EP2576747B1 - Hard surface treatment composition - Google Patents

Hard surface treatment composition Download PDF

Info

Publication number
EP2576747B1
EP2576747B1 EP11719579.2A EP11719579A EP2576747B1 EP 2576747 B1 EP2576747 B1 EP 2576747B1 EP 11719579 A EP11719579 A EP 11719579A EP 2576747 B1 EP2576747 B1 EP 2576747B1
Authority
EP
European Patent Office
Prior art keywords
polymer
composition
group
copolymers
homopolymers
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.)
Active
Application number
EP11719579.2A
Other languages
German (de)
French (fr)
Other versions
EP2576747A1 (en
Inventor
Sameer Keshav Barne
Kalpana Kamalakar Nayak
Aravindakshan Perincheery
Maya Treesa Saji
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 PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=45066199&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2576747(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to PL11719579T priority Critical patent/PL2576747T3/en
Publication of EP2576747A1 publication Critical patent/EP2576747A1/en
Application granted granted Critical
Publication of EP2576747B1 publication Critical patent/EP2576747B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C11D3/16Organic compounds
    • C11D3/18Hydrocarbons
    • C11D3/188Terpenes
    • 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
    • C11D3/2003Alcohols; Phenols
    • C11D3/2006Monohydric alcohols
    • C11D3/2034Monohydric alcohols aromatic
    • 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
    • C11D3/2003Alcohols; Phenols
    • C11D3/2006Monohydric alcohols
    • C11D3/2037Terpenes
    • 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
    • C11D3/2003Alcohols; Phenols
    • C11D3/2041Dihydric alcohols
    • C11D3/2062Terpene
    • 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
    • C11D3/2068Ethers
    • 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
    • C11D3/2072Aldehydes-ketones
    • 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
    • C11D3/2093Esters; Carbonates
    • 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
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3753Polyvinylalcohol; Ethers or esters 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
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid 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
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776Heterocyclic compounds, e.g. lactam
    • 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
    • C11D3/50Perfumes
    • 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
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/24Hydrocarbons
    • C11D7/248Terpenes
    • 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
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/261Alcohols; Phenols
    • 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
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/263Ethers
    • 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
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/264Aldehydes; Ketones; Acetals or ketals
    • 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
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/266Esters or carbonates

