EP4263772A1 - Aqueous cleaning composition - Google Patents

Aqueous cleaning composition

Info

Publication number
EP4263772A1
EP4263772A1 EP21831044.9A EP21831044A EP4263772A1 EP 4263772 A1 EP4263772 A1 EP 4263772A1 EP 21831044 A EP21831044 A EP 21831044A EP 4263772 A1 EP4263772 A1 EP 4263772A1
Authority
EP
European Patent Office
Prior art keywords
acid
composition
composition according
alkyl
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.)
Pending
Application number
EP21831044.9A
Other languages
German (de)
French (fr)
Inventor
Shanthi APPAVOO
Nagaraja ACHARYA
Samiran Mahapatra
Pintu PAUL
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 Global IP Ltd
Unilever IP Holdings BV
Original Assignee
Unilever Global IP Ltd
Unilever IP Holdings BV
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 Global IP Ltd, Unilever IP Holdings BV filed Critical Unilever Global IP Ltd
Publication of EP4263772A1 publication Critical patent/EP4263772A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to aqueous cleaning compositions comprising anionic surfactant, nonionic surfactant and organic acid and a method and use thereof to cleaning and disinfect surfaces.
  • Cleaning products are well-known and play an important role in everyday life. Such products will contain surfactant and, if disinfection is desired, usually also a disinfecting agent like for example chlorine bleach, quaternary ammonium compound, e.g., benzalkonium chloride, or chloroxylenol.
  • a disinfecting agent like for example chlorine bleach, quaternary ammonium compound, e.g., benzalkonium chloride, or chloroxylenol.
  • Such conventional disinfecting agents seems to be effective on wide range of microbes, however, it is reported that such agents may affect one’s health.
  • Organic acids like citric acid and lactic acid are natural alternatives for synthetic disinfectants like chlorine bleach, benzalkonium chloride and chloroxylenol. These organic acids show antibacterial action, but on their own may not display a broad-spectrum antibacterial action, i.e. act against both gram-negative bacteria (e.g. E. coli and P. aeruginosa) and gram-positive bacteria (e.g. S. aureus and E. hirae). Bacteria like E. hirae are known to be more difficult to combat. Also, antiviral action may be limited in efficacy and/or breadth, e.g. only against enveloped virus and not against non-enveloped virus. Non-enveloped viruses are known to be more difficult to combat.
  • WO 2004/18599 discloses an acidic hard surface composition which provides cleaning and disinfecting benefit comprising an acidic constituent, which comprises water soluble organic acid, at least one anionic surfactant constituent, at least one non-ionic surfactant, at least one organic solvent constituent, optionally one or more further constituents and balance water.
  • the composition exhibits surprising efficacy against various gram positive and gram-negative type pathogenic bacteria, as well as against fungi in the absence of known cationic quaternary ammonium compounds known to be effective against pathogenic bacteria, as well as other known-art antimicrobial constituents and bleach are excluded.
  • the invention relates to an aqueous cleaning composition
  • an aqueous cleaning composition comprising: a. 0.1 to 10 wt% anionic surfactant selected from alkyl sulphates, alkyl ether sulphates and combinations thereof; b. 0.1 to 10 wt% nonionic surfactant selected from alcohol ethoxylates, short chain alkyl poly glycosides and combinations thereof; and c. 1 to 20 wt% organic acid having a pKa of 2.5 to 5.5; wherein the composition has a pH of 2 to 4; wherein the alcohol ethoxylate has from 1 to 7 EO; and wherein the alkyl poly glycoside has alkyl groups from C8 to C10, wherein the composition is free of organic solvent.
  • the invention further relates to a method of cleaning a surface comprising the step of contacting the surface with the composition according to present invention in neat or dilute form for at least 15 seconds.
  • the invention also relates to the use of a composition of the present invention for incapacitating germs on a surface.
  • the invention also relates to the use of a composition of the present invention for incapacitating viruses on a surface.
  • the cleaning composition of the present invention is an aqueous cleaning composition, that is to say, the composition comprises water.
  • the amount of water will depend on the desired concentration of the other ingredients but will at least be 50 wt%, like for example at least 60 wt% or at least 70 wt%, but typically not more than 99 wt%.
  • the amount of water preferably is from 50 to 98 wt%, more preferably 60 to 95 wt% and even more preferably 70 to 90 wt%.
  • the composition is liquid, that is, it can be poured, and has viscosity at 25°C of 1 to 1000 mPa.s @ 20 s-1.
  • the viscosity is measured using an AR 1000 Rheometer (TA instruments) using a 4 cm, 2° cone-plate geometry @ 20 s-1 and 25°C.
  • the composition may be more or less viscous. For example, a more water thin viscosity is desired if the composition is to be used in a trigger spray bottle. If dispensed from a squeeze bottle, a more viscous consistency may be desired. A more viscous viscosity may also be desired if the cleaning product is a toilet cleaning product.
  • the composition has a viscosity of 100 to 700 mPa.s @ 20 s-1 and more preferably of 200 to 600 mPa.s @ 20 s-1.
  • the desired viscosity can suitably be obtained by known methods like for example the use of a viscosity modifying agent.
  • the composition of the present invention comprises 0.1 to 10 wt% anionic surfactant.
  • the anionic surfactant can suitably be chosen from known anionic surfactants like sulphate base surfactants (e.g. sodium lauryl ether sulphate and sodium lauryl sulphate) and sulphonate based surfactants (e.g. alpha olefin sulphonates, alkyl benzene sulphonates and methyl ester sulphonates).
  • the anionic surfactant comprises a sulphate-based surfactant.
  • Preferred anionic surfactants are alkyl ether sulphates of Formula I and alkyl sulphates of Formula II.
  • Ri is saturated or unsaturated C8-C16, preferably C12-C14 alkyl chain; preferably, Ri is a saturated C8-C16, more preferably a saturated C12-C14 alkyl chain;
  • R’ is ethylene; n is from 1 to 18, preferably from 1 to 15, more preferably from 1 to 10, still more preferably from 1 to 5, even more preferably from 1 to 3; x is equal to 1 or 2;
  • M x+ is a suitable cation which provides charge neutrality, preferably sodium, calcium, potassium, or magnesium, more preferably a sodium cation.
  • the surfactant of Formula I is sodium lauryl ether sulphate having 1 to 3 ethylene oxide units per molecule, more preferably, sodium lauryl ether sulphate having 1 to 2 ethylene oxide units per molecule.
  • Ri is saturated or unsaturated C8-C16, preferably C12-C14 alkyl chain; preferably, Ri is a saturated C8-C16, more preferably a saturated C12-C14 alkyl chain; x is equal to 1 or 2;
  • M x+ is a suitable cation which provides charge neutrality, preferably sodium, calcium, potassium, or magnesium, more preferably a sodium cation.
  • the surfactant of Formula II is sodium lauryl sulphate.
  • Suitable examples include alkyl sulphates from synthetic origin with trade names Safol 23, Dobanol 23A or 23S, Lial 123 S, Alfol 1412S, Empicol LC3, Empicol 075SR. Further suitable examples, and preferred, include alkyl sulphates commercially available from natural sources with trade names Galaxy 689, Galaxy 780, Galaxy 789, Galaxy 799 SP.
