EP0616028A1 - Cleaning compositions with short chain nonionic surfactants - Google Patents

Cleaning compositions with short chain nonionic surfactants Download PDF

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Publication number
EP0616028A1
EP0616028A1 EP93870050A EP93870050A EP0616028A1 EP 0616028 A1 EP0616028 A1 EP 0616028A1 EP 93870050 A EP93870050 A EP 93870050A EP 93870050 A EP93870050 A EP 93870050A EP 0616028 A1 EP0616028 A1 EP 0616028A1
Authority
EP
European Patent Office
Prior art keywords
hydrocarbon
short chain
mixtures
formula
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.)
Withdrawn
Application number
EP93870050A
Other languages
German (de)
French (fr)
Inventor
Michel Jean Carrié
William Ajalon Cilley
Peter Rosalia Joannes Geboes
Massimo Morini
Louise Gail Scott
Eddy Vos
Ricky Ah-Man Woo
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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 Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP93870050A priority Critical patent/EP0616028A1/en
Priority to EP93870125A priority patent/EP0616026A1/en
Priority to EP93870181A priority patent/EP0600847B2/en
Priority to DE69321562T priority patent/DE69321562T3/en
Priority to DK93870181T priority patent/DK0600847T3/en
Priority to AT93870181T priority patent/ATE172234T1/en
Priority to ES93870181T priority patent/ES2124778T5/en
Priority to EP93870215A priority patent/EP0616027A1/en
Priority to TR01058/93A priority patent/TR28413A/en
Priority to JP6513290A priority patent/JPH08505413A/en
Priority to NZ258466A priority patent/NZ258466A/en
Priority to US08/432,154 priority patent/US5559091A/en
Priority to PCT/US1993/011293 priority patent/WO1994012599A1/en
Priority to CA002149227A priority patent/CA2149227C/en
Priority to BR9307515-4A priority patent/BR9307515A/en
Priority to KR1019950702134A priority patent/KR950704462A/en
Priority to AU56149/94A priority patent/AU681365B2/en
Priority to EG73993A priority patent/EG20373A/en
Priority to MA23345A priority patent/MA23039A1/en
Priority to AU64074/94A priority patent/AU695680B2/en
Priority to CA 2158542 priority patent/CA2158542A1/en
Priority to BR9406015A priority patent/BR9406015A/en
Priority to KR1019950703979A priority patent/KR960701185A/en
Priority to NZ263930A priority patent/NZ263930A/en
Priority to BR9406012A priority patent/BR9406012A/en
Priority to NZ26339494A priority patent/NZ263394A/en
Priority to US08/522,354 priority patent/US5707948A/en
Priority to PCT/US1994/002748 priority patent/WO1994021768A1/en
Priority to AU64073/94A priority patent/AU6407394A/en
Priority to CN94192051A priority patent/CN1122612A/en
Priority to PCT/US1994/002746 priority patent/WO1994021770A1/en
Priority to JP6521160A priority patent/JPH08508765A/en
Priority to BR9406013A priority patent/BR9406013A/en
Priority to PCT/US1994/002747 priority patent/WO1994021767A1/en
Priority to JP6521159A priority patent/JPH08507825A/en
Priority to NZ263393A priority patent/NZ263393A/en
Priority to CN94192049A priority patent/CN1044717C/en
Priority to CA002158541A priority patent/CA2158541C/en
Priority to CA002158543A priority patent/CA2158543C/en
Priority to AU65194/94A priority patent/AU6519494A/en
Priority to US08/522,391 priority patent/US5981455A/en
Priority to CN 94192052 priority patent/CN1122611A/en
Priority to JP6521161A priority patent/JPH08508766A/en
Priority to MA23443A priority patent/MA23136A1/en
Priority to MA23446A priority patent/MA23138A1/en
Priority to MA23445A priority patent/MA23137A1/en
Publication of EP0616028A1 publication Critical patent/EP0616028A1/en
Priority to FI952540A priority patent/FI952540A/en
Priority to NO952058A priority patent/NO952058L/en
Priority to NO953503A priority patent/NO953503L/en
Priority to NO953502A priority patent/NO953502D0/en
Priority to NO953644A priority patent/NO953644D0/en
Priority to FI954395A priority patent/FI954395A/en
Priority to FI954397A priority patent/FI954397A0/en
Priority to FI954396A priority patent/FI954396A/en
Priority to AU74176/98A priority patent/AU7417698A/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—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
    • C11D1/02—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
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C11D1/831—Mixtures of non-ionic with anionic compounds of sulfonates with ethers of polyoxyalkylenes without phosphates
    • 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
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic 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
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the present invention relates to cleaning compositions. Although the present invention applies primarily to hard surface cleaning compositions, it may also be of interest for other cleaning compositions including dishwashing and laundry detergent compositions.
  • short chain alkoxylated alcohols namely alkoxylated alcohols with a short alkyl chain in the alcohol, hereinafter short chain alkoxylated alcohols.
  • said short chain alkoxylated alcohols are particularly efficient in cleaning.
  • Such short chain alkoxylated alcohols further meet the other objects of providing surfactants which are low foaming and which are mild to the skin.
  • Another advantage is that such short chain alkoxylated alcohols are particularly suitable for formulating concentrated cleaning compositions.
