WO2013056901A1 - Cleansing composition - Google Patents

Cleansing composition Download PDF

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Publication number
WO2013056901A1
WO2013056901A1 PCT/EP2012/067839 EP2012067839W WO2013056901A1 WO 2013056901 A1 WO2013056901 A1 WO 2013056901A1 EP 2012067839 W EP2012067839 W EP 2012067839W WO 2013056901 A1 WO2013056901 A1 WO 2013056901A1
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WO
WIPO (PCT)
Prior art keywords
acid
antagonistic
composition according
composition
synergy
Prior art date
Application number
PCT/EP2012/067839
Other languages
French (fr)
Inventor
Stephen John BENNETT
Sarah Louise Hosking
Andrew Stephen Jamieson
Katharine Jane SHAW
Original Assignee
Unilever N.V.
Unilever Plc
Hindustan Unilever Limited
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 Unilever N.V., Unilever Plc, Hindustan Unilever Limited filed Critical Unilever N.V.
Priority to MYPI2014700936A priority Critical patent/MY185985A/en
Priority to BR112014007238A priority patent/BR112014007238A2/en
Priority to EA201400480A priority patent/EA023774B1/en
Priority to CA2851198A priority patent/CA2851198A1/en
Priority to AU2012325190A priority patent/AU2012325190B2/en
Priority to PL12756522T priority patent/PL2771448T3/en
Priority to CN201280050910.XA priority patent/CN103874757A/en
Priority to EP12756522.4A priority patent/EP2771448B1/en
Publication of WO2013056901A1 publication Critical patent/WO2013056901A1/en
Priority to ZA2014/01847A priority patent/ZA201401847B/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2079Monocarboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2082Polycarboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2086Hydroxy carboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2089Ether acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines

Definitions

  • the present invention relates to an anti-bacterial cleansing composition.
  • an anti-bacterial cleansing composition Despite the prior art there remains a need for improved anti-bacterial cleansing compositions.
  • compositions which are able to cleanse hard surfaces.
  • the present invention relates to an antibacterial cleansing
  • composition comprising an antibacterial component which comprises one selected from each of the following two groups:
  • B pyruvic, acetic, isobutyric, proprionic, alpha-ketoglutaric and levulinic acids, wherein A is present at from 40-90% weight of the antibacterial component and B is present at from 10 to 60% by weight of the antibacterial component.
  • the antibacterial component comprises two members from A.
  • the member selected from B is pyruvic acid.
  • the member selected from A is gentisic acid or salicylic acid.
  • the two members selected from A are gentisic acid and salicylic acid.
  • the antibacterial component comprises gentisic acid, pyruvic acid and salicylic acid.
  • the antibacterial component comprises from 40 to 90% wt pyruvic acid; from 5 to 55% wt. gentisic acid and from 5 to 55% wt. salicylic acid.
  • Such compositions are shown by the inventors to have high activity against both enterococcus hirae and staphylococcus aureus.
  • the antibacterial component comprises from 0.001 to 5% wt. of the composition.
  • the composition comprises a cleansing surfactant.
  • the composition is a hard surface cleaning composition.
  • the composition is a toilet block composition.
  • the composition is a toilet cleaning composition
  • the cleaning composition used according to the invention comprises additionally a detergent surfactant at a concentration between 0 and 50% by weight.
  • Said surfactant is generally chosen from anionic and nonionic detergent actives.
  • the cleaning composition may further comprise cationic, amphoteric and zwitterionic surfactants.
  • the total amount of surfactant in said cleaning composition is at least 0.1 %, more preferably at least 0.5%.
  • the maximum amount is usually less than 30%, more preferably not more than 20%, or even at or below 10%, by weight.
  • Suitable synthetic (non-soap) anionic surfactants are 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;
  • alkylglyceryl ether sulphates especially of the ethers of fatty alcohols
  • 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 alkylbenzenesulphonates 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 alkylbenzenesulphonates or of alkyl-toluene-, -xylene- or -phenolsulphonates, alkylnaphthalene-sulphonates, ammonium diamylnaphthalene-sulphonate, and sodium dinonyl-naphthalene-sulphonate.
