ES2672110T3 - Liquid detergent composition comprising an external structuring system comprising a bacterial cellulose network - Google Patents

Abstract

A liquid detergent composition comprising: a. a liquid matrix comprising: i. from 0.005% to 1.0% by weight, preferably less than 0.125%, preferably less than 0.05%, even more preferably from 0.006% to 0.2% of said liquid detergent composition of an external structuring system comprising a network of bacterial cellulose; ii. 1% to 75% by weight, preferably any 1% to 30% or preferably 30% to 75%, of said liquid water detergent composition; iii. from 0.01% to 70% by weight, preferably from 1% to 50%, preferably from 3% to 20%, of said liquid detergent composition of a surfactant system 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. furthermore it comprises a nonionic surfactant; a cationic surfactant; an ampholytic surfactant; a hybrid ion surfactant; or mixtures thereof; and 20 iv. from 0.01% to 5% by weight of said liquid detergent composition of a plurality of suspended particles having a size of 100 nanometers to 8 mm, and an average particle density of 700 kg / 3 to 4,260 kg / m3 a 25 ° C, wherein the plurality of particles in suspension to liquid matrix has a density difference of 10 kg / m3 to 200 kg / m3 at 25 ° C; wherein said liquid matrix has a creep stress of 0.003 Pa to 5.0 Pa, preferably 0.01 Pa to 1.0 Pa, preferably 0.05 Pa to 0.2 Pa, at 25 ° C, even more preferably from 0.005 Pa to 1 Pa; and wherein said surfactant system has a weight ratio of 2.5: 1 to 18: 1 of anionic surfactant to said amine oxide.

Description

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

DESCRIPTION

Liquid detergent composition comprising an external structuring system comprising a bacterial cellulose network

Background of the invention

Conventional approaches to provide distinctive structural and aesthetic properties to liquid compositions include: the addition of specific structuring agents that include both internal and external structuring agents. Examples of known internal structuring agents include: surfactants, electrolytes (which can promote the formation of self-assembled structures similar to a worm). Known external structuring agents include polymers or gums, many of which are known to swell or expand when hydrated to form a random dispersion of independent microgel particles. Examples of polymers and gums include: gellan gum, pectin, alginate, arabinogalactan, carrageenan, xanthan gum, guar gum, ramsano gum, furcellaran gum, carboxymethylcellulose and cellulose. See, p. eg, US 6,258,771, of Buntin et al. US 6,077,816, by Buntin et al. US publications UU. 2005/0203213, by Zerby et al .; and WO 2006/116099 by Fleckenstein et al. Although gums have been used to provide structuring benefits, gums depend on pH, that is to say they fail at a pH greater than 10. Furthermore, it has been found that some gums are susceptible to degradation in the presence of detersive enzymes. Therefore, there remains a need for other external structuring agents less susceptible to these and other known problems.

Another composition that has been reported to provide structuring benefits is cellulose, that is, bacterial celluloses. Conventional uses of bacterial celluloses include improving the rheological properties of hydraulic fracture liquids used in hydraulic fracturing of geological formations; in addition to muds for drilling wells; and as a food ingredient. See p. ex. US 5,350,528, US 5,362,713 and US 5,366,750. Bacterial cellulose is typically grown using a bacterial strain of Acetobacter aceti var. xinum and dried using spray drying or lyophilization techniques. Attempts to manufacture and prepare dry bacterial cellulose compositions that can be rehydrated and activated to achieve a network of bacterial cellulose for use in final products are known. Examples of these attempts are provided in US Pat. No. 6,967,027 to Heux et al. and in patent publication US 2007/0027108 by Yang et al. See also patent publications uS- 2008/0108714 of Swazey et al. and 2007/197779 by Yang et al. and as well as publication WO 2007/068344 by Cai et al.

US-5998349A (Rhodia Chimie), published on December 7, 1999, refers to a formulation for the removal of calcareous deposits comprising cellulose microfibrils, in which at least 80% of the cells have primary walls and no more than 20% of the cells have secondary walls, with a degree of crystallinity not exceeding 50%.

WO89 / 08148 un (BIO fill products biotecnologicos S.A.) published on September 8, 1989 refers to a process for preparing aqueous suspensions or slurries of cellulose microfibrils obtained from bacterial fermentation.

WO03 / 062361 A1 (Henkel) published on July 31, 2003 refers to a conditioning agent for protecting textiles, in addition to the use thereof in a washing method or drying method of textiles.

WO2008 / 076753 A1 (CP Kelco) published on June 26, 2008 refers to surfactant systems, which use microfibrous cellulose to suspend particles therein, and methods to prepare these systems.

US-6241812B1 (Smith Barbara) published on June 5, 2001 refers to crosslinked bacterial cellulose compositions stable in acidic medium and cationically compatible, containing cationic surfactants and / or surfactants, which are rheological modifying agents and stabilizing agents useful for suspensions , emulsions and foams, and their preparation methods.

Two structuring properties that are desired in liquid detergent compositions include suspension capabilities of beads and / or particles and ability to reduce shear viscosity. Although it has been reported that the addition of certain external structuring agents to liquid detergent compositions may provide some effects of shear viscosity reduction, the ability to provide shear viscosity reduction capabilities alone is insufficient to determine whether the composition Liquid detergent is capable of suspending pearl particles over time. Thus, the need for an external structuring agent that provides both benefits of shear viscosity reduction and pearl suspension capacity persists. In addition, these structuring benefits are desired at an external structuring agent level as low as possible due to cost and formulation issues. For example, excessive amounts of external structuring agent can provide the ability to suspend particles but result in the liquid composition becoming too viscous and non-pourable. In addition, too much external structuring agent can result in opacity and turbidity of the composition, which may be undesirable.

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

Thus, there remains a need for an external structuring agent that provides both shear viscosity reduction and sufficient particle suspension capabilities while avoiding one or more of the aforementioned problems that appear with conventional formulations.

Summary of the invention

The present invention relates to a liquid detergent composition according to the claims.

Another aspect of the present invention relates to a process for manufacturing a liquid detergent composition comprising the steps of: providing (a) a feed comprising from 0.005% to 1.0%, preferably less than 0.125%, preferably less than 0 , 05%, even more preferably from 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 food in a mixing chamber to an energy density greater than 1.0 x 105 J / m3 to form a bacterial cellulose network; and (c) providing a surfactant system at a level of 0.01% to 70%, preferably 1% to 50%, preferably 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 which further comprises a nonionic surfactant; a cationic surfactant; an ampholytic surfactant; a hybrid ion surfactant; or mixtures thereof, wherein said step (c) of providing a surfactant system is either performed together with stage (a) or after stage (b), wherein the step of providing said surfactant system with said network of Bacterial cellulose forms a liquid detergent composition comprising a liquid matrix having a creep stress of 0.003 to 5.0 Pa at 25 ° C.

Brief description of the drawings

Fig. 1 shows a graphic representation of the relationship between bacterial cellulose concentrations and creep stress as a function of different processing technologies.

Fig. 2 shows a graphical representation based on the same data as those used in Fig. 1 with the creep tension extrapolation for up to 1% bacterial cellulose concentration.

Fig. 3 shows an illustrative figure of a liquid detergent composition comprising 0.036% by weight of a bacterial cellulose network prepared using a rotor device with stator that generates an energy density of 2 * 106 J / m3, of which an image with a 400x magnification is taken by CytoViva dark field optical microscopy.

Fig. 4 shows an illustrative figure of a liquid detergent composition comprising 0.036% by weight of a bacterial cellulose network prepared using a one-step feeding system with a SONOLATOR® at 34473 kPa (5000 Psi) that generates a density of energy of 3.5 * 107 J / m3, from which an image is taken with a 400x magnification by CytoViva dark field optical microscopy.

Fig. 5 shows an illustrative figure of the same sample whose image appears in Fig. 3 with a 630x magnification by CytoViva dark field optical microscopy.

Fig. 6 shows an illustrative figure of the same sample whose image appears in Fig. 4, image taken with a 630x magnification by CytoViva dark field optical microscopy.

Detailed description of the invention

It has been found in particular that 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 water detergent composition; 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 the liquid detergent composition; b. from 0.1% to 0.25% of an amine oxide by weight of said liquid detergent composition; and c. furthermore it comprises a nonionic surfactant; a cationic surfactant; an ampholytic surfactant; a hybrid ion surfactant; or mixtures thereof; from 0.01% to 5% by weight of said liquid detergent composition of a plurality of suspended particles having a size of 100 nanometers to 8 mm, and an average particle density of 700 kg / 3 to 4,260 kg / m3 a 25 0C, wherein the plurality of particles suspended in liquid matrix has a density difference of 1 kg / m3 to 200 kg / m3 at 25 0C, wherein said liquid matrix has a creep stress of 0.003 Pa to 5.0 Pa at 25 0C; and wherein said surfactant system has a ratio of 2.5: 1 to 18: 1 of anionic surfactant to said amine oxide, it provides sufficient capacity for particle suspension and reduction of shear viscosity. In one embodiment, the bacterial cellulose network is formed by "activating" the bacterial cellulose and a solvent such as water under high and intense shear processing conditions. Without intending to impose any theory, it is believed that a liquid detergent composition comprising a bacterial cellulose network activated in this manner is capable

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

of providing the desired structuring capabilities at relatively low levels while avoiding one or more of the problems that appear with conventional external structuring agents.

Definitions:

As used herein, "practically free" of a component means that no amount of that component has been deliberately incorporated into the composition.

As used herein, "high and intense shear processing conditions" means a mixing stage sufficient to activate bacterial cellulose and provide the required creep stress of the present invention.

As used herein, "liquid matrix" refers to the liquid components of the present liquid detergent composition, wherein measurements made on the liquid matrix are made in the absence of any suspended particles.

As used herein, "beads and / or suspended particles" includes solid beads, capsules either empty or containing functional or non-functional ingredients therein, microcapsules, particles, and fragments thereof. "Plurality of suspended particles" includes both beads and suspended particles that can be formed from suspended beads that decompose.

Here, a "structuring" is any material that is added to the composition to provide rheological and structuring advantages, for example as measured by creep stress. As used herein, "external structuring" means a material whose primary function is to provide a rheological alteration of the liquid matrix. In general, therefore, an external structurant will not provide, in and of itself, any significant cleaning advantage or any significant ingredient solubilization advantage. An external structuring is, therefore, distinct from an internal structuring that can also modify the rheology of the matrix but which has been incorporated into the liquid composition for some alternative or additional main purpose.

Here, all tests and measurements, unless otherwise indicated, are performed at 25 ° C.

1. Liquid matrix comprising an external structuring system

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 0.01% of said external structuring system, alternatively at least 0.01%, alternatively at least 0.05%, by weight of the liquid detergent composition. The external structuring system for use in the present invention comprises a bacterial cellulose network that is formed from individual bacterial cellulose fibers that are activated in the presence of water. In one embodiment, the external structuring system consists essentially of a network of bacterial cellulose.

to. 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. The term "bacterial cellulose" is intended to encompass any type of cellulose produced by fermentation of a bacterium of the genus Acetobacter and includes materials popularly referred to as microfibrillated cellulose, and cross-linked bacterial cellulose.

The bacterial cellulose network is formed by processing a mixture of the bacterial cellulose in a hydrophilic solvent, such as water, polyols (eg, ethylene glycol, glycerin, polyethylene glycol), or mixtures thereof. This processing is called "activation" and generally comprises high pressure homogenization and / or high shear mixing. It should be noted that the activation of bacterial cellulose under sufficiently intense processing conditions provides a greater creep tension for given levels of the bacterial cellulose network. Creep tension, as defined below, is a measure of the force necessary to initiate flow in a gel type system. It is believed that creep stress is indicative of the suspension capacity 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 3D structure of bacterial cellulose is modified in such a way that cellulose transmits functionality to the base solvent or solvent mixture in which activation occurs, or to a composition to which cellulose is added. activated The functionality includes providing such properties as shear thickening, transmission of creep-suspension stress properties, freeze / thaw, and thermal stability. The processing that is followed during the activation process does not require significantly more than dispersing the cellulose in the base solvent. This intense processing "separates" the cellulose fibers to expand the cellulose fibers. Bacterial cellulose activation serves to expand the cellulose portion to create a crosslinked network of bacterial cellulose, which is a crosslinked network of very intertwined fibers with a very high specific surface. The

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

Activated cross-linked bacterial cellulose has an extremely high specific surface area that is believed to be at least 200 times larger than conventional microcrystalline cellulose (i.e., cellulose provided by plant sources).

The bacterial cellulose used herein can be of any type associated with the fermentation product of microorganisms of the genus Acetobacter, and is available previously, an example of CPKelco US, is CELLULON®. Such aerobic culture products are characterized by a highly interconnected network of branched fibers that are insoluble in water. The preparation of these bacterial cellulose products is well known and usually involves a method for producing aerobically cross-linked bacterial cellulose, under agitation culture conditions, using a bacterial strain of Acetobacter aceti var. xylinum. The use of stirring culture conditions results in a sustained production, on an average of 70 hours, of at least 0.1 g / liter per hour of the desired cellulose. A wet cake of crosslinked cellulose can be produced, containing approximately 80-85% water, using the methods and conditions described in the aforementioned patents. A dry cross-linked bacterial cellulose can be produced using drying techniques, such as spray drying or lyophilization, which are well known. See US Patent 5,079,162 and US 5,144,021.

