative treatment of the alkyl glycoside, ie the excess fatty alcohol resulting from the reaction can be removed from the product except for residual values which are less than 1% total. They have been proposed for liquid manual dishwashing detergents, e.g. B.
  • the surfactant sulfates, sulfonates, carboxylates and mixtures thereof are selected is described in EP 0 070074 A2 (Procter & Gamble).
  • alkylbenzenesulfonate, soap, zwitterionic surfactants, amphoteric surfactants, alkanesulfonates, alpha-olefinsulfonates, alkylsulfates, alkylpolyglycol ether sulfates and paraffin sulfonates and mixtures thereof are mentioned as anionic co-surfactants.
  • the surfactant compositions described here are suitable for the production of products which foam strongly when used, such as, for example, manual dishwashing detergents and shampoos. The description also mentions enu eratively a possible addition of abrasives, but no examples are available.
  • liquid, high-foaming detergents for the manual cleaning of dishes are also known which, in addition to fatty alkyl glucosides with a degree of oligomerization of 1 to 1.4, serve as foam enhancers and dialkyl sulfosuccinates with 7 to 9 carbon atoms contained in each of the alkyl radicals. Again, there is no evidence of abrasives. It was therefore not foreseeable that this Alkyl glycosides alone or in combination with other surfactants in scouring powders show only a weak development of foam when used.
  • Preferred scouring powders of the present invention have the following composition:
  • Surfactant mixture from the group of anionic, nio- or amphoteric surfactants, this surfactant or this surfactant mixture consisting of 2-100%, preferably 5-90%, of the alkyl glucoside and
  • Alkyl sulfates which are prepared from natural oils and fats by known processes and have a saturated or unsaturated alkyl radical having 6-20, preferably 10-18 carbon atoms are preferred. Scouring powders which are free from alkylbenzenesulfonates are particularly preferred.
  • Suitable nonionic surfactants are fatty alcohol ethoxylates, ie addition products of 2-16 mol ethylene oxide onto fatty alcohols with branched or straight-chain saturated or unsaturated C16-C20-alkyl radicals.
  • Preferred fatty alcohol ethoxylates are those which are produced from natural fats and oils.
  • conventional amphoteric surfactants and betaines and / or amidobetanes can also be used in small amounts. If this class of surfactants is also used, the amount used is based on the possible amount _T Align the presence of other surfactants so that the overall formulation has the desired foaming behavior.
  • All substances known for scouring powder e.g. B. mineral rock powder, such as quartz, cristobalite, marble, pumice powder u. ⁇ . With a grain size up to 1 mm, preferably up to 0.3 mm, are used. The lower grain size is determined solely by the technical possibilities in the production of abrasive materials, also in the form of flour-like forms suitable for polishing agent additives. Alternatively, plastic granules or powder as well as wood flour or glass beads and similar abrasives with a very mild abrasive effect can be used.
  • the known inorganic or organic compounds which deliver H2O2 or active chlorine in the presence of water are useful as bleaching and disinfecting agents.
  • the per-compounds can be used together with so-called bleach activators, e.g. Tetraacetyl-ethylenediamine or tetraacetyl-glycoluril can be used.
  • scouring powders include inorganic or organic complexing agents and builders that are able to bind alkaline earth ions in the tap water that is used to apply the scouring powder and that lead to an increase in the cleaning effect with the surfactants.
  • This class of active substances includes the known zeolites and organic complexing agents, in particular the sodium salts of the polycarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, carboxyalkyl ethers, polyanionic polymers, in particular the polymeric carboxylic acids.
  • P-containing complexing agents or framework substances should preferably not be used.
  • alkali metal salts in particular sodium salts, from the group of chlorides, carbonates, bicarbonates, sulfates and silicates to the scouring powders.
  • the scouring powders according to the invention can also contain colorants and fragrances.
  • colorants and fragrances.
  • oxidative bleaching agents Known oxidation-stable color pigments such as phthalocyanine pigments or ultramarine and fragrances such as terpene compounds are selected.
  • the scouring powder can be produced in a manner known per se, e.g. B. by drying part or all of the water-soluble components and adding or spraying on the remaining components of the scouring powder.
  • the cleaning effect of the scouring powders according to the invention was tested according to the method published in the trade journal Seifen- ⁇ le-Fette-Wachsen, 112, 371 (1986).
  • the cleaning agent to be tested was placed on an artificially soiled plastic surface.
  • a mixture of petroleum jelly (R), fatty acid glycerol esters and pigments was used as artificial soiling.
  • 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 soaked in tap water.
  • the scouring powder to be tested was applied to the test area as a 1: 1 mixture with tap water.
  • the sponge was then moved mechanically on the test surface. After ten wiping movements, the cleaned test area was kept under running water and the loose dirt was removed.
  • the cleaning effect, d. H. the degree of whiteness of the plastic surface cleaned in this way was determined using a Microcolor color difference measuring device from Dr. Measured for a long time.
  • the clean white plastic surface served as the white standard.
  • the foam behavior was checked in a practical manner using the following method, in which the foam which is produced when scrubbing was tested on a clean tiled table.
  • the relative cleaning power based on the comparison standard was 120%.
  • the foam notes were:
  • Example 2 The same composition as example 2, but marble powder with a grain size of 0-0.2 mm was used instead of the plastic granulate. This agent had a similarly good cleaning performance and low foaming tendency as Example 2.
  • This scouring powder had a good bleaching effect on fruit stains and was stable in storage.
  • Ci2_i4 alkyl glucoside with x 1.2
  • alkyl glucoside is used as the sole surfactant.

