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EP1074606B1 - Reinigungsmittel - Google Patents

Reinigungsmittel Download PDF

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Publication number
EP1074606B1
EP1074606B1 EP00115988A EP00115988A EP1074606B1 EP 1074606 B1 EP1074606 B1 EP 1074606B1 EP 00115988 A EP00115988 A EP 00115988A EP 00115988 A EP00115988 A EP 00115988A EP 1074606 B1 EP1074606 B1 EP 1074606B1
Authority
EP
European Patent Office
Prior art keywords
formulation
alkyl
sulphate
weight
polyglycoside
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00115988A
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English (en)
French (fr)
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EP1074606A2 (de
EP1074606A3 (de
Inventor
Michael Elsner
Helen Elizabeth Herd
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Cognis IP Management GmbH
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Cognis IP Management GmbH
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Publication of EP1074606A3 publication Critical patent/EP1074606A3/de
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the present invention relates to a detergent formulation intended particularly but not exclusively as a so-called “washing up” liquid for use in washing crockery, cutlery, pans and other domestic utensils which have been used in the preparation and/or consumption of food and which have deposits of dirt, food, grease, burnt residues etc.
  • the detergent formulation is also intended, not exclusively, as a "hard surface” cleaner.
  • GB-A-2 290 301 discloses "washing-up" liquid having good cleaning and lathering performance without the use of LABS (linear alkyl benzene sulphonic acid - usually used as the sodium salt) or diethanolamides (which are associated with nitrosamines).
  • LABS linear alkyl benzene sulphonic acid - usually used as the sodium salt
  • diethanolamides which are associated with nitrosamines
  • GB-A-2 321 253 also discloses "washing-up" liquid, containing 10-20wt% of an alkyl sulphate, 1-10wt% of an alkyl ether sulphate, 1-7wt% of an amine oxide, 1-7wt% of an amphoteric betaine surfactant, 1-15wt% of an ethoxylated alcohol and up to 3wt% of an alkyl polyglycoside, although only up to 0.95wt% of the alkyl polyglycoside is specifically used.
  • the present invention aims to provide detergent formulations demonstrating improved performance.
  • a liquid detergent formulation comprising, by weight, 5-10% of an alkyl (C 8-22 ) sulphate, 5-10% of an alkyl (C 8-22 ) ether sulphate, 0-3% of an amine oxide containing at least one C 8-22 alkyl group, 1-6% of an amphoteric betaine surfactant containing at least one C 8-22 alkyl group, 2-10% of an ethoxylated alcohol (C 8-22 ), 2.5-9% of an alkyl (C 8-22 ) polyglycoside and a balance of water.
  • a liquid detergent in accordance with the present invention has excellent cleaning properties.
  • the liquid detergent provides an outstanding foam height, which persists for a long time both on standing and in washing greasy plates, both properties being desirable to the user.
  • the liquid detergent is not only effective at removing greasy deposits from hard surfaces but also for retaining said grease particles in solution stopping them from being re-deposited.
  • composition of the invention includes at least one C 8-22 alkyl sulphate used in an amount of 5-10% by weight of the formulation, more preferably 8-10% and most preferably 9-10%.
  • the invention is particularly beneficial with the use of an amount of alkyl (C 8-22 ) sulphate lower than that disclosed in GB-A-2 321 253 .
  • the benefits of the invention may be obtained with the use of less than 10% by weight of alkyl (C 8-22 ) sulphate, particularly in the range of 8% to less than 10%.
  • the alkyl sulphate is preferably an alkali metal alkyl sulphate with the preferred alkali metal being sodium.
  • the alkyl group of the alkyl sulphate has 8-16 carbon atoms.
  • the alkyl sulphate may be a single compound (preferably C 12 ) or may comprise a mixture of alkyl sulphates of different chain lengths, preferably with C 12 predominating.