Acetobacter is typically a bacillus-shaped gram-negative bacterium of 0.6-0.8 micrometers per 1.0-4 micrometers. It is a strict aerobic organism; that is, the metabolism is respiratory, not fermentative. This bacterium is further distinguished by the ability to produce multiple poly-1,4p-glucan chains, chemically identical to cellulose. Microcellulose chains, or microfibers, of cross-linked bacterial cellulose are synthesized on the bacterial surface, at outer sites of the cell membrane. These microfibers have cross-sectional dimensions of 1.6 nm to 3.2 nm by 5.8 nm to 133 nm. In one embodiment, the bacterial cellulose network has microfibers with a wider cross section, with a width of 1.6 nm to 200 nm, alternatively less than 133 nm, alternatively less than 100 nm, alternatively lower at 5.8 nm. Additionally, the bacterial cellulose network has an average microfiber length of at least 100 nm, alternatively 100 to 1500 nm. In one embodiment, the bacterial cellulose network has a microfiber dimensional ratio, which means the average length of the microfiber divided by the largest width of the microfiber cross section from 10: 1 to 1000: 1, alternatively 100: 1 to 400: 1, alternatively from 200: 1 to 300: 1.

The presence of the bacterial cellulose network can be detected by taking micrograph images with STEM. A sample of liquid detergent composition is obtained. An 18.75 pmm copper TEM grid (1500 mesh) is placed on filter paper and 15 drops of the sample are applied to the TEM grid. The TEM grid is transferred to new filter paper and rinsed with 15 drops of deionized water. An image of the TEM grid is then taken with a STEM S-5200 micrograph instrument to observe the fibrous network. Those skilled in the art will understand that, if a fibrous network is detected, both the transverse dimension of the fibers and the aspect ratio can be determined. Those skilled in the art will also recognize that alternative analytical techniques can be used to detect the presence of the bacterial cellulose network such as atomic force microscopy using the same TEM grid and the reservoir and rinse steps described above. A 3D representation of atomic force microscopy can be obtained that shows both the dimensions of the fiber and the degree of crosslinking.

The small cross-sectional size of these fibers produced by Acetobacter, together with the large length and inherent hydrophilicity of cellulose, provides a cellulose product that has an unusually high capacity to absorb aqueous solutions. Additives have often been used together with bacterial cellulose to aid in the formation of stable viscous dispersions.

Additional non-limiting examples of suitable bacterial celluloses are described in US Patent Nos. 6,967,027 to Heux et al .; US 5,207,826 to Westland et al .; US 4,487,634 to Turbak et al .; US 4,373,702 to Turbak et al. and US-4,863,565 to Johnson and, in patent publication US-2007/0027108 of Yang et al.

i. Methods to activate bacterial cellulose

In one embodiment, the bacterial cellulose network is formed by "activating" the bacterial cellulose under high and intense shear processing conditions. Something important has been discovered: that the use of high and intense shear processing conditions gives the bacterial cellulose network better structuring capabilities. By using intensive processing conditions, the bacterial cellulose network can provide the desired structuring benefits at lower levels and without the need for expensive chemical and physical modifications.

In one embodiment, the step of activating said bacterial cellulose under high and intense shear processing conditions comprises: activating the bacterial cellulose and a solvent, e.g. ex. water, at an energy density greater than 1.0 x 106 J / m3, alternatively, greater than 2.0 x 106 J / m3. In one embodiment, the activation stage is

J 6 3 7 3 1 R 3

It has an energy density of 2.0 x 10 J / m at 5.0 x 10 J / m, alternatively 5.0 x 10 J / m at 2.0 x 10 J / m, alternatively 8, 0 x 10 J / m to 1.0 x 10 J / m. Something important has been discovered: that the activation of bacterial cellulose under high and intense shear processing conditions indicated herein, that formulations having even less than 0.05% by weight of said bacterial cellulose are capable of providing the desired rheological advantages, such as creep stress and particle suspension. In one embodiment, when the activation is carried out with a processing of

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

high and intense shear, the level of bacterial cellulose is from 0.005% by weight to 0.05% by weight, alternatively less than 0.03% by weight, alternatively less than 0.01% by weight.

Processing techniques capable of providing this amount of energy density include conventional high shear mixers, static mixers, propeller and tank mixers, rotor / stator mixers, and Gaulin homogenizers, and SONOLATOR® from Sonic Corp of CT. In one embodiment, the step of activating the bacterial cellulose is carried out with a high pressure homogenizer comprising a mixing chamber and a vibrating blade, where the feeding in the mixing chamber is forced through a hole. Pressure feed is accelerated as it passes through the hole and comes into contact with the vibrating blade.

In one embodiment, the step of activating said bacterial cellulose under high and intense shear processing conditions involves causing hydrodynamic cavitation, which is achieved using a SONOLATOR®. Without intending to impose any theory, it is believed that the mixture within the mixing chamber undergoes hydrodynamic cavitation within the mixing chamber, which causes the bacterial cellulose to form a bacterial cellulose network with sufficient degree of interconnectivity to provide a better capacity. of shear viscosity reduction.

Something important has been discovered: that certain processing conditions improve the ability of bacterial cellulose to provide the desired rheological advantages to the composition, including better creep stress at lower levels of bacterial cellulose. Without attempting to impose any theory, it is believed that this advantage is achieved by increasing the interconnectivity of the bacterial cellulose network formed within the liquid matrix.

One method of improving the ability of bacterial cellulose to form the bacterial cellulose network is to activate bacterial cellulose with an aqueous solution such as a premix under conventional mixing conditions before contacting a second stream. A second stream may be provided comprising the remaining desired components, such as surfactants, perfumes, particles, and auxiliary ingredients. In one embodiment, the bacterial cellulose and an aqueous solution are combined as a premix. This premix can be subjected to high and intense shear conditions but is not necessary. In one embodiment, it is desired to carry out this premixing step using conventional mixing technologies, such as a continuous or discontinuous line mixer at energy densities of up to 1.0 x 106 J / m3.

Another method of improving the capacity of the cellulose network to form by bacterial cellulose is to contact the bacterial cellulose in dry or powder form directly in a feed stream of the liquid active substances directed to the mixing chamber of a homogenizer Ultrasonic or in-line mixer. The powder can be added immediately before the feed enters the mixing chamber or it can be added as a feed independent of the current of active substance (s). Advantageously, by introducing the powdered form without premixing or with an independent activation stage, a single-step system can be achieved that simplifies processing and saves costs / space.

ii. Bacterial cellulose coated with polymeric thickener

In one embodiment, the external structuring system further comprises a bacterial cellulose that is at least partially coated with a polymeric thickener. This at least partially coated bacterial cellulose can be prepared according to the methods described in the patent publication US-2007/0027108 of Yang et al. en ^ 8-19. In a suitable process, the bacterial cellulose is subjected to mixing with a polymeric thickener to at least partially coat the fibers and bundles of bacterial cellulose. It is believed that the dilation of the bacterial cellulose and the polymeric thickener allows the desired generation of a polymeric thickener coating on at least a part of the fibers and / or bundles of bacterial cellulose.

In one embodiment, the method of producing said at least partially coated bacterial cellulose comprises a proportion of bacterial cellulose to polymeric thickener comprising from 0.1% to 5% of the bacterial cellulose, alternatively from 0.5% to 3, 0%, by weight of additional polymeric thickener; and from 10% to 900% of the polymeric thickener by weight of the bacterial cellulose.

In one embodiment, the polymeric thickener comprises a hydrocolloid, at least in charged cellulose ether, at least one polymeric gum, and mixtures thereof. A suitable hydrocolloid includes carboxymethyl cellulose ("CMC"). Suitable polymeric gums comprise products of xanthan, pectin, alginates, gellan gum, welan gum, diutan gum, ramsano gum, carrageenan, guar gum, agar, gum arabic, ghatti gum, karaya gum, tragacanth gum, tamarind gum, gum carob, and mixtures thereof. See US Patent 2007/0027108 in ^ 6 and 16.

In another embodiment, the bacterial cellulose does not undergo any chemical or physical modification apart from the activation and / or the polymeric thickener coating. In one embodiment, the bacterial cellulose is exempt from a chemical modification comprising esterification or etherification by the addition of hydrophobic groups on the fibers, which means that the bacterial cellulose fibers are not modified to be surfactants, where surfactant means that the ingredient decreases the surface tension of the medium in which it dissolves. In another embodiment, the bacterial cellulose is exempt from any physical modification, including coating the fibers with hydrophobic materials. It has been found

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

something important: that when activating the bacterial cellulose network according to the invention herein, the fibers do not have to be modified as mentioned in WO 2007/068344 of Cai et al.

b. Additional structuring agents

In one embodiment, the external structuring system further comprises additional structuring agents such as hydroxyl functionalized non-polymeric crystalline materials, polymeric structuring agents, and mixtures thereof. Preferably, the external structuring system further comprises a carboxymethyl cellulose, a modified carboxymethyl cellulose, and mixtures thereof; and optionally, a polymeric thickener selected from products of xanthan, pectin, alginates, gellan gum, welan gum, diutan gum, rhamsan gum, carrageenan, guar gum, agar, gum arabic, ghatti gum, karaya gum, tragacanth gum, gum of tamarind, locust bean gum, and mixtures thereof.

1. Hydroxyl functionalized non-polymeric crystalline materials

A suitable additional structuring agent comprises non-polymeric materials (except conventional alkoxylation) crystallized with hydroxyl that can form filamentous structuring systems throughout the liquid matrix when crystallized within the matrix in situ. Such materials can generally be characterized as fatty acids, fatty esters or fatty waxes containing crystalline hydroxyl groups. See p. ex. US Patent 7,169,741 to col. 9, line 61 to col. 11, line 4, and US Pat. No. 6,080,708 and WO 2002/0040627.

ii. Polymer Structuring Agents

Other types of organic structuring agents may be used in the liquid compositions herein, in addition to the non-polymeric crystalline structuring agents containing hydroxyl described hereinbefore. Polymeric materials can also be used that will provide shear viscosity reduction capabilities to the liquid matrix. Suitable polymeric structuring agents include those of polyacrylate, polysaccharide or polysaccharide derivative type. Polysaccharide derivatives typically used as structuring agents comprise polymeric rubber materials. Such polymeric gums include pectin, 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 marketed by CP Kelco U.S., Inc. under the trade name KELCOGEL. Gellan gum preparation processes are described in US 4,326,052; US 4,326,053; US 4,377,636 and US 4,385,123.

In one embodiment, the external structuring system is exempt or practically free of any additional structuring agent known in the art such as those related herein, for example: exempt or practically free of hydroxyl functionalized non-polymeric crystalline materials; free or practically free of polymeric structuring agents including polymer gums, pectin, alginate, arabinogalactan (gum arabic), carrageenan, gellan gum, xanthan gum and guar gum. Something important has been discovered: that the external structuring system of the present invention provides sufficient rheological advantages, such as pearl suspension and shear viscosity reduction capabilities, without relying on structuring ingredients beyond the described bacterial cellulose network In the present memory.

2. Structural characteristics of the liquid matrix

to. Creep voltage

The liquid matrix of the liquid detergent composition of the present invention has a creep stress of 0.003 Pa to 5.0 Pa, alternatively 0.01 Pa to 1.0 Pa, alternatively 0.05 Pa to 0 , 2 Pa, as defined by the creep stress test, defined herein. Importantly, although the% bacterial cellulose is determined by the total weight of the liquid detergent composition, which includes both the liquid matrix and the suspended particles, the creep stress is measured only from the liquid matrix. This is important because the presence of suspended particles can vary the creep stress measurements. Something important has been discovered: that the higher energy density used during activation correlates with a higher creep voltage. In one embodiment, where activation is by a SONOLATOR® at an energy density of 2.0 x 106 J / m3 at 5.0 x 107 J / m3, a liquid matrix having 0.006% to 0.2% of Bacterial cellulose network provides a creep tension of 0.005 Pa at 1 Pa, and 0.6% to 1% bacterial cellulose network provides a creep tension of 2.85 to 5 Pa.

Without intending to impose any theory, it is believed that although known structuring agents to provide shear viscosity reduction capabilities are described, the ability of a composition to suspend particles is not a direct correlation to the shear viscosity reduction capabilities of the composition. Instead, the ability of a composition to suspend particles is measured by creep stress. For example, two compositions having the shear viscosity reduction capabilities within a given shear rate range may have different creep stress values. It is believed that to stabilize the suspended particles in the matrix

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

liquid of the liquid detergent composition, the stress exerted by a single bead or particle should not exceed the creep stress of the liquid matrix. If this condition is met, the liquid detergent composition will be less susceptible to, alternatively capable of preventing, sedimentation or cream formation and flotation or sedimentation of particles and / or suspended particulate material under static conditions.

