WO2011056956A1 - Microfibrous cellulose and alkaline earth metal ion structured surfactant composition - Google Patents

Microfibrous cellulose and alkaline earth metal ion structured surfactant composition Download PDF

Info

Publication number
WO2011056956A1
WO2011056956A1 PCT/US2010/055427 US2010055427W WO2011056956A1 WO 2011056956 A1 WO2011056956 A1 WO 2011056956A1 US 2010055427 W US2010055427 W US 2010055427W WO 2011056956 A1 WO2011056956 A1 WO 2011056956A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
alkaline earth
earth metal
metal ion
yield stress
Prior art date
Application number
PCT/US2010/055427
Other languages
French (fr)
Inventor
Robert D'ambrogio
Joan Ethel Gambogi
Original Assignee
Colgate-Palmolive Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=43477914&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2011056956(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Colgate-Palmolive Company filed Critical Colgate-Palmolive Company
Priority to CA2777709A priority Critical patent/CA2777709C/en
Priority to US13/505,669 priority patent/US9506018B2/en
Priority to US13/505,669 priority patent/US20120225804A1/en
Priority to AU2010315151A priority patent/AU2010315151B2/en
Priority to EP10779374.7A priority patent/EP2496675B2/en
Priority to NZ599220A priority patent/NZ599220A/en
Priority to MX2012004687A priority patent/MX352360B/en
Publication of WO2011056956A1 publication Critical patent/WO2011056956A1/en
Priority to IL219220A priority patent/IL219220A0/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/002Surface-active compounds containing sulfur
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013Liquid compositions with insoluble particles in suspension
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
    • C11D3/048Nitrates or nitrites
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC

Definitions

  • Structured liquids are known in the art for suspending materials such as beads in liquid cleaning compositions.
  • the methods of providing structure to the liquid includes using particular surfactants to structure the liquid, or by the addition of suspending agents such as polymers, natural gums and clays that enable the liquid to suspend materials therein for long periods of time.
  • suspending agents such as polymers, natural gums and clays that enable the liquid to suspend materials therein for long periods of time.
  • These suspended materials can be functional, non-functional (aesthetic), or both.
  • aesthetic it is meant that the suspended materials impart a certain visual appearance that is pleasing or eye catching.
  • functional it is meant that the suspended materials contribute to the action of the composition in cleaning, fragrance release, shine enhancement, or other intended action of the composition.
  • An aqueous composition comprising
  • a suspending agent comprising microfibrous cellulose
  • the composition comprises at least one surfactant and microfibrous cellulose in which the yield stress of the composition is increased by the addition of an alkaline earth metal ion.
  • the microfibrous cellulose is present in the composition in an amount of 0.01 to 0.12 weight%. In other embodiments, the amount is at least 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1 up to 0.12 weight%. In one embodiment, the amount is 0.048 weight%.
  • the microfibrous cellulose is a combination of microfibrous cellulose (MFC), xanthan gum, and carboxymethylcellulose (CMC), which is available from CP elco as CellulonTM PX or AxcelTM CG-PX. It is a 6:3:1 blend by weight of MFC:xanthan gum:CMC. It is further described in United States Patent Publication Nos. 2008/0108714A1, 2008/0146485A1, and 2008/0108541A1. On addition of water, the xanthan gum and CMC become hydrated and provide for better dispersion of MFC. CP Kelco reports that salts will impair sufficient hydration of the xanthan gum and CMC co-agents resulting in poor activation of MFC.
  • MFC microfibrous cellulose
  • CMC carboxymethylcellulose
  • the MFC:xanthan gum:CMC is present in the composition in an amount of 0.01 to 0.2 weight%. In other embodiments, the amount is at least 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, or 0.15 up to 0.2 weight%. In one embodiment, the amount is 0.08 weight%.
  • the structuring capability of MFC can be increased by including an alkaline earth metal ion (such as calcium or magnesium) in the composition.
  • an alkaline earth metal ion such as calcium or magnesium
  • the amount of the alkaline earth metal ion is 10 to 600 ppm.
  • the amount of alkaline earth metal ion is 75 to 300 ppm.
  • the amount of ion is at least 75, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, or 250 up to 300 ppm.
  • the amount of ion is 75, 150, or 300 ppm.
  • the alkaline earth metal ion can be provided by any salt that will dissociate the ion.
  • the salts are halide salts, such as chloride, sulfate salts, citrate salts, acetate salts, formate salts, and nitrate salts.
  • hydroxides can be used if the pH is balanced with an acid source.
  • the salt can be at least one salt chosen from magnesium chloride, magnesium chloride hexahydrate, calcium chloride, and magnesium sulfate.
  • anionic agents interact with divalent salts and act as a linking agent between salt and MFC fibers, which are nonionic but are thought to inherit a slight negative charge upon wetting by predominantly anionic surfactants. This then produces increased yield stress (structuring). This increased yield stress can effectively stabilize suspended materials in the composition including those that are non- density matched to the composition.
  • the resulting composition can provide a yield stress that is at least 0.7 Pa.
  • the yield stress is measured using the method described below. In other embodiments, the yield stress is 0.7 to 1 Pa.
  • Suspended materials are defined as water insoluble visible particles. They can be functional or non- functional (aesthetic), i.e. functional materials have components that augment the performance capabilities of the product and non-functional materials are present solely for aesthetic purposes. Functionality can often be provided by encapsulating materials that deliver functional benefits or by providing a tactile benefit (e.g. scrubbing). Functional materials, however, may also have aesthetic purposes.
  • the suspended material can be density matched or non-density matched to the liquid portion. Density matched means that the density of the suspended material is close to the density of the liquid portion so that the suspended material remains suspended.
  • a key benefit of the CellulonTM/AxcelTM material is that it provides a yield stress to suspend particles of varying density range but does not add to the perceived viscosity of the product compared to traditional, unstructured compositions.
  • the density of the suspended material has a density that is 97% to 103% of the density value of the liquid portion.
  • the composition can be designed to provide an aesthetic benefit with suspended material in a clear or colored liquid.
  • aesthetics For more information about different aesthetics that can be used, see United States Patent Publication No. 2007/0010415A1.
  • At least a portion of the suspended material is of any size that is viewable by a person.
  • viewable it is meant that the suspended material can be seen by a non-color blind person with an unaided eye at 20/20 or corrected to 20/20 with glasses or contact lenses at a distance of 30 cm from the composition under incandescent light, florescent light, or sunlight.
  • at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% of the particles are viewable by a person.
  • the particle size is 100 to 2500 microns in a longest dimension of the suspended material.
  • the particle size is 250 to 2250 microns.
  • the particle size is 500 to 1500 microns.
  • the particle size is 700 to 1000 microns.
  • a combination of more than one particle sizes can be used.
  • the suspended material can have any shape.
  • shapes include, but are not limited to, spherical, polyhedral, cubic, box, tetrahedral, irregular three dimensional shapes, flat polygons, triangles, rectangles, squares, pentagons, hexagons, octagons, stars, characters, animals, plants, objects, cars, any other desired shape, or combinations thereof.
  • the suspended material can be present in any amount in the composition that allows the suspended material to remain suspended. In one embodiment, the suspended material is present in an amount of 0.01 and 10% by weight of the total composition.
  • the suspended material can be selected to be of one size and one shape, one size and a combination of shapes, a combination of sizes and one shape, or a combination of sizes and a combination of shapes.
  • the color of the suspended material can be varied along with the size and/or shape. Mixtures of suspended materials that vary by size, shape, and/or color can be used to communicate different attributes that the product can deliver to a consumer.
