WO2012134969A1 - Spray-dried laundry detergent particles - Google Patents
Spray-dried laundry detergent particles Download PDFInfo
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- WO2012134969A1 WO2012134969A1 PCT/US2012/030224 US2012030224W WO2012134969A1 WO 2012134969 A1 WO2012134969 A1 WO 2012134969A1 US 2012030224 W US2012030224 W US 2012030224W WO 2012134969 A1 WO2012134969 A1 WO 2012134969A1
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- particles
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- laundry detergent
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
- B29L2031/7128—Bags, sacks, sachets
Definitions
- the present invention relates to spray-dried laundry detergent particles comprising anionic detersive surfactant and water-soluble salt selected from the group consisting of sodium carbonate and/or sodium sulphate.
- the spray-dried laundry detergent particles of the present invention exhibit good bulk handling characteristics, and have low bulk density variation during plant packaging operations.
- Laundry detergent powders are typically produced by a spray-drying process wherein a detergent- slurry is spray-dried to form spray-dried laundry detergent particles. These spray-dried particles are the base detergent particles to which other particles may be added to form a fully formulated laundry detergent powder; for example: enzyme prills, bleach particles, perfume particles and the like.
- the fully formulated laundry detergent powder is then packaged, for example into cartons, and shipped to trade.
- Some packaging operations are volumetric-based; however, the cartons are sold on a weight-basis. This means that variations in the bulk density of the laundry detergent powder must be compensated for in order to ensure that the carton weight at the point of sale is correct for the consumer.
- laundry detergent powders that exhibit excellent solubility and environmental profiles.
- recent trends in the laundry detergent industry are for laundry detergent powder formulation approaches having significantly reduced levels of water-insoluble materials like zeolite builder, and phosphate builder.
- laundry detergent powders based on spray-dried laundry detergent particles that are essentially free of zeolite and phosphate builder exhibit excessive bulk density variation during the packaging operation in the manufacturing plant. This necessitates the need for laundry detergent manufacturers to increase the level of over-pack to compensate for this increase in bulk density variation, which in turn decreases the efficiency of the laundry powder production process.
- laundry detergent powders based on spray-dried particles that are essential free of zeolite and phosphate builder are more responsive to applied stress loads, and the powder undergoes more variation in bulk density due to the forces they experience (plant stresses) during plant handling operations, especially in the packaging machines.
- Spray dried laundry detergent particles are not uniform in size: i.e. they have a particle size distribution. Typically, this distribution is from 50 micrometers to 1,200 micrometers, and typically having a weight average particle size in the range of from 350 micrometers to 450 micrometers.
- the chemical composition of low-built, and especially unbuilt, spray-dried particles is not uniform across this particle size distribution; the chemical composition changes as the spray-dried particle size changes, particular differences in the chemical composition occur between small spray-dried particles (e.g. having a particle size of less than 250 micrometers) and large spray-dried particles (e.g. having a particle size of 250 micrometers or more).
- the inventors have found that the bulk powder properties of the fully formulated laundry detergent powder are significantly influenced by the small spray-dried particles (fines) having particle sizes below 250 micrometers.
- the inventors have also found that the organic carbon content in these fines is higher than the organic carbon content of the larger spray-dried particles.
- the inventors have found that reducing the variation in the organic carbon content across the large and small spray-dried particles, improves the bulk powder properties of the fully formulated laundry detergent powder, which in turn overcomes the need for excessive over-packing of the cartons.
- this approach avoids the need to remove these fine particles from the rest of the spray-dried laundry detergent particle population. Removal of these fines is difficult to handle in a manufacturing plant: high volume recycle streams result in lower process yields and poorer process reliability (e.g. fine particulate material having a high organic content can block plant screw feeders).
- US4166039 addresses the problem of incorporating a substantial quantity of non- ionic detersive surfactant into spray-dried particles, and allegedly overcomes this problem by incorporating clay together with the non-ionic detersive surfactant into a crutcher mix that is subsequently spray- dried to produce spray-dried particles.
- the slurry is allegedly more homogenous and the resulting spray-dried particles have allegedly superior properties.
- clay is water insoluble, and the resultant spray-dried particles have poor water-solubility profiles.
- non-ionic surfactant has very different phase behavior and dissolution behavior from anionic surfactants. The incorporation of non-ionic detersive surfactant into a spray-dried particle makes their dissolution profile worse.