  • alkyl-aromatic sulphonates such as alkylbenzenesulphonates 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 alkylbenzenesulphonates or of alkyl-toluene-, -xylene- or -phenolsulphonates, alkylnaphthalene
  • the amount present in the cleaning compositions of the invention will generally be at least 0.1 %, preferably at least 0.5%, more preferably at least 1 .0%, but not more than 20%, preferably at most 15%, more preferably at most 10%.
  • 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:
  • nonionic surfactants are:
  • R 1 R 2 R 3 N-O • tertiary amine oxides of structure R 1 R 2 R 3 N-O, 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, e.g. dimethyldodecylamine oxide;
  • R 1 R 2 R 3 P-O ⁇ tertiary phosphine oxides of structure R 1 R 2 R 3 P-O, 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 O, 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 concentration of the nonionic surfactant other than APG to be employed in said cleaning composition of the invention will preferably be at least 0.1 %, more preferably at least 0.5%, most preferably at least 1 %.
  • the amount is suitably at most 20%, preferably not more than 15% and most preferably not more than 10%.
  • amphoteric, cationic or zwitterionic surfactants in said compositions.
  • 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 aralkyl 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-l -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 alkylamid
  • surfactants are compounds commonly used as surface-active agents given in the well-known textbooks: 'Surface Active Agents' Vol.1 , by Schwartz & Perry, Interscience 1949; 'Surface Active Agents' Vol.2 by Schwartz, Perry & Berch, Interscience 1958; the current edition of 'McCutcheon's Emulsifiers and Detergents' published by Manufacturing Confectioners Company; Tenside-Taschenbuch', H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 .
  • the composition according to the invention has a pH of from 2 to 13, more preferably at least 3, and not more than 12.
  • Cleaning methods of the invention intended for cleaning kitchen hard surfaces may advantageously be carried out at a pH in the alkaline range.
  • the method of the invention is carried out either at a pH between roughly 6.0 and 12, more preferred between 7.0 and 10.
  • 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
  • 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 cleaning composition used according to the present invention may include abrasives.
  • the composition used according to the present invention does not contain an abrasive.
  • the compositions may contain other ingredients which aid in their cleaning performance. For example, they 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
  • compositions Suitable inorganic and organic builders are well known to those skilled in the art.
  • a further optional ingredient for compositions used according to 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.
  • 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 0.1 % 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), and/or other suitable ingredients.
  • 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 agents.
  • 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.
  • the 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 composition of the 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 combination of a spray.
  • test mixture was tested against two bacteria typically found on domestic hard surfaces. These were Enterococcus hirae and Staphylococcus aureus. The test mixtures were tested to find the point on the concentration range where 50% kill is achieved. This point defines the activity measure, A.
  • a mix is activity of test mixture of interest
  • A is activity of compound / on its own
  • TFA ⁇ >,/3 ⁇ 4,
  • TFA ⁇ 1 then the mixture has synergistic activity, and a level of TFA ⁇ 0.90 is taken to be strong synergy. This is based on Fractional Inhibitory Concentration work used in biocidal work. For references, see:
  • Botelho MG Fractional inhibitory concentration index of combinations of antibacterial agents against cariogenic organisms. J. Dentistry 28, 565- 570.
  • surfactant chosen from non-ionic, anionic cationic or amphoteric ⁇ Mixtures of the above may be used in any ratio (limited only by phase
  • Cationic surfactants may be specifically included if a hygiene element is required
  • Neodol 91 3.5% Neodol 91 -8 alcohol ethoxylate non-ionic, 8EO
  • surfactant chosen from non-ionic, anionic, cationic & amphoteric
  • Neodol 91 -5 alcohol ethoxylate nonionic, 5EO
  • GPC's tend contain a lower level of components at reduced levels in comparison to Kitchen & Bathroom specialist cleaners. • 0.1 to 10% surfactant, chosen from non-ionic, anionic, cationic & amphoteric
  • Cationic surfactants may be specifically included for hygiene benefits ⁇ 0-5% Chelating agent
  • Toilet cleaning products tend to be acidic in nature and have high viscosity and shear thinning properties generated by a rod micellar structure.
