Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/381—Microorganisms
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/001—Softening compositions
  • C11D3/0015—Softening compositions liquid
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3715—Polyesters or polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3723—Polyamines or polyalkyleneimines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions

Definitions

• the present invention relates to fabric treatment compositions containing sugar polyesters (SPE) and a so-called 'probiotic'.
• Human skin is known to have a resident, transient and temporary resident microflora.
• the resident micro-organisms are in a dynamic equilibrium with the host tissue and the microflora may be considered an integral component of the normal human skin.
• the great majority of these micro-organisms are gram- positive and reside on the skin surface and in the follicles.
• the host has a variety of structures, molecules and mechanisms which restrict the transient and temporary residents as well as controlling the population and dominance of the resident group. These include local skin anatomy, hydration, nutrients and inhibitors of various types.
• the resident microflora is beneficial in occupying a niche and denying its access to transients, which may be harmful and infectious. Also, the residents are important in modifying the immune system.
• EP 110550 proposes using probiotics for regulating the skin microflora. These may be applied directly to the skin in the form of lotions or shampoos.
• WO 02/028402A1 discloses the use of probiotic lactic acid bacteria for balancing the skin's immune function under stress conditions (e.g. UV radiation) and reducing the tendency of skin to develop allergic reactions under such conditions.
• the carrier system for the probiotics is a food, a pharmaceutical product or a cosmetic product for oral or topical application.
• WO 06/000992A1 discloses a cosmetic composition useful for preventing and/or treating sensitive and/or dry skin by treatment with probiotic micro-organisms combined with at least one divalent inorganic cation.
• probiotic micro-organisms into fabric treatment compositions thus enabling delivery of probiotics onto fabrics is desirable. Upon close contact with the skin, it is believed that these probiotics can be transferred from the fabric onto the skin, potentially conferring benefits as outlined above.
• Prebiotics are substances that selectively stimulate the growth and/or activity of one or more micro-organisms.
• Sugars and carbohydrates are included in most prebiotics e.g. sugars (mono- and di- saccharides) and carbohydrates (such as oligosaccharides).
• a number of different carbon and energy sources can be used in the prebiotic.
• prebiotics may be caused by the breakdown of the ingredients of the composition (for example upon storage) and/or their metabolism by the probiotic into substances which are suitable as metabolites for the probiotics thus causing unwanted growth of the probiotic.
• sugar based ingredients such as sugar polyesters (SPE's).
• Sugar polyesters for example sucrose polyester, contain sugar entities which are linked via ester groups to fatty chains. These sugar entities can become freely available for metabolism by the microorganism if the ester bonds are broken, for example enzymatically or hydrolytically.
• This issue is particularly relevant to commercial SPEs which contain fatty acid and soap impurities which can speed up the hydrolytic degradation of SPE as disclosed in Unilever patent WO2006076952(A1 ).
• Sugar polyesters themselves have desirable properties when incorporated as softeners into fabric treatment compositions, such as improved biodegradability, lower cost and less hydrophobing properties without any loss of softening benefit.
• Fabric treatment compositions comprising both SPE softeners and probiotic microorganisms are clearly desirable.
• compositions of the present invention the above problems are solved by using strains of bacteria in the probiotic composition that do not hydrolyse the SPE or utilize this material as a carbon source.
• Stable compositions comprising SPE softeners and probiotics can be prepared and used to deposit probiotics and SPE to fabric.
• probiotic micro-organisms may be incorporated into fabric treatment compositions containing sugar polyester (SPE) type fabric softeners and delivered onto fabrics from laundry applications.
• SPE sugar polyester
• a fabric treatment composition for use in a laundering process which comprises: - A -
• sugar polyester is in the form of an emulsion.
• the present invention provides a fabric carrier comprising probiotic particles, resulting from the treatment process of the second aspect of the invention.
• the sugar polyester is preferably selected from the group consisting of sucrose polyesters, glucose polyesters and cellobiose polyesters, and is most preferably a sucrose polyester.
• the sugar polyester may be liquid. Soft solid or solid.
