EP4396315A1

EP4396315A1 - A hygiene composition for reduction of malodour

Info

Publication number: EP4396315A1
Application number: EP22769203.5A
Authority: EP
Inventors: Samiran Mahapatra; Namisha MOHAPATRA; Ramya SAMPATH KUMAR; Sandeep Varma
Original assignee: Unilever Global IP Ltd; Unilever IP Holdings BV
Current assignee: Unilever Global IP Ltd; Unilever IP Holdings BV
Priority date: 2021-09-02
Filing date: 2022-08-25
Publication date: 2024-07-10
Anticipated expiration: 2042-08-25
Also published as: WO2023031005A1; AR126852A1; ZA202400540B; ES3014770T3; CN117795046A; EP4396315B1

Abstract

The present invention relates to a composition that is used to reduce malodour on surfaces. Particularly, the present invention relates to a hygiene composition that ensures that soft surfaces like those of fabric, and hard surfaces like those on utensils, furniture, floors, walls, and on toilets remain fresh and free of malodour for long time after the surface is cleaned with the composition. This is achieved through a combination of a rhamnolipid with a zinc salt in combination with a polysaccharide selected from one or more of pectin and algin.

Description

A HYGIENE COMPOSITION FOR REDUCTION OF MALODOUR

Field of the invention

The present invention relates to a composition that is used to reduce malodour on surfaces. Particularly, the present invention relates to a hygiene composition that ensures that soft surfaces like those of fabric, and hard surfaces like those on utensils, furniture, floors, walls, and on toilets remain fresh and free of malodours for long time after the surface is cleaned with the composition.

Background of the invention

Washing fabrics, which have soft surfaces, also known as laundering or simply as laundry is a daily chore for most people. Typically, a fabric is washed by contacting it with a detergent composition either in neat or diluted form, rinsing the fabric one or more times with water; and finally, drying it. In the washing step, the fabric is cleaned by mechanically agitating it using hands and/or by using suitable cleaning means e.g. a brush, in so-called hand-wash method. Alternatively, in so-called machine-wash method, a fabric is cleaned by mechanical agitation carried out by a machine. After the wash step involving a detergent composition, the fabric is rinsed free of the composition using copious amounts of water, two or three time. The step of drying may also be carried out by using machines; or simply by exposing the fabric to air, and if possible, under the sun. In spite of using good detergent compositions and sufficient drying, fabric at the end of the process many a times remains with a dank odour. It is observed that the quality of water e.g. hard water has a significant effect on the odour of the fabric washed in it.

Hard surface cleaning is also important for people inhabiting homes and using other common spaces like offices, restaurants, hotels and public places like bus and train stations and airports. Such cleaning generally involves using a cleaning composition that is diluted with water before use. Horizontal surfaces are cleaned by applying the diluted composition. They may then be left to air dry or are wiped dry with a clean cloth or mop. Vertical surfaces may be similarly cleaned by spraying the composition on to the surface followed optionally by wiping. Hard surfaces in such places include utensils which may be made of steel, ceramic, glass etc. Other important hard surfaces in such places include floors, walls, windows, kitchen platforms, and furniture among others. Such places also, many a time, leave an unpleasant odour after the step of cleaning, in spite of them having very good perfumes included therein.

Toilets and bathrooms are places which especially require very frequent cleaning and disinfection as they are places for excrement and personal cleansing. Toilet cleaners include harsher chemicals like bleaches and strong antimicrobial actives which are not often liked by many consumers.

Thus, in cleaning most surfaces whether hard surfaces or soft surfaces, there is a need to ensure sufficient cleaning and hygiene while ensuring that malodour developed over a course of time after the cleaning step, is minimized while at the same time using less harsh chemicals. The present inventors while searching for a solution to this problem hit upon a surprising combination of a zinc salt and a biosurfactant which not only cleaned the surface well but also ensured the place smells fresh for a long time and develops minimal malodour thereafter. The benefit was seen to be further enhanced by inclusion of specific polysaccharides like pectin or algin therein and even further improved by inclusion of a cationic surfactant.

Cleaning composition comprising biosurfactant like rhamnolipids are known e.g. WO1 4173659. However, to the knowledge of the present inventors it is heretofore not known that the combination of this type of surfactant with a zinc salt delivers synergistic anti-malodour benefit.

It is therefore an object of the present invention to provide for a hygiene composition for cleaning surfaces that provides malodour benefits for a long time after they have been cleaned.

Summary of the invention

The first aspect of the present invention relates to a hygiene composition for reduction of malodour comprising

(i) a zinc salt; and

(ii) a rhamnolipid. According to another aspect of the present invention there is provided a method of reducing odour on a surface for up to 48 hours comprising the step of contacting the surface with a composition of the first aspect, preferably diluted with water.

Detailed description of the invention

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". Thus, the term "comprising" is meant not to be limiting to any subsequently stated elements, but rather to optionally also encompass non-specified elements of major or minor functional importance. In otherwords, the listed steps or options need not be exhaustive. Whenever the words "including" or "having" are used, these terms are meant to be equivalent to "comprising" as defined above. 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. Except in the 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". Unless specified otherwise, numerical ranges expressed in the format "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 composition of the invention comprises a rhamnolipid. Rhamnolipids are a class of glycolipid. They are constructed of rhamnose combined with beta-hydroxy fatty acids. Rhamnose is a sugar. Fatty acids are ubiquitous in animals and plants.

