EP2630224A1 - Extern strukturierte wässrige reinigungsflüssigkeit - Google Patents
Extern strukturierte wässrige reinigungsflüssigkeitInfo
- Publication number
- EP2630224A1 EP2630224A1 EP11767995.1A EP11767995A EP2630224A1 EP 2630224 A1 EP2630224 A1 EP 2630224A1 EP 11767995 A EP11767995 A EP 11767995A EP 2630224 A1 EP2630224 A1 EP 2630224A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- citrus
- pulped
- composition according
- surfactant
- lipase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 1
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 210000004899 c-terminal region Anatomy 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical group CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 1
- 229940073507 cocamidopropyl betaine Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 150000001982 diacylglycerols Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 229960002442 glucosamine Drugs 0.000 description 1
- 229940059442 hemicellulase Drugs 0.000 description 1
- 108010002430 hemicellulase Proteins 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 235000014611 low fat mayonnaise Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 210000004738 parenchymal cell Anatomy 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical class OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- WTJKGGKOPKCXLL-RRHRGVEJSA-N phosphatidylcholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCC=CCCCCCCCC WTJKGGKOPKCXLL-RRHRGVEJSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229940057400 trihydroxystearin Drugs 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3715—Polyesters or polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
Definitions
- This invention relates to a structured aqueous detergent liquid composition
- a structured aqueous detergent liquid composition comprising water, surfactant, external structurant and enzymes, the external structurant provides rheological modification to the composition and may also be used to suspend solid materials in the liquid.
- concentrated aqueous laundry detergent liquid is used to reduce the amount of chemicals per wash. This is achieved, without loss of detergency, by reduction of the amount of surfactant used per wash and use, in its place, of highly weight efficient enzymes and polymers to boost detergency on everyday dirt and stains.
- Preferred compositions use lipase enzyme and /or combinations of high levels of ethoxylated polyethyleneimine polymer and polyester soil release polymer.
- the structurant can convey the idea of concentration by increasing low shear viscosity whilst allowing the composition to flow freely when poured.
- Solid materials can be suspended in such liquids to further reinforce the concentration message, for example the liquid can be pearlised by inclusion if mica particles or titanium dioxide particles.
- the external structurant should be capable of suspending these particles, working either alone, or in combination with another rheology modifying system.
- External structurants are also useful for less concentrated aqueous cleaning liquids. In such liquids, surfactant in excess of that required for detergency is often used for thickening and rheology modification. This is undesirable from an environmental standpoint, not only is more chemical sent to waste but frequently the excess surfactant causes the utilisation of more rinse water, which is a big issue when water is a scarce resource.
- HCO hydrogenated castor oil
- Thixcin® is sold under the trade name Thixcin® by Elementis.
- HCO is derived from chemical modification of a plant extract. Then the HCO is converted into an external structurant by crystallising it in the liquid, or in part of the liquid. This crystallisation process may impose formulation constraints, especially when using high surfactant levels. HCO structured liquids are slightly cloudy, which is undesirable when visual cues are suspended in the liquid. We have found that HCO is liable to rapid decomposition in the presence of lipase enzyme.
- MFC microfibrous cellulose
- methylcellulose and xanthan gum as dispersion aids.
- the MFC forms a 3-D network structure, which can suspend inert materials such as sand and nylon beads.
- the xanthan gum part of the dispersant is not a desirable ingredient for many detergent liquids. It poses constraints for inclusion of enzymes that can decompose xanthan gum. Furthermore it can have an undesirable effect in combination with cleaning and soil release polymers.
- Such polymers are proposed to be used at high concentrations in the detergent liquids described in WO09/153184. Thus MFC is not a good choice for the external structuring of such detergent liquids with high levels of polymers.
- WO2009/101545 describes compositions comprising MFC structurant.
- Exemplary compositions contain enzymes; a list of suitable enzymes is given on page 29.
- the preferred enzyme mixture includes cellulase.
- MFC requires the presence of relatively high levels of surfactant to provide effective rheological modification. It would be desirable to find an alternative external structurant that would also perform at low surfactant levels and that would be compatible with a wide range of cellulase enzymes. Based on SEM evidence, MFC forms nanofibres in concentrated aqueous detergent liquids. Uncertainties exist in scientific understanding of the impacts of such fibres, and associated public perception. For this reason, and because of the other disadvantages of MFC outlined previously, the skilled worker desires to find a better substitute for the lipase vulnerable HCO than MFC appears to be.
- US2004/0086626 describes an improved method for refining cellulose that produces a highly refined cellulosic (HRC) material.
- the method comprises soaking raw material from primarily parenchymal cell wall structures in an aqueous solution, using reduced temperatures and pressures, and refining the material with a plate refiner. After drying the resulting HRC fibre displays a water retention capacity of about 25 to at least about 56 g water/g dry HRC and retains moisture under conditions that are ordinarily used to remove moisture from materials.
- the HRC fibre product can also provide excellent thickening properties and may be used in a wide variety of materials, including edible materials. Thickening and suspending properties are particularly attributed to fibres provided by sugar beets. Orange pulps are used in several examples. The main use envisaged for this product is as a food additive.
- the dried HRC product may be rehydrated by the use of a high shear mixer to disperse organic fibre plant mass materials rapidly into solution.
- Other uses mentioned are industrial thickeners, as in paint thickeners, stain thickeners, coating thickeners, and the like.
- Citrus fibres are available for example as "Herbacel AQ plus citrus fibre", from Herba Foods. Summary of the Invention
- a structured aqueous liquid detergent composition comprising:
- enzyme selected from lipase, cellulase and mixtures thereof.