• the preferred sucrose polyesters for use in the conjugates of the present invention have 2 to 4 hydrocarbon chains per sugar ring, where the hydrocarbon chain has a length of from 12 to 22 carbon atoms.
• a particularly preferred sucrose polyester is sucrose tetraerucate.
• An example of a preferred sucrose polyester is Ryoto Sugar Ester ER290 supplied by Mitsubishi Kagaku Foods Corporation, which is a sucrose tetraerucate and according to the manufacturer's specification is mainly Tetraerucate, Pentaerucate and Hexaerucate and has a HLB value of 2.
• the sugar polyester may be pure, or may contain impurities.
• the impurities are preferably selected from the group consisting of free fatty acid, fatty acid methyl ester, soap, inorganic salts and mixtures thereof. If such impurities are present, the total soap and free fatty acid content is preferably at a level of less than 20% by weight, more preferably less than 12%, for example from 5% to 12% or from 6% to 9%.
• the most preferred SPEs are commercially available, such as Emanon SCR-PK (ex KAO), which is a palm kernel derived SPE containing mainly C12-C14 with about 20% C18 mono unsaturatation and SPE-THSBO (ex Clariant), which is derived from touch hardened soy bean oil, having mainly C16-C18 chains with about 80% mono and di unsaturation.
• Emanon SCR-PK ex KAO
• SPE-THSBO Clariant
• the average degree of estehfication of the above preferred SPEs is between 4.2-4.7.
• SCR-PK contains up to 20% impurities but SPE-THSBO is pure.
• SCR-PK contains from 4 to 6 wt% of K soap, 2.5 wt% of free fatty acid, from 10 to 15 wt% of fatty acid methyl ester and less than 1 % of KCI.
• the level of soap impurities increases the rate of hydrolytic ester breakdown in the product.
• the fatty acid works in synergy with the soap to enhance the hydrolysis further.
• the methyl ester level has no effect of the rate of hydrolysis.
• the level of fatty acid For hydrolytic stability at elevated ambient temperatures over a 2 month storage period the level of fatty acid must be less than or equal to about 6%.
• the compositions of the invention preferably comprise less than 0.1 % free sugar.
• the sugar polyester being a non-ionic oil, requires an emulsifier, that is to say, the sugar polyester must be in an emulsified form.
• the emulsifier is preferably selected from cationic surfactant, anionic surfactant, non-ionic surfactant, cationic softening agent and mixtures thereof. When a cationic softening material is present, this can act as the emulsifying agent as well as a co-softener.
• probiotics used herein are generally defined according to genus and species, and may also include the strain. Common abbreviations may be used, for example, Bifidobacterium lactis Bb-12, which may be abbreviated to B. lactis Bb-12 and Bifidobacterium bifidus Bb-12, which may be abbreviated to B. bifidum Bb-12.
• the probiotic is not capable of hydrolysing the sugar polyester or of utilising the sugar polyester as a carbon source.
• the probiotic can be utilised in the presence of materials that discourage metabolism or keep metabolism static until required.
• the probiotic micro-organisms can be used in the viable (live) form or in an inactivated form.
• the probiotic micro-organism can be in any stage of its life cycle (spore or vegetative cell states).
• the colony forming unit (cfu) known in the art refers to the number of bacterial cells as measured by a microbiological count on an agar plate.
• the CFU values typically included in compositions of the invention are from 10 CFU/ml to 1x10 11 CFU/ml, preferably from 1x10 2 CFU/ml to 1x10 9 CFU/ml, mo preferably from 1x10 4 CFU/ml to 1x10 7 CFU/ml of the composition.
• the probiotics are typically included in compositions of the invention at levels of from 0.003 to 0.5 wt %, preferably from 0.003 to 0.25 wt %, more preferably from 0.003 to 0.1 wt %, even more preferably from 0.005 to 0.05 wt %, and most preferably from 0.005 to 0.025 wt % by weight of the total composition.
• the probiotic strains used in the compositions of the invention are not capable of hydrolysing SPE.