  • the suspended material can be functional, non-functional (aesthetic), or a combination of both. They can be made from a variety of materials such as the following non- limiting examples: gelatin, cellulose, agar, waxes, polyethylene, and insoluble inorganic materials like silica and calcium carbonate.
  • the material may also have an encapsulate core containing hydrophobic compounds and mixtures such as these non-limiting examples: aloe, vitamins, essential oils, natural oils, solvents, esters, or any fragrance ingredient. These materials may be density matched by encapsulating oils or other materials that help make the density of the suspended material equal to that of the bulk composition.
  • the particles may be made porous in a way that allows the liquid portion to diffuse into the suspended material in a manner that is self density matching. Density matching produces compositions that can suspend material at a viscosity less than 1500 mPas. Also, the particles may be non-density matched, that is being either less or more dense than the composition. In these compositions, the liquid portion can be designed to have a yield stress to aid in the stabilization of suspended material.
  • Suspending agents are any material that increases the ability of the composition to suspend material.
  • optional suspending agents include, but are not limited to, gellan gum, polymeric gums, polysaccharides, pectine, alginate, arabinogalactan, carageenan, xanthum gum, guar gum, rhamsan gum, furcellaran gum, and other natural gum.
  • a synthetic suspending agent in one embodiment is a polyacrylate.
  • One acrylate aqueous solution used to form a stable suspension of the solid particles is manufactured by Noveon as CARBOPOLTM Aqua 30.
  • the CARBOPOLTM resins also known as CARBOMERTM, are hydrophilic high molecular weight, crosslinked acrylic acid polymers having an average equivalent weight of 76, and the general structure illustrated by the following formula has a molecular weight of 1,250,000; CARBOPOLTM 940 with a molecular weight of approximately 4,000,000 and CARBOPOLTM 934 with a molecular weight of approximately 3,000,000.
  • the CARBOPOLTM resins can be crosslinked with polyalkenyl polyether, e.g. 1% of a polyalkyl ether of sucrose having an average of 5,8 alkyl groups for each molecule of sucrose.
  • the suspending agents can be used alone or in combination.
  • the amount of suspending agent can be any amount that provides for a desired level of suspending ability.
  • the suspending agent is present in an amount from 0.01 to 10% by weight of the composition.
  • the composition contains at least one surfactant.
  • the surfactant is present in an amount that is at least 1% by weight of the composition based on the active amount of the surfactant. In other embodiments, the amount of surfactant is at least 5, 10, 20, 25, 30, 35, or 40% by weight. In another embodiment, the amount of surfactant is 1% to 45% by weight.
  • the surfactant can be any surfactant or any combination of surfactants. Examples of surfactants include anionic, nonionic, cationic, amphoteric, or zwitterionic. For a list of surfactants and other materials that can be included in the composition, see United States Patent Publication No. 2007/0010415A1.
  • the composition can be formulated to be any type of liquid cleaning composition.
  • the composition can be used as a light duty liquid (LDL) dish detergent, hand soap, body wash, or a laundry detergent.
  • LDL light duty liquid
  • One embodiment is for a LDL dish detergent.
  • the composition can be degassed after the suspending agent is mixed with the surfactant and before suspended material is added.
  • the microfibrous cellulose is processed to obtain a particle size distribution that increases the suspending ability.
  • U.S. Application No. 61/257,872 filed on 4 November 2009 entitled “MICROFIBROUS CELLULOSE HAVING A PARTICLE SIZE DISTRIBUTION FOR STRUCTURED SURFACTANT COMPOSITIONS” which is incorporated herein by reference in its entirety.
  • compositions can be made by simple mixing methods from readily available components which, on storage, do not adversely affect the entire composition. Mixing can be done by any mixer that forms the composition. Examples of mixers include, but are not limited to, static mixers and in-line mixers.
  • the composition has a viscosity that allows the composition to be pourable.
  • the viscosity is below 10,000 mPas. Viscosity is measured using a Brookfield RVT Viscometer using spindle 21 at 20 RPM at 25°C. In one embodiment, the viscosity is less than 5,000 mPas. In other embodiments, the viscosity is less than 1,500 mPas, less than 1,000 mPas, less than 750 mPas, or less than 500 mPas.
  • the yield stress is measured on a TA Instruments ARG2 controlled stress rheometer utilizing a small vane (15 mm diameter) geometry and 30 mm jacketed sample cup at 25°C with a 10,000 ⁇ gap.
  • a conditioning step is programmed into the creep test - after loading the sample, a two minute "relaxation" period is used in which the sample is equilibrated to 25°C before measurements are started. The 25°C temperature is maintained by the instrument throughout the test.
  • Yield stress was determined utilizing a sequential creep test method. In this test, to ensure reproducibility, samples were equilibrated in a sequence of four identical stress/relaxation steps at the lowest initial stress of 0.01 Pa.
  • the effect is that the composition maintains a stable suspending system over time.
  • This can be measured by the yield stress of the composition. Over time, the yield stress is maintained. In one embodiment, the yield stress does not decrease by more than 20% of its value over a 3 month period. In other embodiments, the period of time is at least 4, 5, 6, 7, 8, 9, 10, 12, or 18 months. In one embodiment, the drop in yield stress is less than 10 % over any of the previously listed periods of time. The yield stress is measured at an initial time and then after the given period of time.
  • the composition has a yield stress that is at least 0.3 Pa. In other embodiments, the yield stress is at least 0.5, 0.6, 0.7, 0.8, 0.9, or 1 Pa. For most suspended material, a yield stress of up to 1.5 Pa is sufficient. In other embodiments, the yield stress is 0.3 to 1.5 Pa. In other embodiments, the yield stress is 0.5 to 1.5 Pa.
  • MFC/co-agents refers to the 6:3:1 micro fibrous cellulose:xanthan gum:carboxymethyl cellulose, which is sold as CellulonTM PX from CPKelco.
  • Formula Q in the table below has a slightly reduced anionic to nonionic surfactant mixture and reduced total active surfactant as compared to Formula A.
  • Formula Q does not contain MgLAS or NaLAS surfactants.
  • Formula Q contains MgS0 4 .
  • the following formulas were prepared. In each formula, additional water was added until the amount of surfactants on an actives basis was 37.4 weight%. In the table below, the amount of magnesium
  • the MgS0 4 contributes 10 ppm Mg ion to the composition.