- the external structurant comprises at least 0.15 wt%, preferably at least 0.2%, citrus fibre that has been mechanically pulped and swollen in water.
- the composition comprises 0.16 to 0.35 wt% pulped citrus fibre.
- the composition may have a yield stress greater than 0.2 Pa.
- Citrus fibre is derived from citrus fruit; advantageously it comprises the peel of lemons and/or limes.
- the citrus fruit peel is pulped by subjecting it to high shear and the pulped material is referred to as pulped citrus fibre.
- pulped citrus fibres are capable of absorbing and binding at least 15 times its own weight of water, preferably at least 20 times and even up to 30 times.
- the minimum amount of pulped citrus fibre required to deliver an acceptably high critical stress in the final liquid is 0.15 wt%.
- the composition comprises at least one enzyme selected from lipase and cellulase.
- the preferred amount of each enzyme is from 0.0001 to 5 wt%, even more preferably from 0.001 to 0.3 wt% active enzyme.
- the preferred enzyme is lipase.
- the external structurant is a pulped citrus fibre which has undergone a
- mechanical treatment comprising a step of high intensity mixing in water and which material has consequently absorbed at least 15 times its own dry weight of water, preferably at least 20 times its own weight, in order to swell it. It may be derived by an environmentally friendly process from a fruit processing waste stream. This makes it more sustainable than prior art external structurants.
- Pulped citrus fibre is much less expensive to produce than bacterial cellulose because its processing is simpler and it may be made from a waste stream, e.g. from fruit juice production.
- Citrus fruits are preferred as the source of the fibre because they have a large amount of peel that can provide material with the desired water absorbing capacity.
- the most preferred fruits are lemons and limes lemon because the natural pH of the resulting mechanical pulp is about 3.5, which allows use of potassium sorbate at low levels as an effective preservative for the premix before it is dispersed into the detergent liquid.
- the citrus fibre is mechanically pulped by processing it to make a premix preferably in combination with preservative. This is done by adding dried powdered citrus fibre to at least 15 times its own weight of water and dispersing it under very high shear to further break up the citrus fibres and to begin the process of hydration, or swelling.
- the mechanically treated citrus fibre is left in contact with the water for sufficient time for it to swell due it being fully hydrated. This can be several hours.
- pulped citrus fibre is kept separate from surfactant until it is fully swollen. This avoids the possibility for the surfactant to compete with the citrus pulp fibre for the water. Something that becomes more of a problem as the total surfactant concentration increases.
- the very high shear may be provided by a high intensity mixer such as a Silverson mixer, or, less preferably, by means of a High-pressure homogeniser.
- the homogeniser is less preferred because it can suffer from blockage problems with citrus fibre.
- the amount of pulped citrus fibre in the premix is preferably from 1 to 5 wt%.
- Pulped Citrus fibre has different in use pouring properties from other external structurants used in detergent compositions. It exhibits pronounced drainage on walls of a pack, a translucent appearance, and a slightly grainy texture on pouring. This gives a detergent liquid structured with pulped citrus fibre a different look and feel for the consumer. Such a difference is ideal to signal a major shift in liquid detergent composition; especially to a composition that requires lower usage and a change in consumer behaviour.
- pulped citrus fibre does not significantly affect the foam generated by the presence of the surfactant system. This is an advantage for formulation flexibility.
- Pulped Citrus fibre is complex and heterogeneous; it includes both soluble and insoluble cellular materials, which is shown to give rise to a distinctive network of 'sponges' of varying size and geometry in contrast to MFC's essentially fibrous network.
- one advantage we have found for pulped citrus fibre externally structured liquid formulations is its compatibility with enzymes.
- Lipase which is found rapidly to degrade an HCO structured liquid and cellulases which appear to have some effect on MFC.
- at least one enzyme selected from lipase and cellulase is an essential feature of the detergent compositions of the invention.
- Lipase is a preferred enzyme as is known to boost performance on certain types of stains and soil when used in compositions designed to provide low in solution surfactant levels.
- suitable Lipases are Lipomax®, Lipex®, and
- Lipolase® Preferred lipase enzymes include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola, including ones which comprise a polypeptide having an amino acid sequence which has at least 90% sequence identity with the wild-type lipase derived from Humicola lanuginosa, most preferably strain DSM 4109. However, when used at low in wash surfactant levels so-called "multi-wash" lipase enzymes may also show a single-wash benefit. The amount of lipase enzyme protein used in the wash is set to be at the high side of what is normal (>5 mg, preferably greater than 8 mg per wash).
- the composition preferably comprises from about 5 to about 20000 LU/g of a lipase.
- a particularly preferred lipase enzyme has been published under the trademark LipocleanTM by Novozymes. Lipomax® from Genencor is also preferred.
- Cellulases may be included and if they are the formulation should preferably be formulated at a pH where their activity is low. Typically this is an alkaline pH, although mildly acidic conditions of down to pH 6.5 or even as low as pH 6.2 can be tolerated.
- Pulped citrus fibre provides a stable external structuring network in the presence of endoglucanase, which enables addition of this cellulase to a structured aqueous liquid either on its own, or more preferably in combination with lipase.
- Such a mix of enzymes is desirable for compositions that further comprise a soil release polymer to provide a multi wash benefit on a range of stain and fabric types.
- Concentrated laundry detergent liquids may advantageously contain such a combination.
- Cellulase improves the cleaning of cotton
- lipase improves the cleaning of oily soils from cotton and polyester and soil release polymers further boost the multi-wash cleaning benefits of the detergent composition on these fabrics.
- lipase helps remove greasy stains, especially if low surfactant levels are used.