Rhamnolipids are discussed in Applied Microbiology and Biotechnology (2010) 86:1323- 1336 by E. Deziel et al. Rhamnolipids are produced by Glycosurf, AGAE Technologies and Urumqi Unite Bio-Technology Co., Ltd. Rhamnolipids may be produced by strains of the bacteria Pseudomonas Aeruginosa. Rhamnolipids may also be produced by a recombinant cell of Pseudomonas Putida where the recombinant cell comprises increased activity of at least one of the enzymes a/P hydrolase, rhamnosyltransferase I or rhamnosyl-transferase II compared to the wild-type of the cell.

There are two major groups of rhamnolipids; mono-rhamnolipids and di-rhamnolipids. Mono-rhamnolipids have a single rhamnose sugar ring. A typical mono-rhamnolipid produced by P. aeruginosa is L-rhamnosyl-p-hydroxydecanoyl-p-hydroxydecanoate (RhaCwCw). It may be referred to as Rha-Cw-Cw, with a formula of C26H48O9. Monorhamnolipids have a single rhamnose sugar ring.

The IIIPAC Name is 3-[3-[(2R,3R,4R,5R,6S)-3,4,5-trihydroxy-6-methyloxan-2- yl]oxydecanoyloxy]decanoic acid.

Di-rhamnolipids have two rhamnose sugar rings. A typical di-rhamnolipid is L-rhamnosyl- L-rhamnosyl-p-hydroxydecanoyl-p-hydroxydecanoate (Rha2CioC ). It may be referred to as Rha-Rha-C-w-C-10, with a formula of C32H58O13.

The IIIPAC name is 3-[3-[4,5-dihydroxy-6-methyl-3-(3,4, 5-tri hydroxy-6-methyloxan-2- yl)oxyoxan-2-yl]oxydecanoyloxy]decanoic acid.

In practice, a variety of other minor components with different alkyl chain length combinations, depending upon carbon source and bacterial strain, exist in combination with the above more common rhamnolipids. The ratio of mono-rhamnolipid and di- rhamnolipid may be controlled by the production method. Some bacteria only produce monorhamnolipid, see US5767090: Example 1 , some enzymes can convert mono- rhamnolipid to di-rhamnolipid.

In various publications mono-rhamnolipids have the notation Rha-, which may be abbreviated as Rh or RL2. Similarly, di-rhamnolipids have the notation Rha-Rha or Rh- Rh or RL1. For historical reasons "rhamnolipid 2" is a mono-rhamnolipid and "rhamnolipid 1 "is a di-rhamnolipid. This leads to some ambiguity in the usage or "RL1 " and "RL2" in the literature. Throughout this patent specification, we use the terms mono- and di-rhamnolipid in order to avoid this possible confusion. However, if abbreviations are used R1 is monorhamnolipid and R2 is di-rhamnolipid. For more information on the confusion of terminology in the prior art, see the introduction to US 4814272.

The following rhamnolipids have been detected as produced by the following bacteria: (C12:1 , C14:1 indicates fatty acyl chains with double bonds).

Rhamnolipids produced by P. aeruginosa (mono-rhamnolipids):

Rha-C8-C10, Rha-C10-C8, Rha-C10-C10, Rha-C10-C12, Rha-C10-C12:1 , Rha-C12- C10, Rha-C12:1-C10

Rhamnolipids produced by P. aeruginosa (di-rhamnolipids):

Rha-Rha-C8-C10, Rha-Rha-C8-C12:1 , Rha-Rha-C10-C8, Rha-Rha-C10-C10, Rha- Rha-C10-C12:1 , Rha-Rha-C-10-C-12, Rha-Rha-C-12-C-10, Rha-Rha-C-12:1-C-12, Rha-Rha-C10-C14:1

Rhamnolipids produced by P. aeruginosa (unidentified as either mono- or di- rhamnolipids): C8-C8, C8-C10, C10-C8, C8-C12:1 , C12:1-C8, C10-C10, C12-C10, C12:1-C10 C12-C12, C12:1-C12, C14-C10, C14:1-C10, C14-C14.

Rhamnolipids produced by P. chlororaphis (mono-rhamnolipids only):

Rha-C10-C8, Rha-C10-C10, Rha-C12-C10, Rha-C12:1-C10, Rha-C12-C12, Rha- C12:1- C12, Rha-C14-C10. Rha-C-14:1-C-10.

Rhamnolipids produced by Burkholdera pseudomallei (di-rhamnolipids only): Rha-Rha-C14-C14.

Rhamnolipids produced by Burkholdera (Pseudomonas) plantarii (di-rhamnolipids only): Rha-Rha-C14-C14.

There are over 100 strains of P. aeruginosa on file at the American Type Culture Collection (ATCC). There are also a number of strains that are only available to manufacturers of commercial Rhamnolipids. Additionally, there are probably thousands of strains isolated by various research institutions around the world. Some work has gone into typing them into groups. Each strain has different characteristics including how much rhamnolipid is produced, which types of rhamnolipids are produced, what it metabolizes, and conditions in which it grows. Only a small percentage of the strains have been extensively studied.

Through evaluation and selection, strains of P. aeruginosa can be isolated to produce rhamnolipids at higher concentrations and more efficiently. Strains can also be selected to produce less byproduct and to metabolize different feedstock or pollutants. This production is greatly affected by the environment in which the bacterium is grown.

