WO2000024859A1 - Particules detergentes et leurs procedes de fabrication - Google Patents

Particules detergentes et leurs procedes de fabrication Download PDF

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Publication number
WO2000024859A1
WO2000024859A1 PCT/US1999/024685 US9924685W WO0024859A1 WO 2000024859 A1 WO2000024859 A1 WO 2000024859A1 US 9924685 W US9924685 W US 9924685W WO 0024859 A1 WO0024859 A1 WO 0024859A1
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WIPO (PCT)
Prior art keywords
detergent
particulate
acid
mixer
bulk density
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Application number
PCT/US1999/024685
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English (en)
Inventor
Scott William Capeci
Matthew Israel Wasserman
Wayne Edward Beimesch
Mark William Ridyard
Robert Gary Welch
Manivannan Kandasamy
Girish Jagannath
Original Assignee
The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU14491/00A priority Critical patent/AU1449100A/en
Publication of WO2000024859A1 publication Critical patent/WO2000024859A1/fr

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Classifications

    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3915—Sulfur-containing compounds

Definitions

  • the present invention relates to particulate detergent compositions and an improved process for making such compositions.
  • the detergent compositions of the invention are suitable for any cleaning purpose, however, the invention is particularly directed to laundry and dishwashing detergent compositions. These may be used directly in their particulate form or may be formed into detergent tablets, for example by compaction or any of the other standard tabletting processes.
  • the process of the invention is particularly useful for controlling density of the particulate detergent produced.
  • detergent compositions In order to meet the needs of the consumer, in addition to providing good cleaning, detergent compositions must meet many additional requirements including good aesthetics, good flow properties and good solubility and dispensing performance into wash water. In order to try to meet all these requirements, the complexity of detergent compositions and range of products offered has grown. Formulation flexibility in order to incorporate the components needed to produce good cleaning and the additional characteristics outlined above, is therefore extremely important to the detergent formulator and there are many methods for formulating detergent compositions, all of which attempt to produce a product which will be delivered by the consumer uniformly in each use dosage.
  • a significant factor in achieving uniform dosage by the consumer is reduction of particle size variability and density variability in the particulate components in a package of detergent, both of which lead to segregation.
  • a single detergent particle would of course eliminate segregation. However, it would decrease formulation flexibility.
  • the present invention overcomes the problems set out above by providing a process where control of density can be achieved by using a mixture of pre-formed and raw materials fed into a particular mixing process. Furthermore, the process of the present invention enables incorporation of all of the detergent components into a single or minimum number of particulates so that segregation is minimised.
  • a process for making a detergent particle comprising adding to a mixer, first and second particulate components optionally with binder and mixing under conditions of moderate to low shear, wherein the first particulate component comprises a pre-formed particulate comprising at least two detergent ingredients and the second particulate component is selected from particulate detergent raw materials or pre-formed particulates and wherein the geometric mean particle diameter of each of the first and second particulates is above 50 ⁇ m.
  • the present invention also includes detergent particles obtainable by such a process and detergent compositions comprising such particles.
  • a process for controlling bulk density in the manufacture of detergent particles comprising adding to a moderate or low shear mixer a first feed stream of a first particulate comprising a pre-formed particulate having a first bulk density, and a second feed stream of second particulate selected from particulate detergent raw materials and pre-formed particulates and having a second bulk density, the geometric mean particle diameter of both the first and second particulates being greater than 50 ⁇ m, and optionally a third feed stream comprising binder, and selecting the rate of delivery of the first and/or second feed streams and/or bulk density of one or more of the feed streams, to control the bulk density of the detergent particles.
  • the pre-formed particulate may comprise any combination of two or more detergent ingredients.
  • Suitable pre-formed particulates may have been formed by a spray- drying, agglomeration, marumerisation, extrusion or compaction process, all of which methods for combining detergent ingredients are well known in the art.
  • Particularly preferred pre-formed particulates are powders obtained from spray-drying processes, agglomerates and extrudates. Spray dried powders are particularly useful.
  • Suitable spray-drying processes for forming such pre-formed particulates are described for example in EP-A-763 594 or EP-A- 437888.
  • Suitable processes for forming pre-formed particulates which are agglomerates are described for example in W093/25378, EP-A-367339, EP-A-420317 or EP-A-506184 and suitable processes for forming pre-formed particulates by extrusion are described for example in W091/02047.
  • the pre-formed particulates may be added in their wet or dry states for example, it is common in formation of detergent particulates that initially, the particulates are wet and undergo a drying stage.
  • the pre-formed particulate may be a particulate before it has undergone a drying stage.
  • a solvent used as a binding agent for the processing is present in higher amounts that are desirably present in a finished particulate detergent.
  • such a solvent will be water and the particulates may have a water content for example 15 to 30 wt % of the pre-formed particulate.
  • the pre-formed particulate will already have undergone a drying step prior to addition to the mixer so that the water content may be below 15 wt % or even below 10 wt %.
  • any pre-formed particulate component comprises a surfactant or mixture of surfactants. Suitable surfactants are described below.
  • the surfactant content of a pre-formed particulate component is preferably from 5 to 80 % by weight of the particulate component. Amounts of surfactants above 10 or even above 30% may be preferred. Amounts of surfactant below 70% or even below 50% may be preferred.
