EP2195406A1 - Improvements relating to fabric treatment compositions - Google Patents

Improvements relating to fabric treatment compositions

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Publication number
EP2195406A1
EP2195406A1 EP08804200A EP08804200A EP2195406A1 EP 2195406 A1 EP2195406 A1 EP 2195406A1 EP 08804200 A EP08804200 A EP 08804200A EP 08804200 A EP08804200 A EP 08804200A EP 2195406 A1 EP2195406 A1 EP 2195406A1
Authority
EP
European Patent Office
Prior art keywords
fabric
probiotic
treatment composition
composition according
fabric treatment
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.)
Granted
Application number
EP08804200A
Other languages
German (de)
French (fr)
Other versions
EP2195406B1 (en
Inventor
Mansur Sultan Mohammadi
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
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Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP2195406A1 publication Critical patent/EP2195406A1/en
Application granted granted Critical
Publication of EP2195406B1 publication Critical patent/EP2195406B1/en
Active legal-status Critical Current
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions

Definitions

  • the present invention relates to fabric treatment compositions and in particular to fabric treatment compositions comprising a so-called ⁇ probiotic' .
  • This intestinal microflora constitutes a metabolically active microbial environment, dominated by a relatively low diversity of genera, which in the gut of healthy individuals, exist as part of a relatively stable community.
  • probiotics can be defined as defined as:
  • microbes in the human intestinal tract are the Gram-positive lactic acid-producing genera Lactobacillus and Bifidobacterium. Most probiotics are from the Lactobacillus and the Bifidobacterium genera and have been selected for their ability to survive gastric transit and to adhere to intestinal epithelial cells.
  • Such strains can transiently colonise the gut by integrating into existing microflora and are believed to confer certain health benefits to consumers. In recent years the consumption of ⁇ probiotics' has markedly increased.
  • the gut is not the only part of the human body to harbor microorganisms.
  • Human skin has 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 microorganisms 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.
  • WO 05/089560A1 discloses water and milk based products containing probiotic microorganisms which are stable upon storage at 1O 0 C and which are free from carbohydrate metabolites. The products are intended for ingestion where they benefit the gut microflora.
  • WO2005080539 discloses a process for the preparation of a detergent for cleaning fabrics whereby probiotics are introduced into the production process. These microbes then generate enzymes and other actives that remove stains, such that the environmental impact of the detergent is reduced following the cleaning process.
  • probiotic micro-organisms may be incorporated into fabric treatment compositions and delivered onto fabrics from laundry applications. 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.
  • the present invention provides a fabric treatment composition for use in a laundering process which comprises :
  • the present invention provides a fabric article comprising probiotic particles, resulting from the treatment process of the second aspect of the invention.
  • 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 micro-organisms can be used in the viable (live) form, in an inactivated form or in a dead form. They can be used at any stage of their life cycle (for example spore or vegetative cell state) . Inactivated or dead form of the probities may be incorporated without further protective measures.
  • 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 probiotic particles are typically included in compositions of the invention at levels of from 0.003 to 0.1 wt %, preferably from 0.005 to 0.05 wt %, most preferably from 0.005 to 0.025 wt % by weight of the total composition.
  • probiotics for use in the present invention are chosen, in particular, from ascomycetes such as Saccharomyces , Yarrowia , Kluyveromyces , Torulaspora , Schizosaccharomyces pombe, Debaromyces , Candida, Pichia, Aspergillus and Penicillium, bacteria of the genus Bifidobacterium, Bacteroides , Fusobacterium, Melissococcus , Propioibacterium, Enterococcus , Lactococcus , Staphylococcus , Peptostrepococcus , Bacillus, Pediococcus , Micrococcus , Leuconostoc, Weissella, Aerococcus , Oenococcus and Lactobacillus and mixtures thereof.
  • ascomycetes such as Saccharomyces , Yarrowia , Kluyveromyces , Torulaspora , Schizo
  • probiotic microorganisms suitable for use in the present invention are Bifidobacterium adolescentis , Bifidobacterium bifidum, Bifidobacterium infantis , Bifidobacterium lactis , Bifidobacterium longum, Lactobacillus acidophilus , Lactobacillus alimentarius , Lactobacillus easel subsp. Casei, Lactobacillus easel Shirota, Lactobacillus paracasei , Lactobacillus curvatus , Lactobacillus delbruckii subsp.
  • Lactis Lactobacillus gasseri, Lactobacillus johnsonii , Lactobacillus reuteri, Lactobacillus rhamnosus (Lactobacillus GG) , Lactobacillus sake, Lactococcus lactis, Streptococcus thermophilus , Straphylococcus carnosus and Staphylococcus xylosus, and mixtures thereof.
  • the preferred species are Lactobacillus johnsonii , Lactobacillus paracasei , Bifidobacterium adolescentis ,
  • Bifidobacterium longum and Bifidobacterium lactis NCC 2818 (also entitled (Bb 12) (ATCC27536) ) respectively deposited according to the Treaty of Budapest with the Pasteur Institute (28 rue du Dondel Roux, F-75024 Paris Cedex 15) on 30/06/92, 12/01/99, 15/04/99 and 10/06/2005 under the following designations: CNCM 1-1225, CNCM 1-2116, CNCM I- 2168, CNCM 1-2170 and CNCM 1-3446, and the genus Bifidobacterium longum (BB536) .
  • the Bifidobacterium lactis (CNCM 1-3446) strain can be obtained from Hansen (Chr. Hansen A/S, 10-12 Boege AlIe, P.O. Box 407, DK-2970 Hoersholm, Denmark) .
  • micro-organisms must be capable of surviving the acid, alkaline or saline conditions of the laundry compositions of the invention.
  • Lactobacillus reuteri Lactobacillus acidophilus , Lactobacillus animalis , Lactobacillus ruminis , Lactobacillus johnsonii , Lactobacillus easel, Lactobacillus paracasei , Lactobacillus rhamnosus , Lactobacillus fermentum,
