EP0633927A1 - Detergents for hard surfaces. - Google Patents

Detergents for hard surfaces.

Info

Publication number
EP0633927A1
EP0633927A1 EP93906597A EP93906597A EP0633927A1 EP 0633927 A1 EP0633927 A1 EP 0633927A1 EP 93906597 A EP93906597 A EP 93906597A EP 93906597 A EP93906597 A EP 93906597A EP 0633927 A1 EP0633927 A1 EP 0633927A1
Authority
EP
European Patent Office
Prior art keywords
weight
cleaning
foam
fatty alcohol
azr
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
EP93906597A
Other languages
German (de)
French (fr)
Other versions
EP0633927B1 (en
Inventor
Eva Kiewert
Peter Jeschke
Birgit Middelhauve
Giuseppe Carrer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0633927A1 publication Critical patent/EP0633927A1/en
Application granted granted Critical
Publication of EP0633927B1 publication Critical patent/EP0633927B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
    • 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
    • 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
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to low-foaming cleaning agents for hard surfaces. All non-textile surfaces occurring in the household and commercial sector, with the exception of dishes, are to be understood as such.
  • the term all-purpose cleaner hereinafter referred to as AZR
  • Low-foaming AZR are those that develop a small volume of foam when used manually, which significantly reduces within a few minutes.
  • AZR 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 start of his cleaning work in order to prove effectiveness, the foam should then collapse as quickly as possible, so that once cleaned surfaces do not have to be wiped down.
  • alkyl polyglucosides (hereinafter referred to as APG) in washing and cleaning agents is becoming increasingly popular.
  • alkyl polyglucosides are known to be highly foaming surfactants. In particular, however, they are used for products with the desired foaming capacity, for example for manually used products dishwashing detergent or recommended for shampooing.
  • EP 70074, 70075, 70076 and 70 077 (Procter & Gamble) describe such high-foaming detergents and cleaning agents based on various APG-containing surfactant combinations. Consequently, these combinations are not recommended for the AZR area.
  • the object of the invention was to provide means for the manual cleaning of hard surfaces, with the exception of dishes, which at the same time have good cleaning properties, good biodegradability and a distinctly low foaming capacity.
  • the criterion should be that foam that initially forms visibly reduces within 5 minutes.
  • a) 0.1-50, preferably 0.1-45% of alkyl polyglucosides of the formula R 0 Z x with R Cg-Cio
  • a preferred embodiment of the invention includes AZR of the above type with an additional content of conventional anionic surfactants such as fatty alcohol sulfates, fatty alcohol ether sulfates, olefin sulfonates, paraffin sulfonates or mixtures thereof, their amounts being less than 25%, preferably less than 20% of the total surfactant a) + b) + c), so as not to impair the foaming behavior of the cleaning agent.
  • conventional anionic surfactants such as fatty alcohol sulfates, fatty alcohol ether sulfates, olefin sulfonates, paraffin sulfonates or mixtures thereof, their amounts being less than 25%, preferably less than 20% of the total surfactant a) + b) + c), so as not to impair the foaming behavior of the cleaning agent.
  • the APGs to be used in the AZR according to the invention are fatty alcohol polyglycosides of the composition R 0 (Z), where
  • R is an alkyl radical with 8-10 carbon atoms
  • the alkyl radical means the alkyl chains from fatty alcohols of natural or synthetic origin.
  • the fatty alcohol alkoxylates to be used according to the invention are those which have an HLB value greater than 10, preferably greater than or equal to 11. These compounds are even more biodegradable than those with HLB values of less than 10, as described in WO 88/09369 (Staley). According to Griffin, the HLB value is defined as
  • fatty alcohol alkoxylate Addition products of about 3 to 20, preferably about 4 to 10, moles of ethylene oxide (EO) with 1 mole of fatty alcohol having 6 to 16, preferably 8 to 10, carbon atoms in the alkyl chain are particularly preferred.
  • EO ethylene oxide
  • the fatty alcohols used as raw materials can be produced from natural oils and fats as well as synthetically.
  • the fatty acids to be used according to the invention are carboxylic acids with 8 to 22, preferably 10 to 18, carbon atoms in the alkyl chain. Depending on the pH of the agents according to the invention, they are either in free form or partially or completely neutralized, that is to say in salt form. Suitable cations of these salts are alkali metal cations or nitrogen-containing cations such as ammonium or alkanol monium ions.
  • the optional auxiliaries are substances which are used in AZR as builders, solvents, hydrotropes, cleaning enhancers, viscosity regulators, pH regulators, preservatives, colorants and fragrances, opacifiers etc.
  • the AZR according to the invention do not contain any foam-promoting surfactants such as amoxides or fatty acid alkanolamides.
  • Cleaning agents containing 1 to 90 wt .-% Cß - Cis-alkyl polyglucosides with 1.5 to 10 glucose units in the molecule, 1 to 90 wt .-% C8-C22 fatty alcohol ethoxylates with 2 to 12 moles of ethylene oxide and HLB values of 6 to 15, 1 to 15 wt .-% Cß - C24 fatty acids and optionally contain further synthetic anionic surfactants are known from EP 75995 (Procter &Gamble); however, they are only used for and on textile cleaning Foam behavior is not discussed in detail.