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

Abstract

PCT No. PCT/EP91/02451 Sec. 371 Date Jul. 29, 1993 Sec. 102(e) Date Jul. 29, 1993 PCT Filed Dec. 19, 1991 PCT Pub. No. WO92/13936 PCT Pub. Date Aug. 20, 1992.Scouring powders containing abrasives and an alkyl glycoside having a degree of oligomerization of from 1.2. to 1.4. These scouring powders are low foaming in the presence of water.

Description

"Schwachschäumendes Scheuerpulver" "Low-foaming scouring powder"
Die Erfindung betrifft Scheuerpulver, die gleichzeitig eine gute Reini¬ gungswirkung insbesondere gegenüber fettigen Verschmutzungen bieten und bei der Anwendung nur wenig Schaum entwickeln.The invention relates to scouring powders which at the same time offer a good cleaning action, in particular with regard to greasy soiling, and develop only a little foam when used.
Scheuerpulver gehören zu den ältesten und auch heute noch unentbehrlichen Reinigungsmitteln, die in Haushalt und Gewerbe zur Entfernung hartnäckiger Verschmutzungen verwendet werden. Die Grundbestandteile von Scheuerpulvern bilden zum einen die für die mechanische Auflockerung hartnäckigen Schmutzes benötigten Abrasivstoffteilchen und zum andern Tenside als grenzenflächenaktive Substanzen, die für die Entfernung fettigen oder fetthaltigen Schmutzes unerläßlich sind. Die derzeit auf dem Markt be¬ findlichen Scheuerpulver enthalten als Tenside nahezu ausschließlich Alkylbenzolsulfonate, sowie fallweise weitere Wirk- und Hilfsstoffe wie z. B. Bleich- und Desinfektionsmittel, Zeolithe und alkalische Salze. In den deutschen Patentanmeldungen DE 2539733 AI und DE 2739776 AI (Procter & Gamble) werden flüssige und pulverförmige Scheuermittel mit einem Abrasivstoffanteil aus Perlit in einer Menge bis zu 65 % beschrieben. Diese Anmeldungen heben im wesentlichen auf diesen speziellen Abrasivstoff ab. Als Tenside für die pulverförmigen Mittel werden hier Alkylsulfate und Alkylbenzolsulfonate angegeben.Scouring powder is one of the oldest and still indispensable cleaning agents that are used in households and businesses to remove stubborn dirt. The basic constituents of scouring powders form, on the one hand, the abrasive particles required for the mechanical loosening of stubborn dirt and, on the other hand, surfactants as surface-active substances, which are essential for the removal of greasy or greasy dirt. The scouring powders currently on the market contain almost exclusively alkylbenzenesulfonates as surfactants, as well as occasionally other active ingredients and auxiliaries such as. B. bleach and disinfectants, zeolites and alkaline salts. The German patent applications DE 2539733 AI and DE 2739776 AI (Procter & Gamble) describe liquid and powdered abrasives with an abrasive content of pearlite in an amount of up to 65%. These applications essentially focus on this special abrasive. Alkyl sulfates and alkylbenzenesulfonates are specified here as surfactants for the powdery compositions.
In der kanadischen Patentschrift 1 048 365 (Procter & Gamble) werden scheuernd wirkende Pulver mit einem hohen Tensidgehalt von 20 - 35 % und einem Abrasivstoffgehalt von 5 - 20 %, die sowohl als Scheuerpulver als auch als Geschirrspülmittel gempfohlen werden, beschrieben. Als Tenside werden Alkylsulfate, Alkylbenzolsulfonate sowie Fettalkoholethoxilate ge¬ nannt. Die literaturbekannten und die aktuell handelsüblichen Scheuerpul¬ ver haben als gemeinsames Merkmal ein gutes Reinigungsvermögen gegenüber Z fettigem und fetthaltigem Schmutz, schäumen jedoch bei der Anwendung in einem unerwünscht hohen Maß. Um das Schäumen zu vermeiden, wurde sogar der Versuch unternommen, reine Abrasivstoffe ohne jeglichen Tensidzusatz an¬ zubieten. Derartige Scheuerpulver besitzen jedoch keine fettentfernende Wirkung und verhalten sich darüber hinaus bei der Anwendung aufgrund feh¬ lender Dispergierwirkung völlig unbefriedigend. Der Wunsch der Anwender nach nur schwach schäumenden, aber gut reinigenden Scheuerpulvern konnte bisher nicht erfüllt werden.Canadian Patent 1,048,365 (Procter & Gamble) describes abrasive powders with a high surfactant content of 20-35% and an abrasive content of 5-20%, which are recommended as both abrasive powder and dishwashing detergent. Alkyl sulfates, alkylbenzenesulfonates and fatty alcohol ethoxylates are mentioned as surfactants. The common known and currently commercially available scouring powders have a good cleaning ability as a common feature Z greasy and fatty dirt, but foams to an undesirably high degree when used. In order to avoid foaming, an attempt was even made to offer pure abrasives without any surfactant addition. However, scouring powders of this type do not have a grease-removing effect and, moreover, behave completely unsatisfactorily when used because of the lack of dispersing action. So far, the users' wish for scouring powders which only have a low foaming but are easy to clean has not been fulfilled.
Die Aufgabe der Erfindung bestand daher darin, die gewünschten Mittel be¬ reitzustellen, die die beiden Produktwirkungen: gute Schmutzentfernung und geringe Schaumneigung, in sich vereinigen.The object of the invention was therefore to provide the desired agents which combine the two product effects: good dirt removal and low foaming tendency.