  • the alkyl groups are primary alkyl groups and preferably straight chain.
  • the carbon chain of the alkyl sulphate may be produced synthetically or may be derived from natural products (e.g. coconut oil) so that the chain length distribution of the alkyl group will correspond to that in the natural product from which it is derived.
  • natural products e.g. coconut oil
  • the alkyl sulphate may be a "narrow cut" lauryl sulphate having carbon chains principally of C 12 to C 14 (C 12 predominating), e.g. 60-70% C 12 , 20-30% C 14 plus minor amounts of C 10 and C 16 .
  • a preferred alkyl sulphate is available under the name Empicol LX28 (Albright & Wilson).
  • the alkyl (C 8-22 ) ether sulphate is preferably used in an amount of 5-10%, by weight of the formulation, more preferably 6-9% and most preferably 7-8%.
  • the invention is particularly beneficial with the use of an amount of alkyl (C 8-22 ) ether sulphate lower than that disclosed in GB-A-2 321 253 .
  • the benefits of the invention may be obtained with the use of less than 8% by weight of alkyl (C 8-22 ) ether sulphate, particularly in the range of 7% to less than 8%.
  • the alkyl group of the ether sulphate may be as described for the alkyl sulphate.
  • alkyl ether sulphate which may be used is available under the name Empicol 0251 (Albright & Wilson).
  • the formulation of the invention contains 0 to 3%, more preferably 1 to 3%, of an amine oxide containing at least one C 8-22 alkyl group.
  • the amine oxide preferably has one such group of C 8-22 carbon atoms and two C 1-4 alkyl groups. Most preferably the latter alkyl groups are methyl groups. Preferred amine oxides are therefore (C 8-22 ) alkyl dimethyl amine oxides.
  • the long chain alkyl group may, for example, have 8-18 carbon atoms and the compound may comprise a mixture of alkyl groups, which are preferably C 10 to C 18 (with C 12 predominating).
  • a suitable amine oxide is available under the name Genaminox CSX (Hoechst).
  • the betaine surfactant is used in the formulation of the invention in an amount of 1-6%, more preferably 0.5-4%.
  • Preferred betaines may be either of the formula (I) or (II).
  • R 1 and R 2 may be the same or different C 1-4 alkyl groups whereas R 3 is an alkyl group having 8-22 carbon atoms, e.g. mixed C 10 to C 14 .
  • the preferred betaine for use in the formulation of the invention is cocoamidopropyl betaine.
  • a suitable betaine is available under the name Rewoteric AMB14 (Witco).
  • a further component of the formulation of the invention is the ethoxylated alkanol (C 8-22 ) which is used in an amount of 2-10%, more preferably 2-9% and most preferably 2-7%.
  • ethoxylated alkanols which may be used are those in which the alkanol (from which the product is derived) is a primary alcohol and is preferably linear.
  • the alkanol has 6 to 11 carbon atoms (e.g. mixed C 9 -C 11 ) and in which the degree of ethoxylation is 5-15 (particularly 8-10).
  • a suitable fatty alcohol ethoxylate is available under the name Lutensol ON80 (BASF).
  • the formulations of the invention contains 2.5-9% alkyl (C 8-22 ) polyglycoside by weight.
  • a glycoside is a sugar derivative, wherein one or more of the hydroxyl functions, which may preferably be on the first carbon atom of the sugar molecule, is/are replaced by another group such as an alcoholic or phenolic group.
  • functionalised sugar molecules may be linked to one or more other sugar molecules, either before or after functionalisation, to form a polyglycoside.
  • the preferred glycoside employed in the present invention is a glucoside (i.e. based on glucose), functionalised with a primary alcohol (e.g. C 12 -C 14 ). More preferably the glucoside is in the form of a polyglucoside, with a preferable average degree of polymerisation of between 1-2, most preferably about 1.4.
  • a suitable polyglycoside is available under the name Glucopan 600CSUP (Henkel).
  • a further optional component which may be used in the formulation of the invention is a hydrotrope which may be used in an amount up to 7%, e.g. 3%, of the formulation.