- controlling the particle size distribution of water-insoluble clay may be beneficial for the incorporation of non-ionic detersive surfactant, such as that described by US4166039
- non-ionic detersive surfactant such as that described by US4166039
- the Inventors have surprisingly found that controlling the particle size distribution of water-soluble salts such as sodium carbonate and/or sodium sulphate, benefit the plant handling profile when incorporating anionic detersive surfactant into highly water-soluble spray-dried particles that do not comprise water-insoluble material such as zeolite and/or clay. This is particularly surprising because the salts are water-soluble as opposed to water insoluble.
- the present invention seeks to provide spray-dried particles comprising anionic surfactant that has good dissolution profile, good environmental profile, and good handling characteristics and good behaviour during plant packaging operations.
- the spray-dried particles of the present invention exhibit excellent hand-feel when used in a handwash laundering process.
- the present invention relates to: spray-dried laundry detergent particles comprising: (a) organic anionic detersive surfactant; (b) water-soluble inorganic salt selected from the group consisting of sodium carbonate and/or sodium sulphate; (c) essentially no zeolite builder;
- the spray-dried laundry detergent particles comprise: (a) organic anionic detersive surfactant; (b) water-soluble inorganic salt selected from the group consisting of sodium carbonate and/or sodium sulphate; (c) essentially no zeolite builder; (d) essentially no phosphate builder; (e) essentially no bleach; (f) essentially no clay; (g) essentially no non-ionic detersive surfactant; and (h) other detergent ingredients. These detergent ingredients are described in more detail later.
- the spray-dried laundry detergent particles are small particles having a particle size of less than 250 micrometers.
- from 75wt to 95wt preferably from 80wt to 90wt of the particles are large particles having a particle size of 250 micrometers or greater.
- the ratio of the organic carbon content of the small particles in weight percent to the organic carbon content of the large particles in weight percent is in the range of from 1.00 to 1.20, preferably to 1.15, or to 1.12, or to 1.10, or to 1.08, or even to 1.05.
- the water-soluble inorganic salt has a volume average particle size in the range of from 10 micrometers to 50 micrometers, preferably from 20 micrometers 45 micrometers, or from 30 micrometers to 45 micrometers.
- organic means hydrocarbon containing, and inorganic means non-hydrocarbon containing.
- the organic carbon content can be determined by any conventional means. Suitable means include acid treatment (for example 2N H 2 SO 4 - 5 v/vFeS0 4 ) to remove inorganic carbon content, followed by sample drying and high temperature (for example at 1350°C) dry combustion in a pure oxygen environment to evolve carbon dioxide, which can be collected and quantitatively determined by any suitable means, such as gas volumetric, infra-red or thermal conductivity analysis.
- the organic carbon content of the small particles can be controlled by the particle size of the inorganic salt.
- the inorganic salt has a very small particle size, preferably having a volume average particle size of from 10 micrometers to 80 micrometers, preferably from 20 micrometers, or from 30 micrometers, and preferably to 60 micrometers, or even to 50 micrometers.
- the volume average particle size of the inorganic salt can be determined by any conventional means, such as light scattering, for example using a sympatec particle size analyser.
- the particle size of the inorganic salt can be controlled (i.e. reduced) by any suitable means, such as dry grinding (e.g. using pin mills) or wet grinding (e.g. using colloid mill).
- Suitable water-soluble inorganic salts include sodium carbonate salts, sodium sulphate salts, and any mixtures thereof.
- Suitable sodium carbonate salts include sodium bicarbonate.
- Suitable anionic detersive surfactants include sulphate and sulphonate detersive surfactants.
- Suitable sulphonate detersive surfactants include alkyl benzene sulphonate, such as C 10-13 alkyl benzene sulphonate.
- Suitable alkyl benzene sulphonate is obtainable, or even obtained, by sulphonating commercially available linear alkyl benzene (LAB); suitable LAB includes low 2- phenyl LAB, such as those supplied by Sasol under the tradename Isochem® or those supplied by Petresa under the tradename Petrelab®, other suitable LAB include high 2-phenyl LAB, such as those supplied by Sasol under the tradename Hyblene®.
- Another suitable anionic detersive surfactant is alkyl benzene sulphonate that is obtained by DETAL catalyzed process, although other synthesis routes, such as HF, may also be suitable.