  • EP 125 854 discloses a composition comprising 2.7% of C8EO4.8 together with 14.2% of ammonium C11.8 linear alkyl benzene sulphonate, 10.4 of ammonium C12-13 alkyl ethoxylated sulphate, 8.6% magnesium C12-13 alkyl sulphate, 4.0% coconut monoethanolamide and 9.1% ethanol and water. EP 125 854 however fails to draw the difference between long and short chain nonionic surfactants.
  • EP 496 188 discloses an aqueous solution comprising 3% of C8EO6 and 8% maleic acid. EP 486 188 does not draw the difference between long and short chain nonionic surfactants.
  • the present invention encompasses aqueous cleaning compositions comprising a short chain alkoxylated alcohol surfactant according to the formula RO(A)nH, wherein R is a C6 to C10 hydrocarbon chain, A is ethylene oxide or propylene oxide or mixtures thereof and n is of from 1 to 10, or mixtures thereof, and other conventional cleaning ingredients selected from anionic, cationic, zwitterionic and nonionic co-surfactants, including short chain co-surfactants, builders, solvents, bleaches and minors including dyes, perfumes, or mixtures thereof.
  • a short chain alkoxylated alcohol surfactant according to the formula RO(A)nH, wherein R is a C6 to C10 hydrocarbon chain, A is ethylene oxide or propylene oxide or mixtures thereof and n is of from 1 to 10, or mixtures thereof
  • other conventional cleaning ingredients selected from anionic, cationic, zwitterionic and nonionic co-surfactants, including short chain co-surfactants, builders, solvents
  • the present invention also encompasses such compositions in a concentrated form, the use of said surfactants for neat grease cleaning, for dilute grease cleaning and for soap scum cleaning.
  • the present invention further encompasses the use of said surfactants as skin mild surfactants and as low foaming surfactants.
  • the present invention encompasses aqueous compositions which comprise conventional cleaning ingredients and a short chain alkoxylated alcohol surfactant.
  • the short chain nonionic surfactants for use herein are alkoxylated alcohols according to the formula RO(A)nH, wherein R is a C6 to C10 hydrocarbon chain and n, representing the average alkoxylation degree, is from 1 to 10, or mixtures thereof. R is indifferently straight or branched. A is ethylene oxide or propylene oxide or mixtures thereof. Similar nonionic surfactants which have longer R groups than those of the present invention are known in the art and are commonly used in cleaning compositions. The present invention is based on the finding that alkoxylated alcohols with shorter R groups provide better cleaning, as well as the multiple benefits described herein.
  • Suitable surfactants for use herein can be readily made by condensing alcohols having the desired chain length with propylene or ethylene oxide, or mixtures thereof, as disclosed in the art for alkoxylated alcohols with longer chains.
  • Suitable short chain alkoxylated alcohols for use herein are also commercially available from several suppliers, for instance Dehydol 04 R from Henkel (C8EO4), Mergital C4 R from Sidobre (C8EO4), and Imbentin AG/810/050 and AG/810/080 R from Kolb (respectively C8-10EO5 and C8-10EO8).
  • compositions according to the present invention comprise from 0.1% to 50% by weight of the total composition of said short chain alkoxylated alcohols, preferably from 1% to 30%, most preferably from 1.5% to 20%.
  • the short chain alkoxylated alcohols herein are particularly suitable for the formulation of so-called concentrated cleaning compositions. Indeed, the short chain alkoxylated alcohols have a very high solubility in water, but they are also able to solubilize other conventional organic ingredients for cleaning compositions, such as perfumes.
  • cleaning compositions are provided in a concentrated form, which only comprise from 1% to 80% by weight of the total composition of water, preferably from 30% to 70%.
  • Such compositions typically comprise from 0.1% to 50% by weight of the total composition of said short chain alkoxylated alcohols, preferably from 5% to 30%.
  • the present invention encompasses the use of said surfactants for neat grease cleaning.
  • neat grease cleaning means the cleaning of greasy soils, using an aqueous solution comprising at least one of the surfactants according to the present invention, within the ranges above.
  • Greasy soils are typically found in kitchens or bathrooms.
  • Preferred short chain alkoxylated alcohols for use in neat grease cleaning are those according to the formula hereinabove where R is a hydrocarbon chain from C6 to C8 and n is from 1 to 10.
  • Preferred short chain alcohol ethoxylates for neat grease cleaning are the surfactants according to the formula above where R is a C6 hydrocarbon chain and n is 4 or 6 (C6EO4 and C6EO6); or R is a C8 hydrocarbon chain and n is 4 or 6 (C8EO4 and C8EO6); or R is a C8 hydrocarbon chain and n is 10 (C8EO10).
  • dilute grease cleaning means the cleaning of greasy soils using an aqueous solution comprising a surfactant according to the present invention, in the ranges described above, but which is diluted typically in 10 to 150 times its weight in water before it is used to clean the greasy soils.
  • Dilute cleaning compositions and conditions have been described for instance in EP 503 219.
  • Suitable short chain alkoxylated alcohols for use in dilute grease cleaning are those according to the formula hereinabove where R a hydrocarbon chain from C8 to C10, and n is from 1 to 10.
