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WO2000018874A1 - Granular detergent composition having improved appearance and solubility - Google Patents

Granular detergent composition having improved appearance and solubility Download PDF

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Publication number
WO2000018874A1
WO2000018874A1 PCT/US1998/020223 US9820223W WO0018874A1 WO 2000018874 A1 WO2000018874 A1 WO 2000018874A1 US 9820223 W US9820223 W US 9820223W WO 0018874 A1 WO0018874 A1 WO 0018874A1
Authority
WO
WIPO (PCT)
Prior art keywords
detergent composition
particles
granular detergent
sodium
weight
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.)
Ceased
Application number
PCT/US1998/020223
Other languages
French (fr)
Inventor
Jacqueline Westfield
Steven Matthew Gabriel
Scott William Capeci
Kristin Nicole Perkis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to AU95850/98A priority Critical patent/AU9585098A/en
Priority to PCT/US1998/020223 priority patent/WO2000018874A1/en
Priority to TR2001/00848T priority patent/TR200100848T2/en
Priority to ARP990104823A priority patent/AR020517A1/en
Priority to PCT/US1999/022395 priority patent/WO2000018877A1/en
Priority to CA002343810A priority patent/CA2343810A1/en
Priority to HU0103661A priority patent/HUP0103661A3/en
Priority to PCT/US1999/022396 priority patent/WO2000018878A1/en
Priority to ARP990104822A priority patent/AR022097A1/en
Priority to AU62691/99A priority patent/AU6269199A/en
Priority to DE69941983T priority patent/DE69941983D1/en
Priority to AU62689/99A priority patent/AU6268999A/en
Priority to CN99811408.1A priority patent/CN1320159A/en
Priority to MA25786A priority patent/MA24986A1/en
Priority to ARP990104821A priority patent/AR020516A1/en
Priority to US09/787,852 priority patent/US6608021B1/en
Priority to US09/787,452 priority patent/US6906022B1/en
Priority to AU62690/99A priority patent/AU6269099A/en
Priority to CA002345105A priority patent/CA2345105A1/en
Priority to JP2000572323A priority patent/JP2003524672A/en
Priority to AT99949919T priority patent/ATE456647T1/en
Priority to BR9914062-4A priority patent/BR9914062A/en
Priority to KR1020017003752A priority patent/KR20010075335A/en
Priority to MA25783A priority patent/MA24984A1/en
Priority to PCT/US1999/022393 priority patent/WO2000018875A1/en
Priority to CN99813385A priority patent/CN1346400A/en
Priority to EP99949919A priority patent/EP1115837B1/en
Priority to CA002344535A priority patent/CA2344535A1/en
Priority to PCT/US1999/022394 priority patent/WO2000018876A1/en
Priority to BR9914047-0A priority patent/BR9914047A/en
Priority to KR1020017003775A priority patent/KR20010075342A/en
Priority to AU62692/99A priority patent/AU6269299A/en
Priority to CZ20011067A priority patent/CZ20011067A3/en
Priority to CZ2001925A priority patent/CZ2001925A3/en
Priority to JP2000572325A priority patent/JP2003522214A/en
Priority to EP99949917A priority patent/EP1115836A1/en
Priority to HU0103664A priority patent/HUP0103664A3/en
Priority to MA25784A priority patent/MA24985A1/en
Priority to CNB998114073A priority patent/CN1192095C/en
Priority to JP2000572326A priority patent/JP2003527455A/en
Priority to EG119299A priority patent/EG22007A/en
Publication of WO2000018874A1 publication Critical patent/WO2000018874A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06Powder; Flakes; Free-flowing mixtures; Sheets

Definitions

  • the present invention relates to an improved granular detergent composition which has superior solubility, especially in cold temperature laundering solutions (i.e., less than about 30°C), excellent flowability, aesthetics or appearance and friability. More particularly, the detergent composition contains optimal levels of particles having optimally selected particle size and particle size distribution for achieving the desired improvements.
  • 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 granulette.
  • 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.
  • the invention meets the needs above by providing a detergent composition which has improved solubility or dissolution in laundering solutions, especially in solutions kept at cold temperatures (i.e., less than about 30°C), is aesthetically pleasing to consumers and has improved flowability.
  • the granular detergent composition has optimally selected level of particles having a judiciously selected median particle size with a selected standard deviation.
  • a granular detergent composition with improved solubility, aesthetics and flowability comprises at least about 50% by weight of particles having a geometric mean particle diameter of from about 500 microns to about 1500 microns with a geometric standard deviation of from about 1 to about 2, wherein at least a portion of the particles contain a detersive surfactant and a detergent builder.
