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WO2016055264A1 - Composition liquide de nettoyage de surface dure - Google Patents

Composition liquide de nettoyage de surface dure Download PDF

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Publication number
WO2016055264A1
WO2016055264A1 PCT/EP2015/071766 EP2015071766W WO2016055264A1 WO 2016055264 A1 WO2016055264 A1 WO 2016055264A1 EP 2015071766 W EP2015071766 W EP 2015071766W WO 2016055264 A1 WO2016055264 A1 WO 2016055264A1
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WO
WIPO (PCT)
Prior art keywords
weight
composition
cleaning
polymer
surfactant
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.)
Ceased
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PCT/EP2015/071766
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English (en)
Inventor
Patricia Revell
Stephen John Singleton
Jeremy Nicholas Winter
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.)
Unilever NV
Conopco Inc
Original Assignee
Unilever NV
Conopco Inc
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Filing date
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Publication of WO2016055264A1 publication Critical patent/WO2016055264A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D1/66—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
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions

Definitions

  • the present invention relates to a liquid hard surface cleaning composition comprising water, surfactant and a polymeric ingredient. Furthermore, the present invention relates to a method for cleaning a hard surface using such a liquid cleaning composition.
  • the liquid cleaning composition of the present invention may suitably be used to clean surfaces in e.g. kitchens and bathrooms (tiles, floors, cupboards, doors etc.).
  • the cleaning composition can also advantageously be used in hand dishwashing.
  • the liquid surface cleaning composition of the present invention is designed to provide a next time cleaning benefit.
  • compositions which comprise one or more surfactants and possibly also pH adjusters like citric acid or sodium salts of citrate.
  • Such compositions may further comprise additional components for targeting specific stains or soils.
  • the cleaning compositions can be applied in diluted (in water) or undiluted form, in a spray, or rubbed using a cloth and any other convenient way.
  • the cleaning composition may be rinsed from the surface after the cleaning. It would be
  • the hard surface to be cleaned could be treated with a material which would assist in easier removal of soil and/or stains during subsequent cleaning. This is referred to as the next time cleaning benefit.
  • Soils on hard surfaces can become more difficult to remove when not cleaned soon after deposition. When not cleaned promptly, soils can become more adherent to surfaces, more viscous and generally tougher, and require more effort to clean. While not being bound by theory, this more difficult removal of soils can arise from the effects of drying out of soils, from chemical changes in the soils, from reactions of soils with environmental agents such as oxygen, etc. Some soils are more susceptible than others to toughening reactions and processes. Soils comprising or containing chemically unsaturated oils and fat can become very tough and difficult to clean over time, especially when exposed to elevated temperatures. Even light can cause such fatty soils to toughen over time. As well as environmental factors, the processes of toughening of soils can be affected by the nature and composition of the surface on which the soil is located.
  • Hard surface cleaning compositions may be either acidic or alkaline. Acidic
  • compositions often contain citric acid, sorbic acid, acetic acid, formic acid, maleic acid, adipic acid, lactic acid, malic acid and glycolic acid.
  • Acidic cleaners are generally used for removing acid sensitive soil, such as limescale. For removal of fatty soil alkaline compositions are generally preferred.
  • WO 01/42415 describes liquid cleaning compositions comprising a polymeric material and a surfactant.
  • Example 1 describes an aqueous cleaning mousse comprising 2.5% (Dobanol 23 6.5EO), 2.0% 2-butoxy ethoxy ethanol, 4.0% tri-sodium citrate, 6% propellant, 0.5% poly(ethylene imine) (Lupasol PS), a few other minor ingredients, and water.
  • WO 02/018531 describes a method for cleaning hard surfaces, wherein the surface is treated with an antioxidant, followed by allowing the surface to become dirty, and subsequently cleaning the surface. The treatment of the surface with the antioxidant prior to the soiling, leads to easier removal of the soil during the subsequent cleaning step.
  • the antioxidant may be present in a cleaning composition, or in a rinse composition that is applied after the cleaning.
  • cleaning compositions comprising antioxidants, preferably at a concentration of 0.1-10 % by weight, are described. Tannic acid was exemplified to be notably efficient.
  • WO 2006/108475 describes a method for removing soil or stains from a hard surface, the method comprising the steps in sequence of treating the surface with a malonic acid derivative, allowing the soil or stain to deposit and cleaning the surface to remove the soil or stains.
  • Compositions and uses for said method are also described. The method and composition provide an improved next time cleaning benefit, allowing easier removal of stains and soils upon a subsequent cleaning step.
  • WO 2007/135645 describes a liquid detergent composition for grease cleaning from dish surfaces, said composition comprising (a) from 0.1 to 10 wt% of an alkoxylated poly(ethylene imine) polymer comprising a poly(ethylene imine) backbone having an weight-averaged molecular mass of from 400 to 1000 Da and the alkoxylated poly(ethylene imine) polymer further comprises (1 ) one or two alkoxylation
  • the pH is said to be preferably between 6 and 13.
  • Aqueous liquid detergent compositions are described comprising 2 wt% of Cn-alkyl ethoxylated surfactant with on average 9 ethylene oxide units, from 0.1 to 2 wt% of alkoxylated poly(ethylene imine).
  • WO 2007/054126 describes an aqueous composition comprising one or more amphoteric organic polynitrogen-compounds having at least 3 nitrogen atoms contained in the molecule in the form of an amine and/or amide and one or more types of inorganic nanoparticles.
  • Examples 1-5 describe compositions comprising about 93 wt % water, 0.33 wt.% surfactant and 0.5 wt% of an amphoteric polyamine comprising polyethyleneimine and polyacrylic acid, said compositions having a pH of about 10.