  • R a hydrocarbon chain from C8 to C10
  • n is from 1 to 10.
  • Preferred short chain alkoxylated alcohols herein for dilute grease cleaning are those according to the formula herein above where R is a C8 hydrocarbon chain and n is of from 4 to 10, preferably 4, 6 or 10 (C8EO4, C8EO6, C8EO10), R is a C10 hydrocarbon and n ranges from 3 to 6 or n is 10 (C10EO3, C10EO4, C10EO5, C10EO6, C10EO10), as well as a mixture of surfactants where R is a C10 hydrocarbon and a C8 hydrocarbon and n is 5 (C8-10EO5), or n is 8 (C8-C10EO8).
  • the present invention encompasses the use of said surfactants for cleaning soap scum. Soap scum, which is mainly found in bathroom is quite peculiar in its composition and traditionally leads detergent manufacturers to formulate specialty cleaning products for bathroom environment. The present invention is thus particularly applicable to the formulation of such specialty products.
  • Suitable short chain alkoxylated alcohols for use in cleaning soap scum are those wherein, in the formula hereinabove, R a hydrocarbon chain from C8 to C10, and n is from 1 to 10. When R is in the higher range, i.e. towards 10, it is preferred to use lower ethoxylation degrees, typically 1 to 6.
  • Preferred alkoxylated alcohols for cleaning soap scum are those where, in the formula hereinabove, R is a C8 hydrocarbon chain and n is of from 4 to 10, preferably 4, 6 or 10 (C8EO4, C8EO6, C8EO10), R is a C10 hydrocarbon and n ranges from 3 to 6 (C10EO3, C10EO4, C10EO5, C10EO6), as well as a mixture of surfactants where R is a C10 hydrocarbon and a C8 hydrocarbon and n is 5 (C8-10EO5), or n is 8 (C8-C10EO8).
  • the present invention encompasses the use of said surfactants as low foaming surfactants.
  • Low foaming surfactants are usually of interest for heavy duty laundry detergents, but also for hard surface cleaners which are designed to be used as no-rinse products in dilute form.
  • the surfactants within the present invention which have been found to produce low foaming are those according to the formula herein above where R is a C6 to C10 hydrocarbon chain and n is of from 1 to 10.
  • Preferred low foaming surfactants herein are those where R is a C6 hydrocarbon chain and n is 4 or 6 (C6EO4, C6EO6); or R is a C8 hydrocarbon chain and n is 4, 6 or 10 (C8EO4, C8EO6, C8EO10), R is a C10 hydrocarbon and n ranges from 3 to 6 (C10EO3, C10EO4, C10EO5, C10EO6), as well as a mixture of surfactants where R is a C10 hydrocarbon and a C8 hydrocarbon and n is 5 (C8-10EO5), or n is 8 (C8-C10EO8); or mixtures thereof.
  • the present invention encompasses the use of said surfactants as skin mild surfactants. Mildness to the skin is quite an advantage when formulating products which are bound to be in contact with the user's skin. Such is the case for dishwashing compositions, or hard surface cleaning compositions. Skin mildness benefits are usually advertised when they exist in a given product.
  • the surfactants within the present invention which have been found to be particularly mild to the skin are those according to the formula herein above where R is a C6 to C8 hydrocarbon chain and n is of from 1 to 10.
  • Preferred surfactants are those where R is a C6 hydrocarbon chain and n is 4 or 6 (C6EO4, C6EO6), or R is a C8 hydrocarbon chain and n is 4, 6 or 10, or mixtures thereof (C8EO4, C8EO6, C8EO10).
  • compositions according to the invention further comprise conventional ingredients selected from other nonionic, anionic, cationic and zwitterionic co-surfactants (from 0% to 30% by weight of the total composition, preferably from 1% to 20%), builders (from 0% to 20% by weight of the total composition, preferably from 1% to 10%), solvents (from 0% to 20% by weight of the total composition, preferably from 0% to 5%), non-hypochlorite bleaches (from 0% to 10% by weight of the total composition, preferably from 1% to 5%) and minors including dyes, perfumes, all of which are well known and extensively described in the art.
  • nonionic, anionic, cationic and zwitterionic co-surfactants from 0% to 30% by weight of the total composition, preferably from 1% to 20%
  • builders from 0% to 20% by weight of the total composition, preferably from 1% to 10%
  • solvents from 0% to 20% by weight of the total composition, preferably from 0% to 5%
  • compositions according to the present invention depend on the end-use envisioned. Mixtures of the short chain surfactants according to the present invention can also be used in order to combine several benefits. Compositions according to the present invention can be formulated indifferently as alkaline and acidic hard surface cleaners, dishwashing products or laundry detergents.
  • compositions are made by mixing the listed ingredients in the listed proportions.
  • Triethanolamine 1.9 1.9 - 1.0 - MEA up to pH - - - - 7 Ammonia up to pH 3.5 3.5 2.0 - - NaOH up to pH - - - 10.5 - Water and minors -----------up to 100% -------------------- Lutensol AO30 is C13-15(EO)30 Lutensol AO7 is C13-15(EO)7 MEA stands for monoethanolamine.
  • compositions 1 and 2 hereinabove are particularly efficient in removing soapscum and are therefore particularly suitable as a bathroom cleaner.
  • Composition 3 is particularly effective in providing low suds.
  • Composition 4 is particularly effective on dilute and neat grease cleaning.
  • Composition 5 is a concentrated composition.