  • the anionic surfactant is selected from alkyl sulphates, alkyl ether sulphates and combinations thereof.
  • the composition preferably comprises 0.25 to 8 wt% anionic surfactant, more preferably 0.5 to 6 wt% and even more preferably 1 to 5 wt%.
  • composition of the present invention comprises 0.1 to 10 wt% nonionic surfactant selected from alcohol ethoxylates, short chain alkyl poly glycosides and combinations thereof
  • the alcohol ethoxylate has from 1 to 10 EG.
  • Suitable alcohol ethoxylate surfactants include the condensation products of a higher alcohol (e.g. an alkanol containing about 8 to 18 carbon atoms in a straight or branched chain configuration) condensed with about 1 to 10 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with about 16 moles of ethylene oxide (EO), tridecanol condensed with about 6 moles of EO, myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to about 14 carbon atoms in length and wherein the condensate contains either about 6 moles of EO per mole of total alcohol or about 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 10
  • the alcohol ethoxylate has from 3 to 9 EO, more preferably 5 to 8 EO and even more preferably 7 EO. Particularly preferred is Lauryl alcohol condensed with 5, 7 and 9 moles of ethylene oxide (Laureth 5, Laureth 7 and Laureth 9).
  • the alcohol ethoxylate surfactant is selected from Laureth 5, Laureth 7 and Laureth 9, or mixtures thereof.
  • the nonionic surfactant selected may be such that it comprises a mixture of fatty alcohols e.g. a mixture of C12, C13, C14 and C15 in varying proportions along with 1 to 10 ethoxylate groups.
  • Such nonionic surfactants are commercially available under NEODOLTM series from Shell.
  • NEODOLTM 91-51 which is a mixture of C9, C10 and C11 with 5 EO
  • NEODOLTM 91-61 which is a mixture of 09, C10 and C11 with 6 EO
  • NEODOLTM 91-8 which is a mixture of 09, C10, and C11 with 8 EO
  • NEODOLTM 23-2 which is a mixture of C12 and C13 with 2 EO
  • NEODOLTM 25-3 which is a mixture of C12, C13, 014 and 015 with 3 EO
  • NEODOLTM 25-7 which is a mixture of 012, 013, 014 and 015 with 7 EO
  • NEODOLTM 45-7 which is a mixture of 014 and 015 with 7 EO.
  • Particularly preferred nonionic surfactant is a mixture of 012, 013, 014 and 015 with 7 EO.
  • the nonionic surfactant comprises alcohol ethoxylate surfactant.
  • alcohol ethoxylates provide for especially beneficial for antibacterial efficacy in compositions of the present invent it is especially preferred that the nonionic surfactant is alcohol ethoxylate surfactant.
  • alkyl polyglycosides are compounds having the formula RiO(R2O)b(Z) a , wherein Ri is a alkyl radical, having from about 8 to about 10 carbon atoms; R2 is an alkylene radical having from 2 to 4 carbon atoms; Z is a saccharide residue having 5 or 6 carbon atoms; b is a number having a value from 0 to about 12; and a is a number having a value from 1 to about 6 (the degree of polymerization).
  • alkyl polyglycosides are generally present as mixtures of alkyl polyglycosides having varying amounts of carbon atoms in the alkyl radical and varying degrees of polymerization.
  • the alkyl radical is generally referred to as having a range of carbon atoms (e.g. C8/10 referring to a range of alkyl radicals having from 8-10 carbon atoms) and the degree of polymerization is generally referred to as the average degree of polymerization of the mixture.
  • the alkyl poly glycosides is an alkyl polyglucoside surfactant.
  • Prefered alkyl polyglycosides suitable for use in the disclosed cleaning formulation include those having the formula I wherein Z is a glucose residue, b is zero, Ri is an alkyl group that contains 8 to 10 carbon atoms, and the average value of a is about 1-2.
  • Such alkyl polyglucosides are commercially available, for example, as Glucopon® branded alkyl polyglucoside compositions from BASF (formerly Cognis Corporation), including Glucopon® 215CS UP and 225 DK.
  • the composition preferably comprises 0.25 to 8 wt% nonionic surfactant, more preferably 0.5 to 6 wt% and even more preferably 1 to 5 wt%.
  • the weight ratio of anionic to nonionic surfactant is from 4:1 to 1:4, more preferably from 3:1 to 1:3, and even more preferably from 2:1 to 1 :2.
  • the composition comprises 1 to 20 wt% organic acid.
  • the organic acid is used a natural disinfecting agent and together with the anionic surfactant and nonionic surfactant present in the composition of the present invention provides for broad spectrum antibacterial efficacy.
  • the organic acid is selected from lactic acid, glycolic acid and mixtures thereof. Even more preferably, the organic acid is selected from lactic acid, glycolic acid and mixtures thereof. Most preferably, the organic acid selected is glycolic acid.
  • the amount of organic acid in the composition is from 1.5 to 12 wt%, more preferably 2 to 10 wt%.
  • the weight ratio of surfactant to organic acid is from 20:1 to 1 :20, preferably from 10:1 to 1 :10, and more preferably from 5:1 to 1 :5. pH of the composition
  • the composition has a pH in the range from 2.0 to 4.0, preferably from 2.5 to 4.0, even more preferably from 3.0 to 3.5.
  • the pH of the composition may be adjusted using suitable pH adjusting agents e.g., hydrochloric acid and sodium hydroxide.
  • the cleaning composition may comprise 0.01 to 1 wt% water soluble rheology modifying polymer.
  • Rheology modifying polymers are known and their ability to impart viscosity to a composition may, in part, depend on the presence or absence of other ingredients.
  • Water soluble polymers can be used to thicken the composition which includes non-ionic, cationic and amphoteric polymers.
  • Suitable polymers include hydroxy ethyl cellulose, modified hydroxy ethyl cellulose, guar gum, gum tragacanth, xanthan gum, gum arabic, gum acacia, Jaguar® C13S, Jaguar® C14S, Jaguar® C17, Jaguar® HP 105 (hydroxy propyl guar), Jaguar® HP 60 (hydroxylated propylated guar), Jaguar® S (Native guar gum), Carbopol® Agua CC .MerguatTM 100, MerguatTM 280, MerguatTM 281 and MerguatTM 550 from Lubrizol, poly ethylene glycols such as PolyoxTM WSR- 205 (PEG 14), PolyoxTM WSR N-60K (PEG 45), and PolyoxTM WSR-301 (PEG 90), and hydrophobically modified hydroxyethyl celluloses
  • the cleaning composition of the present invention may comprise 0.1 to 10 wt% seguestrant.
  • the amount of seguestrant is 0.25 to 5 wt%, preferably 0.5 to 3 wt%.
  • the seguestrant has a binding capacity of at least 280 mg Ca/g, preferably at least 290 mg Ca/g and more preferably at least 300 mg Ca/g.
  • Suitable sequestrants are those based on organophosphonates, aminopolycarboxylates and carboxylic acids. It will be understood that suitable sequestrants include both the acid form and salts thereof.