- Suitable sulphate detersive surfactants include alkyl sulphate, such as C 8-18 alkyl sulphate, or predominantly C 12 alkyl sulphate.
- the alkyl sulphate may be derived from natural sources, such as coco and/or tallow. Alternative, the alkyl sulphate may be derived from synthetic sources such as C12-15 alkyl sulphate.
- Another suitable sulphate detersive surfactant is alkyl alkoxylated sulphate, such as alkyl ethoxylated sulphate, or a C 8-18 alkyl alkoxylated sulphate, or a C 8-18 alkyl ethoxylated sulphate.
- the alkyl alkoxylated sulphate may have an average degree of alkoxylation of from 0.5 to 20, or from 0.5 to 10.
- the alkyl alkoxylated sulphate may be a C 8-18 alkyl ethoxylated sulphate, typically having an average degree of ethoxylation of from 0.5 to 10, or from 0.5 to 7, or from 0.5 to 5 or from 0.5 to 3.
- the alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzene sulphonates may be linear or branched, substituted or un-substituted.
- the anionic detersive surfactant may be a mid-chain branched anionic detersive surfactant, such as a mid-chain branched alkyl sulphate and/or a mid-chain branched alkyl benzene sulphonate.
- the mid-chain branches are typically C 1-4 alkyl groups, such as methyl and/or ethyl groups.
- anionic detersive surfactant is alkyl ethoxy carboxylate.
- the anionic detersive surfactants are typically present in their salt form, typically being complexed with a suitable cation.
- Suitable counter-ions include Na + and K + , substituted ammonium such as Ci-C 6 alkanolammnonium such as mono-ethanolamine (MEA) tri- ethanolamine (TEA), di-ethanolamine (DEA), and any mixture thereof.
- the spray-dried particles comprise essentially no non-ionic detersive surfactant.
- essentially no non-ionic detersive surfactant typically means comprises from 0wt% to 2wt , or from 0wt% to lwt non- ionic detersive surfactant.
- no deliberately added non- ionic detersive surfactant is incorporated into the spray-dried particles.
- some non-ionic may be present as impurities, for example the unalkoxylated portion of an alkoxylated anionic detersive surfactant.
- Suitable non-ionic detersive surfactants are selected from the group consisting of: Cs-Cis alkyl ethoxylates, such as, NEODOL® non-ionic surfactants from Shell; C 6 -Ci2 alkyl phenol alkoxylates wherein optionally the alkoxylate units are ethyleneoxy units, propyleneoxy units or a mixture thereof; C 12 -C 18 alcohol and C 6 -Ci2 alkyl phenol condensates with ethylene oxide/propylene oxide block polymers such as Pluronic® from BASF; C14-C22 mid-chain branched alcohols; C14-C22 mid-chain branched alkyl alkoxylates, typically having an average degree of alkoxylation of from 1 to 30; alkylpolysaccharides, such as alky lpoly glycosides; polyhydroxy fatty acid amides; ether capped poly (oxy alkylated) alcohol surfactants; and mixtures thereof.
- Suitable non-ionic detersive surfactants include alkyl alkoxylated alcohols, such as C 8-18 alkyl alkoxylated alcohol, or a C 8-18 alkyl ethoxylated alcohol.
- the alkyl alkoxylated alcohol may have an average degree of alkoxylation of from 0.5 to 50, or from 1 to 30, or from 1 to 20, or from 1 to 10.
- the alkyl alkoxylated alcohol may be a C 8-18 alkyl ethoxylated alcohol, typically having an average degree of ethoxylation of from 1 to 10, or from 1 to 7, or from 1 to 5, or from 3 to 7.
- the alkyl alkoxylated alcohol can be linear or branched, and substituted or un-substituted.
- Suitable nonionic detersive surfactants include secondary alcohol-based detersive surfactants.
- Other suitable non- ionic detersive surfactants include EO/PO block co-polymer surfactants, such as the Plurafac ® series of surfactants available from BASF, and sugar-derived surfactants such as alkyl N-methyl glucose amide.
- Suitable cationic detersive surfactants include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulphonium compounds, and mixtures thereof.