  • WO 2014/086577 describes a liquid hard surface cleaning composition comprising: ⁇ 10-85 wt.% of a liquid solvent;
  • the surfactant component preferably comprises at least 50 wt.% anionic surfactant, based on the total amount of surfactant.
  • the inventors have developed a highly stable water-based liquid surface cleaning composition that is easy to manufacture, easy to use and that provides excellent next- time-cleaning benefits.
  • the liquid surface cleaning composition of the present invention contains water, surfactant and at least one (co-)polymer with a high nitrogen content.
  • high nitrogen content (co-)polymers include polymers based on polyethylene imine or polyvinyl amine.
  • a first aspect of the present invention relates to a clear
  • homogeneous liquid hard surface cleaning composition comprising:
  • o 0.3 to 70% by weight of surfactant including at least 50% nonionic surfactant by weight of surfactant and less than 30% anionic surfactant by weight of surfactant; o 0.01 to 5% by weight of a (co-)polymer, said (co-)polymer containing at least 22 wt.% of nitrogen, where the wt.% nitrogen is calculated by weight of the (copolymer, excluding any counter ions;
  • composition has a pH-value in the range of from 6.5-12; and wherein the composition remains a homogeneous liquid when kept under ambient conditions for at least 4 weeks.
  • nonionic surfactant and a co(polymer) with a high nitrogen content enables the preparation of a clear, homogeneous cleaning composition that provides an improved next time cleaning benefit.
  • Another aspect of the invention relates to a method for cleaning a hard surface, said method comprising applying the aforementioned liquid cleaning composition onto the hard surface.
  • Yet another aspect of the invention concerns the use of such a liquid cleaning composition for cleaning a hard surface and obtaining a next time cleaning benefit for said surface.
  • the invention provides a clear, homogeneous liquid hard surface cleaning composition
  • a clear, homogeneous liquid hard surface cleaning composition comprising:
  • o 0.3 to 70% by weight of surfactant including at least 50% nonionic surfactant by weight of surfactant and less than 30% anionic surfactant by weight of surfactant; o 0.01 to 5% by weight of a (co-)polymer, said (co-)polymer containing at least 22 wt.% of nitrogen, where the wt.% nitrogen is calculated by weight of the (copolymer, excluding any counter ions;
  • composition has a pH-value in the range of from 6.5-12; and wherein the composition remains a homogeneous liquid when kept under ambient conditions for at least 4 weeks.
  • the liquid cleaning composition is essentially free from particles (such as abrasive particles) or precipitate that can form a haze or opacity.
  • the cleaning composition has a Light Transmittance at 450 nm of at least 87%, more preferably of at least 90%, wherein Light Transmittance is measured with the help of a UV/vis spectrophotometer, using disposable PMMA cells with a path length of 1 cm. The % transmittance is determined relative to a distilled water sample.
  • (co-)polymer refers to homopolymers, co-polymers and mixtures thereof.
  • the terms “comprising” and “containing” encompass the terms
  • soil and stain generally comprise all kinds of soils and stains generally encountered in the household, either of organic or inorganic origin, whether visible or invisible to the naked eye, including soiling solid debris and/or with bacteria or other pathogens.
  • next time cleaning benefit refers to an improved ease of removal of soil after re-soiling of a hard surface that has previously been cleaned with the liquid hard surface cleaning composition of the present invention.
  • This improved ease may be indicated by an increased amount of soil being removed from a hard surface using a certain fixed cleaning effort (e.g. the same no. of wiping actions using the same force per wiping action).
  • the improved ease of soil removal may also be indicated by the lower effort (e.g. less wiping actions, less force per wiping action or a combination thereof) necessary to reach a similar level of soil removal.
  • the improved ease of removal may also be indicated by a combination of the above- mentioned effects (i.e. increased amount of soil removed with less effort).
  • the (co-)polymer employed in accordance with the present invention can be a homopolymer, a copolymer or a mixture of two or more of these polymers.
  • co-polymer' refers to a polymer comprising two or more different repeating units, e.g. because the polymer was derived from two or more different monomeric species or because some proportion of the same repeating units are subsequently modified.
  • co-polymers encompassed by the present invention include alternating co-polymers, statistical co-polymers and block copolymers.
  • An alternating co-polymer has alternating monomer residues of different types, which means that the probability of finding one kind of monomer residue in the polymer next to one of its own species is close to zero.
  • a statistical co-polymer the sequence of monomer residues follows a statistical rule such that the probability of finding one species of monomer residue next to any other species of monomer residue is between 1 and zero, as governed by statistics that depends on the amounts and reactivity ratios of the co-monomers from which the polymer is grown.
  • An example of a statistical co-polymer is a random co-polymer.
  • Block co-polymers comprise two or more homopolymer subunits linked by covalent bonds such that the probability of finding one species of monomer residue next to one of its own kind is close to 1 .
  • Block copolymers with two or three distinct blocks are called diblock copolymers and triblock copolymers, respectively.
  • the (co-)polymer employed in the cleaning composition is a homopolymer. More preferably, the (co-)polymer is a linear or branched homopolymer.
  • the (co-)polymer is preferably present in the homogeneous liquid hard surface cleaning composition in a concentration of 0.015-2.0 wt.%, more preferably of 0.02-1 wt.% and most preferably 0.025-0.5 wt.%.
  • the (co-)polymer contained in the present cleaning composition is fully dissolved (at 20°C).
  • the (co-)polymer contained in the cleaning composition preferably has a weight- averaged molecular weight (M w ) of at least 3,000 g/mol, more preferably of at least 20,000 g/mol, most preferably of at least 60,000 g/mol.
  • the (co-)polymer contained in the cleaning composition according to the present invention may have any chain topology, i.e. it may be linear or cyclic, and it may have any type of branching, including but not limited to dendritic, hyperbranched, comb and/or graft, with branching factors ranging anywhere between 0 and 1.
