EP2838982B9

EP2838982B9 - Improvements relating to fabric conditioners

Info

Publication number: EP2838982B9
Application number: EP13716273.1A
Authority: EP
Inventors: Kenneth Metcalfe; Ian Karl Smith; Allister John THEOBALD
Original assignee: Unilever PLC; Unilever NV
Current assignee: Unilever PLC; Unilever NV
Priority date: 2012-04-17
Filing date: 2013-04-10
Publication date: 2017-06-14
Anticipated expiration: 2033-04-10
Also published as: BR112014025932A2; CN104220577A; EP2838982B1; WO2013156371A1; IN2014MN02042A; EP2838982A1; PH12014502291A1; ZA201407180B; ES2550989T3; CN104220577B

Description

Technical Field

The present invention relates to dilute fabric conditioner compositions containing unsaturated TEA quaternary ammonium compounds which are stable and deliver both perfume and malodour benefits.

Background and Prior Art

Chlorinated phenyl ethers, and in particular, "Diclosan" (4-4' dichloro-2-hydroxy diphenyl ether) are known for use in laundry products to give a persistent antimicrobial effect which resists exposure to high temperatures and therefore survives machine drying. Antimicrobials are known to have a secondary effect in the prevention of malodours through several microbial pathways. These may include (amongst others) odours generated by skin bacteria such as Staphylococcus epidermidis, decomposition of urine or growth of pathogenic bateria such as Proteus vulgaris, and the formation of foot odour by Micrococcus dermatophytes . Many anti-microbial materials are known or have been suggested for use in laundry products.
The efficacy of such compositions in reducing microbial growth can be measured by various tests. One well known and standard test is the AATCC100 test, which measures bacterial growth on fabrics. While industrial fabric treatments and modification of fibres (such as the incorporation of silver ions) give good results in this and other tests, it has proven difficult to achieve good scores in such tests for both gram positive and gram negative bacteria by treatments which can be used in the home under the diverse washing conditions which end users apply.
Rinse conditioners are one type of laundry product and are essentially metastable dispersions of fabric softening actives in a solvent/water phase. The dispersions are formulated such that they are stable in storage and in transit, but in use they become unstable and the fabric softening active becomes deposited on the articles being treated. The stability of the formulation is dependent on the type of softening active being used and the levels of both that active and other softening components. Loss of stability can lead to changes in viscosity or even worse visible separation of formulation components. Changes in the microstructure of a product can have unexpected effects on perfume behaviour and vice-versa. Even small changes in a formulation can have consequences as regards stability.
Thus, when changing the primary active present in a rinse conditioner, i.e. the cationic softening material, it is almost invariably the case that the new active cannot simply be substituted for the old one without having to make other formulation changes.

Statement of the Invention

We have determined that the combination of a triethanolamine-based quaternary active with a non-ionic antimicrobial gives a stable formulation base which reduces malodour and can be perfumed. As will be discussed in further detail below other antimicrobials did not give this benefit in combination with the particular base.
In a first aspect of the invention there is provided an aqueous fabric conditioner composition comprising:

(a) from 0.5 to 35%, by weight of the total composition, of a fabric softening active, wherein the fabric softening active comprises an ester-linked triethanolamine quaternary ammonium compound,
(b) from 0.002% to 0,4% by weight of the total composition, of a non-ionic, antimicrobial active which is not a perfume component, and,
(c) from 0.01 to 10%, by weight of the total composition, of a perfume.

As described in further detail below it is especially preferred that at least a part of the perfume is encapsulated, preferably in polymeric core-shell encapsulates having a water-insoluble shell.
Surprisingly, the compositions of the invention showed an unexpected improvement in the efficacy of the antimicrobial in a range of wash conditions. The synergistic combination of the conditioner active with Diclosan enables economically sustainable fabric conditioner formulations capable of delivering persistent antimicrobial action for a wide range of domestic laundering practices.
The fabric conditioning compositions of the invention may be dilute or concentrated. Dilute products typically contain up to about 8 %, preferably from 2 to 8 % by weight of softening active, whereas concentrated products may contain from about 8 to about 50 %, preferably from 8 to 25 % by weight active. Compositions of more than about 25 % by weight of active are defined as "super concentrated", depending on the active system, and are also intended to be covered by the present invention. The fabric conditioning agent may, for example, be used in amounts of preferably from 2 % to 30 % more preferably from 5 % to 25 % and most preferably from 8 % to 20 % by weight of the composition.
Typically, triethanolamine (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 TEA-based fabric softening compound, preferably no more than 60 %, e.g. 55 %, or 45 % of the fabric softening compound and at least 10 % of the monoester linked component, for example 11 % monoester.
Especially preferred agents are preparations which are rich in the di-esters of triethanolammonium methylsulphate,
The triester content is preferably below 10 wt %, more preferably from 5 to 9 wt % by total weight of the quaternary active component. Preferred ester-linked triethanolamine quaternary ammonium compounds have a diester content of from 50 to 60 wt %, more preferably from 52 to 59 wt % by total weight of the quaternary active component. Also preferred are TEA quats having a monoester content of from 30 to 45 wt %, more preferably from 32 to 42 wt % by total weight of the quaternary active component.
A preferred TEA quat of the present invention comprises from 32 to 42 wt % of monoester, from 52 to 59 wt % of diester and from 5 to 9 wt % of triester compounds, by total weight of the quaternary active; more preferably from 35 to 39 wt % of monoester, from 54 to 58 wt % of diester and from 7 to 8 wt % of triester compounds, by total weight of the quaternary active component.
A preferred hardened type of TEA active has a typical mono:di:tri ester distribution of from 18 to 22 mono: from 58 to 62 di: from 18 to 22 tri; for example 20:60:20. A soft TEA quat may have a typical mono:di:tri ester distribution of from 25 to 45 %, preferably from 30 to 40 % mono: from 45 to 60 %, preferably from 50 to 55 % di: and from 5 to 25 %, preferably from 10 to 15 % tri; for example 40:60:10.
A further aspect of the invention provides a method of preparing a rinse water, which comprises adding to water a composition as defined in the first aspect.
A yet further aspect of the invention subsists in the use of the rinse water of the second aspect to treat fabrics such that microbial growth on the fabrics is inhibited.

Detailed Description of the Invention

The present invention will be further specified below with reference to certain preferred embodiments and preferred variants on the integers claimed. Any combination of preferred integers can be used together. All percentages given are weight percentages except where otherwise stated.
Preferably, the aqueous fabric conditioner composition has a viscosity of greater than 50 cps, preferably from 55 to 200 cps more preferably from 60 to 175, even more preferably from 80 to 150 and most preferably from 100 to 140 cps as measured on a "cup and bob" viscometer; the viscosity being continuously measured under shear at 106s^-1 for 60 seconds, at 25°C.
Any suitable viscometer can be used to make this measurement, for example, the Haake VT550 with a MV1 cup and bob geometry and the Thermo Fisher RS600 viscometer.