  • Liquid cleaning agents with 2 to 60% by weight of C8-Ci8 alkyl monoglucosides, 0.1 to 10% by weight of nonionic surfactants with an HLB value of less than 5 and 0.1 to 10% by weight of nonionic surfactants with a HLB values of not less than 5 and 0.001 to 8% by weight of one or more intentional organic or inorganic salts are known from EP 408 965 (Kao). You foam strongly. The prior art did not suggest the new and inventive use of the special agents.
  • the test method described below according to "Soap-Oil-Fat-Waxes", 112 .. 371, (1986) was used to test the cleaning power and gives very reproducible results.
  • the cleaning agent to be tested was then placed 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 coated evenly with 2 g of the artificial soiling with the aid of a surface brush.
  • a plastic sponge was soaked in each case with 10 ml of the cleaning agent solution to be tested and moved mechanically on the test surface which was also coated with 10 ml of the cleaning agent solution to be tested. After 10 wiping movements, the cleaned test area was kept under running water and the loose dirt was removed. The cleaning effect, ie the whiteness of the plastic surface cleaned in this way, was measured using a "Microcolor" color difference measuring device (Dr. B. Lange). The clean white plastic surface served as the white standard.
  • the read values for the cleaned plastic areas were to be equated with the percentage of cleaning power (% RV).
  • % RV values given are the values determined by this method for the cleaning ability of the cleaning agents examined. They represent mean values from triplicate determinations.
  • the measured values were set in relation to the cleaning result of a commercially available, low-foaming AZR used as standard.
  • the standard AZR used at the time of the invention had the composition:
  • test product is placed in a large glass beaker. Then, from a height of 30 cm, the amount of tap water is allowed to flow in freely, which, with the amount of product presented, is the recommended application. solution of the product.
  • the foam height in the beaker is read off immediately after the addition of water and after 3 minutes. The foam height after 3 minutes is related to the initial foam and the foam breakdown is calculated as follows:
  • a typical low-foaming AZR has a foam breakdown of over 50%.
  • the example shows an AZR that is used in a 1% solution. Is at this concentration
  • the AZR according to the invention is therefore, despite the extreme lack of foam, significantly more cleaning-efficient than the commercially available comparative product.
  • Example 2 20.0% by weight C8 - Cio fatty alcohol + 4 E0 5.0% by weight palm kernel fatty acid 1.0% by weight citric acid 10.0% by weight cumosulfonate
  • Example 2 represents an AZR high concentrate which is used in 0.1% solution. With this concentration the remedy has
  • Succinic acid 0.05% by weight polyethylene oxide, MW 600000 2.0% by weight butylglycol
  • the example shows a 1% application solution
  • Example 3 0.5% fatty alcohol ether sulfate was added in order to deliberately not let the foam break down to 100%. The content of additional surfactant had no effect on the cleaning performance. The foam disintegration was 90%.
  • the relative cleaning power compared to the 1% application solution of the standard was 180%.
  • Cs-alkyl xyloside with approximately 1.2 xylose units 12.5% by weight
  • Cio-alkyl xyloside with approximately 1.5 xylose units 11.1% by weight Cs-fatty alcohol + 4 EO 2.8% by weight %
  • coconut fatty acid 2.4% by weight citric acid 5.6% by weight cumene sulfonate
  • X% by weight potassium hydroxide solution for adjusting the pH of the finished product to pH 7.5 ad 100% by weight water, color and fragrances.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Lubricants (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Physical Vapour Deposition (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Glass Compositions (AREA)

Abstract

Weakly foaming agents containing alkylpolyglucosides, fatty alcohol alkoxylates with an HLB value higher than 10, preferably equal to or higher than 11, a C8?-C22? fatty acid and water, as well as usual additives for universal detergents, are used to clean hard surfaces.

Description

"Reinigungsmittel für harte Oberflächen" "Cleaning agents for hard surfaces"
Die Erfindung betrifft schwachschäumende Reinigungsmittel für harte Ober¬ flächen. Als solche sind alle im Haushalt- und Gewerbesektor auftretenden, nicht textilen Oberflächen, ausgenommen Geschirr, zu verstehen. Für diese Art von Reinigungsmitteln hat sich der Begriff Allzweckreiniger (im fol¬ genden AZR genannt) eingebürgert. Schwachschäumende AZR sind solche, die bei manueller Anwendung ein geringfügiges Schaumvolumen entwickeln, das sich innerhalb weniger Minuten signifikant weiter verringert.The invention relates to low-foaming cleaning agents for hard surfaces. All non-textile surfaces occurring in the household and commercial sector, with the exception of dishes, are to be understood as such. The term all-purpose cleaner (hereinafter referred to as AZR) has become established for this type of cleaning agent. Low-foaming AZR are those that develop a small volume of foam when used manually, which significantly reduces within a few minutes.
AZR 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 möch¬ te 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 ge¬ reinigte Flächen nicht nachgewischt werden müssen.AZR 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 start of his cleaning work in order to prove effectiveness, the foam should then collapse as quickly as possible, so that once cleaned surfaces do not have to be wiped down.