Definitions

  • the invention is in the field of hard surface cleaning, especially in the field of hard surface cleaning composition having anti-microbial effect.
  • Hygiene is of high priority to present day consumers. Consumers all over the world use various kinds of disinfecting cleaning compositions for hard surfaces.
  • E . coli Escherichia coli
  • Staphylococcus aureus also referred to as S . aureus.
  • S . aureus Several other gram-positive and gram-negative bacteria can be found on any household surface.
  • hypochlorite The most commonly known disinfectant in house hold care is hypochlorite.
  • hypochlorite causes bad smell, bleaches clothes that come in contact with it and is unpleasant to skin mostly caused by its high alkalinity.
  • EP-A-912678 discloses the use of essential oil compounds for anti microbial effect on hard surfaces.
  • essential oils are relatively expensive ingredients. Additionally, essential oils are also known for their fragrances; using high amounts may cause a peculiar smell that is not always appreciated by the consumer.
  • WO1998/20735 (Procter and Gamble) describes a spray-able liquid disinfecting composition comprising a hydrogen peroxide, an antimicrobial essential oil, and a shear thinning polymeric thickener.
  • the hydrogen peroxide in presence shear thinning polymeric thickener provides safe and effective disinfection on clean surfaces.
  • the Application doesn't disclose a composition comprising a polymer complex and an antimicrobial composition.
  • the hygiene benefit is not only active shortly after deposition, but remains on the surface for a longer time.
  • composition that is effective against common bacteria, including both gram-positive and gram-negative bacteria.
  • composition comprising a low amount of essential oil and quaternary ammonium biocide and a polymer complex provides improved hygiene efficacy.
  • the present invention provides in a first aspect a hard surface treatment composition
  • a hard surface treatment composition comprising a polymer complex comprising polymer A selected from the group of homopolymers and copolymers of carboxylic acid, and a polymer B selected from the group of homopolymers and copolymers of alkylene oxides, vinyl pyrrolidone; and/or the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose, wherein polymer A and polymer B are not of the same class and wherein Polymer B has a monomeric unit comprising a group that forms hydrogen bonds with the carboxyl groups of polymer A; and an antimicrobial composition comprising essential oil and a quaternary ammonium biocide, wherein the pH of the hard surface treatment composition is between 2 and less than 6.
  • the invention provides a method for providing an anti-microbial effect to a hard surface comprising the steps of applying a composition according to the first aspect to the surface, and waiting for at least 5 seconds.
  • the invention provides the use of a combination of a polymer complex comprising polymer A selected from the group of homopolymers and copolymers of carboxylic acid, and a polymer B selected from the group of homopolymers and copolymers of alkylene oxides, vinyl pyrrolidone; and/or the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose; wherein polymer A and polymer B are not of the same class and wherein polymer B has a monomeric unit comprising a group that forms hydrogen bonds with the carboxyl groups of polymer A; and an antimicrobial composition comprising essential oil and a quaternary ammonium biocide, wherein the pH of the hard surface treatment composition is between 2 and less than 6, for providing a anti-microbial effect on hard surfaces.
  • anti-microbial effect is meant being able to kill bacteria under the standard European suspension test (EST) - EN 1276.
  • composition according to the invention thus comprises a polymer complex and an antimicrobial composition.
  • the polymer complex according to the invention comprises a polymer A selected from the group of homopolymers and copolymers of carboxylic acid, and a polymer B selected from the group of homopolymers and copolymers of alkylene oxides, vinyl pyrrolidone ; and/or the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose ;
  • composition according to the invention comprises a polymer A and a polymer B.
  • Polymers A and B are typically selected such that they form a complex due to the formation of hydrogen bonds.
  • the polymers may be homo polymers or copolymers, wherein by copolymer of monomer X is meant any polymer that contains the monomer X and at least one further monomer.
  • Polymers A and B are preferably present in the composition in a ratio of between 1:5 and 5:1, more preferably between 1:2 and 2:1
  • polymer A is a polymer selected from the group of homopolymers and copolymers of carboxylic acid.
  • Polymer A has a plurality of carboxyl groups.
  • the polymer A has a molecular mass preferably from 300 to 10 9 D (Dalton, also referred to as atomic mass units, amu).
  • the polymer A is selected from the class consisting of homopolymers or copolymers of carboxylic polymers, including natural synthetic and semi-synthetic polymers in this class.
  • polymer A according to the present invention include:
  • Homopolymers or copolymers of carboxylic acid have a molecular mass of preferably from 2x10 3 to 10 7 D more preferably from 5x10 4 to 10 6 D and most preferably from 9x10 4 to 5x10 5 D.
  • the particle size is preferably less than 200 ⁇ m, preferably less than 100 ⁇ m, more preferably less than 50 ⁇ m still more preferably less than 10 ⁇ m, or even less than 5 ⁇ m.
  • the homopolymers or copolymers of polysaccharide have a molecular mass of preferably from 10 3 to 10 9 D, more preferably from 10 4 to 10 9 D and most preferably from 10 5 to 10 9 D.
  • Polymer A is preferably at least partially neutralised in the Sodium (Na + ) form, preferably at least 10%w of polymer A is neutralised, more preferably at least 20%, still more preferably at least 50%.
  • Polymer A may be synthetic, semi-synthetic or natural. However, synthetic or semi-synthetic polymers are preferred.
  • Polymer A is preferably water soluble or water dispersible, most preferably polymer A is water soluble.
  • the polymer A is selected from a class consisting of homopolymers or copolymers of carboxylic acid.
  • the homopolymers or copolymers of carboxylic acid are preferably a polyacrylic acid or a copolymer thereof.
  • Examples include SOKALAN® PA (BASF) and CARBOPOL® (Lubrizol).
  • the concentration of polymer A in the composition according to the invention is preferably between 0.001 and 25% by weight, more preferably at least 0.002%, or even at least 0.005%, but preferably not more than 15%, more preferably less than 5%, still more preferably less than 1%, even more preferably less than 0.5%, even less than 0.1%, or even less than 0.05% by weight of the composition.
  • polymer B has a monomeric unit comprising a group that forms hydrogen bonds with the carboxyl groups of polymer A.
  • polymer B is selected from the group of homopolymers and copolymers of alkylene oxides, vinyl pyrrolidone; and/or the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose.
  • the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose, is generally not water soluble.
  • the particle size is set such that the particles are easily dispersible in water or and aqueous solution (i.e. a wash or rinse liquor). If the polymers are in particulate form, the particle size is preferably less than 200 ⁇ m, more preferably less than 100 ⁇ m, even more preferably less than 50 ⁇ m still more preferably less than 10 ⁇ m, or even less than 5 ⁇ m.
  • polymer A and polymer B are not of the same class.
  • Polymers A and B are selected from different classes of polymers. Without wishing to be limited by theory, it is believed that the two polymers A and B, when dissolved in water, form a complex with a solubility lower than each of the polymers A and B, which helps in enhanced deposition and other benefits.
  • Polymer B preferably has a molecular mass from 10 3 to 10 9 D.
  • Homopolymers or copolymers of vinyl pyrrolidone or vinyl alcohol preferably have a molecular mass of between 10 3 and 10 7 D, more preferably from 10 4 to 10 6 D and most preferably from 30,000 to 500,000 D.
  • Commercially available polyvinyl pyrrolidone can be used, one example of which is LUVISKOL® (BASF).
  • Homopolymers or copolymers of poly alkylene oxide preferably have a molecular mass greater than 2x10 4 D.
  • the molecular mass is preferably from 2x10 4 to 10 6 D, more preferably from 3x10 4 to 5x10 5 D and most preferably from 5x10 4 to 2x10 5 D.
  • Homopolymers or copolymers of saccharide preferably have a molecular mass of preferably from 10 3 to 10 9 D, more preferably from 10 4 to 10 9 D and most preferably from 10 5 to 10 9 D.
