US20200199801A1

US20200199801A1 - Laundry liquid dispensing system

Info

Publication number: US20200199801A1
Application number: US16/620,062
Authority: US
Inventors: Mark Albert Assies; Hugo Copini; Eric Smeding; Michael Wittenberg; Marije van Zwet
Original assignee: Conopco Inc
Current assignee: Conopco Inc
Priority date: 2017-06-09
Filing date: 2018-05-30
Publication date: 2020-06-25
Also published as: WO2018224379A1; ZA201908009B; CN110998014A; EP3635166A1; BR112019026011A2

Abstract

A laundry liquid dispensing system comprising (a) a container containing a laundry liquid, said container having an elongate cross section adapted for letterbox delivery wherein the container width is at least twice the container depth and the container depth is less than 5 cm; (b) a dispensing device configured to house the container in a dispensing orientation; (c) a metered dosing device for dispensing, a dose of the laundry liquid from the container via a self-closing aperture, wherein the laundry liquid has a viscosity in the range 200-1500 cps @ 21 s−1.

Description

The present invention relates to a laundry liquid dispensing system.
Laundry liquids are commonly provided in bottles from which the liquid may be poured either directly into a washing receptacle such as a washing machine drum or via an intermediate dispensing device such as a washing machine draw, or a dosing shuttle. Concentrated Laundry liquids offer potential benefits in both financial and environmental terms, however such potential benefits may only be realized fully if the consumer doses differently (less) than when dosing more diluted liquids. However, with concentrated liquids, it can be difficult for some consumers to judge the dose visually. Even with tap dispensers and large viewing windows to view fill levels, it can still be difficult especially when doses become smaller (as with concentrated liquids) because the change in the liquid level is so small. Also, if the liquid is viscous it may adhere to any viewing windows to make accurate readings difficult. For smaller laundry loads, the problem is exacerbated as the dosing volumes may be very small. On top of this, some consumers do not have the time or the inclination to measure doses with sufficient accuracy, and end up using much more of the concentrated liquid than is necessary or indeed optimal from a performance standpoint let alone environmental/financial.
At the same time, many time-pressed consumers prefer to buy certain laundry products via the internet for home delivery. If the outer delivery packaging is too large, this may require the consumer to be present at home to receive the package which may defeat the purpose if the reason the consumer is too busy is because they are at work or they travel etc. For more frequent purchases, this may be highly impractical. Letterbox delivery can be effected with the consumer away from home but this imposes certain restraints on the laundry dosing system and components.
One problem with laundry liquids with are posted/delivered to the consumer is that the package does not stand on a shop shelf prior to purchase and use, but is instead in transit, moving. This can give rise to increase stresses and leakage. Whilst outer packaging can provide some protection, very vulnerable items can be damaged as when they drop and hit the floor following letterbox delivery.
The objective of the invention to provide a laundry liquid dispensing system whereby accurate dosing can be achieved without consumer dose measurement and reduced reliance on in-store purchasing which can be at least in part replaced by internet purchases and home delivery
The invention provides a laundry liquid dispensing system comprising:
(a) a container containing a laundry liquid, said container having an elongate cross section adapted for letterbox delivery wherein the container width is at least twice the container depth and the container depth is less than 5 cm;
(b) a dispensing device configured to house the container in a dispensing orientation;
(c) a dosing device for dispensing, on actuation by the consumer, a unit dose of the laundry liquid from the container via a self-closing dispensing aperture;
wherein the laundry liquid has a viscosity in the range 200-1500 cps.
Preferably the dosing device is a metered dosing device.
With a dispensing system of the invention, the laundry containers may be shipped direct to the consumer for letterbox delivery which does not require the consumer to be present to receive the package. The specific range of viscosity of the liquid balances the needs of shock absorption and dispensing. On the one hand a higher viscosity provides constrained internal motion within the liquid and so the liquid can absorb better the energy/forces experienced e.g. during transit, and when the package falls from the letterbox to the floor/collection basket etc. This reduces the possibility of leakage. At the same time the viscosity must allow for fast and accurate dispensing from a shallow container via a metered dosing device. The invention thus can provide an effective and appealing direct-to-consumer laundry liquid dispensing system for the time pressed consumer.
With a elongate cross section, the container may be stackable in a cupboard which can afford space saving benefits.
Preferably the dispensing system incorporates a removable dosing device (shuttle), for dosing which may be located below the dispensing aperture. The laundry liquid may be dispensed into the dosing device and this is then placed directly into the washing drum.
The dispensing system may include a dosing device locator, which constrains the position of the dosing device directly below the dispensing aperture so avoiding spillages. The locator may comprise a recess in the base of the dispensing device.
Preferably the container has a closed base at one end and at an opposing end, a dispensing part, and the dispensing orientation of the container is such that the dispensing part is downward and the closed base upward, often called an ‘upside down’ container or a ‘tote’.
Preferably the dispensing device comprises a membrane comprising a self-closing dispensing aperture and this membrane is operative to close the dispensing aperture after dispensing. Preferably the membrane comprises silicone. This reduces the possibility of leakage after dispensing.
Preferably the dispensing device comprises a housing comprising a container support for supporting the container in the dispensing orientation and which is movable relative to the housing to effect dispensing of the laundry liquid.
Preferably, the dispensing device comprises a squeeze mechanism which squeezes the container to effect dispensing of the laundry liquid via the metered dosing device.
Preferably the squeeze device is connected to the container support such that downward movement of the container support actuates the squeeze mechanism and so in turn effects dispensing. The container support may be manually moved by simply pressing down on the container or container support. Preferably the squeeze mechanism is resilient such that once the container support has moved down, it returns to the its original position. The dispensing of the liquid may take place on the downward stroke or on the return stroke or it may span both.
Either the container or the device may comprise the metered dosing device. The metered dosing device may be removable after use, such that further purchases may re-use a single device, being purchase with a simply cap. A suitable metered dosing device is the Smart Dosing device by Weena Plastics Group (Netherlands).
Suitable metered dosing devices are disclosed in WO16105189 A3, where a liquid dosing device for a container comprises a dosing chamber having a front end and a back end.
An outlet passage is located at the front end. A plunger is located in the dosing chamber, divides it in a front and a back space, and is moveable between a forward position in which the plunger closes off the outlet passage, and a backward position, in which the front space has a maximal volume. An inlet passage provides fluid communication between the front space and the container. A timer passage provides fluid communication between the container and the back space. A release passage, being greater than the timer passage, provides fluid communication between the back space and the container.
A valve assembly at the release passage comprises a valve seat located at the back end of the dosing chamber and a membrane on a side of the valve seat facing away from the back space. The membrane is made of an elastic foil having a uniform thickness. It has a stationary portion that is fixed and at least one moveable flap which is connected to the stationary portion by a hinge portion. The flap is moved away from the valve seat in the open state and bears against the valve seat in the closed state of the valve assembly.
The hinge portion is elastically flexed when the flap is moved away from the valve seat and is in a rest state when the flap bears against the seat.
Any suitable metered dosing device with a self-sealing dispensing aperture may be used. The dispensing device may comprise multiple sections which are provided flat-packed for letterbox delivery to the consumer. The consumer may then assemble the device from said multiple sections. Thus the invention may comprise a kit for assembling the laundry dispensing system. Alternatively the dispensing device may be provided and delivered without the need for any assembly (other than to insert a container).
Preferably the device is manually operated, requiring no power.
Preferably the container has a stepped profile. This provides a force transfer surface for transmitting the downward push force on the container (as the user pushes down on the base) to the container support which then activates the squeeze mechanism.
The container may have all or part of its walls thickened to provide some resistance to the squeezing action of the squeeze mechanism. This allows smaller doses to be achieved per squeeze. Having only those portions thickened which are in the vicinity of the squeezing mechanism enables the remaining part of the bottle to be lightweight.
The container preferably has a primary wall and an opposing rear wall, said walls connected along their two respective sides by respective side walls. Preferably these are flattened but each wall interconnects with its adjacent walls via smooth outer profiles. Preferably the squeeze mechanism engages the primary and rear faces. Advantageously the container support provides a recess which is shaped to ensure the container's primary and rear walls (ie those with larger more flexible areas) are aligned to engage the squeeze mechanism. This is necessary due to the lack of radial symmetry. The width of the primary and rear walls is preferably at least three, more preferably four times the width of the side walls. Preferably the width of the primary wall is preferably substantially the same as that of the rear wall. Preferably the sides walls have substantially equal width.
The container cross section may be curved or angular, or a combination of both. For example the container may have an elongate elliptical cross section whereby all surfaces have some curvature. Alternatively, the container may have a basic elongate elliptical cross section but with each face flattened so that the container has visible edge regions where adjacent walls meet.
Preferably the maximum depth of the container is less than 4 cm, more preferably less than 3 cm. The maximum depth may be less than 2 cm.
Preferably the maximum width of the container is less than 30 cm, preferably less than 25 cm, more preferably less than 20 cm. Most preferably the width is less than 15 cm.
Preferably the laundry benefit agent is a volatile benefit agent. This together with the squeeze-operated device means the laundry liquid exits under increased stress and speed which enhances consumer experience by enhancing release of the volatile benefit agent during dispensing.
The viscosity of 200-700 cPs provides for excellent and rapid dynamic mixing during squeezing but without splashing as it enters the dosing device. Preferably the viscosity is measured at room temperature (21 degrees) using a Brookfield Viscometer. Preferably the viscosity is 200-700 cps measured at at shear rate of 21 s−1.
The fluid may be a liquid or a gel. Preferably the gel is pourable.
The volatile benefit agent is an agent which is volatile and which confers a benefit to fabric.
Suitable volatile benefit agents include but are not limited to perfumes, insect repellents, essential oils, sensates such as menthol and aromatherapy actives, preferably perfumes. Mixtures of volatile benefit agents may be used.
The total amount of volatile benefit agent is preferably from 0.01 to 10% by weight, more preferably from 0.05 to 5% by weight, even more preferably from 0.1 to 4.0%, most preferably from 0.15 to 4.0% by weight, based on the total weight of the fluid.