  • the invention also provides a method of laundering soiled fabrics comprising the step of contacting the soiled fabrics with an aqueous solution containing an effective amount of a detergent composition according the invention described herein.
  • particles means the entire size range of a detergent final product or component or the entire size range of discrete particles, agglomerates, or granules in a final detergent product or component admixture. It specifically does not refer to a size fraction (i.e., representing less than 100% of the entire size range) of any of these types of particles unless the size fraction represents 100% of a discrete particle in an admixture of particles. For each type of particle component in an admixture, the entire size range of discrete particles of that type have the same or substantially similar composition regardless of whether the particles are in contact with other particles.
  • 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.
  • geometric mean particle diameter means the geometric mass median diameter of a set of discrete particles as measured by any standard mass-based particle size measurement technique, preferably by dry sieving.
  • the phrase "geometric standard deviation" or “span” of a particle size distribution means the geometric breadth of the best-fitted log-normal function to the above-mentioned particle size data which can be accomplished by the ratio of the diameter of the 84.13 percentile divided by the diameter of the 50 th percentile of the cumulative distribution (D 84 13 /D 50 ); See Gotoh et al, Powder Technology Handbook, pp. 6-11, Meral Dekker 1997. .
  • 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 granular detergent composition achieves the desired benefits of solubility, improved aesthetics and flowability via optimal selection of the geometric mean particle diameter of certain levels of particles in the composition.
  • improved aesthetics it is meant that the consumer views a granular detergent product which has a more uniform appearance of particles as opposed to past granular detergent products which contained particles of varying size and composition.
  • at least about 50%, more preferably at least about 75%, even more preferably at least about 90%, and most preferably at least about 95%, by weight of the total particles in the detergent product have the selected mean particle size diameter. In this way, a substantial portion of the granular detergent product will have the uniform size so as to provide the aesthetic appearance desired by consumers.
  • the geometric mean particle diameter of the particles is from about 500 microns to about 1500 microns, more preferably from about 600 microns to about 1200 microns, and most preferably from about 700 microns to about 1000 microns.
  • the particle size distribution is defined by a relative tight geometric standard deviation or "span" so as not to have too many particles outside of the target size. Accordingly, the geometric standard deviation is preferably is from about 1 to about 2, more preferably is from about 1.0 to about 1.7, even more preferably is from about 1.0 to about 1.4, and most preferably is from about 1.0 to about 1.2.
  • the average bulk density of the particles is preferably at least about 450 g/1, more preferably at least about 550 g/1, and most preferably at least about 650 g/1. While not intending to be bound by theory, it is believed that solubility is enhanced as a result of the particles in the detergent composition being more of the same size. Specifically, as a result of the particles being more uniform in size, the actual "contact points" among the particles in the detergent composition is reduced which, in turn, reduces the "bridging effect" commonly associated with the "lump-gel" dissolution difficulties of granular detergent compositions. Previous granular detergent compositions contained particles of varying sizes which leads to more contact points among the particles. For example, a large particle could have many smaller particles in contact with it rendering the particle site ripe for lump-gel formation. The level and uniform size of the particles in the granular detergent composition of the present invention avoids such problems.
  • the detergent composition will contain from about 1% to about 50% by weight of a detersive surfactant and from about 1% to about 75% by weight of a detergent builder.
  • the surfactant system of the detergent composition may include anionic, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof.
  • Detergent surfactants are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, and in U.S. Patent 3,919,678, Laughlin et al., issued December 30, 1975, both of which are incorporated herein by reference.
  • Cationic surfactants include those described in U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980, both of which are also incorporated herein by reference.
  • Nonlimiting examples of surfactant systems include the conventional C ⁇ j-Cjg alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C10- 20 alkyl sulfates
  • M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C IQ-C IS alkyl alkoxy sulfates 0'AE ⁇ S"; especially EO 1-7 ethoxy sulfates), CjQ-Cig alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the Cj o-l 8 gly cer ol ethers, the CjQ-Cig alkyl polyglycosides and their corresponding sulfated polyglycosides, and C ⁇ - ig alpha-sulfonated fatty acid esters.
  • unsaturated sulfates such as oleyl sulfate, the C IQ-C IS alkyl alkoxy sulfates 0'AE ⁇ S"; especially EO 1-7 ethoxy sulfates), CjQ
  • the conventional nonionic and amphoteric surfactants such as the C ⁇ -C ⁇ alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg-C ] ⁇ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C ⁇ -Cjg betaines and sulfobetaines ("sultaines”), l0" l8
  • N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C ⁇ -Cj
  • N-methylglucamides See WO 9,206,154.
  • Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as CiQ-C j N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C ⁇ -C j g glucamides can be used for low sudsing.
  • C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain Cjo-Cjg soaps may be used.