- Suitable cationic detersive surfactants are quaternary ammonium compounds having the general formula:
- R is a linear or branched, substituted or unsubstituted C 6 -i8 alkyl or alkenyl moiety
- Ri and R 2 are independently selected from methyl or ethyl moieties
- R3 is a hydroxyl
- X is an anion which provides charge neutrality
- suitable anions include: halides, such as chloride; sulphate; and sulphonate.
- Suitable cationic detersive surfactants are mono-C6-is alkyl mono-hydroxyethyl di-methyl quaternary ammonium chlorides.
- Suitable cationic detersive surfactants are mono-Cs-io alkyl mono-hydroxyethyl dimethyl quaternary ammonium chloride, mono-Cio-i 2 alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride and mono-Cio alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride.
- Suitable zwitterionic and/or amphoteric detersive surfactants include amine oxide such as dodecyldimethylamine N-oxide, alkanolamine sulphobetaines, coco-amidopropyl betaines, HN + - R-C0 2 " based surfactants, wherein R can be any bridging group, such as alkyl, alkoxy, aryl or amino acids.
- the spray-dried laundry detergent particles typically comprise essentially no zeolite: they are typically essentially free of zeolite builder.
- Essential free of zeolite builder typically means comprises from 0wt% to 4wt , or to 3wt , or to 2wt , or even to lwt zeolite builder.
- Essentially free of zeolite builder preferably means comprises no deliberately added zeolite builder.
- Typical zeolite builders include zeolite A, zeolite P, zeolite MAP, zeolite X and zeolite Y.
- the spray-dried laundry detergent particles comprise essentially no phosphate builder: they are typically essentially free of phosphate builder.
- Essential free of phosphate builder typically means comprises from 0wt% to 4wt , or to 3wt , or to 2wt , or even to lwt phosphate builder.
- Essentially free of phosphate builder preferably means comprises no deliberately added phosphate builder.
- Typical phosphate builders include sodium tripolyphosphate (STPP).
- the spray-dried laundry detergent particles comprise essentially no clay: they are typically essentially free of clay.
- Essential free of clay typically means comprises from 0wt to 4wt , or to 3wt , or to 2wt , or even to lwt clay.
- Essentially free of clay preferably means comprises no deliberately added clay.
- Typical clay includes smectite clays such as montmorillonite, bentonite, typical clays also include kaolinite, hectorite and laponite.
- the spray-dried laundry detergent particles comprise essentially no bleach; they are essentially free of bleach.
- Essentially free of bleach typically means comprises from 0wt to 4wt , or to 3wt , or to 2wt , or even to lwt bleach.
- Essentially free of bleach preferably means comprises no deliberately added bleach.
- Typical bleach ingredients include bleach activators, sources of available oxygen, pre-formed peracids, bleach catalysts, reducing bleach, and any combination thereof.
- the spray-dried laundry detergent particles may comprise essentially no chelant; they are essentially free of chelant.
- Essentially free of chelant typically means comprises from 0wt to 4wt , or to 3wt , or to 2wt , or even to lwt chelant.
- Essentially free of chelant preferably means comprises no deliberately added chelant.
- Typical chelant ingredients include diethylene triamine pentaacetate, diethylene triamine penta(methyl phosphonic acid), ethylene diamine - N'N' -disuccinic acid (EDDS), ethylene diamine tetraacetate, ethylene diamine tetra(methylene phosphonic acid), hydroxyethane di(methylene phosphonic acid), and any combination thereof.
- a suitable chelant is ethylene diamine-N'N'-disuccinic acid (EDDS) and/or hydroxyethane diphosphonic acid (HEDP).
- EDDS ethylene diamine-N'N'-disuccinic acid
- HEDP hydroxyethane diphosphonic acid
- Suitable carboxylate polymers include maleate/acrylate random copolymer or polyacrylate homopolymer.
- the carboxylate polymer may be a polyacrylate homopolymer having a molecular weight of from 4,000 Da to 9,000 Da, or from 6,000 Da to 9,000 Da.
- Other suitable carboxylate polymers are co-polymers of maleic acid and acrylic acid, and may have a molecular weight in the range of from 4,000 Da to 90,000 Da.