  • Any commercially available poly alkylene oxide, for example POLYOX® (Dow Chemical Co) can be used according to the present invention.
  • Polymer B may be synthetic, semi-synthetic or natural. However, synthetic or semi-synthetic polymers are preferred.
  • the polymer B is water soluble.
  • the polymer B is selected from a class consisting of homopolymers or copolymers of vinyl pyrrolidone or alkylene oxide.
  • the concentration of polymer B in the composition according to the invention is preferably between 0.001 and 20% by weight, more preferably at least 0.002%, or even at least 0.005%, but preferably not more than 10%, more preferably less than 5%, still more preferably less than 1%, even more preferably less than 0.5%, even less than 0.1 %, or even less than 0.05% by weight of the composition.
  • the most preferred combinations of the polymers are PAA-PVP, PAA-PEO, PAA-PEG Starch-graft-polymethacrylic acid-Polyethylene Oxide.
  • the polymer complex according to the invention comprises an antimicrobial composition comprising essential oil and quaternary ammonium biocide.
  • Essential oils are typically concentrated, hydrophobic liquid containing volatile aroma compounds from plants.
  • Essential oils are also known as volatile, ethereal oils or aetherolea.
  • An oil is "essential” in the sense that it carries a distinctive scent, or essence, of the plant.
  • Essential oils do not as, a group, need to have any specific chemical properties in common, beyond conveying characteristic fragrances.
  • Essential oils may also be obtained though synthetic or semi-synthetic routes.
  • Essential oils are generally extracted by distillation. Other processes include expression, or solvent extraction. They are used in perfumes, cosmetics, soap and other products, for flavoring food and drink, and for scenting incense and household cleaning products.
  • aromatic essential oils suitable for use in the present invention include amyl salicylate, carvacrol, cymene, e.g. p-cymene, dihydroeugenol, eugenol, hexyl eugenol, hexyl salicylate, isoeugenol, methyl eugenol, methyl isoeugenol, methyl salicylate, tert butyl cresol, thymol, and vanillin.
  • non-aromatic essential oils of terpenoid compounds include cedrene, cineole, citral (including geranial and neral), citronellal, citronellol, eucalyptol (also known as 1,8 cineole) paradihydrolinalool, dihydromyrcenol (DH myrcenol), farnesol, geraniol, hexyl cinnamaldehyde, hydroxycitronallol, hydroxycitronellal, isocitral, limonene, preferably d-limonene, linalool, longifolene, menthol, nerol, nerolidiol, pinene, e.g.
  • ⁇ -pinene phellendrene
  • terpinene e.g. ⁇ -terpinene and ⁇ -terpinene
  • terpineol e.g. ⁇ -terpineol and terpin-4-ol
  • THM tetrahydromyrcenol
  • the most preferred essential oils in the context of the present invention are thymol, terpineol and eugenol.
  • the essential oil is preferably present in the composition in a concentration of between 0.001 and 10% by weight of the composition, but preferably at least 0.002%, or even at least 0.005% by weight of the composition, while preferably not more than 5%, more preferably not more than 1%, still more preferably not more than 0.5%, or even not more than 0.1% by weight of the concentration.
  • composition comprises a second essential oil, wherein the essential oils are even more preferably selected from any combination of a thymol, a terpineol and/or a eugenol.
  • composition comprises three essential oils, wherein the essential oils are still more preferably selected from a combination of a thymol, a terpineol and a eugenol.
  • the above mentioned concentrations may be considered to be the concentrations of the combined essential oils, but preferably relate to each of the individual essential oils.
  • a quaternary ammonium biocide is used to provide additional biocidal efficacy.
  • the quaternary ammonium biocide is preferably selected from Cetyl-trimethyl-ammonium Chloride, Cetyl-trimethyl-ammonium Bromide, Tetradecyl-trimethyl-ammonium Chloride, Dodecyl-trimethyl-ammonium Chloride, Stearyl-trimethyl-ammonium Chloride, Octadecyl-trimethyl-ammonium Chloride, Dodecylpyridinium Chloride, Cetylpyridinium Chloride, Benzalkonium Chloride, Tetrabutyl-ammonium Chloride, Tetraheptyl-ammonium Chloride, 1,3-Decyl-2-methyl-imidazolium Chloride, 1-Hexadecyl-3-methyl-imidazolium Chloride, Didecyl-dimethyl-ammonium Bromide, Didecy
  • Bromides are typically not preferred due to their toxicity.
  • the most preferred quaternary ammonium biocide is benzalkonium chloride and cetylpyridinium chloride.
  • the quaternary ammonium biocide is preferably present in the composition in a concentration of between 0.01 and 10% by weight of the composition, but preferably at least 0.02%, or even at least 0.05% by weight of the composition, while preferably not more than 5%, more preferably not more than 1%, still more preferably not more than 0.5%, or even not more than 0.1% by weight of the concentration.
  • the quaternary ammonium biocide provides more complete kill with longer lasting hygiene.
  • compositions according to the invention may be applied in various hard surface cleaning composition, such as concentrated and dilute liquid compositions.
  • Concentrated composition include amongst other floor cleaner composition that need to be diluted by the consumers upon use.
  • concentrations are relating to the diluted concentrations as used by the consumer.
  • Dilute liquid compositions include but are not limited to ready-to-use compositions, such as liquid abrasive cleaners and toilet cleaning compositions, and spray compositions for glass, kitchen surfaces and bathroom surfaces
  • the contact time of the product with the surface before rinsing is at least 5 seconds, more preferably at least 10 seconds, still more preferably at least 15 seconds, or even at least 20 seconds.
  • compositions may stay for a longer period of time, preferably at least 5 minute, more preferably at least 15 minutes, still more preferably at least 1 hour, still more preferably at least 2 hours, or even more than 5 hours, or even days.
  • the pH of the compositions is between pH 2 and less than pH 6, still more preferably at least pH 3.
  • composition is not wiped away or rinsed, but may be wiped of after the indicated time.
  • Example 1 EST challenge This test is not a surface test. It is a suspension test
  • the standard European suspension test (EST) protocol - EN 1276 for antiseptics was followed.
  • the test organisms were Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aureus, and Enterococcus hirae. Under clean conditions the test was done with 0.03% BSA (bovine serum albumin), while in dirty condition 0.3% BSA was used (see table 2 below).
  • BSA bovine serum albumin
  • the contact time was 5 min. A 5 log reduction was required to pass the test.
  • compositions as used are given in table 1 below.
  • the polymer complex comprised PAA (poly acrylic acid; Mw 100,000 D, ex Sigma-Aldrich) and PEO (poly ethylene oxide; Mw 100,000 D, ex Sigma-Aldrich), in a total amount as given in the table.
  • Table 2 E. coli S. aureus P . aeruginosa E.
  • Example 2 Long Lasting hygiene challenge.
  • compositions were used (as is) Comp C (%w) Comp D (%w) Example 2 (%w) Thymol 0.025 0.025 Terpineol 0.05 0.05 Eugenol 0.005 0.005 Poly acrylic acid 1) 0.015 0.015 Poly ethylene oxide 1) 0.01 0.01 Isopropanol 0.65 0.65 Curcuma extract 0.005 0.005 Benzalkonium chloride 0.15 0.15 Citric acid 0.02 0.02 Water Up to 100% Up to 100% Up to 100% 1)
  • the polymer complex comprised PAA (poly acrylic acid; Mw 100,000 D, ex Sigma-Aldrich) and PEO (poly ethylene oxide; Mw 100,000 D, ex Sigma-Aldrich), in a total amount as given in the table, or its individual components.
  • compositions according to the invention still provides anti-microbial activity to the surface, even though the single ingredients do not show the same effect.
  • Example 3 Long Lasting hygiene challenge.
  • compositions were used (as is) Comp E (%w) Example 3 (%w) Example 4 2) (%w) Thymol 0.025 0.025 Terpineol 0.05 0.05 Eugenol 0.005 0.005 Poly acrylic acid 1) 0.015 0.015 0.015 Poly ethylene oxide 1) 0.01 0.01 0.01 C12-EO5 Nonionic 0.15 0.15 Benzalkonium chloride 0.15 Citric acid 0.02 0.02 Water Up to 100% Up to 100% Up to 100% 1)
  • the polymer complex comprised PAA (poly acrylic acid; Mw 100,000 D, ex Sigma-Aldrich) and PEO (poly ethylene oxide; Mw 100,000 D, ex Sigma-Aldrich), in a total amount as given in the table, or its individual components. 2) Comparative
  • compositions according to the invention still provides anti-microbial activity to the surface, even though the single ingredients do not show the same effect.
  • the additional benefit of benzalkonium chloride is also demonstrated.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Molecular Biology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Detergent Compositions (AREA)