Abstract

The present compositions comprise short chain alkoxylated alcohols as nonionic surfactants. The short chain alkoxylated alcohols provide superior cleaning compared to their homologues with longer chains as well as other benefits including, low foaming and skin mildness, and the ability to formulate concentrated compositions.

Description

    Technical field
  • The present invention relates to cleaning compositions. Although the present invention applies primarily to hard surface cleaning compositions, it may also be of interest for other cleaning compositions including dishwashing and laundry detergent compositions.
    • Background
  • A variety of cleaning compositions have been described in the art. There is a constant strive for the development of cleaning compositions with better performance in several respects. Better cleaning on all soils, including greasy soils and soap scum is of course a principal object, both for neat and diluted compositions which are often used in the cleaning of hard surfaces. However other properties are also highly desirable, particularly mildness to the skin, the ability to remove soap scum and to produce limited suds.
  • All such objects can be independently achieved by using various ingredients which are generally added for a specific purpose. For instance silicone oils are typically added solely to control sudsing. Another example is the use of solvents to boost neat cleaning. While such additives meet the desired object, they also grief the cost of formulating efficient cleaning compositions.
  • It has now been found that certain nonionic surfactants, namely alkoxylated alcohols with a short alkyl chain in the alcohol, hereinafter short chain alkoxylated alcohols, meet the above objects. Indeed, it has been found that said short chain alkoxylated alcohols are particularly efficient in cleaning. Such short chain alkoxylated alcohols further meet the other objects of providing surfactants which are low foaming and which are mild to the skin. Another advantage is that such short chain alkoxylated alcohols are particularly suitable for formulating concentrated cleaning compositions.
  • EP 125 854 discloses a composition comprising 2.7% of C8EO4.8 together with 14.2% of ammonium C11.8 linear alkyl benzene sulphonate, 10.4 of ammonium C12-13 alkyl ethoxylated sulphate, 8.6% magnesium C12-13 alkyl sulphate, 4.0% coconut monoethanolamide and 9.1% ethanol and water. EP 125 854 however fails to draw the difference between long and short chain nonionic surfactants.
  • EP 496 188 discloses an aqueous solution comprising 3% of C8EO6 and 8% maleic acid. EP 486 188 does not draw the difference between long and short chain nonionic surfactants.
    • Summary of the invention
  • The present invention encompasses aqueous cleaning compositions comprising a short chain alkoxylated alcohol surfactant according to the formula RO(A)nH, wherein R is a C6 to C10 hydrocarbon chain, A is ethylene oxide or propylene oxide or mixtures thereof and n is of from 1 to 10, or mixtures thereof, and other conventional cleaning ingredients selected from anionic, cationic, zwitterionic and nonionic co-surfactants, including short chain co-surfactants, builders, solvents, bleaches and minors including dyes, perfumes, or mixtures thereof.
  • The present invention also encompasses such compositions in a concentrated form, the use of said surfactants for neat grease cleaning, for dilute grease cleaning and for soap scum cleaning. The present invention further encompasses the use of said surfactants as skin mild surfactants and as low foaming surfactants.
    • Detailed description of the invention
  • In a main embodiment, the present invention encompasses aqueous compositions which comprise conventional cleaning ingredients and a short chain alkoxylated alcohol surfactant.
  • The short chain nonionic surfactants for use herein are alkoxylated alcohols according to the formula RO(A)nH, wherein R is a C6 to C10 hydrocarbon chain and n, representing the average alkoxylation degree, is from 1 to 10, or mixtures thereof. R is indifferently straight or branched. A is ethylene oxide or propylene oxide or mixtures thereof. Similar nonionic surfactants which have longer R groups than those of the present invention are known in the art and are commonly used in cleaning compositions. The present invention is based on the finding that alkoxylated alcohols with shorter R groups provide better cleaning, as well as the multiple benefits described herein.
  • Suitable surfactants for use herein can be readily made by condensing alcohols having the desired chain length with propylene or ethylene oxide, or mixtures thereof, as disclosed in the art for alkoxylated alcohols with longer chains. Suitable short chain alkoxylated alcohols for use herein are also commercially available from several suppliers, for instance Dehydol 04 Ⓡ from Henkel (C8EO4), Mergital C4 Ⓡ from Sidobre (C8EO4), and Imbentin AG/810/050 and AG/810/080 Ⓡ from Kolb (respectively C8-10EO5 and C8-10EO8).
  • The compositions according to the present invention comprise from 0.1% to 50% by weight of the total composition of said short chain alkoxylated alcohols, preferably from 1% to 30%, most preferably from 1.5% to 20%.
  • The short chain alkoxylated alcohols herein are particularly suitable for the formulation of so-called concentrated cleaning compositions. Indeed, the short chain alkoxylated alcohols have a very high solubility in water, but they are also able to solubilize other conventional organic ingredients for cleaning compositions, such as perfumes. Thus, in an embodiment of the present invention, cleaning compositions are provided in a concentrated form, which only comprise from 1% to 80% by weight of the total composition of water, preferably from 30% to 70%. Such compositions typically comprise from 0.1% to 50% by weight of the total composition of said short chain alkoxylated alcohols, preferably from 5% to 30%.
  • Some of said short chain alcohol ethoxylates have been found to provide superior neat grease cleaning, compared to other alcohol ethoxylates with longer chains. Thus, in another embodiment, the present invention encompasses the use of said surfactants for neat grease cleaning. As used herein, neat grease cleaning means the cleaning of greasy soils, using an aqueous solution comprising at least one of the surfactants according to the present invention, within the ranges above. Greasy soils are typically found in kitchens or bathrooms.
  • For use in neat cleaning, and when R is in the higher range, i.e. 10, it is preferred to use lower ethoxylation degrees, typically 1 to 6. Preferred short chain alkoxylated alcohols for use in neat grease cleaning are those according to the formula hereinabove where R is a hydrocarbon chain from C6 to C8 and n is from 1 to 10. Preferred short chain alcohol ethoxylates for neat grease cleaning are the surfactants according to the formula above where R is a C6 hydrocarbon chain and n is 4 or 6 (C6EO4 and C6EO6); or R is a C8 hydrocarbon chain and n is 4 or 6 (C8EO4 and C8EO6); or R is a C8 hydrocarbon chain and n is 10 (C8EO10).