  • 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.
  • 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) .
  • sugars mono- and di- saccharides
  • carbohydrates such as oligosaccharides
  • biocides for use in the present invention include Proxel ( 1 , 2-benzisothiazolin-3-one) , available from, for example, Univar, Avecia and Uniqema; and Kathon CG (Methylchloroisothiazolinone and Methylisothiazolinone) , available from Rhom and Haas.
  • the laundry compositions of the invention may be substantially free from prebiotic substances specific to the particular probiotic particle used in the compositions of the invention, such that the probiotic does not grow excessively in the composition itself.
  • substantially free is meant that, where present, they are present only at a level such that the probiotic does not grow excessively in the composition itself, i.e. does not cause degradation of the properties of the composition.
  • the compositions contain prebiotic substances at a level of not more than 0.1 wt %, preferably not more than 0.05 wt%, more preferably not more than 0.01 wt%, still more preferably not more than 0.005 wt% by weight of the total composition and are most preferably free from prebiotic substances that can be metabolized by the probiotic of the composition.
  • the compositions of the invention are especially preferably free from the group consisting of fructose, glucose and sucrose, most preferably, free of sucrose.
  • 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 .
  • Deposition of micro-organisms from laundry formulations of the invention onto a substrate may be achieved by any suitable route.
  • 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 a size comparable with the interyarn pore size.
  • the particle size is typically in the range of from 1 to 30 microns. Larger particles begin to be visible to the unaided eye, whereas smaller particles tend to be removed in the wash. Particles of around from 5 to 15 microns are preferred as they tend to be invisible to the eye and exhibit good deposition by 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 .
  • Polymers suitable for the deposition of particles are disclosed in WO9709406, particularly high MW polyethylene oxides (PEO) which are used to deposit clay particles in the main wash; EP0299575B1 and WO9527037, where high MW PEO, polyacrylates, polyacryl amides, poly vinyl alcohol and poly ethylene imines are used to deposit clay particles in the main wash; and EP0387426B1 which utilizes a similar list of polymers as well as guar gums.
  • PEO polyethylene oxides
  • EP0387426B1 which utilizes a similar list of polymers as well as guar gums.
  • WO 01/07546 Al discloses 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) and cationic polyacrylamides such as PCG (ex Allied Colloids) .
  • Cationic polymeric aids are particularly preferred where the composition of the invention is a fabric softener wherein the softener is a non-cationic softener.
  • Suitable non-ionic deposition aids include high molecular weight polyethylene glycols, for example PEO WSRN 750 (ex Union Carbide) .
  • the particle size range of the probiotic for polymer aided deposition is from 0.5 to 30 microns and preferably from 1 to 20 microns .
  • a preferred approach for the deposition of probiotic particles, particularly for probiotics deposition from a main wash laundry application, is targeted polymeric deposition based on the polysaccharide conjugate technology as disclosed in WO99/36469, WO2004/056890A1, WO2005/21186A1, where a water-soluble or water-dispersible polysaccharide conjugate comprising a polymeric backbone and a benefit agent group attached to the polymeric backbone by a hydrolytically stable bond is used to deposit the benefit agent onto a fabric during a main wash process.
  • US6773811B2 which describes a particle with a cellulosic polysaccharide attached (cellulose mono acetate - CMA)
  • EP1117756B1 which claims beta 1-4 linked polysaccharides (LBG, xyloglucan etc) with a number of attached benefit agents.
  • the probiotic particle may be chemically bound to such a polysaccharide backbone via a hydrolytically stable bond.
  • This polysaccharide conjugate approach for use in the main wash has the advantage of targeting the substrate such that only the polymer-attached probiotic microorganisms become deposited onto the fabric and not the unwanted oily soil particles .
  • the preferred biomass particle size range for the polysaccharide conjugate approach is from 1 to 15 microns. Most preferably from 1 to 5 ⁇ m. Larger particles require additional polysaccharide (2% as opposed to 1% on particle weight respectively for 30 ⁇ m and 5 ⁇ m) . This approach necessitates the deposition of a nanometer size of PVAC polymer shell on the probiotic to form a chemical bond between the particle and the polymer.
  • the fabric treatment composition of the invention is suitable for use in a laundry process.
  • a softening-in-the-wash main wash composition e.g. conditioner or finisher
  • a rinse treatment e.g. conditioner or finisher
  • a post- treatment ⁇ wet tissue' type product e.g. conditioner or finisher
  • the compositions of the present invention are preferably laundry compositions, especially softening-in-the-wash compositions or 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.
  • the compositions may be liquid, powder, or unit dose such as tablet laundry compositions.
  • the liquid products of the invention may have pH ranging from 2.5 (for fabric care compositions) to 12 (for fabric softening-in-the-wash compositions) . This pH range preferably remains stable over the shelf life of the product .
  • the active ingredient in the compositions is preferably a surface active agent or a fabric conditioning agent. More than one active ingredient may be included. For some applications a mixture of active ingredients may be used, for example, the main wash compositions may also include a fabric softening agent and the rinse-added fabric softening compositions may also include surface-active compounds, particularly non-ionic surface-active compounds.
  • any 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 preferred softening active for use in rinse conditioner compositions of the invention is a quaternary ammonium compound.