  • the term 'branching factor' is intended to mean the total number of branch points in a chain divided by the total possible number of branch points.
  • the term 'hyperbranched' refers to branched topologies in which the branches are themselves branched and the term 'dendritic' refers to a topology in which all possible branching possibilities exist (i.e. the branching factor is 1 ).
  • the term 'graft' refers to a topology of co-polymers in which branching occurs only from a main chain and the chemical composition of the branches is distinct from that of the main chain.
  • a 'comb' co-polymer has a specific type of graft topology, i.e. a graft topology with regular branching in which only one branch is branched further.
  • the (co-)polymer is a branched (co-)polymer. More preferably, the (co-) polymer is a branched (co-)polymer with a branching factor of more than 0. According to a particularly preferred embodiment of the invention the (co-)polymer contains at least 22 wt.% of nitrogen, more preferably at least 26 wt.% of nitrogen and most preferably 30 wt.% of nitrogen, where the wt.% nitrogen is calculated by weight of the (co-)polymer, excluding any counter ions.
  • PEI Polyethylene imine
  • Lupamin 5095 (a polyvinyl amine co-polymer) 3 29.8
  • Examples of (co-)polymers that may be employed in accordance with the present invention include (co-)polymers based on polyethylene imine and/or polyvinyl amine. As is evident from the above table, the nitrogen content of these polymers can be very high. Derivatisation of these polymers reduces the overall nitrogen content of these polymers.
  • the (co-)polymer is based on polyethylene imine and contains at least 60%, preferably at least 70% and most preferably at least 80% of amine-containing repeating and terminating units, calculated on the total number of repeating and terminating units, said amine-containing units represented by formulas (la) and (lb) respectively:
  • A represents NR 1 or N + R 1 (R 2 );
  • R 1 and R 2 independently represent H, a substituent or a chemical bond that links the repeating unit to another repeating unit.
  • R 3 , R 4 and R 5 independently represent H or a substituent.
  • the substituent is preferably selected from C1-5 alkyl and C1-5 1-acylalkyl. More preferably the substituent is selected from C1-3 , even more preferably from methyl and ethyl. Most preferably, the substituent is methyl.
  • the (co-)polymer preferably is not an amphoteric polyethyleneimine that is obtained by reacting polyethylene imine with monoethylenically unsaturated carboxylic acids; salts, esters, amides or nitriles of monoethylenically unsaturated carboxylic acids;
  • the (co-)polymer is not an amphoteric organic polynitrogen compound that is obtainable from reacting: a) polyalkylene polyamines, polyamidoamines, ethyleneimine-grafted
  • the (co-)polymer is not an amphoteric poly(ethylene imine-acrylic acid).
  • At least 60%, more preferably at least 80% and most preferably at least 90% of the repeating units represented by formula (la) are repeating units wherein R 1 and R 2 represent H or a chemical bond that links the repeating unit to another repeating unit.
  • at least 60%, more preferably at least 80% and most preferably at least 90% of the terminating units represented by formula (lb) are repeating units wherein R 3 , R 4 and R 5 represent H.
  • An example of a polyethylene immine homopolymer that meets these criteria is Lupasol® PS (ex BASF).
  • the repeating units represented by formula (la) have a molar mass of not more than 100 g/mol, even more preferably of not more than 70 g/mol and most preferably of note more than 50 g/mol.
  • the terminating units represented by formula (lb) typically have a molar mass of more than 100 g/mol, even more preferably of not more than 70 g/mol and most preferably of note more than 50 g/mol.
  • the (co-)polymer is based on polyvinyl amine and contains at least 60%, preferably at least 70% and most preferably at least 80%, calculated on the total number of repeating units, of amine-containing repeating units represented by formula (II):
  • B represents NR 6 (R 7 ) or N + R 6 (R 7 )(R 8 );
  • R 6 , R 7 and R 8 independently represent H or a substituent.
  • the aforementioned substituent is preferably selected from C1-5 alkyl. More preferably the substituent is selected from C1-3 alkyl, even more preferably from methyl and ethyl. Most preferably, the substituent is methyl.
  • At least 60%, more preferably at least 80% and most preferably at least 90% of the repeating units represented by formula (II) are repeating units in which R 6 , R 7 and R 8 independently represent H.
  • An example of a polyvinyl amine that meets the latter criteria is Lupamin® 5095 (ex BASF).
  • the repeating units represented by formula (II) have a molar mass of not more than 100 g/mol, even more preferably of not more than 70 g/mol and most preferably of not more than 50 g/mol.
  • the homogeneous liquid hard surface cleaning composition of the invention comprises surfactant in an amount of 0.3 to 70 % by weight of the composition.
  • Nonionic surfactant represents at least 50 wt.% of the surfactant, whereas anionic surfactant represent less than 30 wt.% of the surfactant.
  • the cleaning composition may further comprise cationic, amphoteric and zwitterionic surfactants.
  • the total content of surfactant in the cleaning composition is at least 0.4%, more preferably at least 0.5%.
  • the maximum amount is usually less than 50%, preferably less than 40%, more preferably less than 30%, even more preferably not more than 20%, or even at or below 10%, by weight of the composition.
  • the present cleaning composition contains at least 0.1 wt.%, more preferably at least 1 wt.% and most preferably at least 2 wt.% of nonionic surfactant.
  • a suitable class of nonionic surfactants can be broadly described as compounds produced by the condensation of simple alkylene oxides, which are hydrophilic in nature, with an aliphatic or alkyl-aromatic hydrophobic compound having a reactive hydrogen atom.
  • the length of the hydrophilic or polyoxyalkylene chain which is attached to any particular hydrophobic group can be readily adjusted to yield a compound having the desired balance between hydrophilic and hydrophobic elements. This enables the choice of nonionic surfactants with the right HLB.