Perfume

The preferred volatile benefit agent is a perfume.
Thus the consumer experience is greatly enhanced by a greater perfume sensation and this then ‘primes’ the consumer for enhanced enjoyment of the particular perfume during later activities e.g. during hand washing or after washing and drying when handling the fabrics.
The perfumes of the of the invention also comprise an unconfined (also called non-encapsulated) volatile benefit agent. Where the volatile benefit agent is a perfume, the perfumes described below are suitable for use as the encapsulated volatile benefit agent and also as the unconfined perfume component.
Any suitable perfume or mixture of perfumes may be used.
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 liquid 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 within the encapsulate.
Some or all of the perfume or pro-fragrance may be encapsulated, 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 (ie. 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 (tricycico 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 C log P above 3. As used herein, the term “C log P” means the calculated logarithm to base 10 of the octanol/water partition coefficient (P). The octanol/water partition coefficient of a perfume raw material (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), C log P is also a measure of the hydrophobicity of a material—the higher the C log P value, the more hydrophobic the material. C log P values can be readily calculated from a program called “C LOG P” 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 C log P 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 fluids 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 from the list given of delayed blooming perfumes given above and/or the list of perfume components with a Clog P above 3 present in the perfume.

Insect Repellent

In chemical terms, most repellent actives belong to one of four groups: amides, alcohols, esters or ethers. Those suitable for use in the present invention are liquids or solids with a relatively low melting point and a boiling point above 150° C., preferably liquids. They evaporate slowly at room temperature. Where the volatile benefit agent is an insect repellent, the repellents described below are suitable for use as the encapsulated volatile benefit agent and also as the unconfined repellent component.
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. Preferred insect repellents are related to perfume species.
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×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.
Preferred encapsulated insect repellents are mosquito repellents available from Celessence, Rochester, England. Celessence Repel, containing the active ingredient Saltidin™ and Celessence Repel Natural, containing the active Citrepel™ 75. Saltidin is a man made molecule developed originally by the Bayer Corporation. Citrepel is produced from eucalyptus oils and is high in p-menthane-3,8-diol (PMD). A preferred non-encapsulated repellent is Citriodiol™ supplied by Citrefine.