A typical di-rhamnolipid is L-rhamnosyl-L-rhamnosyl-p-hydroxydecanoyl-p- hydroxydecanoate (Rha2CioC with a formula of C32H58O13).

In practice a variety of other minor components with different alkyl chain length combinations, depending upon carbon source and bacterial strain, exist in combination with the above more common rhamnolipids. The ratio of mono-rhamnolipid and di- rhamnolipid may be controlled by the production method. Some bacteria only produce monorhamnolipid, see US6767090: Example 1 , some enzymes can convert mono- rhamnolipid to di-rhamnolipid.

Preferably the rhamnolipid is selected from:

Rhamnolipids produced by P. aeruginosa (mono-rhamnolipids):

Rhamnolipids produced by P. chlororaphis (mono-rhamnolipids only):

Rha-C10-C8, Rha-C10-C10, Rha-C12-C10, Rha-C12:1-C10, Rha-C12-C12, Rha- C12:1- C12, Rha-C14-C10, Rha-C14:1-C10.

Mono-rhamnolipids may also be produced from P.putida by introduction of genes rhIA and rhIB from Psuedomonas aeruginosa [Cha et al. in Bioresour Technol. 2008. 99(7):2192-9] Rhamnolipids produced by P. aeruginosa (di-rhamnolipids):

Rha-Rha-C8-C10, Rha-Rha-C8-C12:1 , Rha-Rha-C10-C8, Rha-Rha-C10-C10, Rha- RhaC10-C12:1 , Rha-Rha-C10-C12, Rha-Rha-C12-C10, Rha-Rha-C12:1-C12, Rha- Rha-C10- C14:1

Rhamnolipids produced by Burkholdera pseudomallei (di-rhamnolipids only):

Rha-Rha-C14-C14.

Rhamnolipids produced by Burkholdera (Pseudomonas) plantarii (di- rhamnolipids only):

Rha-Rha-C14-C14.

Rhamnolipids produced by P. aeruginosa which are initially unidentified as either mono- or di-rhamnolipids:

C8-C8, C8-C10, C10-C8, C8-C12:1 , C12:1-C8, C10-C10, C12-C10, C12:1-C10, C12- C12, C12:1-C12, C14-C10, C14:1-C10, C14-C14.

Preferably the Rhamnolipid is L-rhamnosyl-(3-hydroxydecanoyl-p-hydroxydecanoate (RhaCwCw with a formula of C26H48O9).

Preferably, the rhamnolipid comprises at least 50 wt.% di-rhamnolipid, more preferably at least 60 wt.% di-rhamnolipid, even more preferably 70 wt.% di-rhamnolipid, most preferably at least 80 wt.% di-rhamnolipid.

Preferably the rhamnolipid is a di-rhamnolipid of formula: Rha2C8-i2Cs-i2. The preferred alkyl chain length is from Cs to C12. The alkyl chain may be saturated or unsaturated. The most preferred di-rhamnolipid is an example of a di-rhamnolipid of formula: Rha2Cs- 12C8-12, known as Rhamnolipid R2 herein, and can be supplied from Evonik. The composition preferably comprises rhamnolipid in 0.01 to 15%, more preferably 0.1 to 10% by weight of the composition.

The composition of the invention comprises a zinc salt. The zinc salt is preferably selected from one or more of zinc chloride, zinc sulphate, zinc carbonate, zinc nitrate and zinc salts of organic acids preferably zinc acetate or zinc citrate. The salt is more preferably selected from one or more of zinc acetate, zinc chloride, and zinc sulphate. Of the zinc salts, zinc acetate and zinc chloride are especially preferred.

The composition preferably comprises the zinc salt at a concentration of 0.01 to 5%, preferably 0.03 to 2% by weight of the composition.

The composition preferably additionally comprises one or more polysaccharide selected from algin or pectin preferably pectin.

Alginic acid, also called algin, is a polysaccharide distributed widely in the cell walls of brown algae that is hydrophilic and forms a viscous gum when hydrated. Alginic acid is a linear copolymer with homopolymeric blocks of (1— >4)-linked p-D- mannuronate (M) and a-L-guluronate (G) residues, respectively, covalently linked together in different sequences or blocks. The monomers may appear in homopolymeric blocks of consecutive G-residues (G-blocks), consecutive M-residues (M-blocks) or alternating M and G-residues (MG-blocks). a-L-guluronate is the C-5 epimer of p-D- mannuronate. Alginates are refined from brown seaweeds. Throughout the world, many of the Phaeophyceae class brown seaweeds are harvested to be processed and converted into sodium alginate and alginic acid.

Pectin is a structural acidic heteropolysaccharide contained in the primary and middle lamella and cell walls of terrestrial plants. Its main component is galacturonic acid, a sugar acid derived from galactose. It is produced commercially as a white to light brown powder, mainly extracted from citrus fruits, and is used in food as a gelling agent, particularly in jams and jellies. It is also used in dessert fillings, medicines, sweets, as a stabiliser in fruit juices and milk drinks, and as a source of dietary fibre. Pectin also known as pectic polysaccharides, are rich in galacturonic acid. Several distinct polysaccharides have been identified and characterised within the pectic group. Homogalacturonans are linear chains of a-(1-4)-linked D-galacturonic acid. Substituted galacturonans are characterised by the presence of saccharide appendant residues (such as D-xylose or D-apiose in the respective cases of xylogalacturonan and apiogalacturonan) branching from a backbone of D-galacturonic acid residues. Rhamnogalacturonan pectins (RG-I) contain a backbone of the repeating disaccharide: 4)-a-D-galacturonic acid-(1 ,2)-a-L-rhamnose-(1. From many of the rhamnose residues, sidechains of various neutral sugars branch off. The neutral sugars are mainly D-galactose, L-arabinose and D-xylose, with the types and proportions of neutral sugars varying with the origin of pectin. Another structural type of pectin is rhamnogalacturonan II (RG-II), which is a less frequent, complex, highly branched polysaccharide.