  • the pre-formed particulate component comprises surfactant, generally it will in addition comprise a builder or alkalinity agent such as sodium carbonate, zeolite, or phosphate.
  • each of these components individually, or in mixtures may be present in amounts above 5%, preferably above 10% or even above 20% by weight of the content of the pre-formed particulate component.
  • Particularly preferred builder components are sodium carbonate and/or zeolite. Zeolite A and zeolite MAP are both suitable.
  • a pre-formed particulate component preferably also comprises an organic builder such as a poly carboxylic acid and/or salt such as citric acid, tartaric acid, malic acid, succinic acid and their salts or a polymeric polycarboxylate such as polymers based on acrylic acids or maleic acids or co-polymers thereof.
  • organic builder such as a poly carboxylic acid and/or salt such as citric acid, tartaric acid, malic acid, succinic acid and their salts or a polymeric polycarboxylate such as polymers based on acrylic acids or maleic acids or co-polymers thereof.
  • chelants such as phosphonate chelants NTA, DTPA and succinic acid derivative chelants, as described below. These components are preferably present in a pre-formed particulate component in amounts below 5 wt % or even below 2 wt % of the first particulate component. Suds suppressors and/or soil release polymers and/or bleach activators are also preferred ingredients in pre-formed particulates.
  • any particulate detergent ingredient is suitable.
  • These may be solid surfactants or soaps, or water soluble or dispersable polymeric materials, enzymes, bleaching components such as bleach activators or bleach salts such as peroxy salts, but are generally inorganic components, particularly water soluble inorganic components such as builders. These ingredients are discussed in more detail below.
  • the geometric mean particle diameter of the first and/or second particulate components may vary considerably between the first and second particulate.
  • the geometric mean particle diameter of each of these particulates is generally from 100 microns to as high as 1000 microns. Mean particle diameter is determined using sieves. Generally however, the geometric mean particle diameter of the second particulate component at least will be greater than 60 micron, or even greater than 100 or 120 or even 150 microns. Often, the geometric mean particle diameter of both the first and second particulate components will be as defined.
  • both the first and second particulate components comprise pre-formed detergent particulates.
  • Combinations of spray-dried blown powders and other pre-formed particulate detergents, in particular agglomerates or extrudates are particularly preferred.
  • a further feature which may be preferred is that there will be an additional third particulate component which comprises a particulate detergent raw material.
  • bulk density refers to the uncompressed, untapped powder bulk density, as measured by pouring an excess of particulate sample through a funnel into a smooth metal vessel (e.g. a 500ml volume cylinder) scraping off the excess off the heap above the rim of the vessel, measuring the remaining mass of powder and dividing the mass by the volume of the vessel.
  • a smooth metal vessel e.g. a 500ml volume cylinder
  • the bulk density of the first and second particulate components will generally differ, usually by at least 25 g/1, or even by at least 50 g/1 or at least 75 g/1.
  • the bulk density of the first and second particulate components respectively is generally above 200 g/1 and may be as high as 1500 g/1. It is particularly preferred that the bulk density of at least one particulate component will be greater than 600 g/1, preferably greater than 750 g/1 or even above 800 g/1.
  • the bulk density of the detergent particle produced according to the process of the invention will generally be from 400 to 1 lOOg/l, generally above 450g/l or even above 600 g/1, preferably greater than 650 g/1 or even greater than 700 g/1.
  • the process of the invention may be particularly useful for preparing detergent particles having a bulk density below 500 or even below 450g l.
  • the moderate to low shear mixer to be used in the present invention may be for example a Lodige KM (trademark) (Ploughshare) moderate speed mixer, or mixer made by Fukae, Draes Schugi or similar brand mixers which mix with only moderate to low shear.
  • the Lodige KM (ploughshare) moderate speed mixer which is a preferred mixer for use in the present invention comprises a horizontal hollow static cylinder having a centrally mounted rotating shaft around which several plough-shaped blades are attached.
  • the shaft rotates at a speed of from about 15 rpm to about 140 rpm, more preferably from about 80 rpm to about 120 rpm.
  • the grinding or pulverizing is accomplished by cutters, generally smaller in size than the rotating shaft, which preferably operate at about 3600 rpm.
  • Other mixers similar in nature which are suitable for use in the process include the Lodige PloughshareTM mixer and the Drais® K-T 160 mixer.
  • the shear will be no greater than the shear produced by a Lodige KM mixer with the tip speed of the ploughs below 30 m/s, or even below 10 m/s or even lower.
  • the mean residence time of the various starting detergent ingredients in the low or moderate speed mixer is preferably in range from about 0.1 seconds to about 30 minutes, most preferably the residence time is about 0.5 to about 5 minutes. In this way, the density of the resulting detergent agglomerates is at the desired level.
  • suitable mixers for use in the present invention are low or very low shear mixers such as rotating bowl agglomerators, drum agglomerators, pan agglomerators and fluid bed agglomerators.
  • Fluid bed agglomerators are particularly preferred. Typical fluidised bed agglomerators are operated at a superficial air velocity of from 0.1 to 4 m/s, either under positive or negative pressure. Inlet air temperatures generally range from -10 or 5°C up to 250°C. However inlet air temperatures are generally below 200°C, or even below 150°C.