Aromatherapy Materials and Essential Oils

Another group of volatile benefit agents with which the present invention can be applied are the so-called ‘aromatherapy’ materials. These include components of essential oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian

Viscosity Modifier

The viscosity of the fluid may be achieved intrinsically, arising from the particular ingredients/combinations of the fabric treatment fluid.
The fabric treatment fluid may also comprise a viscosity modifier added to regulate viscosity so that it lies within the range of the invention. The viscosity modifier may comprise any component or combination of components as described hereinbelow which modifies e.g. increases or decreases the viscosity of the composition.
The viscosity modifier may comprise a hydrotrope. The hydrotrope may be a short-chain functionalized amphiphiles. Examples of short-chain amphiphiles include the alkali metal salts of xylenesulfonic acid, cumenesulfonic acid and octyl sulphonic acid, and the like. In addition, organic solvents and monohydric and polyhydric alcohols with a molecular weight of less than about 500, such as, for example, ethanol, isoporopanol, acetone, propylene glycol and glycerol, may also be used as hydrotropes.
The viscosity modifier may comprise one or more salts e.g. CaCl2), MgCl2, NaCl or other salts or combinations thereof containing other alkali or alkaline earth metal cations and halide anions, and the like and any combination thereof.
The viscosity modifier may comprise one or more polysaccharide e.g. GuarGum, Xanthan Gum.
The viscosity modifier may comprise one or more external structurant for example a cellulosic structurant such as micro-fibrous cellulose (MFC) or carboxy methyl cellulos or a clay or CITRUS PULP STUFF or any combination thereof
The viscosity modifier may comprise one or more diluents.
The viscosity modifier may comprise one or more of the below polymers.
The laundry liquid may comprise functional polymers to aid cleaning in a weight-efficient manner which is advantageous for letterbox delivered liquids.

Dye-Transfer Inhibitor Polymers

The polymers may be a so-called ‘dye-transfer inhibitors’ to prevent migration of dyes, especially during long soak times. The dye-transfer inhibition polymer may include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinyl pyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. Nitrogen-containing, dye binding, DTI polymers are preferred. Of these polymers and co-polymers of cyclic amines such as vinyl pyrrolidone (PVP), and/or vinyl imidazole (PVI) are particularly preferred. Polyamine N-oxide polymers suitable for use herein contain units having the following structural formula: R-AX-P; wherein P is a polymerizable unit to which an N—O group can be attached or the N—O group can form part of the polymerizable unit; A is one of the following structures: —NC(O)—, —C(O)O—, —S—, —O—, —N═; x is 0 or 1; and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or combination thereof to which the nitrogen of the N—O group can be attached or the N—O group is part of these groups, or the N—O group can be attached to both units. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
Any polymer backbone can be used provided the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. The polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferably 1,000 to 500,000; most preferably 5,000 to 100,000. This preferred class of materials is referred to herein as “PVNO”. A preferred polyamine N-oxide is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (as a class, referred to as PVPVI) are also preferred. Preferably the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000, as determined by light scattering as described in Barth, et al., Chemical Analysis, Vol. 113. “Modern Methods of Polymer Characterization”. The preferred PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched. Suitable PVPVI polymers include Sokalan™ HP56, available commercially from BASF, Ludwigshafen, Germany.
Also preferred as dye transfer inhibition agents are polyvinylpyrrolidone polymers (PVP) having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 2000,000, and more preferably from about 5,000 to about 50,000. PVP's are disclosed for example in EP-A-262,897 and EP-A-256,696. Suitable PVP polymers include Sokalan™ HP50, available commercially from BASF. Compositions containing PVP can also contain polyethylene glycol (PEG) having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
Also preferred as dye transfer inhibiting agents are those from the class of modified polyethyleneimine polymers, as disclosed for example in WO-A-0005334. These modified polyethyleneimine polymers are water-soluble or dispersible, modified polyamines. Modified polyamines are further disclosed in U.S. Pat. Nos. 4,548,744; 4,597,898; 4,877,896; 4,891,160; 4,976,879; 5,415,807; GB-A-1,537,288; GB-A-1,498,520; DE-A-28 29022; and JP-A-06313271.
The modified ethoxylated polyamines (EPEI) are described above and are generally linear or branched poly (>2) amines. The amines may be primary, secondary or tertiary. A single or a number of amine functions are reacted with one or more alkylene oxide groups to form a polyalkylene oxide side chain. The alkylene oxide can be a homopolymer (for example ethylene oxide) or a random or block copolymer. The terminal group of the alkylene oxide side chain can be further reacted to give an anionic character to the molecule (for example to give carboxylic acid or sulphonic acid functionality).
Preferably the composition according to the present invention comprises a dye transfer inhibition agent selected from polyvinylpyrridine N-oxide (PVNO), polyvinyl pyrrolidone (PVP), polyvinyl imidazole, N-vinylpyrrolidone and N-vinylimidazole copolymers (PVPVI), copolymers thereof, and mixtures thereof.
The amount of dye transfer inhibition agent in the composition according to the present invention will be from 0.01 to 10%, preferably from 0.02 to 8, or even to 5%, more preferably from 0.03 to 6, or even to 2%, by weight of the composition. It will be appreciated that the dye transfer inhibition agents will assist in the preservation of whiteness by preventing the migration of dyes from place to place. This preservation of whiteness assists in cleaning and counteracts the reduction in surfactants present in the wash liquor.

Anti-Redeposition Polymers

The polymer may comprise an anti-redeposition polymer; which may comprise polycarboxylate materials. Polycarboxylate materials, which can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, are preferably admixed in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight of the polymer.
Particularly preferred polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Pat. No. 3,308,067, issued Mar. 7, 1967. In the present invention, the preferred polycarboxylate is sodium polyacrylate.
Acrylic/maleic-based copolymers may also be used as a preferred component of the anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published Dec. 15, 1982, as well as in EP 193,360, published Sep. 3, 1986, which also describes such polymers comprising hydroxypropylacrylate. Still other useful polymers maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
Polyethylene glycol (PEG) can act as a clay soil removal-anti-redeposition agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 3,000 to about 10,000. Polyaspartate and polyglutamate dispersing agents may also be used. Any polymeric soil release agent known to those skilled in the art can optionally be employed in compositions according to the invention. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibres, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibres and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
The amount of anti redeposition polymer in the composition according to the present invention will be from 0.01 to 10%, preferably from 0.02 to 8%, more preferably from 0.03 to 6%, by weight of the composition.