Abstract

An aqueous composition comprising at least one surfactant; a suspending agent comprising micro fibrous cellulose; 10 to 600 ppm of an alkaline earth metal ion,; and water. The composition can be used to structure surfactant systems to suspend material in the composition.

Description

MICROFIBROUS CELLULOSE AND ALKALINE EARTH METAL ION STRUCTURED
SURFACTANT COMPOSITION
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent Application No. 61/257,940, filed on 4 November 2009, which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] Structured liquids are known in the art for suspending materials such as beads in liquid cleaning compositions. The methods of providing structure to the liquid includes using particular surfactants to structure the liquid, or by the addition of suspending agents such as polymers, natural gums and clays that enable the liquid to suspend materials therein for long periods of time. These suspended materials can be functional, non-functional (aesthetic), or both. By aesthetic it is meant that the suspended materials impart a certain visual appearance that is pleasing or eye catching. By functional it is meant that the suspended materials contribute to the action of the composition in cleaning, fragrance release, shine enhancement, or other intended action of the composition.
[0003] To keep the suspended materials suspended in the liquid without sinking or floating requires the yield stress of the composition to be sufficient. It would be desirable to increase the yield stress to keep suspended materials suspended.
BRIEF SUMMARY OF THE INVENTION
[0004] An aqueous composition comprising
a) at least one surfactant;
b) a suspending agent comprising microfibrous cellulose;
c) 10 to 600 ppm of an alkaline earth metal ion; and
d) water.
DETAILED DESCRIPTION OF THE INVENTION
[0005] As used throughout, ranges are used as shorthand for describing each and every value that is within the range. Any value within the range can be selected as the terminus of the range. In addition, all references cited herein are hereby incorporated by reference in their entireties. In the event of a conflict in a definition in the present disclosure and that of a cited reference, the present disclosure controls.
[0006] Unless otherwise specified, all percentages and amounts expressed herein and elsewhere in the specification should be understood to refer to percentages by weight. The amounts given are based on the active weight of the material.
[0007] The composition comprises at least one surfactant and microfibrous cellulose in which the yield stress of the composition is increased by the addition of an alkaline earth metal ion.
[0008] In one embodiment, the microfibrous cellulose is present in the composition in an amount of 0.01 to 0.12 weight%. In other embodiments, the amount is at least 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1 up to 0.12 weight%. In one embodiment, the amount is 0.048 weight%.
[0009] In one embodiment, the microfibrous cellulose is a combination of microfibrous cellulose (MFC), xanthan gum, and carboxymethylcellulose (CMC), which is available from CP elco as Cellulon™ PX or Axcel™ CG-PX. It is a 6:3:1 blend by weight of MFC:xanthan gum:CMC. It is further described in United States Patent Publication Nos. 2008/0108714A1, 2008/0146485A1, and 2008/0108541A1. On addition of water, the xanthan gum and CMC become hydrated and provide for better dispersion of MFC. CP Kelco reports that salts will impair sufficient hydration of the xanthan gum and CMC co-agents resulting in poor activation of MFC.
[0010] In one embodiment, the MFC:xanthan gum:CMC is present in the composition in an amount of 0.01 to 0.2 weight%. In other embodiments, the amount is at least 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, or 0.15 up to 0.2 weight%. In one embodiment, the amount is 0.08 weight%.
[0011] The structuring capability of MFC can be increased by including an alkaline earth metal ion (such as calcium or magnesium) in the composition. In certain embodiments, the amount of the alkaline earth metal ion is 10 to 600 ppm. In another embodiment, the amount of alkaline earth metal ion is 75 to 300 ppm. In other embodiments, the amount of ion is at least 75, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, or 250 up to 300 ppm. In other embodiments, the amount of ion is 75, 150, or 300 ppm.
[0012] The alkaline earth metal ion can be provided by any salt that will dissociate the ion. Examples of the salts are halide salts, such as chloride, sulfate salts, citrate salts, acetate salts, formate salts, and nitrate salts. Also, hydroxides can be used if the pH is balanced with an acid source. In some embodiments, the salt can be at least one salt chosen from magnesium chloride, magnesium chloride hexahydrate, calcium chloride, and magnesium sulfate.
[00131 Without wishing to be limited to theory, it is theorized that anionic agents interact with divalent salts and act as a linking agent between salt and MFC fibers, which are nonionic but are thought to inherit a slight negative charge upon wetting by predominantly anionic surfactants. This then produces increased yield stress (structuring). This increased yield stress can effectively stabilize suspended materials in the composition including those that are non- density matched to the composition.
[0014] The resulting composition can provide a yield stress that is at least 0.7 Pa. The yield stress is measured using the method described below. In other embodiments, the yield stress is 0.7 to 1 Pa.
[0015] Suspended materials are defined as water insoluble visible particles. They can be functional or non- functional (aesthetic), i.e. functional materials have components that augment the performance capabilities of the product and non-functional materials are present solely for aesthetic purposes. Functionality can often be provided by encapsulating materials that deliver functional benefits or by providing a tactile benefit (e.g. scrubbing). Functional materials, however, may also have aesthetic purposes.
[0016] The suspended material can be density matched or non-density matched to the liquid portion. Density matched means that the density of the suspended material is close to the density of the liquid portion so that the suspended material remains suspended. A key benefit of the Cellulon™/Axcel™ material is that it provides a yield stress to suspend particles of varying density range but does not add to the perceived viscosity of the product compared to traditional, unstructured compositions. In one embodiment, the density of the suspended material has a density that is 97% to 103% of the density value of the liquid portion.
[0017] In one embodiment, the composition can be designed to provide an aesthetic benefit with suspended material in a clear or colored liquid. For more information about different aesthetics that can be used, see United States Patent Publication No. 2007/0010415A1.
SUSPENDED MATERIALS
[0018] At least a portion of the suspended material is of any size that is viewable by a person. By viewable it is meant that the suspended material can be seen by a non-color blind person with an unaided eye at 20/20 or corrected to 20/20 with glasses or contact lenses at a distance of 30 cm from the composition under incandescent light, florescent light, or sunlight. In other embodiments, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% of the particles are viewable by a person. In one embodiment, the particle size is 100 to 2500 microns in a longest dimension of the suspended material. In another embodiment, the particle size is 250 to 2250 microns. In another embodiment, the particle size is 500 to 1500 microns. In another embodiment, the particle size is 700 to 1000 microns. In another embodiment, a combination of more than one particle sizes can be used.
[0019] The suspended material can have any shape. Examples of shapes include, but are not limited to, spherical, polyhedral, cubic, box, tetrahedral, irregular three dimensional shapes, flat polygons, triangles, rectangles, squares, pentagons, hexagons, octagons, stars, characters, animals, plants, objects, cars, any other desired shape, or combinations thereof.
[0020] The suspended material can be present in any amount in the composition that allows the suspended material to remain suspended. In one embodiment, the suspended material is present in an amount of 0.01 and 10% by weight of the total composition.
[0021] The suspended material can be selected to be of one size and one shape, one size and a combination of shapes, a combination of sizes and one shape, or a combination of sizes and a combination of shapes. Also, the color of the suspended material can be varied along with the size and/or shape. Mixtures of suspended materials that vary by size, shape, and/or color can be used to communicate different attributes that the product can deliver to a consumer.