- Cellulases help to break down many other food residues.
- the surfactant type is not limited. Synthetic detergents are preferred.
- compositions may be used. It is preferred for the composition to comprise anionic (non-soap) surfactant. Particularly preferred surfactant systems are mixtures of the anionic surfactants linear alkyl benzene sulphonate and sodium lauryl ether sulphate with the nonionic surfactant ethoxylated nonionic fatty alcohol. Betaines, such as sulphobetaine are advantageously used as a cosurfactant.
- the amount of surfactant may range from 0.5 to 65 wt%, preferably 2.5 to 60 wt%, more preferably from 25 to 50 wt%.
- the skilled worker will appreciate that the optimum surfactant concentration will largely depend on the product type and the intended mode of use.
- the amount of external structurant is important. Because it is added to the remainder of the ingredients in admixture with around 20 times its weight of water, it is important to keep the amount of structurant to a minimum. Below 0.15 wt%, pulped citrus fibre fails to provide adequate structuring. The precise lower limit depends to some extent on the remainder of the composition; the skilled worker will know that the aim is to obtain a system in which the rheology exhibits a critical yield stress.
- the amount of pulped citrus fibre is at least 0.2 wt%.
- the structured liquid is shear thinning.
- the preferred pouring viscosity being from 20 - 100 mPa.s and the yield stress or critical stress being about 0.3 Pa.
- the composition may optionally comprise suspended solid material.
- the solid material may be microcapsules such as perfume encapsulates, or care additives in encapsulated form. It may alternatively, or additionally, take the form of insoluble ingredients such as silicones, quaternary ammonium materials, insoluble polymers, insoluble optical brighteners and other known benefit agents found, for example, in EP1328616.
- the amount of suspended solid material may be from 0.001 to up to 10 or even 20 wt%.
- a particular solid material to be suspended is a visual cue, for example the type of flat film cue described in EP131 19706. The cue may itself contain a segregated component of the composition.
- the cue must be water-soluble, yet insoluble in the composition, it is conveniently made from a modified polyvinyl alcohol that is insoluble in the presence of anionic surfactant.
- the detergent composition should comprise some anionic surfactant, preferably at least 5 wt% anionic surfactant.
- citrus fibres from the citrus fruit material, preferably by extraction, c) subjecting the citrus fibres to mechanical processing comprising application of shear in the presence of at least 15 times the amount of water based on the citrus fibres, the shear being sufficient to cause structural disruption and hydration of the citrus fibres to form a structuring premix comprising dispersed pulped citrus fibre;
- the detergent liquid in step (d) contains citrate builder.
- the liquid comprises 1 to 20 wt% hydrotropes. If the liquid is to be clear and the visual distinctiveness of the pulped citrus fibre external structurant is to be utilised fully, it desirably comprises no opacifier or pearliser. It may, however, comprise colorant.
- the dispersal requires no addition of further dispersal aids to the premix formed in step (c).
- a preservative is added to the premix during or after step (c), particularly if the premix will be stored for some time before addition to the detergent liquid.
- a further advantage of the use of pulped citrus fibre as an external structurant is that, unlike some other external structurants, it appears not to modify the type or amount of foam formed by a detergent liquid. This is important because it enables the structurant to be added to an aqueous detergent composition without affecting its in use properties. This is particularly the case for compositions that are mixed with a comparatively large volume of water for cleaning use. In this category may be mentioned especially liquid laundry detergent compositions, both concentrated and dilute, contained in both bottle and unit dose formats, for example sachets, and hand dishwashing compositions.
- compositions that are used neat, including laundry liquids used for pre-treatment and hard surface cleaning compositions of the type that are applied from a spray or pump are beneficially structured with this external structurant as it does not cause over foaming as they are applied and very low levels of surfactant can be structured.
- the structurant is compatible with the inclusion of lipase for grease removal, especially in compositions that may be left on hard surfaces for grease removal purposes and other hard surface cleaning compositions.
- the externally structured enzyme containing compositions are suitable for hand contact after dilution uses, such as hand dishwashing and hand laundry.
- Laundry detergents are generally classified as low foam, used in automatic washing machines, and high foam, used in hand wash and top loading washing machines.
- the pulped citrus fibre advantageously provides the necessary structuring without boosting foam in the low foaming compositions and yet retains adequate foam in high foaming compositions.
- the level of pulped citrus fibre in the premix preferably lies in the range 1 to 2.5 wt%.
- the amount of pulped citrus fibre preferably lies in the range of 0.15 wt% to 0.35 wt%.
- a particularly preferred grade of citrus fibre is supplied under the name "Herbacel AQ plus citrus fibre", ex Herba Foods.
- This citrus fibre has a total (soluble and insoluble) fibre content of greater than 80% and soluble fibre content of greater than 20%. It is supplied as a fine dried powder with low colour and has a water binding capacity of 20 kg water per kg of powder.
- the dispersed pulped citrus fibre is biodegradable, it is advantageous to include a preservative into the premix. In any case, a preservative is normally needed in the liquid detergent composition.
- the albedo of citrus fruits is the main source of the citrus fruit peel used to make the powdered citrus fibre. It has a 'spongy microstructure'. Citrus fruits (mainly lemons and limes) are dejuiced to leave the insoluble plant cell wall material and some internally contained sugars and pectin. It is dried and sieved and then washed to increase the fibre content. The refining process may entail soaking the fibres in NaOH ( ⁇ 1 %), draining and standing to soften, before shearing, refining and & drying. Dried materials are large (100's micron cell fragment, consisting of tightly bound/ bonded fibrils). After drying and milling a powdered citrus fibre material is obtained.