Soil Release Polymers:

The polymer may comprise soil release polymers for polyester comprising polymers of aromatic dicarboxylic acids and alkylene glycols (including polymers containing polyalkylene glycols).
The polymeric soil release agents useful herein especially include those soil release agents having:
(a) one or more nonionic hydrophilic components consisting essentially of:
(i) polyoxyethylene segments with a degree of polymerization of at least 2, or
(ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or
(iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or
(b) one or more hydrophobe components comprising:
(i) C3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate:C3 oxyalkylene terephthalate units is about 2:1 or lower,
(ii) C4-C6 alkylene or oxy C4-C6 alkylene segments, or mixtures therein,
(iii) poly (vinyl ester) segments, preferably polyvinyl acetate), having a degree of polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are present in the form of C1-C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose derivatives are amphiphilic, whereby they have a sufficient level of C1-C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon conventional polyester synthetic fiber surfaces and retain a sufficient level of hydroxyls, once adhered to such conventional synthetic fiber surface, to increase fiber surface hydrophilicity, or a combination of (a) and (b).
Preferably, the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100. Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO3 S(CH2)n OCH2 CH2 O—, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink.
Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C1-C6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Application 0 219 048, published Apr. 22, 1987 by Kud, et al. Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Pat. No. 3,959,230 to Hays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 to Basadur issued Jul. 8, 1975.
Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Examples of this polymer include the commercially available material ZELCON 5126 (from DuPont) and MILEASE T (from ICI). See also U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink.
Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone. These soil release agents are described fully in U.S. Pat. No. 4,968,451, issued Nov. 6, 1990 to J. J. Scheibel and E. P. Gosselink. Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Pat. No. 4,711,730, issued Dec. 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink.
Preferred polymeric soil release agents also include the soil release agents of U.S. Pat. No. 4,877,896, issued Oct. 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
If utilized, soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent composition, typically greater than or equal to 0.2 wt % even from 3 wt % to 9 wt %, but more preferably they are used at greater than 1 wt %, even greater than 2 wt % and most preferably greater than 3 wt %, even more preferably greater than 5 wt %, say 6 to 8 wt % in the composition. Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps. A particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Said soil release agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
Suitable soil release polymers are described in WO 2008095626 (Clariant); WO 2006133867 (Clariant); WO 2006133868 (Clariant); WO 2005097959 (Clariant); WO 9858044 (Clariant); WO 2000004120 (Rhodia Chimie); U.S. Pat. No. 6,242,404 (Rhodia Inc); WO 2001023515 (Rhodia Inc); WO 9941346 (Rhodia Chim); WO 9815346 (Rhodia Inc); WO 9741197 (BASF); EP 728795 (BASF); U.S. Pat. No. 5,008,032 (BASF); WO 2002077063 (BASF); EP 483606 (BASF); EP 442101 (BASF); WO 9820092 (Proctor & Gamble); EP 201124 (Proctor & Gamble); EP 199403 (Proctor & Gamble); DE 2527793 (Proctor & Gamble); WO 9919429 (Proctor & Gamble); WO 9859030 (Proctor & Gamble); U.S. Pat. No. 5,834,412 (Proctor & Gamble); WO 9742285 (Proctor & Gamble); WO 9703162 (Proctor & Gamble); WO 9502030 (Proctor & Gamble); WO 9502028 (Proctor & Gamble); EP 357280 (Proctor & Gamble); U.S. Pat. No. 4,116,885 (Proctor & Gamble); WO 9532232 (Henkel); WO 9532232 (Henkel); WO 9616150 (Henkel); WO 9518207 (Henkel); EP 1099748 (Henkel); FR 2619393 (Colgate Palmolive); DE 3411941 (Colgate Palmolive); DE 3410810 (Colgate Palmolive); WO 2002018474 (RWE-DEA MINERALOEL & CHEM AG; SASOL GERMANY GMBH); EP 743358 (Textil Color AG); PL 148326 (Instytut Ciezkiej Syntezy Organicznej “Blachownia”, Pol.); JP 2001181692 (Lion Corp); JP 11193397 A (Lion Corp); RO 114357 (S.C. “Prod Cresus” S.A., Bacau, Rom.); and U.S. Pat. No. 7,119,056 (Sasol).
Particularly preferred are combinations of relatively high levels of EPEI (>5 wt % on the composition) with soil release polymers, especially, but not exclusively, if betaine is included in the surfactant system.
Particularly preferred are combinations of EPEI and soil release polymers of the above types for enabling increased performance at lower surfactant levels compared to 1.0 g/L or higher non soap surfactant wash liquors with betaine but without either EPEI or SRP. This effect is particularly visible on a range of stains on polyester, most particularly red clay. The effect of the combination on sunflower oil and foundation is also beneficial. SRP performance is enhanced significantly by repeated pre-treatment. There is some evidence of a build-up effect of EPEI performance.
The most preferred soil release polymers are the water soluble/miscible or dispersible polyesters such as: linear polyesters sold under the Repel-O-Tex brand by Rhodia (gerol), lightly branched polyesters sold under the Texcare brand by Clariant, especially Texcare SRN170, and heavily branched polyesters such as those available from Sasol and described in U.S. Pat. No. 7,119,056.
The viscosity modifier may comprise a thickening polymer.
The thickening polymer comprises linear/crosslinked alkali swellable acrylic copolymers/ASE/HASE/C-HASE.
he preferred thickening polymers are linear/crosslinked alkali swellable acrylic copolymers/ASE/HASE/C-HASE. Polymers that require alkaline conditions to swell and so to provide thickening of the detergent fluid should be added such that they are exposed to alkaline conditions at least during the manufacture of the fluid. It is not essential that the finished fluid is alkaline.
The thickening polymer is a water swellable polyacrylate. Such polymers may be alkali swellable copolymers (ASE) optionally with a hydrophobic modification on at least one of the monomers (HASE) or with crosslinking groups (CASE) and possibly with both hydrophobic modification and crosslinking (C-HASE).
As used herein the term “(meth)acrylic” refers to acrylic or methacrylic, and “(meth)acrylate” refers to acrylate or methacrylate. The term “acrylic polymers” refers to polymers of acrylic monomers, i.e., acrylic acid (AA), methacrylic acid (MAA) and their esters, and copolymers comprising at least 50% of acrylic monomers. Esters of AA and MAA include, but are not limited to, methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate (BMA), hydroxyethyl methacrylate (HEMA), methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA), and hydroxyethyl acrylate (HEA), as well as other alkyl esters of AA or MAA.
Preferably, acrylic polymers have at least 75% of monomer residues derived from (meth)acrylic acid or (meth)acrylate monomers, more preferably at least 90%, more preferably at least 95%, and most preferably at least 98%. The term “vinyl monomer” refers to a monomer suitable for addition polymerization and containing a single polymerizable carbon-carbon double bond.
Hydrophobic properties may be imparted by use of lipophilically-modified (meth)acrylate residues each of which may contain either one, or a plurality of, lipophilic groups. Such groups are suitably in the same copolymer component as and attached to hydrophilic chains, such as for example polyoxyethylene chains. Alternatively the copolymer may contain a vinyl group which may be used to copolymerize the polymer to other vinyl-containing entities to alter or improve the properties of the polymer. Polymerizable groups may be attached to lipophilic groups directly, or indirectly for example via one or more, for example up to 60, preferably up to 40, water-soluble linker groups, for example, —CH[R]CH2O— or —CH[R]CH2NH— groups wherein R is hydrogen or methyl.