[0022] The suspended material can be functional, non-functional (aesthetic), or a combination of both. They can be made from a variety of materials such as the following non- limiting examples: gelatin, cellulose, agar, waxes, polyethylene, and insoluble inorganic materials like silica and calcium carbonate. The material may also have an encapsulate core containing hydrophobic compounds and mixtures such as these non-limiting examples: aloe, vitamins, essential oils, natural oils, solvents, esters, or any fragrance ingredient. These materials may be density matched by encapsulating oils or other materials that help make the density of the suspended material equal to that of the bulk composition. Alternatively, they may be made porous in a way that allows the liquid portion to diffuse into the suspended material in a manner that is self density matching. Density matching produces compositions that can suspend material at a viscosity less than 1500 mPas. Also, the particles may be non-density matched, that is being either less or more dense than the composition. In these compositions, the liquid portion can be designed to have a yield stress to aid in the stabilization of suspended material.
SUSPENDING AGENTS
[0023] Suspending agents are any material that increases the ability of the composition to suspend material. Examples of optional suspending agents include, but are not limited to, gellan gum, polymeric gums, polysaccharides, pectine, alginate, arabinogalactan, carageenan, xanthum gum, guar gum, rhamsan gum, furcellaran gum, and other natural gum. A synthetic suspending agent in one embodiment is a polyacrylate. One acrylate aqueous solution used to form a stable suspension of the solid particles is manufactured by Noveon as CARBOPOL™ Aqua 30. The CARBOPOL™ resins, also known as CARBOMER™, are hydrophilic high molecular weight, crosslinked acrylic acid polymers having an average equivalent weight of 76, and the general structure illustrated by the following formula has a molecular weight of 1,250,000; CARBOPOL™ 940 with a molecular weight of approximately 4,000,000 and CARBOPOL™ 934 with a molecular weight of approximately 3,000,000. The CARBOPOL™ resins can be crosslinked with polyalkenyl polyether, e.g. 1% of a polyalkyl ether of sucrose having an average of 5,8 alkyl groups for each molecule of sucrose.
[0024] The suspending agents can be used alone or in combination. The amount of suspending agent can be any amount that provides for a desired level of suspending ability. In one embodiment, the suspending agent is present in an amount from 0.01 to 10% by weight of the composition.
LIQUID PORTION
[0025] The composition contains at least one surfactant. In certain embodiments, the surfactant is present in an amount that is at least 1% by weight of the composition based on the active amount of the surfactant. In other embodiments, the amount of surfactant is at least 5, 10, 20, 25, 30, 35, or 40% by weight. In another embodiment, the amount of surfactant is 1% to 45% by weight. The surfactant can be any surfactant or any combination of surfactants. Examples of surfactants include anionic, nonionic, cationic, amphoteric, or zwitterionic. For a list of surfactants and other materials that can be included in the composition, see United States Patent Publication No. 2007/0010415A1.
[0026] Water is included in the composition. The amount of water is variable depending on the amounts of other materials added to the composition. [0027] The composition can be formulated to be any type of liquid cleaning composition. The composition can be used as a light duty liquid (LDL) dish detergent, hand soap, body wash, or a laundry detergent. One embodiment is for a LDL dish detergent.
[0028] In another embodiment, the composition can be degassed after the suspending agent is mixed with the surfactant and before suspended material is added. For further information, see U.S. Application No. 61/257,885 filed on 4 November 2009 entitled "PROCESS TO PRODUCE STABLE SUSPENDING SYSTEM", which is incorporated herein by reference in its entirety. In another embodiment, the microfibrous cellulose is processed to obtain a particle size distribution that increases the suspending ability. For further information, see U.S. Application No. 61/257,872 filed on 4 November 2009 entitled "MICROFIBROUS CELLULOSE HAVING A PARTICLE SIZE DISTRIBUTION FOR STRUCTURED SURFACTANT COMPOSITIONS", which is incorporated herein by reference in its entirety.
[0029] The compositions can be made by simple mixing methods from readily available components which, on storage, do not adversely affect the entire composition. Mixing can be done by any mixer that forms the composition. Examples of mixers include, but are not limited to, static mixers and in-line mixers.
VISCOSITY
[0030] The composition has a viscosity that allows the composition to be pourable. In certain embodiments, the viscosity is below 10,000 mPas. Viscosity is measured using a Brookfield RVT Viscometer using spindle 21 at 20 RPM at 25°C. In one embodiment, the viscosity is less than 5,000 mPas. In other embodiments, the viscosity is less than 1,500 mPas, less than 1,000 mPas, less than 750 mPas, or less than 500 mPas.
[0031] The yield stress is measured on a TA Instruments ARG2 controlled stress rheometer utilizing a small vane (15 mm diameter) geometry and 30 mm jacketed sample cup at 25°C with a 10,000 μιη gap. A conditioning step is programmed into the creep test - after loading the sample, a two minute "relaxation" period is used in which the sample is equilibrated to 25°C before measurements are started. The 25°C temperature is maintained by the instrument throughout the test. Yield stress was determined utilizing a sequential creep test method. In this test, to ensure reproducibility, samples were equilibrated in a sequence of four identical stress/relaxation steps at the lowest initial stress of 0.01 Pa. Once the sample was equilibrated, a further series of stress/relaxation steps were conducted with gradually increasing applied stress until the resulting plot on creep compliance vs. time graph shows an upward curvature. At this time, the test was stopped and the stress at which the bend occurs is taken as the "yield stress". The yield stress is measured with any suspended material present. When suspended material is present, the gap is selected to provide sufficient clearance so as not to interfere with the suspended material. The 10,000 μηι gap is sufficient for suspended material having a particle size up to 2,000 μη .
STABILITY OF THE COMPOSITION
[0032] When a structured surfactant composition has been degassed prior to the addition of suspended material, the effect is that the composition maintains a stable suspending system over time. This can be measured by the yield stress of the composition. Over time, the yield stress is maintained. In one embodiment, the yield stress does not decrease by more than 20% of its value over a 3 month period. In other embodiments, the period of time is at least 4, 5, 6, 7, 8, 9, 10, 12, or 18 months. In one embodiment, the drop in yield stress is less than 10 % over any of the previously listed periods of time. The yield stress is measured at an initial time and then after the given period of time.
[0033] In one embodiment, the composition has a yield stress that is at least 0.3 Pa. In other embodiments, the yield stress is at least 0.5, 0.6, 0.7, 0.8, 0.9, or 1 Pa. For most suspended material, a yield stress of up to 1.5 Pa is sufficient. In other embodiments, the yield stress is 0.3 to 1.5 Pa. In other embodiments, the yield stress is 0.5 to 1.5 Pa.
SPECIFIC EMBODIMENTS OF THE INVENTION
[0034] The invention is further described in the following examples. The examples are merely illustrative and do not in any way limit the scope of the invention as described and claimed.
[0035] Unstructured Dish Liquid Base Formula A.
Figure imgf000009_0001
Target formula pH between 6.7 to 7.3
[0036] Using the common base formula A, the following formulas were prepared. In each formula, additional water was added until the amount of surfactants on an actives basis was 41 weight%. Magnesium chloride hexahydrate and Calcium chloride anhydrous salts were used for the below experiments.) In the examples, MFC/co-agents refers to the 6:3:1 micro fibrous cellulose:xanthan gum:carboxymethyl cellulose, which is sold as Cellulon™ PX from CPKelco.
Figure imgf000009_0002
[0037] It can be seen that carboxymethyl cellulose and xanthan gum in combination with magnesium ions did not create a yield stress. The yield stress was only created when microfibrous cellulose was included.
[0038] It can be seen that viscosity did not significantly increase with increasing yield stress.
[0039] Additional examples were prepared below with a different surfactant system. Formula Q in the table below has a slightly reduced anionic to nonionic surfactant mixture and reduced total active surfactant as compared to Formula A. Formula Q does not contain MgLAS or NaLAS surfactants.
Figure imgf000010_0001
[0040] Formula Q contains MgS04. Using the common base formula Q, the following formulas were prepared. In each formula, additional water was added until the amount of surfactants on an actives basis was 37.4 weight%. In the table below, the amount of magnesium
7-1- ion is in addition to the amount from the MgS04. The MgS04 contributes 10 ppm Mg ion to the composition.
Figure imgf000011_0001
[0041] Again, it can be seen that carboxymethyl cellulose and xanthan gum in combination with magnesium ions did not create a yield stress. The yield stress was only created when microfibrous cellulose was included. It can be seen that viscosity did not significantly increase with increasing yield stress.
[0042] The above examples show that the yield stress of a system with microfibrous cellulose can be increased with the inclusion of an alkali metal ion, which will result in support of suspended material.