- Suitable detergent ingredients include: detersive surfactants including anionic detersive surfactants, non-ionic detersive surfactants, cationic detersive surfactants, zwitterionic detersive surfactants, amphoteric detersive surfactants, and any combination thereof; polymers including carboxylate polymers, polyethylene glycol polymers, polyester soil release polymers such as terephthalate polymers, amine polymers, cellulosic polymers, dye transfer inhibition polymers, dye lock polymers such as a condensation oligomer produced by condensation of imidazole and epichlorhydrin, optionally in ratio of 1:4:1, hexamethylenediamine derivative polymers, and any combination thereof; builders including zeolites, phosphates, citrate, and any combination thereof; buffers and alkalinity sources including carbonate salts and/or silicate salts; fillers including sulphate salts and bio-filler materials; bleach including bleach activators, sources of available oxygen, pre-formed peracids, bleach catalyst
- the present invention provides a laundry detergent composition comprising the spray-dried particles of the present invention.
- the laundry detergent composition is a fully formulated laundry detergent composition, not a portion thereof such as a spray-dried particle that only forms part of the laundry detergent composition.
- an additional rinse additive composition e.g. fabric conditioner or enhancer
- a main wash additive composition e.g. bleach additive
- the laundry detergent composition comprises a plurality of chemically different particles, such as the spray-dried laundry detergent particles of the present invention that typically form the base laundry detergent particles, to which other particle such as agglomerated detergent particles and/or extruded detergent particles are combined.
- the spray-dried laundry detergent particles are combined with an additional one or more, typically two or more, or three or more, or four or more, or five or more, or six or more, or even ten or more particles selected from: surfactant particles, including surfactant agglomerates, surfactant extrudates, surfactant needles, surfactant noodles, surfactant flakes; polymer particles such as cellulosic polymer particles, polyester particles, polyamine particles, terephthalate polymer particles, polyethylene glycol polymer particles; builder particles, such as sodium carbonate and sodium silicate co-builder particles, phosphate particles, zeolite particles, silicate salt particles, carbonate salt particles; filler particles such as sulphate salt particles; dye transfer inhibitor particles; dye fixative particles; bleach particles, such as percarbonate particles, especially coated percarbonate particles, such as percarbonate coated with carbonate salt, sulphate salt, silicate salt, borosilicate salt, or any combination thereof, perborate particles, bleach catalyst particles such as
- Example 1 preparation of spray-dried laundry detergent particles (comparative example)
- An aqueous alkaline laundry detergent slurry comprising: water, alkyl benzene sulphonate, sodium silicate; acrylic/maleic acid co-polymer, sodium sulphate, sodium carbonate, magnesium sulphate, 1-hydroxy ethylidene-l,l-diphosphonic acid (HEDP), and ethylene diamine disuccinic acid (EDDS) is prepared.
- This aqueous slurry is sprayed into a counter current spray drying tower and spray-dried to produce spray-dried laundry detergent particles.
- the sodium sulphate used was standard (unmilled) grade having a volume average particle size in the range of from 200 micrometers to 250 micrometers, and the sodium carbonate was standard (unmilled) grade having a volume average particle size of 300 micrometers.
- Powder A comparative example spray-dried laundry detergent particles that are not in accordance with the present invention.
- Example 2 preparation of spray-dried laundry detergent particles (in accordance with the present invention)
- Example 1 was repeated except that the standard grade sodium sulphate was replaced with fine grade sodium sulphate that has passed a pin mill grinding unit to produce a volume average particle size of 40 micrometers, and the standard grade sodium carbonate was replaced with fine grade sodium carbonate having a volume average particle size of 40 micrometers.
- Powder B spray-dried laundry detergent particles that are in accordance with the present invention.
- Example 3 physical features of the spray-dried laundry detergent particles
- Both Powder A and Powder B have similar bulk densities, and the same particle size distribution: namely, a bulk density of 467 g/1 (+ lOg/1) and a particle size distribution such that 15wt of the spray-dried powder has a particle size of below 250 micrometers (small particles), and 85wt of the spray-dried powder has a particle size of from 250 micrometers or greater (large particles).
- Example 4 chemical composition of the spray-dried laundry detergent particles
- Both Powder A and Powder B have the same bulk chemical composition, namely: 15.6wt alkyl benzene sulphonate, 8.3wt sodium silicate, 4.2wt acrylic/maleic acid co-polymer, 44.6wt sodium sulphate, 22.8wt sodium carbonate, 1.3wt magnesium sulphate, 0.6wt% 1-hydroxy ethylidene-l,l-diphosphonic acid (HEDP), 0.4wt% ethylene diamine disuccinic acid (EDDS), 2wt water and 2.2wt miscellaneous.
