EP1047767B1 - Granular compositions having improved dissolution - Google Patents
Granular compositions having improved dissolution Download PDFInfo
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- EP1047767B1 EP1047767B1 EP98901782A EP98901782A EP1047767B1 EP 1047767 B1 EP1047767 B1 EP 1047767B1 EP 98901782 A EP98901782 A EP 98901782A EP 98901782 A EP98901782 A EP 98901782A EP 1047767 B1 EP1047767 B1 EP 1047767B1
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- EP
- European Patent Office
- Prior art keywords
- sticky
- particles
- microns
- composition
- surfactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
Definitions
- the present invention relates to improving the dissolution of a granular detergent composition, especially in cold temperature laundering solutions (i.e., less than about 30°C). More particularly, the detergent composition contains particles having optimally selected physical properties, such as particle size, particle density and concentration of detergent ingredients, for achieving improved dissolution performance.
- clumps are especially prevalent under cold temperature washing conditions and/or when the order of addition to the washing machine is laundry detergent first, clothes second and water last (commonly known as the "Reverse Order Of Addition” or "ROOA").
- ROOA Reverse Order Of Addition
- this clumping phenomenon can contribute to the incomplete dispensing of detergent in washing machines equipped with dispenser drawers or in other dispensing devices, such as a granulet. In this case, the undesired result is undissolved detergent residue in the dispensing device.
- inorganic salts In addition to the viscous surfactant "bridging" effect, inorganic salts have a tendency to hydrate which can also cause “bridging” of particles which linked together via hydration. In particular, inorganic salts hydrate with one another to form a cage structure which exhibits poor dissolution and ultimately ends up as a "clump" after the washing cycle. It would therefore be desirable to have a detergent composition which does not experience the dissolution problems identified above so as to result in improved cleaning performance.
- GB2116200 relates to surfactant agglomerates having improved dissolution due to the incorporation therein of an ethoxylated anionic surfactant.
- US5152932 relates to detergent agglomerates made by a continuous neutralization process and having enhanced detergent performance due to the presence therein of PEG and/or an ethoxylated non-ionic surfactant.
- US5366652 relates to detergent agglomerates having improved flowability due to the incorporation therein of an anhydrous material.
- USS431857 relates to surfactant agglomerates having improved solubility due to the incorporation therein of an agglomeration aid such as PEG or PEO.
- GB2289687 relates to anionic surfactant containing detergent compositions having improved cold-water solubility due to the presence therein of a potassium salt.
- the invention meets the needs above by providing a detergent composition which has improved dissolution in laundering solutions, especially in solutions kept at cold temperatures (i.e., less than about 30°C).
- a combination of optimally selected physical properties of various particulate detergent ingredients in a detergent composition is used to achieve improved dissolution performance.
- the detergent composition comprises from 1% to 50%, based on the total number of discrete particles in the composition, of substantially "sticky particles" with certain composition, size and density specifications.
- the substantially sticky particles contain at least 15%, by weight of the sticky particles, of a "substantially sticky surfactant.”
- the substantially sticky particles have a geometric mean particle diameter size of from 300 microns to 700 microns with a geometric standard deviation of less than 1.8, and a bulk density of at least 650 g/l.
- the composition includes at least 35%, based on the total number of discrete particles in the admixture composition, of substantially non-sticky particles having a geometric mean particle diameter size of from 200 microns to 500 microns with a geometric standard deviation of greater than 1.2 and a bulk density of less than 500 g/l.
- the substantially non-sticky particles may include inorganic fillers, builders, "substantially non-sticky surfactants" and other ingredients.
- the non-sticky particles will have a substantially low to nil (i.e., less than 10% on a weight basis) concentration of sticky surfactants.
- the total amount of surfactants, including both sticky and non-sticky surfactants, in the composition is at least 15% by weight of the composition.
- a method of laundering clothes comprising the steps of contacting soiled clothes with an effective amount of a detergent composition according to compositions described herein in an aqueous washing solution is also provided.
- the invention provides a detergent composition which exhibits improved dispersion and dissolution in aqueous laundering solutions. It has been found that by optimally selecting physical properties of various particles contained in granular detergent compositions, the dissolution can be improved. As mentioned previously, typical detergent formulations that dissolve in aqueous laundering solutions form highly viscous surfactant phase or paste which binds or otherwise "bridges” other surfactant-containing particles together into “clumps” ultimately causing "lump-gel” formation.