  • the detergent composition can, and preferably does, include a detergent builder.
  • Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates.
  • the alkali metal especially sodium, salts of the above.
  • Preferred for use herein are the phosphates, carbonates, silicates, C , n , occasional fatty acids, polycarboxylates, and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates, sodium silicate, and mixtures thereof (see below).
  • inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphates.
  • polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-l, 1 -diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid.
  • Other phosphorus builder compounds are disclosed in U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, all of which are incorporated herein by reference.
  • nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of SiO ⁇ to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
  • 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 methylenemalonic acid.
  • Some of these materials are useful as the water-soluble anionic polymer as hereinafter described, but only if in intimate admixture with the nonsoap 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.
  • Water-soluble silicate solids represented by the formula SiO ⁇ M-O, M being an alkali metal, and having a SiO ⁇ :M»O weight ratio of from about 0.5 to about 4.0, are useful salts in the detergent granules of the invention at levels of from about 2% to about 15% on an anhydrous weight basis, preferably from about 3% to about 8%.
  • Anhydrous or hydrated particulate silicate can be utilized, as well. Any number of additional ingredients can also be included as components in the granular detergent composition.
  • Bleaching agents and activators are described in U.S. Patent 4,412,934, Chung et al., issued November 1, 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.
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between
  • MA/AA Copolymer of 4:6 maleic/acrylic acid, average molecular weight about
  • Protease I Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591, sold by Genencor Int. Inc.
  • Alcalase Proteolytic enzyme having 5.3% by weight of active enzyme, sold by
  • Amylase Amylolytic enzyme having 1.6% by weight of active enzyme, sold by
  • Lipase Lipolytic enzyme having 2.0% by weight of active enzyme, sold by
  • Lipase (1) Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by
  • Endolase Endoglucanase enzyme having 1.5% by weight of active enzyme, sold by
  • NAC-OBS (6-nonamidocaproyl) oxybenzene sulfonate
  • Photoactivated Sulfonated zinc phthlocyanine encapsulated in bleach (1) dextrin soluble polymer Photoactivated Sulfonated alumino phthlocyanine encapsulated in bleach (2) dextrin soluble polymer Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 Disodium 4,4'-bis(4-anilino-6-mo ⁇ holino-l .3.5-triazin-2-yl)amino) stilbene-2:2'-disulfonate
  • PEGx Polyethylene glycol, with a molecular weight of x (typically 4,000)
  • PEO Polyethylene oxide with an average molecular weight of 50,000
  • PVNO Polyvinylpyridine N-oxide polymer with an average molecular weight of
  • PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole with an average molecular weight of 20,000
  • SRP1 Anionically end capped poly esters
  • SRP2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer
  • PEI Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen
  • Opacifier Water based monostyrene latex mixture, sold by BASF Aktiengesellschaft under the tradename Lytron 621
  • Example I The following compositions are in accordance with the invention.
  • compositions exemplified above have at least 90% by weight of particles having a geometric mean particle diameter of from about 850 microns with a geometric standard deviation of from about 1.2. Unexpectedly, the compositions have improved aesthetics, flowability and solubility.
  • Example II The following compositions are in accordance with the invention.
  • compositions exemplified above have at least 90% by weight of particles having a geometric mean particle diameter of from about 850 microns with a geometric standard deviation of from about 1.2. Unexpectedly, the compositions have improved aesthetics, flowability and solubility.

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  • Engineering & Computer Science (AREA)
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  • Detergent Compositions (AREA)

Abstract

A detergent composition which has improved solubility or dissolution in laundering solutions, especially in solutions kept at cold temperatures (i.e., less than about 30 °C), is disclosed. The granular detergent composition is aesthetically pleasing to consumers and has improved flowability. The granular detergent composition has optimally selected level of particles having a judiciously selected median particle size diameter with a selected standard deviation.

Description

GRANULAR DETERGENT COMPOSITION HAVING IMPROVED APPEARANCE
AND SOLUBILITY
FIELD OF THE INVENTION
The present invention relates to an improved granular detergent composition which has superior solubility, especially in cold temperature laundering solutions (i.e., less than about 30°C), excellent flowability, aesthetics or appearance and friability. More particularly, the detergent composition contains optimal levels of particles having optimally selected particle size and particle size distribution for achieving the desired improvements.