The Fabric Softening Active

The fabric softening active, for use in the fabric conditioner compositions of the present invention comprises an ester-linked triethanolamine quaternary ammonium compound (QAC). The fabric softening active is present in an amount of from 0.5 to 35 wt %, based on the total weight of the composition, preferably from 6 to 35 wt %.
Preferably, the QAC is derived from palm or tallow feed stocks. These feed stocks may be pure or predominantly palm or tallow based. Blends of different feed stocks may be used.
The fatty acid chains of the QAC preferably comprise from 20 to 35 wt % of saturated C18 chains and from 20 to 35 wt % of monounsaturated C18 chains by weight of total fatty acid chains.
In a preferred embodiment, the fatty acid chains of the QAC comprise from 25 to 30 wt %, preferably from 26 to 28 wt % of saturated C18 chains and from 25 to 30 wt %, preferably from 26 to 28 wt % of monounsaturated C18 chains, by weight of total fatty acid chains.
In a further preferred embodiment, the fatty acid chains of the QAC comprise from 30 to 35 wt %, preferably from 33 to 35 wt % of saturated C18 chains and from 24 to 35 wt %, preferably from 27 to 32 wt % of monounsaturated C18 chains, by weight of total fatty acid chains.
Iodine value as used in the context of the present invention refers to the measurement of the degree of unsaturation present in a material by a method of NMR spectroscopy as described in Anal. Chem, 34, 1136 (1962) Johnson and Shoolery. The preferred quaternary ammonium materials for use in the present invention can be derived from feedstock having an overall iodine value of from 30 to 45, preferably from 30 to 42 and most preferably 36.
Commercial examples include Stepantex™ UL85, ex Stepan, Prapagen™ TQL, ex Clariant, and Tetranyl™ AHT-1, ex Kao, (both di-[hardened tallow ester] of triethanolammonium methylsulphate), AT-1 (di-[tallow ester] of triethanolammonium methylsulphate), and L5/90 (di-[palm ester] of triethanolammonium methylsulphate), both ex Kao, and Rewoquat™ WE15 (a di-ester of triethanolammonium methylsulphate having fatty acyl residues deriving from C10-C20 and C16-C18 unsaturated fatty acids), ex Witco Corporation. Also, quaternary ammonium actives such as Stepantex VK90, Stepantex VT90, SP88 (ex-Stepan), Ceca Noramine, Prapagen TQ (ex-Clariant), Dehyquart AU-57 (ex-Cognis), Rewoquat WE18 (ex-Degussa) and Tetranyl L190 P, Tetranyl L190 SP and Tetranyl L190 S (all ex-Kao) are suitable.

The Nonionic Antimicrobial

Preferably the non-ionic antimicrobial is a halogenated material. Suitable materials include 5-chloro-2-(2,4-dichlorophenoxy)phenol, o-Benzyl-p-chlorophenol, and 4-chloro-3-methylphenol.
Alternatively the material may be non-halogenated. Examples of suitable materials include 2-Phenylphenol and 2-(1-Hydroxy-1-methylethyl)-5-methylcyclohexanol.
Phenyl ethers are one preferred sub-set of the non-ionic antimicrobials.
More preferably the non-ionic antimicrobial is a bi-halogenated compound. Most preferably this comprises 4-4' dichloro-2-hydroxy diphenyl ether, and /or 2,2-dibromo-3-nitrilopropionamide (DBNPA). If the latter is used the pH of the composition needs to be in the acidic range where DBNPA is stable. This presents no difficulty with rinse conditioner compositions as they are usually formulated in that range.
The non-ionic microbial active is present in an amount of from 0.002 to 0.4 wt, by weight of the total composition. The preferred inclusion range for the non-ionic antimicrobial active is from 0.025 to 0.1 wt %, by weight of the total composition.
Suitable materials are known in the marketplace as "Diclosan" and available as products such as Tinosan™ HP 100 ex BASF.
In addition to the non-ionic antimicrobial other antimicrobial agents may also be present, provided that these are not present at a level which causes instability in the formulation. Among such useful further antimicrobial agents are chelating agents, which are particularly useful in reducing the resistance of gram negative microbes in hard water. Acid biocides may also be present.

Perfume

The perfume is preferably present in an amount from 0.05 to 5 % by weight, even more preferably from 0.05 to 2 %, most preferably from 0.05 to 1.5 % by weight, based on the total weight of the composition.
It is highly preferred that the perfume is an at least partially encapsulated perfume. That is, some, if not all, of the perfume material present is encapsulated in perfume particles. Encapsulating materials are not included in the weight of perfume present given above. It is believed that encapsulation of at least part of the perfume has a beneficial effect on the stability of the product. Encapsulation also provides for better perfume delivery especially where a deposition aid is linked to the encapsulate.
In one aspect of the invention the process for the preparation of the perfume particles is preferably a two step process in which the first step forms a particle comprising the benefit agent and the second step applies a coating to the capsule which includes a deposition aid.
The first step can either be step-growth or addition polymerisation and the second step is preferably addition polymerisation.
In the alternative a particle can be formed which does not contain the perfume but which is capable of adsorbing it at some later time. This particle is then optionally decorated with the deposition aid thereby performing a two-step process analogous to that described above. The particle is subsequently exposed to the perfume, which diffuses into the particle. Conveniently, this may be done in-product, for example by adding the particles with deposition aid to a partly or fully formulated product which contains the perfume. The perfume is then adsorbed by the particle and retained within the particle during use of the product, so that at least some of the perfume is released from the particles after the fabric treatment process, when the particles have become deposited on the fabric.
Single step encapsulation can also be used. In general, single step encapsulate particles do possess a deposition aid. Single step perfume particles can be formed either by step-growth polymerisation or addition polymerisation.
Suitable classes of monomers for step-growth polymerization are given in the group consisting of the melamine/urea formaldehyde class, the isocyanate/diol class (preferably the polyurethanes) and polyesters.
Preferred are the melamine/urea formaldehyde class and the polyurethanes.
Suitable classes of monomers for addition/free radical polymerization are given in the group consisting of olefins, ethylene, vinylaromatic monomers, esters of vinyl alcohol with mono- and di- carboxylic acids, esters of α,β-monoethylenically unsaturated mono- and dicarboxylic acids with alcohols, nitriles of α,β-monoethylenically unsaturated carboxylic acids, conjugated dienes, α,β-monoethylenically unsaturated monocarboxylic and dicarboxylic acids and their amides, methacrylic acid and its esters with alcohols and diols, acrylic acid and its esters with alcohols and diols, dimethyl or di-n-butyl maleate, and vinyl-sulfonic acid and its water-soluble salts, and mixtures thereof. The polymer particle may comprise mixtures of monomer units.
The polymer particle may optionally comprise monomers which are cross-linkers. Such cross-linkers may have at least two non-conjugated ethylenically unsaturated double bonds. Examples are alkylene glycol diacrylates and dimethacrylates. A further type of suitable cross-linking monomers are those that are conjugated, such as divinyl benzene. If present, these monomers constitute from 0.1 to 10 % by weight, based on the total amount of monomers to be polymerised.
The monomers are preferably selected from: styrene; α-methylstyrene; o-chlorostyrene; vinyl acetate; vinyl propionate; vinyl n-butyrate; esters of acrylic, methacrylic, maleic, fumaric or itaconic acid with methyl, ethyl, n- butyl, isobutyl, n-hexyl and 2-ethylhexyl alcohol; 1,3-butadiene; 2,3 dimethyl butadiene; and isoprene. The preferred monomers are vinyl acetate and methyl acrylate.
Optionally, the monomers are used as co-monomers with one or more of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, poly (alkylene oxide) monoacrylates and monomethacrylates, N-vinyl-pyrrolidone, methacrylic and acrylic acid, 2-hydroxyethyl acrylates and methacrylates, glycerol acrylates and methacrylates, poly(ethylene glycol) methacrylates and acrylates, n-vinyl pyrrolidone, acryloyl morpholine, vinyl formamide, n-vinyl acetamide and vinyl caprolactone, acrylonitrile (71 g/l), acrylamide, and methacrylamide at levels of less than 10 % by weight of the monomer unit content of the particle; 2-(dimethylamino) ethyl methacrylate, 2-(diethylamino) ethyl methacrylate, 2-(tert-butylamino) ethyl methacrylate, 2 - aminoethyl methacrylate, 2-(2-oxo-1-imidazolidinyl) ethyl methacrylate, vinyl pyridine, vinyl carbazole, vinyl imidazole, vinyl aniline, and their cationic forms after treatment with alkyl halides.
Optional cross linkers include vinyltoluenes, divinyl benzene, ethylene glycol diacrylate, 1,2-propylene glycol diacrylate, 1 ,3-propylene glycol diacrylate, 1 ,3-butylene glycol diacrylate, 1 ,4-butylene glycol diacrylates, ethylene glycol dimethacrylate, 1 ,2-propylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1 ,3-butylene glycol dimethacrylate, 1 ,4-butylene glycol dimethacrylate, divinylbenzene, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate, methylenebisacrylamide, cyclopentadienyl acrylate, and triallyl cyanurate.
It is preferable that the ratio of the monomers used in the overall shell formation and those used in deposition aid attachment are the ratio of 100:1 to 5:1 (as bulk shell former: deposition linker). Preferably, the ratio is 100:1 - 50:1.
As noted above the process for the preparation of the particles is preferably a two step process in which the first step forms a capsule around the benefit agent and the second step applies a coating to the capsule which includes the deposition aid. The first step can either be step-growth or addition polymerization and the second step is preferably addition polymerization.
It is particularly preferably that the first step uses monomers selected from melamine/urea-formaldehyde or methyl-methacrylate or isocyanate/diol, and the second step uses monomers selected from vinyl acetate and/or methyl acyrlate. It is particularly preferred that the deposition aid is not added until the second step.
For step-growth polymerization some heating is generally necessary to cause polymerization to proceed. Initiators and chain transfer agents may also be present in the polymerization mixture where use is made of any addition polymerization. Those skilled in the art will recognize that a chemical initiator will generally be required for addition polymerization but that there are instances in which alternative forms of initiation will be possible, e.g. ultrasonic initiation or initiation by irradiation.
The initiator is preferably a chemical or chemicals capable of forming free radicals. Typically, free radicals can be formed either by homolytic scission (i.e. homolysis) of a single bond or by single electron transfer to or from an ion or molecule (e.g. redox reactions). Suitably, in context of the invention, homolysis may be achieved by the application of heat (typically in the range of from 50 to 100°C). Some examples of suitable initiators in this class are those possessing peroxide (-O-O-) or azo (-N=N-) groups, such as benzoyl peroxide, t-butyl peroxide, hydrogen peroxide, azobisisobutyronitrile and ammonium persulphate. Homolysis may also be achieved by the action of radiation (usually ultraviolet), in which case it is termed photolysis. Examples are the dissociation of 2,2'-azobis (2-cyanopropane) and the formation of free radicals from benzophenone and benzoin. Redox reactions can also be used to generate free radicals. In this case an oxidising agent is paired with a reducing agent which then undergo a redox reaction. Some examples of appropriate pairs in the context of the invention are ammonium persulphate/sodium metabisulphite, cumyl hydroperoxide/ferrous ion and hydrogen peroxide/ascorbic acid.
Preferred initiators are selected from the following:

Homolytic: benzoyl peroxide, t-butyl peroxide, hydrogen peroxide, azobisisobutyronithle, ammonium persulphate, 2,2'-azobis (cyanopropane), benzophenone, benzoin,
Redox: ammonium persulphate/sodium metabisulphite mixture, cumyl hydroperoxide/ferrous ion mixture and/or hydrogen peroxide/ascorbic acid mixture.

Preferred initiators are ammonium persulphate and hydrogen peroxide/ascorbic acid mixture. The preferred level of initiator is in the range of from 0.1 to 5.0% w/w by weight of monomer, more preferably, the level is in the range of from 1.0 to 3.0 % w/w by weight of monomer.
Chain transfer agents can optionally be used. A chain transfer agent contains very labile hydrogen atoms that are easily abstracted by a propagating polymer chain. This terminates the polymerization of the growing polymer, but generates a new reactive site on the chain transfer agent that can then proceed to initiate further polymerization of the remaining monomer. Chain transfer agents in the context of the invention typically contain thiol (mercaptan) functionality and can be represented by the general chemical formula RS-H, such as n-dodecyl mercaptan and 2-mercaptoethanol. Preferred chain transfer agents are monothioglycerol and n-dodecyl mercaptan, used at levels of, preferably from 0 to 5 % w/w based on the weight of the monomer and more preferably at a level of 0.25 % w/w based on the weight of the monomer.
While it is preferred to use polymer particles, preferably core-shell encapsulates, many other types of particle can be envisaged as the perfume carrier and then encapsulated. Perfumes have been adsorbed onto a clay or zeolite material that is then admixed into particulate detergent compositions: U.S. Pat. No. 4,539,135 discloses particulate laundry compounds comprising a clay or zeolite material carrying perfume. Combinations of perfumes generally with larger pore size zeolites such as zeolite X and Y are also taught in the art. East German Patent Publication No. 248,508 , relates to perfume dispensers containing a faujasite-type zeolite (e.g., zeolite X and Y) loaded with perfume. Also, East German Patent Publication No. 137,599, published Sep. 12, 1979 teaches compositions for use in powdered washing agents to provide thermo-regulated release of perfume. Zeolites A, X and Y are taught for use in these compositions. Other perfume delivery systems are taught by WO 97/34982 and WO 98/41607 , published by The Procter & Gamble. WO 97/34982 discloses particles comprising perfume loaded zeolite and a release barrier, which is an agent derived from a wax and having a size (i.e., a cross-sectional area) larger than the size of the pore openings of the zeolite carrier. WO 98/41607 discloses glassy particles comprising agents useful for laundry or cleaning compositions and a glass derived from one or more of at least partially-water-soluble hydroxylic compounds.
Silicas, amorphous silicates, crystalline nonlayer silicates, layer silicates, calcium carbonates, calcium/sodium carbonate double salts, sodium carbonates, sodalites, alkali metal phosphates, pectin, chitin microbeads, carboxyalkyl celluloses, gums, resins, gelatin, gum arabic, porous starches, modified starches, carboxyalkyl starches, cyclodextrins, maltodextrins, synthetic polymers such as polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), cellulose ethers, polystyrene, polyacrylates, polymethacrylates, polyolefins, aminoplast polymers, crosslinkers and mixtures thereof can all provide a basis for perfume particles.
Polymer particles are however preferred, especially polymer particles which comprise a water-insoluble shell comprising an aminoplast polymer. These include core shell encapsulates of which the water-insoluble shell comprises the reaction product of an amine selected from urea and melamine, or mixtures thereof, and an aldehyde selected from formaldehyde, acetaldehyde, glutaraldehyde or mixtures thereof.
The perfume carrying particles are typically of a size (measured as D_4,3) between 100 nanometers and 50 microns. Particles larger than this are entering the visible range.
The preferred particle size range is either in the sub-micron range or the micron range.
Suitable particles in the sub-micron range include nanoparticles, latexes, and mini-emulsion products with a typical size range of 100-600 nanometers.
Suitable particles in the micron range include known types of aminoplast encapsulates, silica, clays starch and zeolite particles and coacervates with a typical size range of 1-50 microns, preferably 5-30 microns.
As mentioned above, the particles may be provided with a deposition aid. These are polymeric materials fixed to the outer surface of the particle which are substantive to cotton and/or polyester. Suitable deposition aids include natural or modified polysaccharides which are substantive to cotton and/or polyester, or phthalate containing species which are substantive to cotton and/or polyester.
Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA). These substances are well known to the person skilled in the art of perfuming, flavouring, and/or aromatizing consumer products, i.e., of imparting an odour and/or a flavour or taste to a consumer product traditionally perfumed or flavoured, or of modifying the odour and/or taste of said consumer product.
By perfume in this context is not only meant a fully formulated product fragrance, but also selected components of that fragrance, particularly those which are prone to loss, such as the so-called 'top notes'.
Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Examples of well known top-notes include citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. Top notes typically comprise 15-25%wt of a perfume composition and in those embodiments of the invention which contain an increased level of top-notes it is envisaged at that least 20%wt would be present in an encapsulated form.
Typical perfume components which it is advantageous to encapsulate, include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100-250 Celsius and pro-fragrances which can produce such components.
It is also advantageous to encapsulate perfume components which have a low Clog P (i.e. those which will be partitioned into water), preferably with a Clog P of less than 3.0. These materials, of relatively low boiling point and relatively low Clog P have been called the "delayed blooming" perfume ingredients and include the following materials:

Allyl Caproate, Amyl Acetate, Amyl Propionate, Anisic Aldehyde, Anisole, Benzaldehyde, Benzyl Acetate, Benzyl Acetone, Benzyl Alcohol, Benzyl Formate, Benzyl Iso Valerate, Benzyl Propionate, Beta Gamma Hexenol, Camphor Gum, Laevo-Carvone, d-Carvone, Cinnamic Alcohol, Cinamyl Formate, Cis-Jasmone, cis-3-Hexenyl Acetate, Cuminic Alcohol, Cyclal C, Dimethyl Benzyl Carbinol, Dimethyl Benzyl Carbinol Acetate, Ethyl Acetate, Ethyl Aceto Acetate, Ethyl Amyl Ketone, Ethyl Benzoate, Ethyl Butyrate, Ethyl Hexyl Ketone, Ethyl Phenyl Acetate, Eucalyptol, Eugenol, Fenchyl Acetate, Flor Acetate (tricyclo Decenyl Acetate), Frutene (tricyclco Decenyl Propionate), Geraniol, Hexenol, Hexenyl Acetate, Hexyl Acetate, Hexyl Formate, Hydratropic Alcohol, Hydroxycitronellal, Indone, Isoamyl Alcohol, Iso Menthone, Isopulegyl Acetate, Isoquinolone, Ligustral, Linalool, Linalool Oxide, Linalyl Formate, Menthone, Menthyl Acetphenone, Methyl Amyl Ketone, Methyl Anthranilate, Methyl Benzoate, Methyl Benyl Acetate, Methyl Eugenol, Methyl Heptenone, Methyl Heptine Carbonate, Methyl Heptyl Ketone, Methyl Hexyl Ketone, Methyl Phenyl Carbinyl Acetate, Methyl Salicylate, Methyl-N-Methyl Anthranilate, Nerol, Octalactone, Octyl Alcohol, p-Cresol, p-Cresol Methyl Ether, p-Methoxy Acetophenone, p-Methyl Acetophenone, Phenoxy Ethanol, Phenyl Acetaldehyde, Phenyl Ethyl Acetate, Phenyl Ethyl Alcohol, Phenyl Ethyl Dimethyl Carbinol, Prenyl Acetate, Propyl Bornate, Pulegone, Rose Oxide, Safrole, 4-Terpinenol, Alpha-Terpinenol, and/or Viridine.

Preferred non-encapsulated perfume ingredients are those hydrophobic perfume components with a ClogP above 3. As used herein, the term "ClogP" means the calculated logarithm to base 10 of the octanol/water partition coefficient (P). The octanol/water partition coefficient of a PRM is the ratio between its equilibrium concentrations in octanol and water. Given that this measure is a ratio of the equilibrium concentration of a PRM in a non-polar solvent (octanol) with its concentration in a polar solvent (water), ClogP is also a measure of the hydrophobicity of a material--the higher the ClogP value, the more hydrophobic the material. ClogP values can be readily calculated from a program called "CLOGP" which is available from Daylight Chemical Information Systems Inc., Irvine Calif., USA. Octanol/water partition coefficients are described in more detail in U.S. Pat. No. 5,578,563 .
Perfume components with a ClogP above 3 comprise: Iso E super, citronellol, Ethyl cinnamate, Bangalol, 2,4,6-Trimethylbenzaldehyde, Hexyl cinnamic aldehyde, 2,6-Dimethyl-2-heptanol, Diisobutylcarbinol, Ethyl salicylate, Phenethyl isobutyrate, Ethyl hexyl ketone, Propyl amyl ketone, Dibutyl ketone, Heptyl methyl ketone, 4,5-Dihydrotoluene, Caprylic aldehyde, Citral, Geranial, Isopropyl benzoate, Cyclohexanepropionic acid, Campholene aldehyde, Caprylic acid, Caprylic alcohol, Cuminaldehyde, 1-Ethyl-4-nitrobenzene, Heptyl formate, 4-Isopropylphenol, 2-Isopropylphenol, 3-Isopropylphenol, Allyl disulfide, 4-Methyl-1-phenyl-2-pentanone, 2-Propylfuran, Allyl caproate, Styrene, Isoeugenyl methyl ether, Indonaphthene, Diethyl suberate, L-Menthone, Menthone racemic, p-Cresyl isobutyrate, Butyl butyrate, Ethyl hexanoate, Propyl valerate, n-Pentyl propanoate, Hexyl acetate, Methyl heptanoate, trans-3,3,5-Trimethylcyclohexanol, 3,3,5-Trimethylcyclohexanol, Ethyl p-anisate, 2-Ethyl-1-hexanol, Benzyl isobutyrate, 2,5-Dimethylthiophene, Isobutyl 2-butenoate, Caprylnitrile, gamma-Nonalactone, Nerol, trans-Geraniol, 1-Vinylheptanol, Eucalyptol, 4-Terpinenol, Dihydrocarveol, Ethyl 2-methoxybenzoate, Ethyl cyclohexanecarboxylate, 2-Ethylhexanal, Ethyl amyl carbinol, 2-Octanol, 2-Octanol, Ethyl methylphenylglycidate, Diisobutyl ketone, Coumarone, Propyl isovalerate, Isobutyl butanoate, Isopentyl propanoate, 2-Ethylbutyl acetate, 6-Methyl-tetrahydroquinoline, Eugenyl methyl ether, Ethyl dihydrocinnamate, 3,5-Dimethoxytoluene, Toluene, Ethyl benzoate, n-Butyrophenone, alpha-Terpineol, Methyl 2-methylbenzoate, Methyl 4-methylbenzoate, Methyl 3, methylbenzoate, sec. Butyl n-butyrate, 1,4-Cineole, Fenchyl alcohol, Pinanol, cis-2-Pinanol, 2,4, Dimethylacetophenone, Isoeugenol, Safrole, Methyl 2-octynoate, o-Methylanisole, p-Cresyl methyl ether, Ethyl anthranilate, Linalool, Phenyl butyrate, Ethylene glycol dibutyrate, Diethyl phthalate, Phenyl mercaptan, Cumic alcohol, m-Toluquinoline, 6-Methylquinoline, Lepidine, 2-Ethylbenzaldehyde, 4-Ethylbenzaldehyde, o-Ethylphenol, p-Ethylphenol, m-Ethylphenol, (+)-Pulegone, 2,4-Dimethylbenzaldehyde, Isoxylaldehyde, Ethyl sorbate, Benzyl propionate, 1,3-Dimethylbutyl acetate, Isobutyl isobutanoate, 2,6-Xylenol, 2,4-Xylenol, 2,5-Xylenol, 3,5-Xylenol, Methyl cinnamate, Hexyl methyl ether, Benzyl ethyl ether, Methyl salicylate, Butyl propyl ketone, Ethyl amyl ketone, Hexyl methyl ketone, 2,3-Xylenol, 3,4, Xylenol, Cyclopentadenanolide and Phenyl ethyl 2 phenylacetate 2.
It is commonplace for a plurality of perfume components to be present in a formulation. In the compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components present in the perfume.
Another group of perfumes with which the present invention can be applied are the so-called 'aromatherapy' materials. These include many components also used in perfumery, including components of essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian.
Another preferred feature is the inclusion of antimicrobial perfume oils in addition to the non-ionic antimicrobial which is not a perfume oil. Examples of these include eucalyptol, thymol and tea-tree oil. Other antimicrobial perfume components are identified in WO 2000/024367 .
A further preferred feature is the inclusion of an insect repellent. Many suitable insect repellents are related to perfume species (many fall into both classes). The most commonly used insect repellents include: DEET (N,N-diethyl-m-toluamide), essential oil of the lemon eucalyptus (Corymbia citriodora) and its active compound p-menthane-3,8-diol (PMD), Icaridin, also known as Picaridin, D-Limonene, Bayrepel, and KBR 3023, Nepetalactone, also known as "catnip oil", Citronella oil, Permethrin, Neem oil and Bog Myrtle.
Known insect repellents derived from natural sources include: Achillea alpina, alpha-terpinene, Basil oil (Ocimum basilicum), Callicarpa americana (Beautyberry), Camphor, Carvacrol, Castor oil (Ricinus communis), Catnip oil (Nepeta species), Cedar oil (Cedrus atlantica), Celery extract (Apium graveolens), Cinnamon (Cinnamomum Zeylanicum, leaf oil), Citronella oil (Cymbopogon fleusus), Clove oil (Eugenic caryophyllata), Eucalyptus oil (70%+ eucalyptol, also known as cineol), Fennel oil (Foeniculum vulgare), Garlic Oil (Allium sativum), Geranium oil (also known as Pelargonium graveolens), Lavender oil (Lavandula officinalis), Lemon eucalyptus (Corymbia citriodora) essential oil and its active ingredient p-menthane-3,8-diol (PMD), Lemongrass oil (Cymbopogon flexuosus), Marigolds (Tagetes species), Marjoram (Tetranychus urticae and Eutetranychus orientalis), Neem oil (Azadirachta indica), Oleic acid, Peppermint (Mentha x piperita), Pennyroyal (Mentha pulegium), Pyrethrum (from Chrysanthemum species, particularly C. cinerariifolium and C. coccineum), Rosemary oil (Rosmarinus officinalis), Spanish Flag Lantana camara (Helopeltis theivora), Solanum villosum berry juice, Tea tree oil (Melaleuca alternifolia) and Thyme (Thymus species) and mixtures thereof.