- the phrase "discrete particles” means individual particles, agglomerates or granules which can be identified via a scanning electron microscope as discrete units of mass. For each type of particle component in an admixture, the discrete particles of that type have the same or substantially similar composition regardless of whether the particles are in contact with other particles. For agglomerated components, the agglomerates themselves are considered as discrete particles and each discrete particle may be comprised of a composite of smaller primary particles and binder compositions.
- the phrase "geometric mean particle diameter” means the geometric mass average diameter of a set of discrete particles as measured by any standard mass-based particle size measurement technique, such as dry sieving.
- the phrase "geometric standard deviation" of a particle size distribution means the geometric breadth of the best-fitted log-normal function to the above-mentioned particle size data.
- the phrase “builder” means any inorganic material having “builder” performance in the detergency context, and specifically, organic or inorganic material capable of removing water hardness from washing solutions.
- the term “bulk density” refers to the uncompressed, untapped powder bulk density, as measured by pouring an excess of powder sample through a funnel into a smooth metal vessel (e.g., a 500 ml volume cylinder), scraping off the excess from the heap above the rim of the vessel, measuring the remaining mass of powder and dividing the mass by the volume of the vessel.
- the term "substantially sticky surfactants” refers to a surfactant or surfactant blend system consisting primarily of surfactants which substantially contribute lump-gel formation in cold temperature washing solutions, including the general classes of alkyl benzene sulfonates, alkyl ethoxy sulfates, and nonionic surfactants.
- the phrase “substantially non-sticky surfactant” refers to a surfactant or surfactant blend system consisting primarily of surfactants which do not substantially contribute to lump-gel formation in cold temperature washing solutions, such as linear-chain alkyl sulfates with an average alkyl carbon chain length of at least 12.
- all specifications of level of composition and size distribution are done on a mass basis unless otherwise specified. In cases where level is specified on a number basis, the calculations used to convert from a mass to number basis are contained in Example III set forth hereinafter.
- the level of the non-sticky particles is based on the total number of discrete particles in the detergent composition.
- the physical properties, such as particle size and distribution and density, of the substantially non-sticky particles are also optimally selected.
- the "discrete particles” which contain surfactants or other ingredients such as inorganic builders can be in the form of admixed particles, spray-dried granules, and/or agglomerates, depending upon the desired overall formulation and product density.
- the particle size of the sticky particles should not be extremely large such that they require an inordinate amount of time before which they dissolve in the aqueous laundering solution.
- the particle size of the substantially non-sticky particles should not be extremely small and have a very low density such that the detergent composition is extremely "dusty”.
- the balance between the larger substantially sticky particles and the smaller substantially non-sticky particles should be selected so as to avoid significant product segregation in the detergent product box prior to use.
- the present invention provides an optimal selection of the various physical properties to provide the desired improved dissolution performance improvement.
- the mass-based geometric mean particle size diameter of the substantially sticky particles is of from 300 microns to 700 microns with a geometric standard deviation of less than 1.8, preferably of from 350 microns to 650 microns with a geometric standard deviation of less than 1.7, and most preferably 400 microns to 600 microns with a geometric standard deviation of less than 1.6.
- the compositions include substantially sticky particles having at least 15%, preferably at least 35%, and most preferably at least 45%, by weight of the sticky particles, of a substantially sticky surfactant.
- an especially preferred substantially sticky surfactant is a potassium salt of a surfactant selected from the group consisting of linear alkyl benzenes, alkyl ethoxy sulfates, and mixtures thereof.
- the average bulk density of the substantially sticky particles is at least 650 g/l.
- the geometric mean particle size diameter of the substantially non-sticky particles is preferably of from 200 microns to 500 microns with a geometric standard deviation of greater than 1.2, preferably of from 250 microns to 450 microns with a geometric standard deviation of greater than 1.4, more preferably of from 300 microns to 400 microns with a geometric standard deviation of greater than 1.6.
- Preferred compositions include inorganic builder-containing particles having less than 10%, more preferably less than 5%, and most preferably less than 1%, by weight of the non-sticky particles, of a substantially sticky surfactant.
- the average bulk density of the non-sticky particles is less than 500 g/l.