Überraschenderweise konnte diese Aufgabe dadurch gelöst werden, daß man den Scheuerpulvern Alkylglycoside mit einem Oligomerisierungsgrad von 1,2 bis 1,4 oder Tensid-Kombinationen mit einem Gehalt an diesen Alkylglyco- siden zusetzt, wobei die Scheuerpulver darüber hinaus übliche Inhalts¬ stoffe enthalten können.Surprisingly, this object was achieved by adding alkyl glycosides with a degree of oligomerization from 1.2 to 1.4 or surfactant combinations containing these alkyl glycosides to the scouring powders, which scouring powders may also contain conventional ingredients.
Die Erfindung betrifft daher schwachschäumende Scheuerpulver mit eine« Gehalt an Abrasivstoffen, sonstigen üblichen Bestandteilen und gegebenen¬ falls sonstigen Tensiden, die dadurch gekennzeichnet sind, daß sie einen Zusatz an Alkylglycosiden mit einem Oligomerisierungsgrad von 1,2 bis 1,4 enthalten.The invention therefore relates to low-foaming scouring powders with a content of abrasives, other customary constituents and, if appropriate, other surfactants, which are characterized in that they contain an addition of alkyl glycosides with a degree of oligomerization of 1.2 to 1.4.
Alkylglykoside sind als abbaubare Tenside nativen Ursprungs bekannt. Ge¬ nerell können die hier als Tenside brauchbaren Alkylglykoside durch die Strukturformel R0(G)x wiedergegeben werden, wobei R einen aliphatischen Rest mit wenigstens 4 Kohlenstoffatomen, insbesondere den Rest eines pri¬ mären Alkohols und ganz besonders einen Fettalkyl- oder Fettalkenyl-Rest mit 8 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen, bedeutet. Das Symbol (G) in der Formel steht für eine Glykoseeinheit, wobei wegen der technischen Verfügbarkeit einerseits und der guten Reaktionsfähigkeit an¬ dererseits die Glucose bevorzugt ist. Schließlich ist die Indexzahl x eine beliebige Zahl zwischen 1,2 und 1,4, womit der sogenannte Oligomerisie¬ rungsgrad, d. h. die Verteilung von Monoglykosiden und Oligoglykosiden angegeben wird. Bei der Wiedergabe der Alkylglykoside durch die Formel R0(G)x wird der Fettalkoholanteil vernachlässigt. Dieser Fettalkoholanteil kann prinzipiell weitgehend durch schonende destillative Behandlung des Alkylglykosids gesteuert werden, d. h. der aus der Reaktion stammende FettalkoholÜberschuß kann bis auf Restwerte, die unter 1 % Gesamtanteil liegen, aus dem Produkt entfernt werden. Sie wurden u. a. für flüssige manuelle Geschirrspülmittel vorgeschlagen, z. B. in WO 86/02943 (A.E.Staley) und WO 89/02912 (Henkel Corp.). Von manuellen Geschirrspül- mitteln wird aber im Gegensatz zum Gebiet anderer Reinigungsmittel für harte Oberflächen vom Verbraucher ein hohes Schäumvermögen gefordert. Eine schäumende Tensidzusa mensetzung, die ein spezielles tensidisches Alkyl- glykosid mit dem Oligomerisierungsgrad x = 1,5 bis 10 und mit einem Alkyl onoglykosidgehalt von 20 bis 70 Gew.-%, zusammen mit einem anio¬ nischen Co-Tensid, das aus der Gruppe der tensidisehen Sulfate, Sulfonate, Carboxylate und deren Mischungen ausgewählt ist, wird in der EP 0 070074 A2 (Procter & Gamble) beschrieben. Als anionische Co-Tenside werden ins¬ besondere Alkylbenzolsulfonat, Seife, zwitterionische Tenside, amphotere Tenside, Alkansulfonate, Alpha-Olefinsulfonate, Alkylsulfate, Alkylpoly- glykolethersulfate und Paraffinsulfonate und deren Mischungen erwähnt. Die hier beschriebenen Tensidzusammensetzungen sind für die Herstellung von Produkten, die bei der Anwendung stark schäumen, wie beispielsweise manu¬ ellen Geschirrspülmitteln und Shampoos, geeignet. In der Beschreibung wird enu erativ auch ein möglicher Zusatz an Abrasivstoffen erwähnt, Beispiele dafür liegen jedoch nicht vor. Aus der DE 35 34 082 AI (Henkel KGaA) sind flüssige Reinigungsmittel für das manuelle Reinigen von Geschirr bekannt, die Sulfat- und/oder Sulfonattenside, Fettsäurealkanolaraide und Fettalkyl- glucoside mit einem Oligomerisierungsgrad von 1 bis 1,4 enthalten, die besondere Schaum- und Reinigungskraft aufweisen. Scheuermittel werden dort nicht beschrieben.Alkyl glycosides are known to be degradable surfactants of native origin. In general, the alkyl glycosides which can be used here as surfactants can be represented by the structural formula R0 (G) x , where R is an aliphatic radical having at least 4 carbon atoms, in particular the remainder of a primary alcohol and very particularly a fatty alkyl or fatty alkenyl radical 8 to 22, preferably 12 to 18 carbon atoms. The symbol (G) in the formula stands for a glycose unit, glucose being preferred because of the technical availability on the one hand and the good reactivity on the other hand. Finally, the index number x is any number between 1.2 and 1.4, which means the so-called degree of oligomerization, ie the distribution of monoglycosides and oligoglycosides is specified. When the alkyl glycosides are represented by the formula R0 (G) x , the percentage of fatty alcohol is neglected. In principle, this fatty alcohol portion can largely be controlled by gentle distillative treatment of the alkyl glycoside, ie the excess fatty alcohol resulting from the reaction can be removed from the product