Description

    Field of the invention
  • The invention is in the field of hard surface cleaning, especially in the field of hard surface cleaning composition having anti-microbial effect.
  • Background of the invention
  • Hygiene is of high priority to present day consumers. Consumers all over the world use various kinds of disinfecting cleaning compositions for hard surfaces.
  • Many micro organisms found on household surfaces are harmless, but there are also various pathogenic types or sub-species present, such as Escherichia coli, also referred to a E. coli, and Staphylococcus aureus, also referred to as S. aureus. Several other gram-positive and gram-negative bacteria can be found on any household surface.
  • Therefore present day consumers appreciate hard surface cleaning products that have anti-microbial activity.
  • The most commonly known disinfectant in house hold care is hypochlorite. However hypochlorite causes bad smell, bleaches clothes that come in contact with it and is unpleasant to skin mostly caused by its high alkalinity.
  • Various alternative hygiene materials have been proposed in the art. In recent years a number of publications have been made on the use of essential oils for anti-bacterial action.
  • EP-A-912678 discloses the use of essential oil compounds for anti microbial effect on hard surfaces.
  • However, essential oils are relatively expensive ingredients. Additionally, essential oils are also known for their fragrances; using high amounts may cause a peculiar smell that is not always appreciated by the consumer.
  • WO1998/20735 (Procter and Gamble) describes a spray-able liquid disinfecting composition comprising a hydrogen peroxide, an antimicrobial essential oil, and a shear thinning polymeric thickener. The hydrogen peroxide in presence shear thinning polymeric thickener provides safe and effective disinfection on clean surfaces. The Application doesn't disclose a composition comprising a polymer complex and an antimicrobial composition.
  • US 2007/0238634 (Foland et.al) describes a treatment formulation comprising of an active material selected from the group consisting of a surfactant, a fragrance, a dye and a combination thereof, and an ionically cross linked polymer for incorporation into nonwoven substrates. The Application doesn't disclose a composition comprising a polymer complex and an antimicrobial composition.
  • It is further desired that the hygiene benefit is not only active shortly after deposition, but remains on the surface for a longer time.
  • Accordingly it remains to be desired to prepare hard surface cleaning composition having a high anti-microbial effect, even with a low dosage of anti-microbial essential oils.
  • It is therefore an object of the invention to provide a hard surface cleaning composition, having good anti-microbial properties, at low levels of essential oil.
  • It is therefore another object of the invention to provide a hygiene benefit is not only active shortly after deposition, but remains on the surface for a longer time.
  • It is a further object of the invention to provide a composition that is effective against common bacteria, including both gram-positive and gram-negative bacteria. Surprisingly it has been found that composition comprising a low amount of essential oil and quaternary ammonium biocide and a polymer complex provides improved hygiene efficacy.
  • Summary of the invention
  • Accordingly the present invention provides in a first aspect a hard surface treatment composition comprising a polymer complex comprising polymer A selected from the group of homopolymers and copolymers of carboxylic acid, and a polymer B selected from the group of homopolymers and copolymers of alkylene oxides, vinyl pyrrolidone; and/or the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose, wherein polymer A and polymer B are not of the same class and wherein Polymer B has a monomeric unit comprising a group that forms hydrogen bonds with the carboxyl groups of polymer A; and an antimicrobial composition comprising essential oil and a quaternary ammonium biocide, wherein the pH of the hard surface treatment composition is between 2 and less than 6.
  • In a second aspect the invention provides a method for providing an anti-microbial effect to a hard surface comprising the steps of applying a composition according to the first aspect to the surface, and waiting for at least 5 seconds.
  • In a third aspect the invention provides the use of a combination of a polymer complex comprising polymer A selected from the group of homopolymers and copolymers of carboxylic acid, and a polymer B selected from the group of homopolymers and copolymers of alkylene oxides, vinyl pyrrolidone; and/or the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose; wherein polymer A and polymer B are not of the same class and wherein polymer B has a monomeric unit comprising a group that forms hydrogen bonds with the carboxyl groups of polymer A; and an antimicrobial composition comprising essential oil and a quaternary ammonium biocide, wherein the pH of the hard surface treatment composition is between 2 and less than 6, for providing a anti-microbial effect on hard surfaces.
  • By anti-microbial effect is meant being able to kill bacteria under the standard European suspension test (EST) - EN 1276.
  • These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. For the avoidance of doubt, any feature of one aspect of the present invention may be utilised 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. It is noted that the examples given in the description below are intended to clarify the invention and are not intended to limit the invention to those examples per se. Similarly, all percentages are weight/weight percentages unless otherwise indicated. 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 "from x to y", it is understood that all ranges combining the different endpoints are also contemplated.
  • Detailed description of the invention
  • The composition according to the invention thus comprises a polymer complex and an antimicrobial composition.
  • Polymer complex
  • The polymer complex according to the invention comprises a polymer A selected from the group of homopolymers and copolymers of carboxylic acid, and a polymer B selected from the group of homopolymers and copolymers of alkylene oxides, vinyl pyrrolidone ; and/or the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose ;
  • The composition according to the invention comprises a polymer A and a polymer B. Polymers A and B are typically selected such that they form a complex due to the formation of hydrogen bonds.
  • The polymers may be homo polymers or copolymers, wherein by copolymer of monomer X is meant any polymer that contains the monomer X and at least one further monomer.
  • Polymers A and B are preferably present in the composition in a ratio of between 1:5 and 5:1, more preferably between 1:2 and 2:1
  • Polymer A
  • According to the present invention, polymer A is a polymer selected from the group of homopolymers and copolymers of carboxylic acid. Polymer A has a plurality of carboxyl groups. The polymer A has a molecular mass preferably from 300 to 109 D (Dalton, also referred to as atomic mass units, amu). The polymer A is selected from the class consisting of homopolymers or copolymers of carboxylic polymers, including natural synthetic and semi-synthetic polymers in this class.
  • Some non-limiting examples of polymer A according to the present invention include:
    1. (a) homopolymers of a carboxylic acid, including but not limited to polycarboxylic acid such as polyacrylic acid, polymaleic acid or copolymers of acrylic and maleic acid.
    2. (b) polysaccharides comprising carboxylic acid groups. Such polysaccharides may include (but are not limited to) sodium alginate, natural gums and sodium carboxymethyl cellulose.
  • Homopolymers or copolymers of carboxylic acid have a molecular mass of preferably from 2x103 to 107 D more preferably from 5x104 to 106 D and most preferably from 9x104 to 5x105 D.
  • If the polymers are in particulate form, the particle size is preferably less than 200µm, preferably less than 100µm, more preferably less than 50µm still more preferably less than 10µm, or even less than 5µm.
  • The homopolymers or copolymers of polysaccharide have a molecular mass of preferably from 103 to 109 D, more preferably from 104 to 109 D and most preferably from 105 to 109 D.