  • surfactant chosen from non-ionic, anionic, cationic & amphoteric
  • ⁇ Cationic surfactants may be specifically included for hygiene benefits
  • HDW Hand Dish Wash
  • Neodol 91-8 alcohol ethoxylate non-ionic 8EO 2.5% MgSO 4

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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Abstract

An antibacterial cleansing composition comprising an antibacterial component which comprises one selected from each of the following two groups: A: gentisic acid, 2-methoxybenzoic acid, 4-methoxybenzoic acid, vanillic acid, methyl salicylic acid, salicylic acid, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 3, 4-dihydroxybenzoic acid, 4-aminobenzoic acid, gallic acid and o-toluic acid, B: pyruvic, acetic, isobutyric, proprionic, alpha-ketoglutaric and levulinic acids, wherein A is present at from 40-90% weight of the antibacterial component and B is present at from 10 to 60% by weight of the antibacterial component.

Description

CLEANSING COMPOSITION
The present invention relates to an anti-bacterial cleansing composition. Despite the prior art there remains a need for improved anti-bacterial cleansing compositions. Particularly, compositions which are able to cleanse hard surfaces.
Accordingly, the present invention relates to an antibacterial cleansing
composition comprising an antibacterial component which comprises one selected from each of the following two groups:
A: gentisic acid, 2-methoxybenzoic acid, 4-methoxybenzoic acid, vanillic acid, methyl salicylic acid, salicylic acid, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 3, 4-dihydroxybenzoic acid, 4-aminobenzoic acid, gallic acid and o- toluic acid,
B: pyruvic, acetic, isobutyric, proprionic, alpha-ketoglutaric and levulinic acids, wherein A is present at from 40-90% weight of the antibacterial component and B is present at from 10 to 60% by weight of the antibacterial component.
Preferably, the antibacterial component comprises two members from A.
Preferably, the member selected from B is pyruvic acid.
Preferably, the member selected from A is gentisic acid or salicylic acid. Preferably, the two members selected from A are gentisic acid and salicylic acid. Preferably, the antibacterial component comprises gentisic acid, pyruvic acid and salicylic acid.
Preferably, the antibacterial component comprises from 40 to 90% wt pyruvic acid; from 5 to 55% wt. gentisic acid and from 5 to 55% wt. salicylic acid. Such compositions are shown by the inventors to have high activity against both enterococcus hirae and staphylococcus aureus.
Preferably, the antibacterial component comprises from 0.001 to 5% wt. of the composition.
Preferably, the composition comprises a cleansing surfactant.
Preferably, the composition is a hard surface cleaning composition.
Preferably, the composition is a toilet block composition.
Preferably, the composition is a toilet cleaning composition Preferably, the cleaning composition used according to the invention comprises additionally a detergent surfactant at a concentration between 0 and 50% by weight. Said surfactant (detergent active) is generally chosen from anionic and nonionic detergent actives. The cleaning composition may further comprise cationic, amphoteric and zwitterionic surfactants.
Preferably, the total amount of surfactant in said cleaning composition is at least 0.1 %, more preferably at least 0.5%. The maximum amount is usually less than 30%, more preferably not more than 20%, or even at or below 10%, by weight. Suitable synthetic (non-soap) anionic surfactants are 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.
Examples of such anionic surfactants are water soluble salts of:
• (primary) long chain (e.g. 6-22 C-atoms) alcohol sulphates (hereinafter referred to as PAS), especially those obtained by sulphating the fatty alcohols produced by reducing the glycerides of tallow or coconut oil;
· alkyl benzene sulphonates, such as those in which the alkyl group contains from 6 to 20 carbon atoms;
• secondary alkanesulphonates;
and mixtures thereof. Also suitable are the salts of:
• alkylglyceryl ether sulphates, especially of the ethers of fatty alcohols
derived from tallow and coconut oil;
• fatty acid monoglyceride sulphates;
• sulphates of ethoxylated aliphatic alcohols containing 1 -12 ethyleneoxy groups;
• 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 reaction product of fatty acids esterified with isethionic acid and
neutralised with alkali,
and mixtures thereof.
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.
The most preferred anionic surfactants are alkyl-aromatic sulphonates such as alkylbenzenesulphonates 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 alkylbenzenesulphonates or of alkyl-toluene-, -xylene- or -phenolsulphonates, alkylnaphthalene-sulphonates, ammonium diamylnaphthalene-sulphonate, and sodium dinonyl-naphthalene-sulphonate.