  • a particular preferred hydrotrope is sodium xylene sulphonate.
  • the formulation may contain the usual minor addition such as preservatives, dyes and/or perfumes.
  • Formulations A to K were prepared as shown below. % by Weight A B C D E F G H I J K Sodium Lauryl Sulphate (Empicol L28) 9.6 9.6 9.6 9.6 9.6 9.6 9.6 9.6 9.6 9.6 9.6 9.6 9.6 9.6 Sodium Lauryl Ether Sulphate (Empicol 0251) 7.4 7.4 7.4 7.4 7.4 7.4 7.4 7.4 7.4 7.8 Fatty Alcohol Ethoxylate (Lutensol ON80) - 12.0 4.0 2.0 - 6.0 8.0 - 6.0 2.0 5.0 Cocoamidopropyl Betaine (Rewoteric AMB14) 6.0 - 4.0 2.0 12.0 - 2.0 - 6.0 8.0 3.0 Alkyl Polyglycoside (Glucopon 600CSUP) 6.0 - 4.0 8.0 - 6.0 2.0 12.0 - 2.0 3.2 Sodium Xylene Sulphonate 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5
  • the plate washing test was a standard test used to determine the number of plates which could be washed using a predetermined quantity (0.2g/litre) of the detergent formulation.
  • the plates had each been soiled with 2 ml of melted lard, which contained a red dye (Red number 17 90095 available from Ellis and Everard) for ease of visibility on the white plates and which was applied in the form of small drops and then allowed to harden for 24 hours.
  • a red dye Red number 17 90095 available from Ellis and Everard
  • the plates were washed one at a time in a 5 litre bowl of water, which had been preheated to 50°C and which contained 0.2g/litre of detergent formulation. The washing was stopped when the foam produced by the formulation no longer covered the surface of the water. After washing the plates were assessed for cleanliness, being divided into three categories, as follows:
  • Formulations C,D and K not only were observed to clean the highest number of plates but also demonstrated a relatively low number of superficially clean plates. Both properties are of utmost importance to the user.
  • Formulations A (lacking the fatty alcohol ethoxylate), E (lacking fatty alcohol ethoxylate and the polyglycoside) and H (lacking the fatty alcohol ethoxylate and betaine) performed considerably worse, leading to a lower number of plates cleaned and an equal or higher number of superficially clean plates.
  • Formulation B (lacking the polyglycoside) performed worse still, leading to a very high number of dirty plates.
  • formulations G, I, J (not containing enough of the polyglycoside) and F (lacking the betaine) did not perform as effectively as formulations C,D and K.
  • Formulations A1 to A7 were prepared as shown in the table below
  • formulations A1-A2 and A4-A6 were prepared in accordance with the present noted that formulations A1-A2 and A4-A6 were prepared in accordance with the present invention.
  • Formulations A3 and A7 were prepared as comparative examples.
  • Platewash (Lard soil) A1 A2 A3 Number of Plates not cleaned 1 2 1 Number of Plates superficially clean 13 13 16 Number of Plates cleaned 11 10 8
  • Formulations A1 and A2 were observed to clean the highest number of plates but also demonstrated the lowest number of superficially clean plates.
  • Formulation A3 did not contain enough of the polyglycoside to perform as effectively as formulations A1 and A2.
  • the plates were washed as in the lard soil platewash and assessed for cleanliness using the same criteria.
  • Platewash (Mixed Soil) A4 A5 A6 A7 Number of Plates not cleaned 6 6 7 9 Number of Plates superficially clean - - - - Number of Plates cleaned 19 19 18 16
  • Formulation A7 performed worse than formulations A4 and A5, as a result of lower polyglycoside content even though the formulation A7 had an equal if not considerably greater concentration of sodium lauryl sulphate.
  • the lathering performance was judged by a standard test in which 200 ml of a 1% solution of the formulation is drained into a measuring cylinder from a separating funnel positioned 75 cm above the base of the cylinder. The height of the lather produced after 1 minute and after 30 minutes was measured.
  • Formulation A3 produced a significantly lower foam that formulations A1 and A2 in both parts of the test, as a result of a lower polyglycoside content.