  • DTPMP diethylenetriamine penta(methylene phosphonic acid)
  • HEDP hydroxyethylidenediphosphonic acid
  • NTMP nitrilotrimethylenephosphonic acid
  • sequestrants based on aminopolycarboxylates include ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA), methylglycine diacetic acid (MGDA), and L-Glutamic acid N,N diacetic acid (GLDA).
  • EDTA ethylenediaminetetraacetic acid
  • DTPA diethylenetriaminepentaacetic acid
  • NTA nitrilotriacetic acid
  • MGDA methylglycine diacetic acid
  • sequestrants based on carboxylic acids include gluconic acid and itaconic acid.
  • the sequestrant is biodegradable.
  • Preferred biodegradable sequestrants are nitrilotriacetic acid (NTA), ethylenediaminedisuccinic acid, (EDDS), iminodisuccinic acid, (IDS), methylglycine diacetic acid, (MGDA), L-Glutamic acid N.Ndiacetic acid (GLDA), 2- hydroxyethyliminodiacetic acid (HEIDA), ethylenediamine-N,N'-dimalonic acid (EDDM), ethylenediamine-N,N'-diglutaric acid (EDDG), 3-hydroxy-2,2-iminodisuccinic acid (HIDS), and 2,6-pyridine dicarboxylic acid (PDA), gluconic acid and itaconic acid.
  • NTA nitrilotriacetic acid
  • EDDS ethylenediaminedisuccinic acid
  • IDDS iminodisuccinic acid
  • MGDA L-Gluta
  • composition according to the present invention is free of organic solvent.
  • free of organic solvent herein refers to the composition comprising less than 0.4 wt%, more preferably less than 0.2 wt% and most preferably less than 0.1 wt% of organic solvent.
  • the cleaning composition comprises from 0 to 0.1 wt% solvent having a flash point of up to 15 °C, more preferably up to 20 °C and even more preferably up to 30 °C.
  • a solvent is isopropyl alcohol having a flash point of 11.7 °C, ethanol having flash point 13°C.
  • the composition is free of solvent having a flash point of up to 15 °C, more preferably up to 20 °C and even more preferably up to 30 °C.
  • At least part of the ingredients of the cleaning composition is biodegradable.
  • a substance or material should break down into carbon dioxide (a nutrient for plants) and water.
  • Naturally occurring minerals that do not cause harm to the ecosystem are already in their natural mineral state and do not need to biodegrade.
  • At least 70 wt%, more preferably at least 90 wt% and still more preferably at least 95 wt% of the ingredients is biodegradable.
  • biodegradable refers to ‘Inherently and Ultimately biodegradable’ as per the OECD 302 guidelines/tests.
  • biodegradable refers to ‘Readily and Ultimately biodegradable’ as per the OECD 301 series or 310 guidelines/tests.
  • At least part of the organic ingredients of the cleaning composition is natural.
  • natural is defined as the ingredient comprising at least 50 wt% plant derived, i.e. from a natural source, material; preferably at least 70 wt%, more preferably at least 90 wt% and still more preferably at least 95 wt%.
  • at least 99 wt% is plant derived and even more preferably essentially all of a natural ingredient is plant derived.
  • At least 70 wt%, more preferably at least 90 wt% and still more preferably at least 95 wt% of the organic ingredients is natural.
  • Preferably at least 99 wt% is natural and even more preferably essentially all organic ingredients are natural.
  • composition of the present invention is free of quaternary ammonium compounds.
  • ABS Alkylbenzene sulphonates
  • ABS is not readily available from renewable carbon or biorenewable carbon sources. Therefore, the cleaning composition of the present composition is free of alkylbenzene sulphonates and derivatives thereof.
  • Alkylbenzene sulphonates (ABS) and derivatives thereof include water-soluble alkali metal salts of organic sulphonates having alkyl radicals typically containing from about 8 to about 22 carbon atoms, preferably 8 to 18 carbon atoms, still more preferably 12 to 15 carbon atoms and may be saturated or unsaturated.
  • Examples include sodium salt of linear alkylbenzene sulphonate, alkyl toluene sulphonate, alkyl xylene sulphonate, alkyl phenol sulphonate, alkyl naphthalene-sulphonate, ammonium diamylnaphthalene-sulphonate and sodium dinonylnaphthalene-sulphonate and mixtures with olefin sulphonates.
  • composition of the present invention is free of any sulphonated surfactant.
  • the invention also relates to a method of cleaning a surface comprising the steps of a. contacting the surface with the composition according to the invention in neat or dilute form for at least 15 seconds; b. optionally rinsing the surface with water; and c. optionally drying the surface.
  • the surface is contacted with the cleaning composition between 15 seconds and 60 minutes. Preferably between 30 seconds and 60 minutes, more preferably 1 to 45 minutes and even more preferably 5 to 30 minutes.
  • a typical contact time for hand washing is at least 20 seconds.
  • the surface may be any surface suitable for cleaning including human skin like e.g. hands, and household hard surfaces like e.g. utensils or kitchenware, floors, toilets, bathroom surfaces and kitchen surfaces.
  • the surface is a household care hard surface and more preferably the surface is a toilet surface.
  • Cleaning of a toilet surface is preferably done with a neat solution that has a more viscous consistency like for example 200 to 600 mPa.s @ 20 s’ 1 .
  • the contact time is usually longer and typically varies between 30 seconds and 60 minutes after which the toilet surface is rinsed with water.
  • the composition of the invention is applied onto a hard surface in neat or diluted form.
  • the composition may be applied by any known method such as by using a cleaning implement, such as scrub, sponge paper, cloth, wipes or any other direct or indirect application.
  • the applied composition may be cleaned using a cleaning implement such as a scrub, sponge, paper, cloth or wipes with or without water, or rinsed off with water, optionally running water.
  • the surface is human skin.
  • an amount of neat cleaning composition with a small amount of water is used to wash the skin surface of the hands such that foam is generated and the cleaning composition is in contact with the skin for at least 15 seconds, preferably at least 20 seconds.
  • a typical dilution rate is 30 to 70 %, preferably 40 to 60% like for example 50%.
  • the cleaning composition including foam is then rinsed of with water and the hands are dried e.g., by using an air blower or paper cloth or towel.
  • Antibacterial efficacy of a compound can be determined using several protocols, with EN1279 and EN 13697 being among the most used.
  • EN1279 is a so-called suspension test and EN 13697 is a so-called surface test.
  • EN 13697 is a better indicator. We have found that some known cleaning compositions do not always show the desired antibacterial efficacy when tested according to EN 13697.
  • the invention also relates to the use of a composition according to the present invention for incapacitating germs on a surface.
  • the specific combination of anionic surfactant, nonionic surfactant and organic acid allows for broad antibacterial efficacy without the need for synthetic disinfecting agents.
  • the invention also relates to the use of a composition according to the present invention for incapacitating viruses on a surface.
  • the specific combination of anionic surfactant, nonionic surfactant and organic acid allows for antiviral efficacy without the need for synthetic disinfecting agents.
  • This specific combination is effective against both enveloped and nonenveloped viruses.
  • the virus includes non-enveloped virus, like for example COVID- 19 (or Sars-Cov-2).