Claims

CLAIMS What is claimed is:
1. An aqueous composition comprising
a) at least one surfactant;
b) a suspending agent comprising microfibrous cellulose;
c) 10 to 600 ppm of an alkaline earth metal ion; and
d) water.
2. The composition of claim 1, wherein the alkaline earth metal is at least one chosen from calcium and magnesium.
3. The composition of claim 1, wherein the alkaline earth metal ion is calcium.
4. The composition of claim 1, wherein the alkaline earth metal ion is magnesium.
5. The composition of any preceding claim, wherein the amount of alkaline earth metal ion is 75 to 300 ppm.
6. The composition of any preceding claim, wherein the suspending agent further comprises xanthan gum and carboxymethyl cellulose.
7. The composition of any preceding claim, wherein the suspending agent comprises a 6:3: 1 blend by weight of microfibrous cellulose:xanthan gumxarboxymethyl cellulose.
8. The composition of any preceding claim further comprising suspended material.
9. The composition of claim 8, wherein the suspended material is non-density matched suspended material.
10. The composition of any preceding claim, wherein the yield stress is at least 0.7.
PCT/US2010/055427 2009-11-04 2010-11-04 Microfibrous cellulose and alkaline earth metal ion structured surfactant composition WO2011056956A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
CA2777709A CA2777709C (en) 2009-11-04 2010-11-04 Microfibrous cellulose and alkaline earth metal ion structured surfactant composition
US13/505,669 US9506018B2 (en) 2009-11-04 2010-11-04 Microfibrous cellulose and alkaline earth metal ion structured surfactant composition
US13/505,669 US20120225804A1 (en) 2009-11-04 2010-11-04 Microfibrous cellulose and alkaline earth metal ion structured surfactant composition
AU2010315151A AU2010315151B2 (en) 2009-11-04 2010-11-04 Microfibrous cellulose and alkaline earth metal ion structured surfactant composition
EP10779374.7A EP2496675B2 (en) 2009-11-04 2010-11-04 Microfibrous cellulose, xanthan gum, carboxymethyl cellulose and alkaline earth metal ion structured surfactant composition
NZ599220A NZ599220A (en) 2009-11-04 2010-11-04 microfibrous cellulose:xanthan gum:carboxymethyl cellulose AND ALKALINE EARTH METAL ION STRUCTURED SURFACTANT COMPOSITION
MX2012004687A MX352360B (en) 2009-11-04 2010-11-04 Microfibrous cellulose and alkaline earth metal ion structured surfactant composition.
IL219220A IL219220A0 (en) 2009-11-04 2012-04-16 Microfibrous cellulose and alkaline earth metal ion structured surfactant composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US25794009P 2009-11-04 2009-11-04
US61/257,940 2009-11-04

Publications (1)

Publication Number Publication Date
WO2011056956A1 true WO2011056956A1 (en) 2011-05-12