  • Particular examples include:
  • condensates of the reaction product of ethylene-diamine and propylene oxide with ethylene oxide the condensates containing from 40 to 80% of ethyleneoxy groups by weight and having a molecular weight of from 5,000 to 1 1 ,000.
  • the surfactant includes 2-25%, more preferably 3-15%, by weight of the composition of a condensation product of a linear or branched C8-C22 alcohol with ethylene oxide.
  • Preferred condensation products of linear or branched Cs- C22 alcohols with ethylene oxide have between 5 and 12 ethylene oxide units per alcohol group and a molecular weight between 300 and 650 g/mol.
  • the condensation products of a linear or branched C8-C22 alcohols with ethylene oxide and the (copolymer are preferably applied in the homogeneous liquid hard surface cleaning composition in a weight ratio that lies in the range of 1 :1 to 200:1 , more preferably in the range of 5:1 to 100:1 .
  • the cleaning composition contains a nonionic surfactant in the form of one or more tertiary amine oxides of structure R 1 R 2 R 3 N-0, where R 1 is an alkyl group of 8 to 20 carbon atoms and R 2 and R 3 are each alkyl or hydroxyalkyi groups of 1 to 3 carbon atoms.
  • a tertiary amine oxide is dimethyldodecylamine oxide.
  • the surfactant component of the cleaning composition includes 0.1-10% by weight, more preferably 0.2-5% by weight and most preferably 0.2-3% by weight of the composition of tertiary amine oxides of structure R 1 R 2 R 3 N-0.
  • the surfactant present in the cleaning composition of the invention includes an alkyl polyglycoside, more preferably an alkyl polyglucoside.
  • Alkyl polyglycosides are nonionic surfactants derived from sugars and fatty alcohols.
  • the surfactant includes 0.1 -10 % of alkyl polyglycosides, even more preferably 0.2-5 %, most preferably 0.2-3 %, by weight of the composition.
  • the alkyl polyglycoside employed in the cleaning composition preferably contains a C6- 22 fatty alcohol residue, more preferably a contains a Ce-ie fatty alcohol residue.
  • the sugar residue of the alkyl polyglycoside preferably comprises a linear oligo- or polysaccharide.
  • alkyl polyglycosides and the (co-)polymer are preferably applied in the
  • homogeneous liquid hard surface cleaning composition in a weight ratio that lies in the range of 1 : 1 to 100: 1 , more preferably in the range of 2: 1 -50: 1 .
  • nonionic surfactants that may be employed in accordance with the present invention are:
  • R 1 R 2 R 3 P-0 ⁇ tertiary phosphine oxides of structure R 1 R 2 R 3 P-0, where R 1 is an alkyl group of 8 to 20 carbon atoms and R 2 and R 3 are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for instance dimethyl-dodecylphosphine oxide;
  • dialkyl sulphoxides of structure R 1 R 2 S 0, where R 1 is an alkyl group of from 10 to 18 carbon atoms and R 2 is methyl or ethyl, for instance methyl-tetradecyl sulphoxide;
  • fatty acid alkylolamides such as the ethanol amides
  • the surfactant component of the present cleaning composition may include anionic surfactant, preferably in concentration that does not exceed 20 wt.% of the surfactant, more preferably in a concentration that does not exceed 10 wt.% of the surfactant, even more preferably in a concentration that does not exceed 5 wt.% of the surfactant. Most preferably, the cleaning composition does not contain anionic surfactant.
  • the liquid cleaning composition of the present invention typically contains not more than 5 wt.% anionic surfactant. Even more preferably, the cleaning composition contains not more than 3 wt.% anionic surfactant, most preferably not more than 1 wt.% anionic surfactant.
  • Suitable synthetic (non-soap) anionic surfactants that may be employed in the hard surface cleaning composition include water-soluble salts of organic sulphuric acid mono-esters and sulphonic acids which have in the molecular structure a branched or straight chain alkyl group containing from 6 to 22 carbon atoms in the alkyl part.
  • anionic surfactants water soluble salts of:
  • PAS primary alcohol sulphates
  • alkyl benzene sulphonates such as those in which the alkyl group contains from 6 to 20 carbon atoms (hereinafter referred to as LAS);
  • alkylglyceryl ether sulphates especially of the ethers of fatty alcohols derived from tallow and coconut oil;
  • alkylphenol ethylenoxy-ether sulphates with from 1 to 8 ethyleneoxy units per molecule and in which the alkyl groups contain from 4 to 14 carbon atoms;
  • the preferred water-soluble synthetic anionic surfactants are the alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of alkyl-benzenesulphonates and mixtures with olefinsulphonates and alkyl sulphates, and the fatty acid mono-glyceride sulphates.
  • alkyl-aromatic sulphonates such as alkylbenzenesulphonat.es containing from 6 to 20 carbon atoms in the alkyl group in a straight or branched chain, particular examples of which are sodium salts of alkylbenzenesulphonat.es or of alkyl-toluene-, -xylene- or -phenolsulphonates, alkylnaphthalene-sulphonates, ammonium diamylnaphthalene-sulphonate, and sodium dinonyl-naphthalene-sulphonate.
  • alkyl-aromatic sulphonates such as alkylbenzenesulphonat.es containing from 6 to 20 carbon atoms in the alkyl group in a straight or branched chain, particular examples of which are sodium salts of alkylbenzenesulphonat.es or of alkyl-toluene-, -xylene- or -phenols
  • the cleaning composition of the present invention may suitably contain amphoteric, cationic or zwitterionic surfactants.