Um diesem vermehrten Wunsch nach geringerem Schäumvermögen nachzukommen, sind einige Hersteller von AZR dazu übergegangen, den Tensidgehalt ihrer Marktprodukte deutlich zu senken, was jedoch naturgemäß wiederum zu erheb¬ lichem Verlust an Reinigungsleistung führt. Der Anwender solcher Produkte muß die verringerte Reinigungswirkung durch vermehrten Aufwand an mecha¬ nischer Wischarbeit ausgleichen.In order to meet this increased desire for less foaming power, some manufacturers of AZR have started to significantly reduce the surfactant content of their market products, which, however, naturally leads to a considerable loss in cleaning performance. The user of such products has to compensate for the reduced cleaning effect through increased expenditure on mechanical wiping work.
Wegen ihrer ökologisch guten Eigenschaften erfreut sich der Einsatz von Alkylpolyglucosiden (im folgenden APG genannt) in Wasch- und Reinigungs¬ mittel wachsender Beliebtheit. Alkylpolyglucoside sind aber als stark schäumende Tenside bekannt. Insbesondere aber werden sie für Produkte mit wunschgemäß hohem Schäumvermögen, also z.B. für manuell anzuwendende Ge- schirrspülmittel oder für die Haarwäsche empfohlen. Die EP 70074, 70075, 70076 und 70 077 (Procter & Gamble) beschreiben derartige hochschäumende Wasch- und Reinigungsmittel auf Basis verschiedener APG-haltiger Tensid- kombinationen. Folgerichtig werden diese Kombinationen auch nicht für das Gebiet der AZR empfohlen.Because of their ecologically good properties, the use of alkyl polyglucosides (hereinafter referred to as APG) in washing and cleaning agents is becoming increasingly popular. However, alkyl polyglucosides are known to be highly foaming surfactants. In particular, however, they are used for products with the desired foaming capacity, for example for manually used products dishwashing detergent or recommended for shampooing. EP 70074, 70075, 70076 and 70 077 (Procter & Gamble) describe such high-foaming detergents and cleaning agents based on various APG-containing surfactant combinations. Consequently, these combinations are not recommended for the AZR area.
Auch spezielle kurzkettige CQ - Cio-Alkylglucoside (z.B. Trition R CG-110 von Röhm & Haas) sind seit langem als gut schäumende und schaumstabile nichtionische Tenside bekannt. Schwachschäumende Reinigungsmittel mit ei¬ nem Gehalt an Al ypolyglucosiden für maschinelle Reinigungsarbeiten, ins¬ besondere Geschirrspülen, werden in WO 88/09369 (Staley) beschrieben. Diese Mittel erreichen eine gewisse Schaumarmut durch Mitverwendung von konventionellen, schwachschäumenden Fettalkoholalkoxylaten, welche einen HLB-Wert von etwa 10 oder weniger aufweisen und Propylenoxideinheiten ent¬ halten können.Special short-chain CQ-Cio-alkyl glucosides (eg Trition R CG-110 from Röhm & Haas) have also been known for a long time as good foaming and foam-stable nonionic surfactants. Low-foaming cleaning agents with a content of aluminum polyglucosides for machine cleaning work, in particular dishwashing, are described in WO 88/09369 (Staley). These agents achieve a certain low foam level by using conventional, low-foaming fatty alcohol alkoxylates, which have an HLB value of about 10 or less and can contain propylene oxide units.
Aufgabe der Erfindung war es, Mittel für die Verwendung zur manuellen Rei¬ nigung von harten Oberflächen, ausgenommen Geschirr, zu schaffen, welche zugleich ein gutes Reinigungsvermögen, gute biologische Abbaubarkeit und ein ausgeprägt schwaches Schäumvermögen besitzen. Als Kriterium sollte gelten, daß sich anfänglich bildender Schaum innerhalb von 5 Minuten sichtbar verringert.The object of the invention was to provide means for the manual cleaning of hard surfaces, with the exception of dishes, which at the same time have good cleaning properties, good biodegradability and a distinctly low foaming capacity. The criterion should be that foam that initially forms visibly reduces within 5 minutes.
Überraschenderweise wurde nun gefunden, daß mit Hilfe von Kombinationen bestimmter als stark schäumend bekannter kurzkettiger Alkylpolyglucoside mit bestimmten nichtionischen Tensiden und Fettsäuren AZR mit hohem Rei¬ nigungsvermögen und extrem schwachem Schäumverhalten bereitgestellt werden können.Surprisingly, it has now been found that combinations of certain short-chain alkyl polyglucosides known to be highly foaming with certain nonionic surfactants and fatty acids can be used to provide AZR with high cleaning power and extremely poor foaming behavior.
Die Aufgabe wurde somit gelöst durch Mittel, die im wesentlichen folgende Inhaltsstoffe enthalten (alle %-Angaben sind als Gewichtsprozent, bezogen auf Aktivsubstanz, zu verstehen): a) 0,1 - 50, vorzugsweise 0,1 - 45 % Alkylpolyglucosiden der Formel R 0 Zx mit R = Cg - Cio, 0 = Sauerstoff und x = 1 - 6, wobei Z eine Zuk- kereinheit, z.B. Glucose- oder Xylose-Einheit darstellt, b) 0,001 - 30, vorzugsweise 0,005 - 20 % eines C - Cj -, vorzugsweise CQ - Cio-Fettalkoholalkoxylates mit einem HLB-Wert größer als 10, vor¬ zugsweise ≥ 11, c) 0,001 - 15, vorzugsweise 0,001 - 10 % Cß - 22"ι vorzugsweise Cio - Ciß- Fettsäuren und d) Rest auf 100 % Wasser und in AZR übliche Hilfsstoffe.The object was therefore achieved by means which essentially contain the following ingredients (all percentages are to be understood as percent by weight, based on the active substance): a) 0.1-50, preferably 0.1-45% of alkyl polyglucosides of the formula R 0 Z x with R = Cg-Cio, 0 = oxygen and x = 1-6, where Z is a sugar unit, for example glucose or Xylose unit, b) 0.001-30, preferably 0.005-20% of a C - Cj -, preferably CQ - Cio-fatty alcohol alkoxylate with an HLB value greater than 10, preferably ≥ 11, c) 0.001 - 15, preferably 0.001 - 10% Cß - 22 " ι preferably Cio - Ciß fatty acids and d) rest on 100% water and auxiliaries customary in AZR.