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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)
  • Detergent Compositions (AREA)
  • Surgical Instruments (AREA)
  • Valve Device For Special Equipments (AREA)
  • Valve-Gear Or Valve Arrangements (AREA)

Claims (33)

  1. Ein Flüssigwaschmittel, enthaltend 5-10 Gew.-% an Alkyl(C8-22)sulfaten, 5-10 Gew.% an Alkyl(C8-22)ethersulfaten, 0-3 Gew.-% an Aminoxiden, die mind. eine C8-22 Alkylgruppe aufweisen, 1-6 Gew.-% an amphoterischen Betaintensiden, die mind. eine C8-22 Alkylgruppe aufweisen, 2-10 Gew.-% an ethoxyliertem Alkoholen (C8-22), 2,5-9 Gew.-% an Alkyl(C8-22)polyglycosiden und den Rest Wasser.
  2. Ein Mittel gem. Anspruch 1, wobei die Alkylsulfate in Mengen von 8-10 Gew.-%, vorzugsweise 9-10 Gew.-% enthalten sind.
  3. Ein Mittel entsprechend den Ansprüchen 1 oder 2, wobei die Alkylsulfate Alkalimetallsulfate sind.
  4. Ein Mittel gem. Anspruch 3, wobei das Alkalimetall Natrium ist.
  5. Ein Mittel gemäß einem der Ansprüche 1 bis 4, wobei die Alkylgruppe der Alkylsulfate 8-16 Kohlenstoffatome aufweist.
  6. Eine Formulierung gem. Anspruch 5, wobei die Alkylsulfate überwiegend Laurylsulfat darstellen.
  7. Eine Formulierung gem. einem der Ansprüche 1-6, wobei die Alkylethersulfate in Mengen von 6-9 Gew.-% enthalten sind.
  8. Ein Mittel gem. Anspruch 7, wobei die Alkylethersulfate in Mengen von 7-8 Gew.-% enthalten sind.
  9. Ein Mittel gem. den Ansprüchen 1-8, wobei das Kation der Alkylethersulfate ein Alkalimetallkation ist, vorzugsweise Natrium oder Ammonium.
  10. Ein Mittel gem. den Ansprüchen 1-9, wobei das Alkylethersulfat ein ethoxyliertes Alkylethersulfat ist.
  11. Ein Mittel gem. Anspruch 10, wobei das ethoxylierte Alkylethersulfat 1-5 Teile Ethylenoxid aufweist.
  12. Ein Mittel gem. Anspruch 11, wobei das ethoxylierte Alkylethersulfat 2 oder 3 Teile EO enthält.
  13. Ein Mittel gem. Anspruch 12, wobei das Alkylethersulfat Natriumlaurylethersulfat ist.
  14. Ein Mittel gem. einem der Ansprüche 1-13, das 1-3 Gew.-% Aminoxid enthält.
  15. Ein Mittel gem. einem der Ansprüche 1-14, wobei das Aminoxid eine Alkylgruppe mit C8-22 C-Atomen und zwei Alkylgruppen mit C1-C4 Alkylgruppen enthält.
  16. Ein Mittel gem. dem Anspruch 15, wobei als Aminoxid C8-22 Alkyldimethylaminoxid ausgewählt ist.
  17. Ein Mittel gem. einem der Ansprüche 1-16, wobei das Betaintensid in Mengen von 0,5-4 Gew.-% enthalten ist.
  18. Ein Mittel gem. einem der Ansprüche 1-17, wobei das Betaintensid in
    Figure imgb0005
    Figure imgb0006
     in denen R1 und R2 gleich oder unterschiedlich sind oder unterschiedliche C1-C4 Alkylgruppen darstellt und R3 eine Alkylgruppe mit 8-22 C-Atomen darstellt.
  19. Ein Mittel gem. Anspruch 18, wobei das Betaincocoamidopropylbetain ist.
  20. Ein Mittel gem. einem der Ansprüche 1-19, wobei die ethoxylierten Alkohole in Mengen von 2-9 Gew.-% enthalten sind.
  21. Ein Mittel gem. Anspruch 20, wobei der ethoxylierter Alkohol in Mengen von 2-7 Gew.-% enthalten ist.
  22. Ein Mittel gem. einem der Ansprüche 1-21, wobei der Alkohol, von dem der ethoxylierte Alkohol abstammt, linear ist.
  23. Ein Mittel gem. einem der Ansprüche 1-22, wobei der Alkohol, von dem der ethoxylierte Alkohol abstammt, 6-11 Kohlenstoffatome aufweist.
  24. Ein Mittel gem. einem der Ansprüche 1-23, in dem der Grad der Ethoxylierung in dem ethoxylierten Alkohol 5-15 ist.
  25. Ein Mittel gem. Anspruch 24, wobei der Ethoxylierungsgrad 8-10 ist.
  26. Ein Mittel gem. einem der Ansprüche 1-25, wobei das Alkyl(C8-C22)polyglycosid ein Polymer der Glucose ist und einen Polymerisationsgrad zwischen 1 und 2 aufweist.
  27. Ein Mittel gem. Anspruch 26, wobei das Alkyl(C8-22)polyglycosid ein Polymer der Glucose mit einem Polymerisationsgrad von 1,4 ist.
  28. Ein Mittel gem. einem der Ansprüche 1-27, dadurch gekennzeichnet, dass es zusätzliche Hydrotope enthält.
  29. Ein Mittel gem. Anspruch 28, wobei das Hydrotop in Mengen von bis zu 7 Gew.-% enthalten ist.
  30. Ein Mittel gem. den Ansprüchen 28 oder 29, wobei das Hydrotop ausgewählt ist aus Natriumxylolsulfonat.
  31. Ein flüssiges Waschmittel gem. Anspruch 1, das enthält 5 Gew.-% bis weniger als 10 Gew.-% an Alkyl(C8-22)sulfat, 7-8 Gew.-% an Alkyl(C8-22)ethersulfat, 0-3 Gew.-% eines Aminoxids enthaltend mind. eine C8-22 Alkylgruppe, 1-6 Gew.-% eines amphoterischen Betaintensids, enthaltend mind. einen C8-22 Alkylgruppe, 2-10 Gew.-% an ethoxylierten Alkoholen mit 8-22 C-Atomen, 2,5-9 Gew.-% an Alkyl(C8-22)polyglycosiden und den Rest Wasser.
  32. Ein Mittel gem. Anspruch 31, wobei das Alkyl(C8-22)polyglycosid in Mengen von größer 3 Gew.-% enthalten ist.
  33. Ein Mittel gem. Anspruch 33, wobei das Alkyl(C8-22)polyglycosid in Mengen von größer 3,5 Gew.-% enthalten ist.
EP00115988A 1999-08-03 2000-07-26 Reinigungsmittel Expired - Lifetime EP1074606B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9918143 1999-08-03
GBGB9918143.0A GB9918143D0 (en) 1999-08-03 1999-08-03 Detergent formulation