If synthetic anionic surfactant is to be employed the amount present in the cleaning compositions of the invention will generally be at least 0.1 %, preferably at least 0.5%, more preferably at least 1 .0%, but not more than 20%, preferably at most 15%, more preferably at most 10%.
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:
• the condensation products of aliphatic alcohols having from 8 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide, such as a coconut alcohol/ethylene oxide condensates having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol;
• condensates of alkylphenols having C6-C15 alkyl groups with 5 to 25
moles of ethylene oxide per mole of alkylphenol; • 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.
Other classes of nonionic surfactants are:
• tertiary amine oxides of structure R1R2R3N-O, where R1 is an alkyl group of 8 to 20 carbon atoms and R2 and R3 are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, e.g. dimethyldodecylamine oxide;
· tertiary phosphine oxides of structure R1R2R3P-O, where R1 is an alkyl group of 8 to 20 carbon atoms and R2 and R3 are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for instance dimethyl-dodecylphosphine oxide;
• dialkyl sulphoxides of structure R1R2S=O, where R1 is an alkyl group of from 10 to 18 carbon atoms and R2 is methyl or ethyl, for instance methyl- tetradecyl sulphoxide;
• fatty acid alkylolamides, such as the ethanol amides;
• alkylene oxide condensates of fatty acid alkylolamides;
• alkyl mercaptans.
The concentration of the nonionic surfactant other than APG to be employed in said cleaning composition of the invention will preferably be at least 0.1 %, more preferably at least 0.5%, most preferably at least 1 %. The amount is suitably at most 20%, preferably not more than 15% and most preferably not more than 10%.
It is also possible optionally to include amphoteric, cationic or zwitterionic surfactants in said compositions.
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. Examples of suitable cationic surfactants can be found among quaternary ammonium salts having one or two alkyl or aralkyl 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. Examples of 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-l -sulphonate betaine, 3-(cetylmethyl- phosphonium)-propane-1 -sulphonate betaine and N,N-dimethyl-N-dodecyl- glycine. Other well known betaines are the alkylamidopropyl betaines e.g. those wherein the alkylamido group is derived from coconut oil fatty acids.
Further examples of suitable surfactants are compounds commonly used as surface-active agents given in the well-known textbooks: 'Surface Active Agents' Vol.1 , by Schwartz & Perry, Interscience 1949; 'Surface Active Agents' Vol.2 by Schwartz, Perry & Berch, Interscience 1958; the current edition of 'McCutcheon's Emulsifiers and Detergents' published by Manufacturing Confectioners Company; Tenside-Taschenbuch', H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 .
In a preferred embodiment the composition according to the invention has a pH of from 2 to 13, more preferably at least 3, and not more than 12. Cleaning methods of the invention intended for cleaning kitchen hard surfaces may advantageously be carried out at a pH in the alkaline range. Preferably the method of the invention is carried out either at a pH between roughly 6.0 and 12, more preferred between 7.0 and 10.
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 cleaning composition used according to the present invention may include abrasives. In a preferred embodiment the composition used according to the present invention does not contain an abrasive. The compositions may contain other ingredients which aid in their cleaning performance. For example, they 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 for compositions used according to 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 0.1 % to 2% by weight of the composition.
Where a 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 1 ,2-benzisothiazolin-3-one), hydrotropes and perfumes.
In a preferred embodiment 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. In another preferred embodiment 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.
In yet another preferred embodiment the 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 composition of the 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. Thus, in a preferred embodiment 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.
EXAMPLE 1
To ascertain antibacterial efficacy each test mixture was tested against two bacteria typically found on domestic hard surfaces. These were Enterococcus hirae and Staphylococcus aureus. The test mixtures were tested to find the point on the concentration range where 50% kill is achieved. This point defines the activity measure, A.
In this analysis, the activity is scaled so that 1 = the lowest concentration possible, and 0 = the highest concentration.
Accordingly, the lower the activity, the better the compound mixture.
To test for synergy mathematically in a mixture of n compounds, calculate Total Fractional Activity (TFA) as follows.