  • incapacitating is defined as including killing, interrupting growth and limiting the ability to infect an animal.
  • incapacitating is defined as killing.
  • Short chain alkyl poly glucoside (APG 215): Glucopon® 215UP ex BASF
  • Germ removal efficacy of the composition along with a control composition shown in table 1 below were carried out using EN13697 or EN 1276 protocol for estimating antimicrobial efficacy. Soil conditions clean were created with 0.03% Bovine Serum Albumin (BSA); and dirty conditions were created by using 0.3% BSA with a contact time of 5 min.
  • BSA Bovine Serum Albumin
  • Differential media was used for enumerating the test organisms (to eliminate the growth of Bacillus along with the test organism).
  • a saline suspension of the above-mentioned test organisms is made.
  • the optical density of the saline suspension is adjusted at 620 nm to obtain 10 8 cells/ mL.
  • All glycerol stocks of bacteria were maintained at - 80°C; and were revived just before the carrying out the experiments. dilution:
  • compositions were tested neat (i.e., undiluted) or diluted. Dilution is indicated by times of dilution. For example, 200x dilution means that to 10 ml of cleaning composition water is added to a total volume of 2000 ml. Determination of antimicrobial efficacy:
  • Dilution neutralization method a. At the end of contact time, 1 mL of test mixture is transferred to 9 mL of neutralizing broth (this is minus 1 (-1) dilution), b. Serial dilutions were prepared to determine the actual survivor counts; and c. Neutralization validation method is described at the end.
  • Dilution neutralization method used was as follows: a. To 8 ml of highest test concentration of test product dilution, 1 ml of saline + 1 ml of BSA (clean or dirty) is added, b. After 5 minutes, transfer 1 ml of above mixture to tube containing 8 ml of neutralizing broth to be validated, c. Add 1 ml of 10' 5 dilution i. e 10 3 cells of test organism suspension (diluted from 10 8 cells/ ml test culture suspension in sterile saline) to the above tube and wait for 30 minutes. Consider this tube as undiluted test system; and d. After 30 minutes, plate out undiluted test system and -1 dilution.
  • N is between 1.5 x io 8 and 5.0 x 1O 8 , (8,17 ⁇ Ig N ⁇ 8.70);
  • Nvo is between 30 and 160, (3.0 x 10 1 and 1.6 x 10 2 );
  • N v is between 3.0 x io 2 and 1.6 x 10 3 ); c) A, B, C are equal to or greater than 0.5 x N v o ;
  • N is the culture control count
  • No is the culture control count in final test system
  • C is the neutralization validation count obtained for test sample.
  • Log reduction is calculated as difference of log of culture control in test mixture from log of count obtained in test mixture.

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Abstract

The present invention relates to an aqueous cleaning composition comprising: a. 0.1 to 10 wt% anionic surfactant selected from alkyl sulphates, alkyl ether sulphates and combinations thereof; b. 0.1 to 10 wt% nonionic surfactant selected from alcohol ethoxylates, short chain alkyl poly glycosides and combinations thereof; and c. 1 to 20 wt% organic acid having a pKa of 2.5 to 5.5; wherein the composition has a pH of 2 to 4; wherein the alcohol ethoxylate has from 1 to 7 EO; and wherein the alkyl poly glycoside has alkyl groups from C8 to C10, wherein the composition is free of organic solvent. The invention also relates to a method and use of said composition for cleaning and disinfecting surfaces.

Description

AQUEOUS CLEANING COMPOSITION
Field of the Invention
The present invention relates to aqueous cleaning compositions comprising anionic surfactant, nonionic surfactant and organic acid and a method and use thereof to cleaning and disinfect surfaces.
Background of the Invention
Cleaning products are well-known and play an important role in everyday life. Such products will contain surfactant and, if disinfection is desired, usually also a disinfecting agent like for example chlorine bleach, quaternary ammonium compound, e.g., benzalkonium chloride, or chloroxylenol. Such conventional disinfecting agents seems to be effective on wide range of microbes, however, it is reported that such agents may affect one’s health.
Traditionally a distinction is made between personal hygiene, i.e. , how one takes care of one’s own body; and home care including laundry and household care, the latter including the cleaning of hard surfaces like toilets, floors and kitchen tops.
More and more consumers prefer cleaning products with a good environmental profile. That is, they prefer products that are ‘eco-friendly’ and have less or no impact on the environment when the product is used. There is thus a growing need for cleaning products that mainly or only contain natural and/or biodegradable ingredients. It is also desired that the products are formulated avoiding disinfecting agents, such as chlorine bleach, quaternary ammonium compound, e.g., benzalkonium chloride, or chloroxylenol etc., yet provide disinfection benefit
Organic acids like citric acid and lactic acid are natural alternatives for synthetic disinfectants like chlorine bleach, benzalkonium chloride and chloroxylenol. These organic acids show antibacterial action, but on their own may not display a broad-spectrum antibacterial action, i.e. act against both gram-negative bacteria (e.g. E. coli and P. aeruginosa) and gram-positive bacteria (e.g. S. aureus and E. hirae). Bacteria like E. hirae are known to be more difficult to combat. Also, antiviral action may be limited in efficacy and/or breadth, e.g. only against enveloped virus and not against non-enveloped virus. Non-enveloped viruses are known to be more difficult to combat.
In this regard, WO 2004/18599 discloses an acidic hard surface composition which provides cleaning and disinfecting benefit comprising an acidic constituent, which comprises water soluble organic acid, at least one anionic surfactant constituent, at least one non-ionic surfactant, at least one organic solvent constituent, optionally one or more further constituents and balance water. The composition exhibits surprising efficacy against various gram positive and gram-negative type pathogenic bacteria, as well as against fungi in the absence of known cationic quaternary ammonium compounds known to be effective against pathogenic bacteria, as well as other known-art antimicrobial constituents and bleach are excluded.
In view of the above, there remains a need for cleaning compositions with a good environmental profile without compromising consumer satisfaction in terms of performance and disinfection efficacy against bacteria and/or viruses.
Summary of the Invention
We have found that specific combinations of organic acid, anionic surfactant and nonionic surfactant allow for the use of organic acid as a natural disinfecting agent whilst the cleaning composition shows broad spectrum antibacterial efficacy. We have also found that said compositions have antiviral properties.
Accordingly, in a first aspect the invention relates to an aqueous cleaning composition comprising: a. 0.1 to 10 wt% anionic surfactant selected from alkyl sulphates, alkyl ether sulphates and combinations thereof; b. 0.1 to 10 wt% nonionic surfactant selected from alcohol ethoxylates, short chain alkyl poly glycosides and combinations thereof; and c. 1 to 20 wt% organic acid having a pKa of 2.5 to 5.5; wherein the composition has a pH of 2 to 4; wherein the alcohol ethoxylate has from 1 to 7 EO; and wherein the alkyl poly glycoside has alkyl groups from C8 to C10, wherein the composition is free of organic solvent.
The invention further relates to a method of cleaning a surface comprising the step of contacting the surface with the composition according to present invention in neat or dilute form for at least 15 seconds.