  • Polymer A is preferably at least partially neutralised in the Sodium (Na+) form, preferably at least 10%w of polymer A is neutralised, more preferably at least 20%, still more preferably at least 50%.
  • Polymer A may be synthetic, semi-synthetic or natural. However, synthetic or semi-synthetic polymers are preferred.
  • Polymer A is preferably water soluble or water dispersible, most preferably polymer A is water soluble.
  • The polymer A is selected from a class consisting of homopolymers or copolymers of carboxylic acid.
  • The homopolymers or copolymers of carboxylic acid are preferably a polyacrylic acid or a copolymer thereof. Examples include SOKALAN® PA (BASF) and CARBOPOL® (Lubrizol).
  • The concentration of polymer A in the composition according to the invention is preferably between 0.001 and 25% by weight, more preferably at least 0.002%, or even at least 0.005%, but preferably not more than 15%, more preferably less than 5%, still more preferably less than 1%, even more preferably less than 0.5%, even less than 0.1%, or even less than 0.05% by weight of the composition.
  • Polymer B
  • According to the present invention, polymer B has a monomeric unit comprising a group that forms hydrogen bonds with the carboxyl groups of polymer A.
  • Accordingly, polymer B is selected from the group of homopolymers and copolymers of alkylene oxides, vinyl pyrrolidone; and/or the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose.
  • The group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose, is generally not water soluble. In order to obtain the benefit of this group of polymers the particle size is set such that the particles are easily dispersible in water or and aqueous solution (i.e. a wash or rinse liquor). If the polymers are in particulate form, the particle size is preferably less than 200µm, more preferably less than 100µm, even more preferably less than 50µm still more preferably less than 10µm, or even less than 5µm.
  • According to an essential aspect, polymer A and polymer B are not of the same class. Polymers A and B are selected from different classes of polymers. Without wishing to be limited by theory, it is believed that the two polymers A and B, when dissolved in water, form a complex with a solubility lower than each of the polymers A and B, which helps in enhanced deposition and other benefits.
  • Polymer B preferably has a molecular mass from 103 to 109 D.
  • Homopolymers or copolymers of vinyl pyrrolidone or vinyl alcohol preferably have a molecular mass of between 103 and 107 D, more preferably from 104 to 106 D and most preferably from 30,000 to 500,000 D. Commercially available polyvinyl pyrrolidone can be used, one example of which is LUVISKOL® (BASF).
  • Homopolymers or copolymers of poly alkylene oxide preferably have a molecular mass greater than 2x104 D. The molecular mass is preferably from 2x104 to 106 D, more preferably from 3x104 to 5x105 D and most preferably from 5x104 to 2x105 D.
  • Homopolymers or copolymers of saccharide preferably have a molecular mass of preferably from 103 to 109 D, more preferably from 104 to 109 D and most preferably from 105 to 109 D. Any commercially available poly alkylene oxide, for example POLYOX® (Dow Chemical Co) can be used according to the present invention.
  • Polymer B may be synthetic, semi-synthetic or natural. However, synthetic or semi-synthetic polymers are preferred.
  • According to a preferred embodiment, the polymer B is water soluble.
  • It is particularly preferred that the polymer B is selected from a class consisting of homopolymers or copolymers of vinyl pyrrolidone or alkylene oxide.
  • The concentration of polymer B in the composition according to the invention is preferably between 0.001 and 20% by weight, more preferably at least 0.002%, or even at least 0.005%, but preferably not more than 10%, more preferably less than 5%, still more preferably less than 1%, even more preferably less than 0.5%, even less than 0.1 %, or even less than 0.05% by weight of the composition.
  • Some examples of combinations of polymer A and polymer B, which are particularly preferred, are given below. Table 1: Preferred combination of the polymers
    Polymer A Polymer B
    Polyacrylic acid (PAA) Poly vinyl pyrrolidone (PVP)
    Polyacrylic acid (PAA) Polyethylene Oxide(PEO)
    Polyacrylic acid (PAA) Polyethylene Glycol (PEG)
    Polyacrylic acid (PAA) Poly vinyl alcohol (PVA)
    Sodium carboxymethyl cellulose (SCMC) Polyethylene Oxide (PEO)
    Polyacrylic acid(PAA) Hydroxyethyl cellulose
    Starch-graft-polymethacrylic acid Polyethylene Oxide
    Starch-graft-polymethacrylic acid Polyvinyl pyrrolidone
    Pluronic-g-Polyacrylic acid Polyethylene Oxide
    Pluronic-g-Polyacrylic acid Polyvinyl pyrrolidone
    Sodium carboxymethyl cellulose Hydroxyethyl cellulose
    Sodium carboxymethyl cellulose Polyvinyl alcohol
  • The most preferred combinations of the polymers are PAA-PVP, PAA-PEO, PAA-PEG Starch-graft-polymethacrylic acid-Polyethylene Oxide.
  • Antimicrobial composition
  • The polymer complex according to the invention comprises an antimicrobial composition comprising essential oil and quaternary ammonium biocide.
  • Essential oil
  • Essential oils are typically concentrated, hydrophobic liquid containing volatile aroma compounds from plants. Essential oils are also known as volatile, ethereal oils or aetherolea. An oil is "essential" in the sense that it carries a distinctive scent, or essence, of the plant. Essential oils do not as, a group, need to have any specific chemical properties in common, beyond conveying characteristic fragrances. Essential oils may also be obtained though synthetic or semi-synthetic routes.
  • Essential oils are generally extracted by distillation. Other processes include expression, or solvent extraction. They are used in perfumes, cosmetics, soap and other products, for flavoring food and drink, and for scenting incense and household cleaning products.
  • Examples of aromatic essential oils suitable for use in the present invention include amyl salicylate, carvacrol, cymene, e.g. p-cymene, dihydroeugenol, eugenol, hexyl eugenol, hexyl salicylate, isoeugenol, methyl eugenol, methyl isoeugenol, methyl salicylate, tert butyl cresol, thymol, and vanillin. Examples of non-aromatic essential oils of terpenoid compounds include cedrene, cineole, citral (including geranial and neral), citronellal, citronellol, eucalyptol (also known as 1,8 cineole) paradihydrolinalool, dihydromyrcenol (DH myrcenol), farnesol, geraniol, hexyl cinnamaldehyde, hydroxycitronallol, hydroxycitronellal, isocitral, limonene, preferably d-limonene, linalool, longifolene, menthol, nerol, nerolidiol, pinene, e.g. α-pinene, phellendrene, terpinene, e.g. α-terpinene and γ-terpinene, terpineol, e.g. γ-terpineol and terpin-4-ol, and tetrahydromyrcenol (THM).
  • The most preferred essential oils in the context of the present invention are thymol, terpineol and eugenol.
  • The essential oil is preferably present in the composition in a concentration of between 0.001 and 10% by weight of the composition, but preferably at least 0.002%, or even at least 0.005% by weight of the composition, while preferably not more than 5%, more preferably not more than 1%, still more preferably not more than 0.5%, or even not more than 0.1% by weight of the concentration.
  • It is preferred that the composition comprises a second essential oil, wherein the essential oils are even more preferably selected from any combination of a thymol, a terpineol and/or a eugenol.
  • It is even more preferred that the composition comprises three essential oils, wherein the essential oils are still more preferably selected from a combination of a thymol, a terpineol and a eugenol.
  • When more than one essential oil is present in the composition, the above mentioned concentrations may be considered to be the concentrations of the combined essential oils, but preferably relate to each of the individual essential oils.
  • Quaternary ammonium biocide
  • A quaternary ammonium biocide is used to provide additional biocidal efficacy. The quaternary ammonium biocide is preferably selected from Cetyl-trimethyl-ammonium Chloride, Cetyl-trimethyl-ammonium Bromide, Tetradecyl-trimethyl-ammonium Chloride, Dodecyl-trimethyl-ammonium Chloride, Stearyl-trimethyl-ammonium Chloride, Octadecyl-trimethyl-ammonium Chloride, Dodecylpyridinium Chloride, Cetylpyridinium Chloride, Benzalkonium Chloride, Tetrabutyl-ammonium Chloride, Tetraheptyl-ammonium Chloride, 1,3-Decyl-2-methyl-imidazolium Chloride, 1-Hexadecyl-3-methyl-imidazolium Chloride, Didecyl-dimethyl-ammonium Bromide, Didecyl-dimethyl-ammonium Chloride.