- the process used leaves much of the natural cell wall intact while the sugars are removed.
- the resulting highly swelling citrus fibre materials are typically used as food additives and have been used in low fat mayonnaise.
- the pH of the dispersed powder is acidic which is ideal for use with a preservative such as potassium sorbate.
- Microscopy shows that the powdered citrus fibre material as supplied it is a heterogeneous mixture of particles with various sizes and shapes. The majority of the material consists of aggregated lumps of cell walls and cell wall debris.
- xylem vessels are water transport channels that are mainly located in the peel of citrus fruits.
- the xylem vessels consists of stacks of dead cells, joined together to form long tubes, 200 to 300 micron long.
- the outside of the tubes is reinforced by lignin, which is often laid down in rings or helices preventing the tubes from collapse due to the capillary forces acting on the tube walls during water transport.
- the citrus fibre as supplied does not contain polymeric or other dispersants that are commonly found at high levels in other external structurants including MFC.
- CP Kelco MFC is a combination of fibre (60%) with other swelling polymers (40%), such as xanthan, to make it easier to disperse.
- other swelling polymers such as xanthan
- the absence of such polymers may avoid negative sensorial attributes such as sliminess or stickiness.
- the absence of any additional polymers or gums ensures the required rheology of the pulped citrus fibre as an external structurant. It also makes this external structurant highly compatible with other polymers or thickeners that may be included into the composition.
- soil release polymers for example those designed to release dirt from polyester fabrics
- cleaning polymers for example ethoxylated polyethylene imines, especially PEI 600 20 EO (EPEI): a polyethylene imine with a Mwt of the polymer backbone of approximately 600 and an average of 20 moles of ethylene oxide for each
- the powdered citrus fibre material Before it can be used as an external structurant it is necessary to process the powdered citrus fibre material as supplied further to break down the tubes to be more space filling. This is done by dispersing it at a low concentration into water. As mentioned previously a preservative is usefully added at this stage. This high shear dispersal opens out the sponge structure to increase the phase volume. The shear should not be high enough to lead to defibrillation. If a high-pressure homogeniser is used it should be operated between 200 and 600 bar. The more shear that is applied the less dense the resulting particles. Whilst the morphology is changed by the high shear, process aggregate size appears not to be changed. At high pressure, the fibres break down and then fill the water phase. The very high shear also forms fibrils by rubbing loose the outer parts of the cell walls and these are able to form a matrix that structures the water outside of the volume of the original fibre.
- a pulped citrus fibre structuring premix may alternatively be made using a high shear mixer, such as a Silverson.
- a high shear mixer such as a Silverson.
- One possible process passes the premix through several sequential high-shear mixing stages in order to ensure full hydration and dispersal of the citrus fibre to form the pulped citrus fibre dispersion.
- the premix can then simply be added to a partially, or formed detergent liquid premix with the surfactant and other components of the liquid detergent
- composition already admixed.
- Ingredients that would be held back at this stage are perfume, enzymes and any solid material that will be suspended by the external structurant.
- Such post-dosed materials are added later to the structured liquid, under low shear mixing conditions.
- pulped citrus fibre has a distinctive appearance.
- the large aggregates give noticeable on wall drainage and the bulk liquid has a translucent appearance due to high light scattering. Both of these attributes are closer to the properties of HCO and can reinforce the impression of a highly concentrated liquid without need to resort to suspended mica or other visual cues that add non-functional, generally insoluble, appearance-altering chemicals to the detergent liquid.
- the use of insoluble materials in concentrated liquids is highly undesirable as it leads to opaque wash liquors and possible unwanted deposition onto the articles being cleaned.
- Pulped citrus fibre benefits from air free processing as this improves the stability of the resulting liquids, especially to bottom clear layer separation. This has been demonstrated successfully for 35ml (so called 3x) and 20ml (so called 5x) dose liquids for European sized washing machines (typically 7 to10 litres fill).
- Microfibrous cellulose has proved extremely difficult to process in a way that prevents bottom clear layer separation for the 20 ml dose liquids.
- the structurant is typically dispersed at very high shear to break up the insoluble fibres and to increase phase volume of the structuring system by maximising break up and contact with anhydrous structuring material.
- the premix may be left to hydrate further (age) after the high shear mixing.
- concentration of pulped citrus fibre in the pre-mix depends on the ability of the equipment to deal with the higher viscosity due to higher concentrations. The minimum will preferably be at least 1 wt% for practical reasons.
- the process gives a stable detergent product with sufficient critical stress, 0.3 Pa, to suspend solid material and suspend itself to give minimal top clear layer separation.
- the pulped citrus fibre structurant will structure any type of surfactant containing detergent liquid.
- preferred surfactants assist in removing soil from the textile materials or from hard surfaces and assist in maintaining removed soil in solution or suspension in water.
- anionic and/or nonionic surfactants are preferred, more preferably provided in a calcium tolerant blend.
- Linear alkyl benzene sulphonate (LAS) used on its own is generally calcium intolerant.
- surfactant systems should generally avoid having levels of LAS above 90 wt%.
- Nonionic- free systems with 95 wt% LAS can be made if some zwitterionic surfactant, such as sulphobetaine, is present.
- pulped citrus fibre advantageously comprise at most 2 wt%, preferably at most 1 wt%, and most preferably zero, nonionic surfactant.
- Preferred alkyl ether sulphates are C8-C15 alkyl and have 1 -10 moles of ethoxylation.
- Preferred alkyl sulphates are alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C8-C15.