Of the polysaccharides, pectin is preferred for inclusion in the composition of the invention. Pectin when included is preferably derived from one or more of a fruit chosen from pear, apple, guava, plum, gooseberry, orange or any other citrus fruit, preferably citrus. It is preferably from apple or citrus fruit.

The composition preferably comprises the polysaccharide at a concentration of 0.001 to 20%, preferably 0.1 to 10% by weight of the composition.

Laundry detergent composition:

The composition may be delivered as a laundry detergent composition which in addition to the essential ingredients of the present invention may also include 1 to 80% surfactant. The laundry detergent composition may be delivered in the form of a solid or as a liquid.

The laundry detergent composition in which the present invention may be delivered is preferably in the liquid form. The term liquid may encompass emulsions, suspensions, and compositions having flowable yet stiffer consistency, known as gels or pastes. Pourable liquid detergent compositions preferably have a viscosity of from 200 to 1 ,500 mPa.s, preferably from 200 to 700 mPa.s. Such compositions generally have an aqueous continuous phase. Preferably, the composition comprises at least 50% wt. water and more preferably at least 70% wt. water. Water is generally present in an amount of 20% to 99.9% preferably from 40% to 80% by weight of the composition.

Liquid laundry detergent compositions generally comprise 1 to 30%, preferably from 2 to 15% by weight of one or more surfactants. The surfactant is generally anionic in nature. Preferred anionic surfactants are of the organic sulfates and sulfonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term “alkyl” being used to include the alkyl portion of higher acyl radicals. Examples of such materials include alkyl sulfates, alkyl ether sulfates, alkaryl sulfonates, alpha-olefin sulfonates and mixtures thereof. The alkyl radicals preferably contain from 10 to 18 carbon atoms and may be unsaturated. The alkyl ether sulfates may contain from one to ten ethylene oxide or propylene oxide units per molecule, and preferably contain one to three ethylene oxide units per molecule. The counterion for anionic surfactants is generally an alkali metal such as sodium or potassium; or an ammoniacal counterion such as monoethanolamine, (MEA) diethanolamine (DEA) or triethanolamine (TEA). Mixtures of such counterions may also be employed. Sodium and potassium are preferred.

Most preferred surfactants are of the alkylbenzene sulfonates type, particularly linear alkylbenzene sulfonates (LAS) with an alkyl chain length of from 10 to 18 carbon atoms. Some alkyl sulfate surfactant (PAS) may be used, such as non-ethoxylated primary and secondary alkyl sulphates with an alkyl chain length of from 10 to 18.

Preferably, the composition comprises from 5 to 20 wt% non-ionic surfactant based on the total weight of composition. A preferred class of nonionic surfactant for use in the invention includes aliphatic Cs to Cis, more preferably C12 to C15 primary linear alcohol ethoxylates with an average of from 3 to 20, more preferably from 5 to 10 moles of ethylene oxide per mole of alcohol. Preferred non-ionic surfactants are the C16/18 alcohol ethoxylates.

Liquid laundry detergent compositions also generally comprise agents like soil release polymers, hydroptropes, co-surfactants, builders, polymeric thickeners, and shading dyes in addition to the above described ingredients. Soil release polymers (SRP) help to improve the detachment of soils from fabric by modifying the fabric surface during washing.

The SRP structure may also include capping groups to control molecular weight or to alter polymer properties such as surface activity. Preferred SRPs for use in the invention include copolyesters formed by condensation of terephthalic acid ester and diol, preferably 1 ,2 propanediol, and further comprising an end cap formed from repeat units of alkylene oxide capped with an alkyl group. The SRP, when included, may range from 0.1 to 10%, desirably from 0.3 to 7%, more preferably from 0.5 to 5% by weight of the composition.

A composition of the invention may incorporate non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers. Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids such as C1 to C5 monohydric alcohols (such as ethanol and n- or i-propanol); C2 to C6 diols (such as monopropylene glycol and dipropylene glycol); C3 to C9 triols (such as glycerol); polyethylene glycols having a weight average molecular weight (M_w) ranging from about 200 to 600; C1 to C3 alkanolamines such as mono-, di- and triethanolamines; and alkyl aryl sulfonates having up to 3 carbon atoms in the lower alkyl group (such as the sodium and potassium xylene, toluene, ethylbenzene and isopropyl benzene (cumene) sulfonates). Non-aqueous carriers, when included, may be present in an amount ranging from 0.1 to 3%, preferably from 0.5 to 1% by weight of the composition. The preferred hydrotropes are monopropylene glycol and glycerol.

The liquid laundry detergent composition of the invention may contain one or more cosurfactants (such as amphoteric (zwitterionic) and/or cationic surfactants) in addition to the non-soap anionic and/or nonionic detersive surfactants described above. Such cosurfactant, when included, may be present in an amount ranging from 0.1 to 5% by weight of the composition.