The invention also relates to the use of a composition of the present invention for incapacitating germs on a surface. The invention also relates to the use of a composition of the present invention for incapacitating viruses on a surface.
Detailed Description of the Invention
Any feature of one aspect of the present invention may be utilized in any other aspect of the invention. The word “comprising” is intended to mean “including” but not necessarily “consisting of’ or “composed of.” In other words, the listed steps or options need not be exhaustive. Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word “about”. Numerical ranges expressed in the format "from x to y" are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format "x to y", it is understood that all ranges combining the different endpoints are also contemplated. Unless specified otherwise, amounts as used herein are expressed in percentage by weight based on total weight of the composition and is abbreviated as “wt%”. The use of any and all examples or exemplary language e.g. “such as” provided herein is intended merely to better illuminate the invention and does not in any way limit the scope of the invention otherwise claimed. Room temperature is defined as a temperature of about 20 degrees Celsius.
Aqueous cleaning composition
The cleaning composition of the present invention is an aqueous cleaning composition, that is to say, the composition comprises water. The amount of water will depend on the desired concentration of the other ingredients but will at least be 50 wt%, like for example at least 60 wt% or at least 70 wt%, but typically not more than 99 wt%. The amount of water preferably is from 50 to 98 wt%, more preferably 60 to 95 wt% and even more preferably 70 to 90 wt%.
The composition is liquid, that is, it can be poured, and has viscosity at 25°C of 1 to 1000 mPa.s @ 20 s-1. The viscosity is measured using an AR 1000 Rheometer (TA instruments) using a 4 cm, 2° cone-plate geometry @ 20 s-1 and 25°C. Depending on the required use characteristics the composition may be more or less viscous. For example, a more water thin viscosity is desired if the composition is to be used in a trigger spray bottle. If dispensed from a squeeze bottle, a more viscous consistency may be desired. A more viscous viscosity may also be desired if the cleaning product is a toilet cleaning product. Preferably the composition has a viscosity of 100 to 700 mPa.s @ 20 s-1 and more preferably of 200 to 600 mPa.s @ 20 s-1. The desired viscosity can suitably be obtained by known methods like for example the use of a viscosity modifying agent.
Anionic surfactant
The composition of the present invention comprises 0.1 to 10 wt% anionic surfactant. The anionic surfactant can suitably be chosen from known anionic surfactants like sulphate base surfactants (e.g. sodium lauryl ether sulphate and sodium lauryl sulphate) and sulphonate based surfactants (e.g. alpha olefin sulphonates, alkyl benzene sulphonates and methyl ester sulphonates).
Typically, the anionic surfactant comprises a sulphate-based surfactant.
Preferred anionic surfactants are alkyl ether sulphates of Formula I and alkyl sulphates of Formula II.
Formula I: (Ri-(OR’)n-O-SO3')xMx+, wherein:
Ri is saturated or unsaturated C8-C16, preferably C12-C14 alkyl chain; preferably, Ri is a saturated C8-C16, more preferably a saturated C12-C14 alkyl chain;
R’ is ethylene; n is from 1 to 18, preferably from 1 to 15, more preferably from 1 to 10, still more preferably from 1 to 5, even more preferably from 1 to 3; x is equal to 1 or 2;
Mx+ is a suitable cation which provides charge neutrality, preferably sodium, calcium, potassium, or magnesium, more preferably a sodium cation.
Preferably, the surfactant of Formula I is sodium lauryl ether sulphate having 1 to 3 ethylene oxide units per molecule, more preferably, sodium lauryl ether sulphate having 1 to 2 ethylene oxide units per molecule.
Formula II: (RI-O-SC>3')XMX+, wherein:
Ri is saturated or unsaturated C8-C16, preferably C12-C14 alkyl chain; preferably, Ri is a saturated C8-C16, more preferably a saturated C12-C14 alkyl chain; x is equal to 1 or 2;
Mx+ is a suitable cation which provides charge neutrality, preferably sodium, calcium, potassium, or magnesium, more preferably a sodium cation.
Preferably the surfactant of Formula II is sodium lauryl sulphate. Suitable examples include alkyl sulphates from synthetic origin with trade names Safol 23, Dobanol 23A or 23S, Lial 123 S, Alfol 1412S, Empicol LC3, Empicol 075SR. Further suitable examples, and preferred, include alkyl sulphates commercially available from natural sources with trade names Galaxy 689, Galaxy 780, Galaxy 789, Galaxy 799 SP.
Preferably the anionic surfactant is selected from alkyl sulphates, alkyl ether sulphates and combinations thereof.
The composition preferably comprises 0.25 to 8 wt% anionic surfactant, more preferably 0.5 to 6 wt% and even more preferably 1 to 5 wt%.
Nonionic surfactant
The composition of the present invention comprises 0.1 to 10 wt% nonionic surfactant selected from alcohol ethoxylates, short chain alkyl poly glycosides and combinations thereof
Alcohol ethoxylate
The alcohol ethoxylate has from 1 to 10 EG. Suitable alcohol ethoxylate surfactants include the condensation products of a higher alcohol (e.g. an alkanol containing about 8 to 18 carbon atoms in a straight or branched chain configuration) condensed with about 1 to 10 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with about 16 moles of ethylene oxide (EO), tridecanol condensed with about 6 moles of EO, myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to about 14 carbon atoms in length and wherein the condensate contains either about 6 moles of EO per mole of total alcohol or about 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 10 EO per mole of alcohol. Preferably the alcohol ethoxylate has from 3 to 9 EO, more preferably 5 to 8 EO and even more preferably 7 EO. Particularly preferred is Lauryl alcohol condensed with 5, 7 and 9 moles of ethylene oxide (Laureth 5, Laureth 7 and Laureth 9). Preferably, the alcohol ethoxylate surfactant is selected from Laureth 5, Laureth 7 and Laureth 9, or mixtures thereof.
The nonionic surfactant selected may be such that it comprises a mixture of fatty alcohols e.g. a mixture of C12, C13, C14 and C15 in varying proportions along with 1 to 10 ethoxylate groups. Such nonionic surfactants are commercially available under NEODOLTM series from Shell. For example, NEODOLTM 91-51 which is a mixture of C9, C10 and C11 with 5 EO; NEODOLTM 91-61 which is a mixture of 09, C10 and C11 with 6 EO; NEODOLTM 91-8 which is a mixture of 09, C10, and C11 with 8 EO; NEODOLTM 23-2 which is a mixture of C12 and C13 with 2 EO; NEODOLTM 25-3 which is a mixture of C12, C13, 014 and 015 with 3 EO; NEODOLTM 25-7 which is a mixture of 012, 013, 014 and 015 with 7 EO; and NEODOLTM 45-7 which is a mixture of 014 and 015 with 7 EO. Particularly preferred nonionic surfactant is a mixture of 012, 013, 014 and 015 with 7 EO.
Preferably the nonionic surfactant comprises alcohol ethoxylate surfactant. As alcohol ethoxylates provide for especially beneficial for antibacterial efficacy in compositions of the present invent it is especially preferred that the nonionic surfactant is alcohol ethoxylate surfactant.