except for residual values which are less than 1% total. They have been proposed for liquid manual dishwashing detergents, e.g. B. in WO 86/02943 (AEStaley) and WO 89/02912 (Henkel Corp.). In contrast to the field of other cleaning agents for hard surfaces, however, manual dishwashing detergents demand high foaming power from the consumer. A foaming surfactant composition which contains a special surfactant alkyl glycoside with the degree of oligomerization x = 1.5 to 10 and with an alkyl onoglycoside content of 20 to 70% by weight, together with an anionic co-surfactant from the group The surfactant sulfates, sulfonates, carboxylates and mixtures thereof are selected is described in EP 0 070074 A2 (Procter & Gamble). In particular, alkylbenzenesulfonate, soap, zwitterionic surfactants, amphoteric surfactants, alkanesulfonates, alpha-olefinsulfonates, alkylsulfates, alkylpolyglycol ether sulfates and paraffin sulfonates and mixtures thereof are mentioned as anionic co-surfactants. The surfactant compositions described here are suitable for the production of products which foam strongly when used, such as, for example, manual dishwashing detergents and shampoos. The description also mentions enu eratively a possible addition of abrasives, but no examples are available. DE 35 34 082 AI (Henkel KGaA) discloses liquid cleaning agents for the manual cleaning of dishes, which contain sulfate and / or sulfonate surfactants, fatty acid alkanolaraids and fatty alkyl glucosides with a degree of oligomerization of 1 to 1.4, which contain special foam and have cleaning power. Abrasives are not described there.
Aus der DE 37 06 015 AI (Henkel KGaA) sind weiterhin flüssige, stark schäumende Reinigungsmittel für das manuelle Reinigen von Geschirr be¬ kannt, die neben Fettalkylglucosiden mit einem Oligomerisierungsgrad von 1 bis 1,4 als Schaumverstärker Dialkylsulfosuccinate mit 7 bis 9 Kohlen¬ stoffatomen in jedem der Alkylreste enthalten. Auch hier findet sich kein Hinweis auf Scheuermittel. Es war daher nicht voraussehbar, daß diese Alkylglykoside allein oder in Kombination mit weiteren Tensiden in Scheuerpulvern eine nur schwache Schaumentwicklung bei Anwendung zeigen.From DE 37 06 015 AI (Henkel KGaA), liquid, high-foaming detergents for the manual cleaning of dishes are also known which, in addition to fatty alkyl glucosides with a degree of oligomerization of 1 to 1.4, serve as foam enhancers and dialkyl sulfosuccinates with 7 to 9 carbon atoms contained in each of the alkyl radicals. Again, there is no evidence of abrasives. It was therefore not foreseeable that this Alkyl glycosides alone or in combination with other surfactants in scouring powders show only a weak development of foam when used.
Bevorzugte Scheuerpulver der vorliegenden Erfindung weisen die folgende Zusammensetzung auf:Preferred scouring powders of the present invention have the following composition:
a) 70 - 99 Gew.-%, insbesondere 80 - 95 Gew.-% eines Abrasivstoffes,a) 70-99% by weight, in particular 80-95% by weight, of an abrasive,
b) 0,5-15 Gew.-%, insbesondere 1 - 10 Gew.-% eines Tensids oder einerb) 0.5-15% by weight, in particular 1-10% by weight, of a surfactant or one
Tensidmischung aus der Gruppe der Anion-, Nio- oder Amphotenside, wobei dieses Tensid bzw. diese Tensid¬ mischung zu 2 -100 %, vorzugsweise zu 5 - 90 % aus dem Alkylglucosid besteht undSurfactant mixture from the group of anionic, nio- or amphoteric surfactants, this surfactant or this surfactant mixture consisting of 2-100%, preferably 5-90%, of the alkyl glucoside and
c) der Rest auf 100 Gew.-% üblicherweise in Scheuerpulvern verwendete Stoffe wie Bleich- und Desinfektionsmittel, anorganische oder organische wasserlösliche oder unlösliche Salze, Färb- und Duftstoffe.c) the remainder to 100% by weight of substances usually used in scouring powders, such as bleaching and disinfecting agents, inorganic or organic water-soluble or insoluble salts, colorants and fragrances.
Als weitere Tenside, die in den erfindungsgemäßen Scheuerpulvern einge¬ setzt werden können, kommen Aniontenside vom Sulfat und Sulfonattyp, wie z. B. Alkylsulfate, Alkylethersulfate, Alkylbenzolsulfonate, Alkylsulfo- nate usw., die für Reinigungsmittel gebräuchlich sind, in Frage. Bevorzugt sind Alkylsulfate, die aus natürlichen Ölen und Fetten nach bekannten Verfahren hergestellt werden und einen gesättigten oder ungesättigten Alkylrest mit 6 - 20, vorzugsweise 10 - 18 Kohlenstoffatomen aufweisen. Besonders bevorzugt sind Scheuerpulver, die frei sind von Alkylbenzolsulfonaten.Other surfactants that can be used in the scouring powders according to the invention are anionic surfactants of the sulfate and sulfonate type, such as. B. alkyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, alkyl sulfonates, etc., which are common for cleaning agents, in question. Alkyl sulfates which are prepared from natural oils and fats by known processes and have a saturated or unsaturated alkyl radical having 6-20, preferably 10-18 carbon atoms are preferred. Scouring powders which are free from alkylbenzenesulfonates are particularly preferred.