  • Suitable amphoteric surfactants are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8 to 20 carbon atoms and an aliphatic group substituted by an anionic water-solubilising group, for instance sodium 3- dodecylamino-propionate, sodium 3-dodecylaminopropane-sulphonate and sodium N-2-hydroxy-dodecyl-N-methyltaurate.
  • Suitable cationic surfactants can be found among quaternary ammonium salts having one or two alkyl or aralkyi groups of from 8 to 20 carbon atoms and two or three small aliphatic (e.g. methyl) groups, for instance cetyltrimethylammonium chloride.
  • a specific group of surfactants are the tertiary amines obtained by condensation of ethylene and/or propylene oxide with long chain aliphatic amines.
  • the compounds behave like nonionic surfactants in alkaline medium and like cationic surfactants in acid medium.
  • Suitable zwitterionic surfactants can be found among derivatives of aliphatic quaternary ammonium, sulphonium and phosphonium compounds having an aliphatic group of from 8 to 18 carbon atoms and an aliphatic group substituted by an anionic water-solubilising group, for instance betaine and betaine derivatives such as alkyl betaine, in particular C12-C16 alkyl betaine, 3-(N,N-dimethyl-N- hexadecylammonium)-propane-1 -sulphonate betaine, 3-(dodecylmethyl-sulphonium)- propane-1-sulphonate betaine, 3-(cetylmethyl-phosphonium)-propane-1 -sulphonate betaine and N,N-dimethyl-N-dodecyl-glycine.
  • betaines are the alkylamidopropyl betaines e.g. those wherein the alkylamido group is derived
  • surfactants are compounds commonly used as surface- active agents given in the well-known textbooks: 'Surface Active Agents' Vol.1 , by
  • the liquid hard surface cleaning composition of the present invention typically contains 29.9-99.5 wt.% water. More preferably, the water content of the cleaning composition is in the range of 60-97.5 wt.%, most preferably in the range of 40-95 wt.%.
  • the liquid hard surface cleaning composition according to the invention is a shelf- stable homogeneous liquid composition.
  • the homogeneous liquid hard surface cleaning composition remains a homogenous liquid when kept under ambient conditions for at least 4 weeks, more preferably for at least 2 months, even more preferably for at least 6 months. This means that within said period no significant phase separation occurs when the cleaning composition is kept in closed container under ambient conditions.
  • the term 'kept under ambient conditions' as used herein refers to a temperature of 20°C and atmospheric pressure.
  • the cleaning composition shows less than 5 vol.%, more preferably less than 1 vol.% and most preferably less than 0.5 vol.% phase separation when the composition is kept under ambient conditions for at least 4 weeks, or even for at least 2 months.
  • the vol.% phase separation is calculated by determining the volume of the cleaning composition that has phase separated from the bulk (as sediment and/or top layer) and by expressing this volume as a percentage of the total volume of the composition.
  • the cleaning composition of the invention has a pH-value of from 6.5 to 12. More preferably, the composition has a pH in the range of 7.5 to 1 1.5, even more preferably in the range of 8.0 to 1 1 .4.
  • the pH of the cleaning composition used in the method of the invention may be adjusted with organic or inorganic acids or bases.
  • Preferred inorganic bases are preferably alkali or alkaline earth hydroxides, ammonia, carbonates or bicarbonates, the alkali metal preferably being sodium or potassium or the alkaline earth metal preferably being calcium or magnesium.
  • the organic bases are preferably amines, alkanolamines and other suitable amino compounds.
  • Inorganic acids may include hydrochloric acid, sulphuric acid or phosphoric acid, and organic acids may include acetic acid, citric acid or formic acid as well as dicarboxylic acid mixtures such as Radimix (trade mark, Radici Group) and Sokalan DCS (trade mark, BASF).
  • the homogeneous liquid hard surface cleaning composition may comprise 0-40% by weight, preferably 0-30 % by weight and most preferably 0.2-20% by weight of the composition of other components, i.e. components other than surfactant, the (copolymer and water.
  • the cleaning composition of the present invention may include abrasives. However, these are generally not preferred as abrasives tend to damage or remove the thin layer being deposited on the surface when carrying out the method of the invention. In a preferred embodiment the composition of the present invention does not contain an abrasive.
  • the composition may contain other ingredients which aid in its cleaning performance.
  • the builder may contain detergent builders and mixtures of builders in an amount of up to 25%, in particular when the composition contains one or more anionic surfactants If present, the builder preferably will form at least 0.1 % of the cleaning composition. Suitable inorganic and organic builders are well known to those skilled in the art.
  • a further optional ingredient of the composition of the invention is a suds regulating material, which can be employed in compositions which have a tendency to produce excessive suds in use. Examples thereof are fatty acids or their salts (soap), isoparaffins, silicone oils and combinations thereof.
  • Soaps are salts of fatty acids and include alkali metal soaps such as the sodium, potassium and ammonium salts of fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 10 to about 20 carbon atoms. Particularly useful are the sodium and potassium and mono-, di- and triethanolamine salts of the mixtures of fatty acids derived from palm oil, coconut oil and ground nut oil. When employed, the amount of fatty acid or soap can form at least 0.005%, preferably 0.05% to 2% by weight of the composition.
  • hydrocarbon solvent is present at a sufficiently high level this may itself provide some or all of the required antifoaming activity.
  • Compositions may also contain, in addition to the ingredients already mentioned, various other optional ingredients such as colourants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents (particularly peroxide compounds and active chlorine releasing compounds), solvents, co-solvents, gel-control agents, further freeze-thaw stabilisers, bactericides, preservatives (for example l ⁇ -benziso-'thiazolin-S-one), hydrotropes and perfumes.
  • various other optional ingredients such as colourants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents (particularly peroxide compounds and active chlorine releasing compounds), solvents, co-solvents, gel-control agents, further freeze-thaw stabilisers, bactericides, preservatives (for example l ⁇ -benziso-'thiazolin-S-one), hydrotropes and perfumes.