- the counter ion for anionic surfactants is generally an alkali metal, typically sodium, although other counter-ions such as MEA, TEA or ammonium can be used.
- Suitable anionic surfactant materials are available as the 'Genapol'TM range from Clariant.
- Nonionic surfactants include primary and secondary alcohol ethoxylates, especially C8-C20 aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
- Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers and polyhydroxy amides (glucamide). Mixtures of nonionic surfactant may be used.
- the composition contains from 0.2 wt% to 40 wt%, preferably 1 wt% to 20 wt%, more preferably 5 to 15 wt% of a non-ionic surfactant, such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside,
- a non-ionic surfactant such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside
- alkyldimethylamineoxide ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine ("glucamides").
- Preferred nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C8-C20 aliphatic alcohols ethoxylated with an average of from 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
- the Calcium Tolerance Test used herein is that defined in EP1771543.
- a surfactant blend is prepared at a concentration of 0.7 g/l in water containing sufficient calcium ions to give a French Hardness of 40 degrees.
- Other electrolytes such as sodium chloride, sodium sulphate, sodium hydroxide are added as necessary to adjust the ionic strength to 0.5M and the pH to 10.
- the absorption of light of wavelength 540 nm through 4 mm of sample is measured 15 minutes after sample preparation. Ten measurements are made and an average value is calculated. Samples that give an absorption value of less than 0.08 are deemed calcium tolerant. Water
- compositions are aqueous, that is to say that water forms the majority of the solvent system. Hydrotropes such as propylene glycol and glycerol/glycerine may be used but they will be present at a lesser amount than the water.
- the minimum water level for an aqueous liquid is 10 wt%. In order to incorporate 0.15% pulped citrus fibre with 20 times its own weight water absorbing capacity it is normal to have a minimum of 3 wt% water added with the pulped citrus fibre (from the pre- mix). For the preferred level of about 0.25 wt% pulped citrus fibre, the amount of water added from a 2.5 wt% premix is 9.75%. Additional water is needed in the composition in order to keep the surfactant, any polymers, soluble builders, enzymes etc in solution. The water amount stated includes both free and any bound water.
- the suspended material can be any type. This includes perfume encapsulates, care encapsulates and/ or visual cues or suspended solid opacifier such as mica or other suspended pearlescent materials and mixtures of these materials.
- perfume encapsulates, care encapsulates and/ or visual cues or suspended solid opacifier such as mica or other suspended pearlescent materials and mixtures of these materials.
- up to 5 wt% of insoluble solid material may be suspended stably using the pulped citrus fibre external structuring system, however amounts up to 20 wt% are possible.
- Polymeric thickening systems may be added to the liquid to increase the viscosity and further modify the rheology.
- Pulped citrus fibre is especially compatible with such thickening systems and it is compatible with other external structurants.
- one or more further enzymes may be present in a composition of the invention and when practicing a method of the invention.
- Essential enzymes are lipase and/or cellulase, most preferably lipase.
- Further enzymes may be selected from the enzymes known to be compatible with surfactant containing compositions, in particular proteases, mannanases and amylases.
- Suitable lipases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful lipases include lipases from Humicola (synonym Thermomyces), e.g. from H. lanuginosa (7.
- lanuginosus as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580, a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseudoalcaligenes (EP 218 272), P. cepacia (EP 331 376), P. stutzeri (GB
- P. fluorescens Pseudomonas sp. strain SD 705 (WO 95/06720 and WO 96/27002), P. wisconsinensis (WO 96/12012), a Bacillus lipase, e.g. from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1 131 , 253-360), B. stearothermophilus (JP 64/744992) or B. pumilus (WO 91/16422). Preferred ones have a high degree of homology with the wild-type lipase derived from Humicola lanuginosa.
- lipase variants such as those described in WO 92/05249, WO 94/01541 , EP 407 225, EP 260 105, WO 95/35381 , WO 96/00292, WO 95/30744, WO 94/25578, WO 95/14783, WO 95/22615, WO 97/04079 and WO 97/07202.
- lipase enzymes include LipolaseTM and Lipolase UltraTM, LipexTM and LipocleanTM (Novozymes A/S). Also LipomaxTM a lyophilized lipase-preparation from pseudomonas alcaligenes (originally from Gist-brocades, more recently from the Genencor division of Danisco). In addition to, or as an alternative to, lipase one or more other enzymes may be present. However, lipase is particularly preferred. Lipase is preferably included in an amount of from 0.001 to 0.3 wt% active enzyme.
- the presence of relatively high levels of calcium in poorly built unbuilt wash liquors has a beneficial effect on the turnover of certain enzymes, particularly lipase enzymes and preferably lipases from Humicola.
- the preferred lipases include first wash lipases which comprise a polypeptide having an amino acid sequence which has at least 90% sequence identity with the wild-type lipase derived from Humicola lanuginosa strain DSM 4109 and compared to said wild-type lipase, comprises a substitution of an electrically neutral or negatively charged amino acid within 15 A of E1 or Q249 with a positively charged amino acid; and may further comprise:
- (III) meets the following limitations: i. comprises a negatively charged amino acid in position E210 of said wild-type lipase;
- ii. comprises a negatively charged amino acid in the region
- iii. comprises a neutral or negatively charged amino acid at a position corresponding to N94 of said wild-type lipase; and/or iv. has a negative charge or neutral charge in the region corresponding to positions 90-101 of said wild-type lipase;
- Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable 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 disclosed in US 4,435,307, US 5,648,263, US 5,691 , 178, US 5,776,757, WO 89/09259, WO 96/029397, and WO 98/012307.