The liquid laundry detergent composition may also optionally contain relatively low levels of organic detergent builder or sequestrant material. Examples include the alkali metal citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates aminocarboxylates and polyacetyl carboxylates. If utilized, the organic builder materials may comprise from about 0.5 percent to 20 wt percent, preferably from 1 wt percent to 10 wt percent, of the composition.

When the composition is a liquid laundry detergent composition, it may be diluted with water in ratios like 1 :50, 1 :100, 1 :200 to form the wash liquor. The solid laundry compositions herein can take a variety of physical solid forms including forms such as powder, granule, ribbon, noodle, paste, tablet, flake, pastille and bar, and preferably the composition is in the form of powder, granule or a bar.

The composition according to the present invention may be made via a variety of conventional methods known in the art including dry-mixing, compaction such as agglomerating, extrusion, tableting, or spray-drying of the various compounds comprised in the detergent component, or combinations of these techniques. The powder or granule compositions preferably have a density of more than 350 grams/litre, more preferably more than 450 grams/litre or even more than 570 grams/litre.

Typical solid laundry detergent compositions comprise one or more of surfactants chosen from anionic, nonionic, zwitterionic, cationic, amphoteric types, preferably it is of the anionic type. These compositions in solid form typically comprise from 1 to 30% by weight anionic surfactants. Details on the various ingredients like the anionic and nonionic surfactants, the SRPs, hydroptopes, builders etc which are described for the liquid detergent composition may also be included in the solid detergent composition. Additionally, they may also comprise other adjuvents to provide benefits to the fabric being washed e.g. antiredeposition polymers which together may be included in 0 to 5% by weight of the composition. Builders are generally included especially to counteract the ill effects of hardness of water being used to wash the fabric and these account for up to 50% typically 10 to 30% by weight of the composition. Other fabric benefit agents like shading dyes and optical brightener may be included in up to 1 % by weight of the composition. Bleaches may sometimes be included and when it is included it accounts for up to 10% by weight of the composition and fillers generally account for up to 40% by weight of the composition.

The solid laundry detergent composition according to the present invention preferably has a pH from 7.0 to 10.5, preferably 7.0 to 10.2, still preferably from 8.5 to 10.2, when measured at 1 wt.% dilution in de-ionised water at 25°C. The composition may preferably include a buffer. Fabric conditioning composition

The composition of the invention may also be delivered as a fabric conditioning composition which additionally comprises 1 to 50% of a fabric softening active.

The fabric conditioner composition is also referred to as a fabric softener. Fabric conditioners comprise active materials which soften or condition fabric. Examples of suitable fabric softening actives include: quaternary ammonium compounds, silicone polymers, polysaccharides, clays, amines, fatty esters, dispersible polyolefins, polymer latexes and mixtures thereof. The fabric softening active is preferably selected from a quaternary ammonium compound, or silicone polymer and mixtures thereof, more preferably a quaternary ammonium compound.

The fabric softening compounds may preferably be cationic or non-ionic. Preferably, the fabric softening compounds of the present invention are cationic.

Fabric conditioning compositions for use in accordance with the invention may be dilute or concentrated. Dilute products typically contain up to about 6 wt.% of the composition softening compounds, generally about 1 to 5 wt.%, whereas concentrated products may contain up to about 50 wt. % of the composition softening compounds, preferably from about 5 to about 50 wt.%, more preferably from 6 to 25 wt.%. Overall, the products of the invention may contain from 1 to 50 wt. %, preferably from 2 to 25 wt. % of the composition softening compounds, more preferably 2 to 20 wt. % of softening compounds.

The preferred softening compounds for use in fabric conditioner compositions of the invention are quaternary ammonium compounds (QAC). The QAC preferably comprises at least one chain derived from fatty acids, more preferably at least two chains derived from fatty acids. Generally, fatty acids are defined as aliphatic monocarboxylic acids having a chain of 4 to 28 carbons. Preferably the fatty acid chains are palm or tallow fatty acids. Preferably the fatty acid chains of the QAC comprise from 10 to 50 wt. % of saturated C18 chains and from 5 to 40 wt. % of monounsaturated C18 chains by weight of total fatty acid chains. In a further preferred embodiment, the fatty acid chains of the QAC comprise from 20 to 40 wt. %, preferably from 25 to 35 wt. % of saturated C18 chains and from 10 to 35 wt. %, preferably from 15 to 30 wt. % of monounsaturated C18 chains, by weight of total fatty acid chains.

The preferred quaternary ammonium fabric softening compounds for use in compositions of the present invention are so called "ester quats". Particularly preferred materials are the ester-linked triethanolamine (TEA) quaternary ammonium compounds comprising a mixture of mono-, di- and tri-ester linked components.

The composition of the invention delivered as fabric conditioning compositions may further comprise a nonionic surfactant. Typically these can be included for the purpose of stabilising the compositions. Suitable nonionic surfactants include addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines.

Preferably the nonionic surfactant has an HLB of from about 7 to about 20, more preferably from 10 to 18, e.g. 12 to 16. Genapol™ C200 (Clariant) based on coco chain and 20 EO groups is an example of a suitable nonionic surfactant.