  • the quaternary ammonium fabric softening material for use in compositions of the present invention can be an ester-linked triethanolamine (TEA) quaternary ammonium compound comprising a mixture of mono-, di- and tri-ester linked components.
  • 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) :
  • each R is independently selected from a C5-35 alkyl or alkenyl group;
  • R 1 represents a C1-4 alkyl, C2-4 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 .
  • Di-esters variants of formula I i.e.
  • the second group of QACs suitable for use in the invention is represented by formula (II) :
  • each R 1 group is independently selected from C1-4 alkyl, hydroxyalkyl or C 2 _ 4 alkenyl groups; and wherein each R 2 group is independently selected from Cs- 2 8 alkyl or alken ⁇ groups; and wherein n, T, and X ⁇ are as defined above.
  • Preferred materials of this second group include 1,2 bis [ tallowoyloxy] -3-trimethylamine propane chloride, 1,2 bis [hardened tallowoyloxy] -3-trimethylamine propane chloride, 1, 2-bis [oleoyloxy] -3-trimethylamine propane chloride, and 1,2 bis [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 (III) :
  • 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 Cs- 2 8 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. - I i
  • non-ester softening compound is a quaternary ammonium material represented by formula (IV)
  • each R 1 group is independently selected from C1-4 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 l%-25%, more preferably 1.5-20%, most preferably 2%-15%, based on the total weight of the composition.
  • compositions may alternatively or additionally contain nonionic fabric softening agents such as lanolin and derivatives thereof.
  • nonionic fabric softening agent suitable for use in the compositions of the invention is Castor oil, for example, from Now Chemicals.
  • Nonionic stabilising agent may be present in fabric softening compositions.
  • Suitable nonionic stabilising agents may be present such as linear C8 to C22 alcohols alkoxylated with 10 to 20 moles of alkylene oxide, ClO to C20 alcohols, or mixtures thereof.
  • Other stabilising agents include the deflocculating polymers as described in EP 0415698A2 and EP 0458599 Bl.
  • the nonionic stabilising agent is a linear C8 to C22 alcohol alkoxylated with 10 to 20 moles of alkylene oxide.
  • the level of nonionic stabiliser 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 composition can also contain fatty acids, for example C8 to C24 alkyl or alkenyl monocarboxylic acids or polymers thereof.
  • the fatty acid is non-saponified, more preferably the fatty acid is free, for example oleic acid, lauric acid or tallow fatty acid.
  • the level of fatty acid material is preferably more than 0.1% by weight, more preferably more than 0.2% by weight.
  • Concentrated compositions may comprise from 0.5 to 20% by weight of fatty acid, more preferably 1% to 10% by weight.
  • the weight ratio of quaternary ammonium material or other cationic softening agent to fatty acid material is preferably from 10:1 to 1:10.
  • Cationic surfactants which can be used in main-wash compositions for fabrics.
  • Cationic surfactants that may be used include quaternary ammonium salts of the general formula R1R2R3R4N + X ⁇ wherein the R groups are long or short hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a counter-ion (for example, compounds in which Rl is a C8-C22 alkyl group, preferably a C8-C10 or C12-C14 alkyl group, R2 is a methyl group, and R3 and R4, which may be the same or different, are methyl or hydroxyethyl groups) ; and cationic esters (for example, choline esters) .
  • Softening in the wash compositions in accordance with the invention comprise a surface-active compound, selected from anionic surfactants, cationic surfactants, non-ionic surfactants, zwitterionic surfactants, amphoteric surfactants and mixtures thereof.
  • surface- active compound surfactant
  • the choice of surface- active compound (surfactant) , and the amount present, will depend on the intended use of the detergent composition. In fabric washing compositions, different surfactant systems may be chosen, as is well known to the skilled formulator, for handwashing products and for products intended for use in different types of washing machine.
  • the total amount of surfactant present will also depend on the intended end use and may be as high as 60 wt%, for example, in a composition for washing fabrics by hand. In compositions for machine washing of fabrics, an amount of from 5 to 40 wt% is generally appropriate. Typically the compositions will comprise at least 2 wt% surfactant e.g. 2- 60%, preferably 15-40% most preferably 25-35%, by weight of the composition.
  • 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, photobleaches (singlet oxygen or radical type) 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, photobleaches (singlet oxygen or radical type) 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
  • 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.
  • Example 1 Fabric conditioner compositions 1 and 2 containing probiotic micro-organisms according to the invention
  • TEA quat is a cationic softener based on triethanolamine with tallow or hard tallow chains and 15% IPA as solvent.
  • Plantatex LLE is a lipid found in skin.
  • Example 2 Fabric conditioner compositions 3 and 4 containing probiotic micro-organisms according to the invention and comparative compositions A to E
  • compositions shown in Table 2 were prepared at 200 ml scale in a bench top vessel with a three-stage agitator at 5O 0 C.
  • Table 2 Probiotics in fabric conditioner compositions
  • **Castor oil (ex Now Chemicals) is a non-ionic oil softener.
  • Example 3 Evaluation of deposition of probiotic onto fabric from the fabric conditioner compositions of example 2.
  • compositions shown in table 2 were evaluated for pH change and malodour with storage and for deposition onto fabrics.
  • Deposition of probiotic onto fabric was carried out as follows :
  • each composition (C, D, E and 4) was diluted in a litre of water in a tergometer and used to rinse two pieces of black cotton cord and one piece of black polyester sheeting.
  • the black background facilitated the microscopic identification of the probiotic particles on the fabrics.
  • Table 3 pH of fabric conditioner compositions of example 2 upon storage for 1 week at room temperature (RT) and 41 °C .