BACKGROUND OF THE INVENTION
Recently, there has been considerable interest within the detergent industry for laundry detergents which have the convenience, aesthetics and solubility of liquid laundry detergent products, but retain the cleaning performance and cost of granular detergent products. The problems, however, associated with past granular detergent compositions with regard to aesthetics, solubility and user convenience are formidable. Such problems have been exacerbated by the advent of "compact" or low dosage granular detergent products which typically do not dissolve in washing solutions as well as their liquid laundry detergent counterparts. These low dosage detergents are currently in high demand as they conserve resources and can be sold in small packages which are more convenient for consumers prior to use, but less convenient upon dispensing into the washing machine as compared to liquid laundry detergent which can be simply poured directly from the bottle as opposed to "scooped" from the box and then dispensed into the washing solution.
As mentioned, such low dosage or "compact" detergent products unfortunately experience dissolution problems, especially in cold temperature laundering solutions (i.e., less than about 30°C). More specifically, poor dissolution results in the formation of "clumps" which appear as solid white masses remaining in the washing machine or on the laundered clothes after conventional washing cycles. These "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"). Such undesirable "clumps" are also formed if the consumer loads the washing machine in the order of clothes, detergent and then water. Similarly, 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 granulette. In this case, the undesired result is undissolved detergent residue in the dispensing device.
It has been found that the cause of the aforementioned dissolution problem is associated with the "bridging" of a "gel-like" substance between surfactant-containing particles to form undesirable "clumps." The gel-like substance responsible for the undesirable "bridging" of particles into "clumps" originates from the partial dissolution of surfactant in the aqueous laundering solutions, wherein such partial dissolution causes the formation of a highly viscous surfactant phase or paste which binds or otherwise "bridges" other surfactant-containing particles together into "clumps." This undesirable dissolution phenomena is commonly referred to as "lump-gel" formation. 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.
The prior art is replete with disclosures addressing the dissolution problems associated with granular detergent compositions. For example, the prior art suggests limiting the use and manner of inorganic salts which can cause clumps via the "bridging" of hydrated salts during the laundering cycle. Specific ratios of selected inorganic salts are contemplated so as to minimize dissolution problems. Such a solution, however, constricts the formulation and process flexibility which are necessary for current commercialization of large-scale detergent products. Various other mechanisms have been suggested by the prior art, all of which involve formulation alteration, and thereby reduce formulation flexibility. As a consequence, it would therefore be desirable to have a detergent composition having improved dissolution without significantly inhibiting formulation flexibility.
Accordingly, despite the disclosures in the prior art discussed previously, it would be desirable to have a granular detergent composition which exhibits improved solubility, is more aesthetically pleasing to consumers, has improved flowability and exhibits improved cleaning performance. Also, it would be desirable to have such a detergent composition which exhibits such improved dissolution without significantly inhibiting formulation flexibility. SUMMARY OF THE INVENTION
The invention meets the needs above by providing a detergent composition which has improved solubility or dissolution in laundering solutions, especially in solutions kept at cold temperatures (i.e., less than about 30°C), is aesthetically pleasing to consumers and has improved flowability. The granular detergent composition has optimally selected level of particles having a judiciously selected median particle size with a selected standard deviation.
In accordance with one aspect of the invention, a granular detergent composition with improved solubility, aesthetics and flowability is provided. The detergent composition comprises at least about 50% by weight of particles having a geometric mean particle diameter of from about 500 microns to about 1500 microns with a geometric standard deviation of from about 1 to about 2, wherein at least a portion of the particles contain a detersive surfactant and a detergent builder. The invention also provides a method of laundering soiled fabrics comprising the step of contacting the soiled fabrics with an aqueous solution containing an effective amount of a detergent composition according the invention described herein.
Accordingly, it is an advantage of the invention to provide a granular detergent composition which exhibits improved solubility, is more aesthetically pleasing to consumers, has improved flowability and exhibits improved cleaning performance. It is also an advantage to have such a detergent composition which exhibits such improved dissolution without significantly inhibiting formulation flexibility.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT Definitions
As used herein, the word "particles" means the entire size range of a detergent final product or component or the entire size range of discrete particles, agglomerates, or granules in a final detergent product or component admixture. It specifically does not refer to a size fraction (i.e., representing less than 100% of the entire size range) of any of these types of particles unless the size fraction represents 100% of a discrete particle in an admixture of particles. For each type of particle component in an admixture, the entire size range of 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. As used herein, the phrase "geometric mean particle diameter" means the geometric mass median diameter of a set of discrete particles as measured by any standard mass-based particle size measurement technique, preferably by dry sieving. As used herein, the phrase "geometric standard deviation" or "span" of a particle size distribution means the geometric breadth of the best-fitted log-normal function to the above-mentioned particle size data which can be accomplished by the ratio of the diameter of the 84.13 percentile divided by the diameter of the 50th percentile of the cumulative distribution (D84 13/D50); See Gotoh et al, Powder Technology Handbook, pp. 6-11, Meral Dekker 1997. .