  • the composition of the present invention does not comprise tannic acid or related compounds such as gallic acid and/or propyl gallate. It was found that when tannic acid is formulated into alkaline liquid cleaning compositions it produces aesthetically less-pleasing yellow-brown coloured solutions, and it may lead to browning of cement in joints between tiles.
  • the composition of the present invention does not comprise malonic acid. An antioxidant like malonic acid needs relatively high concentrations to achieve a next time cleaning benefit. Moreover consumers may regard residues of malonic acid on the hard surfaces in e.g. kitchen and bathroom to be harmful and undesired.
  • composition of the present invention does not comprise formic acid.
  • Formic acid has a pungent odour, and residues on hard surfaces are aesthetically undesirable.
  • the liquid cleaning composition of the present invention preferably has a relatively low viscosity that allows the composition to be readily poured from a e.g. bottle or even to be spayed through a nozzle.
  • the cleaning composition has a viscosity of less than 100 mPa.s, more preferably of less than 80 mPa.s, and most preferably of less than 60 mPa.s at 25°C and 21 s "1 .
  • Viscosity of the cleaning composition can suitably be determined by using an Anton Paar ASC rheometer fitted with a smooth cup and bob measuring system, thermostatted at 25°C. Liquid dispensers
  • the aqueous cleaning composition of the present invention may be stored in and dispensed by any suitable means, but spray applicators are particularly preferred. Pump dispensers (whether spray or non-spray pumps) and pouring applicators (bottles etc) are also possible.
  • the second aspect of the invention provides the use of an aqueous cleaning composition according to the invention, wherein said composition is comprised in a container, and wherein the container further comprises a spray dispenser for dispensing said composition in the form of a spray.
  • the spray dispenser is preferably a trigger spray but may be any mechanical means for ejecting the liquid in spray or aerosol form.
  • Another aspect of the invention relates to a concentrate for preparing a homogeneous liquid hard surface cleaning composition, wherein dilution of 1 part by weight of the concentrate with 2 to 50 parts by weight of water yields a liquid hard surface cleaning composition as defined herein before. More preferably, 1 part of the concentrate can be diluted with 2.5 to 30 parts by weight of water, most preferably 3 to 15 parts by weight of water to yield the aforementioned liquid cleaning composition.
  • the concentrate of the present invention may suitably be diluted with water to prepare a homogeneous ready-to-use cleaning composition that remains homogeneous for at least 4 weeks when kept under ambient conditions.
  • the concentrate of the present invention can be liquid, a paste, a gel or a solid (e.g a powder).
  • the concentrate is a liquid.
  • the concentrate of the present invention typically comprises:
  • a method for cleaning a hard surface preferably a metal surface, the method comprising applying to the surface a
  • the cleaning composition is applied to the surface of an immobile hard surface, such as a wall, a floor, a worktop, a stove, a bath or a lavatory.
  • Yet another aspect of the invention relates to a method of hand washing dishes, the method comprising either combining the homogeneous liquid cleaning composition with water to produce a cleaning liquid and using this cleaning liquid to wash dishes by hand, or alternatively applying the liquid cleaning composition directly onto the dishes to be washed or onto the implement eg cloth or sponge being used to clean the dishes
  • the invention also relates to the use of the homogeneous liquid cleaning composition for cleaning a hard surface (including dishes) and obtaining a next time cleaning benefit for said surface.
  • the use of the cleaning composition comprises the following sequential steps:
  • the cleaning step (c) cleaning the surface to remove said soil or stains.
  • the cleaning step (c) may employ an aqueous cleaning composition according to the present invention or it may employ a different cleaning composition.
  • the surface to be cleaned in step (c) comprises deposits of soil or stain containing fatty material, which has undergone a toughening reaction.
  • the soil or stain experiences toughening reactions and processes after having been deposited on the surface, and therewith requires more effort to clean.
  • toughening can arise from the effects of drying out of soils, from chemical changes in soils, from reactions of soils with environmental agents such as oxygen, etc. Some soils are more susceptible than others to toughening reactions and processes. Soils comprising or containing chemically unsaturated oils and fats can become very tough and difficult to clean over time, especially when exposed to elevated temperatures.
  • DHCO toughened dehydrated castor oil
  • Treatments are evaluated on 10.0 x 10.0 cm pieces of 304 grade brushed stainless steel. Test pieces are previously unused, and are pre-cleaned prior to use. Pre-cleaning of Stainless Steel Test Surfaces
  • Test pieces are soaked for at least 1 hour in -17 % by weight potassium hydroxide in 50/50 % by weight aqueous ethanol to remove any surface contamination from the metal-working process, which might influence wetting of the surface by the test treatment or DHCO soil. After soaking, surfaces are thoroughly rinsed in running (demineralised)water and allowed to dry naturally in air, stored vertically.
  • the stainless steel tile is pre-weighed (to 4 decimal places). A 5.0 x 5.0 cm area in the centre of the stainless steel surface is marked out by a square of adhesive masking tape. 0.010 - 0.015 ml of test solution is applied to the central 25cm 2 area of surface and distributed uniformly over the area using a glass spreader. The treatment is allowed to dry naturally. Soiling of Surfaces
  • DHCO 0.040 gram (+1-4 mg) of DHCO (John L Seaton & Co, Humberside, UK) is applied to the central templated area of the treated surface and distributed over the 25cm 2 area of surface using a purpose-made spreader, to produce an even film of oil.
  • the masking tape template is carefully removed and the soiled tile is reweighed.
  • test surfaces are heated in an oven at 100°C for 60 minutes. Test surfaces are allowed to cool and equilibrate for at least 1 hour. The test surface is reweighed and the weight of aged oil (W initial) calculated.