Als Niotenside kommen Fettalkoholethoxilate, d. h. Anlagerungsprodukte von 2 - 16 Mol Ethylenoxid an Fettalkohole mit verzweigten oder geradkettigen gesättigten oder ungesättigten C16-C20-Alkylresten. Bevorzugt sind solche Fettalkoholethoxilate, die aus natürlichen Fetten und Ölen hergestellt werden. In geringen Mengen können gegebenenfalls auch übliche Amphotenside und Betaine und/oder Amidobetaiπe eingesetzt werden. Bei Mitverwendung dieser Tensidklasse ist aber deren Einsatzmenge auf die eventuelle _T Anwesenheit weiterer Tenside auszurichten, so daß die Gesamtformulierung das gewünschte Schaumverhalten aufweist.Suitable nonionic surfactants are fatty alcohol ethoxylates, ie addition products of 2-16 mol ethylene oxide onto fatty alcohols with branched or straight-chain saturated or unsaturated C16-C20-alkyl radicals. Preferred fatty alcohol ethoxylates are those which are produced from natural fats and oils. If desired, conventional amphoteric surfactants and betaines and / or amidobetanes can also be used in small amounts. If this class of surfactants is also used, the amount used is based on the possible amount _T Align the presence of other surfactants so that the overall formulation has the desired foaming behavior.
Als Abrasiva können alle für Scheuerpulver bekannten Stoffe, z. B. mine¬ ralische Gesteinsmehle, wie Quarz-, Cristobalit-, Marmor-, Bimsmehl u. ä. mit einer Korngröße bis zu 1 mm, bevorzugt bis zu 0,3 mm, eingesetzt wer¬ den. Die untere Korngröße wird allein durch die technischen Möglichkeiten bei der Herstellung von Abrasivstoffen, auch in Form von für Poliermit¬ telzusätze geeigneten mehlartigen Formen, bestimmt. Es können alternativ auch Kunststoffgranulate bzw. -pulver sowie Holzmehl oder Glasperlen und ähnliche Abrasiva mit sehr milder Scheuerwirkung verwendet werden.All substances known for scouring powder, e.g. B. mineral rock powder, such as quartz, cristobalite, marble, pumice powder u. Ä. With a grain size up to 1 mm, preferably up to 0.3 mm, are used. The lower grain size is determined solely by the technical possibilities in the production of abrasive materials, also in the form of flour-like forms suitable for polishing agent additives. Alternatively, plastic granules or powder as well as wood flour or glass beads and similar abrasives with a very mild abrasive effect can be used.
Als Bleich- und Desinfektionsmittel sind die bekannten anorganischen oder organischen, in Gegenwart von Wasser H2O2 oder Aktivchlor liefernden Ver¬ bindungen brauchbar. Die Perverbindungen können zusammen mit sogenannten Bleichaktivatoren, wie z.B. Tetraacetyl-äthylendiamin oder Tetraacetyl- glykoluril eingesetzt werden.The known inorganic or organic compounds which deliver H2O2 or active chlorine in the presence of water are useful as bleaching and disinfecting agents. The per-compounds can be used together with so-called bleach activators, e.g. Tetraacetyl-ethylenediamine or tetraacetyl-glycoluril can be used.
Zu weiteren, gegebenenfalls in Scheuerpulvern verwendbaren Stoffen zählen anorganische oder organische Komplexbildner und Gerüstsubstanzen, die in der Lage sind, Erdalkaliionen des Leitungswassers, welches zur Anwendung der Scheuerpulver verwendet wird, zu binden und die mit den Tensiden zu einer Steigerung der Reinigungswirkung führen. Zu dieser Klasse an Wirk¬ stoffen zählen die bekannten Zeolithe sowie organische Komplexbildner, insbesondere die Natriumsalze der Polycarbonsäuren, Hydroxycarbonsäuren, Aminocarbonsäuren, Carboxyalkylethern, polyanionische Polymere, insbe¬ sondere der polymeren Carbonsäuren. P-haltige Komplexbildner oder Gerüst¬ substanzen sollen vorzugsweise nicht eingesetzt werden.Other substances that can possibly be used in scouring powders include inorganic or organic complexing agents and builders that are able to bind alkaline earth ions in the tap water that is used to apply the scouring powder and that lead to an increase in the cleaning effect with the surfactants. This class of active substances includes the known zeolites and organic complexing agents, in particular the sodium salts of the polycarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, carboxyalkyl ethers, polyanionic polymers, in particular the polymeric carboxylic acids. P-containing complexing agents or framework substances should preferably not be used.
Schließlich kann es erwünscht sein, den Scheuerpulvern neutral oder al¬ kalisch reagierende Alkalisalze, insbesondere Natriumsalze, aus der Gruppe der Chloride, Carbonate, Bicarbonate, Sulfate und Silikate hinzuzufügen.Finally, it may be desirable to add neutral or alkaline-reacting alkali metal salts, in particular sodium salts, from the group of chlorides, carbonates, bicarbonates, sulfates and silicates to the scouring powders.
Die erfindungsgemäßen Scheuerpulver können ferner Färb- und Duftstoffe enthalten. Im Falle der Anwesenheit von oxidativ wirkenden Bleichmitteln wählt man bekannte oxidationsstabile Farbpigmente wie Phthalocyaninpig- mente oder Ultramarin und Duftstoffe wie Terpenverbindungen aus.The scouring powders according to the invention can also contain colorants and fragrances. In the presence of oxidative bleaching agents Known oxidation-stable color pigments such as phthalocyanine pigments or ultramarine and fragrances such as terpene compounds are selected.