Short chain alkyl poly glycosides
As used herein alkyl polyglycosides are compounds having the formula RiO(R2O)b(Z)a, wherein Ri is a alkyl radical, having from about 8 to about 10 carbon atoms; R2 is an alkylene radical having from 2 to 4 carbon atoms; Z is a saccharide residue having 5 or 6 carbon atoms; b is a number having a value from 0 to about 12; and a is a number having a value from 1 to about 6 (the degree of polymerization). Due to the method by which they are synthesized, alkyl polyglycosides are generally present as mixtures of alkyl polyglycosides having varying amounts of carbon atoms in the alkyl radical and varying degrees of polymerization. Thus, when referring to alkyl polyglycosides, the alkyl radical is generally referred to as having a range of carbon atoms (e.g. C8/10 referring to a range of alkyl radicals having from 8-10 carbon atoms) and the degree of polymerization is generally referred to as the average degree of polymerization of the mixture.
Preferably the alkyl poly glycosides is an alkyl polyglucoside surfactant. Prefered alkyl polyglycosides suitable for use in the disclosed cleaning formulation include those having the formula I wherein Z is a glucose residue, b is zero, Ri is an alkyl group that contains 8 to 10 carbon atoms, and the average value of a is about 1-2. Such alkyl polyglucosides are commercially available, for example, as Glucopon® branded alkyl polyglucoside compositions from BASF (formerly Cognis Corporation), including Glucopon® 215CS UP and 225 DK.
The composition preferably comprises 0.25 to 8 wt% nonionic surfactant, more preferably 0.5 to 6 wt% and even more preferably 1 to 5 wt%.
Preferably the weight ratio of anionic to nonionic surfactant is from 4:1 to 1:4, more preferably from 3:1 to 1:3, and even more preferably from 2:1 to 1 :2.
Organic acid
The composition comprises 1 to 20 wt% organic acid.. The organic acid is used a natural disinfecting agent and together with the anionic surfactant and nonionic surfactant present in the composition of the present invention provides for broad spectrum antibacterial efficacy.
The organic acid is selected from , lactic acid (pKa = 3.86), acetic acid (pKa = 4.76), malonic acid (pKa = 2.85), adipic acid (pKa = 4.43), glutaric acid (pKa = 3.76), glycolic acid (pKa = 3.83), maleic acid (pKa = 1.9), succinic acid (pKa = 4.2), malic acid (pKa = 3.4), tartaric acid (for L+ pKa = 2.89; and for meso pKa = 3.22), hexanoic acid (pKa = 4.88), cyclohexanoic acid (pKa = 4.82), heptanoic acid (pKa = 4.8), octanoic acid (pKa = 4.89), 4-methyl octanoic acid (pKa = 5.23), nonanoic acid (pKa = 4.95), decanoic acid (pKa = 4.9), benzoic acid (pKa = 4.2), 4- methoxy benzoic acid (pKa = 4.37), and combinations thereof.
More preferably, the organic acid is selected from lactic acid, glycolic acid and mixtures thereof. Even more preferably, the organic acid is selected from lactic acid, glycolic acid and mixtures thereof. Most preferably, the organic acid selected is glycolic acid.
Preferably the amount of organic acid in the composition is from 1.5 to 12 wt%, more preferably 2 to 10 wt%.
Preferably the weight ratio of surfactant to organic acid is from 20:1 to 1 :20, preferably from 10:1 to 1 :10, and more preferably from 5:1 to 1 :5. pH of the composition
The composition has a pH in the range from 2.0 to 4.0, preferably from 2.5 to 4.0, even more preferably from 3.0 to 3.5. The pH of the composition may be adjusted using suitable pH adjusting agents e.g., hydrochloric acid and sodium hydroxide.
Water soluble rheology modifying polymer
To achieve the desired viscosity, the cleaning composition may comprise 0.01 to 1 wt% water soluble rheology modifying polymer. Rheology modifying polymers are known and their ability to impart viscosity to a composition may, in part, depend on the presence or absence of other ingredients.
Water soluble polymers can be used to thicken the composition which includes non-ionic, cationic and amphoteric polymers. Suitable polymers include hydroxy ethyl cellulose, modified hydroxy ethyl cellulose, guar gum, gum tragacanth, xanthan gum, gum arabic, gum acacia, Jaguar® C13S, Jaguar® C14S, Jaguar® C17, Jaguar® HP 105 (hydroxy propyl guar), Jaguar® HP 60 (hydroxylated propylated guar), Jaguar® S (Native guar gum), Carbopol® Agua CC .Merguat™ 100, Merguat™ 280, Merguat™ 281 and Merguat™ 550 from Lubrizol, poly ethylene glycols such as Polyox™ WSR- 205 (PEG 14), Polyox™ WSR N-60K (PEG 45), and Polyox™ WSR-301 (PEG 90), and hydrophobically modified hydroxyethyl celluloses like PolySurf™ 67 CS, i.e. cetyl hydroxyethylcellulose.
Seguestrant
The cleaning composition of the present invention may comprise 0.1 to 10 wt% seguestrant. Preferably the amount of seguestrant is 0.25 to 5 wt%, preferably 0.5 to 3 wt%. The seguestrant has a binding capacity of at least 280 mg Ca/g, preferably at least 290 mg Ca/g and more preferably at least 300 mg Ca/g.
Typical values are mentioned in the table below.
Suitable sequestrants are those based on organophosphonates, aminopolycarboxylates and carboxylic acids. It will be understood that suitable sequestrants include both the acid form and salts thereof.
Examples of sequestrants based on organophosphonates include diethylenetriamine penta(methylene phosphonic acid) (DTPMP), hydroxyethylidenediphosphonic acid (HEDP), and nitrilotrimethylenephosphonic acid (NTMP).
Examples of sequestrants based on aminopolycarboxylates include ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA), methylglycine diacetic acid (MGDA), and L-Glutamic acid N,N diacetic acid (GLDA).
Examples of sequestrants based on carboxylic acids include gluconic acid and itaconic acid.
Preferably the sequestrant is biodegradable. Preferred biodegradable sequestrants are nitrilotriacetic acid (NTA), ethylenediaminedisuccinic acid, (EDDS), iminodisuccinic acid, (IDS), methylglycine diacetic acid, (MGDA), L-Glutamic acid N.Ndiacetic acid (GLDA), 2- hydroxyethyliminodiacetic acid (HEIDA), ethylenediamine-N,N'-dimalonic acid (EDDM), ethylenediamine-N,N'-diglutaric acid (EDDG), 3-hydroxy-2,2-iminodisuccinic acid (HIDS), and 2,6-pyridine dicarboxylic acid (PDA), gluconic acid and itaconic acid.
Solvent
The composition according to the present invention is free of organic solvent. The term free of organic solvent herein refers to the composition comprising less than 0.4 wt%, more preferably less than 0.2 wt% and most preferably less than 0.1 wt% of organic solvent.