• Strains which cannot metabolise SPE as a substrate include Lactobacillus delbruecki subsp bulaga ⁇ cus (ATCC11842) and Lactobacillus helveticus (ATCC15009).
• suitable probiotics are given in WO 2005/089560A1.
• Suitable micro-organisms include strains selected from the group consisting of Lactobacillus, Bifidobacterium, Streptococcus, Lactococcus, Enteroccus and mixtures of these.
• the micro-organism is a Lactobacillus-stra ⁇ r ⁇ . More preferably it is selected from the group consisting of L.casei, Lparacasei, L.acidophilus, L.plantarum, and mixtures of these.
• the micro-organism is a L.paracase/ ' -strain, for example, the micro-organism is Lactobacillus paracasei (CNCM 1-2116).
• micro-organisms must be capable of surviving the acid, alkaline or saline conditions of the laundry compositions of the invention.
• freeze-thawing temperatures mean those temperatures typically experienced during storage, in both domestic and commercial environments, where the temperature may drop (typically during the night) to less than 5°C and then rise during the day to, for example, above 20°C. Such fluctuations are commonplace in colder climates and during the winter season. In warm climates, the probiotics should be resistant to higher ambient temperatures and typical fluctuations therein, for example from 20 to 40°C.
• the probiotic biomass can be frozen, dry powder, or wet (for example when separated from a fermented medium).
• the biomass incorporation into formulations can be by post dosing after the formulation has been structured, by co-blending with one of the components, such as the oil phase, or by dispersing in the water phase before the active materials are added.
• the biomass can be in a granulated form with protective waxes before addition to the compositions in particular for detergent powder compositions.
• the most preferred method of incorporation is to add the biomass at the end of the process when the process temperature is dropped to ambient temperatures and where the water activity of the formulation is reduced (due to the high phase volume of the fabric conditioner particles).
• Deposition of micro-organisms from laundry formulations of the invention onto a substrate may be achieved by any suitable route, for example by adsorption, filtration (entrapment) or both.
• the particle size of the probiotic particles is such that the particles are trapped between the fibres of the fabric.
• the filtration mechanism requires particles or clusters of primary particles of size comparable with the interyarn pore size.
• the particle size is typically in the 1-30 microns range. Larger particles begin to be visible to the unaided eye, whereas smaller particles tend to be removed in the wash. Particles of around 5-15 microns are invisible to the eye and exhibit good filtration onto fabrics.
• Deposition of micro-organisms from laundry formulations of the invention may also be achieved and enhanced over and above the delivery by filtration method, by polymer aided deposition as applied to other particulate matters.
• Polymers suitable for the deposition of particles are disclosed in WO9709406 (P&G), where high MW polyethylene oxide (PEO) are used to deposit clay particles in the main wash, EP0299575B1 and WO9527037 (P&G), where high MW PEO, polyacrylates, polyacryl amides, poly vinyl alcohol, poly ethylene imines are used to deposit clay particles in the main wash, EP0387426B1 (P&G) a similar list of polymers and guar gums.
• WO 01/07546 A1 suggests suitable rinse stage polymeric deposition aids for emulsion droplets including cationic guar polymers, cationic polyacrylamides, cationic potato starch, and cationic cellulose derivates.
• Suitable examples of cationic polymers include cationic guar polymers such as Jaguar (ex Rhone Poulenc), cationic cellulose derivatives such as Celquats (ex National Starch), Flocaid (ex National Starch), cationic potato starch such as SoftGel (ex Aralose), cationic polyacrylamides such as PCG (ex Allied Colloids).
• Low charge density cationic polymeric aids are particularly preferred where the composition of the invention comprises an anionic or non ionic emulsifier for the emulsification of SPE oil.
• Suitable low charge density cationics include the modified potato starch Softgel BDA and Softgel BDA CS range (ex Avebe).
• Suitable non-ionic deposition aids include high molecular weight PEO WSRN 750 (ex Union Carbide).
• the particle size range for polymer aided deposition is between 0.5-30 microns and preferably between 1 -20 microns.