Especially Preferred Embodiments:

Especially preferred embodiments of the invention provide an aqueous fabric conditioner composition comprising:

(a) from 0.5 to 35%, by weight of the total composition, of a fabric softening active, wherein the fabric softening active includes an ester-linked triethanolamine quaternary ammonium compound,
(b) from 0.01 % to 2%, by weight of the total composition, a non-ionic antimicrobial which is not a perfume component, preferably including a chlorinated phenyl ether, and/or 2,2-dibromo-3-nitrilopropionamide,
(c) from 0.01 to 10%, by weight of the total composition, of a perfume, of which at least a part is encapsulated.

Further Optional Ingredients

Floc Prevention Agents:

The compositions of the invention preferably comprise a floc prevention agent, which is a non-ionic alkoxylated material having an HLB value of from 8 to 18, preferably from 11 to 16, more preferably from 12 to 16 and most preferably 16. The flocculation prevention agent, enables the formation of a thick "dilute" fabric conditioner composition, which does not flocculate upon use.
The non-ionic alkoxylated material can be linear or branched, preferably linear.
The floc prevention agent is preferably present in an amount of from 0.01 to 0.5 wt %, preferably from 0.02 to 0.4 wt %, more preferably from 0.05 to 0.25 wt % and most preferably 0.1 wt % by total weight of the composition.
Suitable floc prevention agents include nonionic surfactants. Suitable non-ionic surfactants include addition products of ethylene oxide and/or propylene oxide with fatty alcohols, fatty acids and fatty amines. The floc prevention agent is preferably selected from addition products of (a) an alkoxide selected from ethylene oxide, propylene oxide and mixtures thereof with (b) a fatty material selected from fatty alcohols, fatty acids and fatty amines.
Suitable surfactants are substantially water soluble surfactants of the general formula:

R-Y-(C₂H₄O)_z-CH₂-CH₂-OH

where R is selected from the group consisting of primary, secondary and branched chain alkyl and/or acyl hydrocarbyl groups (when Y = -C(O)O, R ≠ an acyl hydrocarbyl group); primary, secondary and branched chain alkenyl hydrocarbyl groups; and primary, secondary and branched chain alkenyl-substituted phenolic hydrocarbyl groups; the hydrocarbyl groups having a chain length of from 10 to 60, preferably 10 to 25, e.g. 14 to 20 carbon atoms.
In the general formula for the ethoxylated nonionic surfactant, Y is typically:

-O-, -C(O)O-, -C(O)N(R)- or -C(O)N(R)R-

in which R has the meaning given above or can be hydrogen; and Z is at least about 6, preferably at least about 10 or 11.
Lutensol™ AT25 (BASF) based on coco chain and 25 EO groups is an example of a suitable nonoionic surfactant. Other suitable surfactants include Renex 36 (Trideceth-6), ex Uniqema; Tergitol 15-S3, ex Dow Chemical Co.; Dihydrol LT7, ex Thai Ethoxylate Itd; Cremophor CO40, ex BASF and Neodol 91-8, ex Shell.

Polymeric Thickening Agent

Thickening polymers may be added to the compositions of the invention for further thickening. Any suitable thickener polymer may be used.
Suitable polymers are water soluble or dispersable. A high M.Wt, (for example, in the region of about 100,000 to 5,000,000) which can be achieved by crosslinking, is advantageous. Preferably, the polymer is cationic.
Polymers particularly useful in the compositions of the invention include those described in WO2010/078959 (SNF S.A.S.). These are crosslinked water swellable cationic copolymers having at least one cationic monomer and optionally other non-ionic and/or anionic monomers. Preferred polymers of this type are copolymers of acrylamide and trimethylaminoethylacrylate chloride.
Preferred polymers comprise less than 25 % of water soluble polymers by weight of the total polymer, preferably less than 20 %, and most preferably less than 15%, and a cross-linking agent concentration of from 500 ppm to 5000 ppm relative to the polymer, preferably from 750 ppm to 5000 ppm, more preferably from 1000 to 4500 ppm (as determined by a suitable metering method such as that described on page 8 of patent EP 343840 ). The cross-linking agent concentration must be higher than about 500 ppm relative to the polymer, and preferably higher than about 750 ppm when the crosslinking agent used is the methylene bisacrylamide, or other cross-linking agents at concentrations that lead to equivalent cross-linking levels of from 10 to 10,000 ppm.
Suitable cationic monomers are selected from the group consisting of the following monomers and derivatives and their quaternary or acid salts: dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide, diallylamine, methyldiallylamine, dialkylaminoalkyl-acrylates and methacrylates, dialkylaminoalkyl-acrylamides or -methacrylamides.
Following is a non-restrictive list of monomers performing a non-ionic function: acrylamide, methacrylamide, N-Alkyl acrylamide, N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl acetamide, vinylacetate, vinyl alcohol, acrylate esters, allyl alcohol.
Following is a non-restrictive list of monomers performing an anionic function: acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, as well as monomers performing a sulfonic acid or phosphonic acid functions, such as 2-acrylamido-2-methyl propane sulfonic acid (ATBS) etc.
The monomers may also contain hydrophobic groups.
Following is a non-restrictive list of cross-linking agents: methylene bisacrylamide (MBA), ethylene glycol diacrylate, polyethylene glycol dimethacrylate, diacrylamide, triallylamine, cyanomethylacrylate, vinyl oxyethylacrylate or methacrylate and formaldehyde, glyoxal, compounds of the glycidyl ether type such as ethyleneglycol diglycidyl ether, or the epoxydes or any other means familiar to the expert permitting cross-linking.
By way of preeminent preference the cross-linking rate preferably ranges from 800 to 5000 ppm (on the basis of methylene bisacrylamide) relative to the polymer or equivalent cross-linking with a cross-linking agent of different efficiency.
As described in US 2002/0132749 and Research Disclosure 429116, the degree of non-linearity can additionally be controlled by the inclusion of chain transfer agents (such as isopropyl alcohol, sodium hypophosphite, mercaptoethanol) in the polymerisation mixture in order to control the polymeric chain's length and the cross-linking density.
The amount of polymer used in the compositions of the invention is suitably from 0.001 to 0.5 wt %, preferably from 0.005 to 0.4 wt %, more preferably from 0.05 to 0.35 wt % and most preferably from 0.1 to 0.25 wt %, by weight of the total composition.
An example of a preferred polymer is Flosoft 270LS ex SNF.

