EP2242832B1 - Composition détergente liquide comprenant une structure externe constituée d'un réseau de cellulose bactérienne - Google Patents

Composition détergente liquide comprenant une structure externe constituée d'un réseau de cellulose bactérienne Download PDF

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Publication number
EP2242832B1
EP2242832B1 EP09709696.0A EP09709696A EP2242832B1 EP 2242832 B1 EP2242832 B1 EP 2242832B1 EP 09709696 A EP09709696 A EP 09709696A EP 2242832 B1 EP2242832 B1 EP 2242832B1
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Prior art keywords
detergent composition
liquid detergent
bacterial cellulose
surfactant
liquid
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German (de)
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EP2242832A1 (fr
Inventor
Marco Caggioni
Rafael Ortiz
Freddy Arthur Barnabas
Raul Victorino Nunes
Janine A. Flood
Francesc Corominas
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Procter and Gamble Co
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Procter and Gamble Co
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    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin

Definitions

  • Conventional approaches for providing distinctive structural and aesthetic properties to liquid compositions include: the addition of specific structuring agents including both internal and external structuring agents.
  • Examples of known internal structuring agents include: surfactants, electrolytes (which can promote the formation of worm like micellar self assembly structures).
  • Known external structuring agents include polymers or gums, many of which are known to swell or expand when hydrated to form random dispersion of independent microgel particles. Examples of polymers and gums include: gellan gum, pectine, alginate, arabinogalactan, caageenan, xanthum gum, guar gum, rhamsan gum, furcellaran gum, carboxymethylcellulose and cellulose. See e.g. U.S. Pat. No.
  • cellulose i.e. bacterial celluloses.
  • Conventional uses of bacterial celluloses include improving rheological properties for hydraulic fracturing fluids used for hydraulic fracturing of geological formations; addition to well bore drilling muds; and as a food ingredient. See e.g. U.S. Patent Nos. 5,350,528 , 5,362,713 , and 5,366,750 .
  • the bacterial cellulose is typically cultured using a bacterial strain of Acetobacter aceti var. xylinum and dried using spray drying or freeze drying techniques.
  • US5998349A (Rhodia Chimie) published on 7 December 1999 , relates to a descaling formulation comprising cellulose microfibrils, in which at least 80% of the cells have primary walls and not more than 20% of the cells have secondary walls, with a degree of crystallinity of not more than 50%.
  • WO89/08148 A (BIO fill productos biotecnologicos S.A.) published on 8 September 1989, relates to a process for preparing aqueous suspensions or slurries of cellulose microfibrils obtained from bacterial fermentation.
  • WO03/062361 A1 (Henkel) published on 31 July 2003 , relates to a conditioning agent for protecting textiles, in addition to the use thereof in a washing method or textile drying method.
  • WO2008/076753 A1 (CP Kelco) published on 26 June 2008 , relates to surfactant systems, using microfibrous cellulose to suspend particulates therein, and methods of making these systems.
  • Two structuring properties which are desired in liquid detergent compositions include bead and/or particle suspension capabilities and shear thinning capabilities.
  • the addition of certain external structuring agents into liquid detergent compositions may provide certain shear thinning benefits, the ability to provide shear thinning capabilities alone is insufficient to determine whether the liquid detergent composition is capable of suspending bead particles over time.
  • an external structuring agent which provides both shear thinning benefits and bead suspension capabilities.
  • these structuring benefits are desired at as low a level of external structurant as possible for cost and formulation concerns. For example, excessive amounts of external structuring agent may provide the particle suspension capability but result in the liquid composition becoming overly viscous and non-pourable. Further, too much external structuring agent may also result in compositional opacity and cloudiness which can be undesirable.
  • the present invention relates a liquid detergent composition in accordance with the claims.
  • Another aspect of the present invention relates to a process of making a liquid detergent composition
  • a process of making a liquid detergent composition comprising the steps of: (a) providing a feed comprising from 0.005 % to 1.0%, preferably less than 0.125 %, preferably less than 0.05 %, even more preferably 0.006 % to 0.2 % by weight of a liquid detergent composition of an external structuring system comprising a bacterial cellulose network with water; (b) activating said feed in a mixing chamber to energy density in excess of 1.0 x 10 5 J/m 3 to form a bacterial cellulose network; and (c) providing a surfactant system at a level of from 0.01 % to 70 %, preferably from 1 % to 50 %, preferably from 3% to 20%, by weight of said liquid detergent composition, said surfactant system comprising: from 5% to 60% by weight of said liquid detergent composition of an anionic surfactant; from 0.1% to 25% by weight of said liquid detergent composition of an amine oxide; and further compris
  • a liquid detergent composition comprising a liquid matrix comprising: from 0.005 % to 1.0 % by weight of said liquid detergent composition of an external structuring system comprising a bacterial cellulose network; from 30% to 75% by weight of said liquid detergent composition of water; from 0.01 % to 70 % by weight of said liquid detergent composition of a surfactant system comprising: a. from 5% to 60% of an anionic surfactant by weight of sthe liquid detergent composition; b. from 0.1% to 0.25% of an amine oxide by weight of said liquid detergent composition; and c.
  • a nonionic surfactant further comprising a nonionic surfactant; a cationic surfactant; an ampholytic surfactant; a zwitterionic surfactant; or mixtures thereof; from 0.01 % to 5 % by weight of said liquid detergent composition of a plurality of suspension particles having a particle size from 100 nanometers to 8 mm, and an average particle density of from 700 kg/m 3 to 4,260 kg/m 3 at 25 °C, wherein the plurality of suspension particles to liquid matrix have density difference of from 1 kg/m 3 to 200 kg/m 3 at 25 °C, wherein said liquid matrix has a yield stress of from 0.003 Pa to 5.0 Pa at 25 °C; and wherein said surfactant system has a ratio of 2.5 : 1 to 18 : 1 of anionic surfactant to said amine oxide, provides sufficient particle suspending and shear thinning capabilities.
  • the bacterial cellulose network is formed by "activating" the bacterial cellulose and a solvent such as water under intense high shear processing conditions.
  • a liquid detergent composition comprising a bacterial cellulose network activated in this manner is capable of providing the desired structuring capabilities at relatively low levels while avoiding one or more of the problems encountered with conventional external structuring agents.
  • essentially free of a component means that no amount of that component is deliberately incorporated into the composition.
  • intense high shear processing conditions means a mixing step sufficient to activate the bacterial cellulose and provide the requisite yield stress of the present invention.
  • liquid matrix refers to the liquid components of the present liquid detergent composition, where measurements made on the liquid matrix are performed in the absence of any suspension particles.
  • suspension beads and/or particles includes solid beads, capsules either empty or containing functional or non-functional ingredients therein, microcapsules, particles, and fragments thereof.
  • “Plurality of suspension particles” includes both suspension beads and particles which can form from suspension beads which have broken apart.
  • a “structurant” is any material which is added to the composition to provide rheological and structuring benefits, for example as measured by yield stress.
  • “external structurant” means a material which has as its primary function that of providing rheological alteration to the liquid matrix. Generally, therefore, an external structurant will not, in and of itself, provide any significant cleaning benefits or any significant ingredient solubilization benefits. An external structurant is thus distinct from an internal structurant which may also alter matrix rheology but which has been incorporated into the liquid composition for some additional or alternative primary purpose.
  • the liquid detergent composition of the present invention comprises a liquid matrix comprising from 0.005 % to 1.0 % of an external structuring system, alternatively less than 0.125 %, alternatively less than 0.05 %, alternatively less than 0.01 % of said external structuring system, alternatively at least 0.01%, alternatively at least 0.05%, by weight of liquid detergent composition.
  • the external structuring system for use in with the present invention comprises a bacterial cellulose network which is formed from individual bacterial cellulose fibers which are activated in the presence of water.
  • the external structuring system consists essentially of a bacterial cellulose network.
  • the external structuring system of the present invention comprises a bacterial cellulose network at a level of up to 100%, alternatively up to 99 %, alternatively up to 95 %, alternatively up to 80 %, alternatively up to 70 % by weight of said external structuring system.
  • bacterial cellulose is intended to encompass any type of cellulose produced via fermentation of a bacteria of the genus Acetobacter and includes materials referred popularly as microfibrillated cellulose, and reticulated bacterial cellulose.
  • the bacterial cellulose network is formed by processing of a mixture of the bacterial cellulose in a hydrophilic solvent, such as water, polyols (e.g., ethylene glycol, glycerin, polyethylene glycol), or mixtures thereof.
  • a hydrophilic solvent such as water, polyols (e.g., ethylene glycol, glycerin, polyethylene glycol), or mixtures thereof.
  • This processing is called “activation” and comprises, generally, high pressure homogenization and/or high shear mixing. It has importantly been found that activating the bacterial cellulose under sufficiently intense processing conditions provides for increased yield stress at given levels of bacterial cellulose network. Yield stress, as defined below, is a measure of the force required to initiate flow in a gel-like system. It is believed that yield stress is indicative of the suspension ability of the liquid composition, as well as the ability to remain in situ after application to a vertical surface.
  • Activation is a process in which the 3-dimensional structure of the bacterial cellulose is modified such that the cellulose imparts functionality to the base solvent or solvent mixture in which the activation occurs, or to a composition to which the activated cellulose is added.
  • Functionality includes providing such properties as shear-thickening, imparting yield stress - suspension properties, freeze-thaw and heat stability.
  • the processing that is followed during the activation process does significantly more than to just disperse the cellulose in base solvent.
  • Such intense processing "teases apart" the cellulose fibers to expand the cellulose fibers.
  • the activation of the bacterial cellulose expands the cellulose portion to create a bacterial cellulose network, which is a reticulated network of highly intermeshed fibers with a very high surface area.
  • the activated reticulated bacterial cellulose possesses an extremely high surface area that is thought to be at least 200-fold higher than conventional microcrystalline cellulose (i.e., cellulose provided by plant sources).
  • the bacterial cellulose utilized herein may be of any type associated with the fermentation product of Acetobacter genus microorganisms, and was previously available, one example, from CPKelco U.S. is CELLULON®. Such aerobic cultured products are characterized by a highly reticulated, branching interconnected network of fibers that are insoluble in water.