• deposition aid polymers are the phthalate-containing ones. These polymers are polyester-substantive deposition aids, i.e. polymers derivable from dicarboxylic acids and polyols, particularly a phthalate containing polymer. More preferably, a polymer comprising units derived from (poly)ethylene glycol (PEG), (poly)ethylene terephthalate (PET) and/or polyoxyethylene terephthalate (POET). Most preferably the polymer is selected from the group comprising PET/POET, PEG/POET, PET/PEG and phthalate/glycerol/ethylene glycol polymers.
• polyester-substantive deposition aids i.e. polymers derivable from dicarboxylic acids and polyols, particularly a phthalate containing polymer. More preferably, a polymer comprising units derived from (poly)ethylene glycol (PEG), (poly)ethylene terephthalate (PET) and/or polyoxyethylene terephthalate (
• polymeric soil release agent Any polymeric soil release agent known to those skilled in the art can be employed in compositions according to the invention.
• Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This is commonly done to enable stains occurring subsequent to treatment with the soil release agent to be more easily removed in later washing procedures.
• the polymeric deposition aids useful herein especially include those soil release agents having one or more nonionic hydrophilic components comprising oxyethylene, polyoxyethylene, oxypropylene or polyoxypropylene segments, and, one or more hydrophobic components comprising terephthalate segments.
• oxyalkylene segments of these deposition aids will have a degree of polymerization of from 1 to about 400, although higher levels can be used, preferably from 100 to about 350, more preferably from 200 to about 300.
• One type of preferred deposition aid is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide terephthalate.
• the preferred molecular weight of this class of polymeric deposition aid agent is in the range of from about 5kD to about 55kD.
• Another preferred polymeric deposition aid is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyethylene glycol of average molecular weight 0.2kD-40kD.
• this class of polymer include the commercially available material ZELCON 5126 (from DuPont) and MILEASE T (from ICI). Examples of related polymers can be found in US 4702857.
• Another preferred polymeric deposition aid for non-cationic softeners is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
• soil release agents are described fully in US 4968451.
• Other suitable polymeric soil release agents include the terephthalate polyesters of US 4711730, the anionic end-capped oligomeric esters of US 4721580, and the block polyester oligomeric compounds of US 4702857.
• Preferred polymeric deposition aids also include the soil release agents of US 4877896 which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
• Still another preferred deposition aid is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1 ,2- propylene units.
• the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps.
• a particularly preferred deposition aid of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1 ,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2- hydroxyethoxy)-ethanesulfonate.
• Said soil release agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
• a crystalline-reducing stabilizer preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
• a preferred approach for the deposition of probiotics is the targeted polymeric deposition based on the polysaccharide conjugate technology as disclosed in WO99/36469, WO2004/056890A1 , WO2005/21186A1 (to Unilever) where a chemical bond is formed between the polymer and particle to be deposited, US6773811 B2 Unilever), particle with cellulose polysaccharide attached (CMA), and EP1117756B1 (Unilever), which claims beta 1 -4 linked polysaccharides (LBG, xyloglucan etc) with a number of attached benefit agents.
• the polysaccharide conjugate approach for the main wash has the advantage of targeting the substrate where only the polymer-attached probiotics become deposited and not the unwanted oily soil particles. If PET/POET polymers are used in the conjugate approach the probiotic particles become more substantive to polyester and polycotton.
• the polysaccharide and PET/POET conjugate approaches can be combined.
• the preferred biomass particle size range for the polysaccharide conjugate approach is between 1 -15 microns. This approach necessitates the deposition of a nanometer size PVAC polymer shell on the probiotic to form a chemical bond between the particle and the polymer as described in the aforementioned art.
• the fabric treatment composition of the invention is suitable for use in a laundry process.
• a rinse treatment e.g. conditioner or finisher
• a combined fabric washing and softening from the main wash product e.g. conditioner or finisher
• the compositions of the present invention are preferably laundry compositions, especially rinse-added softening compositions.
• compositions of the invention may be in any physical form e.g. a solid such as a powder or granules, a tablet, a solid bar, a paste, gel or liquid, especially, an aqueous based liquid, spray, stick, impregnated substrates, foam or mousse.