Non-ionic Softener

The compositions of the invention may contain a non-cationic softening material, which is preferably an oil and more preferably an oily sugar derivative.
"Oils" as used in this specification are distinguished from perfume materials in that perfume materials are listed as odiferous materials in Arctander's "Perfume and Flavor Materials of Natural Origin" (ISBN-10: 0-931710-36-7), or listed as odiferous materials in various databases including Flavourbase 2010, ESO 2000 (2006 update) and PMP 2001. Perfume materials are generally present as part of a complex mixture of components where each odiferous component is present at a level of below 0.5%wt of the composition as a whole. Oils present for other purposes are present at levels above 0.5%wt of the composition as a whole.
An oily sugar derivative is a liquid or soft solid derivative of a cyclic polyol (CPE) or of a reduced saccharide (RSE), said derivative resulting from 35 to 100% of the hydroxyl groups in said polyol or in said saccharide being esterified or etherified. The derivative has two or more ester or ether groups independently attached to a C₈-C₂₂ alkyl or alkenyl chain.
Advantageously, the CPE or RSE does not have any substantial crystalline character at 20°C. Instead it is preferably in a liquid or soft solid state as herein defined at 20°C.
The liquid or soft solid (as hereinafter defined) CPEs or RSEs suitable for use in the present invention result from 35 to 100% of the hydroxyl groups of the starting cyclic polyol or reduced saccharide being esterified or etherified with groups such that the CPEs or RSEs are in the required liquid or soft solid state. These groups typically contain unsaturation, branching or mixed chain lengths.
Typically the CPEs or RSEs have 3 or more ester or ether groups or mixtures thereof, for example 3 to 8, especially 3 to 5. It is preferred if two or more of the ester or ether groups of the CPE or RSE are independently of one another attached to a C₈ to C₂₂ alkyl or alkenyl chain. The C₈ to C₂₂ alkyl or alkenyl groups may be branched or linear carbon chains.
Preferably 35 to 85% of the hydroxyl groups, most preferably 40-80%, even more preferably 45-75%, such as 45-70% are esterified or etherified.
Preferably the CPE or RSE contains at least 35% tri or higher esters, e.g. at least 40%.
The CPE or RSE has at least one of the chains independently attached to the ester or ether groups having at least one unsaturated bond. This provides a cost effective way of making the CPE or RSE a liquid or a soft solid. It is preferred if predominantly unsaturated fatty chains, derived from, for example, rape oil, cotton seed oil, soybean oil, oleic, tallow, palmitoleic, linoleic, erucic or other sources of unsaturated vegetable fatty acids, are attached to the ester/ether groups.
These chains are referred to below as the ester or ether chains (of the CPE or RSE).
The ester or ether chains of the CPE or RSE are preferably predominantly unsaturated. Preferred CPEs or RSEs include sucrose tetratallowate, sucrose tetrarapeate, sucrose tetraoleate, sucrose tetraesters of soybean oil or cotton seed oil, cellobiose tetraoleate, sucrose trioleate, sucrose triapeate, sucrose pentaoleate, sucrose pentarapeate, sucrose hexaoleate, sucrose hexarapeate, sucrose triesters, pentaesters and hexaesters of soybean oil or cotton seed oil, glucose tiroleate, glucose tetraoleate, xylose trioleate, or sucrose tetra-,tri-, penta-or hexa- esters with any mixture of predominantly unsaturated fatty acid chains.
The most preferred CPEs or RSEs are those with monosaturated fatty acid chains, i.e. where any polyunsaturation has been removed by partial hydrogenation. However some CPEs or RSEs based on polyunsaturated fatty acid chains, e.g. sucrose tetralinoleate, may be used provided most of the polyunsaturation has been removed by partial hydrogenation.
The most highly preferred liquid CPEs or RSEs are any of the above but where the polyunsaturation has been removed through partial hydrogenation. Preferably 40% or more of the fatty acid chains contain an unsaturated bond, more preferably 50% or more, most preferably 60% or more. In most cases 65% to 100%, e.g. 65% to 95% contain an unsaturated bond.
CPEs are preferred for use with the present invention. Inositol is a preferred example of a cyclic polyol. Inositol derivatives are especially preferred.
In the context of the present invention, the term cyclic polyol encompasses all forms of saccharides. Indeed saccharides are especially preferred for use with this invention. Examples of preferred saccharides for the CPEs or RSEs to be derived from are monosaccharides and disaccharides.
Examples of monosaccharides include xylose, arabinose, galactose, fructose, sorbose and glucose. Glucose is especially preferred. Examples of disaccharides include maltose, lactose, cellobiose and sucrose. Sucrose is especially preferred. An example of a reduced saccharide is sorbitan.
The liquid or soft solid CPEs can be prepared by methods well known to those skilled in the art. These include acylation of the cyclic polyol or reduced saccharide with an acid chloride; trans-esterification of the cyclic polyol or reduced saccharide fatty acid esters using a variety of catalysts; acylation of the cyclic polyol or reduced saccharide with an acid anhydride and acylation of the cyclic polyol or reduced saccharide with a fatty acid. See for instance US 4 386 213 and AU 14416/88 (both P&G).
It is preferred if the CPE or RSE has 3 or more, preferably 4 or more ester or ether groups. If the CPE is a disaccharide it is preferred if the disaccharide has 3 or more ester or ether groups. Particularly preferred CPEs are esters with a degree of esterification of 3 to 5, for example, sucrose tri, tetra and penta esters.
Where the cyclic polyol is a reducing sugar it is advantageous if each ring of the CPE has one ether or ester group, preferably at the C₁ position. Suitable examples of such compounds include methyl glucose derivatives.
Examples of suitable CPEs include esters of alkyl(poly)glucosides, in particular alkyl glucoside esters having a degree of polymerisation from 1 to 2.
The length of the unsaturated (and saturated if present) chains in the CPE or RSE is C₈-C₂₂, preferably C₁₂-C₂₂. It is possible to include one or more chains of C₁-C₈, however these are less preferred.
The liquid or soft solid CPEs or RSEs which are suitable for use in the present invention are characterised as materials having a solid: liquid ratio of between 50:50 and 0:100 at 20°C as determined by T₂ relaxation time NMR, preferably between 43:57 and 0:100, most preferably between 40:60 and 0:100, such as, 20:80 and 0:100. The T₂ NMR relaxation time is commonly used for characterising solid:liquid ratios in soft solid products such as fats and margarines. For the purpose of the present invention, any component of the signal with a T₂ of less than 100 µs is considered to be a solid component and any component with T₂ ≥ 100 µs is considered to be a liquid component.
For the CPEs and RSEs, the prefixes (e.g. tetra and penta) only indicate the average degrees of esterification. The compounds exist as a mixture of materials ranging from the monoester to the fully esterified ester. It is the average degree of esterification which is used herein to define the CPEs and RSEs.
The HLB of the CPE or RSE is typically between 1 and 3.
Where present, the CPE or RSE is preferably present in the composition in an amount of 0.5-50% by weight, based upon the total weight of the composition, more preferably 1-30% by weight, such as 2-25%, e.g. 2-20%.
The CPEs and RSEs for use in the compositions of the invention include sucrose tetraoleate, sucrose pentaerucate, sucrose tetraerucate and sucrose pentaoleate.

Shading Dyes

Optional shading dyes can be used. Preferred dyes appear violet or blue. Suitable and preferred classes of dyes are discussed below. The unsaturated quaternary ammonium compounds are subject to some degree of UV light and/or transition metal ion catalysed radical auto-oxidation, with an attendant risk of yellowing of fabric. The present of shading dye also reduces the risk of yellowing from this source.
Different shading dyes give different levels of colouring. The level of shading dye present in the compositions of the present invention depends, therefore, on the type of shading dye. Preferred overall ranges, suitable for the present invention are from 0.00001 to 0.1 wt %, more preferably 0.0001 to 0.01 wt %, most preferably 0.0005 to 0.005 wt % by weight of the total composition.
Direct Dyes: Direct dyes (otherwise known as substantive dyes) are the class of water soluble dyes which have a affinity for fibres and are taken up directly. Direct violet and direct blue dyes are preferred.
Preferably the dye are bis-azo or tris-azo dyes are used.
Most preferably, the direct dye is a direct violet of the following structures:
or
wherein:

ring D and E may be independently naphthyl or phenyl as shown;
R₁ is selected from: hydrogen and C1-C4-alkyl, preferably hydrogen;
R₂ is selected from: hydrogen, C1-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;
R₅ and R₄ are independently selected from: hydrogen and C1-C4-alkyl, preferably hydrogen or methyl;
X and Y are independently selected from: hydrogen, C1-C4-alkyl and C1-C4-alkoxy; preferably the dye has X= methyl; and, Y = methoxy and n is 0, 1 or 2, preferably 1 or 2.

Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99. Bis-azo copper containing dyes such as direct violet 66 may be used. The benzidene based dyes are less preferred.
Preferably the direct dye is present at 0.00001 wt% to 0.0010 wt% of the formulation.
In another embodiment the direct dye may be covalently linked to the photo-bleach, for example as described in WO2006/024612 .
Acid Dyes: Cotton substantive acid dyes give benefits to cotton containing garments. Preferred dyes and mixes of dyes are blue or violet. Preferred acid dyes are:

(i) azine dyes, wherein the dye is of the following core structure:
- wherein R_a, R_b, R_c and R_d are selected from: H, an branched or linear C1 to C7-alkyl chain, benzyl a phenyl, and a naphthyl;
- the dye is substituted with at least one SO₃ ^- or -COO^- group;
- the B ring does not carry a negatively charged group or salt thereof;
- and the A ring may further substituted to form a naphthyl;
- the dye is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, Cl, Br, I, F, and NO₂.

Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98.
Other preferred non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29.
Preferably the acid dye is present at 0.0005 wt% to 0.01 wt% of the formulation.
Hydrophobic Dyes: The composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores. Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
Preferably, where present, the hydrophobic dye is present at 0.0001 wt% to 0.005 wt% of the formulation.
Basic Dyes: Basic dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International.
Preferred examples include triarylmethane basic dyes, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141.
Reactive Dyes: Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton.
Preferably the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this species. Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International.
Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96.
Dye Conjugates: Dye conjugates are formed by binding direct, acid or basic dyes to polymers or particles via physical forces.
Dependent on the choice of polymer or particle they deposit on cotton or synthetics. A description is given in WO2006/055787 .
Particularly preferred dyes are: direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, direct violet 99, acid blue 98, acid violet 50, acid blue 59, acid violet 17, acid black 1, acid blue 29, solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63, disperse violet 77 and mixtures thereof.

Co-Softeners And Fatty Complexing Agents

Co-softeners may be used. Suitable co-softeners include fatty acids. When employed, they are typically present at from 0.1 to 20% and particularly at from 0.5 to 10%, based on the total weight of the composition. Preferred co-softeners include fatty esters, and fatty N-oxides. Fatty esters that may be employed include fatty monoesters, such as glycerol monostearate, fatty sugar esters, such as those disclosed WO 01/46361 (Unilever).
Preferred fatty acids include hardened tallow fatty acid (available under the tradename Pristerene™, ex Uniqema). Preferred fatty alcohols include hardened tallow alcohol (available under the tradenames Stenol™ and Hydrenol™, ex Cognis and Laurex™ CS, ex Albright and Wilson).
The compositions for use in the present invention may comprise a fatty complexing agent.
Especially suitable fatty complexing agents include fatty alcohols.
Fatty complexing material may be used to improve the viscosity profile of the composition.
The fatty complexing agent is preferably present in an amount greater than 0.3 to 5% by weight based on the total weight of the composition. More preferably, the fatty component is present in an amount of from 0.4 to 4%. The weight ratio of the mono-ester component of the quaternary ammonium fabric softening material to the fatty complexing agent is preferably from 5:1 to 1:5, more preferably 4:1 to 1:4, most preferably 3:1 to 1:3, e.g. 2:1 to 1:2.
The compositions of the invention may contain one or more other ingredients. Such ingredients include further preservatives (e.g. further bactericides and fungicides), pH buffering agents, hydrotropes, anti-redeposition agents, soil-release agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, antioxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids pearlisers and/or opacifiers, natural oils/extracts, processing aids, e.g. electrolytes, and skin benefit agents.
A particularly preferred optional ingredient is a suitable polyoxyalkylene material at a level effective to give a rinse aid benefit. A suitable material is polypropylene glycol at 0.15-5.0%wt.
A preferred method of preparation for a dilute is as follows:-

1. Heat water to about 40 to 50°C.
2. Add the non-ionic floc prevention agent to the water.
3. Add the polymer to the water with stirring and mix thoroughly.
4. Add any minor ingredients, such as the antimicrobial, antifoams, acid, sequestrants and preservatives.
5. Melt the softening active and any co-active together to form a co-melt.
6. Add the co-melt to the heated water phase.
7. Add dyes and perfumes.
8. Cool.

Product Form

The compositions of the present invention are aqueous fabric conditioning compositions suitable for use in a laundry process.
The compositions of the invention may also contain pH modifiers such as hydrochloric acid or lactic acid. The liquid compositions preferably have a pH of about 2.5 to 3.0.
The composition is preferably for use in the rinse cycle of a home textile laundering operation, where, it may be added directly in an undiluted state to a washing machine, e.g. through a dispenser drawer or, for a top-loading washing machine, directly into the drum. The compositions may also be used in a domestic hand-washing laundry operation.
In order that the invention may be further understood and carried forth into practice, embodiments of the invention will now be illustrated by the following nonlimiting examples. Further modifications will be apparent to the person skilled in the art.

Examples

Examples of the invention are represented by a number following the point. Comparative examples are represented in the same manner by a letter. Unless otherwise stated, amounts of components are expressed as a percentage of the total weight of the composition. All experiments were performed in a 200 litre mixer.
Tinosan™ HP 100 is a 30% solution of Diclosan (4,4'-Dichloro-2-hydroxy diphenyl ether) in a solvent (polypropylene glycol). It was used at various effective levels from 0.1-0.025% In these examples this is compared with Benzalkonium chloride (BKC - Barquat MB50), which was used at an effective level of 0.4%.

Example 1: Comparison of TEA base with 2HT base:

Work was done in two bases:

1) 2HT-base:

Component	% as 100%	Active %
Active (Arquad™ 2HT 7SE)¹	9.55	75
Fatty Acid (Pristerine 4916)	0.95	100
Nonionic (Lutensol AT25)	1.0	100
Sequestrant	-	-
Preservative (Proxel GXL)	0.008	20
Antifoam (Silfoam SE47M)	0.12	10
pH modifier (Citric Acid)	0.18	100
Salt (Calcium Chloride)	0.04	10
Polymer	-	-
Pearlescer (Iriodin 111)	0.05	100
Antimicrobial	0.4	50
Minors: Dye, Perfume (free oil and encapsulate)	minor
Water (demineralised)	To 100%

¹Arquad is a di(hydrogenated tallow)dimethylammonium chloride based cationic fabric softening active.

This base was processed by mixing water, preservative, peralescer citric acid and antimicrobial in a mixer at 28 rpm, 55 Celsius for 12 minutes before starting recirculation and milling. Agitator speed was then increased to 38 rpm and a premix of the active and the fatty acid were added together with the salt with mixing for 10 min. Dyes were added over 10 min with further stirring and milling. The mill was then stopped and the mixture cooled with recirculation to 45 Celsius, perfume was added and further recirculation and cooling was continued until the temperature reached 41 Celsius, at which point the antifoam was added.

2) TEA-base:

Component	% as 100%	Active %
Active (TEP 88L)¹	12	88
Fatty Acid	-	-
Nonionic (Lutensol AT25)	0.75	1.08
Sequestrant (Dequest 2010)	0.005	0.4
Preservative (Proxel GXL™)	0.008	20
Antifoam (Silfofoam SRE CN)	0.12	20
Ph modifier (Hydrochloric Acid 22%)	0.0125	22
Salt (Calcium Chloride)	0.0025	10
Polymer (Flowsoft 270LS)	0.175	56
Pearlescer (Iriodin 111)	0.05	100
Antimicrobial	0.05	30
Minors: Perfume (free oil and encapsulate)	minor
Water (demineralised)	To 100%

¹TEP 88L is a palm based soft TEA quaternary fabric softening active (ester linked), available from FXG (Feixiang Chemicals (Zhangjiagang) Co., Ltd., China.

This base was processed by mixing water and the polymer in a mixer at 74 rpm, 50 Celsius for 12 minutes before slowing to 65 rpm. Preservative, sequestrant, acid and antimicrobial are then added with further mixing over 2 minutes. A premix of the active and non-ionic are added over 7 minutes. Salt and pearlescer are added with a further 6 minutes mixing. Perfume added (encapsulates first) and the mix is cooled to 35 Celcius with recirculation before adding free perfume oil and antifoam mixing for a further 5 minutes after the target temperature is reached.

Storage:

Example	Active	Antimicrobial	Stability
1.A	2HT	BKC	Excellent
1.B	2HT	Diclosan	Poor - less than 1 month
1.C	TEA	BKC	Poor - less than 1 month
1.1	TEA	Diclosan	Excellent

Example 1.B formed rust-coloured precipitates within 3 weeks using all processes and concentrations.
When 1.1 was used in combination with the other antibacterial agents than that of the present invention precipitates again formed. With the following materials it was not possible to make a product which was stable for more than a month

Akacid Plus: Poly(oxyalkyleneguanidine) hydrochloride +Poly(hexa-methyleneguanidine) hydrochloride,
Tego 2000VT25: Dodecyl-di(aminoethyl)glycine,
Merquat 100: Dimethyl di-allyl ammonium chloride homopolymer, or
Lonzabac 12: N,N'-Bis(3-aminopropyl)dodecylamine).