  • Some of the short chain alcohol ethoxylates herein have also been found to provide superior dilute grease cleaning, compared to solvents. Therefore, in a further embodiment, the present invention encompasses the use of said surfactants for dilute grease cleaning. As used herein, dilute grease cleaning means the cleaning of greasy soils using an aqueous solution comprising a surfactant according to the present invention, in the ranges described above, but which is diluted typically in 10 to 150 times its weight in water before it is used to clean the greasy soils. Dilute cleaning compositions and conditions have been described for instance in EP 503 219.
  • Suitable short chain alkoxylated alcohols for use in dilute grease cleaning are those according to the formula hereinabove where R a hydrocarbon chain from C8 to C10, and n is from 1 to 10. For dilute cleaning, it has been found that for a given R group, it is preferred to use higher ethoxylation degrees. Preferred short chain alkoxylated alcohols herein for dilute grease cleaning are those according to the formula herein above where R is a C8 hydrocarbon chain and n is of from 4 to 10, preferably 4, 6 or 10 (C8EO4, C8EO6, C8EO10), R is a C10 hydrocarbon and n ranges from 3 to 6 or n is 10 (C10EO3, C10EO4, C10EO5, C10EO6, C10EO10), as well as a mixture of surfactants where R is a C10 hydrocarbon and a C8 hydrocarbon and n is 5 (C8-10EO5), or n is 8 (C8-C10EO8).
  • Furthermore, some of the short chain alcohol ethoxylates herein have been found to be particularly efficient in cleaning soap scum, compared to other alkoxylated alcohols with longer chains. Accordingly, in a further embodiment, the present invention encompasses the use of said surfactants for cleaning soap scum. Soap scum, which is mainly found in bathroom is quite peculiar in its composition and traditionally leads detergent manufacturers to formulate specialty cleaning products for bathroom environment. The present invention is thus particularly applicable to the formulation of such specialty products.
  • Suitable short chain alkoxylated alcohols for use in cleaning soap scum are those wherein, in the formula hereinabove, R a hydrocarbon chain from C8 to C10, and n is from 1 to 10. When R is in the higher range, i.e. towards 10, it is preferred to use lower ethoxylation degrees, typically 1 to 6. Preferred alkoxylated alcohols for cleaning soap scum are those where, in the formula hereinabove, R is a C8 hydrocarbon chain and n is of from 4 to 10, preferably 4, 6 or 10 (C8EO4, C8EO6, C8EO10), R is a C10 hydrocarbon and n ranges from 3 to 6 (C10EO3, C10EO4, C10EO5, C10EO6), as well as a mixture of surfactants where R is a C10 hydrocarbon and a C8 hydrocarbon and n is 5 (C8-10EO5), or n is 8 (C8-C10EO8).
  • Furthermore, some of the short chain alcohol ethoxylates herein have been found to be of particular interest as they produce very limited sudsing or foaming compared to other alcohol ethoxylates. Accordingly, in a further embodiment, the present invention encompasses the use of said surfactants as low foaming surfactants. Low foaming surfactants are usually of interest for heavy duty laundry detergents, but also for hard surface cleaners which are designed to be used as no-rinse products in dilute form.
  • The surfactants within the present invention which have been found to produce low foaming are those according to the formula herein above where R is a C6 to C10 hydrocarbon chain and n is of from 1 to 10. Preferred low foaming surfactants herein are those where R is a C6 hydrocarbon chain and n is 4 or 6 (C6EO4, C6EO6); or R is a C8 hydrocarbon chain and n is 4, 6 or 10 (C8EO4, C8EO6, C8EO10), R is a C10 hydrocarbon and n ranges from 3 to 6 (C10EO3, C10EO4, C10EO5, C10EO6), as well as a mixture of surfactants where R is a C10 hydrocarbon and a C8 hydrocarbon and n is 5 (C8-10EO5), or n is 8 (C8-C10EO8); or mixtures thereof.
  • Furthermore, some of the short chain alcohol ethoxylates herein have been found to be of particular interest as they are particularly mild to the skin. Accordingly, the present invention encompasses the use of said surfactants as skin mild surfactants. Mildness to the skin is quite an advantage when formulating products which are bound to be in contact with the user's skin. Such is the case for dishwashing compositions, or hard surface cleaning compositions. Skin mildness benefits are usually advertised when they exist in a given product.
  • The surfactants within the present invention which have been found to be particularly mild to the skin are those according to the formula herein above where R is a C6 to C8 hydrocarbon chain and n is of from 1 to 10. Preferred surfactants are those where R is a C6 hydrocarbon chain and n is 4 or 6 (C6EO4, C6EO6), or R is a C8 hydrocarbon chain and n is 4, 6 or 10, or mixtures thereof (C8EO4, C8EO6, C8EO10).
  • The compositions according to the invention further comprise conventional ingredients selected from other nonionic, anionic, cationic and zwitterionic co-surfactants (from 0% to 30% by weight of the total composition, preferably from 1% to 20%), builders (from 0% to 20% by weight of the total composition, preferably from 1% to 10%), solvents (from 0% to 20% by weight of the total composition, preferably from 0% to 5%), non-hypochlorite bleaches (from 0% to 10% by weight of the total composition, preferably from 1% to 5%) and minors including dyes, perfumes, all of which are well known and extensively described in the art.
  • The exact formulation of the compositions according to the present invention depend on the end-use envisioned. Mixtures of the short chain surfactants according to the present invention can also be used in order to combine several benefits. Compositions according to the present invention can be formulated indifferently as alkaline and acidic hard surface cleaners, dishwashing products or laundry detergents.
  • The present invention will be further illustrated by the following examples.
    • Examples
  • The following compositions are made by mixing the listed ingredients in the listed proportions.
    Ingredients: Weight %
    1 2 3 4 5
    C8EO4 2.5 - 2.0 4.0 20
    C8EO10 - 4.0 - - -
    Lutensol AO30 Ⓡ - - - 2.0 20
    Lutensol AO7 Ⓡ - - - 1.0 -
    Na Paraffin Sulfonate - - - 3.0 -
    Fatty Acid - - - 0.4 -
    Citric Acid 5.5 5.5 3.0 2.0 3
    Triethanolamine 1.9 1.9 - 1.0 -
    MEA up to pH - - - - 7
    Ammonia up to pH 3.5 3.5 2.0 - -
    NaOH up to pH - - - 10.5 -
    Water and minors -----------up to 100% --------------
    Lutensol AO30 is C13-15(EO)30
    Lutensol AO7 is C13-15(EO)7
    MEA stands for monoethanolamine.
  • Compositions 1 and 2 hereinabove are particularly efficient in removing soapscum and are therefore particularly suitable as a bathroom cleaner. Composition 3 is particularly effective in providing low suds. Composition 4 is particularly effective on dilute and neat grease cleaning. Composition 5 is a concentrated composition.