Alternatively, the polymerizable group may be attached to the lipophilic group by reaction of the hydrophilic, for example polyoxyethylene, component with a urethane compound containing unsaturation. The molecular weight of the lipophilic-modifying group or groups is preferably selected together with the number of such groups to give the required minimum lipophilic content in the copolymer, and preferably, for satisfactory performance in a wide range of liquids.
The amount of lipophilically-modified component in the copolymers preferably is at least 5%, more preferably at least 7.5%, and most preferably at least 10%; and preferably is no more than 25%, more preferably no more than 20%, more preferably no more than 18%, and most preferably no more than 15%.
The lipophilic-modifying groups themselves are preferably straight chain saturated alkyl groups, but may be aralkyl or alkyl carbocyclic groups such as alkylphenyl groups, having at least 6, and up to 30 carbon atoms although branched chain groups may be contemplated. It is understood that the alkyl groups may be either of synthetic or of natural origin and, in the latter case particularly, may contain a range of chain lengths.
The chain length of the lipophilic-modifying groups is preferably is below 25, more preferably from 8 to 22, and most preferably from 10 to 18 carbon atoms. The hydrophilic component of the lipophilically-modified copolymer may suitably be a polyoxyethylene component preferably comprising at least one chain of at least 2, preferably at least 5, more preferably at least 10, and up to 60, preferably up to 40, more preferably up to 30 ethylene oxide units. Such components are usually produced in a mixture of chain lengths.
Preferably, the C2-C4 alkyl (meth)acrylate residues in the copolymer are C2-C3 alkyl (meth)acrylate residues, and most preferably EA. Preferably, the amount of C2-C4 alkyl (meth)acrylate residues is at least 20%, more preferably at least 30%, more preferably at least 40% and most preferably at least 50%. Preferably, the amount of C2-C4 alkyl (meth)acrylate residues is no more than 75%, more preferably no more than 70%, and most preferably no more than 65%. Preferably, the amount of acrylic acid residues in the copolymer used in the present invention is at least 5%, more preferably at least 7.5%, more preferably at least 10%, and most preferably at least 15%. Preferably, the amount of acrylic acid residues is no more than 27.5%, more preferably no more than 25%, and most preferably no more than 22%. Acrylic acid residues are introduced into the copolymer by inclusion of either acrylic acid, or an acrylic acid oligomer having a polymerizable vinyl group, in the monomer mixture used to produce the copolymer.
Preferably, the copolymer contains residues derived from methacrylic acid in an amount that provides a total acrylic acid plus methacrylic acid content of at least 15%, more preferably at least 17.5%, and most preferably at least 20%. Preferably, the total acrylic acid plus methacrylic acid content of the copolymer is no more than 65%, more preferably no more than 50%, and most preferably no more than 40%.
Optionally, the copolymer also contains from 2% to 25%, preferably from 5% to 20%, of a hydrophilic comonomer, preferably one having hydroxyl, carboxylic acid or sulphonic acid functionality. Examples of hydrophilic comonomers include 2-hydroxyethyl (meth)acrylate (HEMA or HEA), itaconic acid and acrylamido-2-methylpropanesulfonic acid.
The fluids of the present invention contain from 0.1% and preferably no more than 10% of thickening polymer; i.e., the total amount of copolymer(s) is in this range. Preferably, the amount of copolymer in the fluid is at least 0.3%, more preferably at least 0.5%, more preferably at least 0.7%, and most preferably at least 1%. Preferably, the amount of copolymer in the aqueous fluid is no more than 7%, more preferably no more than 5%, and most preferably no more than 3%. Preferably, the copolymer is an acrylic polymer.
The copolymer, in aqueous dispersion or in the dry form, may be blended into an aqueous system to be thickened followed, in the case of a pH-responsive thickener, by a suitable addition of acidic or basic material if required. In the case of copolymeric pH-responsive thickeners, the pH of the system to be thickened is at, or is adjusted to, at least 5, preferably at least 6, more preferably at least 7; preferably the pH is adjusted to no more than 13. The neutralizing agent is preferably a base such as an amine base or an alkali metal or ammonium hydroxide, most preferably sodium hydroxide, ammonium hydroxide or triethanolamine (TEA). Alternatively, the copolymer may first be neutralized in aqueous dispersion and then blended. The surfactant preferably is blended into the aqueous fluid separately from the copolymer prior to neutralization.
The molecular weight of uncrosslinked polymer is typically in the range of about 100,000 to 1 million.
In the case that the polymer is crosslinked, a crosslinking agent, such as a monomer having two or more ethylenic unsaturated groups, is included with the copolymer components during polymerization. Examples of such monomers include diallyl phthalate, divinylbenzene, allyl methacrylate, diacrylobutylene or ethylene glycol dimethacrylate. When used, the amount of crosslinking agent is typically from 0.01% to 2%, preferably from 0.1 to 1% and more preferably from 0.2 to 0.8%, based on weight of the copolymer components.
The copolymer may be prepared in the presence of a chain transfer agent when a crosslinking agent is used. Examples of suitable chain transfer agents are carbon tetrachloride, bromoform, bromotrichloromethane, and compounds having a mercapto group, e.g., long chain alkyl mercaptans and thioesters such as dodecyl-, octyl-, tetradecyl- or hexadecyl-mercaptans or butyl-, isooctyl- or dodecyl-thioglycolates. When used, the amount of chain transfer agent is typically from 0.01% to 5%, preferably from 0.1% to 1%, based on weight of the copolymer components. If the crosslinking agent is used in conjunction with a chain transfer agent, which are conflicting operations for polymerization purposes, not only is exceptional efficiency observed but also very high compatibility with hydrophilic surfactants, as manifested by increased product clarity.
Hydrophobically modified polyacrylate thickening polymers are available as Acusol polymers from Dow.
An alternative or additional polymer type that may be utilised is described in WO2011/117427 (Lamberti). These polymers comprise:
i) from 0.2 to 10% by weight of a thickening agent which is a crosslinked alkali swellable polyacrylate obtainable by polymerization of:
a) from 20 to 70% by weight of a monoethylenically unsaturated monomer containing a carboxylic group;
b) from 20 to 70% by weight of a (meth)acrylic acid ester;
c) from 0.05 to 3% by weight of an unsaturated monomer containing one or more acetoacetyl or cyanoacetyl groups;
d) from 0.01 to 3% by weight of a polyethylenically unsaturated monomer; e) from 0 to 10% by weight of a nonionic acrylic associative monomer; ii) from 5 to 60% by weight of a detergent component consisting of at least one compound selected from anionic surfactants, amphoteric surfactants, cationic surfactants, zwitterionic surfactants, non-ionic surfactants and mixture thereof.
Such crosslinked alkali swellable polyacrylates containing one or more acetoacetyl or cyanoacetyl groups possess high thickening capability in the presence of surfactants and electrolytes, provide homogeneous and clear solutions and possess improved suspending and thickening properties in comparison with crosslinked alkali swellable polyacrylates of the prior art. Crosslinked thickening polymers of this type are available as Viscolam thickening polymers from Lamberti.
The laundry liquid may comprise one or more enzymes.