Creep tension tests:

For samples that have less than 0.1% bacterial cellulose, a dynamic creep stress test is performed. The dynamic creep stress test is performed as follows: a sample is placed in a controlled effort AR G2 rheometer with concentric double cylinder geometry of TA Instruments (“Rheometer”) and subjected to a shear range of 100 s-1 to 0.001 s-1. Fifty measurements, uniformly separated from each other on a logarithmic scale (as determined with the rheometer) are made at variable shear rates in the indicated range, and the steady state viscosity and the applied voltage for each imposed level of shear speed. The applied voltage vs. data Imposed shear rates are plotted and conform to a modified Hershel-Bulkley model to account for the presence of a constant viscosity at high shear rates provided by the surfactant and adjuvant ingredients present in the liquid matrix.

The following equation is used to model the stress of the liquid matrix:

image 1

where: a: Voltage, dependent variable; P1: Creep voltage, setting parameter; P2: Viscosity term in the Hershel-Bulkley model, adjustment parameter; j: Shear speed, independent variable; P3: Exponent in the Hershel-Bulkley model, adjustment parameter; and P4: Asymptotic viscosity at high shear rates, adjustment parameter. One skilled in the art will understand that the adjustment procedure due to the Hershel-Bulkley model of the data collected from the sample will provide the parameters from P1 to P4, which include creep stress (P1). The Hershel-Bulkley model is described in “Rheometry of Pastes Suspensions and Granular Material” page 163, Philippe Coussot, John Wiley & Sons, Inc., Hoboken, New Jersey (2005).

For samples that have 0.1% or more bacterial cellulose, a multiple creep test is performed where the sample is placed in the same Rheometer previously used and a range of stresses are applied. First, a sample is introduced into the rheometer equipped with concentric double disk geometry, a 100 s-1 shear is applied for 1 minute, and then 1 minute is expected. Next, the measurements are made for varying amounts of applied stress and the Rheometer records the deformation of the induced sample at each level of effort. 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 on at intervals of 0.001 Pa until it is record a continuous displacement of the sample. The level of effort that results in this continuous displacement is considered the point at which the applied stress is greater than the creep stress of the sample. If even the lowest amount of tension applied causes continuous displacement, the creep tension of the material is below the resolution limit of the instrument.

Without intending to impose any theory, creep stress is believed to be indicative of the ability of the liquid detergent composition to suspend beads. When the creep stress of the liquid detergent composition is equal to or greater than the stress applied by a single suspension bead, the bead, once suspended in the liquid matrix, must remain suspended and not tend to float or sink. The tension applied by a suspended globule is determined according to the net force applied by a single bead, F, divided by the surface on which this force is applied, S.

F

image2

F depends on the difference in densities between the liquid matrix and the suspended particle, as well as the volume of suspended particles.

image3

Ps and pi are the densities of the suspended globule and the liquid matrix, respectively, and R is the radius of the pearl, and g is gravity.

S, is calculated by:

image4

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

K has been calculated as a constant of 3.5.

In addition to this basic condition that the stress exerted by a single bead or particle should not exceed the creep stress of the liquid matrix under static conditions, the behavior of the system is further complicated when external stress is applied to the liquid detergent composition. Under the action of external forces such as during the pouring of the product, the liquid detergent composition is forced to flow, therefore, the creep stress during the pouring process is reduced and, after the pouring, the microstructure requires some time to return to its properties at rest. The use test during pouring described in the following section is used to assess the stability of the suspended particles during said external stress.

b. Use test during pouring

To confirm the ability of the liquid detergent composition to suspend beads under conditions of use, such as when it is poured or pressurized by pumping, a use test can be performed during pouring. In one embodiment, the liquid detergent composition is capable of suspending beads and / or particles according to the present invention according to the use test during pouring.

Use test during pouring: The test is performed at 23 ° C. Stage 1: Introduce 600 ml of the sample into a 600 ml clear plastic bottle such as the Dawn PLUS container currently available with a Power Scrubbers bottle or a bottle as described in USD55503. Stage 2: At time 0, invert the 135 ° bottle and manually squeeze the bottle with one hand exerting a pressure of 34.5 kPa at 69 kPa (5 psi at 10 psi) on the bottle leaving 9.4 grams of composition of Sample come out of the bottle. Stage 3: Place the bottle in an upright position, in a resting position and take a picture of the front of the bottle and the base of the bottle. Stage 4: Wait 15 minutes, then repeat Stages 2 and 3, but turning the bottle 90 ° before manually squeezing the bottle. Repeat Stage 4 until 450 ml of sample is released from the bottle. Compare the distribution of pearls in the images, and if more than 1/2 pearls float to the top of the bottle or sink to the bottom of the bottle, the sample does not pass the test. Samples that do not pass the test are outside the scope of the present invention.

C. Shear viscosity reduction capabilities

The liquid matrix of the present invention is a fluid that exhibits reduced shear viscosity, which means that the liquid matrix has a specific pour viscosity, a low stress viscosity, and a ratio of these two viscosity values. These viscosities are measured herein using a Carrimed CLS 100 viscometer with a 40 mm parallel stainless steel plate having a 500 micrometer gap, at 25 ° C.

The pouring viscosity, as defined herein, is measured at a shear rate of 20 s-1. Suitable external structuring agents are those that provide a liquid matrix having a pouring viscosity that is generally in the range of 100 mPa.s to 2500 mPa.s (100 to 2500 cps), alternatively 100 mPa.sa 1500 mPa.s (100 to 1500 cps).

The low stress viscosity, as defined herein, is determined at a constant low stress of 0.1 Pa. The liquid matrix has a low stress viscosity of at least 1500 MPa.s (1500 cps), so alternatively at least 10,000 MPa.s (10,000 cps), and alternatively at least 50,000 MPa. (50,000 cps). This low stress viscosity represents the viscosity of the liquid matrix under typical stress conditions of use and during transport and packaging. The low stress viscosity is measured using a Carrimed viscometer in a low stress viscosity creep experiment at 5 minute intervals, performed again at 25 ° C. Rheology measurements at 5 minute intervals are performed once the rheology of the matrix has fully recovered from any past high shear event and has remained at a zero shear rate for 10 minutes between loading the sample into the viscometer and Run the test. The data of the last 3 minutes are used to adjust a straight line and, from the slope of this line, the viscosity is calculated.

Finally, in order to present suitable shear viscosity reduction characteristics, in one embodiment, the liquid matrix has a ratio of the value of its viscosity at low stress to the value of its pour viscosity, which is at least 2, alternatively to the minus 10, alternatively at least 100, up to 2000 or 1000.

d. Freeze / thaw stability

In another embodiment, the liquid detergent composition provides freeze / thaw stability. The freeze / thaw stability means that the composition generally maintains the same creep stress and shear viscosity reduction index after 1 to 3 freeze / thaw cycles. As used herein, "generally retains" means that creep stress, the shear viscosity reduction behavior, remains within the value of 1% to 5% of what it had before the cycle, after each cycle. (s) successive freeze / thaw. In addition, the use test during pouring is measured as if it continues to pass after a subsequent freeze / thaw cycle (s). The person skilled in the art will know how to perform a test of

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

freezing / thawing: in short, a sample is prepared and stored in a 600 ml clear plastic bottle. The sample is then frozen quickly, then allowed to defrost at room temperature, resulting in a freeze / thaw cycle. The creep stress, the shear viscosity reduction characteristics and the use test during pouring can be calculated.

3. Surfactant system

The liquid matrix of the liquid detergent composition may be prepared for any suitable cleaning purpose, including but not limited to, laundry; hard surface cleaning, such as manual dishwashing, countertop or table cleaning, window cleaning, and automatic dishwashing; and as a personal hygiene product for hair (shampoo or conditioner) or body soap. Thus, the surfactant system is selected depending on the desired application. Suitable surfactants include any conventional surfactant known for use with the above cleaning purposes.

However, surfactants can provide some structuring and rheology modifying benefits. The surfactant system of the present invention is not included in the definition of external structuring.

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 comprises: 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. furthermore it comprises a nonionic surfactant; a cationic surfactant; an ampholytic surfactant; a hybrid ion 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. Surfactants suitable for use herein are described in US Pat. No. 2005/0203213 of Pommiers et al., US 2004/0018950 of Foley et al., WO 2006/116099 of Fleckenstein et al., And US- 7,169,741 to Barry et al.

In one embodiment, the liquid matrix comprises a weight ratio of the surfactant system to the external structurant, that is, the bacterial cellulose network, from 1: 1 to 5000: 1, alternatively from 100: 1 to 2000: 1, of alternative form of 500: 1 to 1000: 1. Notably, although the amounts of both the external structurant and the surfactants may vary, the present invention is capable of providing adequate shear viscosity and creep stress reduction capacities with greater amounts of external structurant relative to the surfactant system, such as more of 1000: 1.

to. Anionic surfactants

In one embodiment, 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 following anionic surfactants . Suitable anionic surfactants include alkyl sulfonic acids, alkyl benzene sulfonic acids, ethoxylated alkyl sulfates and salts thereof as well as alkoxylated or non-alkoxylated alkyl sulfate materials.

In one embodiment, the anionic surfactant comprises an alkali metal salts of C10-16 alkylbenzenesulfonic acids, preferably C11-14 alkylbenzenesulfonic acids. In one embodiment, the alkyl group is linear and said linear alkylbenzene sulphonates are known as "LAS". The alkylbenzene sulphonates, and in particular LAS, are well known in the art. Such surfactants and their preparation are described, for example, in US-2,220,099 and US-2,477,383. Other suitable anionic surfactants include: sodium and potassium straight chain alkylbenzenesulfonates in which the average number of carbon atoms in the alkyl group is 11 to 14. C11-C14 sodium, e.g. eg, C12, LAS is an anionic surfactant suitable for use herein.

Another preferred anionic surfactant comprises ethoxylated alkyl sulfate surfactants. Such materials, also known as alkylether sulfates or polyethoxylated alkyl sulfates, are those corresponding to the formula:

R'-O- (C2FUO) n-SO3M

wherein R 'is a C8-C20 alkyl group, n is from 1 to 20, and M is a salt-forming cation; alternatively, R 'is C10-C18 alkyl, n is 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium. In another embodiment, R 'is a C12-C16, n is 1 to 6 and M is sodium. Alkyl ether sulfates will generally be used in the form of mixtures comprising varying R 'chain lengths and varying degrees of ethoxylation. Frequently, said mixtures will inevitably also contain some non-ethoxylated alkyl sulfate materials, that is, surfactants of the above ethoxylated alkyl sulfate formula, where n = 0. Non-ethoxylated alkyl sulfates can also be added separately to the compositions of this invention and used as such or in any other anionic surfactant component that may be present.

Suitable non-alkoxylated alkyl ether sulfate surfactants, e.g. eg, non-ethoxylated, are those produced by the sulfation of higher C8-C20 fatty alcohols. Conventional primary alkyl sulfate surfactants have the general formula: ROSO3-M +, where R is typically a linear C8-C20 hydrocarbyl group, which

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

it can be straight chain or branched chain, and M is a water solubilization cation; alternatively, R is a C10-C15 alkyl and M is alkali metal. In one embodiment, R is C12-C14 and M is sodium.

One embodiment provides a surfactant system comprising from 10% to 35% by weight of said liquid detergent composition of an anionic surfactant comprising: C10-16 alkylbenzene linear sulphonates, C8-20 alkyl polyethoxylated sulfates having 1 to 20 moles of ethylene oxide, C8-16 polyethoxylated alcohols having 1 to 16 moles of ethylene oxide, and mixtures thereof.

When the liquid detergent composition is for personal hygiene (ie, shampoo or body soap), the anionic surfactant may include: ammonium lauryl sulfate, ammonium laureth sulfate, triethylamine lauryl sulfate, triethylamine laureth sulfate, triethanolamine lauryl sulfate, triethanolamine triethalamine sulfate , monoethanolamine laureth sulfate, diethanolamine lauryl sulfate, diethanolamine laureth sulfate, lauryl monoglyceride sodium sulfate, sodium lauryl sulfate, potassium laureth sulfate, potassium lauryl sulfate, sodium lauryl sulfate, coconut ammonium sulfate, sodium ammonium sulfate, coconut sulfate, sodium ammonium sulfate, coconut ammonium sulfate sulfate, coconut ammonium sulfate sulfate, coconut sulfate, sodium ammonium sulfate sulfate, coconut sulfate ammonium sulfate sulfate sulfate sulfate sulfate sulfate sulfate ammonium ammonium sulfate sulfate sulfate sulfate sulfate sulfate sulfate ammonium sulfate sulfate sulfate sulfate sulfate sulfate sulfate sulfate sodium, sodium lauroylsulfate, potassium cocoylsulfate, potassium lauryl sulfate, triethanolamine lauryl sulfate, triethanolamine lauryl sulfate, monoethanolamine cocoylsulfate, monoethanolamine lauryl sulfate, tridecylbenzenesulfonate s sodium, sodium dodecylbenzenesulfonate, and mixtures thereof. Non-limiting examples of other anionic, hybrid ion, amphoteric or optional surfactants, as well as other adjuvant ingredients, suitable for use in personal hygiene compositions are described in Emulsifiers and Detergents of McCutcheon, 1989 Annual, published by MCC Publishing Co., and patents US-3,929,678; US 2,658,072; US 2,438,091; and US 2,528,378.

b. Nonionic Surfactants

In one embodiment, 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 one or more anionic surfactants. Suitable nonionic surfactants include any of the types of conventional nonionic surfactants commonly used in liquid cleaning compositions. These include alkoxylated fatty alcohols, ethylene oxide (EO) -propylene oxide (PO) block polymers, and amine oxide surfactants. Nonionic surfactants that are normally liquid are suitable for use in the liquid detergent compositions herein.