Die Herstellung der Scheuerpulver kann in an sich bekannter Weise erfol¬ gen, z. B. durch Trocknen eines Teils oder aller wasserlöslicher Kompo¬ nenten und Zumischen bzw. Aufsprühen der restlichen Komponenten des Scheuerpulvers.The scouring powder can be produced in a manner known per se, e.g. B. by drying part or all of the water-soluble components and adding or spraying on the remaining components of the scouring powder.
TestmethodeTest method
Die Prüfung der Reinigungswirkung der erfindungsgemäßen Scheuerpulver er¬ folgte nach der in der Fachzeitschrift Seifen - Öle - Fette - Wachse, 112, 371 (1986) veröffentlichten Methode. Dabei wurde das zu prüfende Reini¬ gungsmittel auf eine künstlich angeschmutzte KunststoffOberfläche gegeben. Als künstliche Anschmutzung diente eine Mischung aus Vaseline (R), Fett- säureglycerinestern und Pigmenten eingesetzt. Die Testfläche von 26 x 28 cm wurde mit Hilfe eines Flächenstreichers gleichmäßig mit 2 g der künst¬ lichen Anschmutzung beschichtet.The cleaning effect of the scouring powders according to the invention was tested according to the method published in the trade journal Seifen-Öle-Fette-Wachsen, 112, 371 (1986). The cleaning agent to be tested was placed on an artificially soiled plastic surface. A mixture of petroleum jelly (R), fatty acid glycerol esters and pigments was used as artificial soiling. 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 mit Leitungswasser getränkt. Auf die Testflä¬ che wurde das zu prüfende Scheuerpulver als 1 : 1 -Mischung mit Leitungs¬ wasser aufgetragen. Der Schwamm wurde dann mechanisch auf der Testfläche bewegt. Nach zehn Wischbewegungen wurde die gereinigte Testfläche unter fließendes Wasser gehalten und der lose sitzende Schmutz entfernt. Die Reinigungswirkung, d. h. der Weißgrad der so gereinigten Kunststoffober¬ fläche wurde mit einem Farb-Differenz-Meßgerät Microcolor der Firma Dr. Lange gemessen. Als Weiß-Standard diente die saubere weiße Kunststoff¬ oberfläche.A plastic sponge was soaked in tap water. The scouring powder to be tested was applied to the test area as a 1: 1 mixture with tap water. The sponge was then moved mechanically on the test surface. After ten wiping movements, the cleaned test area was kept under running water and the loose dirt was removed. The cleaning effect, d. H. the degree of whiteness of the plastic surface cleaned in this way was determined using a Microcolor color difference measuring device from Dr. Measured for a long time. The clean white plastic surface served as the white standard.
Da bei der Messung der sauberen Oberfläche auf 100 % eingestellt und die angeschmutzte Fläche mit 0 angezeigt wurde, sind die abgelesenen Werte bei den gereinigten Kunststoff-Flächen mit dem Prozentgehalt Reinigungsver- ögen (% RV) gleichzusetzen. Bei den nachstehenden Versuchen sind die an¬ gegebenen Werte RL rei. (%) die nach dieser Methode ermittelten Werte für das Reiπigungsvermögen der untersuchten Reinigungsmittel, bezogen auf die Reinigungsleistung des Vergleichsstandards (RL = 100 %). Sie stellen je¬ weils Mittelwerte aus 3fachen Bestimmungen dar.Since the measurement of the clean surface was set to 100% and the soiled area was displayed with 0, the read values for the cleaned plastic areas are to be equated with the percentage cleaning power (% RV). In the experiments below, the values RL given are free. (%) the values determined by this method for the cleaning ability of the investigated cleaning agents, based on the Cleaning performance of the comparison standard (RL = 100%). They each represent mean values from triplicate determinations.
Das Schaumverhalten wurde praxisnah nach folgender Methode überprüft, wo¬ bei der Schaum, der beim Scheuern entsteht, auf einem sauberen gekachelten Tisch geprüft wurde. Für den Schaumtest wurden 1,0 g Scheuerpulver und 10 ml Leitungswasser auf den Tisch gegeben. Man scheuerte in 15 Kreisbewe¬ gungen mit angefeuchteten Handbürsten und beurteilte den gebildeten Schaum in Noten von 1 - 4, wobei 4 = sehr viel Schaum und 1 = kein oder nur sehr wenig Schaum bedeuten.The foam behavior was checked in a practical manner using the following method, in which the foam which is produced when scrubbing was tested on a clean tiled table. For the foam test, 1.0 g scouring powder and 10 ml tap water were placed on the table. It was scrubbed in 15 circular movements with moistened hand brushes and the foam formed was assessed in grades of 1-4, 4 = very much foam and 1 = little or no foam.