Example 2: Storage Stability:

Dose response of wt% Diclosan in the TEA base as described in Example #1 for viscosity at 84 days storage gave the results presented in the table below at the temperature as indicated. Viscosity (mPas) was measured at 106 sec^-1. It will be seen that except under the most harsh conditions the product viscosity remained within the preferred range of 55-200 mPas and the trend is towards the viscosity stability being better as more of the Diclosan is included.

Example Diclosan 5 Celsius 28 Celsius 40 Celsius

2.A 0 (control) 84 94 193

2.1 0.1% 76 90 169

2.2 0.05% 80 94 186

2.3 0.025% 82 97 200
These are acceptable viscosity changes on storage. Changing the nature of the perfume showed some differences at higher temperatures, but the viscosity was still acceptable.

Examples 3 and 4: Antimicrobial Benefits:

Antimicrobial effects were determined in the TEA base of example #1 using the EN1276 suspension method (with a 5 minute contact time at 20 Celsius) and by the AATCC TM100 surface method. The first of these tests (which is the standard EU test method) looks at hygiene in wash, while the second looks at hygiene in wear. Results are shown in the tables below:
EN1276: Log reduction in bacteria (cfu)

Example	Diclosan	E. hirae	P. aeruginosa	E. coli	S. aureus
3.A	0 (control)	5	0	0.5	4
3.1	0.025%	5	0.5	0.75	5
3.2	0.05%	5	0.5	1.25	5
3.3	0.1%	5	0.5	2.25	5

TM100: Bacterial Number (log cfu) (S. aureus)

Example	Diclosan	T=0 on cotton	24 hours on cotton	T=0 on polycotton	24 hours on polycotton
4.A	0 (control)	6.15	7.79	6.35	6.67
4.1	0.025%	6.15	3.51	6.35	6.49
4.2	0.05%	6.15	3.36	6.35	6.47
4.3	0.1%	6.15	2.08	6.35	3.59

Example 5: Synergistic interaction with active.

Treated textile (∼10g) was quantitatively extracted by repeated reflux and concentration into ethanol (Soxhlet extraction). Following fifteen extraction cycles the volume of ethanol was reduced to 5 to 10 mls, allowed to cool and accurately weighed.
An aliquot was taken and made alkaline by adding an equal volume of aqueous NaOH (0.01 M); following this step the mixture was centrifuged to remove any solids and an aliquot of supernatant was taken for high performance liquid chromatography (HPLC). An Agilent 1100 HPLC fitted with guard and Hypersil ODS (C18) separation column was used with an eluent comprising 70parts Acetonitrile to 30 parts of an aqueous 0.033M H₃PO₄ / 0.0825M Na₂HPO₄ buffer.
One microlitre of the alkaline extract was injected and eluted at 1.5ml/min through the column incubated at 40°C and with UV-vis diode array detection. Diclosan was found to have a retention time of approximately 4.2 minutes, was quantifiable at 280nm or 210nm by reference to a previously determined calibration and was clearly separated from other compounds extracted from the textile.
The TEA base 2 with and without 0.05wt% Diclosan was prepared as given in the table below.

TEA-base2:

Component	% as 100%	Active %
Active (Tetranyl L1/90N)	12	90
Sequestrant (Dequest 2010)	0.005	40
Preservative (Proxel GXL™)	0.008	20
Antifoam (BC2600 ex. Basildon Chemicals))	0.01	20
pH modifier (Hydrochloric Acid 22%)	0.0117	22
Salt (Calcium Chloride)	0.025	10
Antimicrobial (Diclosan - [Tinosan HP100])	0.05	30
Minors: Perfume (free oil and encapsulate)	minor
Water (demineralised)	To 100%

TEA base 2 was used in the final rinse at 35g dose using European wash conditions i.e. a Zanusi FLA machine on 40°C, cotton cycle, with a wash load comprising 1.5Kg knitted cotton and 1.5Kg polyester in which the main was was conducted using an 85gm dose of Persil non bio washing powder in 26°FH water. Following line-drying the knitted cotton from these washes was tested using the AATCC TM100 surface method.
Diclosan treated fabrics were also prepared by evenly wetting the fabric with diclosan solutions (in 90:10 water: ethanol) and then evaporating to dryness. The levels of Diclosan retained on fabric were extracted and quantified as described previously. These Diclosan treated fabrics were tested using the AATCC TM100 surface method. This method provides a dose response indication of the level of Diclosan needed to achieve a reduction in bacterial growth.
The results from the AATCC TM100 testing and the levels of Diclosan recovered are presented in the following table. Examples 5.B-5.G below provide data for the dried-down solutions, and examples 5.A and 5.1 provide data for the fully formulated products.

TM100: bacterial Number (Log cfu; S. aureus)

Ex.	Diclosan in product	Diclosan dep mg/Kg (cotton)	Diclosan rec mg/Kg cotton	T=0 on cotton	24 hrs on cotton
5.A	0 (control)	-	0	5.4	3.6
5.1	0.05%	-	2.5	5.4	1.0
5.B	-	0 (control)	0	4.6	5.5
5.C	-	2	1.7	4.6	5.6
5.D	-	6	5.6	4.6	4.9
5.E	-	12**	7.6	4.6	1.0
5.F	-	8	7.8	4.0*	1.0
5.G	-	12	12	4.0	1.0

**Suspected error after extraction hence repeat below
*All T=zero should be same but kill becomes easier when challenged with fewer CFU's

Extraction of the knitted cotton fabric treated with the TEA base 2 containing 0.05wt% Diclosan reveals that Diclosan deposition is 2.5 mg/Kg cotton (std dev=0.8), and a better than 4 log reduction (bacterial number) was obtained (example 5.1). This observation is consistent with a synergistic contribution to kill from the base since from the direct dose/response examples 5.B to 5.G deposition of Diclosan alone to levels higher than 6mg/kg (examples 5.E-5.G) was needed for a 4 log reduction in S aureus.

Claims

An aqueous fabric conditioner composition comprising:
(a) from 0.5 to 35%, by weight of the total composition, of a fabric softening active, wherein the fabric softening active comprises an ester-linked triethanolamine quaternary ammonium compound, and,

(b) from 0.002% to 0.4%, by weight of the total composition, of a non-ionic antimicrobial active, which is not a perfume component, and,

(c) from 0.01 to 10%, by weight of the total composition, of a perfume.
A composition as claimed in claim 1 wherein at least part of the perfume is encapsulated in particles.
A composition as claimed in claim 2 wherein the encapsulated perfume particles comprise a water-insoluble polymer shell.
A composition according to claim 3 wherein the water-insoluble polymer shell comprises the reaction product of:
(a) an amine selected from urea and melamine, or mixtures thereof, and,

(b) an aldehyde selected from formaldehyde, acetaldehyde, glutaraldehyde or mixtures thereof.
A composition as claimed in any preceding claim wherein the non-ionic antimicrobial comprises a halogenated phenyl ether.
A composition according to any preceding claim wherein the halogenated non-ionic antimicrobial comprises 4-4' dichloro-2-hydroxy diphenyl ether.
A composition according to any preceding claim which further comprises from 0.01 to 0.5 wt %, preferably from 0.05 to 0.25 wt %.by weight of the total composition, of a floc prevention agent, which is a non-ionic alkoxylated material having an HLB value of from 8 to 18.
A composition as claimed in any preceding claim, which further comprises a polymeric thickening agent in an amount of below 0.4 wt %, by weight of the total composition.
A composition as claimed in any preceding claim, which comprises at least one perfume component which is antimicrobial and/or an insect repellent.
A composition as claimed in any preceding claim, which further comprises a shading dye.
A method of preparing a rinse water, which comprises adding to water a composition as defined in any one of claims 1 to 8.
Use of a rinse water prepared according to the method of claim 10, to treat a fabric such that microbial growth on the fabric is inhibited.