• a solid such as a powder or granules, a tablet, a solid bar, a paste, gel or liquid, especially, an aqueous based liquid, spray, stick, impregnated substrates, foam or mousse.
• the compositions may be liquid, powder or tablet laundry compositions.
• the liquid products of the invention may have pH ranging from 2.5 (for fabric care compositions) to 12 (for fabric cleaning compositions). This pH range preferably remains stable over the shelf life of the product.
• the active ingredient in the compositions is an SPE softener.
• the composition may further comprise a surface active agent for the emulsification of SPE or a further fabric conditioning agent for emulsification and deposition of SPE and/or as a co-softener. More than one active ingredient may be included.
• the preferred detergent-active compounds that can be used are soaps and synthetic non-soap anionic, and non-ionic compounds.
• the level of non-ionic surfactant is from 0 wt% to 30 wt%, preferably from 1 wt% to 25 wt%, most preferably from 2 wt% to 15 wt%, by weight of the total composition.
• any further conventional fabric conditioning agent may be used in the compositions of the present invention.
• the conditioning agents may be cationic or non-ionic. If the fabric conditioning compound is to be employed in a main wash detergent composition the compound will typically be non-ionic. For use in the rinse phase, typically they will be cationic. They may for example be used in amounts from 0.5% to 35%, preferably from 1 % to 30% more preferably from 3% to 25% by weight of the composition.
• the quaternary ammonium fabric softening material for use in compositions of the present invention can be an ester-linked thethanolamine (TEA) quaternary ammonium compound comprising a mixture of mono-, di- and th-ester linked components.
• TAA ester-linked thethanolamine
• TEA-based fabric softening compounds comprise a mixture of mono, di- and tri-ester forms of the compound where the di-ester linked component comprises no more than 70% by weight of the fabric softening compound, preferably no more than 60%, e.g. no more than 55%, or even no more than 45% of the fabric softening compound and at least 10 % of the monoester linked component by weight of the fabric softening compound.
• a first group of quaternary ammonium compounds (QACs) suitable for use in the present invention is represented by formula (I): [(CH 2 ) n (TR)] m R 1 -N + -[(CH 2 )n(OH)] 3-m X- (I)
• each R is independently selected from a C 5-35 alkyl or alkenyl group;
• R 1 represents a Ci -4 alkyl, C 2-4 alkenyl or a Ci -4 hydroxyalkyl group;
• T is generally O- CO. (i.e. an ester group bound to R via its carbon atom), but may alternatively be CO-O (i.e. an ester group bound to R via its oxygen atom);
• n is a number selected from 1 to 4;
• m is a number selected from 1 , 2, or 3;
• X ⁇ is an anionic counter- ion, such as a halide or alkyl sulphate, e.g. chloride or methylsulphate.
• TEA ester quats di-esters of thethanolamine methylsulphate, otherwise referred to as "TEA ester quats.”
• Commercial examples include Prapagen TQL, ex Clariant, and Tetranyl AHT-1 , ex Kao, (both di-[hardened tallow ester] of triethanolamine methylsulphate), AT-1 (di-[tallow ester] of triethanolamine methylsulphate), and L5/90 (di-[palm ester] of triethanolamine methylsulphate), both ex Kao, and Rewoquat WE15 (a di-ester of triethanolamine methylsulphate having fatty acyl residues deriving from Ci 0 -C 20 and Ci 6 -Ci 8 unsaturated fatty acids), exWitco Corporation.
• each R 1 group is independently selected from Ci -4 alkyl, hydroxyalkyl or C2 -4 alkenyl groups; and wherein each R 2 group is independently selected from Cs- 28 alkyl or alkenyl groups; and wherein n, T, and X " are as defined above.
• Preferred materials of this second group include 1 ,2 ⁇ b/s[tallowoyloxy]-3- trimethylamine propane chloride, 1 ,2 ⁇ b/s[hardened tallowoyloxy]-3-trimethylamine propane chloride, 1 ,2- ⁇ b/s[oleoyloxy]-3-t ⁇ methylamine propane chloride, and 1 ,2 ib/s[stearoyloxy]-3-trimethylamine propane chloride.