  • the preparation of such bacterial cellulose products are well known and typically involve a method for producing reticulated bacterial cellulose aerobically, under agitated culture conditions, using a bacterial strain of Acetobacter aceti var. xylinum. Use of agitated culture conditions results in sustained production, over an average of 70 hours, of at least 0.1 g/liter per hour of the desired cellulose.
  • Dry cake reticulated cellulose containing approximately 80-85% water, can be produced using the methods and conditions disclosed in the above-mentioned patents.
  • Dry reticulated bacterial cellulose can be produced using drying techniques, such as spray-drying or freeze-drying, that are well known. See U.S. Pat. No. 5,079,162 and 5,144,021 .
  • Acetobacter is characteristically a gram-negative, rod shaped bacterium 0.6-0.8 microns by 1.0-4 microns. It is a strictly aerobic organism; that is, metabolism is respiratory, not fermentative. This bacterium is further distinguished by the ability to produce multiple poly ⁇ -1,4-glucan chains, chemically identical to cellulose.
  • the microcellulose chains, or microfibers, of reticulated bacterial cellulose are synthesized at the bacterial surface, at sites external to the cell membrane. These microfibers have a cross sectional dimensions of 1.6 nm to 3.2 nm by 5.8 nm to 133 nm.
  • the bacterial cellulose network has a widest cross sectional micro fiber width of from 1.6 nm to 200 nm, alternatively less than 133 nm, alternatively less than 100 nm, alternatively less than 5.8 nm. Additionally, the bacterial cellulose network has an average microfiber length of at least 100 nm, alternatively from 100 to 1500 nm. In one embodiment, the bacterial cellulose network has a microfiber aspect ratio, meaning the average microfiber length divided by the widest cross sectional microfiber width, of from 10:1 to 1000:1, alternatively from 100:1 to 400:1, alternatively from 200:1 to 300:1.
  • the presence of the bacterial cellulose network can be detected by a STEM micrograph imaging.
  • a liquid detergent composition sample is obtained.
  • a 1500 mesh copper TEM grid is placed on filter paper and 15 drops of the sample are applied to the TEM grid.
  • the TEM grid is transferred to fresh filter paper and rinsed with 15 drops of deionized water.
  • the TEM grid is then imaged in a S-5200 STEM micrograph instrument to observe for a fibrous network.
  • analytic techniques can be used to detect the presence of the bacterial cellulose network such as Atomic Force Microscopy using the same TEM grid and deposition and rinsing steps as disclosed above.
  • An Atomic Force Microscopy 3D representation can be obtained showing the fiber dimensions as well as degree of networking.
  • the bacterial cellulose network is formed by activating the bacterial cellulose under intense high shear processing conditions. It has importantly been found that the use of intense high shear processing conditions provides the bacterial cellulose network with enhanced structuring capabilities. By using intense processing conditions, the bacterial cellulose network can provide the desired structuring benefits at lower levels and without a need for costly chemical and physical modifications.
  • the step of activating said bacterial cellulose under intense high shear processing conditions comprises: activating the bacterial cellulose and a solvent, e.g. water, at an energy density above 1.0 x 10 6 J/m 3 , alternatively above than 2.0 x 10 6 J/m 3 .
  • the step of activation is performed with an energy density from 2.0 x 10 6 J/m 3 to 5.0 x 10 7 J/m 3 , alternatively from 5.0 x 10 6 J/m 3 to 2.0 x 10 7 J/m 3 , alternatively from 8.0 x 10 6 J/m 3 to 1.0 x 10 7 J/m 3 .
  • the level of bacterial cellulose is from 0.005 wt% to 0.05 wt%, alternatively below 0.03 wt%, alternatively below 0.01 wt%.
  • processing techniques capable of providing this amount of energy density include conventional high shear mixers, static mixers, prop and in-tank mixers, rotor-stator mixers, and Gaulin homogenizers, and SONOLATOR® from Sonic Corp of CT.
  • the step of activating the bacterial cellulose comprising is performed with a high pressure homogenizer comprising a mixing chamber and a vibrating blade, wherein the feed is forced into the mixing chamber through an orifice.
  • the feed which is under pressure accelerates as it passes through the orifice and comes into contact with the vibrating blade.
  • the step of activating said bacterial cellulose under intense high shear processing conditions involves causing hydrodynamic cavitation is achieved using a SONOLATOR®.
  • a SONOLATOR® a SONOLATOR® that the mixture within the mixing chamber undergoes hydrodynamic cavitation within the mixing chamber causing the bacterial cellulose to form a bacterial cellulose network with sufficient degree of interconnectivity to provide enhanced shear thinning capabilities.
  • One method to enhance the ability of the bacterial cellulose to form the bacterial cellulose network is to activate the bacterial cellulose with an aqueous solution as a premix under conventional mixing conditions prior to be placed in contact with a second stream.
  • a second stream can be provided comprising the other desired components, such as the surfactants, perfumes, particles, and adjunct ingredients.
  • the bacterial cellulose and an aqueous solution are combined as a premix.
  • This premix can be subjected to intense high shear conditions but need not be.
  • Another method to enhance the ability of the bacterial cellulose to form the bacterial cellulose network is to contact the bacterial cellulose in dry or powder form directly into a feed stream of the liquid actives into the mixing chamber of an ultrasonic homogenizer or in line mixer.
  • the powder can be added immediately before the feed(s) enter the mixing chamber or can be added as a separate feed from the active feed stream.
  • a single pass system can be achieved which allows for processing simplicity and cost/space savings.
  • the external structuring system further comprises a bacterial cellulose which is at least partially coated with a polymeric thickener.
  • This at least partially coated bacterial cellulose can be prepared in accordance with the methods disclosed in U.S. Pat. Publ. No. 2007/0027108 to Yang et al. at 11 8 - 19.
  • the bacterial cellulose is subjected to mixing with a polymeric thickener to at least partially coat the bacterial cellulose fibers and bundles. It is believed that the commingling of the bacterial cellulose and the polymeric thickener allows for the desired generation of a polymeric thickener coating on at least a portion of the bacterial cellulose fibers and/or bundles.
  • the method of producing said at least partially coated bacterial cellulose comprises a proportion of bacterial cellulose to polymeric thickener comprises from 0.1 % to 5 % of the bacterial cellulose, alternatively from 0.5 % to 3.0 %, by weight of the added polymeric thickener; and from 10 % to 900 % of the polymeric thickener by weight of the bacterial cellulose.
  • the polymeric thickener comprises a hydrocolloid, at least on charged cellulose ether, at least one polymeric gum, and mixtures thereof.
  • One suitable hydrocolloid includes carboxymethylcellulose ("CMC").
  • CMC carboxymethylcellulose
  • Suitable polymeric gums comprises xanthan products, pectin, alginates, gellan gum, welan gum, diutan gum, rhamsan gum, kargeenan, guar gum, agar, gum Arabic, gum ghatti, karay gum, gum tragacanth, tamarind gum, locust bean gum, and mixtures there.: See U.S. Pat. Publ. No. 2007/0027108 at 6 and 16.
  • the bacterial cellulose undergoes no further modified either chemically or physically aside from the activation and/or the polymeric thickener coating.
  • the bacterial cellulose is free of a chemical modification comprising esterification or etherification by the addition of hydrophobic groups onto the fibers, meaning that the bacterial cellulose fibers are not modified to be surface active, wherein surface active means the ingredient lowers the surface tension of the medium in which it is dissolved.
  • the bacterial cellulose is free of any physical modification including coating the fibers with hydrophobic materials. It has importantly been found that by activating the bacterial cellulose network in accordance with the invention herein, the fibers do not need to be modified as mentioned in WO Publication No. 2007/068344 to Cai et al.
  • the external structuring system further comprises additional structuring agents such as non-polymeric crystalline hydroxyl-functional materials, polymeric structuring agents, and mixtures thereof.
  • the external structuring system further comprises a carboxymethylcellulose, a modified carboxymethylcellulose, and mixtures thereof; and optionally, a polymeric thickener selected from xanthum products, pectin, alginates, gellan gum, welan gum, diutan gum, rhamsan gum, carrageenan, guar gum, agar, gum arabic, gum ghatti, karaya gum, gum tragacanth, tamarind gum, locust bean gum, and mixtures thereof.
  • One suitable additional structuring agent comprises a non-polymeric (except for conventional alkyoxlation), crystalline hydroxyl-functional materials, which forms thread-like structuring systems throughout the liquid matrix when they are crystallized within the matrix in situ.
  • Such materials can be generally characterized as crystalline, hydroxyl-containing fatty acids, fatty esters or fatty waxes. See e.g. U.S. Patent No. 7,169,741 at col. 9, line 61 to col. 11, line 4, and 6,080,708 and in WO Publ. No. 2002/0040627 .
  • organic structuring agents besides the non-polymeric, crystalline, hydroxyl-containing structuring agents described hereinbefore, may be utilized in the liquid detergent compositions herein.
  • Polymeric materials which will provide shear-thinning capabilities to the liquid matrix may also be employed.
  • Suitable polymeric structuring agents include those of the polyacrylate, polysaccharide or polysaccharide derivative type.
  • Polysaccharide derivatives typically used as structuring agents comprise polymeric gum materials. Such gums include pectine, alginate, arabinogalactan (gum Arabic), carrageenan, gellan gum, xanthan gum and guar gum.
  • Gellan gum is a heteropolysaccharide prepared by fermentation of Pseudomonaselodea ATCC 31461 and is commercially marketed by CP Kelco U.S., Inc. under the KELCOGEL tradename. Processes for preparing gellan gum are described in U.S. Patent Nos. 4,326,052 ; 4,326,053 ; 4,377,636 and 4,385,123 .