If present, the nonionic surfactant is present in an amount from 0.01 to 10 wt.%, more preferably 0.1 to 5 wt.%, based on the total weight of the composition. Thus, the fabric conditioning composition of the invention preferably comprises 0.1 to 5 wt% of a nonionic surfactant preferably an fatty alcohol ethoxylate.

Co-softeners may be used in the fabric conditioning composition. When employed, they are typically present at from 0.1 to 20 wt.% and particularly at from 0.5 to 10 wt.%, based on the total weight of the composition. Preferred co-softeners include fatty esters, and fatty N-oxides. Fatty esters that may be employed include fatty monoesters, such as glycerol monostearate, fatty sugar esters, such as those disclosed WO 01/46361 (Unilever).

The compositions of the present invention may comprise a fatty complexing agent. Especially suitable fatty complexing agents include fatty alcohols and fatty acids. Of these, fatty alcohols are most preferred. Preferably the composition of the present invention comprises 0.5 to 20 wt.% perfume materials by weight of the composition, more preferably 1 to 15 wt.% perfume materials, most preferably 2 to 10 wt. % perfume materials.

The fabric conditioner composition is preferably in an aqueous form. The compositions preferably comprise from 75 to 95 wt.% water

The fabric conditioning composition may be used to treat fabrics either in a hand washing or a machine washing process. Preferably the fabric conditioner is used in the rinse stage of the washing process.

Preferably the clothes are treated with a 10 to 100 ml dose of fabric conditioner for a 4 to 7 kg load of clothes. More preferably, 10 to 80 ml for a 4 to 7 kg load of clothes.

Liquid dishwash composition

The composition of the invention may be useful for upkeep of kitchen items e.g.. utensils and dishes which may be cleaned using a liquid dishwash compositions. The various ingredients other than the essential ingredients claimed in the present invention are summarized below. Among the various ingredients, anionic surfactants, non-ionic surfactants, and hydrotropes as detailed under liquid laundry detergent composition may be used in liquid dishwash composition. Additionally, other ingredients which may be included are detailed below:

Preferably, the composition further comprises an amphoteric surfactant. Preferably, an amphoteric surfactants is selected from include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, having alkyl radicals containing from about 8 to about 22 carbon atoms, the term “alkyl” being used to include the alkyl portion of higher acyl radicals. More preferably, an amphoteric surfactant selected from alkyl amidopropyl betaines, even more preferably cocoamidopropyl betaine. Amphoteric surfactant, when included, may be present in an amount ranging preferably from 0.1 to 5 wt%, more preferably from 0.1 to 4 wt%, even more preferably from 1 to 3 wt%. Mixtures of any of the above described materials may also be used. A good combination of surfactants for use in the present invention in the form of a dishwash composition is one having 1 to 30 wt% anionic surfactant and 0.1 to 5 wt% an amphoteric surfactant.

Liquid dishwash composition may preferably comprise an organic acid or its salts comprising citric acid or its salt. Preferably, the organic acid or its salt may further comprise succinic acid, malic acid, lactic 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. Examples of salts of organic acid include corresponding salts of these organic acids that are formed preferably with sodium and potassium, more preferably with sodium, e.g. trisodium citrate. More preferably, organic acid or its salt may further comprise maleic acid or its salt. Even more preferably, the organic acid or its salt is selected from citric acid or its salt e.g. trisodium citrate. Preferably, the composition does not comprise silver dihydrogen citrate.

The composition comprises an organic acid or its salts comprising citric acid or its salt from 0.2 to 5 wt%, preferably from 0.3 to 4 wt%, more preferably from 0.4 to 3 wt%, even more preferably from 0.5 to 3 wt%, further more preferably from 1 to 2 wt%.

Preferably, the liquid dishwash composition further comprises water in an amount ranging from 5 to 99 wt%, more preferably from 10 to 90 wt%, even more preferably from 15 to 80 wt%, further more preferably from 20 to 70 wt%, still more preferably from 30 to 65 wt%, yet more preferably from 35 to 60 wt%, yet further more preferably from 40 to 55 wt%.

Preferably, the liquid dishwash composition further comprises one or more sequestrants. Preferably, the composition comprises sequestrant may be present in an amount from 0.1 to 5 wt%, more preferably from 0.25 to 4 wt%, even more preferably from 0.5 to 2.5 wt%.

A preferred sequestrant is a phosphonic acid or a salt thereof. The phosphonic acid (or salt thereof) sequestrant is preferably selected from the group consisting of 1 - Hydroxyethylidene-1 ,1 -diphosphonic acid (HEDP; commercially available as Dequest(R) 2010), Diethylenetriaminepenta(methylenephosphonic acid) (DTPMP; commercially available as Dequest(R) 2066), Hexa methylene diamine tetra(methylenephosphonic acid) (HDTMP), Amino tris(methylenephosphonic acid) (ATMP), Ethylene diamine tetra(methylenephosphonic acid) (EDTMP), Tetra methylene diamine tetra(methylenephosphonic acid) (TDTMP); and Phosphono butane tricarboxylic acid (PBTC). The most preferred sequestrant is 1 -Hydroxyethylidene-1 ,1 - diphosphonic acid (HEDP). It is preferable that the sequestrant is added to the formulation in acid form.

Optionally, liquid dishwash composition further comprises an enzyme with or without a suitable enzyme stabilizer. Preferably the composition further comprises an effective amount of at least one enzyme with or without a suitable enzyme stabilizer. Examples of suitable enzymes include pectate lyase, protease, amylase, cellulase, lipase, mannanase; with or without an appropriate stabilizing agent.