  • the fluidized bed granulator is preferably operated such that the flux number FN of the fluid bed is at least about 2.5 to about 4.5.
  • Flux number (FN m ) is a ratio of the excess velocity (U e ) of the fluidisation gas and the particle density (p p ) relative to the mass flux (q ⁇ q ) of the liquid sprayed into the bed at a normalized distance (D 0 ) of the spraying device.
  • the flux number provides an estimation of the operating parameters of a fluidized bed to control granulation within the bed.
  • the flux number may be expressed either as the mass flux as determined by the following formula:
  • the fluidized bed is generally operated at a Stokes number of less than about 1 , more preferably from about 0.1 to about 0.5.
  • the Stokes number is a measure of particle coalescence for describing the degree of mixing occurring to particles in a piece of equipment such as the fluid bed.
  • the Stokes number is measured by the formula:
  • the mixer is a fluid bed mixer
  • the first and second particulate components of the present invention are passed into a fluid bed having multiple internal "stages" or “zones".
  • a stage or zone is any discrete area within the fluid bed, and these terms are used interchangeably herein.
  • the process conditions within a stage may be different or similar to the other stages in the fluid bed. It is understood that two adjacent fluid beds are equivalent to a single fluid bed having multiple stages.
  • the various feed streams of granules and coating material can be added at the different stages, depending on, for example, the particle size and moisture level of the feed stream. Feeding different streams to different stages can minimize the heat load on the fluid bed, and optimize the particle size and generate detergent particles having more uniform shape.
  • the bed is typically fluidized with heated air in order to dry or partially dry moisture such as the binder liquids from the ingredients in the fluid bed.
  • binder is sprayed into the fluid bed the spraying is generally achieved via nozzles capable of delivering a fine or atomized spray of the binder to achieve intimate mixing with the particulates.
  • the droplet size from the atomizer is less than about 2 times the particles size. This atomization can be achieved either through a conventional two-fluid nozzle with atomizing air, or alternatively by means of a conventional pressure nozzle.
  • the solution or slurry rheology may have a viscosity of less than about 500 centipoise, preferably less than about 200 centipoise at the point of atomization.
  • the nozzle location in the fluid bed may be in most any location, the preferred location is a positioning that allows a vertical down spray of any liquid components such as binder. This may be achieved for example, using a top spray configuration.
  • the nozzle location is placed at or above the fluidized height of the particles in the fluid bed.
  • the fluidized height is typically determined by a weir or overflow gate height.
  • the agglomeration/granulation zone of the fluid bed may be followed by an optional coating zone, followed by a drying zone and a cooling zone.
  • one of ordinary skill in the art will recognize that alternative arrangements are also possible to achieve the resultant particles of the present invention.
  • Typical conditions within a fluid bed apparatus of the present invention include: (i) a mean residence time from about 1 to about 20 minutes, (ii) a depth of unfluidised bed of from about 100 to about 600 mm, (iii) a droplet spray size of less than 2 times the mean particle size in the bed, which is preferably not more than about 100 micron, more preferably not more than 50 microns, (iv) spray height generally from 150 to 1600 mm of spray height from the fluid bed plate or preferably 0 to 600mm from the top of the fluid bed , (v) from about 0.1 to about 4.0 m/s, preferably 1.0 to 3.0m/s of fluidizing velocity and (vi) from about 12 to about 200 °C of bed temperature, preferably 15 to 100°C.
  • the processes of the invention may comprise the step of adding to the mixer a binder to facilitate production of the desired detergent particles.
  • a binder will be liquid or will be added by spraying either directly into the mixer or onto the particulate components as or before they travel into the mixer.
  • the binder is added directly into the mixer for example by spraying.
  • the binder is added for purposes of enhancing agglomeration by providing a binding or sticking agent for detergent components.
  • the binder is preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, polyethylene glycol, polyvinyl pyrrolidone, polyacrylates, organic acids or their salts such as citric acid or citric salts, and mixtures thereof.
  • Other suitable binder materials including those listed herein are described in Beerse et al, US Patent number 5108646 (Procter and Gamble Company), the disclosure of which is incorporated herein by reference.
  • the detergent particles produced in the mixer can be further processed by adding a coating agent to improve the particle colour, increase the particle whiteness or improve the particle flowability after the detergent particles exit the mixer or the dryer if an optional drying step is added subsequently to the mixer or in a later stage in the mixer, to obtain the high density granular detergent compositions produced by the processes of the invention.
  • a coating agent to improve the particle colour, increase the particle whiteness or improve the particle flowability after the detergent particles exit the mixer or the dryer if an optional drying step is added subsequently to the mixer or in a later stage in the mixer, to obtain the high density granular detergent compositions produced by the processes of the invention.
  • Another optional processing step includes continuously adding a coating agent such as zeolite and/or fumed silica to the mixer to facilitate free flowability of the resulting detergent particles and to prevent over agglomeration.
  • a coating agent such as zeolite and/or fumed silica
  • Such coating agents generally have a mean particle size below 100 microns, preferably below 60 microns, even more preferably below 50 microns.