  • the external structuring system is free of essentially free of any additional structuring agent known in the art such as those listed herein, for example: free or essentially free of non-polymeric crystalline hydroxyl-functional materials; free or essentially free of polymeric structuring agents including polymeric gums, pectine, alginate, arabinogalactan (gum Arabic), carrageenan, gellan gum, xanthan gum and guar gum. It has importantly been found that the external structuring system of the present invention provides sufficient rheological benefits, such as bead suspension and shear thinning capabilities, without reliance on structuring ingredients beyond the bacterial cellulose network described herein.
  • the liquid matrix of the liquid detergent composition of the present invention has a yield stress of from 0.003 Pa to 5.0 Pa, alternatively from 0.01 Pa to 1.0 Pa, alternatively from 0.05 Pa to 0.2 Pa, as defined by the Yield Stress Test, defined herein.
  • the yield stress is measured from only the liquid matrix. This is important because the presence of suspended particles can vary the yield stress measurements. It has importantly been found that higher energy density used during activation correlates to higher yield stress.
  • a liquid matrix having from 0.006 % to 0.2 % bacterial cellulose network provides a yield stress is from 0.005 Pa to 1 Pa, and from 0.6 % to 1% bacterial cellulose network provides a yield stress from 2.85 Pa to 5 Pa.
  • the ability of a composition to suspend particles is not a direct correlation to the shear thinning capabilities of the composition. Rather, the ability of a composition to suspend particles is measured by the yield stress. For example, two compositions having the shear thinning capabilities within a given range of shear rate can have different yield stress values. It is believed that in order to stabilize the suspension particles in the liquid matrix of the liquid detergent composition, the stress applied by one single bead or particle should not exceed the yield stress of the liquid matrix. If this condition is fulfilled the liquid detergent composition will be less susceptible to, alternatively able to prevent, sedimentation or creaming and floating or settling of the suspension particles and/or particles under static conditions.
  • a dynamic yield stress test is conducted.
  • the dynamic yield stress is conducted as follows: a sample is placed in an AR G2 Stress Controlled Rheometer equipped with double concentric cylinder geometry from TA Instruments ("Rheometer") and subjected to a range of shear from 100 s -1 to 0.001 s -1 . Fifty measurement, spaced apart evenly in a logarithmic scale (as determined by the Rheometer) are performed at varying shear rates within the range stated, and the steady state viscosity and applied stress are measured and recorded for each imposed level of shear rate. The applied stress vs. imposed shear rate data are plotted on a chart and fitted to a modified Hershel-Bulkley model to account for the presence of a constant viscosity at high shear rate provided by the surfactant and adjunct ingredients present in the liquid matrix.
  • a multiple creep test is conducted wherein the sample is placed in same Rheometer as used above and a range of stress is applied.
  • a sample is loaded into the Rheometer equipped with double concentric cylinder geometry, a shear of 100 s -1 is applied for 1 minute, then wait 1 minute.
  • measurements are conducted at varying amounts of applied stress and the Rheometer records the sample strain induced at each level of stress.
  • the stress levels for this test are: 0.0001 Pa, 0.0005 Pa, 0.001 Pa, 0.0015 Pa, 0.002 Pa, 0.003 Pa, 0.004 Pa, 0.005 Pa, and so forth at 0.001 Pa intervals until a continuous displacement of the sample is recorded.
  • the stress level resulting in this continuous displacement is considered the point where the stress applied is greater than the yield stress of the sample. If even the lowest amount of applied stress causes a continuous displacement, the yield stress of the material is below the resolution limit of the instrument.
  • yield stress is indicative of the ability of the liquid detergent composition to suspend beads.
  • the yield stress of the liquid detergent composition is equal or greater than the stress applied by a single beads suspended, the bead, once suspended in the liquid matrix, should remain suspended and neither tend to float or sink.
  • F depends on the difference in density between the liquid matrix and the suspension particle as well as the suspension particle volume.
  • F 4 3 ⁇ ⁇ ⁇ R 3 ⁇ ⁇ s ⁇ ⁇ l ⁇ g ⁇ s and ⁇ l are the densities of the suspended bead and the liquid matrix, respectively, and R is the radius of the bead, and g is gravity.
  • liquid detergent composition is capable of suspending beads and/or particles in accordance with the present invention under the Pour Use Test.
  • Step 1 fill 600 mL of the sample into a 600 mL clear plastic bottle such as the currently available Dawn PLUS with Power Scrubbers bottle or a bottle such as disclosed in USD55503.
  • Step 2 At time 0, invert the bottle 135° and manually squeezing the bottle with one hand with a pressure of 5 psi to 10 psi upon the bottle allowing 9.4 grams of sample composition to be released from the bottle.
  • Step 3 Place bottle back in upright standing position, at-rest position and take a picture of the front of the bottle and from the base of the bottle.
  • Step 4 Wait 15 minutes, then repeat Steps 2 and 3, but turn the bottle 90° before manually squeezing the bottle.
  • Step 4 Repeat Step 4 until 450 mL of the sample has been released from the bottle. Compare the bead distribution in the pictures and if greater than 1/2 of the beads float to the top of the bottle or sink to the bottom of the bottle, the sample fails the test. Samples which fail the test are outside the scope of the present invention.
  • the liquid matrix of the present invention is a shear thinning fluid, meaning that the liquid matrix has a specific pouring viscosity, a low stress viscosity, and a ratio of these two viscosity values. These viscosities are measured herein by using a Carrimed CLS 100 Viscometer with a 40 mm stainless steel parallel plate having a gap of 500 microns, at 25 °C.
  • the pouring viscosity is measured at a shear rate of 20 sec-1.
  • Suitable external structuring agents are those which provide liquid matrix having a pouring viscosity which generally ranges from 100 to 2500 cps, alternatively from 100 to 1500 cps.
  • the low stress viscosity is determined under a constant low stress of 0.1 Pa.
  • the liquid matrix has a low stress viscosity of at least 1,500 cps, alternatively at least 10,000 cps, and alternatively at least 50,000 cps.
  • This low stress viscosity represents the viscosity of the liquid matrix under typically usage stress conditions and during transportation and packaging.
  • the low stress viscosity is measured using a Cammed Viscometer in a low stress viscosity creep experiment over 5 minute intervals, again conducted at 25° C.
  • the liquid matrix has a ratio of its low stress viscosity to its pouring viscosity value, which is at least 2, alternatively at least 10, alternatively at least 100, up to 2000 or 1000.
  • the liquid detergent composition provides freeze-thaw stability.
  • Freeze-thaw stability means that the composition generally retains the same yield stress and shear thinning index after 1 to 3 freeze-thaw cycles.
  • "generally retains" means that the yield stress, shear thinning remains within 1% to 5% from prior to the cycle, after each successive freeze-thaw cycle(s).
  • the pour use test is measured as continuing to pass after successive freeze-thaw cycle(s).
  • a freeze-thaw test briefly, a sample is prepared and stored in a 600 mL clear plastic bottle. The sample is then flash frozen, then allowed to what at room temperature, resulting in one freeze-thaw cycle. The yield stress, shear-thinning characteristics and pour use test can be calculated.
  • the liquid matrix of the liquid detergent composition can be made for any suitable cleaning purpose, including but not limited to: laundry cleaning; hard surface cleaning, such as hand dish cleaning, counter top or table cleaning, window cleaning, and automatic dish washing; and as a personal care product for hair (shampoo or conditioner) or body wash.
  • the surfactant system is selected based on the desired application. Suitable surfactants include any conventional surfactants known for use with the above cleaning purposes.
  • surfactants can provide some structuring and rheology modifying benefits.
  • the surfactant system of the present invention is not included in the definition of external structurant.
  • the liquid matrix comprises from 0.01 % to 70 %, alternatively from 1 % to 50 %, alternatively from 3% to 20% of a surfactant system, by weight of the liquid detergent composition.
  • the surfactant system of the present invention comprising: a. from 5% to 60% of an anionic surfactant by weight of said liquid detergent composition; b. from 0.1% to 25% of an amine oxide by weight of said liquid detergent composition; and c. further comprising a nonionic surfactant; a cationic surfactant; an ampholytic surfactant; a zwitterionic surfactant; or mixtures thereof, and wherein said surfactant system has a ratio of 2.5 : 1 to 18 : 1 of anionic surfactant to said amine oxide.
  • Suitable surfactants for use herein are disclosed in U.S. 2005/0203213 to Pommiers et al. , 2004/0018950 to Foley et al. , WO 2006/116099 to Fleckenstein et al. , and U.S. 7,169,741 to Barry et al.
  • the liquid matrix comprises a weight ratio of surfactant system to external structurant, i.e. bacterial cellulose network, of from 1:1 to 5000:1, alternatively from 100:1 to 2000:1, alternatively from 500:1 to 1000:1.
  • external structurant i.e. bacterial cellulose network
  • the present invention is capable of providing suitable shear thinning capabilities and yield stress with higher amounts of external structurant to surfactant system, such as greater than 1000:1.
  • the liquid matrix comprises from 5% to 60 %, alternatively from 10% to 40%, alternatively from 15 % to 35% by weight of liquid detergent composition, of one or more of the below anionic surfactants.
  • Suitable anionic surfactants include the alkyl sulfonic acids, alkyl benzene sulfonic acids, ethoxylated alkyl sulfates and their salts as well as alkoxylated or un-alkoxylated alkyl sulfate materials.
  • the anionic surfactant comprises an alkali metal salts of C 10-16 alkyl benzene sulfonic acids, preferably C 11-14 alkyl benzene sulfonic acids.
  • the alkyl group is linear and such linear alkyl benzene sulfonates are known as "LAS".
  • Alkyl benzene sulfonates, and particularly LAS, are well known in the art. Such surfactants and their preparation are described for example in U.S. Patents 2,220,099 and 2,477,383 .
  • anionic surfactants include: sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 14.
  • Sodium C 11 -C 14 e.g., C 12
  • LAS is one suitable anionic surfactant for use herein.
  • Another suitable anionic surfactant comprises ethoxylated alkyl sulfate surfactants.
  • Such materials also known as alkyl ether sulfates or alkyl polyethoxylate sulfates, are those which correspond to the formula: R'-O-(C 2 H 4 O) n -SO 3 M wherein R' is a C 8 -C 20 alkyl group, n is from 1 to 20, and M is a salt-forming cation; alternatively, R' is C 10 -C 18 alkyl, n is from 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium.