Preferably, viscosity of the composition may suitably range from about 200 to about 10,000 mPa.s at 25°C at a shear rate of 21 sec¹. This shear rate is the shear rate that is usually exerted on the liquid when poured from a bottle. Pourable liquid home care compositions generally have a viscosity of from 200 to 1 ,500 mPa.s, preferably from 100 to 800 mPa.s.

The liquid dishwash composition preferably has pH in the range from 2.0 to 8.0, preferably from 2.5 to 7.5, more preferably from 3.0 to 7.0, even more preferably from 3.5 to 7.0, further more preferably from 4.0 to 7.5, still more preferably from 4.5 to 7.5, yet more preferably from 5.0 to 7.5, still further more preferably from 5.5 to 7.5 and yet further more preferably from 6.0 to 6.5.

The liquid dishwash composition may further comprise one or more polymers. Preferably, polymers can be cationic, anionic, amphoteric or nonionic types with molecular weights higher than 100,000 Dalton. They are known to increase the viscosity and stability of liquid compositions, to enhance in-use and after-use skin sensory feels, and to enhance lather creaminess and lather stability. Examples of polymers include polyvinyl alcohol, polyacrylic acid, silane, siloxane and mixtures thereof. If present, polymers may be present in the composition in an amount ranging preferably from 0.001 to 10 wt%, more preferably from 0.1 to 6 wt%, still further more preferably from 1 to 3 wt%.

Preferably, the composition may be used as is, i.e. neat, or it may be diluted before use. The extent of dilution is generally dependent on market choice. In some markets a more concentrated product is desired while in others a more dilute product is preferred. When the composition is a liquid dishwash compositions it is typically diluted with water in a weight ratio in the range of 1 :1 to 1 :10.

The liquid dishwash composition may optionally comprise ingredients, such as fragrance, colorant, foam boosting agents, and odor absorbing materials.

General purpose or toilet cleaners

The composition of the invention may be formulated as a general purpose cleaner which is usually used to clean floors (in which case it may be known as a floor cleaner) or used to clean toilets (in which case it may be known as a toilet cleaner). It may also be used to clean other hard surfaces like furniture, table tops, kitchen platforms and other surfaces in homes, offices, restaurants and other public places. Such compositions preferably include a cationic surfactant which in addition to providing cleaning benefit also ensure instant disinfection i.e killing or inactivation of germs.

Preferably, the cationic surfactant is a quaternary ammonium surfactant, preferably the quaternary ammonium surfactant is selected from one or more of alkyl dimethyl benzylammonium chloride (ADBAC) which is also known as benzalkonium chloride (BKC), bis (C8-C18) alkyl di methyl quaternary ammonium chloride preferably didecyl dimethyl ammonium chloride (DDAC), cetyl trimethyl ammonium chloride (CTAC), cetyl pyridinium chloride (CPC), cetrimonium bromide , benzethonium chloride (BZE); and dimethyldioctadecylammonium chloride. Preferred aspect of the invention provides for the cationic surfactant to be chosen from one or more of BKC or DDAC, preferably BKC.

The quaternary ammonium surfactants mentioned above, are available as a single quaternary ammonium compound, as well as mixtures of two or more different quaternary ammonium compounds e.g. under trademarks BARDAC™, BARQUAT® and HYAMINE® (all by Lonza); and BTC® (by Stepan). Quaternary ammonium compounds available as a single quaternary ammonium compound include didecyl dimethyl ammonium chloride (available as BARDAC™ 2250 R and BTC® 1010, both 50% active; and BARDAC™ 2280 R and BTC® 1010-80, both 80% active), alkyl dimethyl benzyl ammonium chloride (available as BARQUAT® MB-50, BARQUAT® MX-50, BARQUAT® QJ-50, HYAMINE® 3500, BTC® 50, BTC® 50E, BTC® 65, BTC® 776, BTC® 824, BTC® 835; each 50% active; and the same is available as BARQUAT® MB-80, BARQUAT® MX-80, HYAMINE® 3500-80, BTC® 8248, BTC® 8358; each 80% active

The composition when formulated as a general purpose or toilet cleaner preferably comprises 0.1 to 3 wt%, more preferably 0.3 to 2 wt% cationic surfactant.

When the composition is formulated as a toilet cleaner, it may additionally comprise a bleach. The bleach may be a chlorine containing compound or a peroxide compound.

Ingredients like amphoteric surfactant and sequestrant may be included in the floor cleaner and toilet cleaner composition of the present invention. Details on the various types of the amphoteric surfactant and sequestrant are the same as given under the section on liquid dishwash composition. General purpose cleaners and toilet cleaners may be diluted before use. When diluted, they may be diluted with water in a weight ratio in the range of 1 : 10 to 1 : 1000.

The composition of the invention may also be delivered as a rim block. By a rim block is meant a shaped solid composition that is hung on to the rim of the toilet usually in a plastic cage like container so that every time the toilet is flushed, a quantity of water passes over the solid composition, eroding a part thereof before flushing into the toilet bowl. The toilet rim block preferably additionally includes a perfume to provide a lingering pleasant odour after every toilet flush.