- HEDP 1-hydroxy ethylidene-l,l-diphosphonic acid
- EDDS ethylene diamine disuccinic acid
- Powder A and Powder B are sieved through a 250 micrometer sieve and both fractions (small ( ⁇ 250 ⁇ ) and large (>250 ⁇ ) particles) are collected separately.
- the organic carbon content of these fractions is shown below:
- the ratio of the organic carbon content of the small particles in weight percent to the organic carbon content of the large particles in weight percent is 1.29, which is outside of the claim scope of the present invention.
- the consolidated bulk density of a powder is its bulk density under applied normal load.
- the consolidated bulk density profiles of Powders A (comparative) and B (invention) are determined by the following method: The powder samples are over-filled into the shear cell of a Peschl Shear Tester. Overfill of the powder sample in the shear cell is removed (by scraping) such that the height of the powder sample is flat against the opening of the shear cell. The weight of the powder sample in the shear cell is then recorded. The shear cell is then placed into the shear tester; where the first lowest normal load (2kPa) is applied for 15 minutes to allow the powder samples to achieve density equilibrium, this consolidated bulk density is then recorded.
- the next highest normal load is applied, and the technique is repeated for 5kPa, 8kPa, 15kPa and 25kPa normal loads respectively.
- the consolidated bulk density is calculated automatically from the powder sample weight, the fixed volume of the shear cell and the vertical displacement of the piston into the shear cell on application of the normal load.
- the consolidated bulk density profiles of Powders A (comparative) and B (invention) are shown below:
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Abstract
Description
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Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12711331.4A EP2688998A1 (en) | 2011-03-25 | 2012-03-23 | Spray-dried laundry detergent particles |
| CN2012800137889A CN103443260A (en) | 2011-03-25 | 2012-03-23 | Spray-dried laundry detergent particles |
| MX2013010893A MX2013010893A (en) | 2011-03-25 | 2012-03-23 | Spray-dried laundry detergent particles. |
| BR112013023426A BR112013023426A2 (en) | 2011-03-25 | 2012-03-23 | spray-dried laundry detergent particles |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11159799.3 | 2011-03-25 | ||
| EP11159799A EP2502980A1 (en) | 2011-03-25 | 2011-03-25 | Spray-dried laundry detergent particles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2012134969A1 true WO2012134969A1 (en) | 2012-10-04 |
Family
ID=44350560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2012/030224 Ceased WO2012134969A1 (en) | 2011-03-25 | 2012-03-23 | Spray-dried laundry detergent particles |
Country Status (5)
| Country | Link |
|---|---|
| EP (2) | EP2502980A1 (en) |
| CN (1) | CN103443260A (en) |
| BR (1) | BR112013023426A2 (en) |
| MX (1) | MX2013010893A (en) |
| WO (1) | WO2012134969A1 (en) |
Cited By (63)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3075831A1 (en) | 2015-03-30 | 2016-10-05 | The Procter and Gamble Company | Solid free-flowing particulate laundry detergent composition |
| EP3075828A1 (en) | 2015-03-30 | 2016-10-05 | The Procter and Gamble Company | Solid free-flowing particulate laundry detergent composition |
| EP3075830A2 (en) | 2015-04-02 | 2016-10-05 | The Procter and Gamble Company | Solid free-flowing particulate laundry detergent composition |
| EP3075833A2 (en) | 2015-03-30 | 2016-10-05 | The Procter and Gamble Company | Solid free-flowing particulate laundry detergent composition |
| EP3075824A1 (en) | 2015-03-30 | 2016-10-05 | The Procter and Gamble Company | Solid free-flowing particulate laundry detergent composition |
| EP3075829A1 (en) | 2015-03-30 | 2016-10-05 | The Procter and Gamble Company | Solid free-flowing particulate laundry detergent composition |
| EP3075825A1 (en) | 2015-03-30 | 2016-10-05 | The Procter and Gamble Company | Solid free-flowing particulate laundry detergent composition |