- Commercially available cellulases include CelluzymeTM, CarezymeTM, EndolaseTM, RenozymeTM (Novozymes A/S), ClazinaseTM and Puradax HATM (Genencor International Inc.), and KAC-500(B)TM (Kao Corporation).
- Phospholipase may be classified as EC 3.1 .1 .4 and/or EC 3.1 .1 .32. As used herein, the term phospholipase is an enzyme that has activity towards
- Phospholipids such as lecithin or phosphatidylcholine, consist of glycerol esterified with two fatty acids in an outer (sn-1 ) and the middle (sn-2) positions and esterified with phosphoric acid in the third position; the phosphoric acid, in turn, may be esterified to an amino-alcohol.
- Phospholipases are enzymes that participate in the hydrolysis of phospholipids. Several types of phospholipase activity can be distinguished, including phospholipases Ai and A 2 which hydrolyze one fatty acyl group (in the sn-1 and sn-2 position, respectively) to form
- lysophospholipid lysophospholipid
- lysophospholipase or phospholipase B which can hydrolyze the remaining fatty acyl group in lysophospholipid.
- Phospholipase C and phospholipase D release diacyl glycerol or
- proteases include those of animal, vegetable or microbial origin. Microbial origin is preferred. Chemically modified or protein engineered mutants are included.
- the protease may be a serine protease or a metallo protease, preferably an alkaline microbial protease or a trypsin-like protease.
- Preferred commercially available protease enzymes include AlcalaseTM, SavinaseTM, PrimaseTM,
- DuralaseTM DyrazymTM, EsperaseTM, EverlaseTM, PolarzymeTM, and KannaseTM, (Novozymes A/S), MaxataseTM, MaxacalTM, MaxapemTM, ProperaseTM,
- Cutinase is classified in EC 3.1 .1 .74.
- the cutinase may be of any origin.
- cutinases are of microbial origin, in particular of bacterial, of fungal or of yeast origin.
- amylases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain of B. licheniformis, described in more detail in GB 1 ,296,839, or the Bacillus sp. strains disclosed in WO 95/026397 or WO 00/060060. Commercially available amylases are DuramylTM, TermamylTM, Termamyl UltraTM, NatalaseTM,
- Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g. from C. cinereus, and variants thereof as those described in WO 93/24618, WO 95/10602, and WO 98/15257. Commercially available peroxidases include GuardzymeTM and
- NovozymTM 51004 Novozymes A/S.
- Pectate lyases also called polygalacturonate lyases
- pectate lyases include pectate lyases that have been cloned from different bacterial genera such as Erwinia, Pseudomonas, Klebsiella and Xanthomonas, as well as from Bacillus subtilis (Nasser et al. (1993) FEBS Letts. 335:319-326) and Bacillus sp. YA-14 (Kim et al. (1994) Biosci. Biotech. Biochem. 58:947-949).
- the pectate lyase preferably comprises the pectate lyase disclosed in Heffron et al., (1995) Mol. Plant-Microbe Interact. 8: 331 -334 and Henrissat et al., (1995) Plant Physiol. 107: 963-976.
- pectate lyases are disclosed in WO 99/27083 and WO 99/27084.
- Other specifically contemplated pectate lyases (derived from Bacillus licheniformis) are disclosed in US patent no. 6,284,524.
- Specifically contemplated pectate lyase variants are disclosed in WO 02/006442, especially the variants disclosed in the Examples in WO 02/006442.
- alkaline pectate lyases examples include BIOPREPTM and SCOURZYMETM L from Novozymes A/S, Denmark. Mannanases
- mannanases examples include mannanases of bacterial and fungal origin.
- the mannanase may be derived from a strain of the filamentous fungus genus Aspergillus, preferably Aspergillus niger or Aspergillus aculeatus (WO 94/25576).
- WO 93/24622 discloses a mannanase isolated from
- Trichoderma reseei. Mannanases have also been isolated from several bacteria, including Bacillus organisms.
- Talbot et al., Appl. Environ. Microbiol., Vol.56, No. 1 1 , pp. 3505-3510 (1990) describes a beta-mannanase derived from Bacillus stearothermophilus.
- Mendoza et al., World J. Microbiol. Biotech., Vol. 10, No. 5, pp. 551 -555 (1994) describes a beta-mannanase derived from Bacillus subtilis.
- JP-A-03047076 discloses a beta-mannanase derived from Bacillus sp.
- JP-A-63056289 describes the production of an alkaline, thermostable beta- mannanase.
- JP-A-63036775 relates to the Bacillus microorganism FERM P-8856 which produces beta-mannanase and beta-mannosidase.
- JP-A-08051975 discloses alkaline beta-mannanases from alkalophilic Bacillus sp. AM-001 .
- a purified mannanase from Bacillus amyloliquefaciens is disclosed in WO 97/1 1 164.
- WO 91/18974 describes a hemicellulase such as a glucanase, xylanase or mannanase active.
- mannanases derived from Bacillus agaradhaerens, Bacillus licheniformis, Bacillus halodurans, Bacillus clausii, Bacillus sp., and Humicola insolens disclosed in WO 99/64619. Especially contemplated are the Bacillus sp. mannanases used in the Examples of WO 99/64619.
- mannanases examples include MannawayTM available from Novozymes A/S Denmark.
- Any enzyme present in the 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, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708.
- 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
- a preferred polymer is modified polyethylene imine PEI 600(20EO).
- Soil release polymers, especially polyester soil release polymers may also be used.
- the amount of polymers, when used, is preferably greater than 2 wt%, more preferably greater than 5 wt%, even greater than 10 wt%.
- Anti-redeposition polymers such as sodium carboxymethyl cellulose may additionally be used.