Als Vergleichsstandard für die Effekte, die mit den erfindungsgemäßen Scheuerpulvern zu erzielen sind, wurde ein handelsübliches Scheuermittel folgender Zusammensetzung herangezogen:A commercially available scouring agent of the following composition was used as a comparison standard for the effects which can be achieved with the scouring powders according to the invention:
3,0 % Na-Alkylbenzolsulfonat3.0% Na alkyl benzene sulfonate
3,0 % Na-Hydrogencarbonat3.0% Na hydrogen carbonate
1,3 % K-Peroxomonosulfat1.3% K-peroxomonosulfate
0,3 % Na-Sulfat0.3% Na sulfate
4,0 % Na-Chlorid4.0% Na chloride
Rest auf 100 % QuarzmehlRest on 100% quartz flour
Die Reinigungswirkung, die mit diesem Mittel gemäß der beschriebenen Testmethode ermittelt wurde, wurde mit 100 % gleichgesetzt. Im Schaumtest erzielte dieses Produkt folgende Noten:The cleaning effect, which was determined with this agent according to the test method described, was equated with 100%. This product achieved the following marks in the foam test:
Die Prozentangaben der folgenden Beispiele beziehen sich auf Gewichts Aktivsubstanz. 9The percentages in the following examples relate to the weight of active substance. 9
Beispiel 1example 1
0,5 % C*L2-14-Alkylglucosid mit x = 1 ,40.5% C * L2-14 alkyl glucoside with x = 1.4
1 ,0 % Ci2-i4-Fettalkohol sulfat , Na-Salz1.0% Ci2-i4 fatty alcohol sulfate, Na salt
1 ,0 % Zeol ith1.0% Zeol ith
1,5 % Wasserglas1.5% water glass
1,5 % Soda1.5% soda
0,2 % Parfü öl0.2% perfume oil
Rest auf 100 % Quarzmehl der Korngröße 0 - 0,1 mmRest on 100% quartz powder with a grain size of 0 - 0.1 mm
Das auf den Vergleichsstandard bezogene relative Reinigungsvermögen betrug 120 %. Die Schaumnoten waren:The relative cleaning power based on the comparison standard was 120%. The foam notes were:
Beurteilung nach MinutenAssessment after minutes
Noten 1-2Scores 1-2
Beispiel 2Example 2
0,1 % Ci2-l4-Alkylglucosid mit x ***• 1,40.1% Ci2-14-alkyl glucoside with x *** • 1.4
0,05 % Ci2_i8-Fettalkohol + 5 Ethylenoxid (E0)0.05% Ci2_i8 fatty alcohol + 5 ethylene oxide (E0)
1,5 % Cl2-14 Fettalkoholsulfat1.5% Cl2-14 fatty alcohol sulfate
2,0 % Soda 10,0 % Na-Sulfat2.0% soda 10.0% Na sulfate
0,008 % Farbstoff Rest auf 100 % Polypropylengranulat der Korngröße 0 0,3 mm0.008% dye rest on 100% polypropylene granules with grain size 0 0.3 mm
Es handelt sich hier um ein sehr mild-abrasives Scheuerpulver mit einem relativen Reinigungsvermögen von 150 % und geringer Schaumneigung.It is a very mildly abrasive scouring powder with a relative cleaning power of 150% and a low tendency to foam.
Beurteilung nach 1 MinutenAssessment after 1 minute
Noten 1-2 Beispiel 3Scores 1-2 Example 3
Gleiche Zusammensetzung wie Beispiel 2, jedoch wurde Marmormehl der Korn¬ größe 0 - 0,2 mm anstelle des Kunststoffgranulates eingesetzt. Dieses Mittel wies ähnlich gute Reinigungsleistung und geringe Schaumneigung wie das Beispiel 2 auf.The same composition as example 2, but marble powder with a grain size of 0-0.2 mm was used instead of the plastic granulate. This agent had a similarly good cleaning performance and low foaming tendency as Example 2.
Beispiel 4Example 4
0,15 % Ci2-i4-Alkylglucosid mit x = 1,20.15% Ci2-i4 alkyl glucoside with x = 1.2
1,5 % C12-14 Fettalkoholsulfat1.5% C12-14 fatty alcohol sulfate
2,0 % Soda2.0% soda
1,5 % Wasserglas1.5% water glass
1,0 % Zeolith1.0% zeolite
1,0 % Sulfat1.0% sulfate
2,0 % Kaliummonopersulfat2.0% potassium monopersulfate
Rest auf 100 % Marmormehl der Korngröße 0 0,1 mmRest on 100% marble powder with grain size 0 0.1 mm
Dieses Scheuerpulver zeigte gute Bleichwirkung gegenüber Obstflecken, war gut lagerstabil.This scouring powder had a good bleaching effect on fruit stains and was stable in storage.
Relative Reinigungsleistung: 130 %.Relative cleaning performance: 130%.
Beurteilung nach 0 1 MinutenAssessment after 0 1 minutes
Schaumnoten 1-2Foam notes 1-2
Beispiel 5Example 5
0,5 % Ci2-14-Alkylglucosid mit x •**• 1,40.5% Ci2-14 alkyl glucoside with x • ** • 1.4
3,0 % C12-14 Fettalkoholsulfat3.0% C12-14 fatty alcohol sulfate
0,1 % C12-I8 Fettalkohol + 5 E00.1% C12-I8 fatty alcohol + 5 E0
0,5 % Polyacrylat (Sokalan CP 5 der Fa. BASF)0.5% polyacrylate (Sokalan CP 5 from BASF)
3,0 % Zeolith IV3.0% zeolite IV
0,1 % Mg-Perphthalat0.1% Mg perphthalate
Rest auf 100 % Quarzmehl der Korngröße 0 - 0,05 mmRest on 100% quartz powder with a grain size of 0 - 0.05 mm
Diese bleichenden Scheuerpulver hatten trotz der hervorragenden relativen Reinigungswirkung von 200 % nur eine geringe Schaumneigung.These bleaching scouring powders had only a slight tendency to foam despite the excellent relative cleaning effect of 200%.