For each compound / in the mixture (i=1,2, ...n) , calculate Fractional Activity, FA
For com ound /', this is defined as:
Figure imgf000011_0001
where Amix is activity of test mixture of interest and
A; is activity of compound / on its own
Then the Total Fractional Activity (TFA) for the mixture is calculated as: TFA =∑>,/¾,
i=l
n
where w, is weight based on the concentration used and ^ w; = 1 .
i=l
Thus if:
TFA = 1 then the mixture has additive activity
TFA > 1 then the mixture has antagonistic activity
TFA < 1 then the mixture has synergistic activity, and a level of TFA < 0.90 is taken to be strong synergy. This is based on Fractional Inhibitory Concentration work used in biocidal work. For references, see:
Berenbaum MC (1978) A Method for testing synergy with any number of agents. J. Infectious Diseases 137(2), 122-130
Botelho MG (2000) Fractional inhibitory concentration index of combinations of antibacterial agents against cariogenic organisms. J. Dentistry 28, 565- 570.
Hall, M.J. et al (1983) The fractional inhibitory concentration (FIC) index as a measure of synergy J. Antimicrobial Chemotherapy 1 1 , 427-433
EXAMPLE 2
This table shows the antibacterial test results against entercoccus and
staphylococcus aureus.
Entero Staph
Synergy Synergy
Source X Y Z measure Summary measure Summary
120 0 0
0 120 0
0 0 120
1 10 1 10 0 0.51 Synergy
2 10 1 10 0 1 .02 Additive 0.54 Synergy
3 20 100 0 3.99 Antagonistic
4 20 100 0 4.46 Antagonistic 5.63 Antagonistic
5 30 90 0 1 .54 Antagonistic
6 30 90 0 4.12 Antagonistic 4.38 Antagonistic
7 30 90 0 2.25 Antagonistic 1 .47 Antagonistic
8 40 80 0 1 .18 Antagonistic 1 .13 Antagonistic
9 40 80 0 0.93 Additive 0.19 Synergy
10 40 80 0 0.89 Synergy 0.65 Synergy
1 1 40 80 0 4.03 No activity 2.63 No activity
12 40 80 0 3.77 Antagonistic 6.1 1 Antagonistic
13 50 70 0 5.20 Antagonistic 60 60 0 5.60 Antagonistic
60 60 0 1 .82 Antagonistic 5.53 Antagonistic
60 60 0 0.59 Synergy 0.75 Synergy
60 60 0 2.53 Antagonistic 2.24 No activity
60 60 0 2.09 Antagonistic 6.58 Antagonistic
60 60 0 1 .18 Antagonistic 1 .22 Antagonistic
80 40 0 0.58 Synergy 1 .88 Antagonistic
80 40 0 3.61 Antagonistic 0.86 Synergy
80 40 0 2.55 No activity 1 .32 Antagonistic
80 40 0 1 .73 Antagonistic 7.06 Antagonistic
90 30 0 1 .30 Antagonistic 5.50 Antagonistic
90 30 0 0.78 Synergy 1 .77 Antagonistic
100 20 0 0.1 1 Synergy 0.32 Synergy
100 20 0 1 .36 Antagonistic 7.54 Antagonistic
1 10 10 0 0.60 Synergy 0.26 Synergy
20 0 100 3.41 Antagonistic
30 0 90 2.45 Antagonistic 8.86 Antagonistic
40 0 80 0.43 Synergy 2.87 Antagonistic
60 0 60 0.15 Synergy 0.68 Synergy
60 0 60 1 .97 Antagonistic 8.13 Antagonistic
60 0 60 5.85 No activity 2.01 Antagonistic
80 0 40 6.32 Antagonistic 0.90 Synergy
90 0 30 1 .48 Antagonistic 6.77 Antagonistic
0 20 100 8.94 Antagonistic
0 30 90 2.98 Antagonistic
0 30 90 3.49 Antagonistic 6.29 Antagonistic
0 40 80 2.57 Antagonistic
0 50 70 3.43 Antagonistic
0 60 60 3.02 Antagonistic
0 60 60 4.32 No activity 6.09 Antagonistic
0 90 30 3.13 Antagonistic 4.30 Antagonistic
10 60 50 1 .50 Antagonistic 0.19 Synergy
20 40 60 0.77 Synergy 0.79 Synergy
20 70 30 1 .86 Antagonistic 4.95 Antagonistic
30 30 60 2.35 Antagonistic 6.77 Antagonistic
30 60 30 3.56 Antagonistic 5.93 Antagonistic