Eine bevorzugte Ausführungsform der Erfindung beinhaltet AZR der vorste¬ henden Art mit einem zusätzlichen Gehalt an üblichen Aniontensiden wie Fettalkoholsulfaten, Fettalkoholethersulfaten, Olefinsulfonaten, Paraffin- sulfonaten oder Mischungen davon, wobei deren Mengen weniger als 25 %, vorzugsweise weniger als 20 % der Gesamttensid enge gemäß a) + b) + c) beträgt, um das Schaumverhalten des Reinigungsmittels nicht zu beeinträch¬ tigen.A preferred embodiment of the invention includes AZR of the above type with an additional content of conventional anionic surfactants such as fatty alcohol sulfates, fatty alcohol ether sulfates, olefin sulfonates, paraffin sulfonates or mixtures thereof, their amounts being less than 25%, preferably less than 20% of the total surfactant a) + b) + c), so as not to impair the foaming behavior of the cleaning agent.
Bei den in den erfindungsgemäßen AZR einzusetzenden APG's handelt es sich um Fettalkoholpolyglycoside der Zusammensetzung R 0 (Z), wobeiThe APGs to be used in the AZR according to the invention are fatty alcohol polyglycosides of the composition R 0 (Z), where
R ein Alkylrest mit 8 - 10 Kohlenstoffatomen,R is an alkyl radical with 8-10 carbon atoms,
Z eine Zuckereinheit, z.B. Glucose- oder Xylose-Einheit sowie x = 1 - 6, vorzugsweise 1-3 bedeuten.Z a sugar unit, e.g. Glucose or xylose unit and x = 1-6, preferably 1-3 mean.
Unter Alkylrest sind die Alkylketten aus Fettalkoholen natürlichen oder synthetischen Ursprungs zu verstehen.The alkyl radical means the alkyl chains from fatty alcohols of natural or synthetic origin.
Bei den erfindungsgemäß einzusetzenden Fettalkoholalkoxylaten handelt es sich um solche, die einen HLB-Wert größer als 10, vorzugsweise größer/- gleich 11 aufweisen. Diese Verbindungen sind biologisch noch besser abbau¬ bar als solche mit HLB-Werten von kleiner als 10, wie sie in WO 88/09369 (Staley) beschrieben werden. Der HLB-Wert ist nach Griffin definiert alsThe fatty alcohol alkoxylates to be used according to the invention are those which have an HLB value greater than 10, preferably greater than or equal to 11. These compounds are even more biodegradable than those with HLB values of less than 10, as described in WO 88/09369 (Staley). According to Griffin, the HLB value is defined as
Molgewicht des hydrophilen AnteilsMolecular weight of the hydrophilic part
HLB = • 20HLB = • 20
Molgewicht des Fettalkoholalkoxylats Besonders bevorzugt sind Anlagerungsprodukte von etwa 3 bis 20, vorzugs¬ weise etwa 4 bis 10 Mol Ethylenoxid (EO) an 1 Mol Fettalkohol mit 6 bis 16, vorzugsweise 8 bis 10 Kohlenstoffatomen in der Alkylkette. Die als Ausgangsrohstoffe dienenden Fettalkohole können sowohl aus natürlichen Ölen und Fetten als auch auf synthetischem Wege hergestellt werden.Molecular weight of the fatty alcohol alkoxylate Addition products of about 3 to 20, preferably about 4 to 10, moles of ethylene oxide (EO) with 1 mole of fatty alcohol having 6 to 16, preferably 8 to 10, carbon atoms in the alkyl chain are particularly preferred. The fatty alcohols used as raw materials can be produced from natural oils and fats as well as synthetically.
Bei den erfindungsgemäß einzusetzenden Fettsäuren handelt es sich um Car¬ bonsäuren mit 8 bis 22, vorzugsweise 10 bis 18 C-Atomen in der Alkylkette. Sie liegen in Abhängigkeit vom pH-Wert der erfindungsgemäßen Mittel entwe¬ der in freier Form oder teilweise oder vollständig neutralisiert, also in Salzform vor.- Geeignete Kationen dieser Salze sind Alkalimettalkationen oder stickstoffhaltige Kationen wie Ammonium- oder Alkanola moniumionen.The fatty acids to be used according to the invention are carboxylic acids with 8 to 22, preferably 10 to 18, carbon atoms in the alkyl chain. Depending on the pH of the agents according to the invention, they are either in free form or partially or completely neutralized, that is to say in salt form. Suitable cations of these salts are alkali metal cations or nitrogen-containing cations such as ammonium or alkanol monium ions.