  • R' is a C 12 -C 16
  • n is from 1 to 6
  • M is sodium.
  • Unethoxylated alkyl sulfates may also be added separately to the compositions of this invention and used as or in any anionic surfactant component which may be present.
  • Suitable unalkoyxylated, e.g., unethoxylated, alkyl ether sulfate surfactants are those produced by the sulfation of higher C 8 -C 20 fatty alcohols.
  • Conventional primary alkyl sulfate surfactants have the general formula of: ROSO 3 - M + , wherein R is typically a linear C 8 -C 20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation; alternatively R is a C 10 -C 15 alkyl, and M is alkali metal. In one embodiment, R is C 12 -C 14 and M is sodium.
  • a surfactant system comprises from 10% to 35% by weight of said liquid detergent composition of an anionic surfactant comprising: C10-16 linear alkylbenzene sulfonates, C8-20 alkyl polyethoxylate sulfates having from 1 to 20 moles of ethylene oxide, C8-16 alcohol polyethoxylates having from 1 to 16 moles of ethylene oxide, and mixtures thereof.
  • the anionic surfactant can include: ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine laureth sulfate, monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium laureth sulfate, potassium lauryl sulfate, potassium laureth sulfate, sodium lauryl sarcosi ⁇ nate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoyl sarcosine,
  • Non limiting examples of other anionic, zwitterionic, amphoteric or optional additional surfactants, and other adjunct ingredients suitable for use in the personal care compositions are described in McCutcheon's, Emulsifiers and Detergents, 1989 Annual, published by M. C. Publishing Co. , and U.S. Patent Nos. 3,929,678 ; 2,658,072 ; 2,438,091 ; and 2,528,378 .
  • the liquid matrix comprises from 0.1 % to 20 %, alternatively from 0.2 % to 15 %, alternatively from 0.5 % to 10 %, by weight of the liquid detergent composition, of a nonionic surfactant(s).
  • Suitable nonionic surfactants include any of the conventional nonionic surfactant types typically used in liquid cleaning compositions. These include alkoxylated fatty alcohols, ethylene oxide (EO)-propylene oxide (PO) block polymers, and amine oxide surfactants. Suitable for use in the liquid cleaning compositions herein are those nonionic surfactants which are normally liquid.
  • Suitable nonionic surfactants for use herein include the alcohol alkoxylate nonionic surfactants.
  • Alcohol alkoxylates are materials which correspond to the general formula of: R 1 (C m H 2m O) n OH, wherein R 1 is a C 8 - C 16 alkyl group, m is from 2 to 4, and n ranges from 2 to 12; alternatively R 1 is an alkyl group, which may be primary or secondary, that contains from 9 to 15 carbon atoms, alternatively from 10 to 14 carbon atoms.
  • the alkoxylated fatty alcohols will be ethoxylated materials that contain from 2 to 12, alternatively 3 to 10, EO moieties per molecule.
  • alkoxylated fatty alcohol materials useful in the liquid compositions herein will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from 3 to 17, alternatively from 6 to 15, alternatively from 8 to 15.
  • HLB hydrophilic-lipophilic balance
  • Alkoxylated fatty alcohol nonionic surfactants have been marketed under the tradenames Neodol and Dobanol by the Shell Chemical Company.
  • Nonionic surfactant suitable for use includes ethylene oxide (EO) - propylene oxide (PO) block polymers, such as those marketed under the tradename Pluronic. These materials are formed by adding blocks of ethylene oxide moieties to the ends of polypropylene glycol chains to adjust the surface active properties of the resulting block polymers. See Davidsohn and Milwidsky; Synthetic Detergents. 7th Ed.; Longman Scientific and Technical (1987) at pp. 34-36, 189-191 and in U.S. Patents 2,674,619 and 2,677,700 .
  • EO ethylene oxide
  • PO propylene oxide
  • the liquid detergent compositions comprise from 0.1% to 25% by weight of the liquid detergent composition of an amine oxide surfactant.
  • Amine oxides are often referred to in the art as "semi-polar" nonionics, and have the formula: R(EO) x (PO) y (BO) z N(O)(CH 2 R') 2 .qH 2 O.
  • R is a relatively long-chain hydrocarbyl moiety which can be saturated or unsaturated, linear or branched, and can contain from 8 to 20, alternatively from 10 to 16 carbon atoms, and alternatively a C 12 -C 16 primary alkyl.
  • R' is a short-chain moiety such as a hydrogen, methyl and -CH 2 OH.
  • EO ethyleneoxy
  • PO propyleneneoxy
  • BO butyleneoxy, i.e. C 12-14 alkyldimethyl amine oxide.
  • the surfactant system comprises anionic surfactant and amine oxide at a weight ratio of from 2.5:1 to 18:1.
  • Cationic surfactants when present in the detersive form of the composition, is present in an effective amount, such as from 0.1 % to 20 %, alternatively from 0.2 % to 5 %, alternatively from 0.5 % to 1 %, by weight of the liquid detergent composition.
  • Suitable cationic surfactants are quaternary ammonium surfactants. Suitable quaternary ammonium surfactants are selected from the group consisting of mono C 6 -C 16 , preferably C 6 -C 10 N-alkyl or alkenyl ammonium surfactants, wherein the remaining N positions are substituted by methyl, hydroxyehthyl or hydroxypropyl groups. Another preferred cationic surfactant is an C 6 -C 18 alkyl or alkenyl ester of an quaternary ammonium alcohol, such as quaternary chlorine esters.
  • the cationic surfactants have the following formula: wherein R1 is C 8 -C 18 hydrocarbyl and mixtures thereof, alternatively C 8-14 alkyl, alternatively C 8 , C 10 or C 12 alkyl, and X is an anion such as chloride or bromide.
  • Suitable surfactants include ampholytic surfactants, zwitterionic surfactants, or mixtures thereof.
  • Suitable ampholytic surfactants for uses herein include amido propyl betaines and derivatives of aliphatic or heterocyclic secondary and ternary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from 8 to 24 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
  • ampholytic surfactants comprise from 0.01% to 20%, alternatively from 0.5% to 10% by weight of the liquid detergent composition.
  • liquid detergent compositions according to the present invention is a diamine.
  • the liquid surfactant system can contain from 0% to 15%, alternatively from 0.1% to 15%, alternatively from 0.2% to 10%, alternatively from 0.25% to 6%, alternatively from 0.5% to 1.5% by weight of said liquid detergent composition of at least one diamine.
  • Suitable organic diamines are those in which pK1 and pK2 are in the range of 8.0 to 11.5, alternatively in the range of 8.4 to 11, alternatively from 8.6 to 10.75.
  • Other suitable materials diamines include primary/primary diamines with alkylene spacers ranging from C 4 to C 8 .
  • pKa1 and pKa2 are quantities of a type collectively known to those skilled in the art as “pKa” pKa is used herein in the same manner as is commonly known to people skilled in the art of chemistry. Values referenced herein can be obtained from literature, such as from “ Critical Stability Constants: Volume 2, Amines” by Smith and Martel, Plenum Press, NY and London, 1975 . Additional information on pKa's can be obtained from relevant company literature, such as information supplied by DUPONT®, a supplier of diamines. As a working definition herein, the pKa of the diamines is specified in an all-aqueous solution at 25 °C and for an ionic strength from 0.1 to 0.5 M.
  • said surfactant system is free or essentially free of any of said above surfactants, for example: free or essentially free of non-ionic surfactant, free or essentially free of cationic surfactant.
  • the liquid detergent compositions comprises a plurality of suspension particles at a level of from 0.01 % to 5% by weight, alternatively from 0.05% to 4% by weight, alternatively from 0.1% to 3% by weight, of said liquid detergent composition.
  • suitable suspension particles are provided in U.S. Patent No. 7,169,741 to Barry et al. at col. 12 - 18 and U.S. Patent Publ. No. 2005/0203213 to Pommiers et al. , 14 - 60.
  • one or more of the suspension particles have liquid cores. These particles function especially well in terms of stability within the detergent composition prior to use, yet are suitably unstable in the washing liquors formed from such products.
  • the liquid core has an ionically charged polymeric material encapsulated by a semipermeable membrane. This membrane is one which can be formed by interaction of some of the ionically charged polymer in the core with another polymeric material of opposite charge.
  • suitable liquid core suspension particles are available in U.S. 7,169,741 .
  • suspension particle which is suitable for use herein includes particles (or beads) with solid cores.
  • the plurality of suspension particles comprises a friable bead such as disclosed in EP 670 712 .
  • a friable bead such as disclosed in EP 670 712 .
  • One suitable use for such a friable bead is for exfoliation of the skin.
  • Suitable beads or particles for exfoliating can have a particle size in the range of 0.03 to 3 mm. Further, these beads can be friable meaning that during use they break up into particles having an average size of less than 50 microns.
  • the suspension particle comprises a pearlescence modifier. Suitable pearlescence modifiers include ethylene glycol distearate (EGDS), TiO 2 , ZnO, Mica and mixtures thereof.
  • the suspension particles are visibly distinct beads suspended within the liquid detergent composition. In another embodiment, the suspension particles are not visibly distinct in the liquid detergent composition. Particle or bead visibility is, of course, determined by a number of interrelated factors including size of the beads and the various optical properties of the beads and of the liquid composition they are dispersed within.
  • a transparent or translucent liquid matrix in combination with opaque or translucent beads will generally render the particles visible if they have a minor dimension of 0.2 mm or greater, but smaller beads may also be visible under certain circumstances. Even transparent beads in a transparent liquid matrix might be visibly distinct if the refractive properties of the particles and liquid are sufficiently different.
  • visibly distinct refers to particles having a minor dimension of 0.2 mm or greater, whereas not visibly distinct refers to particles having a minor dimension of less than 0.2 mm.
  • the suspension particles have a particle size in the range from 100 nanometers to 8 mm.
  • particle size means that at least one of said suspension particles have a longest linear dimension as defined.