Publications (3)

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EP1074606A2 EP1074606A2 (de) 2001-02-07
EP1074606A3 EP1074606A3 (de) 2001-05-02
EP1074606B1 true EP1074606B1 (de) 2010-04-07

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EP (1) EP1074606B1 (de)
AT (1) ATE463554T1 (de)
DE (1) DE60044111D1 (de)
GB (1) GB9918143D0 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2429459A (en) * 2005-08-23 2007-02-28 Reckitt Benckiser Inc Dishwashing detergent composition
US20130298948A1 (en) 2010-12-07 2013-11-14 Akzo Nobel Chemicals International B.V. Composition for Cleaning of Hard Surfaces
DE102018206661A1 (de) * 2018-04-30 2019-10-31 Henkel Ag & Co. Kgaa Detergenszusammensetzung zur Filterreinigung beim automatischen Geschirrspülen

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4444094A1 (de) * 1994-12-10 1996-06-13 Henkel Kgaa Spezielle Niotenside in Handgeschirrspülmitteln
WO1998005743A1 (en) * 1996-08-06 1998-02-12 Colgate-Palmolive Company High foaming nonionic surfactant based liquid detergent
GB2321253B (en) * 1997-01-16 2000-10-18 Mcbride Robert Ltd Liquid detergent formulation

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GB9918143D0 (en) 1999-10-06
ATE463554T1 (de) 2010-04-15
EP1074606A2 (de) 2001-02-07
EP1074606A3 (de) 2001-05-02
DE60044111D1 (de) 2010-05-20

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