Preferably the cleaning composition comprises from 0 to 0.1 wt% solvent having a flash point of up to 15 °C, more preferably up to 20 °C and even more preferably up to 30 °C. An example of such a solvent is isopropyl alcohol having a flash point of 11.7 °C, ethanol having flash point 13°C. More preferably the composition is free of solvent having a flash point of up to 15 °C, more preferably up to 20 °C and even more preferably up to 30 °C. Biodegradability
At least part of the ingredients of the cleaning composition, calculated on total product excluding water and inorganic materials, is biodegradable. To be truly biodegradable, a substance or material should break down into carbon dioxide (a nutrient for plants) and water. Naturally occurring minerals that do not cause harm to the ecosystem are already in their natural mineral state and do not need to biodegrade.
Preferably at least 70 wt%, more preferably at least 90 wt% and still more preferably at least 95 wt% of the ingredients is biodegradable. Preferably at least 99 wt% is biodegradable and even more preferably essentially all ingredients are biodegradable.
For the purpose of the invention the term ‘biodegradable’ refers to ‘Inherently and Ultimately biodegradable’ as per the OECD 302 guidelines/tests. Preferably the term ‘biodegradable’ refers to ‘Readily and Ultimately biodegradable’ as per the OECD 301 series or 310 guidelines/tests.
Preferably at least part of the organic ingredients of the cleaning composition, calculated on total product excluding water, is natural. For the purpose of this invention, natural is defined as the ingredient comprising at least 50 wt% plant derived, i.e. from a natural source, material; preferably at least 70 wt%, more preferably at least 90 wt% and still more preferably at least 95 wt%. Preferably at least 99 wt% is plant derived and even more preferably essentially all of a natural ingredient is plant derived.
Preferably at least 70 wt%, more preferably at least 90 wt% and still more preferably at least 95 wt% of the organic ingredients is natural. Preferably at least 99 wt% is natural and even more preferably essentially all organic ingredients are natural.
Preferably the composition of the present invention is free of quaternary ammonium compounds.
Alkylbenzene sulphonates (ABS)
ABS is not readily available from renewable carbon or biorenewable carbon sources. Therefore, the cleaning composition of the present composition is free of alkylbenzene sulphonates and derivatives thereof. Alkylbenzene sulphonates (ABS) and derivatives thereof include water-soluble alkali metal salts of organic sulphonates having alkyl radicals typically containing from about 8 to about 22 carbon atoms, preferably 8 to 18 carbon atoms, still more preferably 12 to 15 carbon atoms and may be saturated or unsaturated. Examples include sodium salt of linear alkylbenzene sulphonate, alkyl toluene sulphonate, alkyl xylene sulphonate, alkyl phenol sulphonate, alkyl naphthalene-sulphonate, ammonium diamylnaphthalene-sulphonate and sodium dinonylnaphthalene-sulphonate and mixtures with olefin sulphonates.
Preferably the composition of the present invention is free of any sulphonated surfactant.
Method of cleaning
The invention also relates to a method of cleaning a surface comprising the steps of a. contacting the surface with the composition according to the invention in neat or dilute form for at least 15 seconds; b. optionally rinsing the surface with water; and c. optionally drying the surface.
Typically, the surface is contacted with the cleaning composition between 15 seconds and 60 minutes. Preferably between 30 seconds and 60 minutes, more preferably 1 to 45 minutes and even more preferably 5 to 30 minutes. A typical contact time for hand washing is at least 20 seconds.
The surface may be any surface suitable for cleaning including human skin like e.g. hands, and household hard surfaces like e.g. utensils or kitchenware, floors, toilets, bathroom surfaces and kitchen surfaces.
Preferably the surface is a household care hard surface and more preferably the surface is a toilet surface.
Cleaning of a toilet surface is preferably done with a neat solution that has a more viscous consistency like for example 200 to 600 mPa.s @ 20 s’1. The contact time is usually longer and typically varies between 30 seconds and 60 minutes after which the toilet surface is rinsed with water.
Typically, the composition of the invention is applied onto a hard surface in neat or diluted form. The composition may be applied by any known method such as by using a cleaning implement, such as scrub, sponge paper, cloth, wipes or any other direct or indirect application. The applied composition may be cleaned using a cleaning implement such as a scrub, sponge, paper, cloth or wipes with or without water, or rinsed off with water, optionally running water.
Preferably the surface is human skin. For handwashing, typically an amount of neat cleaning composition with a small amount of water is used to wash the skin surface of the hands such that foam is generated and the cleaning composition is in contact with the skin for at least 15 seconds, preferably at least 20 seconds. A typical dilution rate is 30 to 70 %, preferably 40 to 60% like for example 50%. The cleaning composition including foam is then rinsed of with water and the hands are dried e.g., by using an air blower or paper cloth or towel.
Use
Antibacterial efficacy of a compound can be determined using several protocols, with EN1279 and EN 13697 being among the most used. EN1279 is a so-called suspension test and EN 13697 is a so-called surface test. For household hard surfaces, EN 13697 is a better indicator. We have found that some known cleaning compositions do not always show the desired antibacterial efficacy when tested according to EN 13697.
The invention also relates to the use of a composition according to the present invention for incapacitating germs on a surface. The specific combination of anionic surfactant, nonionic surfactant and organic acid allows for broad antibacterial efficacy without the need for synthetic disinfecting agents.
The invention also relates to the use of a composition according to the present invention for incapacitating viruses on a surface. The specific combination of anionic surfactant, nonionic surfactant and organic acid allows for antiviral efficacy without the need for synthetic disinfecting agents. This specific combination is effective against both enveloped and nonenveloped viruses. Preferably the virus includes non-enveloped virus, like for example COVID- 19 (or Sars-Cov-2).
For the purpose of the invention ‘incapacitating’ is defined as including killing, interrupting growth and limiting the ability to infect an animal. Preferably ‘incapacitating’ is defined as killing.
The invention will now be illustrated by means of the following non-limiting examples.
Sodium Lauryl Sulphate (SLS)
C12-C15 fatty alcohol polyethylene glycol ether with about 7 moles (EO7): Lialet® 125-7 ex
SASOL
Short chain alkyl poly glucoside (APG 215): Glucopon® 215UP ex BASF
Long chain poly glucoside (APG 420): Glucopon® 420UP ex BASF
Protocols:
Germ removal efficacy of the composition along with a control composition shown in table 1 below were carried out using EN13697 or EN 1276 protocol for estimating antimicrobial efficacy. Soil conditions clean were created with 0.03% Bovine Serum Albumin (BSA); and dirty conditions were created by using 0.3% BSA with a contact time of 5 min.
The following organisms used were as test organisms:
Gram positive bacteria:
• Staphylococcus aureus (ATCC 6538); and
• Enterococcus hirae (ATCC 10541 ) ,
Gram negative bacteria:
• Escherichia coli (ATCC 10536); and
• Pseudomonas aeruginosa (ATCC 15442).
Differential media was used for enumerating the test organisms (to eliminate the growth of Bacillus along with the test organism).
From a 24 hours old plate culture (not more than 3 passages), a saline suspension of the above-mentioned test organisms is made. The optical density of the saline suspension is adjusted at 620 nm to obtain 108 cells/ mL. All glycerol stocks of bacteria were maintained at - 80°C; and were revived just before the carrying out the experiments. dilution:
Compositions were tested neat (i.e., undiluted) or diluted. Dilution is indicated by times of dilution. For example, 200x dilution means that to 10 ml of cleaning composition water is added to a total volume of 2000 ml. Determination of antimicrobial efficacy:
1) 1 mL of sterile BSA (clean or dirty) was taken in a sterile 15 mL falcon tube and 1 mL of test culture suspension was added.