Bei den fakultativ einzusetzenden Hilfsstoffen handelt es sich um Stoffe, die als Builder, Lösungsmittel, Hydrotrope, Reinigungsverstärker, Visko¬ sitätsregler, pH-Regulatoren, Konservierungsmittel, Färb- und Duftstoffe, Trübungsmittel usw. in AZR gebräuchlich sind.The optional auxiliaries are substances which are used in AZR as builders, solvents, hydrotropes, cleaning enhancers, viscosity regulators, pH regulators, preservatives, colorants and fragrances, opacifiers etc.
Werden für Zusatzeffekte, wie z.B. Viskositätssteigerung oder zur Verbes¬ serung der Benetzung schwer benetzbarer Oberflächen zusätzlich bekannte Aniontenside mitverwendet, ist es nötig, deren Auswirkungen auf das Schaumverhalten der Endformulierung zu überprüfen. Ihre Mengen sollten jedenfalls weniger als 25 %, vorzugsweise weniger als 20 % der Gesamtmenge an APG, speziellen FA-AlkylalkoxyTaten und Fettsäuren ausmachen. Als Vis¬ kositätsregulatoren können auch C2 - Cß-Alkylglucoside mit 1 bis 10 Glu- coseeinheiten eingesetzt werden, wie sie z.B. aus EP 136 844 (Staley) be¬ kannt sind.Are used for additional effects, e.g. Increasing viscosity or using known anionic surfactants to improve the wetting of surfaces that are difficult to wet, it is necessary to check their effects on the foaming behavior of the final formulation. In any case, their amounts should make up less than 25%, preferably less than 20%, of the total amount of APG, special FA-alkylalkoxyates and fatty acids. C2 - Cβ-alkyl glucosides with 1 to 10 glucose units, such as those used, for example, can also be used as viscosity regulators. are known from EP 136 844 (Staley).
Selbstverständlich enthalten die erfindungsgemäßen AZR keinerlei schaum¬ fördernde Tenside wie A imoxide oder Fettsäurealkanolamide.Of course, the AZR according to the invention do not contain any foam-promoting surfactants such as amoxides or fatty acid alkanolamides.
Reinigungsmittel, die 1 bis 90 Gew.-% Cß - Cis-Alkylpolyglucoside mit 1,5 bis 10 Glucoseeinheiten im Molekül, 1 bis 90 Gew.-% C8 -C22-Fettalkohol- ethoxylate mit 2 bis 12 Mol Ethylenoxid und HLB-Werten von 6 bis 15, 1 bis 15 Gew.-% Cß - C24-Fettsäuren und gegebenenfalls weitere synthetische Aniontenside enthalten, sind aus EP 75995 (Procter & Gamble) bekannt; sie werden jedoch ausschließlich zur Textilreinigung verwendet und auf ihr Schaumverhalten wird nicht näher eingegangen.Cleaning agents containing 1 to 90 wt .-% Cß - Cis-alkyl polyglucosides with 1.5 to 10 glucose units in the molecule, 1 to 90 wt .-% C8-C22 fatty alcohol ethoxylates with 2 to 12 moles of ethylene oxide and HLB values of 6 to 15, 1 to 15 wt .-% Cß - C24 fatty acids and optionally contain further synthetic anionic surfactants are known from EP 75995 (Procter &Gamble); however, they are only used for and on textile cleaning Foam behavior is not discussed in detail.
Aus EP 199 765 (Henkel KGaA) sind CJO - C24-Alkylmonoglucoside als Visko¬ sitätsregler u.a. für Seifenlösungen bekannt, die nur geringe Mengen an nichtionischen Tensiden enthalten dürfen, da sonst die Viskosität negativ beeinflußt wird.From EP 199 765 (Henkel KGaA) CJO - C24-alkyl monoglucosides as viscosity regulators are among others. known for soap solutions, which may only contain small amounts of non-ionic surfactants, otherwise the viscosity is negatively affected.
Flüssige Reinigungsmittel mit 2 bis 60 Gew.-% C8 -Ci8-Alkylmonoglucosiden, 0,1 bis 10 Gew.-% nichtionischen Tensiden mit einem HLB-Wert von kleiner als 5 und 0,1 bis 10 Gew.-% nichtionischen Tensiden mit einem HLB-Wert von nicht kleiner als 5 sowie 0,001 bis 8 Gew.-% eines oder mehrerer vorsätz¬ licher organischer oder anorganischer Salze sind aus EP 408 965 (Kao) be¬ kannt. Sie schäumen stark. Der Stand der Technik legte die neue und erfin¬ dungsgemäße Verwendung der speziellen Mittel nicht nahe.Liquid cleaning agents with 2 to 60% by weight of C8-Ci8 alkyl monoglucosides, 0.1 to 10% by weight of nonionic surfactants with an HLB value of less than 5 and 0.1 to 10% by weight of nonionic surfactants with a HLB values of not less than 5 and 0.001 to 8% by weight of one or more intentional organic or inorganic salts are known from EP 408 965 (Kao). You foam strongly. The prior art did not suggest the new and inventive use of the special agents.