Beurteilung nach 0 1 MinutenAssessment after 0 1 minutes
Schaumnoten 1-2Foam notes 1-2
Beispiel 6Example 6
0,15 % Ci2_i4-Alkylglucosid mit x = 1,20.15% Ci2_i4 alkyl glucoside with x = 1.2
0,5 % Alkylbenzolsulfonat, Na-Salz0.5% alkylbenzenesulfonate, Na salt
2,0 H Soda2.0 H soda
1,5 % Wasserglas1.5% water glass
3,0 % Na-Su fat3.0% Na-Su fat
1,0 % Zeolith1.0% zeolite
0,1 % Trichlorisocyanursäure0.1% trichloroisocyanuric acid
0,002 % Farbstoff0.002% dye
0,2 % Parfümöl0.2% perfume oil
Rest auf 100 % Quarzmehl der Korngröße 0 - 0,1 mmRest on 100% quartz powder with a grain size of 0 - 0.1 mm
Relative Reinigungsleistung: 180 %Relative cleaning performance: 180%
Selbst bei einem Gehalt an Alkylbenzolsulfonat wird der Schaum durch den Zusatz des Alkylglucosids noch erkennbar reduziert. ifEven with an alkyl benzene sulfonate content, the foam is still noticeably reduced by the addition of the alkyl glucoside. if
Beispiel 7Example 7
5 % Ci2-i4-Alkylglucosid mit x = 1,45% Ci2-i4 alkyl glucoside with x = 1.4
5 % Soda5% soda
90 % Quarzmehl der Korngröße 0 - 0,1 mm Relative Reinigerleistung: 150 %90% quartz powder with a grain size of 0 - 0.1 mm Relative cleaning performance: 150%
Beurteilung nach 1 MinutenAssessment after 1 minute
Schaumnoten 1 1Foam notes 1 1
Die beste Wirkung tritt ein, wenn Alkylglucosid als alleiniges Tensid eingesetzt wird. The best effect occurs when alkyl glucoside is used as the sole surfactant.

Claims

Patentansprüche Claims
1. Schwachschäumendes Scheuerpulver mit einem Gehalt an scheuernd wir¬ kenden Stoffen sowie mit einem Gehalt an Tensiden, dadurch gekenn¬ zeichnet, daß es als Tensid oder neben anderen Tensiden 0,05 Gew.-% oder mehr, bezogen auf das gesamte Scheuermittel, eines Alkylglykosids mit einem Oligomerisierungsgrad von 1,1. Low-foaming abrasive powder with a content of abrasive substances and with a content of surfactants, characterized in that it contains 0.05% by weight or more, based on the total abrasive, as a surfactant or in addition to other surfactants Alkyl glycoside with a degree of oligomerization of 1,
2 bis 1,4 enthält.Contains 2 to 1.4.
Mittel nach Anspruch 1, dadurch gekennzeichnet, daß esAgent according to claim 1, characterized in that it
a) 70 - 99 Gew.-%, insbesondere 80 - 95 Gew.-% eines Abrasivstoffes b) 0,5 - 15 Gew.-%, insbesondere 1 - 10 Gew.-% eines Tensids oder ei¬ ner Tensid ischung aus der Gruppe der Anion-, Nio- oder Amphoten¬ side, wobei dieses Tensid bzw. diese Tensidmischung zu 2 - 100 %, vorzugsweise zu 5 - 90 % aus Alkylglucosid besteht und c) als Rest auf 100 % üblicherweise in Scheuerpulvern verwendete Stof¬ fe wie Bleich- und Desinfektionsmittel, anorganische oder organi¬ sche wasserlösliche oder unlösliche Salze, Färb- und Duftstoffe enthält.a) 70-99% by weight, in particular 80-95% by weight of an abrasive b) 0.5-15% by weight, in particular 1-10% by weight of a surfactant or a surfactant mixture from the Group of anion, nio- or amphotenides, where this surfactant or surfactant mixture consists of 2 to 100%, preferably 5 to 90%, of alkyl glucoside and c) the remainder to 100% of substances commonly used in scouring powders such as Contains bleaching agents and disinfectants, inorganic or organic water-soluble or insoluble salts, colorants and fragrances.
3. Scheuerpulver nach Anspruch 1 und 2, dadurch gekennzeichnet, daß das Alkylglucosid der Formel R0(G)x entspricht, wobei R = C _ 2-Alkyl,3. scouring powder according to claim 1 and 2, characterized in that the alkyl glucoside corresponds to the formula R0 (G) x , where R = C _ 2-alkyl,
0 = Sauerstoff, G s Glucose-Einheit und X - 1,2 - 1,4 bedeuten.0 = oxygen, G s glucose unit and X - 1.2 - 1.4 mean.
4. Scheuerpulver nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß es frei von Alkylbenzolsulfonaten ist.4. scouring powder according to claims 1 to 3, characterized in that it is free of alkylbenzenesulfonates.
5. Scheuerpulver nach den Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß es frei von P-haltigen Komplexbildnern und Gerüstsubstanzen ist. 5. scouring powder according to claims 1 to 4, characterized in that it is free of P-containing complexing agents and builders.
EP92900845A 1991-01-30 1991-12-19 Low-foam scouring powder Expired - Lifetime EP0569366B1 (en)

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DE4102744A DE4102744A1 (en) 1991-01-30 1991-01-30 LOW-FOAMING SCRUBBING POWDER
PCT/EP1991/002451 WO1992013936A1 (en) 1991-01-30 1991-12-19 Low-foam scouring powder

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