Family

ID=43477914

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2010/055427 WO2011056956A1 (en) 2009-11-04 2010-11-04 Microfibrous cellulose and alkaline earth metal ion structured surfactant composition

Country Status (12)

Country Link
US (2) US9506018B2 (en)
EP (1) EP2496675B2 (en)
AU (1) AU2010315151B2 (en)
CA (1) CA2777709C (en)
DO (1) DOP2012000090A (en)
EC (1) ECSP12011785A (en)
IL (1) IL219220A0 (en)
MX (1) MX352360B (en)
MY (1) MY165827A (en)
NZ (1) NZ599220A (en)
UY (1) UY33004A (en)
WO (1) WO2011056956A1 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012164266A1 (en) * 2011-05-27 2012-12-06 Reckitt Benckiser N.V. Composition
WO2013152992A1 (en) * 2012-04-12 2013-10-17 Henkel Ag & Co. Kgaa Microfibrillar cellulose as dirt-removing active substance
WO2013160023A1 (en) * 2012-04-23 2013-10-31 Unilever Plc Externally structured aqueous isotropic liquid laundry detergent compositions
EP2496675B1 (en) 2009-11-04 2017-09-27 Colgate-Palmolive Company Microfibrous cellulose and alkaline earth metal ion structured surfactant composition
EP3339411A1 (en) 2016-12-22 2018-06-27 The Procter & Gamble Company Fabric softener composition having improved viscosity stability
EP3339408A1 (en) 2016-12-22 2018-06-27 The Procter & Gamble Company Fabric softener composition having improved dispensing properties
EP3339409A1 (en) 2016-12-22 2018-06-27 The Procter & Gamble Company Fabric softener composition having improved freeze thaw stability
EP3428259A1 (en) 2017-07-10 2019-01-16 The Procter & Gamble Company Packaged liquid fabric softener composition having improved stability
US10676694B2 (en) 2016-12-22 2020-06-09 The Procter & Gamble Company Fabric softener composition having improved detergent scavenger compatibility

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9045716B2 (en) * 2006-11-08 2015-06-02 Cp Kelco U.S., Inc. Surfactant thickened systems comprising microfibrous cellulose and methods of making same
EP2824169A1 (en) * 2013-07-12 2015-01-14 The Procter & Gamble Company Structured fabric care compositions
EP2824170B1 (en) * 2013-07-12 2018-11-14 The Procter & Gamble Company Structured liquid compositions

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060019860A1 (en) * 2004-07-22 2006-01-26 The Procter & Gamble Company Detergent compositions comprising coloured particles
US20070000415A1 (en) 2005-03-01 2007-01-04 Moore Roy E Jr Thermoplastic article having portions with different fire resistances
US20070010415A1 (en) 2005-04-21 2007-01-11 Kevin Kinscherf Composition for Visibility and Impact of Suspended Materials
US20080108541A1 (en) 2006-11-08 2008-05-08 Swazey John M Surfactant Thickened Systems Comprising Microfibrous Cellulose and Methods of Making Same
US20080108714A1 (en) 2006-11-08 2008-05-08 Swazey John M Surfactant Thickened Systems Comprising Microfibrous Cellulose and Methods of Making Same
US20080146485A1 (en) 2006-12-19 2008-06-19 Swazey John M Cationic Surfactant Systems Comprising Microfibrous Cellulose

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5653970A (en) * 1994-12-08 1997-08-05 Lever Brothers Company, Division Of Conopco, Inc. Personal product compositions comprising heteroatom containing alkyl aldonamide compounds
US7101612B2 (en) * 2000-05-04 2006-09-05 Kimberly Clark Worldwide, Inc. Pre-moistened wipe product
MXPA04003015A (en) 2001-10-03 2004-07-15 Procter & Gamble Shampoo containing particles and a deposition aid.
DE10203192A1 (en) 2002-01-25 2003-08-14 Henkel Kgaa Liquid conditioner and substrate impregnated with conditioner, used in textile drying process, contains fluff-reducing component, preferably cellulose, hydrogel or acrylic polymer
WO2006084190A1 (en) * 2005-02-04 2006-08-10 Stepan Company Liquid cleansing composition
RU2428482C2 (en) 2005-05-23 2011-09-10 СиПи Келко, Ю.Эс., Инк Method of preparing composition with improved rheological properties (versions) and composition obtained using said methods
US20080070823A1 (en) 2006-09-15 2008-03-20 Philip Gorlin Liquid Detergent Composition
CA2672566C (en) * 2006-12-15 2013-10-08 Colgate-Palmolive Company Structured liquid detergent composition for suspending materials
US20080242581A1 (en) 2007-04-02 2008-10-02 Colgate-Palmolive Company Liquid Detergent With Refractive Particle
USD629215S1 (en) * 2007-06-15 2010-12-21 Don Charles Burkman Frame for displaying photos, pictures, and other flat art objects
US8512480B2 (en) 2008-01-22 2013-08-20 The Procter & Gamble Company Liquid detergent composition comprising a hydrophobically modified cellulosic polymer
JP5871468B2 (en) 2008-02-15 2016-03-01 ザ プロクター アンド ギャンブルカンパニー Liquid detergent composition comprising an external structured system containing a bacterial cellulose network
US7776807B2 (en) 2008-07-11 2010-08-17 Conopco, Inc. Liquid cleansing compositions comprising microfibrous cellulose suspending polymers
CA2777709C (en) 2009-11-04 2015-03-24 Colgate-Palmolive Company Microfibrous cellulose and alkaline earth metal ion structured surfactant composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060019860A1 (en) * 2004-07-22 2006-01-26 The Procter & Gamble Company Detergent compositions comprising coloured particles
US20070000415A1 (en) 2005-03-01 2007-01-04 Moore Roy E Jr Thermoplastic article having portions with different fire resistances
US20070010415A1 (en) 2005-04-21 2007-01-11 Kevin Kinscherf Composition for Visibility and Impact of Suspended Materials
US20080108541A1 (en) 2006-11-08 2008-05-08 Swazey John M Surfactant Thickened Systems Comprising Microfibrous Cellulose and Methods of Making Same
US20080108714A1 (en) 2006-11-08 2008-05-08 Swazey John M Surfactant Thickened Systems Comprising Microfibrous Cellulose and Methods of Making Same
US20080146485A1 (en) 2006-12-19 2008-06-19 Swazey John M Cationic Surfactant Systems Comprising Microfibrous Cellulose