The one or more enzymes may comprise any one or combination of the following enzymes. Enzymes may be from bacterial or fungal origin. Chemically modified or protein engineered mutants are included. As used herein the term “enzyme” includes enzyme variants (produced, for example, by recombinant techniques) are included. Examples of such enzyme variants are disclosed, e.g., in EP 251,446 (Genencor), WO 91/00345 (Novo Nordisk), EP 525,610 (Solvay) and WO 94/02618 (Gist-Brocades NV).
Preferably said one or more enzymes comprise one or more proteases. Preferred proteases include serine protease or a metallo protease, preferably an alkaline microbial protease or a trypsin-like protease. Alkaline proteases include subtilisins, especially those derived from Bacillus, e.g., subtilisin Novo, subtilisin Carlsberg, subtilisin 309, subtilisin 147 and subtilisin 168. Trypsin-like (i.e. capable of cleaving peptide bonds at the C-terminal side of lysine or arginine.) Such proteases may be of porcine or bovine origin. Fusarium derived trypsin proteases are also included.
Commercially available protease enzymes include Alcalase™, Savinase™, Primase™, Duralase™, Dyrazym™, Esperase™, Everlase™, Polarzyme™, and Kannase™ (Novozymes NS), Maxatase™, Maxacal™, Maxapem™, Properase™, Purafect™, Purafect OxP™, FN2™, and FN3™ (Genencor International Inc.).
Preferably said one or more enzymes comprise one or more lipases. Preferred lipases include lipases from Humicola (synonym Thermomyces), e.g. from H. lanuginosa (T. lanuginosus) or from H. insolens, a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes,
P. cepacia, P. stutzeri, P. fluorescens, Pseudomonas sp. strain SD 705 (WO 95/06720 and WO 96/27002), P. wisconsinensis, a Bacillus lipase, e.g. from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360), B. stearothermophilus (JP 64/744992) or B. pumilus (WO 91/16422).
Commercially available lipase enzymes include Lipolase™ and Lipolase Ultra™, Lipex™ (Novozymes NS).
Preferably said one or more enzymes comprise one or more phospholipases. Preferred Phospholipases (EC 3.1.1.4 and/or EC 3.1.1.32) include enzymes which hydrolyse phospholipids. Phospholipases A1 and A2 which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form lysophospholipid; and lysophospholipase (or phospholipase B) which can hydrolyze the remaining fatty acyl group in lysophospholipid are included as are Phospholipase C and phospholipase D (phosphodiesterases) which release diacyl glycerol or phosphatidic acid respectively.
The term “phospholipase A” used herein in connection with an enzyme of the invention is intended to cover an enzyme with Phospholipase A1 and/or Phospholipase A2 activity. The phospholipase activity may be provided by enzymes having other activities as well, such as, e.g., a lipase with phospholipase activity.
The phospholipase may be of any origin, e.g., of animal origin (such as, e.g., mammalian), e.g. from pancreas (e.g., bovine or porcine pancreas), or snake venom or bee venom. Preferably the phospholipase may be of microbial origin, e.g., from filamentous fungi, yeast or bacteria, such as the genus or species Aspergillus, e.g., A. niger; Dictyostelium, e.g., D. discoideum; Mucor, e.g. M. javanicus, M. mucedo, M. subtilissimus; Neurospora, e.g. N. crassa; Rhizomucor, e.g., R. pusillus; Rhizopus, e.g. R. arrhizus, R. japonicus, R. stolonifer; Sclerotinia, e.g., S. libertiana; Trichophyton, e.g. T. rubrum; Whetzelinia, e.g., W. sclerotiorum; Bacillus, e.g., B. megaterium, B. subtilis; Citrobacter, e.g., C. freundii; Enterobacter, e.g., E. aerogenes, E. cloacae Edwardsiella, E. tarda; Erwinia, e.g., E. herbicola; Escherichia, e.g., E. coli; Klebsiella, e.g., K. pneumoniae; Proteus, e.g., P. vulgaris; Providencia, e.g., P. stuartii; Salmonella, e.g. S. typhimurium; Serratia, e.g., S. liquefasciens, S. marcescens; Shigella, e.g., S. flexneri; Streptomyces, e.g., S. violeceoruber; Yersinia, e.g., Y. enterocolitica. Thus, the phospholipase may be fungal, e.g., from the class Pyrenomycetes, such as the genus Fusarium, such as a strain of F. culmorum, F. heterosporum, F. solani, or a strain of F. oxysporum. The phospholipase may also be from a filamentous fungus strain within the genus Aspergillus, such as a strain of Aspergillus awamori, Aspergillus foetidus, Aspergillus japonicus, Aspergillus niger or Aspergillus oryzae.
Preferred phospholipases are derived from a strain of Humicola, especially Humicola lanuginosa or variant; and from strains of Fusarium, especially Fusarium oxysporum. The phospholipase may be derived from Fusarium oxysporum DSM 2672.
Preferably phospholipases comprise a phospholipase A1 (EC. 3.1.1.32). or a phospholipase A2 (EC.3.1.1.4.).
Examples of commercial phospholipases include LECITASE™ and LECITASE™ ULTRA, YIELSMAX, or LIPOPAN F (available from Novozymes NS, Denmark).
Preferably said one or more enzymes comprise one or more cutinases. Preferred cutinases (EC 3.1.1.74.) are derived from a strain of Aspergillus, in particular Aspergillus oryzae, a strain of Alternaria, in particular Alternaria brassiciola, a strain of Fusarium, in particular Fusarium solani, Fusarium solani pisi, Fusarium roseum culmorum, or Fusarium roseum sambucium, a strain of Helminthosporum, in particular Helminthosporum sativum, a strain of Humicola, in particular Humicola insolens, a strain of Pseudomonas, in particular Pseudomonas mendocina, or Pseudomonas putida, a strain of Rhizoctonia, in particular Rhizoctonia solani, a strain of Streptomyces, in particular Streptomyces scabies, or a strain of Ulocladium, in particular Ulocladium consortiale. Most preferably cutinase is derived from a strain of Humicola insolens, in particular the strain Humicola insolens DSM 1800.
Commercial cutinases include NOVOZYM™ 51032 (available from Novozymes NS, Denmark).
Preferably said one or more enzymes comprise one or more amylases. Preferred amylases (alpha and/or beta) are included for example, alpha-amylases obtained from Bacillus, e.g. from strains of B. licheniformis NCIB8059, ATCC6634, ATCC6598, ATCC11945, ATCC 8480, ATCC9945a, or the Bacillus sp. strains DSM 12649 (AA560 alpha-amylase) or Bacillus sp. DSM 12648 (AA349 alpha-amylase).
Commercially available amylases are Duramyl™, Termamyl™, Termamyl Ultra™ Natalase™, Stainzyme™, Fungamyl™ and BAN™ (Novozymes NS), Rapidase™ and Purastar™ (from Genencor International Inc.).
Preferably said one or more enzymes comprise one or more cellulases. Preferred cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum.
Especially preferred cellulases are the alkaline or neutral cellulases having color care benefits. Commercially available cellulases include Celluzyme™, Carezyme™, Endolase™ Renozyme™ (Novozymes NS), Clazinase™ and PuradaxHA™ (Genencor International Inc.), and KAC-500(B)™ (Kao Corporation).
Preferably said one or more enzymes comprise one or more mannanases. Preferred mannanases (EC 3.2.1.78) include derived from a strain of the filamentous fungus genus Aspergillus, preferably Aspergillus niger or Aspergillus aculeatus or Trichoderma reseei or from the Bacillus microorganism FERM P-8856 which produces beta-mannanase and beta-mannosidase or from alkalophilic Bacillus sp. AM-001 or from Bacillus amyloliquefaciens. The mannanase may comprise alkaline family 5 and 26 mannanases derived from Bacillus agaradhaerens, Bacillus licheniformis, Bacillus halodurans, Bacillus clausii, Bacillus sp., and Humicola insolens.
Examples of commercially available mannanases include Mannaway™ available from Novozymes NS Denmark.
Preferably said one or more enzymes comprise one or more peroxidases and/or oxidases. Preferred peroxidases/oxidases include peroxidases from Coprinus, e.g. from C. cinereus, and variants thereof. Commercially available peroxidases include Guardzyme™ and Novozym™ 51004 (Novozymes NS).
Any enzyme present in a composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid.
The fluid may be a fabric or hard surface treatment liquid.
Fluids according to the invention may also contain various functional ingredients: surfactants, builders, various adjuncts, sequesterants, optical brighteners, dyes, softeners etc.