Versuchetries
Zum Nachweis der Vorteile der erfindungsgemäßen gegenüber den bekannten Reinigungsmitteln für harte Oberflächen wurden Vergleiche hinsichtlich ihres Reinigungsvermögens angestellt.To demonstrate the advantages of the cleaning agents according to the invention over the known cleaning agents for hard surfaces, comparisons were made with regard to their cleaning ability.
Zur Prüfung des Reinigungsvermögens diente die unten nach "Seifen-Öle-Fet¬ te-Wachse", 112.. 371, (1986) beschriebene Testmethode, die sehr gut repro¬ duzierbare Ergebnisse liefert. Danach wurde das zu prüfende Reinigungsmit¬ tel 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 Test¬ fläche 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 "Soap-Oil-Fat-Waxes", 112 .. 371, (1986) was used to test the cleaning power and gives very reproducible results. The cleaning agent to be tested was then placed 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 coated evenly with 2 g of the artificial soiling with the aid of a surface brush.
Ein Kunststoffschwamm wurde jeweils mit 10 ml der zu prüfenden Reinigungs ittellösung getränkt und mechanisch auf der ebenfalls mit 10 ml der zu prüfenden Reinigungsmittellösung beschichteten Testfläche bewegt. Nach 10 Wischbewegungen wurde die gereinigte Testfläche unter fließendes Wasser gehalten und der lose sitzende Schmutz entfernt. Die Reinigungs¬ wirkung, d.h., der Weißgrad der so gereinigten KunststoffOberfläche wurde mit einem Farb-Differenz-Meßgerät "Microcolor" (Dr. B. Lange) gemessen. Als Weiß-Standard diente die saubere weiße Kunststoffoberfläche.A plastic sponge was soaked in each case with 10 ml of the cleaning agent solution to be tested and moved mechanically on the test surface which was also coated with 10 ml of the cleaning agent solution to be tested. After 10 wiping movements, the cleaned test area was kept under running water and the loose dirt was removed. The cleaning effect, ie the whiteness of the plastic surface cleaned in this way, was measured using a "Microcolor" color difference measuring device (Dr. B. Lange). 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, waren die abgelesenen Werte bei den gereinigten Kunststoff-Flächen mit dem Prozentgehalt Reinigungs¬ vermögen (% RV) gleichzusetzen. Bei den nachstehenden Versuchen sind die angegebenen % RV-Werte die nach dieser Methode ermittelten Werte für das Reinigungsvermögen der untersuchten Reinigungsmittel. Sie stellen jeweils 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 were to be equated with the percentage of cleaning power (% RV). In the experiments below, the% RV values given are the values determined by this method for the cleaning ability of the cleaning agents examined. They represent mean values from triplicate determinations.
Die Meßwerte wurden in Relation zum Reinigungsergebnis einer als Standard benutzten handelsüblichen, schwachschäumenden AZR gesetzt.The measured values were set in relation to the cleaning result of a commercially available, low-foaming AZR used as standard.
Meßwerte Probe • 100 = %RV relativ Meßwert StandardMeasured values sample • 100 =% RV relative measured value standard
Der als Standard benutzte zum Zeitpunkt der Erfindung handelsübliche AZR hatte die Zusammensetzung:The standard AZR used at the time of the invention had the composition:
2,0 % Alkansulfonat 1,5 % Fettalkoholethoxilat 0,5 % Seife 4,0 % Butyldiglykol ad 100,0 % Wasser, Färb- und Duftstoffe, Konservierungsmittel2.0% alkane sulfonate 1.5% fatty alcohol ethoxylate 0.5% soap 4.0% butyl diglycol ad 100.0% water, colors and fragrances, preservatives
Das Schaumverhalten der erfindungsgemäßen AZR wurde folgendermaßen ge¬ prüft:The foaming behavior of the AZR according to the invention was tested as follows:
In ein weitlumiges Becherglas wird das Prüfprodukt vorgelegt. Sodann wird darauf aus 30 cm Höhe im freien Fall die Menge an Leitungswasser zufließen gelassen, die mit der Menge an vorgelegtem Produkt die empfohlene Anwen- dungslösung des Produkts ergibt. Die Schaumhöhe im Becherglas wird sofort nach Beendigung der Wasserzugabe und nach 3 Minuten abgelesen. Die Schaum¬ höhe nach 3 Minuten wird in Relation zum Anfangsschaum gesetzt und der Schaumzerfall folgendermaßen berechnet:The test product is placed in a large glass beaker. Then, from a height of 30 cm, the amount of tap water is allowed to flow in freely, which, with the amount of product presented, is the recommended application. solution of the product. The foam height in the beaker is read off immediately after the addition of water and after 3 minutes. The foam height after 3 minutes is related to the initial foam and the foam breakdown is calculated as follows:
Schaumhöhe Anfang - Schaumhöhe 3 MinutenFoam height beginning - foam height 3 minutes
Schaumzerfall (%) = • 100Foam breakdown (%) = • 100
Schaumhöhe AnfangFoam height beginning
Ein typischer schaumarmer AZR hat einen Schaumzerfall von über 50 %. A typical low-foaming AZR has a foam breakdown of over 50%.
BeispieleExamples
Die folgenden Beispiele wurden durch Zusammenmischen der Komponenten und anschließende Einstellung des gewünschten pH-Wertes hergestellt. Alle Pro¬ zentangaben beziehen sich auf Gewichtsprozent Aktivsubstanz.The following examples were prepared by mixing the components together and then adjusting the desired pH. All percentages relate to percent by weight of active substance.