As used herein, 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. As used herein, 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. Physical Properties
The granular detergent composition achieves the desired benefits of solubility, improved aesthetics and flowability via optimal selection of the geometric mean particle diameter of certain levels of particles in the composition. By "improved aesthetics", it is meant that the consumer views a granular detergent product which has a more uniform appearance of particles as opposed to past granular detergent products which contained particles of varying size and composition. To that end, at least about 50%, more preferably at least about 75%, even more preferably at least about 90%, and most preferably at least about 95%, by weight of the total particles in the detergent product, have the selected mean particle size diameter. In this way, a substantial portion of the granular detergent product will have the uniform size so as to provide the aesthetic appearance desired by consumers.
Preferably, the geometric mean particle diameter of the particles is from about 500 microns to about 1500 microns, more preferably from about 600 microns to about 1200 microns, and most preferably from about 700 microns to about 1000 microns. The particle size distribution is defined by a relative tight geometric standard deviation or "span" so as not to have too many particles outside of the target size. Accordingly, the geometric standard deviation is preferably is from about 1 to about 2, more preferably is from about 1.0 to about 1.7, even more preferably is from about 1.0 to about 1.4, and most preferably is from about 1.0 to about 1.2.
The average bulk density of the particles is preferably at least about 450 g/1, more preferably at least about 550 g/1, and most preferably at least about 650 g/1. While not intending to be bound by theory, it is believed that solubility is enhanced as a result of the particles in the detergent composition being more of the same size. Specifically, as a result of the particles being more uniform in size, the actual "contact points" among the particles in the detergent composition is reduced which, in turn, reduces the "bridging effect" commonly associated with the "lump-gel" dissolution difficulties of granular detergent compositions. Previous granular detergent compositions contained particles of varying sizes which leads to more contact points among the particles. For example, a large particle could have many smaller particles in contact with it rendering the particle site ripe for lump-gel formation. The level and uniform size of the particles in the granular detergent composition of the present invention avoids such problems.
By "a portion" of the particles, it is meant that at least some particles in the detergent composition contain a detersive surfactant and/or a detergent builder to provide the fundamental building blocks of a typical detergent composition. The various surfactants and builders as well as their respective levels in the composition are set forth hereinafter. Typically, the detergent composition will contain from about 1% to about 50% by weight of a detersive surfactant and from about 1% to about 75% by weight of a detergent builder.
DETERGENT COMPONENTS The surfactant system of the detergent composition may include anionic, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof. Detergent surfactants are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, and in U.S. Patent 3,919,678, Laughlin et al., issued December 30, 1975, both of which are incorporated herein by reference. Cationic surfactants include those described in U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980, both of which are also incorporated herein by reference.
Nonlimiting examples of surfactant systems include the conventional C\ j-Cjg alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C10- 20 alkyl sulfates
("AS"), the C10-C18 secondary (2,3) alkyl sulfates of the formula CH3(CH2)x(CHOSO3"M+)
CH3 and CH3 (CH )y(CHOSO3"M+) CH2CH3 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, unsaturated sulfates such as oleyl sulfate, the C IQ-C IS alkyl alkoxy sulfates 0'AEχS"; especially EO 1-7 ethoxy sulfates), CjQ-Cig alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the Cj o-l 8 glycerol ethers, the CjQ-Cig alkyl polyglycosides and their corresponding sulfated polyglycosides, and C^- ig alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C^-C^ alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg-C]^ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C^-Cjg betaines and sulfobetaines ("sultaines"), l0" l8
Figure imgf000008_0001
N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C^-Cj
N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as CiQ-Cj N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C^-Cjg glucamides can be used for low sudsing. C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain Cjo-Cjg soaps may be used.
Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
The detergent composition can, and preferably does, include a detergent builder. Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates. Preferred are the alkali metal, especially sodium, salts of the above. Preferred for use herein are the phosphates, carbonates, silicates, C , n , „ fatty acids, polycarboxylates, and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates, sodium silicate, and mixtures thereof (see below).
Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphates. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-l, 1 -diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid. Other phosphorus builder compounds are disclosed in U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, all of which are incorporated herein by reference. Examples of nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of SiO^ to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates. Examples of 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 methylenemalonic acid. Some of these materials are useful as the water-soluble anionic polymer as hereinafter described, but only if in intimate admixture with the nonsoap anionic surfactant.
Other suitable polycarboxylates 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.
Water-soluble silicate solids represented by the formula SiO^M-O, M being an alkali metal, and having a SiO^:M»O weight ratio of from about 0.5 to about 4.0, are useful salts in the detergent granules of the invention at levels of from about 2% to about 15% on an anhydrous weight basis, preferably from about 3% to about 8%. Anhydrous or hydrated particulate silicate can be utilized, as well. Any number of additional ingredients can also be included as components in the granular detergent composition. These include other detergency builders, bleaches, bleach activators, suds boosters or suds suppressors, anti-tarnish and anti-corrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, nonbuilder 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.