  • the mean particle diameter of the detergent particles produced will generally be from 500 - 2500 microns, preferably being at least 550, more preferably being at least 600 microns.
  • the mean particle diameter will generally be below 1500 microns or even below 1300 microns.
  • 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.
  • a suitable sieving method is in accordance with ISO 3118 (1976).
  • a suitable device is a Ro-Tap testing sieve shaker Model B using 8 inch sieves of selected sizes.
  • 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. 6-1 1, Marcel Dekker 1997.
  • the detergent particles preferably have a geometric standard deviation of from 1 to about 2, preferably from 1.0 to 1.7, more preferably from about 1.0 to about 1.4.
  • Preferred fully formulated detergents comprising the detergent particles also have such a geometric standard deviation.
  • the bulk density of powders produced by spray drying processes will be lower than the bulk density of other pre-formed particulates such as agglomerates and other intermediates.
  • the density of agglomerates and other intermediates may be from 600 or even above 700 g/1 or above 750 g/1.
  • the bulk density of spray dried powders is generally from 150 g/1 to 600 g/1. More usually, the bulk density of blown powder is at least 300 g/1, but is generally no greater than 550 g/1 after drying and aging for at least 24 hours in ambient conditions.
  • feed streams comprising mixtures or spray dried powders and/or agglomerates and/or raw material ingredients or other co-compacted combinations of detergent ingredients will not only vary the chemical composition of the detergent particles produced, but will also vary the density.
  • pre-formed particulates comprising surfactant and builder may be added to (i) raw materials comprising builder and (ii) binder comprising surfactant, so that the binder and raw material contain builder and surfactant in the same weight ratios as in the pre-formed particulates, so that the chemical composition of the finally produced detergent particle will be the same, but the density will be either lower or higher than that of the pre-formed detergent particulate.
  • the starting pre-formed particulate is a spray-dried powder having low density and a second feed has higher density
  • variation of the respective rates of the feeds to the moderate to low speed mixer will tend to increase the bulk density of the finished detergent particles relative to the spray-dried powder in a varying amount dependent upon the respective feed rates.
  • the bulk density of the binder and raw materials will of course also be significant.
  • combining spray-dried powders and agglomerates/extrudates will tend to result in a finished detergent particle composition having a density between the density of these two components. Varying the relative feed rates of these two components to the mixer will therefore change the finished product density.
  • combinations of the particulates may be used to give a pre-selected bulk density for the finished detergent particles.
  • sophisticated control of the processing can be omitted.
  • the detergent particles produced according to the present invention may comprise all of the detergent ingredients for a fully formulated detergent composition.
  • additional detergent ingredients may be mixed with the detergent particles to produce fully formulated detergent compositions.
  • fully formulated detergent compositions will comprise at least 20 wt %, more preferably at least 40 wt % or even at least 50 wt % or even higher than 70 or 90 wt % of the detergent particles of the invention.
  • Suitable detergent ingredients for incorporation either into the detergent particles themselves, or for post-addition to formulate a fully formulated detergent composition are discussed below.
  • Suitable surfactants for use in the invention are anionic, nonionic, ampholytic, and zwitterionic classes of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents” (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31, 1981.
  • the detergent particle of the present invention and compositions comprising such particles comprises an additional anionic surfactant.
  • anionic surfactants useful for detersive purposes can be comprised in the detergent composition. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.
  • Anionic sulfate and sulfonate surfactants are preferred.
  • the anionic surfactants may be present in the detergent particle in amounts below 25 wt % or even below 20 wt % but in a final detergent composition comprising the particle, is preferably present at a level of from 0.1% to 60%, more preferably from 1 to 40%, most preferably from 5% to 30% by weight.
  • anionic surfactants include the anionic carboxylate surfactants such as alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylates and soaps ("alkyl carboxyls") such as water-soluble members selected from the group consisting of the water-soluble salts of 2- methyl- 1 -undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l-nonanoic acid, 2-butyl-l- octanoic acid and 2-pentyl- 1 -heptanoic acid. Certain soaps may also be included as suds suppressors.
  • suitable anionic surfactants are the alkali metal sarcosinates of formula R-
  • R is a C5-C17 linear or branched alkyl or alkenyl group
  • R* is a C1-C4 alkyl group
  • M is an alkali metal ion.
  • anionic surfactants include isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C- --C. dilemma monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C,-C - . diesters), N-acyl sarcosinates.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
  • Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C ] 7 acyl-N-(Cj-C4 alkyl) and -N-(C ⁇ -C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Alkyl sulfate surfactants are preferably selected from the linear and branched primary C J Q-C j g alkyl sulfates, more preferably the C1 j -C ] 5 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C 1 -C j g alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule.
  • the alkyl ethoxysulfate surfactant is a Cj 1 -C13, most preferably Cj 1-C15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
  • Preferred surfactant combinations are mixtures of the preferred alkyl sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants optionally with cationic surfactant. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
  • Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, Cg-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
  • any alkoxylated nonionic surfactant or mixture is suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.
  • Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
  • condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are particularly suitable for use herein.