• Such materials are described in US 4,137,180 (Lever Brothers).
• these materials also comprise an amount of the corresponding mono-ester.
• a third group of QACs suitable for use in the invention is represented by formula
• each R 1 group is independently selected from Ci -4 alkyl, or C 2-4 alkenyl groups; and wherein each R 2 group is independently selected from C 8-2 S alkyl or alkenyl groups; and n, T, and X " are as defined above.
• Preferred materials of this third group include bis(2-tallowoyloxyethyl)dimethyl ammonium chloride and hardened versions thereof.
• the iodine value of the quaternary ammonium fabric softening material is from 0 to 60, preferably from 0 to 45, more preferably from 0 to 30, and most preferably from 0 to 20.
• Iodine value is defined as the number of grams of iodine absorbed per 100 g of test material. NMR spectroscopy is a suitable technique for determining the iodine value of the softening agents of the present invention, using the method described in Anal. Chem., 34, 1136 (1962) by Johnson and Shoolery and in EP 593,542 (Unilever, 1993).
• the softening agent is present in the compositions of the invention at a level of 10% to 40% by weight of the total composition, preferably between 10 to 30%.
• the non-ester softening compound preferably has the alkyl or alkenyl chain lengths referred to above for the non-ester softening compound.
• non-ester softening compound is a quaternary ammonium material represented by formula (IV):-
• each R 1 group is independently selected from Ci -4 alkyl, hydroxyalkyl or C2 -4 alkenyl groups; R 2 group is independently selected from Cs-28 alkyl or alkenyl groups, and X " is as defined above.
• compositions may comprise a total amount of between 0.5%wt-30% by weight of the cationic fabric softening compounds, preferably 1 %-25%, more preferably 1.5-20%, most preferably 2%-15%, based on the total weight of the composition.
• compositions may additionally contain nonionic fabric softening agents such as lanolin and derivatives thereof and other non-SPE softening oils known in the art.
• nonionic fabric softening agent suitable for use in the compositions of the invention is castor oil, which is available in pure form, for example, Now Chemicals.
• Lecithins and other phospholipids are also suitable softening compounds.
• nonionic stabilizing and/or emulsifying agent may be present. Where a cationic co-softener is present, the nonionic both stabilizes the cationic softener and emulsifies the SPE.
• the preferred number of ethoxylate groups (EO) for stabilizing the co-softener is from 10 to 20, whereas for emulsification the number of ethoxylates can be from 5 to 20.
• Suitable nonionic stabilising and/or emulsifying agents include linear C8 to C22 alcohols alkoxylated with from 5 to 20 moles of alkylene oxide, C10 to C20 alcohols, or mixtures thereof.
• Other stabilising and/or emulsifying agents include the deflocculating polymers as described in EP 0415698A2 and EP 0458599 B1.
• the level of nonionic stabiliser and/or emulsifier is within the range from 0.1 to 10% by weight, more preferably from 0.5 to 5% by weight, most preferably from 1 to 4% by weight.
• the mole ratio of the quaternary ammonium compound and/or other cationic softening agent to the nonionic stabilising agent is suitably within the range from 40:1 to about 1 :1 , preferably within the range from 18:1 to about 3:1.
• the fabric treatment compositions of the invention can also contain adjuvants that are normal in the cosmetic, pharmaceutical and/or dermatological field, such as hydrophilic or lipophilic gelling agents, hydrophilic or lipophilic active agents, preserving agents, antioxidants, solvents, fragrances, fillers, screening agents, bactericides, odour absorbers, photo-bleaches, fluorescers and dyestuffs.
• adjuvants that are normal in the cosmetic, pharmaceutical and/or dermatological field, such as hydrophilic or lipophilic gelling agents, hydrophilic or lipophilic active agents, preserving agents, antioxidants, solvents, fragrances, fillers, screening agents, bactericides, odour absorbers, photo-bleaches, fluorescers and dyestuffs.