- non-sticky particles comprise sodium or potassium salts selected from the group consisting of sodium chloride, sodium carbonate, sodium sulfate, tetrasodium pyrophosphate, trisodium pyrophosphate, disodium pyrophosphate, monosodium pyrophosphate, potassium chloride, potassium carbonate, potassium sulfate, tetrapotassium pyrophosphate, tripotassium pyrophosphate, dipotassium pyrophosphate, monopotassium pyrophosphate and mixtures thereof.
- sodium or potassium salts selected from the group consisting of sodium chloride, sodium carbonate, sodium sulfate, tetrasodium pyrophosphate, trisodium pyrophosphate, disodium pyrophosphate, monosodium pyrophosphate, potassium chloride, potassium carbonate, potassium sulfate, tetrapotassium pyrophosphate, tripotassium pyrophosphate, dipotassium pyr
- potassium ions useful herein are derived from potassium salts.
- the potassium salts useful herein are potassium salts of alkali builders (e.g. potassium salt of carbonates, potassium salt of silicates). potassium salt of mid-chain branched surfactants. and mixtures thereof.
- inorganic potassium salts are preferred. and are more preferably selected from the group consisting of potassium chloride (KCl), potassium carbonate (K 2 CO 3 ), potassium sulfate (K 2 SO 4 ), and mixtures thereof. These are commercially available. Potassium carbonate is most preferred.
- Inorganic potassium salts may include dehydrated (preferably) or hydrated tetrapotassium pyrophosphate (K 4 P 2 O 7 ; preferred), tripotassium pyrophosphate (HK 3 P 2 O 7 ), dipotassium pyrophosphate (H 2 K 2 P 2 O 7 ), and monopotassium pyrophosphate (H 3 KP 2 O 7 ). Of the hydrates.
- potassium salts for use herein are dehydrated (preferably) or hydrated pentapotassium tripolyphosphate (K 5 P 3 O 10 ), tetrapotassium tripolyphosphate (K 5 P 3 O 10 ), tetrapotassium tripolyphosphate (HK 4 P 3 O 10 ), tripotassium tripolyphosphate (H 2 K 3 P 3 O 10 ), dipotassium tripolyphosphate (H 3 K 2 P 3 O 10 ), and monopotassium tripolyphosphate (H 4 KP 3 O 10 ); potassium hydroxide (KOH); potassium silicate; and potassium neutralized surfactant such as potassium longer alkyl chain, mid chain-branched surfactant compounds, liner potassium alkylbenzene sulfonate, potassium alkyl sulfate, and/or potassium alkylpolyethoxylate.
- salts of film forming polymers as described in U.S. Pat. No. 4,379,080, Murphy, issued Apr. 5, 1983, column 8, line 44 to column 10, line 37, incorporated herein, which are either partially or wholly neutralized with potassium.
- Particularly preferred are the potassium salts of copolymers of acrylamide and acrylate having a molecular weight between about 4,000 and 20,000.
- the combination of both types of the aforementioned particles must net an overall particle size distribution that has less than about 5% fine and less than about 5% oversize particles, where the fine limit is defined at 150 microns and the oversize limit is defined at 1180 microns.
- Nonlimiting examples of the preferred substantially sticky surfactants include anionic surfactants which include the conventional C 11 -C 18 alkyl benzene sulfonates, branched-chain and random C 10 -C 20 alkyl sulfates, the C 10 -C 18 secondary (2,3) alkyl sulfates of the formula CH 3 (CH 2 ) x (CHOSO 3 - M + ) CH 3 and CH 3 (CH 2 ) y (CHOSO 3 - M + ) CH 2 CH 3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium or potassium, unsaturated sulfates such as oleyl sulfate, and the C 10 -C 18 alkyl alkoxy sulfates ("AE x S"; especially EO 1-7 ethoxy sulfates).
- anionic surfactants which include the conventional C 11 -C 18 alkyl
- exemplary surfactants useful include and C 10 -C 18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C 10-18 glycerol ethers, the C 10 -C 18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and C 12 -C 18 alpha-sulfonated fatty acid esters.
- the conventional nonionic and amphoteric surfactants such as the C 12 -C 18 alkyl ethoxylates including the so-called narrow peaked alkyl ethoxylates and C 6 -C 12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C 12 -C 18 betaines and sulfobetaines ("sultaines"), C 10 -C 18 amine oxides, and the like, can also be included in the overall compositions.