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Abstract

A fabric treatment composition which comprises at least one cationic softener or nonionic softener, and a probiotic microorganism particle, results in the deposition of the probiotic onto fabric during a laundry treatment process.

Description

IMPROVEMENTS RELATING TO FABRIC TREATMENT COMPOSITIONS
Technical Field
The present invention relates to fabric treatment compositions and in particular to fabric treatment compositions comprising a so-called λprobiotic' .
Background
The concept of probiotics is believed to have evolved from a hypothesis proposed by the Nobel Prize winning Russian scientist Metchnikoff, who postulated that the long healthy life of Bulgarian peasants resulted to their consumption of fermented milk products. It was believed that, when consumed, the fermenting bacillus (Lactobacillus) positively influenced the microflora of the colon, decreasing toxic microbial activities.
This intestinal microflora constitutes a metabolically active microbial environment, dominated by a relatively low diversity of genera, which in the gut of healthy individuals, exist as part of a relatively stable community.
Based on the guidelines of the WHO and FAO (FAO/WHO 2002) and the ILSI Europe workgroup on probiotics, probiotics can be defined as defined as:
"living micro-organisms, which, when ingested or locally applied in sufficient numbers confer one or more specifically demonstrated functional or health benefits on the consumer beyond basic nutrition".
Among the microbes in the human intestinal tract are the Gram-positive lactic acid-producing genera Lactobacillus and Bifidobacterium. Most probiotics are from the Lactobacillus and the Bifidobacterium genera and have been selected for their ability to survive gastric transit and to adhere to intestinal epithelial cells.
Such strains can transiently colonise the gut by integrating into existing microflora and are believed to confer certain health benefits to consumers. In recent years the consumption of λprobiotics' has markedly increased.
The gut is not the only part of the human body to harbor microorganisms. Human skin has 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 microorganisms 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.
Prior Art
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.
WO 05/089560A1 discloses water and milk based products containing probiotic microorganisms which are stable upon storage at 1O0C and which are free from carbohydrate metabolites. The products are intended for ingestion where they benefit the gut microflora.
WO2005080539 discloses a process for the preparation of a detergent for cleaning fabrics whereby probiotics are introduced into the production process. These microbes then generate enzymes and other actives that remove stains, such that the environmental impact of the detergent is reduced following the cleaning process.
None of the prior art suggests the use of probiotics in fabric treatment compositions, such as fabric softening compositions or softening-from-the-wash compositions, where particles of probiotic micro-organisms may be deposited onto a fabric carrier during a laundry process, such as a rinse process.
Brief Description of the Invention
We have now determined that probiotic micro-organisms may be incorporated into fabric treatment compositions and delivered onto fabrics from laundry applications. 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.
Definition of the Invention
In a first aspect, the present invention provides a fabric treatment composition for use in a laundering process which comprises :
a) at least one cationic softening agent or nonionic softening agent, and b) a probiotic particle. In a second aspect of the present invention there is provided a process of depositing probiotic particles on a fabric article comprising the step of:
treating a fabric article with a fabric treatment composition according to the first aspect of the present invention .
In a further aspect, the present invention provides a fabric article comprising probiotic particles, resulting from the treatment process of the second aspect of the invention.
Detailed Description of the Invention
The Probiotic Particle
For the purposes of this patent, the 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 micro-organisms can be used in the viable (live) form, in an inactivated form or in a dead form. They can be used at any stage of their life cycle (for example spore or vegetative cell state) . Inactivated or dead form of the probities may be incorporated without further protective measures. 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 probiotic particles are typically included in compositions of the invention at levels of from 0.003 to 0.1 wt %, preferably from 0.005 to 0.05 wt %, most preferably from 0.005 to 0.025 wt % by weight of the total composition.
Generally suitable probiotics for use in the present invention are chosen, in particular, from ascomycetes such as Saccharomyces , Yarrowia , Kluyveromyces , Torulaspora , Schizosaccharomyces pombe, Debaromyces , Candida, Pichia, Aspergillus and Penicillium, bacteria of the genus Bifidobacterium, Bacteroides , Fusobacterium, Melissococcus , Propioibacterium, Enterococcus , Lactococcus , Staphylococcus , Peptostrepococcus , Bacillus, Pediococcus , Micrococcus , Leuconostoc, Weissella, Aerococcus , Oenococcus and Lactobacillus and mixtures thereof.
More specific examples of probiotic microorganisms suitable for use in the present invention are Bifidobacterium adolescentis , Bifidobacterium bifidum, Bifidobacterium infantis , Bifidobacterium lactis , Bifidobacterium longum, Lactobacillus acidophilus , Lactobacillus alimentarius , Lactobacillus easel subsp. Casei, Lactobacillus easel Shirota, Lactobacillus paracasei , Lactobacillus curvatus , Lactobacillus delbruckii subsp. Lactis, Lactobacillus gasseri, Lactobacillus johnsonii , Lactobacillus reuteri, Lactobacillus rhamnosus (Lactobacillus GG) , Lactobacillus sake, Lactococcus lactis, Streptococcus thermophilus , Straphylococcus carnosus and Staphylococcus xylosus, and mixtures thereof.