30 60 30 1 .80 Antagonistic
40 20 60 2.36 Antagonistic
50 30 40 0.81 Synergy 0.54 Synergy
50 50 20 0.24 Synergy 0.40 Synergy 54 50 50 20 1 .35 Antagonistic
55 60 30 30 0.47 Synergy 0.49 Synergy
56 60 30 30 2.52 Antagonistic 6.45 Antagonistic
57 60 50 10 0.54 Synergy 0.31 Synergy
58 70 40 10 0.50 Synergy 0.36 Synergy
59 80 20 20 1 .27 Antagonistic 0.71 Synergy
Test mixtures comprising higher levels of pyruvic acid, gentisic acid and salicylic acid are seen to have high synergistic activity against both test organisms. EXAMPLE 3
Bathroom Cleaner:
• 0.1 to 10% surfactant, chosen from non-ionic, anionic cationic or amphoteric · Mixtures of the above may be used in any ratio (limited only by phase
behaviour)
• Cationic surfactants may be specifically included if a hygiene element is required
• 0.1 to 5% organic acid
· Optional ingredients
o Solvents (0.1 -5%)
o Polymers (0.01 -2%)
o Hydrotropes
o Buffer
o Perfume
o Dye
o Preservative
• Usually pH less than 4 (alkaline variants are available on market, with these containing a sequestrant)
Specific Examples
3.5% Neodol 91 -8 alcohol ethoxylate non-ionic, 8EO
4% Citirc acid
1 % Dipropylene glycol n-butyl ether
0.2% Xanthan gum polymer
+ minors (perfume, dye etc)
pH 3.8 5% Neodol 91 -8 alcohol ethoxylate non-ionic, 8EO 4% Citric acid
0.5% Poly acrylic acid
+ minors (perfume, dye etc)
pH 4
Kitchen Cleaner: Generic
• 0.1 to 10% surfactant, chosen from non-ionic, anionic, cationic & amphoteric
• Mixtures of the above may be used in any ratio (limited only by phase
behaviour)
• Cationic surfactants may be specifically included for hygiene benefits
• 0-5% Chelating agent
• Optional ingredients
o Solvents (0.1 -5%)
o Polymers (0.01 -2%)
o Hydrotropes
o Buffer
o Perfume
o Dye
o Preservative
• Usually pH >10
Specific Examples 5% Neodol 91 -5 alcohol ethoxylate nonionic, 5EO
4% Monoethanolamine
1 % Di-propylene glycol n-butyl ether
0.15% Carbopol EDT2623 cross-linked acrylic polymer
+ minors (perfume, dye etc)
pH 1 1 .2
3% Neodol 91 -5 alcohol ethoxylate non-ionic, 5EO
2% SLES 1 EO lauryl ether sulphate, 1 EO
4% Monoethanol amine
1 % Dipropylene glycol n-butyl ether
pH 1 1
EXAMPLE 4 General Purpose Cleaner (GPC - Floor Cleaner): Generic
GPC's tend contain a lower level of components at reduced levels in comparison to Kitchen & Bathroom specialist cleaners. • 0.1 to 10% surfactant, chosen from non-ionic, anionic, cationic & amphoteric
• Mixtures of the above may be used in any ratio (limited only by phase
behaviour)
• Cationic surfactants may be specifically included for hygiene benefits · 0-5% Chelating agent
• Optional ingredients
o Solvents (0.1 -5%)
o Polymers (0.01 -2%)
o Hydrotropes
o Buffer
o Perfume
o Dye
o Preservative
• Any pH
General Purpose Cleaner (GPC - Floor Cleaner): Specific
3% Neodol 91 -5 alcohol ethoxylate non-ionic, 5EO
1 .5% Benzalkyammoinium chloride cationic surfactant
1 .5% STP Sodium tri-polyphoshate
0.3% Na2CO3
+ minors (perfume, dye etc)
pH -1 1 3% SLES 1 EO sodium lauryl ether sulphate, 1 EO
1 % Citric acid
+ minors (perfume, dye etc)
pH 4 EXAMPLE 5
A toilet cleaning composition
Toilet cleaning products tend to be acidic in nature and have high viscosity and shear thinning properties generated by a rod micellar structure.