Various non-limiting embodiments of the invention will now be more particularly described with reference to the following figures in which:

FIG. 1 is a side view of an embodiment of a direct to consumer laundry liquids dispensing system according to the invention, with the container support and squeeze mechanism shown in section.

FIG. 2 is an enlarged front view of the embodiment shown in FIG. 1

FIG. 3 is an enlarged view of the spring component of FIG. 2

FIG. 4 is an enlarged sectional view of the upper part of the system

FIG. 5 is an enlarged and exploded view of the container support and squeeze mechanism in perspective

FIG. 6 is an enlarged view of the force translation mechanism

FIG. 7 is an enlarged view of the metered dosing device in place

FIG. 8 is a side view of the container

An Exemplary Fabric Treatment Laundry Liquid is below


	Ingredient as 100% active	Wt %

	Neodol 25-9*	6-8
	Alcohol ethoxy sulfate	12-15
	Linear alkylbenzene sulfonate	6-9
	Sodium citrate, dihydrate	3-6
	Propylene glycol	4-8
	Sorbitol	3-6
	Sodium tetraborate pentahydrate	2-4
	Volatile benefit agent: perfume	1
	Minor additives and water	to 100%

A further exemplary laundry liquid is below


	LAS	11
	Sodium Laureth Sulfate (SLES) 3EO 70%	12.0
	Alcohol Ethoxylate	8.4
	Hardened Topped Coconut Fatty Acid	3.5
	MEA	6
	Citric Acid 50% solution	5
	triethanolamine TEA	4
	EHDP 60% Solution	2.5
	ACRYLATE COPOLYMER HASE30	2
	Ethoxylated Polyethylene Imine EPEI	4
	Mono Propylene Glycol	8.0%
	enzymes
	3
	Volatile benefit agent: perfumes	1.5
	Minor additives and water	To 100