Bleaching agents and activators are described in U.S. Patent 4,412,934, Chung et al., issued November 1, 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 following examples are presented for illustrative purposes only and are not to be construed as limiting the scope of the appended claims in any way. Abbreviations used in Examples
In the detergent compositions, the abbreviated component identifications have the following meanings:
LAS Sodium linear Cl 1-13 alkyl benzene sulfonate
TAS Sodium tallow alkyl sulfate
CxyAS Sodium Clx - Cly alkyl sulfate
C46SAS Sodium C14 - C16 secondary (2,3) alkyl sulfate
CxyEzS Sodium Clx-Cly alkyl sulfate condensed with z moles of ethylene oxide
CxyEz C lx-C ly predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide QAS R2.N+(CH3)2(C2H40H) with R2 = C12 - C14
QAS 1 R2.N+(CH3)2(C2H4OH) with R2 = C8 - C 11
APA C8 - CIO amido propyl dimethyl a ine
Soap Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut fatty acids
STS Sodium toluene sulphonate
CFAA C12-C14 (coco) alkyl N-methyl glucamide
TFAA C16-C18 alkyl N-methyl glucamide
TPKFA C12-C14 topped whole cut fatty acids
STPP Anhydrous sodium tripolyphosphate
TSPP Tetrasodium pyrophosphate
Zeolite A Hydrated sodium aluminosilicate of formula Nal2(AlO2SiO2)12.27H2O having a primary particle size in the range from 0.1 to 10 micrometers
(weight expressed on an anhydrous basis)
NaSKS-6 Crystalline layered silicate of formula δ- Na2Si2O5 Citric acid Anhydrous citric acid Borate Sodium borate Carbonate Anydrous sodium carbonate with a particle size between 200μm and
900μm
Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between
400μm and 1200μm
Silicate Amorphous sodium silicate (Si02:Na2O = 2.0:1) Sulfate Anhydrous sodium sulfate Mg sulfate Anhydrous magnesium sulfate Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425μm and 850μm
MA AA Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about
70,000
MA/AA (1) Copolymer of 4:6 maleic/acrylic acid, average molecular weight about
10,000
AA Sodium polyacrylate polymer of average molecular weight 4,500 CMC Sodium carboxymethyl cellulose Cellulose ether Methyl cellulose ether with a degree of polymerization of 650 available from Shin Etsu Chemicals
Protease Proteolytic enzyme, having 3.3% by weight of active enzyme, sold by
NOVO Industries A/S under the tradename Savinase
Protease I Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591, sold by Genencor Int. Inc.
Alcalase Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by
NOVO Industries A/S
Cellulase Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by
NOVO Industries A/S under the tradename Carezyme
Amylase Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by
NOVO Industries A/S under the tradename Termamyl 120T
Lipase Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by
NOVO Industries A/S under the tradename Lipolase
Lipase (1) Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by
NOVO Industries A/S under the tradename Lipolase Ultra
Endolase Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by
NOVO Industries A/S
PB4 Sodium perborate tetrahydrate of nominal formula NaB02.3H2 O.H2O2-
PB1 Anhydrous sodium perborate bleach of nominal formula NaBO2.H 202
Percarbonate Sodium percarbonate of nominal formula 2Na2CO3.3H2O2
NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt
NAC-OBS (6-nonamidocaproyl) oxybenzene sulfonate
TAED Tetraacetylethylenediamine
DTPA Diethylene triamine pentaacetic acid
DTPMP Diethylene triamine penta (methylene phosphonate), marketed by
Monsanto under the Tradename Dequest 2060
EDDS Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its sodium salt.
Photoactivated Sulfonated zinc phthlocyanine encapsulated in bleach (1) dextrin soluble polymer Photoactivated Sulfonated alumino phthlocyanine encapsulated in bleach (2) dextrin soluble polymer Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 Disodium 4,4'-bis(4-anilino-6-moφholino-l .3.5-triazin-2-yl)amino) stilbene-2:2'-disulfonate
HEDP 1,1-hydroxyethane diphosphonic acid
PEGx Polyethylene glycol, with a molecular weight of x (typically 4,000)
PEO Polyethylene oxide, with an average molecular weight of 50,000
TEPAE Tetraethylenepentaamine ethoxylate
PVI Polyvinyl imidosole, with an average molecular weight of 20,000
PVP Polyvinylpyrolidone polymer, with an average molecular weight of
60,000
PVNO Polyvinylpyridine N-oxide polymer, with an average molecular weight of
50,000
PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole, with an average molecular weight of 20,000
QEA bis((C2H5O)(C2H4O)n)(CH3) -N+-C6H12-N+-(CH3) bis((C2H5O)-
(C2H4 O))n, wherein n = from 20 to 30
SRP1 Anionically end capped poly esters SRP2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer PEI Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen
Silicone antifoam Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1
Opacifier Water based monostyrene latex mixture, sold by BASF Aktiengesellschaft under the tradename Lytron 621
Wax Paraffin wax
In the following examples all levels are quoted as % by weight of the composition:
Example I The following compositions are in accordance with the invention.