  • suitable techniques to measure particle size are available, for example, suspension particles having a particle size from 10 nanometers to 5000 nanometers is by light scattering technique such as with a Brookhaven 90Plus Nanoparticle Size Analyzer, wherein a sample of the composition is diluted to a concentration ranging from 0.001% to 1% v/v using a suitable wetting and/or dispersing agents.
  • a 10 mL sample of the diluted sample is placed into a sample cell and measurements are recorded providing average particle diameter; optical microscopy can be used to detect particle sizes between 5 microns to 500 microns; and macroscopic measuring techniques can measure from 0.5 mm to 8 mm.
  • the liquid detergent composition of the present invention is capable of suspending a vast range of particles, from visibly distinct particles with particle size up to 8 mm to pearlescence agents which have particle sizes typically below 500 ⁇ m.
  • the particle size is from 0.1 mm to 8 mm, alternatively from 0.3 mm to 3 mm, and alternatively from 0.5 to 4 mm.
  • the suspension particles are not visibly distinct, comprising a particle size of from about 100 nanometers to 500 ⁇ m, alternatively from 1 ⁇ m to 300 ⁇ m, alternatively from 50 ⁇ m to 200 ⁇ m.
  • the liquid detergent composition comprises from 0.1 % to 2 % of said suspension particles in the range of 50 to 750 microns of particle size, such as a Silica-TiO 2 particles which function as sensory and skin exfoliating signals and a grease removal enhancing agent on dishes.
  • microns of particle size such as a Silica-TiO 2 particles which function as sensory and skin exfoliating signals and a grease removal enhancing agent on dishes.
  • polyethylene beads and butylene/ethylene copolymers of a particle size ranging from 50 to 350 microns can be used. See WO 2005/010138 to Paye et al.
  • the suspension particles used herein have a density of from 700 kg/m 3 to 4,260 kg/m 3 , alternatively from 800 kg/m 3 to 1,200 kg/m 3 , alternatively from 900 kg/m 3 to 1,100 Kg/m 3 , alternatively from 940 kg/m 3 to 1,050 kg/m 3 , alternatively from 970 kg/m 3 to 1,047 kg/m 3 , alternatively from 990 kg/m 3 to 1,040 kg/m 3 at 25°C.
  • the liquid detergent composition of the present invention is capable of suspending particles for 4 weeks at 25°C. Stability can be evaluated by the Pour Use test, by direct observation or by image analysis, by having colored particles suspended in a transparent liquid contained in a transparent bottle. A freshly made composition of the present invention is considered to be stable if less than 10%, preferably less than 5% and more preferably less than 1% by weight of the particles settle to the bottom of the container after 4 weeks static storage.
  • the difference between the density of the liquid matrix and the density of the particles is less than 10% of the liquid matrix density, alternatively less than 5% and alternatively less than 3%, alternatively less than 1%, alternatively less than 0.5%, at 25 °C.
  • the liquid matrix and the suspension particle have a density difference of from 10 kg/m 3 to 200 kg/m 3 , alternatively from 50 kg/m 3 to 100 kg/m 3 .
  • the particles are suspended so that the liquid detergent compositions are stable for 4 weeks at 25 °C. Stability can be evaluated by direct observation or by image analysis, by having colored particles suspended in a transparent liquid contained in a transparent bottle.
  • a detergent composition freshly made is considered to be stable if less than 10%, alternatively less than 5%, alternatively less than 1% by weight of the particles settle to the bottom of the bottle after 4 weeks static storage.
  • Particles suitable for use in the liquid detergents herein should be physically and chemically compatible with the detergent matrix ingredients, but they can disintegrate in use without leaving residues on fabrics, hair or body parts, such as hands, and/or hard surfaces such as dishes or being treated.
  • the particles are capable of withstanding a force before bursting or breaking of from 20 mN to 20,000 mN, alternatively from 50 mN to 15,000 mN, alternatively from 100 mN to 10,000 mN. This strength makes them suitable for industrial handling, including liquid detergent making processes. They can also withstand pumping and mixing operations without significant breakage and are also stable on transport.
  • the particles herein disintegrate readily in use by virtue of their osmotic behavior in dilute aqueous media such as agitated washing liquors.
  • the liquid detergent composition comprises a perfume.
  • Perfume is typical incorporated in the present compositions at a level of at least 0.001%, preferably at least 0.01%, more preferably at least 0.1%, and no greater than 10%, preferably no greater than 5%, more preferably no greater than 3%, by weight.
  • the perfume of the fabric conditioning composition of the present invention comprises an enduring perfume ingredient(s) that have a boiling point of 250°C or higher and a ClogP of 3.0 or higher, more preferably at a level of at least 25%, by weight of the perfume.
  • Suitable perfumes, perfume ingredients, and perfume carriers are described in US 5,500,138 ; and US 20020035053 A1 .
  • the perfume comprises a perfume microcapsule and/or a perfume nanocapsule.
  • Suitable perfume microcapsules and perfume nanocapsules include those described in the following references: US 2003215417 A1 ; US 2003216488 A1 ; US 2003158344 A1 ; US 2003165692 A1 ; US 2004071742 A1 ; US 2004071746 A1 ; US 2004072719 A1 ; US 2004072720 A1 ; EP 1393706 A1 ; US 2003203829 A1 ; US 2003195133 A1 ; US 2004087477 A1 ; US 20040106536 A1 ; US 6645479 ; US 6200949 ; US 4882220 ; US 4917920 ; US 4514461 ; US RE 32713 ; US 4234627 .
  • the liquid detergent composition comprises odor control agents such as described in US5942217 : "Uncomplexed cyclodextrin compositions for odor control", granted August 24, 1999.
  • Other agents suitable odor control agents include those described in: US 5968404 , US 5955093 ; US 6106738 ; US 5942217 ; and US 6033679 .
  • the liquid detergent compositions of the present invention will contain the suitable amounts of water in order to form the structured liquid matrix thereof.
  • water comprises from 30% to 75%, alternatively from 35% to 72%, alternatively from 40% to 70%, alternatively greater than 50% by weight of the liquid detergent compositions herein.
  • the liquid detergent composition is a concentrated formulation comprising as low as 1 % to 30 % water, alternatively from 5 % to 15%, alternatively from 10% to 14%. Concentrated formulations would be particularly desirable for embodiments where the present composition is encapsulated in a unit dose article.
  • the present compositions may optionally comprise an organic solvent.
  • Suitable organic solvents include C 4-14 ethers and diethers, glycols, alkoxylated glycols, C 6 -C 16 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C 1 -C 5 alcohols, linear C 1 -C 5 alcohols, amines, C 8 -C 14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof.
  • the liquid detergent composition comprises from 0.0% to less than 50% of a solvent. When present, the liquid detergent composition will contain from 0.01% to 20%, alternatively from 0.5% to 15%, alternatively from 1% to 10% by weight of the liquid detergent composition of said organic solvent. These organic solvents may be used in conjunction with water, or they may be used without water.
  • the present composition may comprise a polycarboxylate polymer, a co-polymer comprising one or more carboxylic acid monomers.
  • a water soluble carboxylic acid polymer can be prepared by polyimerizing a carboxylic acid monomer or copolymerizing two monomers, such as an unsaturated hydrophilic monomer and a hydrophilic oxyalkylated monomer.
  • unsaturated hydrophilic monomers include acrylic acid, maleic acid, maleic anhydride, methacrylic acid, methacrylate esters and substituted methacrylate esters, vinyl acetate, vinyl alcohol, methylvinyl ether, crotonic acid, itaconic acid, vinyl acetic acid, and vinylsulphonate.
  • the hydrophilic monomer may further be copolymerized with oxyalkylated monomers such as ethylene or propylene oxide. Preparation of oxyalkylated monomers is disclosed in U.S. Pat. No. 5,162,475 and U.S. Pat. No. 4,622,378 .
  • the hydrophilic oxyalkyated monomer preferably has a solubility of 500 grams/liter, more preferably 700 grams/liter in water.
  • the unsaturated hydrophilic monomer may further be grafted with hydrophobic materials such as poly(alkene glycol) blocks. See, for example, materials discussed in U.S. 5,536,440 , US 5,147,576 , US 5,073,285 , US 5,534,183 U. S. 5,574,004 , and WO 03/054044 .
  • magnesium ions may be utilized in the detergent composition when the liquid detergent compositions are used in softened water that contains few divalent ions.
  • the magnesium ions are added as a hydroxide, chloride, acetate, sulfate, formate, oxide or nitrate salt to the liquid detergent compositions of the present invention.
  • the magnesium ions are present at an active level of from 0.01 % to 1.5 %, alternatively from 0.015 % to 1%, alternatively from 0.025 % to 0.5 %, by weight of the liquid detergent composition.
  • the liquid detergent compositions optionally comprises a hydrotrope in an effective amount, i.e. from 0 % to 15%, or 1 % to 10 % , or 3 % to 6 %, so that the liquid detergent compositions are compatible in water.
  • Suitable hydrotropes for use herein include anionic-type hydrotropes, particularly sodium, potassium, and ammonium xylene sulfonate, sodium, potassium and ammonium toluene sulfonate, sodium potassium and ammonium cumene sulfonate, and mixtures thereof, as disclosed in U.S. Patent 3,915,903 .
  • the liquid detergent compositions of the present invention may optionally contain a polymeric suds stabilizer at a level from 0.01% to 15%. These polymeric suds stabilizers provide extended suds volume and suds duration of the liquid detergent compositions. These polymeric suds stabilizers may be selected from homopolymers of (N,N-dialkylamino) alkyl esters and (N,N-dialkylamino) alkyl acrylate esters.
  • the weight average molecular weight of the polymeric suds boosters, determined via conventional gel permeation chromatography, is from 1,000 to 2,000,000, alternatively from 5,000 to 1,000,000, alternatively from 10,000 to 750,000, alternatively from 20,000 to 500,000, alternatively from 35,000 to 200,000.
  • the polymeric suds stabilizer can optionally be present in the form of a salt, either an inorganic or organic salt, for example the citrate, sulfate, or nitrate salt of (N,N-dimethylamino)alkyl acrylate ester.