Claims (12)

  1. An aqueous cleaning composition comprising a nonionic surfactant and conventional cleaning ingredients selected from anionic, cationic, zwitterionic and nonionic co-surfactants, builders, solvents, bleaches and minors including dyes, perfumes, or mixtures thereof, characterized in that said nonionic surfactant is a short chain alkoxylated alcohol according to the formula RO(A)nH, wherein R is a C6 to C10 hydrocarbon chain, A is ethylene oxide or propylene oxide, and n is from 1 to 10, or mixtures thereof, with the exclusion of compositions comprising 8% maleic acid and 3% of said short chain nonionic surfactant where R is C8 and n is 6, and with the exclusion of composition comprising 2.7% of said short chain surfactants wherein R is C8 and n is 4.8 and 14.2% of ammonium C11.8 linear alkyl benzene sulphonate and 10.4 of ammonium C12-13 alkyl ethoxylated sulphate and 8.6% magnesium C12-13 alkyl sulphate and 4.0% coconut monoethanolamide and 9.1% ethanol and water.
  2. A composition according to claim 1 which comprises from 0.1% to 50% by weight of the total composition, preferably from 1% to 30%, most preferably from 1.5% to 20% of said short chain alkoxylated alcohol, or mixtures thereof.
  3. A composition according to claims 1 and 2 which is in a concentrated form in that it comprises only from 30% to 70% by weight of the total composition of water, and from 5% to 30% by weight of the total composition of said short chain alkoxylated alcohol.
  4. The use of a short chain alkoxylated alcohol according to the formula RO(A)nH, wherein R is a C6 to C8 hydrocarbon chain, A is ethylene oxide or propylene oxide, and n is from 1 to 10, or mixtures thereof, for neat grease cleaning.
  5. The use of a short chain alkoxylated alcohol according to the formula RO(A)nH, wherein R is a C6 to C8 hydrocarbon chain and n is from 1 to 10, or mixtures thereof, as skin mild surfactants.
  6. A composition or use according to the preceding claims wherein in said formula, R is 6 and n is 4 or 6 (C6EO4 and C6EO6); or R is 8 and n is 4 or 6 or 10 (C8EO4, C8EO6 and C8EO10); or mixtures thereof.
  7. The use of a short chain alkoxylated alcohol according to the formula RO(A)nH, wherein R is a C6 to C10 hydrocarbon chain and n is from 1 to 10, or mixtures thereof, as low foaming surfactants.
  8. A composition according to claims 1-3 or use according to claim 7 wherein , in said formula, R is a C6 hydrocarbon chain and n is 4 or 6 (C6EO4, C6EO6); or R is a C8 hydrocarbon chain and n is 4, 6 or 10 (C8EO4, C8EO6, C8EO10), R is a C10 hydrocarbon and n ranges from 3 to 6 (C10EO3, C10EO4, C10EO5, C10EO6), as well as a mixture of surfactants where R is a C10 hydrocarbon and a C8 hydrocarbon and n is 5 (C8-10EO5), or n is 8 (C8-C10EO8); or mixtures thereof.
  9. The use of a short chain alkoxylated alcohol according to the formula RO(A)nH, wherein R a hydrocarbon chain from C8 to C10, A is ethylene oxide or propylene oxide and n is of from 1 to 10, or mixtures thereof, for dilute grease cleaning.
  10. A composition according to claims 1-3 or use according to claim 9 wherein in said formula, R is a C8 hydrocarbon chain and n is of from 4 to 10, preferably 4, 6 or 10 (C8EO4, C8EO6, C8EO10), R is a C10 hydrocarbon and n ranges from 3 to 6 or 10 (C10EO3, C10EO4, C10EO5, C10EO6, C10EO10), as well as a mixture of surfactants where R is a C10 hydrocarbon and a C8 hydrocarbon and n is 5 (C8-10EO5), or n is 8 (C8-C10EO8).
  11. The use of a short chain alkoxylated alcohol according to the formula RO(A)nH, wherein R is a hydrocarbon chain, A is ethylene oxide or propylene oxide and n is of from 1 to 10, or mixtures thereof, for soap scum cleaning.
  12. A composition according to claims 1-3 or use according to claim 11 wherein in said formula, R is a C8 hydrocarbon chain and n is of from 4 to 10, preferably 4, 6 or 10 (C8EO4, C8EO6, C8EO10), R is a C10 hydrocarbon and n ranges from 3 to 6 (C10EO3, C10EO4, C10EO5, C10EO6), as well as a mixture of surfactants where R is a C10 hydrocarbon and a C8 hydrocarbon and n is 5 (C8-10EO5), or n is 8 (C8-C10EO8).
EP93870050A 1992-11-26 1993-03-19 Cleaning compositions with short chain nonionic surfactants Withdrawn EP0616028A1 (en)