According to another aspect of the present invention there is provided a method of reducing odour on a surface for up to 48 hours comprising the step of contacting the surface with a composition of the invention preferably diluted with water. The invention will now be illustrated with the help of the following non-limiting examples.

Examples

The materials used in the examples in the present invention are commercially available and were purchased from its supplier indicated below. Algin and Pectin were sourced from CP Kelco, United Kingdom. Rhamnolipid used in the experiments below was obtained from Evonik Industries, Germany.

Example A,B, 1 : Reduction of dank malodour measured with a sniff test in a combination of two actives.

The samples as shown in Table-1 were taken and the malodour generated was measured using the following protocol.

Urine Malodour assay

Materials:

• Water of standard Hardness (French Hardness 55)

• Artificial Urine media (AUM; as described in Letters in Applied Microbiology, 1997, 24, 203-206)

• Malodour causing bacteria (as described below)

• Sterile dextrose solution (1%)

• Clean glass slides and sterile Duran scott bottles for preparation of artificial urine and of WSH

• Sterile distilled water

Malodour causing bacteria (Ref: The influence of thermal reaction and microbial transformation on the odour of human urine. Flavour Fragr. J. 2013, 28, 200-211 , DOI 10.1002/ffj.3143) 10⁸ cfu/mL of urine bacteria in saline were prepared as the stock for malodour causing bacteria. 1 mL from suspensions of each of these bacteria were mixed together in a separate test tube which is a 10⁸ cfu/mL mixed culture. The mixed culture was serially diluted to get a 10⁴ cfu/mL. This is used as the mixed bacterial inoculum for generation of malodour. Incubation solution composition

The incubation solution was prepared freshly every time before the experiment by mixing 396 mL sterile distilled water, 400 mL 2X concentrated water of standard hardness, 4 mL of 1 % dextrose solution, 10mL of mixed bacterial inoculum 10⁴ cfu/mL and 200 mL of artificial urine media, were combined in a sterile 1 L Scott-Duran bottle. After this, 40 mL of the incubation solution was aliquoted in to a 100 mL sterile sample container.

To this, the zinc salt and/or an rhamnolipids were added in amounts as shown in table 1 below. The incubation solution alone (neither zinc salt nor rhamnolipid added to it) serves as the control. Incubation was carried out at 37°C for 48hours for allowing the malodour to develop inside the container.

Malodour detection by sniff test

Malodour is measured on a scale from 0 (No urine like odour) and 5 (strong pungent ammonia/urine odour). The untreated control has the maximum malodour. The odour scores are given by expert panellists in a blinded test.

Table - 1 :

The data in the table above indicates that the combination of a pzinc salt and a rhamnolipid provides for synergistic interaction in reducing malodour on fabric.

Examples C-G, 2-4: Reduction of dank malodour measured with a sniff test in a combination of three actives.

The samples as shown in Table -2 were taken and the malodour generated, measured using the protocol as disclosed above, is summarized in table -2. Table - 2:

The data in the table above indicates that combination of rhamnolipid with a zinc salt (zinc acetate) and additionally comprising a polysaccharide (algin or pectin) provides for synergistic anti malodour benefit.

Claims

23 Claims

1 . A hygiene composition for reduction of malodour comprising

(i) a zinc salt; and

(ii) a rhamnolipid; and

(iii) one or more polysaccharide selected from algin or pectin preferably pectin.

2. A composition as claimed in claim 1 wherein the zinc salt is selected from one or more of zinc chloride, zinc sulphate, zinc carbonate, zinc nitrate and zinc salts of organic acids preferably zinc acetate or zinc citrate.

3. The composition as claimed in claim 2 wherein the zinc salt is selected from one or more of zinc acetate, zinc chloride, and zinc sulphate.

4. The composition as claimed in any one of the preceding claims wherein the zinc salt is present in 0.01 to 5% by weight of the composition.

5. The composition as claimed in any one of the preceding claims wherein the rhamnolipid is present in 0.01 to 15% by weight of the composition.

6. The composition as claimed in any one of the preceding claims wherein the polysaccharide is present at a concentration of 0.001 to 20 % by weight of the composition.

7. The composition as claimed in any one of the preceding claims wherein the pectin is derived from one or more of a fruit selected from pear, apple, guava, plum, gooseberry, orange and any other citrus fruit, preferably citrus fruit.

8. The composition as claimed in any one of the preceding claims which is a solid laundry detergent composition additionally comprising 1 to 30 wt% anionic surfactant. The composition as claimed in any one of the preceding claims 1 to 7 which is a liquid laundry detergent composition additionally comprising 1 to 30 wt% anionic surfactant. The composition as claimed in any one of the preceding claims 1 to 7 which is a fabric conditioning composition additionally comprising 1 to 50% of a fabric softening active. The composition as claimed in any one of the preceding claims 1 to 7 which is a liquid dishwash composition additionally comprising 1 to 30 wt% anionic surfactant and 0.1 to 5 wt% an amphoteric surfactant. The composition as claimed in any one of the preceding claims 1 to 7 which is a general purpose or a toilet cleaning composition additionally comprising 0.1 to 3 wt% of a cationic surfactant preferably BKC or DDAC. A composition as claimed in any one of the preceding claims 1 to 7 which is a toilet rim block in shaped solid form additionally comprising a perfume. A method of reducing odour on a surface for up to 48 hours comprising the step of contacting the surface with a composition as claimed in any one of the preceding claims preferably diluted with water.