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
The compositions exemplified above have at least 90% by weight of particles having a geometric mean particle diameter of from about 850 microns with a geometric standard deviation of from about 1.2. Unexpectedly, the compositions have improved aesthetics, flowability and solubility.
Example II The following compositions are in accordance with the invention.
Figure imgf000016_0002
Figure imgf000017_0001
Figure imgf000018_0001
The compositions exemplified above have at least 90% by weight of particles having a geometric mean particle diameter of from about 850 microns with a geometric standard deviation of from about 1.2. Unexpectedly, the compositions have improved aesthetics, flowability and solubility. Having thus described the invention in detail, it will be obvious to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification.

Claims

What is claimed is:
1. A granular detergent composition comprising at least about 50% by weight of particles having a geometric mean particle diameter of from about 500 microns to about 1500 microns with a geometric standard deviation of from about 1 to about 2, wherein at least a portion of said particles contain a detersive surfactant and a detergent builder.
2. The granular detergent composition of claim 1 wherein said particles comprise at least about 75% by weight of said detergent composition.
3. The granular detergent composition of claim 1 wherein the geometric standard deviation is from about 1.0 to about 1.7.
4. The granular detergent composition of claim 1 wherein the geometric standard deviation if from about 1.0 to about 1.4.
5. The granular detergent composition of claim 1 wherein said particles comprise at least about 90% by weight of said detergent composition.
6. The granular detergent composition of claim 1 wherein the geometric mean particle diameter of said particles are from about 600 microns to about 1200 microns.
7. The granular detergent composition of claim 1 wherein the geometric mean particle diameter of said particles are from about 700 microns to about 1000 microns.
8. The granular detergent composition of claim 1 wherein the geometric standard deviation if from about 1.0 to about 1.2.
9. The granular detergent composition of claim 1 wherein said particles comprise at least about 95% by weight of said detergent composition.
10. A method of laundering soiled fabrics comprising the step of contacting said soiled fabrics with an aqueous solution containing an effective amount of a detergent composition according to claim 1.
PCT/US1998/020223 1998-09-25 1998-09-25 Granular detergent composition having improved appearance and solubility Ceased WO2000018874A1 (en)

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AU95850/98A AU9585098A (en) 1998-09-25 1998-09-25 Granular detergent composition having improved appearance and solubility
PCT/US1998/020223 WO2000018874A1 (en) 1998-09-25 1998-09-25 Granular detergent composition having improved appearance and solubility
TR2001/00848T TR200100848T2 (en) 1998-09-25 1999-09-24 Gran l detergent composition with a better appearance and ‡ ”weight
ARP990104823A AR020517A1 (en) 1998-09-25 1999-09-24 DETERGENT COMPOSITIONS THAT HAVE IMPROVED SOLUBILITY PROFILES.
PCT/US1999/022395 WO2000018877A1 (en) 1998-09-25 1999-09-24 Granular detergent compositions having homogenous particles and process for producing same
CA002343810A CA2343810A1 (en) 1998-09-25 1999-09-24 Granular detergent composition having improved appearance and solubility
HU0103661A HUP0103661A3 (en) 1998-09-25 1999-09-24 Granular detergent composition having improved solubility profiles
PCT/US1999/022396 WO2000018878A1 (en) 1998-09-25 1999-09-24 Granular detergent compositions having improved solubility profiles
ARP990104822A AR022097A1 (en) 1998-09-25 1999-09-24 COMPOSITIONS OF GRANULATED DETERGENTS THAT HAVE HOMOGENEOUS PARTICLES AND A PROCESS FOR PRODUCERS
AU62691/99A AU6269199A (en) 1998-09-25 1999-09-24 Granular detergent compositions having homogenous particles and process for producing same
DE69941983T DE69941983D1 (en) 1998-09-25 1999-09-24 Granular detergent compositions containing homogeneous particles and methods for their preparation
AU62689/99A AU6268999A (en) 1998-09-25 1999-09-24 Granular detergent composition having improved appearance and solubility
CN99811408.1A CN1320159A (en) 1998-09-25 1999-09-24 Granular detergent composition having improved appearance and solubility
MA25786A MA24986A1 (en) 1998-09-25 1999-09-24 GRANULAR DETERGENT COMPOSITIONS HAVING IMPROVED SOLUBILITY PROFILE
ARP990104821A AR020516A1 (en) 1998-09-25 1999-09-24 GRANULATED DETERGENT COMPOSITIONS THAT HAVE IMPROVED APPEARANCE AND SOLUBILITY.