- water-soluble sequestrants are preferred. When included they are advantageously used at levels of from 0.3 to 3 wt%.
- Water-soluble builders may be included in the compositions of the invention.
- compositions are aqueous but the need to keep high levels of surfactants and other water-soluble ingredients in solution may
- hydrotropes are propylene glycol, glycerol, glycerine and mixtures thereof.
- Hydrotropes when used, are preferably present at levels of from 1 to 20 wt%. pH adjustment
- the composition may further comprise MEA and / or TEA and/ or sodium hydroxide for alkalinity. As mentioned above it may comprise citric acid. Levels of citric acid preferably range from 0.5 to 5 wt% Optical brighteners
- Soluble fabric whitening agents may be included.
- the use of the external structurant also makes it possible to use insoluble OBA but this is not preferred if it is desired that the liquid is clear (i.e. that it is possible to see through it).
- Proxel is a preferred preservative for the liquid compositions. Potassium Sorbate is also preferred.
- Figure 1 is a graph showing rheology for pulped CF at various inclusion levels
- Figure 2 is a graph showing rheology for pulped CF and HCO with Lipex (24 hours);
- Figure 3 is a graph showing rheology for pulped CF with cellulases
- Figure 4 is a graph showing rheology for MFC with cellulase.
- Figure 5 is a graph showing rheology for pulped CF structured liquids with polymers or sequestrant.
- CPF pulped citrus fibre
- CF is Herbacel AQ plus citrus fibre, a powdered citrus peel fruit
- MFC Microfibrous cellulose ex CP Kelco.
- HCO Thixin R hydrogenated castor oil ex Elementis.
- LAS is sodium linear alkyl benzene sulphonate anionic surfactant.
- LAS acid is acid form of LAS.
- SLES is Sodium Lauryi Ether Sulphate with average of 3EO.
- SLES(1 EO) is Sodium Lauryi (C12-14) Ether Sulphate with average 1 EO.
- PAS is Sodium Primary Alcohol (alkyl) sulphate (C12-14).
- Nl is ethoxylated alcohol nonionic surfactant.
- Nl 7EO is alcohol ethoxylate 7EO (Neodol 25-7 ex Shell Chemicals).
- 91 -8 is C9-C1 1 Neodol alcohol nonionic with average 8 moles
- Empigen® BB is an alkyl betaine ex Huntsman.
- CAPB is cocamidopropyl betaine.
- Prifac® 5908 is saturated lauric fatty acid ex Croda.
- Prifac® 7907 is distilled topped coconut fatty acid ex Croda.
- MPG is mono propylene glycol.
- PPG is propylene glycol (hydrotrope).
- TEA Triethanolamine
- ME A is Monoethanolamine.
- NaOH is 47% sodium hydroxide
- Dequest® 2066 is Diethylenetriamine penta(methylene phosphonic acid (or
- Dequest® 2010 is HEDP (1 -Hydroxyethylidene -1 , 1 ,-diphosphonic acid).
- Lipex® is Lipex 100L ex Novozymes
- Carezyme® is a cellulase ex Novozymes
- Endolase® is an endocellulase promoted for its whitening benefits ex
- Stainzyme 12L is an amylase formulated for liquids ex Novozymes
- Mannaway is a mannanase ex Novozymes
- EPEI is ethoxylated polyethylene imine cleaning polymer PEI 600 20EO ex BASF.
- SRP is Texcare SRN170 polyester soil release polymer ex Clariant.
- Acusol® 190 is water soluble polycarboxylate polymeric calcium dispersant ex
- Dowanol DPnB is dipropylene glycol n-butyl ether ex Dow.
- the powdered Citrus fibre powder was added directly to the prepared detergent liquid and an attempt was made to disperse it using a Silverson high shear mixer. No structuring was formed. The particles of powdered material added did not swell and simply sank to the bottom of the liquid when shear was removed.
- Premixes of 1 to 2.5 wt% pulped citrus fibre in water were prepared using high intensity mixing. We used a Silverson mixer located in a recycle loop around a batch vessel. The premixes formed were all homogeneous.
- Example 3 As an alternative to example 1 we used a high pressure homogeniser was used to supply the shear. Like example 1 , a homogeneous well dispersed structured premix was obtained. The maximum premix concentration is limited by the maximum viscosity that the equipment is capable of handling. Example 3
- the pulped citrus fibre premix made in Example 1 or Example 2 (1 or 2 wt% used) was added to a detergent liquid comprising 40 wt% Active detergent (LAS, SLES, Nl 1 :1 :2) and 15 wt% propylene glycol hydrotrope, the balance being water.
- LAS Active detergent
- SLES SLES
- propylene glycol hydrotrope the balance being water.
- Two orders of addition were successfully used: (3a) Free water, pulped citrus fibre premix then a premixed surfactant concentrate (-60% AD), or
- Part A Structurant pre-mix
- a structurant pre-mix was prepared using 2% Herbacel plus AQ (type N) citrus fibre powder, 97.9% tap water and 0.1 % Potassium Sorbate preservative.
- the pre-mix was prepared using a pilot plant scale Gaulin high pressure Homogeniser operating at 350 bar.
- the resulting pulped citrus fibre (PCF) pre-mix was readily handleable and pumpable.
- Part B Concentrated base detergent liquid
- a concentrated base detergent liquid B having the composition shown in Table 1 (except for the 2 wt% PCF premix and the perfume) was prepared using a 50 litre capacity pilot plant vessel equipped with a mixing element of the 'Flexible Agitator System (FAS)' geometry. 12.5% of the water had been removed from the formulation to allow for post dosing of the 2% PCF pre-mix: Part A. The concentrated mixture was allowed to de-aerate for > 1 hr.