  • a salt either an inorganic or organic salt, for example the citrate, sulfate, or nitrate salt of (N,N-dimethylamino)alkyl acrylate ester.
  • One suitable polymeric suds stabilizer is (N,N-dimethylamino)alkyl acrylate esters, namely the acrylate ester represented by the following formula:
  • the polymeric suds booster may be present in the liquid detergent composition from 0.01% to 15%, alternatively from 0.05% to 10%, alternatively from 0.1% to 5%, by weight of the liquid detergent composition.
  • the liquid detergent compositions according to the present invention may comprise a linear or cyclic carboxylic acid or salt thereof to improve the rinse feel of the liquid detergent composition.
  • Carboxylic acids useful herein include salicylic acid, maleic acid, acetyl salicylic acid, 3 methyl salicylic acid, 4 hydroxy isophthalic acid, dihydroxyfumaric acid, 1,2, 4 benzene tricarboxylic acid, pentanoic acid and salts thereof and mixtures thereof.
  • the carboxylic acid exists in the salt form, the cation of the salt is selected from alkali metal, alkaline earth metal, monoethanolamine, diethanolamine or triethanolamine and mixtures thereof.
  • the carboxylic acid or salt thereof when present, is present at the level of from 0.1% to 5%, alternatively from 0.2% to 1%, alternatively from 0.25% to 0.5%.
  • the liquid detergent composition has a pH of from 4 to 14, alternatively from 6 to 13, alternatively from 6 to 10, alternatively an basic pH of greater than 7. It has importantly been found that the bacterial cellulose network is capable of providing the desired structuring benefits at pH above 7, or 10.
  • the liquid detergent compositions herein can further comprise a number of adjunct components.
  • the liquid detergent compositions comprises from 0.1% to 30%, alternatively from 0.5% to 20%, alternatively from 1% to 10%, of one or more of said additional adjunct components, alternatively the liquid matrix comprises from 0.1% to 50% by weight of said liquid detergent composition of one or more adjunct components.
  • the additional adjunct component may comprise one or more detersive enzymes which provide cleaning performance and/or fabric care benefits.
  • suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, mannanases, pentosanases, malanases, ⁇ -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and known amylases, or combinations thereof.
  • a preferred enzyme combination comprises a cocktail of conventional detersive enzymes like protease, lipase, cutinase and/or cellulase in conjunction with amylase.
  • detersive enzymes are described in greater detail in U.S. Pat. No. 6,579,839 .
  • the aqueous liquid detergent compositions herein can typically comprise from 0.001% to 5%, alternatively from 0.01% to 1% by weight, of a commercial enzyme preparation.
  • Protease enzymes for example, are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of detergent composition.
  • the present external structuring agent is believed to provide sufficient structuring capabilities, including bead suspension and shear thinning capabilities, in the presence of detersive enzymes for extended periods of time, such as for 6 months or more.
  • Additional adjunct components are optical brighteners at levels of from 0.01% to 1%, dye transfer inhibition agents at levels of from 0.0001% to 10%, suds suppressors at levels of from 0.001% to 2%, soil release polymers at levels of from 0.01% to 10%, silicone polymers from 0.01% to 50%, perfume, dyes, opacifiers, chelants, thickening agents and pH buffering agent.
  • optical brighteners at levels of from 0.01% to 1%
  • dye transfer inhibition agents at levels of from 0.0001% to 10%
  • suds suppressors at levels of from 0.001% to 2%
  • soil release polymers at levels of from 0.01% to 10%
  • silicone polymers from 0.01% to 50%
  • perfume, dyes, opacifiers, chelants, thickening agents and pH buffering agent may be found in U.S. Patent Publ. 2005/0203213 A1 to Pommiers et al. at 128 - 164.
  • adjunct components for a liquid laundry detergent include: detersive enzymes, optical brighteners, dye transfer inhibition agents, suds suppressors, detersive soil release polymers, other fabric care benefit agents, stabilizers, ancillary detersive surfactants, detersive builders, perfumes, coloring agents, enzymes, bleaches, mal-odor control agents, antimicrobials, anti-static agents, fabric softening agents, grease cleaning polymers including graft polymers, and combinations of thereof. All of these materials are of the type conventionally utilized in laundry detergent products.
  • Non-limiting examples of suitable laundry adjuncts are provided in U.S. Patent No. 7,169,741 to Barry et al. at col. 5, line 49 to col. 8, line 15 and col. 19, line 8 - col. 20, line 10, U.S. Patent Publ. 2007/0281879A1 to Sharma et al.
  • the invention provides for a process of making a liquid detergent composition comprising the steps of: (a) providing a feed comprising from 0.005% to 1.0%, preferably less than 0.125 %, preferably less than 0.05%, even more preferably 0.006% to 0.2%, by weight of a liquid detergent composition of an external structuring system comprising a bacterial cellulose network with water; (b) activating said feed in a mixing chamber to energy density in excess of 1.0 x 10 5 J/m 3 to form a bacterial cellulose network; and (c) providing a surfactant system at a level of from 0.01% to 70%, preferably from 1% to 50%, preferably from 3% to 20%, by weight of said liquid detergent composition, said surfactant system comprising: from 5% to 60%, by weight of said liquid detergent composition of an anionic surfactant; from 0.1% to 25% by weight of said liquid detergent composition of an amine oxide; and further comprising a nonionic surfactant; a cationic surfactant; an ampholytic surfact
  • the step of activating said bacterial cellulose is performed under intense high shear processing conditions such as with an ultra-sonic homogenizer like the SONOLATOR® from Sonic Corp. It has importantly been found that when the bacterial cellulose is activated under a sufficiently intense processing step, the bacterial cellulose network achieved provides enhanced yield stress without requiring additional levels of bacterial cellulose to be added. It is believed that intense high shear processing conditions such as ultra-sonic processing which can create hydrodynamic cavitation (i.e. via a SONOLATOR®) allows the crystalline fibers of the bacterial cellulose to create a more homogenous dispersion of the crystalline fibers.
  • intense high shear processing conditions such as ultra-sonic processing which can create hydrodynamic cavitation (i.e. via a SONOLATOR®) allows the crystalline fibers of the bacterial cellulose to create a more homogenous dispersion of the crystalline fibers.
  • the process of making the liquid detergent composition comprises: subjecting the bacterial cellulose and a solvent, e.g. water, to an energy density in excess of 1.0 x 10 5 J/m 3 , alternatively greater than 2.0 x 10 6 J/m 3 .
  • the liquid detergent composition comprises subjecting said bacterial cellulose and water to an energy density from 2.0 x 10 6 J/m 3 to 5.0 x 10 7 J/m 3 , alternatively from 5.0 x 10 6 J/m 3 to 2.0 x 10 7 J/m 3 , or from 8.0 x 10 6 J/m 3 to 1.0 x 10 7 J/m 3 .
  • a liquid detergent composition is formed using a static mixer, such as Koch/Sulzer Model SMX from Sulzer Corporation at an energy density of from 1.6 x 10 5 J/m 3 to 4.8 10 5 J/m 3 .
  • a liquid detergent composition is formed using a high shear mixer, such as an IKA mixer at an energy density of from 1.0 J/m 3 to 2.0 x 10 6 J/m 3 .
  • a liquid detergent composition is formed using an ultrasonic homogenizer, such as the SONOLATOR®, at an energy density of from 7.0 x 10 6 J/m 3 to 4.0 x 10 7 J/m 3 .
  • Single pass and multipass processing is also within the scope of the invention. Additionally, the step of activation can be performed with any of the above processing techniques as a premix of the bacterial cellulose and solvent prior to contact and subsequent mixing with other ingredients such as the surfactant system or in the presence of one or more other ingredients.
  • residence time means the average amount of time a vesicle remains within the mixing chamber. Residence time is determined by calculating the cavity size divided by the flow rate of liquid composition out of the mixing chamber.
  • the liquid detergent compositions of the present invention require relatively higher power density than conventional high sheer mixing.
  • the energy density is generated from a power density of from 0.5 W/ml to 100,000 W/ml, alternatively from 50 W/ml to 30,000 W/ml. It is observed that the minimum Power Density required to achieve the liquid detergent composition of the present invention is 0.5 W/ml at 20kHz.
  • the residence time is 15 minutes; alternatively, where the power density is 100,000 W/ml the residence time is 5 milliseconds. In one embodiment, the residence time is from 1 millisecond (ms) to 1 second, alternatively from 1 ms to 100 ms, alternatively from 5 ms to 50 ms. Further, where the residence time is less than 1 minute, the power density needs to be greater than 10 W/ml. Where the residence time is less than 1 second, the power density needs to be greater than 500 W/ml; alternatively. Where the residence time is less than 10 ms, the power density needs to be greater than 50,000 W/ml.
  • the liquid detergent composition is discharged at a flow rate from 1 kg/min to 1000 kg/min, alternatively 10 kg/min to about 500 kg/min.
  • orifice size is the orifice cross sectional area. In one embodiment, the orifice size is from 0.0005 inches 2 to 0.1 inches 2 .
  • the liquid detergent composition of the present invention can be manufactured with a variety of feed systems.
  • a single feed system the components of the liquid detergent composition comprising said bacterial cellulose, said surfactant system, said solvent such as water and other optional ingredients are fed into a mixing chamber as a single feed; where the step of activating said bacterial cellulose to form a bacterial cellulose network occurs in the same step as the mixing of the other components.
  • the process comprises a dual feed system comprising a first feed comprising the bacterial cellulose and solvent and a second feed comprises a surfactant system and any other components. The feeds are concurrently introduced into the mixing chamber.
  • one or more of the feeds are premixed prior to entry into the mixing chamber. In another embodiment, one or more of the feeds are not premixed prior to entry into the mixing chamber. In one embodiment, where a dual feed system is used, the first feed comprising the bacterial cellulose and solvent are activated or at least partially activated by premixing prior to introduction into the mixing chamber. In one embodiment, the premix is subjected to intense ultra-sonic processing conditions.
  • a premixing step is used to at least partially activate the bacterial cellulose in the presence of aqueous solution to form a first feed.