  • Cleaning is carried out in a Martindale Abrasion Tester apparatus (SDL International) over one full lissajous figure (16 cycles) using a 1.5 cm diameter circle of non-woven cleaning cloth ('Ballerina', supplied by J. Dittrich & Sohne Vliesstoftechnik GmbH) attached to the cleaning head. By each full lissajous figure, the entire surface of the tile is cleaned once.
  • the head has a total mass of 994 gram, applying a cleaning force of about 560 gram/cm 2 to the soiled test surface.
  • Cleaning is carried out using a simple detergent base (e.g. 5.0% in water of Neodol 91 -8 (an ethoxylated alcohol nonionic surfactant), adjusted to the required pH with sodium hydroxide or hydrochloric acid, as necessary).
  • the soiled tile is fixed centrally in the abrasion tester's sample well and 20.0 gram cleaning product is introduced. Immediately, the cleaning head is secured in place and the Abrasion Tester apparatus run for one full lissajous figure. The cleaned tile is removed and rinsed free from cleaning product and any loose soil under a running tap. The surface is allowed to dry, stored vertically, and then reweighed. The weight of any remaining DHCO soil (Wfi na i) is calculated.
  • W initial weight of initial DHCO, before cleaning
  • W final weight of residual DHCO, after cleaning
  • test formulations were prepared having varying pH-values and compositions. The pH-value of these formulations was adjusted using sodium hydroxide solution or hydrochloric acid solution as appropriate. These test formulations were aqueous formulations containing 1 %wt of Glucopon 425 N/HH (Alkylpolyglucoside ex Cognis) and optionally 0.5%wt of a polymer (Lupasol PS ex BASF).
  • test formulations were used to treat stainless steel tiles whereby the test method described above was applied.
  • the cleaning formulation used for cleaning the re-soiled surface in the Abrasion Tester Apparatus was an aqueous solution containing 5% Neodol 91.8 at its natural pH.
  • the various test formulations have the following compositions:
  • Lupasol PS 0.5 0.5 0.0 0.0 0.5 0.5 pH-value 5.0 7.0 5.0 7.0 2.5 4.0
  • Glucopon 425 N/HH alkylpolyglucoside, ex Cognis
  • Lupasol PS hyperbranched polyethyleneimine (PEI) Average molecular weight:
  • test formulations were aqueous formulations having the following compositions:
  • Neodol 91 -5 and Neodol 91 -8 ethoxylated alcohols, ex Shell Chemicals; Lupamin 5095: a polymer based on vinyl amine and N-vinyl formamide, wt% N: 30.52, ex BASF.
  • test formulations had following compositions:
  • pH-value 7 1 1.4 7 1 1 .4 wherein: PMPEI is a branched permethylated polyethyleneimine, wt% N: >22 ex Polysciences. It is derived from MW 1800 branched poly(ethyleneimine) which has been permethylated with methyl bromine.
  • polyethyleneimine is also a suitable polymer for use in the cleaning composition of the present invention.
  • Test formulations were prepared having the following compositions:
  • Lupasols are polyethyleneimine homopolymers from BASF, wt% N: 32.51 ;
  • Epomin P-1050 is a polyethyleneimine homopolymer from Nippon Shokubi, wt% N 32.51. These test formulations were used for treating pre-cleaned stainless steel tiles whereby a test method similar to the above-described test method as used for examples 1 and 2, was applied. The difference is that after treatment of the stainless steel substrates with a test formulation, said substrates were allowed to dry and subsequently the surface thereof was rinsed using cold water delivered from a shower head operating at a flow rate of 6L/minute for duration of 2 seconds. During this rinsing step, the distance between the shower head and the surface of the stainless steel substrates was approximately 0.5 m. After rinsing, said substrates were left to drain dry before soiling, oxidative toughening of the DHCO and cleaning in accordance with the test method used for examples 1 and 2.
  • test formulations were prepared and their pH was adjusted at a value of 7 using sodium hydroxide or hydrochloric acid as appropriate.
  • test formulations were aqueous formulations containing 1 %wt of Glucopon 425 N/HH (Alkylpolyglycoside ex Cognis) and optionally 0.5 %wt of a polymer (Lupasol PS, wt% N: 32.51 , ex BASF).
  • the compositions of the test formulations are shown in the following table:
  • test formulations were used to pre-treat stainless steel tiles as described above.
  • the cleaning formulation used for cleaning the re-soiled surface in the Abrasion Tester Apparatus was an aqueous solution containing 5% Glucopon 425 N/HH and having a pH of 7.
  • test formulations were prepared and their pH adjusted. These test formulations were aqueous formulations containing 1 %wt of glucopon 425 N/HH and optionally Poly(ethyleneimine) linear 250 k, wt% N: 29.44, ex Polysciences, code 24314-2. The compositions of the test formulations are shown in the following table:
  • test formulations were used to pre-treat stainless steel tiles as described above.
  • the cleaning formulation used for cleaning the re-soiled surface in the Abrasion Tester Apparatus was an aqueous solution containing 5% Neodol 91-8 and having a pH of 7. The following results were obtained for these test formulations:
  • aqueous test formulations containing 1 wt% of Glucopon 425N/HH (Alkylpolyglucoside ex Cognis) and optionally 0.5 wt% of Lupasol PS (polyethylene imine, wt% N: 32.51 ) were prepared.
  • the pH of these formulations was adjusted to pH 7 using sodium hydroxide or hydrochloric acid as appropriate.
  • the compositions of the test formulations are shown in the following table:
  • the cleaning solution used for cleaning the re-soiled surface in the Abrasion Tester Apparatus is an aqueous solution containing 5% Neodol 91 -8 and having natural pH.