The preferred species are Lactobacillus johnsonii , Lactobacillus paracasei , Bifidobacterium adolescentis ,
Bifidobacterium longum and Bifidobacterium lactis NCC 2818 (also entitled (Bb 12) (ATCC27536) ) respectively deposited according to the Treaty of Budapest with the Pasteur Institute (28 rue du Docteur Roux, F-75024 Paris Cedex 15) on 30/06/92, 12/01/99, 15/04/99 and 10/06/2005 under the following designations: CNCM 1-1225, CNCM 1-2116, CNCM I- 2168, CNCM 1-2170 and CNCM 1-3446, and the genus Bifidobacterium longum (BB536) . The Bifidobacterium lactis (CNCM 1-3446) strain can be obtained from Hansen (Chr. Hansen A/S, 10-12 Boege AlIe, P.O. Box 407, DK-2970 Hoersholm, Denmark) .
The micro-organisms must be capable of surviving the acid, alkaline or saline conditions of the laundry compositions of the invention.
Lactobacillus reuteri, Lactobacillus acidophilus , Lactobacillus animalis , Lactobacillus ruminis , Lactobacillus johnsonii , Lactobacillus easel, Lactobacillus paracasei , Lactobacillus rhamnosus , Lactobacillus fermentum,
Bifdobacterium sp . , Enterococcus faecium, Enterococcus sp all have good resistance to low pH environments (including for example pH 2-5) and to ambient temperature fluctuations (including freeze-thawing temperatures) experienced by the compositions on storage. For the purposes of this application, "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.
Prebiotics
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) . Depending on the metabolism of the desired microbe for the probiotic then a number of different carbon and energy sources can be used in the prebiotic.
Excessive growth of the probiotics in the composition of the invention itself is not desirable because this can cause degradation of product properties. It is well known in the art to use biocides at low concentrations to keep microbial activity static. This inhibitory effect on microbial growth can be removed upon product dilution. Examples of suitable biocides for use in the present invention include Proxel ( 1 , 2-benzisothiazolin-3-one) , available from, for example, Univar, Avecia and Uniqema; and Kathon CG (Methylchloroisothiazolinone and Methylisothiazolinone) , available from Rhom and Haas.
Alternatively where the presence of prebiotics and breakdown of some ingredients (particularly upon storage) into substances which are suitable as metabolites for the probiotics, unwanted growth of the probiotic as a result of the presence of these spurious prebiotics is minimized by using strains of probiotics that lack the enzymes necessary to metabolise the ingredients of the formulation or the breakdown products thereof. Some examples of suitable probiotics are given in WO 2005/089560A1, for example, Lactobacillus delbruecki subsp bulagaricus (ATCC11842) and Lactobacillus helveticus (ATCC15009) .
The laundry compositions of the invention may be substantially free from prebiotic substances specific to the particular probiotic particle used in the compositions of the invention, such that the probiotic does not grow excessively in the composition itself. By substantially free is meant that, where present, they are present only at a level such that the probiotic does not grow excessively in the composition itself, i.e. does not cause degradation of the properties of the composition. Preferably, the compositions contain prebiotic substances at a level of not more than 0.1 wt %, preferably not more than 0.05 wt%, more preferably not more than 0.01 wt%, still more preferably not more than 0.005 wt% by weight of the total composition and are most preferably free from prebiotic substances that can be metabolized by the probiotic of the composition. The compositions of the invention are especially preferably free from the group consisting of fructose, glucose and sucrose, most preferably, free of sucrose.
According to the invention 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 .
Deposition of the Probiotic Particle
Deposition of micro-organisms from laundry formulations of the invention onto a substrate may be achieved by any suitable route.
For example, by filtration, in which 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 a size comparable with the interyarn pore size.
The particle size is typically in the range of from 1 to 30 microns. Larger particles begin to be visible to the unaided eye, whereas smaller particles tend to be removed in the wash. Particles of around from 5 to 15 microns are preferred as they tend to be invisible to the eye and exhibit good deposition by 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 .
Polymers suitable for the deposition of particles are disclosed in WO9709406, particularly high MW polyethylene oxides (PEO) which are used to deposit clay particles in the main wash; EP0299575B1 and WO9527037, where high MW PEO, polyacrylates, polyacryl amides, poly vinyl alcohol and poly ethylene imines are used to deposit clay particles in the main wash; and EP0387426B1 which utilizes a similar list of polymers as well as guar gums.
WO 01/07546 Al discloses 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) and cationic polyacrylamides such as PCG (ex Allied Colloids) . Cationic polymeric aids are particularly preferred where the composition of the invention is a fabric softener wherein the softener is a non-cationic softener. Suitable non-ionic deposition aids include high molecular weight polyethylene glycols, for example PEO WSRN 750 (ex Union Carbide) .
The particle size range of the probiotic for polymer aided deposition is from 0.5 to 30 microns and preferably from 1 to 20 microns .
A preferred approach for the deposition of probiotic particles, particularly for probiotics deposition from a main wash laundry application, is targeted polymeric deposition based on the polysaccharide conjugate technology as disclosed in WO99/36469, WO2004/056890A1, WO2005/21186A1, where a water-soluble or water-dispersible polysaccharide conjugate comprising a polymeric backbone and a benefit agent group attached to the polymeric backbone by a hydrolytically stable bond is used to deposit the benefit agent onto a fabric during a main wash process. Similarly, US6773811B2, which describes a particle with a cellulosic polysaccharide attached (cellulose mono acetate - CMA) , and EP1117756B1, which claims beta 1-4 linked polysaccharides (LBG, xyloglucan etc) with a number of attached benefit agents. In the context of the present invention, the probiotic particle may be chemically bound to such a polysaccharide backbone via a hydrolytically stable bond.