• 0.1 to 10% surfactant, chosen from non-ionic, anionic, cationic & amphoteric
• Mixtures of the above may be used in any ratio (limited only by phase
behaviour)
· Cationic surfactants may be specifically included for hygiene benefits
• 0-5% bleaching agent
• 0-10% acid
• 0-5% Chelating agent • Optional ingredients
o Solvents (0.1 -5%)
o Polymers (0.01 -2%)
o Hydrotropes
o Buffer
o Perfume
o Dye
o Preservative
• pH generally <4
Toielt cleaner specific example
3% ethomeen BTB12 ethoxylated amine surfactant
4% Sulphamic acid
0.5% Sodium cumene sulphonate (hydrotrope)
4% Hydrogen peroxide
+ minors (perfume, dye etc)
pH ~1 EXAMPLE 6
A Hand dishwash composition
Hand Dish Wash (HDW) : Generic · 0.1 to 40% surfactant, with surfactant chosen from anionic, non-ionic, cationic or amphoteric
• Mixtures of the above may be used in any ratio (limited only by phase
behaviour)
• Cationic surfactants may be specifically included for hygiene benefits
· Optional ingredients
o Solvents (0.1 -5%)
o Polymers (0.01 -2%)
o Hydrotropes
o Buffer
o Perfume
o Dye
o Preservative
• Any pH, but tend to be ~ 4 to 10 HDW: Specific
20% SLES 1 EO sodium lauryl ether sulphate, 1 EO 8% NaLAS sodium linear alkyl benzene sulphonate 5% CAPB Cocoamido propyl betaine
1% Neodol 91-8 alcohol ethoxylate non-ionic, 8EO 2.5% MgSO4
+ minors (perfume, dye etc)
pH ~7
11% NaLAS sodium linear alkyl benzene sulphonate 3.5% SLES 1EO sodium lauryl ether sulphate, 1EO 1%MgSO4
+ minors (perfume, dye etc)
pH ~7

Claims

1 . An antibacterial cleansing connposition comprising an antibacterial
component which comprises one selected from each of the following two groups:
A: gentisic acid, 2-methoxybenzoic acid, 4-methoxybenzoic acid, vanillic acid, methyl salicylic acid, salicylic acid, 4-hydroxybenzoic acid, 3- hydroxybenzoic acid, 3, 4-dihydroxybenzoic acid, 4-aminobenzoic acid, gallic acid and o-toluic acid,
B: pyruvic, acetic, isobutyric, proprionic, alpha-ketoglutaric and levulinic acids, wherein A is present at from 40-90% weight of the antibacterial component and B is present at from 10 to 60% by weight of the antibacterial component.
2. Composition according to claim 1 wherein the antibacterial component comprises two members from A.
3. Composition according to claim 1 or 2 wherein the member selected from B is pyruvic acid.
4. Composition according to any preceding claim wherein the member
selected from A is gentisic acid or salicylic acid.
5. Composition according to claim 2 wherein the two members selected from A are gentisic acid and salicylic acid.
6. Connposition according to any preceding claim wherein the antibacterial component comprises gentisic acid, pyruvic acid and salicylic acid.
7. Composition according to claim 6 wherein the antibacterial component comprises from 40 to 90% wt pyruvic acid; from 5 to 55% wt. gentisic acid and from 5 to 55% wt. salicylic acid.
8. Composition according to any preceding claim wherein the antibacterial component comprises from 0.001 to 5% wt. of the composition.
9. Composition according to any preceding claim comprising a cleansing surfactant.
10. Composition according to any preceding claim which is a hard surface cleaning composition.
1 1 . Composition according to any preceding claim which is a toilet cleaning composition.
12. Composition according to any preceding claim which is a handdishwash composition.
PCT/EP2012/067839 2011-10-18 2012-09-12 Cleansing composition WO2013056901A1 (en)

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