Beispiel 1example 1
5,0 Gew.-% Cs - Cχo APG 2,0 Gew.-% Cs - Cχo Fettalkohol + 4 EO 0,5 Gew.-% Kokosfettsäure 2,0 Gew.-% Zitronensäure5.0% by weight Cs - Cχo APG 2.0% by weight Cs - Cχo fatty alcohol + 4 EO 0.5% by weight coconut fatty acid 2.0% by weight citric acid
X Gew.-% Natronlauge zur Einstellung des pH-Wertes des Fertigproduktes auf pH 7,5 ad 100,0 Gew.-% Wasser, Färb- und Duftstoffe, KonservierungsmittelX% by weight of sodium hydroxide solution to adjust the pH of the finished product to pH 7.5 ad 100.0% by weight of water, colorants and fragrances, preservatives
Das Beispiel stellt einen AZR dar, der in 1 %iger Lösung zur Anwendung kommt. Bei dieser Konzentration istThe example shows an AZR that is used in a 1% solution. Is at this concentration
- der Schaumzerfall: 100 %,- foam breakdown: 100%,
- das relative Reinigungsvermögen im Vergleich zum ebenfalls in 1 %iger Lösung geprüften Standard: 150 %- the relative cleaning power compared to the standard, which was also tested in a 1% solution: 150%
Der erfindungsgemäße AZR ist also trotz extremer Schaumarmut deutlich rei¬ nigungswirksamer als das handelsübliche Vergleichsprodukt.The AZR according to the invention is therefore, despite the extreme lack of foam, significantly more cleaning-efficient than the commercially available comparative product.
Beispiel 2 20,0 Gew.-% C8 - Cio Eettalkohol + 4 E0 5,0 Gew.-% Palmkernfettsäure 1,0 Gew.-% Zitronensäure 10,0 Gew.-% Cumo sulfonatExample 2 20.0% by weight C8 - Cio fatty alcohol + 4 E0 5.0% by weight palm kernel fatty acid 1.0% by weight citric acid 10.0% by weight cumosulfonate
X Gew.-% Kalilauge zur Einstellung des pH-Wertes des Fertigproduktes auf pH 8 ad 100,0 Gew.-% Wasser, Färb- und DuftstoffeX% by weight potassium hydroxide solution for adjusting the pH of the finished product to pH 8 ad 100.0% by weight water, colorants and fragrances
Das Beispiel 2 stellt ein AZR-Hochkonzentrat dar, welches in 0,1 %iger Lösung zur Anwendung kommt. Bei dieser Konzentration hat das MittelExample 2 represents an AZR high concentrate which is used in 0.1% solution. With this concentration the remedy has
- einen Schaumzerfall von 100 %, - ein Reinigungsvermögen im Vergleich zum Standard , welche in 1 %iger Lösung eingesetzt wurde, von 170 %.- 100% foam breakdown, - A cleaning ability compared to the standard, which was used in 1% solution, of 170%.
Beispiel 3Example 3
2,0 Gew.-% Cs - Cio Alkylpolyglucosid2.0 wt% Cs - Cio alkyl polyglucoside
0,5 Gew.-% C4 APG0.5 wt% C4 APG
1,0 Gew.-% C12 - C14 Fettalkohol + 1 PO + 5 E01.0% by weight C12 - C14 fatty alcohol + 1 PO + 5 E0
1,0 Gew.-% Palmkernfettsäure1.0% by weight of palm kernel fatty acid
2,0 Gew.-% Dicarbonsäurege isch (Glutar-, Adipin- und2.0% by weight of dicarboxylic acid (glutaric, adipic and
Bernsteinsäure) 0,05 Gew.-% Polyethylenoxid, MG 600000 2,0 Gew.-% ButylglykolSuccinic acid) 0.05% by weight polyethylene oxide, MW 600000 2.0% by weight butylglycol
X Gew.-% Natronlauge zur Einstellung auf pH 8 ad 100,0 Gew.-% Wasser, Färb- und Duftstoffe, KonservierungsmittelX% by weight sodium hydroxide solution for adjustment to pH 8 ad 100.0% by weight water, colorants and fragrances, preservatives
Das Beispiel zeigt in 1 %iger AnwendungslösungThe example shows a 1% application solution
- einen Schaumzerfall von 100 %,- 100% foam breakdown,
- ein relatives Reinigungsvermögen im Vergleich zum ebenfalls in 1 %iger Lösung geprüften Standard von 130 %.- a relative cleaning capacity compared to the standard of 130%, which was also tested in a 1% solution.
Beispiel 4Example 4
Dem Beispiel 3 wurden 0,5 % Fettalkoholethersulfat zugesetzt, um den Schaumzerfall bewußt nicht auf 100 % abfallen zu lassen. Auf die Reini¬ gungsleistung wirkte sich der Gehalt an Zusatztensid nicht aus. Der Schaum¬ zerfall betrug 90 %.In Example 3, 0.5% fatty alcohol ether sulfate was added in order to deliberately not let the foam break down to 100%. The content of additional surfactant had no effect on the cleaning performance. The foam disintegration was 90%.