  • Particularly preferred are the condensation products of straight or branched, primary or secondary alcohols having an alkyl group containing from 6 to 22 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
  • Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R ⁇ CONR ⁇ Z wherein : Rl is H, C1 -C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C ] -C4 alkyl; and R2 is a C5-C31 hydrocarbyl; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
  • alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21 , 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
  • Preferred alkylpolyglycosides have the formula:
  • R2 ⁇ (C n H 2n O)t(gIycosyl) x wherein R ⁇ is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
  • the glycosyl is preferably derived from glucose.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula wherein R is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R ⁇ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R ⁇ is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are Ci Q-Ci g alkyl dimethylamine oxide, and Cj ⁇ -18 acylamido alkyl dimethylamine oxide.
  • Zwitterionic surfactants can also be incorporated into the detergent compositions in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaines such as Cj2_ ⁇ g dimethyl-ammonio hexanoate and the C J Q- 18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable cationic surfactants to be used herein include the quaternary ammonium surfactants.
  • the quaternary ammonium surfactant is a mono Cg-Cj , preferably Cg-
  • N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
  • Cationic ester surfactants such as choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529 are also suitable as are cationic mono-alkoxylated amine surfactants preferably of the general formula I: H 2 ) 2- 4 ⁇ ),.5H
  • R ⁇ is C ] Q-C I hydrocarbyl and mixtures thereof, especially C J -C 14 alkyl, preferably C] ⁇ and C j 2 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
  • the levels of the cationic mono-alkoxylated amine surfactants in the detergent compositions of the invention are generally from 0.1% to 20%, preferably from 0.2% to 7%, most preferably from 0.3% to 3.0% by weight.
  • Cationic bis-alkoxylated amine surfactant such as are also useful, wherein R' is C j Q -C ] g hydrocarbyl and mixtures thereof, preferably C j ⁇ , C12, Cj4 alkyl and mixtures thereof.
  • X is any convenient anion to provide charge balance, preferably chloride.
  • the detergent particles or detergent compositions containing them preferably comprise a bleach activator, preferably comprising an organic peroxyacid bleach precursor. It may be preferred that the composition comprises at least two peroxy acid bleach precursors, preferably at least one hydrophobic peroxyacid bleach precursor and at least one hydrophilic peroxy acid bleach precursor, as defined herein.
  • the production of the organic peroxyacid occurs then by an in situ reaction of the precursor with a source of hydrogen peroxide.
  • the bleach activator may alternatively, or in addition comprise a preformed peroxy acid bleach.
  • the bleach activator is present in the detergent particle. It may be preferred that the bleach activator is present as a separate, admixed particle.
  • At least one of the bleach activators preferably a peroxy acid bleach precursor, is present in a particulate component having an average particle size, by weight, of from 600 microns to 1400 microns, preferably from 700 microns to 1 100 microns. More preferably, all of the activator are present in one or more particulate components having the specified weight average particle size.
  • At least 80%, preferably at least 90% or even at least 95 % or even substantially 100% of the component or components comprising the bleach activator have a particle size of from 300 microns to 1700 microns, preferably from 425 microns to 1400 microns.
  • Preferred hydrophobic peroxy acid bleach precursor preferably comprise a compound having an oxy-benzene sulphonate group, preferably NOBS, DOBS, LOBS and/ or NACA-OBS.
  • Preferred hydrophilic peroxy acid bleach precursors preferably comprises TAED.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as O
  • hydrophobic peroxyacid bleach precursors produce a peroxy acid of the formula above wherein X is a group comprising at least 6 carbon atoms and a hydrophilic peroxyacid bleach precursor produces a peroxyacid bleach of the formula above wherein X is a group comprising 1 to 5 carbon atoms.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing from 1 to 14
  • R is an alkyl chain containing from 1 to 8 carbon atoms
  • R is H or R
  • Y is
  • R , R and R may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
  • the preferred solubilizing groups are -SO, M , -CO- M , -SO . M , -N (R ) .X and
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred
  • X is a halide, hydroxide, methylsulfate or acetate anion.
  • Peroxyacid bleach precursor compounds are preferably incorporated in final detergent compositions at a level of from 0.5% to 30% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight.
  • the ratio of hydrophilic to hydrophobic bleach precursors, when present, is preferably from 10: 1 to 1 : 10, more preferably from 5;1 to 1 :5 or even from 3: 1 to 1 :3.
  • Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB- A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1 147871, 2143231 and EP- A-0170386.
  • Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
  • Preferred precursors of this type provide peracetic acid on perhydrolysis.
  • Preferred alkyl percarboxylic precursor compounds of the i ide type include the N-,N,N ⁇ Nl tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms.
  • Tetraacetyl ethylene diamine (TAED) is particularly preferred as hydrophilic peroxy acid bleach precursor.
  • alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyI hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
  • Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
  • R' is an aryl or alkaryl group with from about 1 to about 14 carbon atoms
  • R ⁇ is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms
  • R-> is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • R' preferably contains from about 6 to 12 carbon atoms.
  • R ⁇ preferably contains from about 4 to 8 carbon atoms.
  • R' may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R ⁇ .
  • R2 can include alkyl, aryl, wherein said R ⁇ may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • R' and R-> should not contain more than 18 carbon atoms total.