  • Bromides are typically not preferred due to their toxicity.
  • The most preferred quaternary ammonium biocide is benzalkonium chloride and cetylpyridinium chloride.
  • The quaternary ammonium biocide is preferably present in the composition in a concentration of between 0.01 and 10% by weight of the composition, but preferably at least 0.02%, or even at least 0.05% by weight of the composition, while preferably not more than 5%, more preferably not more than 1%, still more preferably not more than 0.5%, or even not more than 0.1% by weight of the concentration.
  • The quaternary ammonium biocide provides more complete kill with longer lasting hygiene.
  • Compositions
  • The compositions according to the invention may be applied in various hard surface cleaning composition, such as concentrated and dilute liquid compositions.
  • Concentrated composition include amongst other floor cleaner composition that need to be diluted by the consumers upon use. For this kind of composition, the above mentioned concentrations are relating to the diluted concentrations as used by the consumer.
  • Dilute liquid compositions include but are not limited to ready-to-use compositions, such as liquid abrasive cleaners and toilet cleaning compositions, and spray compositions for glass, kitchen surfaces and bathroom surfaces
  • It is preferred that the contact time of the product with the surface before rinsing is at least 5 seconds, more preferably at least 10 seconds, still more preferably at least 15 seconds, or even at least 20 seconds.
  • Stay on compositions, may stay for a longer period of time, preferably at least 5 minute, more preferably at least 15 minutes, still more preferably at least 1 hour, still more preferably at least 2 hours, or even more than 5 hours, or even days.
  • The pH of the compositions is between pH 2 and less than pH 6, still more preferably at least pH 3.
  • Method
  • Consequently there is provided a method for providing an anti-microbial effect to hard surfaces comprising the steps of applying a composition according to the invention to the surface, waiting for at least 5 seconds.
  • It is preferred that the composition is not wiped away or rinsed, but may be wiped of after the indicated time.
  • Examples
  • The invention will now be illustrated by means of the following non-limiting examples.
  • Example 1: EST challenge This test is not a surface test. It is a suspension test
  • The standard European suspension test (EST) protocol - EN 1276 for antiseptics was followed. The test organisms were Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aureus, and Enterococcus hirae. Under clean conditions the test was done with 0.03% BSA (bovine serum albumin), while in dirty condition 0.3% BSA was used (see table 2 below). The contact time was 5 min. A 5 log reduction was required to pass the test.
  • The compositions as used are given in table 1 below. Table 1
    Comparative A (%w) Comparative B (%w) Example 12) (%w)
    PAA 1) 0.015 0.015
    PEO 1) 0.01 0.01
    Thymol 0.025 0.025
    Terpineol 0.05 0.05
    Eugenol 0.005 0.005
    1) The polymer complex comprised PAA (poly acrylic acid; Mw 100,000 D, ex Sigma-Aldrich) and PEO (poly ethylene oxide; Mw 100,000 D, ex Sigma-Aldrich), in a total amount as given in the table.
    Table 2
    E. coli S. aureus P. aeruginosa E. hirea
    clean dirty clean dirty clean dirty clean dirty
    Comparative A Failed
    Comparative B Failed
    Example 12) Passed
    The test results against the individual organisms are given below.
    EST - E.coli (5 min contact time)
    Sample Avg.cfu/ml Log Reduction
    Clean Dirty Clean Dirty
    E.coli 135000000 125000000 0.0 0.0
    Comparative B 4700000 17500000 1.4 0.8
    Comparative A 130000000 128000000 0.0 0.0
    Example 12) 0.0 0.0 8.1 8.0
    EST- S.aureus (5 min contact time)
    Sample Avg.cfu/ml Log Reduction
    Clean Dirty Clean Dirty
    S.aureus 4000000 4000000 0.0 0.0
    Comparative B 2700000 2800000 0.2 0.2
    Example 1 4.0 0.0 6.0 6.6
    EST - P.aeruginosa (5 min contact time)
    Sample Avg.cfu/ml Log Reduction
    Clean Dirty Clean Dirty
    P.aeruginosa 11000000 7300000 0.0 0.0
    Comparative B 870000 3900000 1.1 0.3
    Example 1 0.0 0.0 7.0 6.9
    EST - Enterococcus hirae (5 min contact time)
    Sample Avg.cfu/ml Long Reduction
    Clean Dirty Clean Dirty
    E. hirae 3300000 2400000 0 0
    Comparative B 2200000 2400000 0.2 0
    Example 1 0.0 0.0 6.5 6.4
    2) Comparative
  • The results above show that very high reduction of bacteria is achieved with the compositions according to the inventions, while the single components do not achieve even a remotely similar effect.
  • Example 2: Long Lasting hygiene challenge.
  • In this example a multi day test has been done.
  • The following compositions were used (as is)
    Comp C (%w) Comp D (%w) Example 2 (%w)
    Thymol 0.025 0.025
    Terpineol 0.05 0.05
    Eugenol 0.005 0.005
    Poly acrylic acid 1) 0.015 0.015
    Poly ethylene oxide 1) 0.01 0.01
    Isopropanol 0.65 0.65
    Curcuma extract 0.005 0.005
    Benzalkonium chloride 0.15 0.15
    Citric acid 0.02 0.02
    Water Up to 100% Up to 100% Up to 100%
    1) The polymer complex comprised PAA (poly acrylic acid; Mw 100,000 D, ex Sigma-Aldrich) and PEO (poly ethylene oxide; Mw 100,000 D, ex Sigma-Aldrich), in a total amount as given in the table, or its individual components.
  • Day 1
    • Clean ceramic tiles of 10 by 10 cm are washed with Isopropanol (IPA, 70%) and dried.
    • 10 microliter of a 108 cfu/ml E.coli (ATCC 10536) suspension was spread over the tile and dried.
    • 1 ml of the fest formulations of the table above was spread over the tiles and left for 10 minutes and the tiles were dried afterwards.
    • The tiles were left overnight under moist conditions
    Day 2
    • The tiles were wiped with one wet wipe (DM water only) and one dry wipe.
    • Rinsed with water and left to dry
    • Left over night under moist conditions
    Day 3
    • 10 microliter of a 108 cfu/ml E.coli suspension was spread over the tile and dried.
    • The tiles were wiped with one wet wipe (DM water only) and one dry wipe.
    • 10 microliter of a 108 cfu/ml E.coli suspension was spread over the tile and dried for 10 min
    • 0.5 ml of a neutraliser (D/E Neutraliser) was spread over the tile and left for 5 min
    • Neutraliser was collected from the tiles
    • Collected neutraliser liquid was serially diluted and plated on CY Agar plate from HiMedia.
  • Test results (n=3) are given below
    Blank Comp C Comp D Example 2
    Start colonies (E.coli) 2.8x106 2.8x106 2.8x106 2.8x106
    Colonies in collected neutraliser 2.8x106 2.8x106 2.1x106 0
    Log reduction 0.0 0.0 0.1 6.4
  • The above results show that even after 2 days, the compositions according to the invention still provides anti-microbial activity to the surface, even though the single ingredients do not show the same effect.
  • Example 3: Long Lasting hygiene challenge.
  • In this example a multi day test has been done as in example 2, but using different compositions.
  • The following compositions were used (as is)
    Comp E (%w) Example 3 (%w) Example 42) (%w)
    Thymol 0.025 0.025
    Terpineol 0.05 0.05
    Eugenol 0.005 0.005
    Poly acrylic acid 1) 0.015 0.015 0.015
    Poly ethylene oxide 1) 0.01 0.01 0.01
    C12-EO5 Nonionic 0.15 0.15
    Benzalkonium chloride 0.15
    Citric acid 0.02 0.02
    Water Up to 100% Up to 100% Up to 100%
    1) The polymer complex comprised PAA (poly acrylic acid; Mw 100,000 D, ex Sigma-Aldrich) and PEO (poly ethylene oxide; Mw 100,000 D, ex Sigma-Aldrich), in a total amount as given in the table, or its individual components.
    2) Comparative
  • Test results (n=3) are given below
    Blank Comp E Example 3 Example 42)
    Start colonies (E.coli) 2.8x106 2.8x106 2.8x106 2.8x106
    Colonies in collected neutraliser 2.8x106 2.8x106 60 1100
    Log reduction 0.0 0.0 4.6 3.4
    2) Comparative
  • The above results show that even after 2 days, the compositions according to the invention still provides anti-microbial activity to the surface, even though the single ingredients do not show the same effect. The additional benefit of benzalkonium chloride is also demonstrated.