Nonionic surfactants suitable for use in the present invention include nonionic alcohol alkoxylate surfactants. Alcohol alkoxylates are materials that correspond to the general formula: R1 (CmH2mO) pOH wherein R1 is a C8-C16 alkyl group, m is from 2 to 4 and n is in the range of 2 to 12; alternatively, R1 is an alkyl group that can be primary or secondary, containing from 9 to 15 carbon atoms, alternatively from 10 to 14 carbon atoms. In another embodiment, the alkoxylated fatty alcohols will be ethoxylated materials containing from 2 to 12, alternatively from 3 to 10, EO moieties per molecule.

The alkoxylated fatty alcohol type materials useful in the liquid compositions herein will frequently have a hydrophilic-lipophilic balance (HLB) in the range of 3 to 17, alternatively 6 to 15, alternatively 8 to 15 Non-ionic alkoxylated fatty alcohol surfactants have been marketed under the trade names Neodol and Dobanol of Shell Chemical Company.

Another suitable non-ionic surfactant for use includes block polymers of ethylene oxide (EO) -propylene oxide (PO), such as those sold under the trade name Pluronic. These materials are formed by adding blocks of ethylene oxide moieties to the ends of polypropylene glycol chains to adjust the surfactant properties of the resulting block polymers. See Davidsohn and Milwidsky; Synthetic Detergents, 7th Ed .; Longman Scientific and Technical (1987) pp. 34-36, 189-191 and in patents US-2,674,619 and US-2,677,700.

Liquid detergent compositions comprise from 0.1% to 25% by weight of the liquid detergent composition of an amine oxide surfactant. Frequently, amine oxides are referred to in the art as "semipolar" nonionic surfactants, and have the formula: R (EO) x (PO) and (BO) zN (O) (CH2R ') 2.qH2O. In this formula, R is a relatively long chain hydrocarbyl moiety that can be saturated or unsaturated, linear or branched, and can contain from 8 to 20, alternatively from 10 to 16 carbon atoms and, alternatively, is a C12-C16 primary alkyl. R 'is a short chain residue, such as hydrogen, methyl and -CH2OH. When x + y + z is different from 0, EO is ethyleneoxy, PO is propyleneoxy and BO is butyloxy, that is, C 12-14 alkyldimethyl oxide.

The surfactant system comprises anionic surfactant and amine oxide in a weight ratio of 2.5: 1 to 18: 1.

C. Cationic surfactants

Cationic surfactants, when present in the detersive form of the composition, are present in an effective amount, such as 0.1% to 20%, alternatively 0.2% to 5%, alternatively 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 N-alkyl or alkenyl ammonium surfactants

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

C6-C16, preferably N-alkyl or C6-C10 alkenyl ammonium, wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Another preferred cationic surfactant is a C6-C18 alkyl or alkenyl ester of a quaternary ammonium alcohol, such as quaternary chlorine esters. More preferably, cationic surfactants have the following formula:

R1 (CH2CH20) nH

[\ /] x

CH3 CH3

wherein R1 is C8-C18 hydrocarbyl and mixtures thereof, alternatively C8-14 alkyl, alternatively C8, C10 or C12 alkyl, and X is an anion, such as chloride or bromide.

d. Additional surfactants

Other suitable surfactants include ampholytic surfactants, hybrid ion surfactants, or mixtures thereof. Ampholytic surfactants suitable for use herein include amidopropyl betaines and derivatives of aliphatic or heterocyclic secondary and ternary amines in which the aliphatic moiety can be straight or branched chain and wherein one of the aliphatic substituents contains 8 to 24 atoms Carbon and at least one aliphatic substituent contains a water soluble anionic group. When present, ampholytic surfactants comprise from 0.01% to 20%, alternatively from 0.5% to 10%, by weight of the liquid detergent composition.

4. Diamines

Another optional ingredient of the liquid detergent compositions according to the present invention is a diamine. When the liquid detergent composition is a detersive composition, the liquid surfactant system may 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 both pK1 and pK2 are in the range of 8.0 to 11.5, alternatively in the range of 8.4 to 11, alternatively 8.6 to 10.75 . Suitable materials include 1,3-bis (methylamine) -cyclohexane (pKa = 10 to 10.5), 1,3-propanediamine (pK1 = 10.5; pK2 = 8.8), 1,6-hexanediamine (pK1 = 11; pK2 = 10), 1,3-pentanediamine (dYTeK Ep®) (pK1 = 10.5; pK2 = 8.9), 2-methyl-1,5-pentanediamine (DYTEK A®) (pK1 = 11 , 2; pK2 = 10.0). Other suitable diamine materials include primary / primary diamines with alkylene separators in the range of C4 to C8.

Definition of pK1 and pK2 - As used herein, "pKa1" and "pKa2" are amounts of a type collectively known to those skilled in the art as "pKa". PKa is used herein in the same manner as is usually known to the person skilled in the art of chemistry. The values cited herein can be extracted from the bibliography, such as "Critique! Stability Constants: Volume 2, Amines ”by Smith and Martel, Plenum Press, NY and London, 1975. Additional information on“ pKa ”can be found in the relevant bibliography of the company, such as information provided by DUPONT®, a diamine supplier. As a working definition herein, the pKa of the diamines is specified for an aqueous solution at 25 ° C and for an ionic strength of 0.1 M to 0.5 M.

In one embodiment of the present invention, the surfactant system is exempt or virtually free of any of the aforementioned surfactants, for example: exempt or practically free of non-ionic surfactant, exempt or practically free of cationic surfactant.

5. Suspended particles

Liquid detergent compositions comprise a plurality of suspended particles at a level of 0.01% to 5% by weight, alternatively 0.05% to 4% by weight, alternatively 0.1% to 3% by weight, of said liquid detergent composition. Examples of suitable suspended particles are provided in US Patent 7,169,741 to Barry et al. in cabbage 12-18 and in patent publications US-2005/0203213 by Pommiers et al., ^ 14-60.

to. Suspended particles with liquid core

In one embodiment, one or more of the suspended particles have liquid cores. These particles work especially well in terms of stability within the detergent composition before use; but they are adequately unstable in washing solutions formed from said products. In one embodiment, the liquid core has an ionically charged polymeric material encapsulated in a semipermeable membrane. This membrane can be formed by interaction of part of the ionically charged polymer in the core with another

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

polymeric material of opposite charge. Non-limiting examples of suitable liquid core suspension particles are available in US-7,169,741.

b. Suspended particles with solid core

Another type of suspended particle that is suitable for use herein includes particles (or beads) with solid nuclei. In one embodiment, the plurality of suspended particles comprises a friable pearl as described in EP-670 712. A suitable use of said friable pearl is skin exfoliation. Pearls or particles suitable for exfoliation may have a particle size in the range of 0.03 to 3 mm. In addition, these pearls can be friable, which means that during use they disintegrate into particles that have an average size of less than 50 micrometers. In one embodiment, the suspended particle comprises a teenage modifier. Suitable adolescent modifiers include ethylene glycol distearate (EGDS), TiO2, ZnO, mica, and mixtures thereof.

C. Particle size / shape

In one embodiment, the suspended particles are distinguishable beads at a glance suspended within the liquid detergent composition. In another embodiment, the suspended particles cannot be distinguished with the naked eye in the liquid detergent composition. The visibility of the particle or pearl is determined, of course, by different interrelated factors that include the size of the beads and the various optical properties of the beads and the liquid composition in which they are dispersed. A transparent or translucent liquid matrix combined with opaque or translucent beads will generally make the particles visible if they have a dimension less than 0.2 mm or greater, but smaller pearls may also be visible under certain circumstances. Even transparent pearls in a transparent liquid matrix could be distinguished with the naked eye if the refractive properties of the particles and the liquid are sufficiently different. Furthermore, even the particles dispersed in a somewhat opaque liquid matrix could be distinguished with the naked eye if they are large enough and have a different color than the matrix. As used herein, "distinguishable by the naked eye" refers to particles having a dimension less than 0.2 mm or greater, while not distinguishable to the naked eye refers to particles having a dimension less than 0.2 mm.

The suspended particles have a particle size in the range of 100 nanometers to 8 mm. As defined herein, "particle size" means that at least one of said suspended particles has a longer linear dimension as defined. Those skilled in the art will understand that suitable techniques for measuring particle size are available, for example, suspended particles having a size of 10 nanometers to 5000 nanometers are measured by a technique such as light scattering with a size analyzer. Brookhaven 90Plus nanoparticles, wherein a sample of the composition is diluted to a concentration of 0.001% to 1% v / v using suitable wetting and / or dispersing agents. A 10 ml sample of the diluted sample is introduced into a sample cell and the measurements that provide the average particle diameter are recorded; Optical microscopy can be used to detect particle sizes from 5 micrometers to 500 micrometers; and macroscopic measurement techniques can measure from 0.5 mm to 8 mm.

Something important has been discovered: that the liquid detergent composition of the present invention is capable of suspending a wide range of particles, from distinguishable particles with the naked eye with a particle size of up to 8 mm to adolescent agents having generally smaller particle sizes at 500 pm In one embodiment, the particle size is 0.1 mm to 8 mm, alternatively 0.3 mm to 3 mm, and alternatively 0.5 to 4 mm. In another embodiment, the suspended particles are not distinguishable to the naked eye, comprising a particle size of about 100 nanometers at 500 pm, alternatively from 1 pm to 300 pm, alternatively from 50 pm to 200 pm.

In another embodiment the liquid detergent composition comprises from 0.1% to 2% of said particles in suspension in the range of 50 to 750 micrometers in particle size, such as silica-TiO2 particles that function as sensory signals and exfoliating agents of the skin and an agent that improves fat removal from dishes. In addition, polyethylene beads and butylene / ethylene copolymers of a particle size ranging from 50 to 350 microns can be used. See WO 2005/010138 of Paye et al.

d. Particle density

The suspended particles used herein have a density of 700 kg / m3 to 4260 kg / m3, alternatively 800 kg / m3 to 1200 kg / m3, alternatively 900 kg / m3 to 1100 Kg / m3 , alternatively from 940 kg / m3 to 1050 kg / m3, alternatively from 970 kg / m3 to 1047 kg / m3, alternatively from 990 kg / m3 to 1040 kg / m3 at 25

The liquid detergent composition of the present invention is capable of suspending particles for 4 weeks at 25 ° C. Stability can be assessed by the use test during pouring, by direct observation or by image analysis, having colored particles suspended in a transparent liquid contained in a transparent bottle. A freshly prepared composition of the present invention is considered stable at least

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

10%, preferably less than 5% and more preferably less than 1% by weight of the particles settling in the bottom of the container after 4 weeks of static storage.

In one embodiment, the difference between the density of the liquid matrix and the density of the particles is less than 10% of the density of the liquid matrix, alternatively less than 5% and alternatively less than 3%, alternately less than 1%, alternatively less than 0.5%, at 25 ° C. The liquid matrix and the suspended particle have a density difference of 10 kg / m3 from 200 kg / m3, alternatively from 50 kg / m3 to 100 kg / m3.

Suitably, the particles are suspended so that the liquid detergent compositions are stable for 4 weeks at 25 ° C. Stability can be assessed by direct observation or by image analysis, having colored particles suspended in a transparent liquid contained in a transparent bottle. A freshly prepared detergent composition is considered stable if less than 10%, alternatively less than 5%, alternatively less than 1% by weight of the particles settling at the bottom of the bottle after 4 weeks of static storage.

Particles and / or additional particles suitable for use herein are described in patent publication US-2005/0203213 of Pommiers et al., And WO 2005/010138 of Paye et al. on p. 9-10.

and. Resistance of the particle to burst

Particles suitable for use in the liquid detergents herein should be physically and chemically compatible with the detergent matrix ingredients, but may disintegrate during use without leaving residues in tissues, hair or body parts, such as hands, and / or hard surfaces such as dishes or those being treated. Thus, within the liquid matrix of the detergent compositions, the particles have the ability to withstand a force before bursting or breaking from 20 mN to 20,000 mN, alternatively from 50 mN to 15,000 mN, alternatively from 100 mN to 10,000 mN This resistance makes them suitable for industrial handling, including the processes of manufacturing liquid detergents. They can also withstand pumping and mixing operations with virtually no breakage, and are also stable during transport. At the same time, the particles herein readily disintegrate during use due to their osmotic behavior in dilute aqueous media such as stirred wash solutions.