  • Amide substituted bleach activator compounds of this type are described in EP-A-0170386. It can be preferred that
  • Rl and R-> forms together with the nitrogen and carbon atom a ring structure.
  • bleach precursors of this type include amide substituted peroxyacid precursor compounds selected from (6-octanamido-caproyl)oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzene- sulfonate, and the highly preferred (6- nonanamidocaproyl)oxy benzene sulfonate, and mixtures thereof as described in EP-A-0170386.
  • Perbenzoic acid precursor compounds which provide perbenzoic acid on perhydrolysis benzoxazin organic peroxyacid precursors as disclosed for example in EP-A-332294 and EP-A- 482807 and cationic peroxyacid precursor compounds which produce cationic peroxyacids on perhydrolysis are also suitable.
  • Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451 ; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
  • the particles or compositions of the present invention may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 0.1 % to 15% by weight, more preferably from 1% to 10% by weight.
  • a preferred class of organic peroxyacid compounds are the amide substituted compounds as described in EP-A-0170386.
  • organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • diacyl and tetraacylperoxides especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
  • Inorganic perhydrate salts are a preferred source of peroxide.
  • these salts are present at a level of from 0.01% to 50% by weight, more preferably of from 0.5% to 30% by weight of the composition or component.
  • inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts.
  • the inorganic perhydrate salts are normally the alkali metal salts.
  • the inorganic perhydrate salt may be included as the crystalline solid without additional protection.
  • the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.
  • Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.
  • Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaB ⁇ 2H2 ⁇ 2 or the tetrahydrate NaB ⁇ 2H2 ⁇ 2-3H2 ⁇ .
  • Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates herein.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C ⁇ 3.3H2 ⁇ 2, and is available commercially as a crystalline solid.
  • Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.
  • chelants refers to detergent ingredients which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
  • Chelants are generally present in the detergent particle or final detergent composition at a level of from 0.005% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most preferably from 0.3% to 2% by weight of the compositions or component
  • Suitable chelants include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates, preferably diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate), hydroxy- ethylene 1,1 diphosphonate, 1,1 hydroxethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.
  • organic phosphonates such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates, preferably diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate), hydroxy- ethylene 1,1 diphospho
  • Suitable chelants for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof, and iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.
  • nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof, and iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,54
  • EP-A-516,102 The iminodiacetic acid-N-2- hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
  • the ⁇ -alanine-N,N'- diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.
  • EP-A-476,257 describes suitable amino based sequestrants.
  • EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
  • EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane- 1 ,2,4-tricarboxylic acid are alos suitable. Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
  • Glycinamide-N,N'-disuccinic acid Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
  • diethylenetriamine pentacetic acid ethylenediamine-N,N'-disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • the chelating agents comprising a amino or amine group can be bleach-sensitive and are suitable in the compositions of the invention.
  • the component or compositions herein preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight, preferably from 10% to 60% by weight, most preferably from 15% to 40%o by weight.
  • the detergent compositions of the invention preferably comprise phosphate-containing builder material. Preferably present at a level of from 0.5% to 60%, more preferably from 5% to 50%, more preferably from 8% to 40%.
  • the phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.
  • Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfmyl carboxylates.
  • Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
  • Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
  • Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
  • organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB- A- 1,596,756.
  • salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.
  • polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
  • Partially Soluble or Insoluble Builder Compound is included in EP-A-305282, EP-A-305283 and EP-A-351629.
  • the component in accord with the present invention or the compositions herein may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 0.5% to 60% by weight, preferably from 5% to 50% by weight, most preferably from 8% to 40% weight.
  • a partially soluble or insoluble builder compound typically present in detergent compositions at a level of from 0.5% to 60% by weight, preferably from 5% to 50% by weight, most preferably from 8% to 40% weight.
  • largely water insoluble builders include the sodium aluminosilicates.
  • Suitable aluminosilicate zeolites have the unit cell formula Na z [(Al ⁇ 2) z (Si ⁇ 2)y]. H2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least
  • the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18%o to 22% water in bound form.
  • the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula: Na 12 [Al ⁇ 2) i2 (Si ⁇ 2)i2]. H 2 0 wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na g
  • zeolite MAP builder Another preferred aluminosilicate zeolite is zeolite MAP builder.
  • the zeolite MAP can be present at a level of from 1% to 80%, more preferably from 15% to 40%) by weight.
  • Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
  • zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
  • the zeolite MAP detergent builder has a particle size, expressed as a median particle size d5Q value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.
  • the d5 ⁇ value indicates that 50%> by weight of the particles have a diameter smaller than that figure.
  • the particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer, described herein. Other methods of establishing d5Q values are disclosed in EP 384070A.
  • Other Detergent Ingredients are disclosed in EP 384070A.
  • a preferred ingredient of the compositions herein are dyes and dyed particles or speckles, which can be bleach-sensitive.
  • the dye as used herein can be a dye stuff or an aqueous or nonaqueous solution of a dye stuff. It may be preferred that the dye is an aqueous solution comprising a dyestuff, at any level to obtain suitable dyeing of the detergent particles or speckles, preferably such that levels of dye solution are obtained up to 2% by weight of the dyed particle, or more preferably up to 0.5% by weight, as described above.