  • a second feed can be provided comprising the other desired components, such as the surfactants, perfumes, particles, and adjunct ingredients.
  • the process comprises: Step 1: activating the bacterial cellulose (optionally in powder form) with water or an aqueous solution, by means of any conventional and well known batch or continuous systems forming a premix of bacterial cellulose.
  • Step 2 The premix of bacterial cellulose and a second feed are mixed together and subjected to the intense high shear processing conditions defined above.
  • Step 3 Product obtained through step 2 is added to the liquid detergent composition in a conventional mixer.
  • certain particles suitable for use with the compositions herein can be either shear sensitive or intolerant (meaning that they can suffer undesirable structural damage if subjected to intense high shear processing conditions - i.e. microcapsules). In these instances, it could be desirable to add these shear intolerant particles after the step of activating the bacterial cellulose. Additionally, there may be particles which can be abrasive to the mixing chamber and/or vibrating blade of the ultrasonic homogenizer. These abrasive particles can also advantageously be added later in the making process. Other particles which can be damaged by intense high shear processing, and/or be abrasive the mixing apparatus can be added to the feed streams as needed.
  • the liquid detergent composition comprises a turbidity of below 320 NTU, alternatively less than 250 NTU, alternatively less than 200 NTU, alternatively less than 150 NTU, alternatively less than 100 NTU, as measured by Turbimeter test method disclosed herein.
  • Compositions with a turbidity below 150, alternatively below 100 are "clear" while those with a turbidity below 320, alternatively below 250 are “translucent.”
  • the liquid detergent composition is pearlescent.
  • the liquid matrix has a turbidity of 20 to 320 Nephelometric Turbidiy Units.
  • turbidity is determined using a Hach Model 2100P Portable Turbidimeter ("Turbimeter”), by Hach Company, Loveland, CO. StablCal is a trademark of Hach Company.
  • Turbidimeter Turbidity Method The Turbidimeter measures the turbidity from 0.01 NTU to 1000 NTU.
  • the Turbidimeter operates on the nephelometric principle of turbidity measurement.
  • the Turbidimeter's optical system includes a tungsten-filament lamp, a 90° detector to monitor scattered light and a transmitted light detector.
  • the Turbidimeter's microprocessor calculates the ratio of the signals from the 90° and of transmitted light detectors. This ratio technique corrects for the interferences from color and or light absorbing materials and compensates for fluctuations in the lamp intensity.
  • Calibration is by StablCal ® Secondary standards provided with the Turbidimeter.
  • the undiluted sample is contained in the sample cell, the outer cell wall is wiped free of water and finger prints.
  • a thin coat of silicone oil is applied to the outer wall of the sample cell in order to mask minor imperfections and scratches on the sample cell wall, which may contribute to turbidity or stray light.
  • a measurement is taken and result is displayed in NTU units. All samples are equilibrated and measured at 25°C. The samples are measured within 24h after making.
  • the liquid detergent compositions of the present invention may be packages in any suitable packaging for delivering the liquid detergent composition for use.
  • the package is a clear package made of glass or plastic.
  • the liquid detergent composition is packaged in a unit dose pouch, wherein the pouch is made of a water soluble film material, such as a polyvinyl alcohol.
  • the unit dose pouch comprises a single or multi-compartment pouch where the present liquid detergent composition can be used in conjunction with any other conventional powder or liquid detergent composition. Examples of suitable pouches and water soluble film materials are provided in U.S. Patent Nos. 6,881,713 to Sommerville-Roberts et al. , 6,815,410 to boutique et al. , and 7,125,828 to Catlin et al.
  • a drop of sample (approximately 5 ⁇ L) is placed on a standard glass microscope slide and spread into a thin film by covering with a standard 22mmx22mm coverglass. The edges of the coverglass are then sealed with wax. At least two slide preparations are made from each sample.
  • the prepared slides are viewed using a compound light microscope (we used a Zeiss AxioVert200), fitted with a CytoViva darkfield condenser system (CytoViva Inc, Alburn, AL, USA), and an oil immersion 63x objective lens possessing a numerical aperture-reducing iris, as well as 40x and 10x dry objective lenses.
  • node quantification thirty representative images of each sample preparation are captured, at each of two magnifications (400x and 630x) using a digital CCD camera, (we used a monochrome 12bit Zeiss AxioCam MRm version 3, with 2x2binning, calibrated for length scale (pixels per micrometer) (we used Zeiss AxioVision software).
  • Ten low magnification (100x) images of each sample are also captured, using a traditional condenser darkfield patchstop or mismatched phase rings, and long camera exposure times, to assess the overall homogeneity of the fiber network.
  • the number of nodes (fiber intersections) per image is determined using the free image analysis software, Image J (National Institutes of Health, Bethesda, MD).
  • Images are first processed by application of algorithms for smoothing, background subtraction and contrast enhancement.
  • the images are then thresholded (so that all fibers are shown in a binarized image with the background being the liquid medium).
  • Threshold setting is described in detail in The Image Processing Handbook, 4th Edition, 2002, by John C. Russ, published by CRC Press LLC, Boca Raton, Florida, ISBN 0-8493-1142-X .
  • the threshold range should be adjusted to maximize selection of fiber pixels and minimize selection of background noise.
  • the thresholded images are then processed with the skeletonization algorithm.
  • Step C Calculating number of node points:
  • the degree of fiber connectivity is quantified by determining the mean number of nodes (fiber intersections) in 30 representative images at two different magnifications (400x & 630x). It has importantly been found that node counts per image are significantly lower in High Shear Mixing samples (HSM) prepared using a rotor stator device generating an energy density of 2*10 6 J/m 3 than in samples processed under intense high shear processing conditions using a single pass fed system with a SONOLATOR® at 5000psi generating an energy density of 3.5*10 7 J/m 3 , indicating a lower connectivity of the fiber network.
  • HSM High Shear Mixing samples
  • the degree of connectivity quantified by determining the average number of nodes is also consistent with a lower yield stress measured in the HSM sample (0.006 Pa) as compared to the yield stress measured in the sample processed under intense high shear processing condition using a single pass fed system with a SONOLATOR® at 5000 psi (0.014 Pa).
  • a higher degree of fiber connectivity results in a higher yield stress and consequently in better suspending properties in the final product.
  • the bacterial cellulose network of the present invention comprises a SMNI Index of at least 0.099, at least 0.105, at least 0.110, at least 0.15, at least 0.2. In another embodiment, the SMNI index can be up to 1.
  • FIG. 3 provides one example skeletonized image of the HSM sample having 233 nodes/image viewed under 400x magnification (447 ⁇ m x 336 ⁇ m).
  • Distance 100 points out a straight line distance between the boundary of the image and a portion of the skeletonized fiber network.
  • FIG. 4 provides one example skeletonized image of a sample processed under intense processing conditions having 639 nodes/image viewed under 400x magnification.
  • Distance 200 demonstrates a straight line distance between two portions of the skeletonized fiber network.
  • FIG. 5 provides another skeletonized image of the sample imaged in FIG. 3 , having 279 nodes/image viewed under 630x magnification (284 ⁇ m x 213 ⁇ m).
  • Distance 300 demonstrates a straight line distance between two portions of the skeletonized fiber network.
  • FIG. 6 provides another skeletonized image of the sample imaged in FIG. 4 , having 367 nodes/image viewed under 630x magnification.
  • Distance 400 demonstrates a straight line distance between two portions of the skeletonized fiber network.
  • the samples shown in FIGs. 3 - 6 are made with 0.036 wt% bacterial cellulose. It is believed that these exemplary images show how the processing conditions impact the connectivity of the bacterial cellulose fibers holding the formulations constant. Without intending to be bound by theory, it is believed that the increased connectivity allows for enhanced rheology benefits including increased yield stress and bead suspension capabilities. Further distances 100, 200, 300 and 400 are provided merely for illustrative purposes of how one would measure a straight line distance between two points of the skeletonized bacterial fiber network, when viewed under varying magnifications.
  • the bacterial cellulose network comprises a mean node of from 350 mean nodes/image (447 ⁇ m x 336 ⁇ m), alternatively greater than 500 mean nodes/image, alternatively greater than 580 mean nodes/image, alternatively greater than 600 mean nodes/image.
  • the bacterial cellulose network comprises a mean node of from 210 mean nodes/image (284 ⁇ m x 213 ⁇ m) alternatively greater than 300 mean nodes/image, alternatively greater than 350 mean nodes/image, alternatively greater than 400 mean nodes/image.
  • the CV as used herein is the ratio of the standard deviation to the mean as a percentage, (standard deviation/mean x 100), for a given magnification, and therefore provides a relative measure of variation between data series.
  • CV400 is the ratio at a magnification of 400x. Without intending to be bound it is believed that although the mean nodes/image can be impacted by the threshold setting. The CV, however, should be less sensitive to variations in the threshold setting.
  • the bacterial cellulose network comprises a CV400 and/or the CV630 is from 10% to 39%, alternatively from 15% to 25%, alternatively 20%.
  • the greatest straight line distance between two points of the skeletonized bacterial fiber network is less than 250 microns in length, alternatively less than 100 microns, alternatively less than 50 microns, alternatively less than 15 microns, alternatively less than 5 microns.
  • Table 1 Samples prepared and viewed at 400x magnification HSM Intense High Shear Procesing Sample Number Image Node # Image Node # 1 0043 338 0008 598 2 0044 236 0012 542 3 0045 284 0013 557 4 0046 450 0014 633 5 0047 332 0015 670 6 0049 279 0016 498 7 0050 267 0017 530 8 0051 459 0018 578 9 0052 208 0019 772 10 0053 361 0020 572 11 0054 265 0021 615 12 0055 309 0022 717 13 0056 275 0023 663 14 0057 422 0024 739 15 0058 204 0026 414 16 0059 352 0027 689 17 0060 277 0028 528 18 0061 289 0029 618 19 0062 493 0030 368 20 0063 553 0031 563
  • Example 1 Heavy duty Liquid Laundry Detergent in accordance with the present invention are prepared in the following proportions.