F. Perfume Microcapsules

In one embodiment, the liquid detergent composition comprises a perfume. The perfume is typically incorporated into the present compositions at a level of at least 0.001%, preferably at least 0.01%, more preferably at least 0.1%, and not more than 10%, preferably not more than 5% , more preferably not more than 3%, by weight.

In one embodiment, the perfume of the fabric softener composition of the present invention comprises one or more durable perfume ingredients having a boiling point of 250 ° C or more and a ClogP of 3.0 or more, more preferably at a level of at least 25% by weight of the perfume. Suitable perfumes, perfume ingredients and perfume vehicles are described in US-5,500,138; and document US-20020035053 A1.

In another embodiment, the perfume comprises a perfume microcapsule and / or a perfume nanocapsule. Suitable perfume microcapsules and 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-2003 195133 A1; US-2004087477 A1; US-20040106536 A1; US-6645479; US-6200949; US-4882220; US-4917920; US-4514461; US-RE 32713; US-4234627.

In another embodiment, the liquid laundry detergent composition comprises odor control agents such as those described in US-5942217: "Uncomplexed cyclodextrin compositions for odor control", issued August 24, 1999. Other odor control agents Suitable include those described in: US-5968404, US-5955093; US-6106738; US 5942217; and US-6033679.

6. Water

The liquid detergent compositions of the present invention will contain adequate amounts of water to form the structured liquid matrix thereof. In one embodiment, the 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 of the present memory

In one embodiment, the liquid detergent composition is a concentrated formulation comprising even as little as 1% to 30% water, alternatively 5% to 15%, alternatively 10% to 14%. Concentrated formulations would be especially desirable for embodiments in which the present composition is encapsulated in a unit dose article.

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

7. Adjuvant ingredients

to. Organic solvents

The present compositions may optionally comprise an organic solvent. Suitable organic solvents include C4-14 ethers and diesters, glycols, alkoxylated glycols, C6-C16 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated branched aliphatic alcohols, C1-C5 linear alkoxylated alcohols, C1- alcohols C5 linear, amines, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof. In one embodiment, 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. . Such organic solvents can be used together with water, or they can be used without water.

b. Polycarboxylate

The present composition may comprise a polymer, a polycarboxylate copolymer comprising a carboxylic acid monomer. A water soluble carboxylic acid polymer can be prepared by polymerization of a carboxylic acid monomer or by copolymerizing two monomers, such as an unsaturated hydrophilic monomer and an oxyalkylated hydrophilic monomer. Examples of 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 vinyl sulfonate . The hydrophilic monomer can be further copolymerized with oxyalkylated monomers such as ethylene or propylene oxide. The preparation of oxyalkylated monomers is described in patents US 5,162,475 and US 4,622,378. The hydrophilic oxyalkylated monomer has a solubility of 500 grams / liter, more preferably 700 grams / liter in water. The unsaturated hydrophilic monomer may also be grafted with hydrophobic materials, such as polyalkylene glycol blocks. See, for example, the materials described in patents US-5,536,440, US-5,147,576, US-5,073,285, US-5,534,183, US-5,574,004 and WO 03/054044.

d. Magnesium ions

The optional presence of magnesium ions can be used in the detergent composition when the liquid detergent compositions are used in softened water containing some divalent ions. When used, magnesium ions are added as a hydroxide, chloride, acetate, sulfate, formate, oxide or nitrate salt to the liquid detergent compositions of the present invention. When included, magnesium ions are present at an active level of 0.01% to 1.5%, alternatively 0.015% to 1%, alternatively 0.025% to 0.5%, by weight of The liquid detergent composition.

d. Hydrotrope

Liquid detergent compositions optionally comprise a hydrotrope in an effective amount, that is, from 0% to 15% or from 1% to 10%, or from 3% to 6%, so that the liquid detergent compositions are compatible with water. Hydrotropes suitable for use in the present invention include anionic type hydrotropes, particularly sodium, potassium and xylene ammonium sulphonate, sodium, potassium and toluene ammonium sulphonate, sodium potassium and cumenium ammonium sulphonate, and mixtures thereof, as described in US Patent 3,915,903.

and. Stabilizer of polymeric soaps

The liquid detergent compositions of the present invention may optionally contain a polymeric soap stabilizer at a level of 0.01% to 15%. These polymeric soaps stabilizers provide greater volume and duration of soaps of liquid detergent compositions. These polymeric soap stabilizers can be selected from homopolymers of (N, N-dialkylamino) alkyl esters and esters of (N, N-dialkylamino) alkyl acrylate. The weight average molecular weight of the polymeric soap formation enhancer, determined by conventional gel filtration chromatography, is 1000 to 2,000,000, alternatively 5000 to 1,000,000, alternatively 10,000 to 750,000, alternatively from 20,000 to 500,000, alternatively from 35,000 to 200,000. The polymeric soap stabilizer may optionally be present in the form of both an organic and inorganic salt, for example, a citrate, sulfate or nitrate salt of the (N, N-dimethylamino) alkylacrylate ester.

A suitable polymeric soap stabilizer is the esters of (N, N-dimethylamino) alkylacrylate, especially the acrylate ester represented by the following formula:

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

image5

When present in the liquid detergent compositions, the polymeric soap forming enhancer may be present in the liquid detergent composition of 0.01% to 15%, alternatively 0.05% to 10%, alternatively 0.1% to 5%, by weight of the liquid detergent composition.

F. Carboxylic acid

The liquid detergent compositions according to the present invention may comprise a linear or cyclic carboxylic acid or a salt thereof to improve the rinsing feel of the liquid detergent composition. The presence of anionic surfactants, especially when present in larger amounts in the range of 15-35% by weight of the liquid detergent composition, causes the liquid detergent composition to transmit a slippery touch to the hands. This feeling of unctuousness is reduced when carboxylic acid is used as defined herein, that is, the rinsing touch becomes rough.

The carboxylic acids useful herein include salicylic acid, maleic acid, acetylsalicylic acid, 3-methyl salicylic acid, 4-isophthalic hydroxy acid, dihydroxypumaric acid, 1,2,4-tricarboxylic acid, pentanoic acid and salts thereof and mixtures thereof. the same. If the carboxylic acid exists as a salt, the salt cation is selected from alkali metal, alkaline earth metal, monoethanolamine, diethanolamine or triethanolamine and mixtures thereof.

In one embodiment, the carboxylic acid or its salt, when present, is at a level of 0.1% to 5%, alternatively 0.2% to 1% and alternatively 0.25% to 0 ,5 %.

g. pH of the composition

In one embodiment, the liquid detergent composition has a pH of 4 to 14, alternatively 6 to 13, alternatively 6 to 10, alternatively a basic pH greater than 7. Something important has been discovered: that the Bacterial cellulose network is able to provide the desired structuring benefits at a pH greater than 7, or 10.

h. Additional adjuvant components

The liquid detergent compositions herein may also comprise different adjuvant components. In one of these embodiments, the liquid detergent compositions comprise from 0.1% to 30%, alternatively from 0.5% to 20%, alternatively from 1% to 10%, of one or more of said components additional adjuvants, alternatively the liquid matrix comprises from 0.1% to 50% by weight of said liquid detergent composition of one or more adjuvant components.

The additional adjuvant component may comprise one or more detersive enzymes that provide advantages of cleaning ability and / or tissue care. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratinases, reductases, oxidases, phenoxidases, lipoxygenases, ligninases, pulses, pulses , pentosanases, malanases, p-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and known amylases, or combinations thereof. A preferred enzyme combination comprises a combination of conventional detersive enzymes such as protease, lipase, cutinase and / or cellulase together with amylase. Detersive enzymes are described in greater detail in US Pat. No. 6,579,839.

When used, enzymes will normally be incorporated into liquid laundry detergent compositions herein at levels sufficient to provide up to 10 mg by weight, more commonly 0.01 mg to 5 mg, of active enzyme by gram of the composition. In other words, the aqueous liquid detergent compositions herein typically can comprise from 0.001% to 5%, alternatively from 0.01% to 1% by weight, of a commercial enzyme preparation. Protease enzymes, for example, are generally present in such commercial preparations at levels sufficient to provide 0.005 to 0.1 Anson (AU) units of activity per gram of detergent composition. Notably, it is believed that the present external structuring agent provides sufficient structuring capacity, including the capabilities of pearl suspension and shear viscosity reduction, in the presence of detersive enzymes for prolonged periods of time, such as for 6 months or more.

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

Additional adjuvant components are optical brighteners at levels of 0.01% to 1%, dye transfer inhibitors at levels of 0.0001% to 10%, suds suppressors at levels of 0.001% to 2%, release polymers of dirt at levels of 0.01% to 10%, silicone polymers from 0.01% to 50%, perfumes, dyes, opacifiers, chelants, thickening agents and pH buffering agent. Another discussion of acceptable optional ingredients suitable for use in a mild-acting liquid detergent composition can be found in US Pat. No. 2005/0203213 A1 of Pommiers et al. in ^ 128 - 164.

In one embodiment, when the liquid detergent composition is a liquid laundry detergent, one or more of the adjuvant components described are included in the formulation. Attachment components suitable for a liquid laundry detergent include: detersive enzymes, optical brighteners, dye transfer inhibitors, soap suppressants, detersive dirt release polymer, other tissue-beneficial agents , stabilizers, auxiliary detersive surfactants, detersive detergent builder, perfumes, coloring agents, enzymes, bleaches, odor control agents, antimicrobials, antistatic agents, fabric softening agents, grease cleaning polymers including polymers of grafting, and combinations thereof. All these materials are of the type commonly used in laundry detergent products. However, they can be supplied to aqueous wash solutions, and / or to the fabrics that are being washed there, especially efficiently by the compositions of the present invention. Non-limiting examples of suitable laundry aids are provided in US Patent 7,169,741 to Barry et al. of cabbage 5, line 49 to col. 8, line 15 and col. 19, line 8 - col. 20, line 10, patent publication US-2007 / 0281879A1 of Sharma et al.

8. Manufacturing process

In one embodiment, the invention provides a process for manufacturing a liquid detergent composition comprising the steps of: providing (a) a feed comprising from 0.005% to 1.0%, preferably less than 0.125%, preferably less than 0.05 %, even more preferably from 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 food in a mixing chamber to an energy density greater than 1.0 x 105 J / m3 to form a bacterial cellulose network; and (c) providing a surfactant system at a level of 0.01% to 70%, preferably 1% to 50%, preferably 3% to 20%, by weight of said liquid detergent composition of an anionic surfactant; 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 which further comprises a nonionic surfactant; a cationic surfactant; an ampholytic surfactant; a hybrid ion surfactant; or mixtures thereof, wherein said step of providing a surfactant system is either performed together with step (a) or after step (b), wherein the step of providing said surfactant system with said bacterial cellulose network forms a liquid matrix having a creep stress of 0.003 to 5.0 at 25 ° C. In one embodiment, the process further comprises: adding the suspended particles to the liquid matrix.

As described in the present invention, the step of activating said bacterial cellulose is performed under high and intense shear processing conditions such as with an ultrasonic homogenizer such as SONOLATOR® from Sonic Corp. Something important has been discovered: that when cellulose bacterial is activated at a sufficiently intense processing stage, the bacterial cellulose network achieved provides improved creep tension without having to add additional levels of bacterial cellulose. It is believed that high and intense shear processing conditions such as ultrasonic processing that can create hydrodynamic cavitation (i.e., using a SONOLATOR®) allows the crystalline fibers of the bacterial cellulose to generate a more homogeneous dispersion of the crystalline fibers. It is believed that the advantage of using high and intense shear processing conditions compared to lower energy processes is shown from the correlation between the energy density of the process and the resulting creep stress. It is believed that when the fibers disperse more fully during activation, the greater the effective volume occupied by the bacterial cellulose network and the degree of interconnectivity within the bacterial cellulose network will be greater. Said dispersion difference can be observed with the optical microscope since fiber bundles having average lengths of 1 micrometer to 20 micrometers can be observed in conventionally processed samples that have an average length less than 2 micrometers, alternatively less than 1, 5 micrometers

to. Energy density

The energy density is generated by exerting a power density in a feed within the mixing chamber during a residence time. In one embodiment, the process of manufacturing the liquid detergent composition comprises: subjecting the bacterial cellulose and a solvent, e.g. ex. water, at an energy density greater than

1.0 x 105 J / m3, alternatively greater than 2.0 x 106 J / m3. In one embodiment, the liquid detergent composition comprises subjecting said bacterial cellulose and water to an energy density of 2.0 x 106 J / m3 to 5.0 x 107 J / m3, alternatively 5.0 x 106 J / m3 to 2.0 x 107 J / m3, or 8.0 x 106 J / m3 to 1.0 x 107 J / m3.