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2496675B1 (en) 2009-11-04 2017-09-27 Colgate-Palmolive Company Microfibrous cellulose and alkaline earth metal ion structured surfactant composition
WO2012164266A1 (en) * 2011-05-27 2012-12-06 Reckitt Benckiser N.V. Composition
WO2013152992A1 (en) * 2012-04-12 2013-10-17 Henkel Ag & Co. Kgaa Microfibrillar cellulose as dirt-removing active substance
WO2013160023A1 (en) * 2012-04-23 2013-10-31 Unilever Plc Externally structured aqueous isotropic liquid laundry detergent compositions
CN104364362A (en) * 2012-04-23 2015-02-18 荷兰联合利华有限公司 Externally structured aqueous isotropic liquid laundry detergent compositions
EP3339408A1 (en) 2016-12-22 2018-06-27 The Procter & Gamble Company Fabric softener composition having improved dispensing properties
EP3339411A1 (en) 2016-12-22 2018-06-27 The Procter & Gamble Company Fabric softener composition having improved viscosity stability
EP3339409A1 (en) 2016-12-22 2018-06-27 The Procter & Gamble Company Fabric softener composition having improved freeze thaw stability
WO2018118446A1 (en) 2016-12-22 2018-06-28 The Procter & Gamble Company Fabric softener composition having improved freeze thaw stability
WO2018118445A1 (en) 2016-12-22 2018-06-28 The Procter & Gamble Company Fabric softener composition having improved viscosity stability
WO2018118447A1 (en) 2016-12-22 2018-06-28 The Procter & Gamble Company Fabric softener composition having improved dispensing properties
US10676694B2 (en) 2016-12-22 2020-06-09 The Procter & Gamble Company Fabric softener composition having improved detergent scavenger compatibility
EP3428259A1 (en) 2017-07-10 2019-01-16 The Procter & Gamble Company Packaged liquid fabric softener composition having improved stability
WO2019014156A1 (en) 2017-07-10 2019-01-17 The Procter & Gamble Company Packaged liquid fabric softener composition having improved stability

Also Published As

Publication number Publication date
MY165827A (en) 2018-05-17
UY33004A (en) 2010-12-31
EP2496675B1 (en) 2017-09-27
ECSP12011785A (en) 2012-07-31
US20120225804A1 (en) 2012-09-06
NZ599220A (en) 2013-06-28
AU2010315151B2 (en) 2013-06-06
MX2012004687A (en) 2012-06-14
CA2777709C (en) 2015-03-24
IL219220A0 (en) 2012-06-28
US9506018B2 (en) 2016-11-29
DOP2012000090A (en) 2012-07-15
EP2496675A1 (en) 2012-09-12
MX352360B (en) 2017-11-22
EP2496675B2 (en) 2021-12-01
CA2777709A1 (en) 2011-05-12
AU2010315151A1 (en) 2012-05-03

Similar Documents

Publication Publication Date Title
CA2777709C (en) Microfibrous cellulose and alkaline earth metal ion structured surfactant composition
US8703691B2 (en) Liquid detergent composition comprising an external structuring system comprising a bacterial cellulose network
AU2007317389B2 (en) Surfactant thickened systems comprising microfibrous cellulose and methods of making same
AU2010315146B2 (en) Microfibrous cellulose having a particle size distribution for structured surfactant compositions
WO2009101545A1 (en) Liquid detergent composition comprising an external structuring system comprising a bacterial cellulose network
WO2008079693A1 (en) Cationic surfactant systems comprising microfibrous cellulose
US8541355B2 (en) Process to produce stable suspending system
WO2006116099A1 (en) Liquid detergent composition
CN114317140A (en) Fragrance-enhancing softening detergent composition
AU2010315148B9 (en) Process to produce stable suspending system
US20170283744A1 (en) Pearly liquid detergent composition
WO2011084780A1 (en) Dishwashing paste
BR112020009637A2 (en) non-spherical microcapsule, process for preparing non-spherical microcapsules and composition of home or personal care

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10779374

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2010315151

Country of ref document: AU

REEP Request for entry into the european phase

Ref document number: 2010779374

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2777709

Country of ref document: CA

Ref document number: 2010779374

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 219220

Country of ref document: IL

WWE Wipo information: entry into national phase

Ref document number: MX/A/2012/004687

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 13505669

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2010315151

Country of ref document: AU

Date of ref document: 20101104

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 12012500880

Country of ref document: PH

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 1201002066

Country of ref document: TH