- Table 1 Composition of Structured liquid of Example 4
- the concentrated base detergent mixture B was circulated via a 150/250
- Silverson high shear mill by means of a recycle loop to ensure all lines were fully primed and purged of air. Flow rate 1450 l/hr (single pass residence time in mill 0.1 seconds). The Silverson mill was turned on at 6250 rpm (9063 w/kg) to simulate large scale operating conditions. Then the structurant Pre-mix A was dosed into the main recirculation loop close to the high shear mixer inlet to minimise interaction between the streams prior to intimate dispersion. The perfume was then added using low shear mixing. The pulped citrus fibre structured liquid was then sampled and its rheology measured. Again, after 1 week storage at ambient temperature, the rheology was remeasured and the samples were visually assessed to see if there was either top clear layer separation or bottom clear layer separation.
- Example 4 was repeated, but the amount of PCF in the premix A was varied so that when it was added to concentrated base detergent mix B the final level of PCF in the detergent liquid was only 0.12%.
- the rheology of this liquid was not sufficient for suspending duty. See Figure 1 , which shows that at 0.12% PCF there was insufficient formulation stability and viscosity build (low critical stress). It is thought that this was due to insufficient PCF being present to establish a stable network with which to provide suspending duty.
- the process was repeated to form a liquid with 0.16 wt% PCF external structurant. After storage for a week, this liquid was showing signs of top clear layer separation. This was at the margins of acceptability.
- Example 4 Lipase could be added to Example 4 and Example 5 liquids structured with PCF without loss of structuring.
- Example 6 and Comparative example B Lipase resistance of structurant
- Comparative example B representing the prior art, was structured with 0.25 wt% HCO, crystallised from a hot melt, in place of the PCF in table 2.
- the 3% "hole” was filled with either Lipex® 100L or a 30 parts sorbitol/64parts demin. water, i.e. the solvent/stabiliser for commercial samples of Lipex. Rheology was measured at 25°C using an Anton Paar ASC rheometer.
- Figure 2 shows the rheology data after 24 hours.
- Comparative example B shows that when using Lipex in an HCO structured liquid there is complete loss of structuring within 24 hours at ambient temperature. In contrast, Lipex has no effect on the otherwise identical liquid structured with PCF, as in example 6.
- Example 7 and Comparative example C Cellulase resistance of structurant Cellulase was not tested on HCO, as it was not expected that cellulase would have any effect on such an oily material. For example 7 two types of cellulase were added to a liquid detergent structured with 0.25% PCF, as described in Example 4.
- Figure 3 shows the effect of adding each type of cellulase at 1 %. It can be seen that for both Carezyme and Endolase there is no significant effect on the rheoiogy after 2 weeks storage at 37°C.
- Figure 4 shows the corresponding result for Comparative example C, which is a detergent liquid structured by dispersing a premix of 0.1 wt% MFC using a process analogous to Example 4 above. It can be seen that for the addition of cellulase (Carezyme 1 %) @ 37 °C; there is an initial drop in plateau viscosity which may be caused by the cellulase attacking part of the structurant, but not causing it to fail as catastrophically as the HCO formulated with lipase. It is clear that this causes a reduction in the range between the resting viscosity (no shear) and the pouring viscosity (high shear); this range is already lower than that obtained with the PCF structured example 6.
- Table 3 shows a range of heavy duty laundry detergent liquids that may be structured with pulped citrus fibre. Examples 8, 9, 10 and 1 1 are so called 3 times concentrated laundry liquid suitable for use at approx 35 ml dose to a standard European front loading automatic washing machine. Examples 12, 13, and 14 are compositions suitable for use at a 20 ml dose to the same type of machine. Table 3
- Table 4 shows the rheology obtained by variants of Examples 12 and 14.
- the composition examples 15 to 18 were tested as described above to obtain the rheology profiles shown in Figure 5; without yet adding in the enzyme. Based on the findings for the lack of effect of Lipase on similar compositions the addition of the Lipase would not affect the Rheology. Lipase and cellulase can be added without affecting the stability of the rheological profile over time.
- These examples show that the rheology is usefully obtained with the inclusion of various levels of cleaning and soil release polymers, also the addition of high levels of polymer and the addition of relatively high levels of sequestrant. All of these ingredients might have had a detrimental effect on the rheology.
- liquids in examples 19 to 26 can simply be reformulated to contain Lipase and/ or cellulase at levels of from 0.0001 to 5 wt%, preferably from 0.001 to 0.3 wt%.
- the structuring rheology is not affected by such enzyme inclusion.
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IN2014MN02034A (de) * | 2012-04-23 | 2015-10-09 | Unilever Plc | |
EP2841550B1 (de) * | 2012-04-23 | 2016-01-20 | Unilever Plc. | Extern strukturierte wässrige isotrope flüssigwaschmittelzusammensetzungen |
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- 2011-10-07 EP EP11767995.1A patent/EP2630224B1/de active Active
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EP2630224B1 (de) | 2016-06-29 |
ES2593728T3 (es) | 2016-12-12 |
CL2013001087A1 (es) | 2014-02-21 |
CN103180423B (zh) | 2015-08-12 |
IN2013MN00618A (de) | 2015-06-12 |
CN103180423A (zh) | 2013-06-26 |
WO2012052306A1 (en) | 2012-04-26 |
BR112013009456B1 (pt) | 2021-11-30 |
ZA201302069B (en) | 2014-05-28 |
BR112013009456A2 (pt) | 2021-03-09 |
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