This polysaccharide conjugate approach for use in the main wash has the advantage of targeting the substrate such that only the polymer-attached probiotic microorganisms become deposited onto the fabric and not the unwanted oily soil particles . The preferred biomass particle size range for the polysaccharide conjugate approach is from 1 to 15 microns. Most preferably from 1 to 5 μm. Larger particles require additional polysaccharide (2% as opposed to 1% on particle weight respectively for 30 μm and 5 μm) . This approach necessitates the deposition of a nanometer size of PVAC polymer shell on the probiotic to form a chemical bond between the particle and the polymer.
The Fabric Treatment Compositions
The fabric treatment composition of the invention is suitable for use in a laundry process. Examples include a softening-in-the-wash main wash composition, a rinse treatment (e.g. conditioner or finisher), or a post- treatment λwet tissue' type product. The compositions of the present invention are preferably laundry compositions, especially softening-in-the-wash compositions or rinse-added softening compositions.
The 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. In particular the compositions may be liquid, powder, or unit dose such as tablet laundry compositions.
The liquid products of the invention may have pH ranging from 2.5 (for fabric care compositions) to 12 (for fabric softening-in-the-wash compositions) . This pH range preferably remains stable over the shelf life of the product .
The active ingredient in the compositions is preferably a surface active agent or a fabric conditioning agent. More than one active ingredient may be included. For some applications a mixture of active ingredients may be used, for example, the main wash compositions may also include a fabric softening agent and the rinse-added fabric softening compositions may also include surface-active compounds, particularly non-ionic surface-active compounds.
The Softening Agent
Any 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 preferred softening active for use in rinse conditioner compositions of the invention is a quaternary ammonium compound. The quaternary ammonium fabric softening material for use in compositions of the present invention can be an ester-linked triethanolamine (TEA) quaternary ammonium compound comprising a mixture of mono-, di- and tri-ester linked components. Typically, 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) :
[ (CH2)n(TR) ]m
Ri-N+- [ (CH2) n (OH) ]3_m X" (I)
wherein each R is independently selected from a C5-35 alkyl or alkenyl group; R1 represents a C1-4 alkyl, C2-4 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; and X~ is an anionic counter-ion, such as a halide or alkyl sulphate, e.g. chloride or methylsulphate . Di-esters variants of formula I (i.e. m = 2) are preferred and typically have mono- and tri-ester analogues associated with them. Such materials are particularly suitable for use in the present invention. Especially preferred agents are di-esters of triethanolamine methylsulphate, otherwise referred to as "TEA ester quats.". Commercial examples include Prapagen TQL, ex Clariant, and Tetranyl AHT-I, ex Kao, (both di- [hardened tallow ester] of triethanolamine methylsulphate), AT-I (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 C10-C20 and C16-C18 unsaturated fatty acids), ex Witco Corporation.
The second group of QACs suitable for use in the invention is represented by formula (II) :
(R1J3N+- (CH2) n-CH-TR2 X" (II)
CH2TR2
wherein each R1 group is independently selected from C1-4 alkyl, hydroxyalkyl or C2_4 alkenyl groups; and wherein each R2 group is independently selected from Cs-28 alkyl or alken^ groups; and wherein n, T, and X~ are as defined above.
Preferred materials of this second group include 1,2 bis [ tallowoyloxy] -3-trimethylamine propane chloride, 1,2 bis [hardened tallowoyloxy] -3-trimethylamine propane chloride, 1, 2-bis [oleoyloxy] -3-trimethylamine propane chloride, and 1,2 bis [stearoyloxy] -3-trimethylamine propane chloride. Such materials are described in US 4,137,180 (Lever Brothers) . Preferably, 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 (III) :
(R1J2-N+-C (CH2) n-T-R2] 2 X" (HI)
wherein each R1 group is independently selected from Ci_4 alkyl, or C2-4 alkenyl groups; and wherein each R2 group is independently selected from Cs-28 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. - I i
One preferred type of non-ester softening compound is a quaternary ammonium material represented by formula (IV)
R1
(IV) R N R X
R2
wherein each R1 group is independently selected from C1-4 alkyl, hydroxyalkyl or C2-4 alkenyl groups; R2 group is independently selected from Cs-28 alkyl or alkenyl groups, and X~ is as defined above.
The compositions may comprise a total amount of between 0.5%wt-30% by weight of the cationic fabric softening compounds, preferably l%-25%, more preferably 1.5-20%, most preferably 2%-15%, based on the total weight of the composition.
The compositions may alternatively or additionally contain nonionic fabric softening agents such as lanolin and derivatives thereof. A further nonionic fabric softening agent suitable for use in the compositions of the invention is Castor oil, for example, from Now Chemicals.
Lecithins and other phospholipids are also suitable softening compounds. In fabric softening compositions nonionic stabilising agent may be present. Suitable nonionic stabilising agents may be present such as linear C8 to C22 alcohols alkoxylated with 10 to 20 moles of alkylene oxide, ClO to C20 alcohols, or mixtures thereof. Other stabilising agents include the deflocculating polymers as described in EP 0415698A2 and EP 0458599 Bl.