*C₁₂-C₁₅alkoxylated (9EO) chain group

Referring to the figures, a direct-to-consumer laundry liquid dispensing system 1 is shown comprising:
(a) a container 3 containing a liquid laundry 5 (which may be as in the above examples), said container having an elongate cross section adapted for letterbox delivery wherein the container width is at least twice the container width and the container depth is less than 5 cm;
(b) a dispensing device 7 configured to house the container 3 in a dispensing orientation;
(c) a metered dosing device 9 with a self-closing dispensing aperture 11, metered dosing device 9 attached to the container for dispensing a unitized dose of the laundry liquid 5 (sufficient for washing one load) from the container 3 via a dispensing aperture 11, on actuation by the consumer.
The system further includes a dosing shuttle 15, and this is located below the dispensing aperture 11 when the container 3 is in placed in the dispensing device 7. The laundry liquid 5 is dispensed into the shuttle 15 and this is then placed directly into the washing drum or other washing receptacle (not shown). A dosing device locator 17 constrains the position of the dosing device so that it stays directly below and in line with the dispensing aperture so avoiding spillages during dispensing. The locator 17 comprises a shallow recess 17 in the base of the dispensing device 7, the recess 17 corresponding to the base of the dosing shuttle 15.
The container 3 has a longitudinal axis Y with a closed base at one end and at an opposing (longitudinally) end, a dispensing part, and the dispensing orientation of the container 3 is such that the dispensing part is downward of the closed base.
The dispensing device 7 has a housing 21 comprising a container support 23 for supporting the container 3 in the dispensing orientation as shown in the figures, and which container support 23 is movable relative to the housing 21 to effect dispensing of the laundry liquid 5. The dispensing device 7 further comprises a squeeze mechanism 25 which is operative to squeeze the container 3 to effect dispensing of a unitized (sufficient for treating one load) dose of the laundry liquid 5 via the metered dosing device 9. The squeeze mechanism 25 is connected to the container support 23 such that downward movement of the container support actuates the squeeze mechanism 25 upon the container sides 3 and so in turn effects dispensing. The squeeze mechanism 25 comprises squeeze arms 27 connected by a series of pivoted levers to a force transmitting mechanism 29
Dispensing may thus be achieved by simply pressing down on the container 3 in direction A shown on FIG. 1 or container support 23. The squeeze mechanism is resilient in that once the container support has moved down for dispensing, it returns to the its original position via a return spring 33. The dispensing of the liquid 5 takes place on the downward stroke.
The device is manually operated, requiring no power.
The container 3 has a stepped profile shown more clearly in figure. This provides a force transfer surface 31 for transmitting the downward pushing from the container to the support and to the force transfer mechanism 29.
The container 3 has a primary face and an opposing rear face, said faces connected along their two respective sides by respective side walls. These walls are flattened faces which are interconnected with smooth outer profiles. The container 3 has a cross section generally based on an elongate ellipse with flattened surfaces defining discrete walls whereby there are distinct edge regions where adjoining walls meet. In other embodiments (not shown) the container 3 has curved faces which create smoother edge regions and more of a continuous curved wall. The primary and rear faces are at least four times the width of the side walls.
The squeeze mechanism 25 engages the primary and rear faces by means of a specifically shaped recess which corresponds with the containers cross sectional shape to ensure that the container's primary and rear walls (ie those with larger more flexible areas) are aligned to engage the squeeze mechanism. This is necessary due to the lack of radial symmetry of the container and the need to engage certain walls for squeezing. The recess serves to provide a guide so that as the consumer pushes down the movement is downward and not sideward, and also as a resistance to prevent the cartridge from shooting out the device on the return stroke.
When the container 3 is being compressed the metered dosing device 9 releases a fixed amount of detergent. Once the cartridge is released the metered dosing device 9 will refill itself automatically, and is ready to dispense another fixed amount. The silicone membrane stops the flow after decompressing begins on the return stroke.
In another embodiment, the container has all or part of its walls thickened to provide some resistance to the squeezing action of the squeeze mechanism. This allows smaller doses to be achieved. Having only those portions thickened which are in the vicinity of the squeezing mechanism enables the remaining part of the bottle to be lightweight.
The maximum depth of the container 3 is less than 4 cm, preferably less than 3 cm. The maximum depth may be less than 2 cm.
The maximum width of the container is less than 30 cm, preferably less than 25 cm, more preferably less than 20 cm. Most preferably the width is less than 15 cm.
The container 3 is transparent or translucent with translucent labels except for text.
The container 3 can be formed from polyethylene, polyethylene terephthalate, polypropylene, and other polymers from which clear or transparent or translucent containers 3 may be formed.
The inclusion of a volatile perform in a liquid of viscosity 200-700 cPs at 21 s−1 together with the squeeze-operated device means the laundry liquid exits under increased stress and speed which enhances consumer experience by enhancing release of the volatile benefit agent during dispensing.
The viscosity of 200-700 cPs at 21 s−1 provides for excellent and rapid dynamic mixing during squeezing but without splashing as it enters the dosing device. Preferably the viscosity is measured at room temperature (21 degrees) using a Brookfield Viscometer. The fluid is a liquid or pourable gel
The dispensing device comprises multiple sections and these sections may themselves comprise sub sections which may be provided unassembled and ‘flat-packed’ for letterbox delivery to the consumer. The consumer may then assemble the device from said multiple sections. Alternatively the dispensing device may be provided fully assembled as shown, and delivered without the need for any assembly, other than to insert a container.
It is of course to be understood that the invention is not intended to be restricted to the details of the above embodiment which are described by way of example only.

Claims

1. A laundry liquid dispensing system comprising:

(a) a container containing a laundry liquid, the container having an elongate cross section configured for letterbox delivery,

wherein the container width is at least twice the container depth and the container depth is in the range between 5 cm and 1 cm;

(b) a dispensing device configured to house the container in a dispensing orientation;

(c) a dosing device configured for dispensing, on actuation, a dose of the laundry liquid from the container via a self-closing dispensing aperture,

wherein the laundry liquid has a viscosity in the range between 200 to 1500 cps.

2. A laundry liquid dispensing system according to claim 1 wherein the dosing device is a metered dosing device attached either to the dispensing device or the container.

3. A laundry liquid dispensing system according to claim 1 wherein the system includes a membrane configured to close the dispensing aperture after dispensing.

4. A laundry liquid dispensing system according to claim 1 wherein the dispensing device has a housing comprising a container support configured to support the container in the dispensing orientation and which is movable relative to the housing to effect dispensing of the laundry liquid.

5. A laundry liquid dispensing system according to claim 1 wherein the dispensing device comprises a squeeze mechanism which squeezes the container to effect dispensing of the laundry liquid via the metered dosing device.

6. A laundry liquid dispensing system according to claim 5, wherein the squeeze mechanism is connected to the container support such that downward movement of the container support actuates the squeeze mechanism and so in turn effects dispensing.

7. A laundry liquid dispensing system according to claim 6 wherein the squeeze mechanism is resilient such that once the container support has moved down, it returns to the its original position.

8. A laundry liquid dispensing system according to claim 1 wherein the container has a stepped profile.

9. A laundry liquid dispensing system according to claim 1 wherein the container has a primary wall and an opposing rear wall and the squeeze mechanism engages the primary and rear faces.

10. A laundry liquid dispensing system according to claim 4, wherein the container support provides a recess with a corresponding cross sectional shape to that of the container.

11. A laundry liquid dispensing system according to claim 1 wherein the maximum depth of the container is in the rage between 4 cm and 1 cm and the maximum width of the container is in the range between 30 cm and 2 cm.

12. A laundry liquid dispensing system according to claim 3, wherein the membrane comprises a silicone material.

13. A laundry liquid dispensing system according to claim 1 wherein the laundry liquid comprises a volatile benefit agent.

14. A laundry liquid dispensing system according to claim 1 wherein the laundry liquid comprises a cleaning polymer.

15. A laundry liquid dispensing container wherein the container comprises an elongate cross section with maximum depth in the range between 4 cm and 1 cm and maximum width in the range between 30 cm and 2 cm, the container containing a laundry liquid comprising viscosity in the range between 200 to 1500 cps.