  • Example 2 - 6 Light Duty Liquid Detergents in accordance with the present invention are prepared in the following proportions.
  • Example 2 Example 3
  • Example 4 Example 5
  • Example 6 INGREDIENT % by Wt. % by Wt. % by Wt. % by Wt. % by Wt. % by Wt. % by Wt.
  • FIG. 1 shows a plot of % bacterial cellulose to yield stress obtained by activating a sample in accordance with Example 3 wherein the % bacterial cellulose is varied up to 0.1% with varying processing techniques.
  • Line 10 represents the linear extrapolation for test A;
  • Line 20 represents the linear extrapolation for Test B;
  • Line 30 represents the linear extrapolation for Test C.
  • Test A Two step process 1) premix of bacterial cellulose and water with SONOLATOR® at an energy density of 7.155 x 10 6 J/m 3 a premix solution followed by 2) mixing of premix solution with the other components in a SONOLATOR® at 5000 psi providing an energy density of 3.47 x 10 7 J/m 3 .
  • Solid squares represent experimental data points while the empty square represents an extrapolated data point, determined by a scaled extrapolation comparing the Test A data point at 0.06% bacterial cellulose vs. the Test B data point at 0.06% bacterial cellulose. A straight line extrapolation is fit to the three data points.
  • Test B One step process: Activation and mixing in 1 pass in a SONOLATOR® at 5000 psi providing an energy density of 3.47 x 10 7 J/m 3 . All three Test B data points were obtained experimentally. Data is represented by circles plotted on chart with a straight line extrapolation fit to the data points.
  • Test C One step process: Activation and mixing in a high shear mixer set at 7900 rpm, providing an energy density of 2 x 10 6 J/m 3 . Both Test C data points were obtained experimentally. Data is represented in triangles plotted on chart with a straight line extrapolation fit to the data points.
  • FIG. 2 shows a linear extrapolation of the % bacterial cellulose network to yield stress for bacterial cellulose network concentration above 0.1% processed with the same three techniques described in FIG. 1 . Note that the same data points are used in both FIG. 1 and 2 .
  • Every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification includes every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification includes every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein.

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Claims (13)

  1. Composition détergente liquide comprenant :
    a. une matrice liquide comprenant :
    i. de 0,005 % à 1,0 % en poids, de préférence moins de 0,125 %, de préférence moins de 0,05 %, encore plus préférablement 0,006 % à 0,2 % de ladite composition détergente liquide d'un système structurant externe comprenant un réseau de cellulose bactérienne ;
    ii. de 1 % à 75 % en poids, de préférence soit de 1 % à 30 % soit de préférence de 30 % à 75 %, de ladite composition détergente liquide, d'eau ;
    iii. de 0,01 % à 70 % en poids, de préférence de 1 % à 50 %, de préférence de 3 % à 20 %, de ladite composition détergente liquide, d'un système tensioactif comprenant :
    a. de 5 % à 60 % d'un agent tensioactif anionique en poids de ladite composition détergente liquide ;
    b. de 0,1 % à 25 % d'un oxyde d'amine en poids de ladite composition détergente liquide ; et
    c. comprenant en outre un agent tensioactif non ionique ; un agent tensioactif cationique ; un agent tensioactif ampholytique ; un agent tensioactif zwittérionique ; ou leurs mélanges ; et
    iv. de 0,01 % à 5 %, en poids de ladite composition détergente liquide, d'une pluralité de particules en suspension ayant une taille de particules allant de 100 nanomètres à 8 mm, et une masse volumique moyenne de particules allant de 700 kg/m3 à 4260 kg/m3 à 25 °C, dans laquelle la pluralité de particules en suspension par rapport à la matrice liquide a une différence de masse volumique allant de 10 kg/m3 à 200 kg/m3 à 25 °C ;
    dans laquelle ladite matrice liquide a une limite d'élasticité allant de 0,003 Pa à 5,0 Pa, de préférence de 0,01 Pa à 1,0 Pa, de préférence de 0,05 Pa à 0,2 Pa, à 25 °C, même plus préférablement de 0,005 Pa à 1 Pa ; et dans laquelle ledit système tensioactif a un rapport pondéral de 2,5 : 1 à 18 : 1 de l'agent tensioactif anionique audit oxyde d'amine.
  2. Composition détergente liquide selon la revendication 1, dans laquelle ladite matrice liquide est un fluide rhéofluidifiant ayant un rapport de la viscosité à faible contrainte à la viscosité de déversement allant de 2 à 2000, de préférence de 10 à 1000.
  3. Composition détergente liquide selon la revendication 1 ou la revendication 2, dans laquelle ledit système structurant externe comprend en outre une carboxyméthylcellulose, une carboxyméthylcellulose modifiée, et leurs mélanges ; et éventuellement, un épaississant polymère choisi parmi des produits de xanthum, de la pectine, des alginates, de la gomme gellane, de la gomme de welan, de la gomme de diutane, de la gomme de rhamsane, du carraghénane, de la gomme de guar, de l'agar-agar, de la gomme arabique, de la gomme ghatti, de la gomme karaya, de la gomme adragante, de la gomme de tamarin, de la gomme de caroube, et des mélanges de ceux-ci.
  4. Composition détergente liquide selon l'une quelconque des revendications précédentes, dans laquelle ledit réseau de cellulose bactérienne comprend une largeur la plus grande en coupe transversale de microfibre allant de 1,6 nm à 200 nm et un rapport d'aspect de microfibre de 10:1 à 1000:1, de préférence 100:1 à 400:1.
  5. Composition détergente liquide selon l'une quelconque des revendications précédentes, dans laquelle ladite matrice liquide comprend en outre de 0,01 % à 20 %, en poids de ladite composition détergente liquide, d'un solvant organique.
  6. Composition détergente liquide selon l'une quelconque des revendications précédentes, dans laquelle ladite matrice liquide a un pH allant de 6 à 13.
  7. Composition détergente liquide selon l'une quelconque des revendications précédentes, dans laquelle ladite matrice liquide a une turbidité de 20 à 320 unités de turbidité néphélométriques.
  8. Composition détergente liquide selon l'une quelconque des revendications précédentes, dans laquelle ladite matrice liquide comprend en outre :
    a. de 0,001 % à 5 %, en poids de ladite composition détergente liquide, d'une enzyme détersive ;
    b. de 0,1 % à 50 %, en poids de ladite composition détergente liquide, d'un ou plusieurs composants additifs.
  9. Composition détergente liquide selon l'une quelconque des revendications précédentes, comprenant en outre un Indice SMNI tel que défini ici d'au moins 0,099, de préférence au moins 0,105, plus préférablement au moins 0,11, jusqu'à 1.
  10. Composition détergente liquide selon l'une quelconque des revendications précédentes, dans laquelle ledit réseau de cellulose bactérienne comprend au moins l'un parmi un CV400 et un CV630, tels que définis ici, allant de 10 % à 39 %.
  11. Composition détergente liquide selon l'une quelconque des revendications précédentes, dans laquelle ledit réseau de cellulose bactérienne, lorsqu'on observe sous une imagerie sur fond noir à 400x, comprend une distance linéaire la plus grande entre deux points du réseau de fibres bactériennes squelettisé, inférieure à 250 micromètres, de préférence inférieure à 100 micromètres.
  12. Procédé de fabrication d'une composition détergente liquide selon l'une quelconque des revendications précédentes, comprenant les étapes consistant à :
    a. fournir une charge d'alimentation comprenant de 0,005 % à 1,0 %, de préférence moins de 0,125 %, de préférence moins de 0,05 %, encore plus préférablement 0,006 % à 0,2 %, en poids d'une composition détergente liquide, d'un système structurant externe comprenant un réseau de cellulose bactérienne avec de l'eau ;
    b. activer ladite charge d'alimentation dans une chambre de mélange à une densité énergétique de plus de 1,0 x 105 J/m3 pour former un réseau de cellulose bactérienne ; et
    c. fournir un système tensioactif à un taux allant de 0,01 % à 70 %, de préférence de 1 % à 50 %, de préférence de 3 % à 20 % en poids de ladite composition détergente liquide, ledit système tensioactif comprenant : de 5 % à 60 %, en poids de ladite composition détergente liquide, d'un agent tensioactif anionique ; de 0,1 % à 25 %, en poids de ladite composition détergente liquide, d'un oxyde d'amine ; et comprenant en outre un agent tensioactif non ionique ; un agent tensioactif cationique ; un agent tensioactif ampholytique ; un agent tensioactif zwittérionique ; ou leurs mélanges,
    dans lequel ladite étape (c) est effectuée soit en même temps que l'étape (a) soit après l'étape (b), et dans lequel l'étape de fourniture audit système tensioactif dudit réseau de cellulose bactérienne forme une composition détergente liquide comprenant une matrice liquide comprenant une limite d'élasticité allant de 0,003 Pa à 5,0 Pa à 25 °C.
  13. Procédé selon la revendication 12, dans lequel l'étape a) comprend une étape de prémélange consistant à mettre la cellulose bactérienne en contact avec de l'eau, et l'étape b) consistant à soumettre ce prémélange dans la chambre de mélange à une densité énergétique de plus de 1,0 x 105 J/m3, conjointement avec une deuxième charge d'alimentation comprenant un système tensioactif comprenant : un agent tensioactif anionique ; un agent tensioactif non ionique ; un agent tensioactif cationique ; un agent tensioactif ampholytique ; un agent tensioactif zwittérionique ; et leurs mélanges.
EP09709696.0A 2008-02-15 2009-02-02 Composition détergente liquide comprenant une structure externe constituée d'un réseau de cellulose bactérienne Active EP2242832B1 (fr)

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EP2242832A1 (fr) 2010-10-27
CA2715652A1 (fr) 2009-08-20
JP5871468B2 (ja) 2016-03-01
CA2715652C (fr) 2014-08-12
MX2010008933A (es) 2010-09-09
WO2009101545A1 (fr) 2009-08-20
ES2672110T3 (es) 2018-06-12
AR070384A1 (es) 2010-03-31

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