Claims (9)

  1. A hard surface treatment composition comprising:
    a a polymer complex comprising
    i polymer A selected from the group of homopolymers and copolymers of carboxylic acid, and
    ii a polymer B selected from the group of homopolymers and copolymers of alkylene oxides, vinyl pyrrolidone; and/or the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose,
    wherein polymer A and polymer B are not of the same class and wherein polymer B has a monomeric unit comprising a group that forms hydrogen bonds with the carboxyl groups of polymer A; and
    b an antimicrobial composition comprising:
    i essential oil; and
    ii quaternary ammonium biocide,
    wherein the pH of the hard surface treatment composition is between 2 and less than 6.
  2. A composition according to any one of claims 1 wherein polymer A is present in a concentration of between 0.001 and 25% by weight of the composition.
  3. A composition according to any one of claim 1 to 2, wherein polymer B is present in a concentration of between 0.001 and 20% by weight by weight of the composition.
  4. A composition according to any one of claim 1 to 3, wherein the essential oil is present in a concentration of between 0.001 and 10% by weight of the composition.
  5. A composition according to any one of the preceding claims, wherein the composition further comprises a second essential oil, preferably a second and a third essential oil.
  6. A composition according to any one of the preceding claims, wherein the essential oil is selected from amyl salicylate, carvacrol, cymene, e.g. p-cymene, dihydroeugenol, eugenol, hexyl eugenol, hexyl salicylate, isoeugenol, methyl eugenol, methyl isoeugenol, methyl salicylate, tert butyl cresol, thymol, vanillin, cedrene, cineole, citral (including geranial and neral), citronellal, citronellol, eucalyptol (also known as 1,8 cineole) paradihydrolinalool, dihydromyrcenol (DH myrcenol), farnesol, geraniol, hexyl cinnamaldehyde, hydroxycitronallol, hydroxycitronellal, isocitral, limonene, preferably d-limonene, linalool, longifolene, menthol, nerol, nerolidiol, pinene, e.g. α-pinene, phellendrene, terpinene, e.g. α-terpinene and γ-terpinene, terpineol, e.g. γ-terpineol and terpin-4-ol, and tetrahydromyrcenol (THM).
  7. A method for providing an anti-microbial effect to a hard surface comprising the steps of:
    a applying a composition according to any one of claim 1 to 6 to the surface, and
    b waiting for at least 5 seconds.
  8. A method according to claim 7, wherein the composition is wiped of the surface or rinsed of the surface after step 'b'.
  9. Use of a combination of
    a a polymer complex comprising
    i polymer A selected from the group of homopolymers and copolymers of carboxylic acid, and
    ii a polymer B selected from the group of homopolymers and copolymers of alkylene oxides, vinyl pyrrolidone; and/or the group of homopolymers and copolymers of vinyl alcohol, saccharides, hydroxyalkyl cellulose; and
    wherein polymer A and polymer B are not of the same class and wherein polymer B has a monomeric unit comprising a group that forms hydrogen bonds with the carboxyl groups of Polymer A; and
    b an antimicrobial composition comprising
    i essential oil; and
    ii quaternary ammonium biocide,
    wherein the pH of the hard surface treatment composition is between 2 and less than 6, for providing an anti-microbial effect on hard surfaces.
EP11719579.2A 2010-05-31 2011-05-17 Hard surface treatment composition Active EP2576747B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL11719579T PL2576747T3 (en) 2010-05-31 2011-05-17 Hard surface treatment composition

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IN1652MU2010 2010-05-31
EP10169776 2010-07-16
PCT/EP2011/057930 WO2011151169A1 (en) 2010-05-31 2011-05-17 Hard surface treatment composition

Publications (2)

Publication Number Publication Date
EP2576747A1 EP2576747A1 (en) 2013-04-10
EP2576747B1 true EP2576747B1 (en) 2014-04-23

Family

ID=45066199

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11719579.2A Active EP2576747B1 (en) 2010-05-31 2011-05-17 Hard surface treatment composition

Country Status (8)