In one example, a liquid detergent composition is formed using a static mixer, such as a Koch / Sulzer model SMX from Sulzer Corporations at an energy density of 1.6 x 105 J / m3 to 4.8 105 J / m3. In another example, a liquid detergent composition is formed using a high shear mixer, such as an IKA mixer at a

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

energy density from 1.0 J / m3 to 2.0 x 106 J / m3. In yet another example, a liquid detergent composition is formed using an ultrasonic homogenizer, such as SONOLATOR®, at an energy density of 7.0 x 106 J / m3 at

4.0 x 107 J / m3. Single-step and multi-step processing is also within the scope of the invention. Additionally, the activation step can be carried out with any of the above processing techniques such as a premix of the bacterial cellulose and solvent before contacting and subsequent mixing with other ingredients such as the surfactant system or in the presence of one or more additional ingredients

The energy density can be represented by the equation: E = W * AT, where E represents the energy density, W represents the power density, and AT represents the residence time. As defined herein, residence time means the average amount of time a vesicle remains within the mixing chamber. The residence time is determined by calculating the size of the cavity divided by the liquid composition output flow of the mixing chamber.

b. Power density and residence time

The liquid detergent compositions of the present invention require a relatively higher power density than conventional high shear mixing. As used herein, the power density can be determined by the equation: W = AP / AT, where W is the power density, AP is the pressure applied within the mixing chamber, and AT is the time of home.

In one embodiment, the energy density is generated from a power density of 0.5 x 106 W / m3 at

100,000 x 106 W / m3 (from 0.5 W / ml to 100,000 W / ml), alternatively from 50 x 106 W / m3 to 30,000 x 106 W / m3 (from 50 W / ml to 30,000 W / ml) . It is noted that the minimum power density necessary to achieve the liquid detergent composition of the present invention is 0.5 x 106 W / m3 (0.5 W / ml) at 20 kHz.

When the power density is 0.5 x 106 W / m3 (0.5 W / ml), the residence time is 15 minutes; alternatively, when the power density is 100,000 x 106 W / m3 (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. In addition, when the residence time is less than 1 minute, the power density must be greater than 10 x 106 W / m3 (10 W / ml). When the residence time is less than 1 second, the power density must be greater than 500 x 106 W / m3 (greater than 500 W / ml); alternatively. When the residence time is less than 10 ms, the power density must be greater than 50,000 x 106 W / m3 (greater than 50,000 W / ml).

After the feed is subjected to the necessary energy, the liquid detergent composition is discharged at a flow rate of 1 kg / min at 1000 kg / min and, alternatively from 10 kg / min to approximately 500 kg / min. The flow rate can be represented by the following equation Q = 30 A V (AP), where Q = flow rate, A = hole size, and AP = pressure inside the mixing chamber. As defined herein, the size of the hole is the cross-sectional area of the hole. In one embodiment, the hole size is 32.25 cm2 to 0.65 cm2 (0.0005 inches2 to 0.1 inches2).

C. Feeding systems

The liquid detergent composition of the present invention can be manufactured with a variety of feeding systems. For example, in 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 is performed in the same step as the mixing of the other components. In another embodiment, the process comprises a double feed system comprising a first feed comprising bacterial cellulose and solvent, and a second feed comprises a surfactant system and any other component. The feeds are introduced simultaneously in the mixing chamber.

In one embodiment, one or more feeds are premixed before entering the mixing chamber. In another embodiment, one or more of the feeds are not premixed before entering the mixing chamber. In one embodiment, when a double feed system is used, the first feed comprising the bacterial cellulose and solvent is activated or activated at least partially with the premixed before being introduced into the mixing chamber. In one embodiment, the premix is subjected to conditions of intense ultrasonic processing.

In one embodiment, a premixing step is used to at least partially activate the bacterial cellulose in the presence of an aqueous solution to form a first feed. A second feed can be provided comprising the other desired components, such as surfactants, perfumes, particles, and auxiliary ingredients. The process comprises: Step 1: Activate the bacterial cellulose (optionally in powder form) with water or an aqueous solution, by means of any conventional and well-known discontinuous or continuous system and to form a bacterial cellulose premix. Stage 2: The bacterial cellulose premix and a second feed are mixed together and subjected to the high shear intense processing conditions defined above. Stage 3: The product obtained in stage 2 is added to the liquid detergent composition in a conventional mixer.

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

It should be understood that certain particles suitable for use in the compositions of the present invention may be both sensitive and intolerant of shear (which means that they may suffer undesirable structural damage if they are subjected to high shear processing conditions - i.e., microcapsules ). In these cases, it may be desirable to add these intolerant particles to shear after the stage of activating bacterial cellulose. In addition, there may be particles that are abrasive to the mixing chamber and / or the vibrating blade of the ultrasonic homogenizer. These abrasive particles can also be added advantageously later in the manufacturing process. Other particles that can be damaged by high and intense shear processing, and / or be abrasive to the mixing apparatus can be added to the feed streams as necessary.

9. Turbidity

In one embodiment, the liquid detergent composition comprises a turbidity of less than 320 UTN, alternatively less than 250 UTN, alternatively less than 200 UTN, alternatively less than 150 UTN, alternatively less than 100 UTN, measured according to the turbidity test method described herein. Compositions with a turbidity of less than 150, alternatively less than 100 are "transparent" while those with a turbidity of less than 320, alternatively less than 250 are "translucent". In another embodiment, the liquid detergent composition is permeable. Alternatively, the liquid matrix has a turbidity of 20 to 320 nephelometric turbidity units.

Here, turbidity is determined using a Hach model 2100P portable turbidimeter ("Turbidimeter"), from Hach Company, Loveland, CO. StablCal is a registered trademark of Hach Company.

Turbidity method with turbidimeter: The turbidimeter measures turbidity from 0.01 UTN to 1000 UTN. The turbidimeter works according to the nephelometric turbidity measurement principle. The turbidimeter's optical system includes a tungsten filament bulb, a 90 ° detector to monitor the scattered light and a transmitted light detector. The turbidimeter microprocessor calculates the signal ratio of the detector at 90 ° and the transmitted light detectors. This relationship technique corrects interference from colored or light absorbing materials, and compensates for fluctuations in the intensity of the bulb.

Calibration is performed using StablCal x® secondary standards provided with the turbidimeter. The undiluted sample is contained in the sample cell, the outer wall of the cell is kept clean of water and fingerprints. A thin film of silicone oil is applied to the outer wall of the sample cell to mask minor imperfections and scratches on the sample cell wall, which can contribute to turbidity or light scattering. A measurement is taken and the result is displayed in UTN units. All samples are equilibrated and measured at 25 ° C. Samples are measured within 24 hours after manufacture.

The liquid detergent compositions of the present invention can be conditioned in any suitable packaging to deliver the liquid detergent composition for use. In one embodiment, the package is a transparent container made of glass or plastic.

In another embodiment, the liquid detergent compositions are packaged in a unit dose bag, wherein the bag is made of a water-soluble film material, such as a polyvinyl alcohol. In one embodiment, the unit dose bag comprises a single or multi-compartment bag where the present liquid detergent composition can be used together with any other conventional liquid powder detergent composition. Examples of suitable water-soluble film bags and materials are provided in US Patents 6,881,713 to Sommerville-Roberts et al., US 6,815,410 to Boutique et al., And US 7,125,828 to Catlin et al.

10. Measurement of the degree of connectivity in the bacterial cellulose network as a result of the processing conditions

Stage A: Sample preparation

A drop of sample (approximately 5 pl) is placed on a conventional glass slide and dispersed as a thin film when covered with a 22 mm x 22 mm cover glass of conventional glass. The edges of the glass coverslip are then sealed with wax. At least two slide preparations of each sample are manufactured.

The prepared slides are observed with a compound optical microscope (the inventors used a Zeiss AxioVert200 microscope), equipped with a dark field CytoViva condensing system (CytoViva Inc, Alburn, AL, USA), and an oil immersion objective 63x which has a digital aperture reduction diaphragm, thus 40x and 10x dry targets.

For quantification of nodes, thirty representative images of each sample preparation are captured, at each of the two extensions (400x and 630x) with a digital CCD camera, (the inventors used a 12-bit monochrome Zeiss AxioCam MRm version 3, with 2x2 areas, calibrated for length scale (pixels per micrometer) (the inventors used a Zeiss AxioVision software). Ten images were also captured at low magnification

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

(100x) of each sample, using a traditional dark field condenser or uncoupled phase rings, and long exposure times of the chamber, to assess the overall homogeneity of the fiber network.

Stage B: Image Analysis

The number of nodes (fiber intersections) per image is determined using the free image analysis software, Image J (National Institutes of Health, Bethesda, MD).

The images are first processed by application of algorithms for smoothing, background subtraction and contrast enhancement. Next, the threshold of the images is determined (in such a way that all the fibers are shown in a binarized image, the background being the liquid medium). Those skilled in the art will understand that different samples will require different threshold values depending on the formulation from which the image was obtained, as well as the imaging equipment used. The threshold configuration 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. Those skilled in the art will understand that the threshold range should be adjusted to maximize fiber pixel selection and minimize background noise selection. Subsequently, the threshold images are processed with the skeletonization algorithm.

Image analysis processing stages (Image J)

1. Open image

2. Smoothing processes

3. Process - Subtract the Background (sliding paraboloid; 10 pixels)

4. Process - Improve contrast (Normalize, 0.5% pixels)

5. Image - Adjust - Threshold

6. Image - Search tables - Invert LUT

7. Edit— ^ Reverse

8. Process - Binary - Skeletonize Stage C: Calculation of the number of node points:

The numerical data on the number of node points in each skeletonized image is extracted using the Image J macro / module provided below as Program A (in Java) and exported to a spreadsheet for statistical analysis.

Program A:

import ij. *; import ij.process. *; import ij.gui. *; import java.awt. *; import ij.plugin.filter. *; import java.util. *; import java.math. *; import ij.text. *;

/ **

* Only applies to full images, waiting for a black silhouette on a white background

* @author Bob Reeder

* /

public class Node_Count implements PlugInFilter {

ImagePlus imp;

private boolean remove_isolated_pixels = true;

private ArrayList <Point> isolatedPixels = new ArrayList <Point> (1000); private ArrayList <Point> endpointPixels = new ArrayList <Point> (1000); private ArrayList <Point> nodePixels = new ArrayList <Point> (1000); private ImageProcessor imageCopy;

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

deprive ImageProcessor imagePadded;

public int setup (String arg, ImagePlus imp) {this.imp = imp; return DOES_ALL;

}

public void run (ImageProcessor ip) {

TextWindow output = new TextWindow (“Output Window”, "", 200, 50);

imageCopy = ip.createProcessor (ip.getWidth (), ip.getHeightO); imageCopy = ip.duplicate ();

imagePadded = ip.createProcessor (ip.getWidth () + 2, ip.getHeight () + 2); imageCopy.invert ();

imageCopy = binarizeImage (imageCopy); imagePadded = padImage (imageCopy, 0);

imagePadded = classifyPixels (imagePadded, isolatedPixels, endpointPixels, nodePixels); imagePadded = fixNodes (imagePadded, 4, nodePixels);

ImagePlus imp2 = new ImagePlus (“Fixed Nodes”, imagePadded);

imp2.setDisplayRange (0.0, 5.0);

imp2.show ();

output.append ("Total Number of Nodes:" + nodePixels.size () + "\ n"); output.append (“Total Number of Endpoints:” + endpointPixels.size () + “\ n”);

}

/ ** Convert the image into an authentic binary file

* that is, 0 is still 0, the rest of the values become 1

* (Written: 11/21/08)

* @param ImageProcessor imageProc - ImageProcessor to binarize

* @return Object contains the binarized image

* /

private ImageProcessor binarizeImage (ImageProcessor imageProc) {

ImageProcessor tmpImageProc;

tmpImageProc = imageProc.createProcessor (imageProc.getWidth (), imageProc.getHeight ());

for (int i = 0; i <imageProc.getWidth (); i ++) {for (int j = 0; j <imageProc.getHeight (); j ++) {

tmpImageProc.putPixel (i, j, (imageProc.getPixel (i, j) == 0)? 0: 1);

}

}

return (tmpImageProc);

}

/ ** Enlarge the image by 2 pixels in each direction and fill the border with padValue

* (Written: 11/21/08)

* @param ImageProcessor imageProc: ImageProcessor to grid

* @param int padValue - value to be placed in the limit

* @return Object contains the grid image

* /

private ImageProcessor padImage (ImageProcessor imageProc, int padValue) {int imageWidth = imageProc.getWidth () + 2; int imageHeight = imageProc.getHeight () + 2;

ImageProcessor tmpImageProc;

tmpImageProc = imageProc.createProcessor (imageWidth, imageHeight);

for (int i = 0; i <imageWidth; i ++) {for (int j = 0; j <imageHeight; j ++) {

if ((0 == i) || ((imageWidth-1) == i) || (0 == j) || ((imageHeight - 1) == j)) tmpImageProc.putPixel (i, j, padValue ); else

tmpImageProc.putPixel (i, j, imageProc.getPixel (i-1, j-1));