Advantageously the nonionic stabilising agent is a linear C8 to C22 alcohol alkoxylated with 10 to 20 moles of alkylene oxide. Preferably, the level of nonionic stabiliser 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 composition can also contain fatty acids, for example C8 to C24 alkyl or alkenyl monocarboxylic acids or polymers thereof. Preferably the fatty acid is non-saponified, more preferably the fatty acid is free, for example oleic acid, lauric acid or tallow fatty acid. The level of fatty acid material is preferably more than 0.1% by weight, more preferably more than 0.2% by weight. Concentrated compositions may comprise from 0.5 to 20% by weight of fatty acid, more preferably 1% to 10% by weight. The weight ratio of quaternary ammonium material or other cationic softening agent to fatty acid material is preferably from 10:1 to 1:10. It is also possible to include certain mono-alkyl cationic surfactants which can be used in main-wash compositions for fabrics. Cationic surfactants that may be used include quaternary ammonium salts of the general formula R1R2R3R4N+ X~ wherein the R groups are long or short hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a counter-ion (for example, compounds in which Rl is a C8-C22 alkyl group, preferably a C8-C10 or C12-C14 alkyl group, R2 is a methyl group, and R3 and R4, which may be the same or different, are methyl or hydroxyethyl groups) ; and cationic esters (for example, choline esters) .
Softening in the wash compositions in accordance with the invention comprise a surface-active compound, selected from anionic surfactants, cationic surfactants, non-ionic surfactants, zwitterionic surfactants, amphoteric surfactants and mixtures thereof. The choice of surface- active compound (surfactant) , and the amount present, will depend on the intended use of the detergent composition. In fabric washing compositions, different surfactant systems may be chosen, as is well known to the skilled formulator, for handwashing products and for products intended for use in different types of washing machine.
The total amount of surfactant present will also depend on the intended end use and may be as high as 60 wt%, for example, in a composition for washing fabrics by hand. In compositions for machine washing of fabrics, an amount of from 5 to 40 wt% is generally appropriate. Typically the compositions will comprise at least 2 wt% surfactant e.g. 2- 60%, preferably 15-40% most preferably 25-35%, by weight of the composition.
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, photobleaches (singlet oxygen or radical type) 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/or into the aqueous phase. Examples of suitable biocides for use in the present invention include Proxel (1, 2-benzisothiazolin-3-one) , available from, for example, Univar, Avecia and Uniqema; and Kathon CG (Methylchloroisothiazolinone and Methylisothiazolinone) , available from Rhom and Haas.
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.
In particular, the substrate may be a textile fabric. Treatment
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. Alternatively, 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
Embodiments of the invention are now illustrated with reference to the following non-limiting examples. Unless stated otherwise, all proportions are given in weight percent by weight of the total composition. Example 1: Fabric conditioner compositions 1 and 2 containing probiotic micro-organisms according to the invention
Table 1 Composition of compositions 1 and 2
** TEA quat is a cationic softener based on triethanolamine with tallow or hard tallow chains and 15% IPA as solvent. *** Plantatex LLE is a lipid found in skin.
Example 2: Fabric conditioner compositions 3 and 4 containing probiotic micro-organisms according to the invention and comparative compositions A to E
The compositions shown in Table 2 were prepared at 200 ml scale in a bench top vessel with a three-stage agitator at 5O0C. Table 2 Probiotics in fabric conditioner compositions
* Probiotic capsules ex Boots Pharmacy contain Microcrystalline cellulose, hydroxypropylmethylcellulose, Magnesium stearate, Lactobocillus Acidophilus 1.5mg, cfu = 75x10 and Bifidobacterium Bifidum 0.2mg, cfu = 25xlO6.
**Castor oil (ex Now Chemicals) is a non-ionic oil softener.
Example 3: Evaluation of deposition of probiotic onto fabric from the fabric conditioner compositions of example 2.
Compositions shown in table 2 were evaluated for pH change and malodour with storage and for deposition onto fabrics. Deposition of probiotic onto fabric was carried out as follows :
2 ml of each composition (C, D, E and 4) was diluted in a litre of water in a tergometer and used to rinse two pieces of black cotton cord and one piece of black polyester sheeting. The black background facilitated the microscopic identification of the probiotic particles on the fabrics.
Evaluation of the level of deposition was determined by microscopy examination with top light. In a visual observation of the fabrics probiotic particles were identified on fabrics treated with compositions 4, C and E. Fabrics treated with comparative composition C had fewer probiotic particles than those treated with compositions 4 and E. Composition D acted as a control in these observations to identify the existence of any spurious non- probiotic particles. No particulate matter could be found on the fabrics treated with D.
Both cationic starch polymer and cationic softener aided the deposition of the probiotic particles. Example 4: Evaluation of chemical stability of the fabric conditioner compositions of example 2
Table 3: pH of fabric conditioner compositions of example 2 upon storage for 1 week at room temperature (RT) and 41 °C .
Composition A B C D E 3 4 pH (initial) 6. 53 4. 9 6. 83 6. 65 3. 15 6 .25 3 .11 pH( 1 week) RT 6. 57 4. 66 6. 53 6. 64 3. 16 5 .92 3 .2 pH (1 week) 41°C - 6. 1 6. 37 6. 29 3. 17 6 .11 3 .15
The comparison of pH values initially and after one week storage indicated that the compositions were stable upon storage and that excessive probiotic activity and growth in the products did not occur.
No malodour was detected by an expert panel in compositions with probiotic compared to control compositions B and D. This is a further indication of stability and that the products have not provided a culture for growth of the probiotic .