- the C 10 -C 18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C 12 -C 18 N-methylglucamides. See WO 9,206,154.
- sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10 -C 18 N-(3-methoxypropyl) glucamide.
- the N-propyl through N-hexyl C 12 -C 18 glucamides can be used for low sudsing.
- C 10 -C 20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C 10 -C 16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
- a variety inorganic builders are suitable for use herein and include aluminosilicates. crystalline layered silicates. MAP zeolites. citrates, amorphous silicates. sodium carbonates and mixtures thereof.
- the aluminosilicate ion exchange materials used herein as a detergent builder preferably have both a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several interrelated factors which derive from the method by which the aluminosilicate ion exchange material is produced.
- aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill et al, U.S. Patent No. 4,605,509 (Procter & Gamble), the disclosure of which is incorporated herein by reference.
- the aluminosilicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit the as high of an exchange rate and capacity as provided by the sodium form.
- the aluminosilicate ion exchange material preferably is in over dried form so as to facilitate production of crisp detergent agglomerates as described herein.
- the aluminosilicate ion exchange materials used herein preferably have particle size diameters which optimize their effectiveness as detergent builders.
- particle size diameter represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope (SEM).
- the preferred particle size diameter of the aluminosilicate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns. Most preferably, the particle size diameter is from about 1 microns to about 8 microns.
- the aluminosilicate ion exchange material has the formula Na z [(AlO 2 ) z .(SiO 2 ) y ]xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is from about 1 to about 5 and x is from about 10 to about 264. More preferably, the aluminosilicate has the formula Na 12 [(AlO 2 ) 12 .(SiO 2 ) 12 ]xH 2 O wherein x is from about 20 to about 30, preferably about 27.
- These preferred aluminosilicates are available commercially, for example under designations Zeolite A, Zeolite B and Zeolite X.
- Naturally-occurring or synthetically derived aluminosilicate ion exchange materials suitable for use herein can be made as described in Krummel et al, U.S. Patent No. 3,985,669, the disclosure of which is incorporated herein by reference.
- the aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaCO 3 hardness/gram, calculated on an anhydrous basis, and which is preferably in a range from about 300 to 352 mg equivalent of CaCO 3 hardness/gram. Additionally, the instant aluminosilicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca ++ /gallon/minute/-gram/gallon, and more preferably in a range from about 2 grains Ca ++ /gallon/minute/-gram/gallon to about 6 grains Ca ++ /gallon/minute/-gram/gallon.
- crystalline layered sodium silicates exhibit a clearly increased calcium and magnesium ion exchange capacity.
- the layered sodium silicates prefer magnesium ions over calcium ions, a feature necessary to insure that substantially all of the "hardness" is removed from the wash water.
- These crystalline layered sodium silicates are generally more expensive than amorphous silicates as well as other builders. Accordingly, in order to provide an economically feasible laundry detergent, the proportion of crystalline layered sodium silicates used must be determined judiciously.
- the crystalline layered sodium silicates suitable for use herein preferably have the formula NaMSi x O 2x+1 .yH 2 O wherein M is sodium or hydrogen, x is from about 1.9 to about 4 and y is from about 0 to about 20. More preferably, the crystalline layered sodium silicate has the formula NaMSi 2 O 5 .yH 2 O wherein M is sodium or hydrogen, and y is from about 0 to about 20.
- Adjunct ingredients include other detergency builders, bleaches, bleach activators, suds boosters or suds suppressors, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays. enzymes, enzyme-stabilizing agents and perfumes. See U.S. Patent 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al., incorporated herein by reference. Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates.
- polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
- Polymeric polycarboxylate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, the disclosure of which is incorporated herein by reference.
- Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylene malonic acid.
- Some of these materials are useful as the water-soluble anionic polymer as hereinafter described, but only if in intimate admixture with the non-soap anionic surfactant.
- polyacetal carboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al, and U.S. Patent 4,246,495, issued March 27, 1979 to Crutchfield et al, both of which are incorporated herein by reference.
- These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a detergent composition.
- Particularly preferred polycarboxylate builders are the ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate described in U.S. Patent 4,663.071, Bush et al., issued May 5, 1987, the disclosure of which is incorporated herein by reference.