Priority Applications (55)

Application Number Priority Date Filing Date Title
EP93870050A EP0616028A1 (en) 1993-03-19 1993-03-19 Cleaning compositions with short chain nonionic surfactants
EP93870125A EP0616026A1 (en) 1993-03-19 1993-07-07 Concentrated cleaning compositions
EP93870181A EP0600847B2 (en) 1992-11-26 1993-08-31 Cleaning compositions with combined highly hydrophilic and highly hydrophobic nonionic surfactants
DE69321562T DE69321562T3 (en) 1992-11-26 1993-08-31 Detergent compositions with a combination of highly hydrophilic and highly hydrophobic nonionic surfactants
DK93870181T DK0600847T3 (en) 1992-11-26 1993-08-31 Purification Composition with Combined Highly Hydrophilic and Highly Hydrophobic Nonionic Surfactants
AT93870181T ATE172234T1 (en) 1992-11-26 1993-08-31 CLEANING AGENT COMPOSITIONS WITH A COMBINATION OF HIGHLY HYDROPHILIC AND HIGHLY HYDROPHOBIC NON-IONIC SURFACTANTS
ES93870181T ES2124778T5 (en) 1992-11-26 1993-08-31 CLEANING COMPOSITIONS WITH VERY HYDROPHILE AND VERY HYDROPHOBIC COMBINED NON-IONIC TENSIANS.
EP93870215A EP0616027A1 (en) 1993-03-19 1993-11-16 Concentrated cleaning compositions
TR01058/93A TR28413A (en) 1992-11-26 1993-11-16 Cleaning compositions with high-scale hydrophilic and high-scale hydrophobic nonionic surfactants.
JP6513290A JPH08505413A (en) 1992-11-26 1993-11-19 Cleaning composition combining high hydrophilicity and high hydrophobicity nonionic surfactant
NZ258466A NZ258466A (en) 1992-11-26 1993-11-19 Cleaning compositions comprising a non-ionic surfactant system containing a mixture of highly hydrophilic and highly hydrophobic non-ionic surfactants and at least one alkanolamine
US08/432,154 US5559091A (en) 1992-11-26 1993-11-19 Alkaline cleaning compositions with combined highly hydrophilic and highly hydrophobic nonionic surfactants
PCT/US1993/011293 WO1994012599A1 (en) 1992-11-26 1993-11-19 Cleaning compositions with combined highly hydrophilic and highly hydrophobic nonionic surfactants
CA002149227A CA2149227C (en) 1992-11-26 1993-11-19 Cleaning compositions with combined highly hydrophilic and highly hydrophobic nonionic surfactants
BR9307515-4A BR9307515A (en) 1992-11-26 1993-11-19 Cleaning compositions with highly hydrophilic and highly hydrophobic non-ionic surfactants combined
KR1019950702134A KR950704462A (en) 1992-11-26 1993-11-19 CLEANING COMPOSITIONS WITH COMBINED HIGHLY HYDROPHILIC AND HIGHLY HYDROPHOBIC NONIONIC SURFACTANTS
AU56149/94A AU681365B2 (en) 1992-11-26 1993-11-19 Cleaning compositions with combined highly hydrophilic and highly hydrophobic nonionic surfactants
EG73993A EG20373A (en) 1992-11-26 1993-11-24 Cleaning compositions with combined highly hydrophilic and highly hydrophobic monionic surfactants
MA23345A MA23039A1 (en) 1992-11-26 1993-11-25 CLEANING COMPOSITION WITH HIGHLY HYDROPHILIC AND HIGHLY HYDROPHOBIC NON-IONIC SURFACTANTS.
AU64074/94A AU695680B2 (en) 1993-03-19 1994-03-14 Concentrated cleaning compositions
CA 2158542 CA2158542A1 (en) 1993-03-19 1994-03-14 Concentrated cleaning compositions
BR9406015A BR9406015A (en) 1993-03-19 1994-03-14 Concentrated cleaning compositions
KR1019950703979A KR960701185A (en) 1993-03-19 1994-03-14 Cleaning compositions with short chain nonionic surfactants
NZ263930A NZ263930A (en) 1993-03-19 1994-03-14 Aqueous cleaning composition comprising short chain alkoxylated alcohols as nonionic surfactants
BR9406012A BR9406012A (en) 1993-03-19 1994-03-14 Cleaning compositions with short-chain nonionic surfactants
NZ26339494A NZ263394A (en) 1993-03-19 1994-03-14 Cleaning composition; stable, concentrated and clear composition comprising at least one short chain surfactant, the composition not being in the form of a microemulsion
US08/522,354 US5707948A (en) 1993-03-19 1994-03-14 Stable and clear concentrated cleaning compositions comprising at least one short chain surfactant
PCT/US1994/002748 WO1994021768A1 (en) 1993-03-19 1994-03-14 Concentrated cleaning compositions
AU64073/94A AU6407394A (en) 1993-03-19 1994-03-14 Concentrated cleaning compositions
CN94192051A CN1122612A (en) 1993-03-19 1994-03-14 Cleaning compositions with short chain nonionic surfactants
PCT/US1994/002746 WO1994021770A1 (en) 1993-03-19 1994-03-14 Cleaning compositions with short chain nonionic surfactants
JP6521160A JPH08508765A (en) 1993-03-19 1994-03-14 Concentrated cleaning composition
BR9406013A BR9406013A (en) 1993-03-19 1994-03-14 Concentrated cleaning compositions
PCT/US1994/002747 WO1994021767A1 (en) 1993-03-19 1994-03-14 Concentrated cleaning compositions
JP6521159A JPH08507825A (en) 1993-03-19 1994-03-14 Cleaning composition containing short-chain nonionic surfactant
NZ263393A NZ263393A (en) 1993-03-19 1994-03-14 Cleaning composition; stable, clear, concentrated composition comprising at least one long chain surfactant and stabilised by the additional presence of short chain surfactants
CN94192049A CN1044717C (en) 1993-03-19 1994-03-14 Concentrated cleaning compositions
CA002158541A CA2158541C (en) 1993-03-19 1994-03-14 Cleaning compositions with short chain nonionic surfactants
CA002158543A CA2158543C (en) 1993-03-19 1994-03-14 Concentrated cleaning compositions
AU65194/94A AU6519494A (en) 1993-03-19 1994-03-14 Cleaning compositions with short chain nonionic surfactants
US08/522,391 US5981455A (en) 1993-03-19 1994-03-14 Cleaning compositions with short chain nonionic surfactants
CN 94192052 CN1122611A (en) 1993-03-19 1994-03-14 Concentrated cleaning compositions
JP6521161A JPH08508766A (en) 1993-03-19 1994-03-14 Concentrated cleaning composition
MA23443A MA23136A1 (en) 1993-03-19 1994-03-16 CLEANING COMPOSITION COMPRISING SHORT CHAIN SURFACTANTS.
MA23446A MA23138A1 (en) 1993-03-19 1994-03-17 CONCENTRATED CLEANING COMPOSITIONS COMPRISING AT LEAST ONE SHORT ACHENED SURFACTANT
MA23445A MA23137A1 (en) 1993-03-19 1994-03-17 CONCENTRATED CLEANING COMPOSITION
FI952540A FI952540A (en) 1992-11-26 1995-05-24 Cleaning compositions with both highly hydrophilic and surface residual hydrophobic non-ionic surfactants
NO952058A NO952058L (en) 1992-11-26 1995-05-24 Purification mixtures with combined high hydrophilic and high hydrophobic nonionic surfactants
NO953503A NO953503L (en) 1993-03-19 1995-09-06 Concentrated cleaning mixtures
NO953502A NO953502D0 (en) 1993-03-19 1995-09-06 Purification mixtures with short-chain nonionic surfactants
NO953644A NO953644D0 (en) 1993-03-19 1995-09-15 Concentrated cleaning mixtures
FI954395A FI954395A (en) 1993-03-19 1995-09-18 Cleaning compositions containing short-chain non-ionic inactive substances
FI954397A FI954397A0 (en) 1993-03-19 1995-09-18 Concentrated cleaning compositions
FI954396A FI954396A (en) 1993-03-19 1995-09-18 Concentrated cleaning compositions
AU74176/98A AU7417698A (en) 1993-03-19 1998-07-06 Cleaning compositions with short chain nonionic surfactants