| EP3075827A1 (en) | 2015-03-30 | 2016-10-05 | The Procter and Gamble Company | Solid free-flowing particulate laundry detergent composition |
| EP3075823A1 (en) | 2015-03-30 | 2016-10-05 | The Procter and Gamble Company | A spray-dried laundry detergent base particle |
| EP3075826A1 (en) | 2015-03-30 | 2016-10-05 | The Procter and Gamble Company | Solid free-flowing particulate laundry detergent composition |
| EP3075834A1 (en) | 2015-04-02 | 2016-10-05 | The Procter and Gamble Company | Solid free-flowing particulate laundry detergent composition |
| WO2016161219A1 (en) | 2015-04-02 | 2016-10-06 | The Procter & Gamble Company | Solid free-flowing particulate laundry detergent composition |
| EP3153425A1 (en) | 2015-10-06 | 2017-04-12 | The Procter and Gamble Company | Flexible box bag comprising detergent powder and a scoop |
| US9758286B2 (en) | 2015-10-06 | 2017-09-12 | The Procter & Gamble Company | Flexible box bag comprising soluble unit dose detergent pouch |
| WO2018067486A1 (en) | 2016-10-03 | 2018-04-12 | The Procter & Gamble Company | Low ph laundry detergent composition |
| WO2018067489A1 (en) | 2016-10-03 | 2018-04-12 | The Procter & Gamble Company | Low ph laundry detergent composition |
| WO2018067488A1 (en) | 2016-10-03 | 2018-04-12 | The Procter & Gamble Company | Low ph laundry detergent composition |
| WO2018067483A1 (en) | 2016-10-03 | 2018-04-12 | The Procter & Gamble Company | Laundry detergent composition |
| WO2018067482A1 (en) | 2016-10-03 | 2018-04-12 | The Procter & Gamble Company | Laundry detergent composition |
| WO2018067481A1 (en) | 2016-10-03 | 2018-04-12 | The Procter & Gamble Company | Laundry detergent composition |
| WO2018067484A1 (en) | 2016-10-03 | 2018-04-12 | The Procter & Gamble Company | Laundry detergent composition |
| WO2018067487A1 (en) | 2016-10-03 | 2018-04-12 | The Procter & Gamble Company | Low ph laundry detergent composition |
| WO2018067485A1 (en) | 2016-10-03 | 2018-04-12 | The Procter & Gamble Company | Low ph laundry detergent composition |
| EP2674476B1 (en) | 2012-06-11 | 2018-04-18 | The Procter & Gamble Company | Detergent composition |
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| EP4512730A1 (en) | 2023-08-23 | 2025-02-26 | The Procter & Gamble Company | Consumer products and methods for operating the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3919393A1 (en) * | 2020-06-01 | 2021-12-08 | The Procter & Gamble Company | Process of making water-soluble unit dose articles |
| MX2022008133A (en) | 2020-06-01 | 2022-07-27 | Procter & Gamble | Water-soluble unit dose article. |
| PE20221809A1 (en) | 2020-06-01 | 2022-11-29 | Procter & Gamble | WATER SOLUBLE UNIT DOSE ARTICLE |
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| US4166039A (en) | 1973-10-15 | 1979-08-28 | The Proctor & Gamble Company | Detergent composition and process |
| WO2000024863A1 (en) * | 1998-10-26 | 2000-05-04 | The Procter & Gamble Company | Processes for making granular detergent composition having improved appearance and solubility |
-
2011
- 2011-03-25 EP EP11159799A patent/EP2502980A1/en not_active Withdrawn
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2012
- 2012-03-23 CN CN2012800137889A patent/CN103443260A/en active Pending
- 2012-03-23 BR BR112013023426A patent/BR112013023426A2/en not_active IP Right Cessation
- 2012-03-23 MX MX2013010893A patent/MX2013010893A/en not_active Application Discontinuation
- 2012-03-23 EP EP12711331.4A patent/EP2688998A1/en not_active Withdrawn
- 2012-03-23 WO PCT/US2012/030224 patent/WO2012134969A1/en not_active Ceased
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4166039A (en) | 1973-10-15 | 1979-08-28 | The Proctor & Gamble Company | Detergent composition and process |
| WO2000024863A1 (en) * | 1998-10-26 | 2000-05-04 | The Procter & Gamble Company | Processes for making granular detergent composition having improved appearance and solubility |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN103443260A (en) | 2013-12-11 |
| EP2688998A1 (en) | 2014-01-29 |
| MX2013010893A (en) | 2013-12-06 |
| EP2502980A1 (en) | 2012-09-26 |
| BR112013023426A2 (en) | 2016-12-13 |
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