  • test formulations were prepared and their pH-value adjusted as required with either HCI or NaOH solution.
  • test formulations had the following compositions:
  • Sokalan HP20 is an ethoxylated polyethyleneimine (EPEI) with a molecular weight of about 14,000, wt% N: 18.19, ex BASF
  • EPEI ethoxylated polyethyleneimine
  • Lupasol G100 is a polyethyleneimine homopolymer with a molecular weight of about 5,000, wt% N: 32.51 , ex BASF
  • Lupsol HF is a polyethyleneimine homopolymer with a molecular weight of about 25,000, wt% N: 32.51 , ex BASF
  • test formulations were prepared and their pH-value adjusted as required with either HCI or NaOH solution.
  • test formulations had the following compositions:
  • Ammonyx DO is an aqueous solution of decylamine oxide manufactured by
  • Sokalan HP70 is an amphoteric poly(ethyleneimine-acrylic acid) copolymer
  • Lupasol SC-61 B is an ethoxylated water soluble polyethylenimine formed by reaction of a relatively high molecular weight polyethylenimine with ethylene oxide available commercially from BASF, wt% N: 19.18. These test formulations were used for treating pre-cleaned stainless steel tiles whereby a test method similar to the above-described test method as used for example 1 was applied. The difference being that after treatment of the stainless steel substrates with a test formulation, said substrates were allowed to dry and subsequently the surface thereof was rinsed using cold water delivered from a shower head operating at a flow rate of 6L/minute for duration of 2 seconds.
  • the distance between the shower head and the surface of the stainless steel substrates was approximately 0.5 m. After rinsing, said substrates were left to drain dry before soiling, oxidative toughening of the DHCO and cleaning in accordance with the test method used in example 1 .
  • test formulations were used for treating pre-cleaned stainless steel tiles whereby a test method similar to the test method as used for example 27 was applied. The difference being that the application volume of oil was reduced to 0.02g and the baking conditions changed to 80 minutes at 100°C. After baking the tiles were allowed to cool for at least an hour before cleaning on the Martindale abrasion tester. The % soil removal, determined gravimetrically, is as shown in the table below.
  • Example 21 comparative example and Q
  • the formulation was made without calcite abrasive.
  • the formulation of the test sample is described in the following table.

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Abstract

L'invention concerne une composition liquide homogène limpide de nettoyage de surface dure comprenant : de 0,3 à 70% en poids de tensioactif, dont au moins 50% de tensio-actif non ionique en poids de tensioactif et moins de 30% d'un tensioactif anionique en poids de tensioactif ; de 0,01 à 5% en poids d'un (co-)polymère, ledit (co-)polymère contenant au moins 22% d'azote, où le % en poids de l'azote est calculé en poids du (co-)polymère, à l'exclusion de tous contre-ions ; de 29,9 à 99,5% en poids d'eau ; et de 0 à 40% en poids d'autres constituants ; où la composition a une valeur de pH comprise entre 6,5 et 12 ; et où la composition reste un liquide homogène lorsqu'elle est maintenue sous des conditions ambiantes durant au moins 4 semaines. Cette composition liquide de nettoyage des surfaces est facile à fabriquer, facile à utiliser et assure d'excellents avantages pour le prochain nettoyage. L'invention concerne également un concentré qui peut être utilisé pour préparer la composition de nettoyage de surface dure susmentionnée par dilution du concentré dans de l'eau.
PCT/EP2015/071766 2014-10-09 2015-09-22 Composition liquide de nettoyage de surface dure Ceased WO2016055264A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10676621B2 (en) 2016-03-04 2020-06-09 S. C. Johnson & Son, Inc. Multi-purpose floor finish composition
US20240060736A1 (en) * 2021-02-24 2024-02-22 Vgp Ipco Llc Foaming evaporator coil cleaner

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0911022A1 (fr) * 1997-09-26 1999-04-28 Unilever N.V. Compositions de nettoyage antibactériennes ultradouces pour usage fréquent
WO2001042415A1 (fr) * 1999-12-08 2001-06-14 Unilever N.V. Utilisation de matiere polymere dans le traitement de surfaces dures
US20080132437A1 (en) * 2006-12-05 2008-06-05 The Procter & Gamble Company Fabric care compositions for softening, static control and fragrance benefits
EP2420557A1 (fr) * 2010-08-17 2012-02-22 The Procter & Gamble Company Procédé pour laver la vaisselle à la main avec une mousse de longue durée
WO2014086577A1 (fr) * 2012-12-04 2014-06-12 Unilever N.V. Composition de nettoyage de surface dure

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0911022A1 (fr) * 1997-09-26 1999-04-28 Unilever N.V. Compositions de nettoyage antibactériennes ultradouces pour usage fréquent
WO2001042415A1 (fr) * 1999-12-08 2001-06-14 Unilever N.V. Utilisation de matiere polymere dans le traitement de surfaces dures
US20080132437A1 (en) * 2006-12-05 2008-06-05 The Procter & Gamble Company Fabric care compositions for softening, static control and fragrance benefits
EP2420557A1 (fr) * 2010-08-17 2012-02-22 The Procter & Gamble Company Procédé pour laver la vaisselle à la main avec une mousse de longue durée
WO2014086577A1 (fr) * 2012-12-04 2014-06-12 Unilever N.V. Composition de nettoyage de surface dure

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10676621B2 (en) 2016-03-04 2020-06-09 S. C. Johnson & Son, Inc. Multi-purpose floor finish composition
US11214697B2 (en) 2016-03-04 2022-01-04 S. C. Johnson & Son, Inc. Multi-purpose floor finish composition
US20240060736A1 (en) * 2021-02-24 2024-02-22 Vgp Ipco Llc Foaming evaporator coil cleaner

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