Applications Claiming Priority (1)

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EP93870050A EP0616028A1 (en) 1993-03-19 1993-03-19 Cleaning compositions with short chain nonionic surfactants

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EP (1) EP0616028A1 (en)
JP (1) JPH08507825A (en)
KR (1) KR960701185A (en)
CN (1) CN1122612A (en)
AU (2) AU6519494A (en)
BR (1) BR9406012A (en)
CA (1) CA2158541C (en)
FI (1) FI954395A (en)
MA (1) MA23136A1 (en)
NO (1) NO953502D0 (en)
NZ (1) NZ263930A (en)
WO (1) WO1994021770A1 (en)

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CN1122612A (en) 1996-05-15
BR9406012A (en) 1996-01-02
KR960701185A (en) 1996-02-24
CA2158541A1 (en) 1994-09-29
AU6519494A (en) 1994-10-11
NO953502L (en) 1995-09-06
FI954395A0 (en) 1995-09-18
WO1994021770A1 (en) 1994-09-29
AU7417698A (en) 1998-10-01
JPH08507825A (en) 1996-08-20
FI954395A (en) 1995-09-18
CA2158541C (en) 1999-05-18
NZ263930A (en) 1998-03-25
NO953502D0 (en) 1995-09-06
MA23136A1 (en) 1994-10-01

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