}

}

return (tmpImageProc);

}

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

/ ** Sort the pixels according to the connection level

* (Written 11/21/08)

* @param imageProc - image processor to work on it

* @param isolatedPixelsCoords - matrix to store 0 connected pixel coordinates

* @param endpointPixelCoords - matrix to store 1 connected pixel coordinates

* @param nodePixelCoords - matrix to store 3 or more connected pixel coordinates

* @return Object containing the classification map

* /

private ImageProcessor classifyPixels (ImageProcessor imageProc,

ArrayList <Point> isolatedPixelsCoords,

ArrayList <Point> endpointPixelCoords,

ArrayList <Point> nodePixelCoords) {int connectionValue = 0; int connectionValue2 = 0; isolatedPixelsCoords.clear (); endpointPixelCoords.clear (); nodePixelCoords.clear ();

ImageProcessor tmpImageProc;

tmpImageProc = imageProc.createProcessor (imageProc.getWidth (), imageProc.getHeight ());

for (int i = 1; i <imageProc.getWidth () - 1; i ++) {for (int j = 1; j <imageProc.getHeight () - 1; j ++) {if (0 == imageProc.getPixel (i , j))

{

tmpImageProc.putPixel (i, j, 0);

}

else

{

connectionValue = 0; connectionValue2 = 0;

connectionValue = imageProc.getPixel (i-1, j-1) + imageProc.getPixel (i, j-1) + imageProc.getPixel (i + 1, j-1) + imageProc.getPixel (i-1, j) + imageProc.getPixel (i + 1, j) + imageProc.getPixel (i-1, j + 1) + imageProc.getPixel (i, j + 1) + imageProc.getPixel (i + 1, j + 1);

connectionValue2 = imageProc.getPixel (i-2, j-2) + imageProc.getPixel (i-1, j-2) + imageProc.getPixel (i, j-2) + imageProc.getPixel (i + 1, j-2 ) + imageProc.getPixel (i + 2, j-2) + imageProc.getPixel (i + 2, j-1) + imageProc.getPixel (i + 2, j) + imageProc.getPixel (i + 2, j + 1 ) + imageProc.getPixel (i + 2, j + 2) + imageProc.getPixel (i + 1, j + 2) + imageProc.getPixel (i, j + 2) + imageProc.getPixel (i-1, j + 2 ) + imageProc.getPixel (i-2, j + 2) + imageProc.getPixel (i-2, j + 1) + imageProc.getPixel (i-2, j) + imageProc.getPixel (i-2, j-1 );

/ * if (connectionValue2 <connectionValue && connectionValue> 2) connectionValue--;

* /

switch (connectionValue)

{

case 0: {

isolatedPixelsCoords.add (new Point (i, j)); tmpImageProc.putPixel (i, j, connectionValue); break;

}

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

case 1: {

if (! ((1 == i) || (1 == j) || ((tmpImageProc.getWidth () - 2) == i) || ((tmpImageProc.getHeight () - 2) == j) )) {tmpImageProc.putPixel (i, j, connectionValue); endpointPixelCoords.add (new Point (i, j));

}

break;

}

case 2: {

tmpImageProc.putPixel (i, j, connectionValue); break;

}

case 3: {

nodePixelCoords.add (new Point (i, j)); tmpImageProc.putPixel (i, j, connectionValue); break;

}

case 4: {

nodePixelCoords.add (new Point (i, j)); tmpImageProc.putPixel (i, j, connectionValue); break;

}

case 5: {

nodePixelCoords.add (new Point (i, j)); tmpImageProc.putPixel (i, j, connectionValue); break;

}

case 6: {

nodePixelCoords.add (new Point (i, j)); tmpImageProc.putPixel (i, j, connectionValue); break;

}

case 7: {

nodePixelCoords.add (new Point (i, j)); tmpImageProc.putPixel (i, j, connectionValue); break;

}

case 8: {

nodePixelCoords.add (new Point (i, j)); tmpImageProc.putPixel (i, j, connectionValue); break;

}

default: {break;

}

} // end switch} // end else} // end for j} // end for i

return (tmpImageProc);

}

/ **

* Reduce the number of 3 or more pixels connected in nodes to a single pixel

* selected by choosing the pixel closest to the center of mass of the pixel group.

* (Written 11/22/08)

* @ param imageProc: ImageProcessor to act on

* @param radius: search radius to investigate the 3 adjacent pixels connected

* @param nodePixelCoords: matrix containing the list of 3 or more connected pixels

* @return modified ImageOricessor showing new connections

* Note: the nodePixelCoordinates array is updated to reflect the new nodes

* /

private ImageProcessor fixNodes (ImageProcessor imageProc, int radius, ArrayList <Point> nodePixelCoords) {double dist; double minDist = 0; double xSum = 0; double ySum = 0;

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

Point centerOfMassPixel = new Point (0,0); int nNeighbors = 0;

Point coord1 = new Point (0, 0);

Point coord2 = new Point (0, 0);

ArrayList <Point> neighborList = new ArrayList <Point> (50);

ImageProcessor tmpImageProc;

tmpImageProc = imageProc.createProcessor (imageProc.getWidth (), imageProc.getHeight ()); tmpImageProc = imageProc.duplicate ();

radius * = radius;

for (int i = 0; i <nodePixelCoords.size (); i ++) {nNeighbors = 0; neighborList.clear (); coord1 = nodePixelCoords.get (i); neighborList.add (coord1);

xSum = coord1.x; ySum = coord1.y;

tmpImageProc.putPixel (coord1 .x, coord1 .y, 2); for (int j = i + 1; j <nodePixelCoords.size (); j ++) {coord2 = nodePixelCoords.get (j);

/ * dist = (int) Math.round (coord1 .distance (coord2)); * /

dist = (coord1 .x - coord2.x) * (coord1 .x - coord2.x) + (coord1 .y - coord2.y) * (coord1 .y - coord2.y); if (dist <radius) {nNeighbors ++; xSum + = coord2.x; ySum + = coord2.y; neighborList.add (coord2); tmpImageProc.putPixel (coord2.x, coord2.y, 2); nodePixelCoords.remove (j);

j- = 1;

}

} // end for j

centerOfMassPixel.x = (int) Math.round (xSum / (nNeighbors + 1)); centerOfMassPixel.y = (int) Math.round (ySum / (nNeighbors + 1));

coord2 = neighborList.get (0); // assume first pixel is closest pixel / * minDist = coord2.distance (centerOfMassPixel); * /

minDist = (coord2.x - centerOfMassPixel.x) * (coord2.x - centerOfMassPixel.x) +

(coord2.y - centerOfMassPixel.y) * (coord2.y - centerOfMassPixel.y); if (neighborList.size ()> 1) {

for (int k = 1; k <neighborList.size (); k ++) {coord1 = neighborList.get (k);

/ * dist = coord1 .distance (centerOfMassPixel); * /

dist = (coord1.x - centerOfMassPixel.x) * (coord1 .x - centerOfMassPixel.x) +

(coord1.y - centerOfMassPixel.y) * (coord1.y - centerOfMassPixel.y); if (dist <minDist) coord2 = coord1;

}

}

tmpImageProc.putPixel (coord2.x, coord2.y, 3);

nodePixelCoords.set (i, coord2); // Update the array to reflect the new nodes} // end for i

return (tmpImageProc);

}

} // end class

In one embodiment, the degree of fiber connectivity is quantified by determining the average number of nodes (fiber intersections) in 30 representative images with two different extensions (400X and 630x). Something important has been discovered: that the count of nodes per image is significantly lower in samples made with high shear mixing (HSM) prepared using a rotor-stator type device that generates an energy density of 2 * 106 J / m3 than in samples processed under high and intense shear processing conditions using a one-step feeding system with a SONOLATOR® at 34473 kPa (5000 Psi) that generates an energy density of 3.5 * 107 J / m3, indicating less connectivity of the

5

10

fifteen

twenty

25

30

35

40

Four. Five

fifty

55

60

65

fiber network Without attempting to impose any theory, it is believed that the degree of quantified connectivity when determining the average number of nodes is also consistent with a lower creep voltage measured in the HSM sample (0.006 Pa) compared to the creep voltage measured in the Sample processed under high and intense shear processing conditions using a one-step feeding system with a SONOLATOR® at 34473 kPa (5000 Psi). A higher degree of fiber connectivity results in a higher creep tension and, consequently, better suspension properties in the final product.

A conventional image area of the average nodes / pm2 is calculated for each bacterial cellulose concentration (then in the memory, "SMNI index") by the following formula: (Average nodes determined for an image / image size in pm2 ) / (% by weight of bacterial cellulose). Thus, in one embodiment, the bacterial cellulose network of the present invention comprises an SMNI index of at least 0.099, at least 0.105, at least 0.115, at least 0.15, at least 0.2. In another embodiment, the SMNI index can be up to 1.

Fig. 3 provides an example of a skeletonized image of the HSM sample having 233 nodes / image observed under a 400x magnification (447 pm x 336 pm). The distance 100 represents a straight line distance between the image boundary and a part of the skeletonized fiber network. Fig. 4 provides an example of a skeletonized image of a sample processed under conditions of intense processing having 639 nodes / image observed under a magnification of 400x. Distance 200 demonstrates a straight line distance between two parts of the skeletonized fiber network. Fig. 5 provides another skeletonized image of the sample of Fig. 3 having 279 nodes / image observed under a 630x magnification (284 pm x 213 pm). Distance 300 demonstrates a straight line distance between two parts of the skeletonized fiber network. Fig. 6 provides another skeletonized image of the sample of Fig. 4 having 367 nodes / image observed under a 630x magnification. Distance 400 demonstrates a straight line distance between two parts of the skeletonized fiber network. The samples shown in Figs. 3-6 were made with bacterial cellulose at 0.036% by weight. It is believed that these illustrative images show how the processing conditions affect the connectivity of the bacterial cellulose fibers that keep the formulations constant. Without attempting to impose any theory, it is believed that greater connectivity allows for better rheological advantages that include increased creep stress and pearl suspension capacity. Other distances 100, 200, 300 and 400 are provided simply for illustrative purposes of how a straight line distance is measured between two points of the skeletal bacterial fiber network, when viewed under various extensions.

Samples:

The independent samples prepared according to Example 3, below, except with 0.036% by weight of bacterial cellulose, 0.018 xanthan gum, and 0.006 CMC were manufactured by HSM and high and intense shear processing conditions. The calculations of the nodes are given below in Tables 1 and 2. At an increase of 400x: 340 average nodes / image (447 pm x 336 pm = 150,192 pm2) by HSM (which has a SMNI index of 0.0629) . vs. 580 average nodes / image (447 pm x 336 pm) under high and intense shear processing conditions (which has a SMNI index of 0.107). At an increase of 630x: 214 average nodes / image (284 pm x 213 pm = 60,492 pm2) by HSM (which has a SMNI index of 0.0983), vs. 343 average nodes / image (284 pm x 213 pm) under high and intense shear processing conditions (which has an SMNI index of 0.158). In one embodiment, the bacterial cellulose network comprises an average of 350 nodes average / image nodes (447 pm x 336 pm), alternatively more than 500 average nodes / image, alternatively more than 580 average nodes / image, alternatively more than 600 average nodes / image. In another embodiment, the bacterial cellulose network comprises an average of nodes of 210 average / image nodes (284 pm x 213 pm) alternatively more than 300 average / image nodes, alternatively more than 350 average / image nodes, of alternatively more than 400 average nodes / image.

The low fiber connectivity in the HSM sample is also reflected in a higher coefficient of variation (CV) of the number of nodes. At an increase of 400x: 39% CV per HSM, vs. 18% CV per sonification. At an increase of 630x: 59% CV per HSM, vs. 22% CV per sonification. The CV values calculated herein were determined based on the relative difference in the average nodes observed for a given image area of a given sample. It is believed that the CV between samples prepared by different processing conditions should be consistent for the different% by weight of bacterial cellulose. The CV as used herein is the ratio of the standard deviation to the average as a percentage, (standard deviation / average x 100), for a given increase and, therefore, provides a relative measure of variation between the series of data. CV400 is the relationship with an increase of 400x. Without attempting to impose any theory, it is believed that although the value of average nodes / image may be altered by the threshold configuration. The CV, however, should be less sensitive to variations in the threshold configuration. In one embodiment, the bacterial cellulose network comprises a CV400 and / or the CV630 is from 10% to 39%, alternatively from 15% to 25%, alternatively 20%.

The lower fiber connectivity in samples with high shear can be easily observed with dark field images at low magnification (400x). In these images, numerous large gaps / tears can be observed in the fiber network for samples with high shear, while fiber network samples that are activated under high and intense shear processing conditions appear dense and homogeneous, no breaks or gaps in the fiber network. In one embodiment, when observed under obtaining dark field images at 400x, the greatest straight line distance between two points in the network

25

Skeletonized bacterial fiber (or between the limit of the image and a network point) is less than 250 micrometers in length, alternatively less than 100 micrometers, alternatively less than 50 micrometers and alternatively less than 15 micrometers , alternatively less than 5 micrometers.