Country Link
EP (1) EP2576747B1 (en)
CN (1) CN102906237B (en)
AR (1) AR081502A1 (en)
BR (1) BR112012028719B1 (en)
EA (1) EA020708B1 (en)
PL (1) PL2576747T3 (en)
WO (1) WO2011151169A1 (en)
ZA (1) ZA201208409B (en)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX2011004155A (en) 2008-10-20 2011-05-23 Unilever Nv An antimicrobial composition.
PL2480090T3 (en) 2009-09-24 2014-04-30 Unilever Nv Disinfecting agent comprising eugenol, terpineol and thymol
EA022660B1 (en) 2010-05-31 2016-02-29 Юнилевер Н.В. Method of providing and anti-microbial effect to skin
CN103354741B (en) 2010-12-07 2016-01-13 荷兰联合利华有限公司 Oral care composition
WO2013064360A2 (en) 2011-11-03 2013-05-10 Unilever N.V. A personal cleaning composition
ES2556981T3 (en) * 2012-04-24 2016-01-21 Enthone Inc. Composition of chemical pre-attack and chemical attack process for plastic substrates
CN106367229A (en) * 2016-08-26 2017-02-01 广西棕海园林工程有限公司 Efficient tile surface detergent as well as preparation method and use method thereof
CN107523442A (en) * 2017-07-29 2017-12-29 马鞍山市康辉纸箱纸品有限公司 A kind of stupefied groove cleaning agent of Corrugator roller
EP3572492A1 (en) 2018-05-24 2019-11-27 The Procter & Gamble Company Fine mist hard surface cleaning spray
EP3572491A1 (en) 2018-05-24 2019-11-27 The Procter & Gamble Company Spray container comprising a detergent composition
EP3572490A1 (en) 2018-05-24 2019-11-27 The Procter & Gamble Company Spray container comprising a detergent composition
EP3572493A1 (en) * 2018-05-24 2019-11-27 The Procter & Gamble Company Spray container comprising a detergent composition
EP3572489A1 (en) 2018-05-24 2019-11-27 The Procter & Gamble Company Spray container comprising a detergent composition
US20200179299A1 (en) * 2018-12-07 2020-06-11 Global Biolife Inc. Composition and method of controlling infectious diseases with functional fragrances
WO2021180936A1 (en) * 2020-03-13 2021-09-16 Unilever Ip Holdings B.V. A cleaning composition
WO2021257970A1 (en) * 2020-06-19 2021-12-23 Aire Fresco Compositions and methods for sanitizing and disinfecting environments

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5437810A (en) * 1994-04-26 1995-08-01 Colgate-Palmolive Co. Aqueous liquid detergent compositions containing oxidized polysaccharides
WO1996017591A1 (en) * 1994-12-06 1996-06-13 The Procter & Gamble Company Shelf stable skin cleansing liquid with gel forming polymer and lipid
GB9613967D0 (en) 1996-07-03 1996-09-04 Unilever Plc Improvements relating to antimicrobial cleaning compositions
EP0842604A1 (en) * 1996-11-13 1998-05-20 The Procter & Gamble Company Sprayable disinfecting compositions and processes for disinfecting surfaces therewith
US7012053B1 (en) * 1999-10-22 2006-03-14 The Procter & Gamble Company Fabric care composition and method comprising a fabric care polysaccharide and wrinkle control agent
US7612029B2 (en) * 2006-04-11 2009-11-03 The Clorox Company Controlled release using gels in a melamine foam
EP2033626A3 (en) * 2007-09-05 2010-03-17 Basf Se Imidazoliumalkyl(meth)acrylate polymers

Also Published As

Publication number Publication date
EA020708B1 (en) 2015-01-30
PL2576747T3 (en) 2014-09-30
ZA201208409B (en) 2014-01-29
CN102906237A (en) 2013-01-30
BR112012028719A2 (en) 2016-07-19
AR081502A1 (en) 2012-09-19
WO2011151169A1 (en) 2011-12-08
CN102906237B (en) 2014-10-29
BR112012028719B1 (en) 2020-12-01
EP2576747A1 (en) 2013-04-10
EA201201618A1 (en) 2013-04-30

Similar Documents

Publication Publication Date Title
EP2576747B1 (en) Hard surface treatment composition
US20130061865A1 (en) Skin treatment composition
EP3223612B1 (en) Surface disinfectant with residual biocidal property
US7465697B1 (en) Essential oils based cleaning and disinfecting compositions
CN103890160B (en) A kind of liquid hard-surface antibacterial cleansing composition
JP6251787B1 (en) Disinfecting sheet
US20070082935A1 (en) Method for disinfecting or sanitizing a surface
EP2780438B1 (en) A liquid hard surface antimicrobial cleaning composition
EP2575744B1 (en) Skin treatment composition
WO2022038630A1 (en) Surface cleaning composition and use thereof
CN112852556B (en) Household sterilizing, cleaning and mite-removing wet tissue
JP5769570B2 (en) Biofilm remover, biofilm removal composition, and biofilm removal method
JP4781663B2 (en) Antibacterial agent
EP2576744B1 (en) Laundry treatment composition
KR20080089891A (en) Liquid detergent composition for multi-purpose
US20100173011A1 (en) Disinfectant cleaning composition and method
JP7264735B2 (en) Hard surface treatment agent composition
JP6961777B1 (en) Cleaning sheet
JP5982088B2 (en) Biofilm removing agent and biofilm removing composition
WO2024218380A1 (en) Laundry sanitizing compositions

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20121016

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RIC1 Information provided on ipc code assigned before grant

Ipc: C11D 3/22 20060101ALI20131024BHEP

Ipc: C11D 3/50 20060101ALI20131024BHEP

Ipc: C11D 3/20 20060101ALI20131024BHEP

Ipc: C11D 7/24 20060101ALI20131024BHEP

Ipc: C11D 3/48 20060101ALI20131024BHEP

Ipc: C11D 3/00 20060101AFI20131024BHEP

Ipc: C11D 3/18 20060101ALI20131024BHEP

Ipc: C11D 3/37 20060101ALI20131024BHEP

Ipc: C11D 7/26 20060101ALI20131024BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20131218

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 663880

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140515

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602011006386

Country of ref document: DE

Effective date: 20140605

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 663880

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140423

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20140423

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140823

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140724

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140723

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140723

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140825

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602011006386

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140531

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140531

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20150130

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: HENKEL AG & CO. KGAA

Effective date: 20150123

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602011006386

Country of ref document: DE

Effective date: 20150123

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140517

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140623

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20110517

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140517

PLCK Communication despatched that opposition was rejected

Free format text: ORIGINAL CODE: EPIDOSNREJ1

REG Reference to a national code

Ref country code: DE

Ref legal event code: R100

Ref document number: 602011006386

Country of ref document: DE

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: OPPOSITION REJECTED

27O Opposition rejected

Effective date: 20170102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140423

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20210524

Year of fee payment: 11

Ref country code: DE

Payment date: 20210520

Year of fee payment: 11

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602011006386

Country of ref document: DE

Owner name: UNILEVER GLOBAL IP LIMITED, WIRRAL, GB

Free format text: FORMER OWNER: UNILEVER NV, ROTTERDAM, NL

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20210525

Year of fee payment: 11

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20220127 AND 20220202

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20220513

Year of fee payment: 12

Ref country code: PL

Payment date: 20220513

Year of fee payment: 12

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602011006386

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20220517

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220517

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20221201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220517