US09/787,852 US6608021B1 (en) 1998-09-25 1999-09-24 Granular detergent composition having improved appearance and solubility
US09/787,452 US6906022B1 (en) 1998-09-25 1999-09-24 Granular detergent compositions having homogenous particles and process for producing same
AU62690/99A AU6269099A (en) 1998-09-25 1999-09-24 Granular detergent compositions having improved solubility profiles
CA002345105A CA2345105A1 (en) 1998-09-25 1999-09-24 Granular detergent compositions having improved solubility profiles
JP2000572323A JP2003524672A (en) 1998-09-25 1999-09-24 Particulate detergent composition with improved appearance and solubility
AT99949919T ATE456647T1 (en) 1998-09-25 1999-09-24 GRANULAR DETERGENT COMPOSITIONS WITH HOMOGENEOUS PARTICLES AND METHOD FOR THE PRODUCTION THEREOF
BR9914062-4A BR9914062A (en) 1998-09-25 1999-09-24 Granular detergent composition having improved solubility and appearance
KR1020017003752A KR20010075335A (en) 1998-09-25 1999-09-24 Granular detergent compositions having improved solubility profiles
MA25783A MA24984A1 (en) 1998-09-25 1999-09-24 GRANULAR DETERGENT COMPOSITION HAVING IMPROVED APPEARANCE AND SOLUBILITY
PCT/US1999/022393 WO2000018875A1 (en) 1998-09-25 1999-09-24 Granular detergent composition having improved appearance and solubility
CN99813385A CN1346400A (en) 1998-09-25 1999-09-24 Solubility-improved granular detergent composition
EP99949919A EP1115837B1 (en) 1998-09-25 1999-09-24 Granular detergent compositions having homogenous particles and process for producing same
CA002344535A CA2344535A1 (en) 1998-09-25 1999-09-24 Granular detergent compositions having homogenous particles and process for producing same
PCT/US1999/022394 WO2000018876A1 (en) 1998-09-25 1999-09-24 Granular detergent compositions having improved solubility profiles
BR9914047-0A BR9914047A (en) 1998-09-25 1999-09-24 Granular detergent compositions having improved solubility profiles
KR1020017003775A KR20010075342A (en) 1998-09-25 1999-09-24 Granular detergent composition having improved appearance and solubility
AU62692/99A AU6269299A (en) 1998-09-25 1999-09-24 Granular detergent compositions having improved solubility profiles
CZ20011067A CZ20011067A3 (en) 1998-09-25 1999-09-24 Granulated detergent composition
CZ2001925A CZ2001925A3 (en) 1998-09-25 1999-09-24 Granulated detergent mixture and process of washing soiled fabrics
JP2000572325A JP2003522214A (en) 1998-09-25 1999-09-24 Granular detergent composition having homogeneous particles and method for producing the same
EP99949917A EP1115836A1 (en) 1998-09-25 1999-09-24 Granular detergent composition having improved appearance and solubility
HU0103664A HUP0103664A3 (en) 1998-09-25 1999-09-24 Granular detergent composition
MA25784A MA24985A1 (en) 1998-09-25 1999-09-24 GRANULAR DETERGENT COMPOSITIONS HAVING HOMOGENEOUS PARTICLES, AND METHOD FOR THE PRODUCTION THEREOF
CNB998114073A CN1192095C (en) 1998-09-25 1999-09-24 Granular detergent compositions having homogenous particles and process for producing same
JP2000572326A JP2003527455A (en) 1998-09-25 1999-09-24 Granular detergent composition with improved solubility properties
EG119299A EG22007A (en) 1998-09-25 1999-09-25 Granular detergent composition having improved appearance and solability

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EP0816485A1 (en) * 1996-07-04 1998-01-07 The Procter & Gamble Company Process for making detergent compositions
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US5332519A (en) * 1992-05-22 1994-07-26 Church & Dwight Co., Inc. Detergent composition that dissolves completely in cold water, and method for producing the same
JPH062000A (en) * 1992-06-22 1994-01-11 Kao Corp Method for producing high-density granular detergent composition
EP0816485A1 (en) * 1996-07-04 1998-01-07 The Procter & Gamble Company Process for making detergent compositions
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