Beispiel 5Example 5
0,1 Gew.-% Cs - Cio Alkylpolyglucosid0.1% by weight of Cs-Cio alkyl polyglucoside
0,05 Gew.-% C12 - C14 Fettalkohol + 6 E00.05% by weight C12 - C14 fatty alcohol + 6 E0
0,001 Gew.-% Kokosfettsäure0.001% by weight coconut fatty acid
7,0 Gew.-% Ethanol7.0% by weight of ethanol
X Gew.-% Ammoniak zur Einstellung auf pH 10 ad 100,0 Gew.- WasserX% by weight ammonia to adjust to pH 10 ad 100.0% by weight water
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 Sprüh¬ vorganges: die angesprühte zu reinigende 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. With this offer form the foam decay was 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.
Das relative Reinigungsvermögen im Vergleich zur 1 %igen Anwendungslösung des Standards betrug 180 %.The relative cleaning power compared to the 1% application solution of the standard was 180%.
Beispiel 6Example 6
12,5 Gew.-% Cs-Alkylxylosid mit etwa 1,2 Xyloseeinheiten 12,5 Gew.-% Cio-Alkylxylosid mit etwa 1,5 Xyloseeinheiten 11,1 Gew.-% Cs-Fettalkohol + 4 EO 2,8 Gew.-% Kokosfettsäure 2,4 Gew.-% Zitronensäure 5,6 Gew.-% Cumolsulfonat X Gew.-% Kalilauge zur Einstellung des pH-Wertes des Fertigproduk¬ tes auf pH 7,5 ad 100 Gew.-% Wasser, Färb- und Duftstoffe.12.5% by weight Cs-alkyl xyloside with approximately 1.2 xylose units 12.5% by weight Cio-alkyl xyloside with approximately 1.5 xylose units 11.1% by weight Cs-fatty alcohol + 4 EO 2.8% by weight % Coconut fatty acid 2.4% by weight citric acid 5.6% by weight cumene sulfonate X% by weight potassium hydroxide solution for adjusting the pH of the finished product to pH 7.5 ad 100% by weight water, color and fragrances.
In 1 %iger Lösung fand ein 80 %iger Schaumzerfall statt. Das relative Reinigungsvermögen im Vergleich zum Standard betrug dabei 126 %. In 1% solution, 80% foam disintegration took place. The relative cleaning power compared to the standard was 126%.

Claims

Patentansprüche Claims
1. Verwendung schwach schäumender Mittel mit einem Gehalt an etwa a) 0,1 - 50 , vorzugsweise 0,1 - 45 %, Alkylpolyglucosiden der Formel R 0 Zx mit1. Use of low-foaming agents with a content of about a) 0.1-50%, preferably 0.1-45%, of alkyl polyglucosides of the formula R 0 Z x
R = c8 ' c10< 0 = Sauerstoff, x = 1 - 6, vorzugsweise x = 1-3 und R = c 8 ' c 10 <0 = oxygen, x = 1-6, preferably x = 1-3 and
Z = Zuckereinheit, vorzugsweise eine Glucose- oder Xyloseeinheit. b) 0,001 - 30, vorzugsweise 0,005 - 20 % eines C - Ciß-, vorzugsweise .Cs - Cio-Fettalkoholalkoxylats mit einem HLB-Wert größer 10, vor¬ zugsweise ≥ 11, c) 0,001 - 15, vorzugsweise 0,001 - 10 % einer C& - C22-» vorzugsweise Cio ~ Ci8-Fettsäure, die in Abhängigkeit vom pH-Wert auch teilweise oder vollständig neutralisiert sein kann und d) Rest auf 100 % aus Wasser und in gegebenenfalls Allzweckreinigern üblichen Hilfsstoffen für die Reinigung von harten Oberflächen in Haushalt und Gewerbe.Z = sugar unit, preferably a glucose or xylose unit. b) 0.001-30, preferably 0.005-20% of a C - Ciss, preferably .Cs - Cio fatty alcohol alkoxylate with an HLB value greater than 10, preferably vor 11, c) 0.001 - 15, preferably 0.001 - 10% one C & - C22- » preferably Cio ~ Ci8 fatty acid, which can also be partially or completely neutralized depending on the pH value and d) rest on 100% water and, if applicable, all-purpose cleaners for cleaning hard surfaces in the home and Business.
2. Verwendung von Reinigungsmitteln nach Anspruch 1 die zusätzlich weniger als 25 %, vorzugsweise weniger als 20 der Gesamttensidmenge aus a) + b) + c) an anionischen enthalten. 2. Use of cleaning agents according to claim 1 which additionally contain less than 25%, preferably less than 20 of the total amount of surfactants from a) + b) + c) of anionic.
EP93906597A 1992-03-30 1993-03-24 Detergents for hard surfaces Expired - Lifetime EP0633927B1 (en)

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Also Published As

Publication number Publication date
EP0633927B1 (en) 1996-05-01
ES2086223T3 (en) 1996-06-16
DE4210365A1 (en) 1993-10-07
DK0633927T3 (en) 1996-09-09
ATE137531T1 (en) 1996-05-15
BR9306163A (en) 1998-01-13
DE4210365C2 (en) 1995-06-08
DE59302457D1 (en) 1996-06-05
US5591376A (en) 1997-01-07
WO1993020179A1 (en) 1993-10-14
JPH07505183A (en) 1995-06-08

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