Claims

1. A fabric treatment composition for use in a laundering process which comprises:
a) at least one cationic softening agent or nonionic softening agent, and b) a probiotic particle.
2. A fabric treatment composition according to claim 1, wherein the probiotic particle is selected from the genera Lactobacillus, Bifidobacterium, Streptococcus, Lactococcus, Entercoccus and mixtures thereof.
3. A fabric treatment composition according to claim 2, wherein the probiotic particle is selected from Lactobacillus Acidophilus , Bifidobacterium Bifidum, Lactobacillus johnsonii , Lactobacillus paracasei , Bifidobacterium adolescentis , Bifidobacterium longum and Bifidobacterium lactis NCC 2818.
4. A fabric treatment composition according to any preceding claim, wherein the probiotic particle is present in an amount of from 0.003 to 0.1 wt %, preferably from 0.005 to 0.05 wt %, most preferably from 0.005 to 0.025 wt % by weight of the total composition .
5. A fabric treatment composition according to any preceding claim, wherein the probiotic is in a form selected from viable (live) form, inactivated form and dead form.
6. A fabric treatment composition according to any preceding claim, which is a fabric conditioning composition .
7. A fabric treatment composition according to any preceding claim, wherein the cationic softening agent is a quaternary ammonium compound.
8. A fabric treatment composition according to claim 7, wherein the quaternary ammonium compound is an ester- linked triethanolamine (TEA) quaternary ammonium compound comprising a mixture of mono-, di- and tri- ester linked components.
9. A fabric treatment composition according to any preceding claim, which additionally comprises a deposition aid.
10. A fabric treatment composition according to claim 9, wherein the deposition aid is selected from polyethylene oxide (PEO), polyethylene imine (PEI), poly (acrylate) , poly (acrylamide) , cationic starches, polyethylene terephthalate-polyoxyethylene terephthalate (PET/POET) polymers and mixtures thereof.
11. A fabric treatment composition according to claim 9, wherein the deposition aid is a low charge density cationic polymer.
12. A fabric treatment composition according to claim 10, wherein the low charge density cationic polymer is a modified potato starch.
13. A process of depositing probiotic particles on a fabric article comprising the step of treating a fabric article with a laundering composition as defined in any preceding claim.
14. A fabric article comprising probiotic particles, resulting from the treatment process of claim 13.
EP08804200.7A 2007-10-01 2008-09-15 Improvements relating to fabric treatment compositions Active EP2195406B1 (en)

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WO2015000812A1 (en) * 2013-07-03 2015-01-08 Basf Se Process for cleaning surfaces
KR102087120B1 (en) * 2018-10-16 2020-03-10 (주)올바른컴퍼니 Detergent, softener and fabric deoderizer compostion containing probiotics
EP4123086A1 (en) * 2021-07-19 2023-01-25 The Procter & Gamble Company Fabric treatment

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6716435B1 (en) * 1997-04-18 2004-04-06 Ganeden Biotech, Inc. Absorbent product containing absorbent structure and Bacillus coagulans

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009043707A1 *

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BRPI0818429A2 (en) 2015-04-22
EP2195406B1 (en) 2016-03-23
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AR068586A1 (en) 2009-11-18
CN101878289B (en) 2013-09-25
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ZA201001830B (en) 2011-05-25
CN101878289A (en) 2010-11-03

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