- Bleaching agents and activators are described in U.S. Patent 4,412,934, Chung et al., issued November I, 1983, and in U.S. Patent 4,483,781, Hartman, issued November 20. 1984, both of which are incorporated herein by reference.
- Chelating agents are also described in U.S. Patent 4.663,071, Bush et al., from Column 17, line 54 through Column 18, line 68, incorporated herein by reference.
- Suds modifiers are also optional ingredients and are described in U.S. Patents 3,933,672, issued January 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gault et al., both incorporated herein by reference.
- Suitable smectite clays for use herein are described in U.S. Patent 4.762,645. Tucker et al, issued August 9, 1988, Column 6, line 3 through Column 7, line 24, incorporated herein by reference. Suitable additional detergency builders for use herein are enumerated in the Baskerville patent, Column 13, line 54 through Column 16, line 16, and in U.S. Patent 4,663,071, Bush et al, issued May 5, 1987, both incorporated herein by reference.
- the spray-dried granules are prepared using a standard spray drying process in which the ingredients are mixed together to form a slurry which is then sprayed into a spray drying tower to form spray dried granules.
- the detergent agglomerates are prepared by combining the surfactant paste and other ingredients together in one or more mixers until detergent agglomerates are formed.
- the admixed components are simply added to the granules and agglomerates if it a dry ingredient and sprayed on if in liquid form.
- the various physical properties of the compositions are shown below: Physical Properties Control I II Spray dried granules Total sticky surfactant level (wt.
- the Control composition is a typical detergent composition having about 90% of substantially sticky particles (spray dried granules plus agglomerates) based on the total number of particles in the composition.
- the Control composition has a high number of sticky particle contact points which renders it susceptible to "bridging" effects ultimately causing lump-gel formation.
- the Example I and II compositions only contain sticky surfactants in the higher-density agglomerates, and therefore, have about 30% or fewer sticky particles, based on the total number of particles in the composition.
- ROOA Reverse Order Of Addition
- This Example illustrates one of the many means by which the particle number percentage of sticky particles and/or non-sticky particles can be determined relative to the total number of discrete particles in the composition.
- the input variables describe the physical characteristics of each admixture component within the mixture:
- the weight fraction of each mixture component, w i is converted to the total mixture volume fraction, V i . This is done using an intermediate volume, v i , and the component bulk density, ⁇ i (eq. A1).
- the component volumes are normalized to total mixture volume fractions (eq. A2).
- v i w i ⁇ i ; conversion of weight to volume
- the log-normal distribution describes a differential mass fraction per log(size), y ij , as follows (eq. A5). Converting from mass to number population, we calculate a population, z ij , of particles (i) associated with each discrete mass fraction (eq. A6), and a normalized population, Z ij , (eq. A7).
- the number density, n i , of component i particles is defined as the population of component (i) particles per unit volume of mixture; this is the product of the volume fraction and the sum of the (i) populations over all size classes, j (eq. A7).
- the number fraction, N i , of each component is calculated by normalizing the number population over all components in the mixture (eq. A8). The number percent is simply the number fraction times 100.