5 Table 1: Samples prepared and observed with a 400x magnification

 HSM High and intense shear processing

 Sample number

 Image No.Nodes Image No.Nodes

 one

 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

 eleven

 0054 265 0021 615

 12

 0055 309 0022 717

 13

 0056 275 0023 663

 14

 0057 422 0024 739

 fifteen

 0058 204 0026 414

 16

 0059 352 0027 689

 17

 0060 277 0028 528

 18

 0061 289 0029 618

 19

 0062 493 0030 368

 twenty

 0063 553 0031 563

 twenty-one

 0064 606 0032 441

 22

 0065 320 0033 436

 2. 3

 0066 132 0034 653

 24

 0067 233 0035 437

 25

 0068 301 0036 639

 26

 0069 261 0038 692

 27

 0070 382 0039 460

 28

 0071 191 0040 572

 29

 0072 765 0041 568

 30

 0073 364 0042 642

 Average nodes

   340 580

 Standard deviation

   134 102

 CV

   39.26 17.55

Table 2:

 HSM

 Sample number

 Image nodes

 one

 0074 406

 2

 0075 193

 3

 0076 117

 4

 0077 7

 High and intense shear processing

 Image

 No. nodes

 0105

 403

 0106

 424

 0107

 259

 0108

 336

 5

 0078 248 0109 331

 6

 0079 254 0110 279

 7

 0080 150 0111 315

 8

 0081 311 0112 514

 9

 0082 128 0113 261

 10

 0083 248 0114 269

 eleven

 0084 263 0115 271

 12

 0085 1 0116 370

 13

 0086 304 0117 417

 14

 0087 666 0118 397

 fifteen

 0088 198 0119 397

 16

 0089 126 0120 262

 17

 0090 282 0121 248

 18

 0091 205 0122 295

 19

 0092 153 0123 514

 twenty

 0093 146 0124 320

 twenty-one

 0094 302 0125 234

 22

 0095 323 0126 348

 2. 3

 0096 172 0127 278

 24

 0097 164 0128 358

 25

 0098 290 0129 273

 26

 0099 279 0130 357

 27

 0100 149 0131 441

 28

 0101 106 0132 389

 29

 0102 88 0133 374

 30

 0103 147 0134 367

 Average nodes

   214 343

 Standard deviation

   127 75

 CV

   59.16 21.86

11. Examples

Any of the following examples can be packaged in a water-soluble film bag in unit dose form. Those skilled in the art will understand that the% bacterial cellulose is representative of the% by weight of the bacterial cellulose network formed after activation.

Example 1: Detergent for washing of intensive cleaning clothes according to the present invention was prepared as follows.

10

 C12 linear alkylbenzenesulfonate

 7.9

 Non-ionic alcohol ethoxylated C14-15 EO8

 5.7

 C12-14 amine oxide

 one

 Citric acid

 2

 C12-18 fatty acid

 5.2

 Enzymes (protease, amylase, mannanase)

 0.6

 MEA Borate

 1.5

 Chelator (DTPMP)

 0.2

 Ethoxylated polyamine dispersants

 1.2

 Silicone / silica soaps suppressants

 0.002

 Ethanol

 1.4

 Propanediol

 5

 NaOH

 3.2

 Bacterial cellulose

 0.1

 Particle suspension according to US Patent 7,169,741 Col. 22, Example II

 one

 Perfume, brightener, hydrotrope, dyes, other minor components

 4.2

 Water

 Rest up to 100

Example 2-6 Soft-acting liquid detergents according to the present invention were prepared in the following proportions.

 Example 2 Example 3 Example 4 Example 5 Example 6

 INGREDIENT

   % by weight% by weight% by weight% by weight% by weight

 Ethoxylated alkyl sulfate, sodium salt, EO 0.5-1

   26.97 26.97 26.97 20.25 20.25

 Amine oxide

   5.61 5.61 5.61 6.65 6.65

 C11EO9 ethoxylated nonionic alcohol

   2.21 2.21 2.21 0.00 0.00

 Polycarboxylate polymer

   0.00 0.00 0.00 0.39 0.39

 Polypropylene glycol

   0.80 0.80 0.80 1.00 1.00

 Solvent (ethanol)

   3.69 3.69 3.69 0.00 0.00

 NaCl salt

   1.60 1.60 1.60 1.20 1.20

 Bacterial cellulose

   0.024 0.024 0.024 0.03 0.06

 Carboxymethyl cellulose

   0.012 0.012 0.012 0.015 0.03

 Xanthan gum

   0.004 0.004 0.004 0.005 0.01

 Teen (EGDS)

   0.00 0.00 0.00 0.00 2.00

 Perfume Microcapsules

   0.00 0.00 0.00 1.00 0.00

 ISP Captivates HC1955 from ISP Corp

   0.10 0.00 0.00 0.00 0.00

 ISP MicroBead 20305 from ISP Corp

   0.00 0.10 0.00 0.00 0.00

 Lipo LTI-0526 Bead of Lipo Chemicals Inc.

   0.00 0.00 0.10 0.00 0.00

 Water + adjuvant ingredients such as perfume and dye

   Rest Rest Rest Rest Rest

 pH at a dilution of 10%

   9.00 9.00 9.00 9.00 9.00

5

12. Detailed description of the figures:

Fig. 1 shows a graph of the% of bacterial cellulose versus the creep stress obtained by activating a sample according to Example 3 where% of bacterial cellulose varies up to 0.1% with various processing techniques. Line 10 represents the linear extrapolation of test A; line 20 represents the linear extrapolation of Test B; and line 30 represents the linear extrapolation of Test C.

Test A: Two-stage process 1) Premix of bacterial cellulose and water with SONOLATOR® at an energy density of 7,155 x 106 J / m3 to a premix solution followed by 2) mixing of the premix solution with the other components in a SONOLATOR® at 34473 kPa (5000 psi) that provides an energy density of 3.47 x 107 J / m3. The filled squares represent experimental data points while the empty square represents an extrapolated data point, determined by an extrapolation to scale comparing the data point of Test A at 0.06% bacterial cellulose vs. the data point of Test B at 0.06% bacterial cellulose. A straight line extrapolation fits the three data points.

twenty

Test B: One-stage process: Activation and mixing in 1 step in a SONOLATOR® at 34473 kPa (5000 Psi) that provides an energy density of 3.47 x 107 J / m3. The three data points from Test B were obtained experimentally. The data is represented by circles represented in the graph with an extrapolated straight line adjusted to the data points.

25

Test C: One-stage process: Activation and mixing in a high shear mixer set at 7900 rpm, which provides an energy density of 2 x 106 J / m3. Both data points from Test C were obtained experimentally. The data is represented by triangles represented in the graph with an extrapolated straight line adjusted to the data points.

5

Fig. 2 shows a linear extrapolation of the% bacterial cellulose network versus creep stress for bacterial cellulose network concentrations greater than 0.1% processed with the same three techniques described in Fig. 1. Note that use the same data points in Figs. 1 and 2.

10 It will be understood that each maximum numerical limitation given in this specification includes all lower numerical limitations, as if the lower numerical limitations were expressly written herein. Any minimum numerical limit cited in this specification includes any greater numerical limit, as if such higher numerical limits had been explicitly mentioned herein. Any numerical range cited in this specification includes any minor interval that falls within the greater numerical range, as if all 15 minor numerical intervals had been explicitly cited herein.

All parts, proportions and percentages herein, in the specification, examples and claims, are by weight and all numerical limits are used with the normal degree of accuracy offered by the technique, unless otherwise indicated.

twenty

Unless otherwise specified, the articles "a", "one (a)" and "the (a)" mean "one (a) or more".

Claims (12)

10 fifteen twenty 25 30 2. 35 3. 40 Four. Four. Five 5. fifty 6. 7. 55 8. MODIFIED CLAIMS A liquid detergent composition comprising: to. a liquid matrix comprising: i. from 0.005% to 1.0% by weight, preferably less than 0.125%, preferably less than 0.05%, even more preferably from 0.006% to 0.2% of said liquid detergent composition of an external structuring system comprising a network of bacterial cellulose; ii. 1% to 75% by weight, preferably any 1% to 30% or preferably 30% to 75%, of said liquid water detergent composition; iii. from 0.01% to 70% by weight, preferably from 1% to 50%, preferably from 3% to 20%, of said liquid detergent composition of a surfactant system comprising: to. 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; Y C. furthermore it comprises a nonionic surfactant; a cationic surfactant; an ampholytic surfactant; a hybrid ion surfactant; or mixtures thereof; Y iv. from 0.01% to 5% by weight of said liquid detergent composition of a plurality of suspended particles having a size of 100 nanometers to 8 mm, and an average particle density of 700 kg / 3 to 4,260 kg / m3 a 25 0C, wherein the plurality of particles in suspension to liquid matrix has a density difference of 10 kg / m3 to 200 kg / m3 at 25 0C; wherein said liquid matrix has a creep stress of 0.003 Pa to 5.0 Pa, preferably 0.01 Pa to 1.0 Pa, preferably 0.05 Pa to 0.2 Pa, at 25 ° C, even more preferably from 0.005 Pa to 1 Pa; and wherein said surfactant system has a weight ratio of 2.5: 1 to 18: 1 of anionic surfactant to said amine oxide. The liquid detergent composition of claim 1, wherein said liquid matrix is a fluid with reduced shear viscosity having a low stress viscosity ratio to pour viscosity of 2 to 2000, preferably 10 to 1000. The liquid detergent composition of claim 1 or claim 2, wherein said external structuring system further comprises a carboxymethyl cellulose, a modified carboxymethyl cellulose, and mixtures thereof; and optionally, a polymeric thickener selected from products of xanthan, pectin, alginates, gellan gum, welan gum, diutan gum, rhamsan gum, carrageenan, guar gum, agar, gum arabic, ghatti gum, karaya gum, tragacanth gum, gum of tamarind, locust bean gum, and mixtures thereof. The liquid detergent composition of any of the preceding claims, wherein said bacterial cellulose network comprises a microfiber with a wider cross-section of 1.6 nm to 200 nm and a microfiber aspect ratio of 10: 1 to 1000: 1, preferably from 100: 1 to 400: 1. The liquid detergent composition of any of the preceding claims, wherein said liquid matrix further comprises from 0.01% to 20% by weight of said liquid detergent composition of an organic solvent. The liquid detergent composition of any of the preceding claims, wherein said liquid matrix has a pH of 6 to 13. The liquid detergent composition of any of the preceding claims, wherein said liquid matrix has a turbidity of 20 to 320 nephelometric turbidity units. The liquid detergent composition of any of the preceding claims, wherein said liquid matrix further comprises: to. from 0.001% to 5% by weight of said liquid detergent composition of a detersive enzyme; b. from 0.1% to 50% by weight of said liquid detergent composition of one or more adjuvant components. 9. The liquid detergent composition of any of the preceding claims, further comprising an SMNI index as defined herein of at least 0.099, preferably at least 0.105, more preferably at least 0.11, up to 1. The liquid detergent composition of any of the preceding claims, wherein said network Bacterial cellulose comprises at least one of a CV400 and a CV630, as defined herein, from 10% to 39%. 11. The liquid detergent composition of any of the preceding claims, wherein said bacterial cellulose network, when viewed under a dark field image at 400x, comprises a distance linear greater between two points of the skeletal bacterial fiber network less than 250 micrometers, preferably less than 100 micrometers. 12. fifteen A process for manufacturing a liquid detergent composition according to any of the preceding claims, comprising the steps of: twenty 25 30 35 13. 40 to. providing a feed comprising from 0.005% to 1.0%, preferably less than 0.125%, preferably less than 0.05%, even more preferably from 0.006% to 0.2%, by weight of a liquid detergent composition of a system external structuring comprising a network of bacterial cellulose with water; b. activating said food in a mixing chamber to an energy density greater than 1.0 x 105 J / m3 to form a bacterial cellulose network; Y C. providing a surfactant system at a level of 0.01% to 70%, preferably 1% to 50%, preferably 3% to 20%, by weight of said liquid detergent composition, said surfactant system comprising: 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 which further comprises a nonionic surfactant; a cationic surfactant; an ampholytic surfactant; a hybrid ion surfactant; or mixtures thereof, wherein said stage (c) is either performed simultaneously with stage (a) or after stage (b), and wherein the stage of providing said surfactant system with said bacterial cellulose network forms a liquid detergent composition comprising a liquid matrix comprising a creep stress of 0.003 to 5.0 Pa at 25 ° C. The process of claim 12, wherein step a) comprises a premixing step of subjecting the bacterial cellulose in contact with water, and step b) subjecting this premix in the mixing chamber to an energy density greater than 1 , 0 x 105 J / m3, together with a second feed comprising a surfactant system comprising: an anionic surfactant; a nonionic surfactant; a cationic surfactant; an ampholytic surfactant; a hybrid ion surfactant; and mixtures thereof.