• the amounts of these various adjuvants are those conventionally used in the field under consideration and are, for example, from 0.01 to 20 % of the total weight of the composition. Depending on their nature, these adjuvants can be introduced into the fatty phase and/
• the substrate When used in laundering, the substrate may be any substrate onto which it is desirable to deposit probiotic particles and which is subjected to treatment such as a washing or rinsing process.
• the substrate may be a textile fabric.
• the treatment of the substrate with the composition of the invention can be made by any suitable method such as washing, soaking or rinsing of the substrate but also by direct application such as spraying, rubbing, spotting, smearing, etc.
• the treatment may involve contacting the substrate with an aqueous medium comprising the material of the invention.
• the treatment may be provided as a spray composition e.g., for domestic (or industrial) application to fabric in a treatment separate from a conventional domestic laundering process.
• Suitable spray dispensing devices are disclosed in WO 96/15310 (Procter & Gamble) and are incorporated herein by reference.
• the composition may be applied through the iron's water tank, a separate reservoir or a spray cartridge in an iron, as described in EP1201816 and WO 99/27176. Examples
• Lactobacillus helveticus is a strain of probiotic micro-organism that is incapable of using sucrose as a substrate
• L. helveticus can be isolated from Grana cheese (strain TH456, ex Veneto
• **SCR-PK is a sucrose polyester with an average of 4 ester linkages, based on palm kernel oil.
• Ethoquad 0-12 is a single chain oleyl base cationic emulsifier with 25% IPA.
• Divalent calcium soap is used to stimulate growth of the probiotic on skin. We have established that the presence of quat softeners helps to deposit the probiotic particles (as in Example 3). Additional deposition aid increases the level of deposition.
• Table 2 The examples in Table 2 were prepared at 200 ml scale in a bench top vessel with a three-stage agitator thermostated to 5O 0 C and evaluated for pH change and malodour upon storage (indicating the fermentation of the probiotics) and for deposition on to fabrics.
• compositions containing an SPE the probiotic particles were dispersed in oil before addition to the batch water and emulsification.
• the probiotic was post-dosed after addition of perfume.
• Examples C, 4, 5 and 6 were evaluated in a Tergotometer for deposition using 2 ml of the sample in a litre of water each with two pieces of black cotton cord and one piece of black polyester sheeting.
• Microscopy examination with top light revealed more particle count/unit surface area on Examples 4, 5, and 6 compared to C.
• the Softgel cationic polymer and the cationics both had increased the deposition of probiotic particles.
• Table 3 Change in pH of the probiotic fabric conditioner compositions upon storage.
• Example B shows the pH of the perfume solution. Comparison of the first day pH values between B (with perfume but no probiotics) and C (perfume+ probiotic) shows that the probiotic has adsorbed or neutralised some perfume components leading to the increased pH. This could lead to chemical stability of perfume ingredients against hydrolysis for example. Surprisingly we find no sign of fermentation in the softener composition with these probiotics. The comparison of pH values initially and after one week on storage can indicate lack of microbial activity and hence no growth (fermentation) in the products. No malodour was detected by an expert panel in the Examples with probiotics compared to control samples without probiotics. This further supports that the ingredients have not acted as medium for growth.
• the liquid products of the invention have a shelf-life of at least 2 months at temperatures ranging from 5 to 37 0 C.

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• 2007
  • 2007-10-01 GB GB0719164A patent/GB0719164D0/en not_active Ceased
• 2008
  • 2008-09-15 CN CN2008801096748A patent/CN101809140B/zh not_active Expired - Fee Related
  • 2008-09-15 EP EP08804201A patent/EP2193190A1/en not_active Withdrawn
  • 2008-09-15 WO PCT/EP2008/062241 patent/WO2009043708A1/en active Application Filing
  • 2008-09-15 BR BRPI0817598-5A patent/BRPI0817598A2/pt not_active Application Discontinuation
  • 2008-09-30 AR ARP080104261 patent/AR068585A1/es not_active Application Discontinuation
• 2010
  • 2010-03-15 ZA ZA2010/01831A patent/ZA201001831B/en unknown

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