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- Detergent Compositions (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1998/000567 WO1999036503A1 (en) | 1998-01-13 | 1998-01-13 | Granular compositions having improved dissolution |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1047767A1 EP1047767A1 (en) | 2000-11-02 |
EP1047767B1 true EP1047767B1 (en) | 2004-08-04 |
Family
ID=22266188
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98901782A Expired - Lifetime EP1047767B1 (en) | 1998-01-13 | 1998-01-13 | Granular compositions having improved dissolution |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP1047767B1 (es) |
JP (1) | JP2002509187A (es) |
CN (1) | CN1285868A (es) |
AR (1) | AR014301A1 (es) |
AT (1) | ATE272705T1 (es) |
BR (1) | BR9814589A (es) |
CA (1) | CA2318491C (es) |
DE (1) | DE69825487T2 (es) |
ES (1) | ES2226092T3 (es) |
WO (1) | WO1999036503A1 (es) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AR020517A1 (es) * | 1998-09-25 | 2002-05-15 | Procter & Gamble | Composiciones detergentes que tienen perfiles de solubilidad mejorada. |
JP2003527455A (ja) * | 1998-09-25 | 2003-09-16 | ザ、プロクター、エンド、ギャンブル、カンパニー | 改善された溶解度特性を有する粒状洗剤組成物 |
US6906022B1 (en) * | 1998-09-25 | 2005-06-14 | The Procter & Gamble Company | Granular detergent compositions having homogenous particles and process for producing same |
JP3872293B2 (ja) * | 1999-01-18 | 2007-01-24 | 花王株式会社 | 高密度洗剤組成物 |
WO2000077158A1 (fr) * | 1999-06-14 | 2000-12-21 | Kao Corporation | Base granulaire et detergent particulaire |
AU777235B2 (en) * | 1999-08-10 | 2004-10-07 | Procter & Gamble Company, The | Granular detergent compositions having surfactant particle with reduced electrolyte concentrations |
DE102008038479A1 (de) | 2008-08-20 | 2010-02-25 | Henkel Ag & Co. Kgaa | Wasch- oder Reinigungsmittel mit gesteigerter Waschkraft |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4487710A (en) * | 1982-03-01 | 1984-12-11 | The Procter & Gamble Company | Granular detergents containing anionic surfactant and ethoxylated surfactant solubility aid |
AU582519B2 (en) * | 1985-10-09 | 1989-03-23 | Procter & Gamble Company, The | Granular detergent compositions having improved solubility |
US5080848A (en) * | 1988-12-22 | 1992-01-14 | The Proctor & Gamble Company | Process for making concentrated surfactant granules |
US5152932A (en) * | 1989-06-09 | 1992-10-06 | The Procter & Gamble Company | Formation of high active detergent granules using a continuous neutralization system |
US5494599A (en) * | 1991-04-12 | 1996-02-27 | The Procter & Gamble Company | Agglomeration of high active pastes to form surfactant granules useful in detergent compositions |
US5366652A (en) * | 1993-08-27 | 1994-11-22 | The Procter & Gamble Company | Process for making high density detergent agglomerates using an anhydrous powder additive |
ATE188991T1 (de) * | 1993-09-13 | 2000-02-15 | Procter & Gamble | Granulare waschmittelzusammensetzungen mit nichtionischem tensid und verfahren zu ihrer herstellung |
US5431857A (en) * | 1994-01-19 | 1995-07-11 | The Procter & Gamble Company | Process for producing a high density detergent composition having improved solubility by agglomeration of anionic surfactants and an agglomerating agent |
GB2289687A (en) * | 1994-04-11 | 1995-11-29 | Procter & Gamble | Agglomerated Detergent Composition Containing High Levels Of Anionic Surfactants And Potassium Salt For Improved Solubility In Cold Temperature Laundering Sol |
-
1998
- 1998-01-13 CN CN98813090.4A patent/CN1285868A/zh active Pending
- 1998-01-13 AT AT98901782T patent/ATE272705T1/de not_active IP Right Cessation
- 1998-01-13 WO PCT/US1998/000567 patent/WO1999036503A1/en active IP Right Grant
- 1998-01-13 BR BR9814589-4A patent/BR9814589A/pt not_active IP Right Cessation
- 1998-01-13 EP EP98901782A patent/EP1047767B1/en not_active Expired - Lifetime
- 1998-01-13 ES ES98901782T patent/ES2226092T3/es not_active Expired - Lifetime
- 1998-01-13 CA CA002318491A patent/CA2318491C/en not_active Expired - Fee Related
- 1998-01-13 JP JP2000540207A patent/JP2002509187A/ja active Pending
- 1998-01-13 DE DE69825487T patent/DE69825487T2/de not_active Expired - Lifetime
-
1999
- 1999-01-13 AR ARP990100109A patent/AR014301A1/es not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
ATE272705T1 (de) | 2004-08-15 |
DE69825487D1 (de) | 2004-09-09 |
CA2318491C (en) | 2005-01-04 |
DE69825487T2 (de) | 2005-08-18 |
CN1285868A (zh) | 2001-02-28 |
JP2002509187A (ja) | 2002-03-26 |
WO1999036503A1 (en) | 1999-07-22 |
EP1047767A1 (en) | 2000-11-02 |
ES2226092T3 (es) | 2005-03-16 |
BR9814589A (pt) | 2000-10-24 |
CA2318491A1 (en) | 1999-07-22 |
AR014301A1 (es) | 2001-02-07 |
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