2) The above mixture was then added to 8 mL of test product at the required dilution.
3) At the end of the contact time, the dilution neutralization method as describe below, was used to neutralize the samples.
4) Dilution neutralization method: a. At the end of contact time, 1 mL of test mixture is transferred to 9 mL of neutralizing broth (this is minus 1 (-1) dilution), b. Serial dilutions were prepared to determine the actual survivor counts; and c. Neutralization validation method is described at the end.
Neutralization validation method:
This was performed for all test organisms for all test products at the highest test concentration that was tested. Dilution neutralization method used was as follows: a. To 8 ml of highest test concentration of test product dilution, 1 ml of saline + 1 ml of BSA (clean or dirty) is added, b. After 5 minutes, transfer 1 ml of above mixture to tube containing 8 ml of neutralizing broth to be validated, c. Add 1 ml of 10'5 dilution i. e 103 cells of test organism suspension (diluted from 108 cells/ ml test culture suspension in sterile saline) to the above tube and wait for 30 minutes. Consider this tube as undiluted test system; and d. After 30 minutes, plate out undiluted test system and -1 dilution.
All plating was carried out on sterile tryptic soy agar (TAS) plates. The plates were incubated 37°C for 24 to 48 hours; and results were recorded.
Passing criteria a) N is between 1.5 x io8and 5.0 x 1O8, (8,17 < Ig N < 8.70);
No is between 1.5 x io7and 5.0 x 1 o7, (7,17 < Ig No < 7.70); b) Nvo is between 30 and 160, (3.0 x 101 and 1.6 x 102);
Nvis between 3.0 x io2and 1.6 x 103); c) A, B, C are equal to or greater than 0.5 x Nvo; where,
N is the culture control count, No is the culture control count in final test system,
Nvo is the neutralization validation culture control count; and
C is the neutralization validation count obtained for test sample.
Log reduction is calculated as difference of log of culture control in test mixture from log of count obtained in test mixture.
Example 1
To show the effect of non-ionic surfactant, formulations according to Tables 1A and 1B were prepared. Anti-bacterial efficacy was tested as indicated and the results are shown.
TABLE 1A (wt% calculated on total product)
TABLE 1 B (wt% calculated on total product)
Example 2
To show the effect of different types of non-ionic surfactant, formulations according to Tables 2 and 3 were prepared. Anti-bacterial efficacy was tested as indicated and the results are shown.
TABLE 2 (wt% calculated on total product)
TABLE 3 (wt% calculated on total product
Example 3
To show the effect of different types of organic acids, formulations according to Table 4 were prepared. Anti-bacterial efficacy was tested as indicated and the results are shown.
TABLE 4 (wt% calculated on total product)
Example 4
To show the effect of different pH, formulations according to Table 5 were prepared. Antibacterial efficacy was tested as indicated and the results are shown.
TABLE 5 (wt% calculated on total product)
Example 5
A diluted formulation according to Table 6 was prepared. Anti-bacterial efficacy was tested as indicated and the results are shown.
TABLE 6 (wt% calculated on total product)
Example 6 Virus data
To test anti-virus efficacy the composition as in Table 7 was used in standard protocol EN 14476 under clean condition. The test results are shown in Table 8.
TABLE 7 (wt% calculated on total product)
TABLE 8, Results

Claims

Claims
1. Aqueous cleaning composition comprising: a. 0.1 to 10 wt% anionic surfactant selected from alkyl sulphates, alkyl ether sulphates and combinations thereof; b. 0.1 to 10 wt% nonionic surfactant selected from alcohol ethoxylates, short chain alkyl poly glycosides and combinations thereof; and c. 1 to 20 wt% organic acid selected from lactic acid, acetic acid, malonic acid, adipic acid, glutaric acid, glycolic acid, maleic acid, succinic acid, malic acid, tartaric acid, hexanoic acid, cyclohexanoic acid, heptanoic acid, octanoic acid, 4-methyl octanoic acid, nonanoic acid, decanoic acid, benzoic acid, 4-methoxy benzoic acid and mixtures thereof; wherein the composition has a pH of 2 to 4; wherein the alcohol ethoxylate has from 1 to 7 EO; and wherein the alkyl poly glycoside has alkyl groups from C8 to C10, wherein the composition is free of organic solvent.
2. Composition according to claim 1 wherein the anionic surfactant is alkyl sulphate.
3. Composition according to claim 1 or claim 2 wherein the alcohol ethoxylate has from 3 to 7 EO.
4. Composition according to any one of claims 1 to 3 wherein the nonionic surfactant comprises alcohol ethoxylate surfactant
5. Composition according to claim 4 wherein the nonionic surfactant is alcohol ethoxylate surfactant.
6. Composition according to any one of claims 1 to 5 wherein the composition comprises from 1.5 to 12 wt%, preferably 2 to 10 wt% organic acid.
7. Composition according to any of claims 1 to 6 wherein the organic acid is selected from lactic acid, glycolic acid and mixtures thereof.
8. Composition according to any one of claims 1 to 7 wherein the weight ratio of anionic to nonionic surfactant is from 4:1 to 1 :4, preferably from 3:1 to 1 :3, and more preferably from 2:1 to 1 :2. Composition according to any one of claims 1 to 8 wherein the weight ratio of surfactant to organic acid is from 20:1 to 1:20, preferably from 10:1 to 1 :10, and more preferably from 5:1 to 1 :5. Method of cleaning a surface comprising the steps of a. contacting the surface with the composition according to any one of claims 1 to 9 in neat or dilute form for at least 15 seconds; b. optionally rinsing the surface with water; and c. optionally drying the surface. Method according to claim 10 wherein the surface is a household hard surface, preferably a toilet surface. Use of a composition according to claims 1 to 9 for incapacitating germs on a surface. Use of a composition according to claims 1 to 9 for incapacitating viruses on a surface.
EP21831044.9A 2020-12-17 2021-12-16 Aqueous cleaning composition Pending EP4263772A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20215090 2020-12-17
PCT/EP2021/086068 WO2022129269A1 (en) 2020-12-17 2021-12-16 Aqueous cleaning composition

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EP4263772A1 true EP4263772A1 (en) 2023-10-25

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Publication number Priority date Publication date Assignee Title
US6221823B1 (en) * 1995-10-25 2001-04-24 Reckitt Benckiser Inc. Germicidal, acidic hard surface cleaning compositions
DE19918183A1 (en) * 1999-04-22 2000-10-26 Cognis Deutschland Gmbh Cleaning agent for hard surfaces, typically in the form of a high foaming viscous gel, includes a combination of cationic surfactants, oligoglycosides and sulf(on)ate surfactants
GB2392167A (en) 2002-08-22 2004-02-25 Reckitt Benckiser Inc Composition containing an acid with anionic and nonionic surfactants

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WO2022129269A1 (en) 2022-06-23
CN116490597A (en) 2023-07-25

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