  • the dye may also be mixed with a non-aqueous carrier material, such as non-aquous liquid materials including nonionic surfactants.
  • the dye also comprises other ingredients such as organic binder materials, which may also be a non-aqueous liquid.
  • the dyestuff can be any suitable dyestuff.
  • suitable dyestuffs include E104 - food yellow 13 (quinoline yellow), El 10 - food yellow 3 (sunset yellow FCF), E131 - food blue 5 (patent blue V), Ultra Marine blue (trade name), E133 - food blue 2 (brilliant blue FCF), El 40 - natural green 3 (chlorophyll and chlorphyllins), El 41 and Pigment green 7 (chlorinated Cu phthalocyanine).
  • Preferred dyestuffs may be Monastral Blue BV paste (trade name) and/ or Pigmasol Green (trade name).
  • perfume or perfume composition is a perfume or perfume composition. Any perfume composition can be used herein.
  • the perfumes may also be encapsulated.
  • Preferred perfumes containing at least one component with a low molecular weight volatile component e.g. having a molecular weight of from 150 to 450 or preferably 350.
  • the perfume component comprises an oxygen-containing functional group.
  • Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or mixtures thereof.
  • Another highly preferred ingredient useful in the particles or compositions herein is one or more additional enzymes.
  • Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
  • Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001%) to 4% active enzyme by weight of the composition.
  • Preferred amylases include, for example, -amylases described in more detail in GB- 1,269,839 (Novo).
  • Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A/S.
  • Highly preferred amylase enzymes maybe those described in PCT/ US 9703635, and in W095/26397 and WO96/23873.
  • Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001%) to 2% active enzyme by weight.
  • Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001%) to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5%> by weight.
  • the lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein.
  • a preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.
  • Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge- Jensen et al, issued March 7, 1989.
  • the component or compositions herein also preferably contain from about 0.005%> to 5% by weight of certain types of hydrophilic optical brighteners, as mentioned above.
  • Tinopal-UNPA-GX examples are commercially marketed under the tradenames Tinopal-UNPA-GX and Tinopal-CBS-X by Ciba-Geigy Corporation.
  • Tinopal 5BM-GXTM Tinopal-DMS-XTM
  • Tinopal AMS-GXTM Tinopal AMS-GXTM by Ciba Geigy Corporation.
  • Photo-bleaching agents are preferred ingredients of the compositions or components herein.
  • Preferred photo-bleaching agent herein comprise a compounds having a porphin or porphyrin structure.
  • Porphin and porphyrin in the literature, are used as synonyms, but conventionally porphin stands for the simplest porphyrin without any substituents; wherein porphyrin is a sub-class of porphin.
  • the references to porphin in this application will include po ⁇ hyrin.
  • the porphin structures preferably comprise a metal element or cation, preferably Ca, Mg, P, Ti, Cr, Zr, In, Sn or Hf, more preferably Ge, Si or Ga, or more preferably Al , most preferably Zn.
  • the photo-bleaching compound or component is substituted with substituents selected from alkyl groups such as methyl, ethyl, propyl, t-butyl group and aromatic ring systems such as pyridyl, pyridyl-N-oxide, phenyl, naphthyl and anthracyl moieties.
  • substituents selected from alkyl groups such as methyl, ethyl, propyl, t-butyl group and aromatic ring systems such as pyridyl, pyridyl-N-oxide, phenyl, naphthyl and anthracyl moieties.
  • the photo-bleaching compound or component can have solubilizing groups as substituents.
  • the photo-bleaching agent can comprise a polymeric component capable of solubilizing the photo-bleaching compound, for example PVP, PVNP, PVI or co-polymers thereof or mixtures thereof.
  • Highly preferred photo-bleaching compounds are compounds having a phthalocyanine structure, which preferably have the metal elements or cations described above.
  • the phthalocyanines can be substituted for example the phthalocyanine structures which are substituted at one or more of the 1-4, 6, 8-1 1, 13, 15-18, 20, 22-25, 27 atom positions.
  • Organic polymeric compounds are preferred additional herein and are preferably present as components of any particulate components where they may act such as to bind the particulate component together.
  • organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, including quaternised ethoxylated (poly) amine clay-soil removal/ anti-redeposition agent in accord with the invention.
  • Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.01% to 30%, preferably from 0.1%) to 15%, most preferably from 0.5%) to 10%) by weight of the compositions or component.
  • Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
  • organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
  • Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
  • Highly preferred polymeric components herein are cotton and non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent 5,415,807, Gosselink et al., and in particular according to US application no.60/051517.
  • Another organic compound which is a preferred clay dispersant/ anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula:
  • X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof
  • a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene)
  • the components and detergent compositions herein, when formulated for use in machine washing compositions, may comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to 3% by weight of the composition or component.
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds or soap.
  • antifoam compound any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
  • Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component.
  • Such silicone antifoam compounds also typically contain a silica component.
  • Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
  • Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof as described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • Suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C j 3-C4Q ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
  • high molecular weight fatty esters e.g. fatty acid triglycerides
  • fatty acid esters of monovalent alcohols e.g. fatty acid esters of monovalent alcohols
  • a preferred suds suppressing system comprises antifoam compound, preferably comprising in combination polydimethyl siloxane, at a level of from 50% to 99%>, preferably 75%) to 95%) by weight of the silicone antifoam compound; and silica, at a level of from 1%> to 50%>, preferably 5%> to 25% by weight of the silicone/silica antifoam compound wherein said silica/silicone antifoam compound is incorporated at a level of from 5% to 50%>, preferably 10% to 40%> by weight a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78%) and an ethylene oxide to propylene oxide ratio of from 1 :0.9 to 1 : 1.1, at a level of from 0.5% to 10% such as DCO544, commercially available from DOW Corning, and an inert carrier fluid compound, most preferably comprising a Cjg-C j ethoxylated alcohol with
  • EP-A-0210731 A highly preferred particulate suds suppressing system is described in EP-A-0210731.
  • EP-A-0210721 discloses other preferred particulate suds suppressing systems.
  • suds suppressing systems comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxylic polymers, such as copolymers of laic and acrylic acid.
  • Polymeric dye transfer inhibiting agents when present are generally in amounts from 0.01% to 10 %, preferably from 0.05%> to 0.5%> and are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross- linked polymers.
  • SRA Polymeric soil release agents
  • SRAs can optionally be employed in the present components or compositions. If utilized, SRAs will generally be used in amounts from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight.
  • Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.
  • Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide.
  • esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
  • Suitable SRAs are for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • Other SRAs include the nonionic end-capped 1,2- propylene/polyoxyethylene terephthalate polyesters of U.S. 4,71 1 ,730, December 8, 1987 to Gosselink et al.
  • Other examples of SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink; the nonionic-capped block polyester oligomeric compounds of U.S.
  • SRAs also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S.
  • methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2%> aqueous solution.
  • Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
  • SRAs include those described in U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; U.S. 4,525,524 Tung et al., and U.S. 4,201,824, Violland et al.
  • compositions of the invention include colours and filler salts, with sodium sulfate being a preferred filler salt.
  • compositions contain from about 2%> to about 10% by weight of an organic acid, preferably citric acid.
  • an organic acid preferably citric acid.
  • minor amounts e.g., less than about 20% by weight
  • neutralizing agents e.g., buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, antioxidants, bactericides and dyes, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25, 1981 (herein incorporated by reference), can be present.
  • the detergent compositions can include as an additional component a chlorine-based bleach.
  • a chlorine-based bleach can be added to the detergent composition by the user at the beginning or during the washing process.
  • the chlorine-based bleach is such that a hypochlorite species is formed in aqueous solution.
  • the hypochlorite ion is chemically represented by the formula OCI " .
  • Those bleaching agents which yield a hypochlorite species in aqueous solution include alkali metal and alkaline earth metal hypochlorites, hypochlorite addition products, chloramines, chlorimines, chloramides, and chlorimides.
  • Specific examples include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3- dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dichloramine T, chloramine B and Dichloramine B.
  • a preferred bleaching agent for use in the compositions of the instant invention is sodium hypochlorite, potassium hypochlorite, or a mixture thereof.
  • a preferred chlorine-based bleach can be Tri
  • hypochlorite-yielding bleaching agents are available in solid or concentrated form and are dissolved in water during preparation of the compositions of the instant invention. Some of the above materials are available as aqueous solutions.
  • Laundry Washing Method Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention.
  • an effective amount of the detergent composition it is meant from lOg to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
  • Preferred washing machines may be the so-called low-fill machines.
  • the composition is formulated such that it is suitable for hard- surface cleaning or hand washing.
  • the detergent composition is a pre- treatment or soaking composition, to be used to pre-treat or soak soiled and stained fabrics.
  • Nal2(A102Si02)12.27H2O having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis)
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between
  • MA AA Copolymer of 4:6 maleic/acrylic acid, average m. wt. about 10,000
  • 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 (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 NOVO Industries A/S
  • NAC-OBS (6-nonamidocaproyl) oxybenzene sulfonate
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2'-disulfonate
  • PEGx Polyethylene glycol, with a m. x (typically 4,000)
  • PVNO Polyvinylpyridine N-oxide polymer with an av. m. wt. 50,000
  • PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole, with an average molecular weight of 20,000
  • SRP 1 Anionically end capped poly esters
  • SRP 2 Diethoxylated poly (1, 2 propylene terephthalate) 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
  • HMEO Hexamethylenediamine tetra(ethylene oxide)24
  • finished agglomerates are produced. These may be added to other detergent ingredients as outlined above to make fully formulated detergents.
  • peroxide source salts such as alkali metal percarbonates or perborates, soil release polymers, nonionic surfactants and other ingredients may be added.
  • Two streams of detergent starting ingredients comprising spray dried powder and agglomerates are continuously fed at a rate of 660g/hr into a Lodige KM (Ploughshare) 600 mixer which is a horizontally positioned moderate speed mixer.
  • the rotational speed of the shaft in the mixer is about 100 RPM and the rotational speed of the cutters is about 3600RPM.
  • the starting detergent ingredients which are continuously passed into a Lodige KM (Ploughshare) 600 have a mean residence time in the mixer of about 5 to 10 minutes.
  • a binder comprising 60 wt% C 9 . 13 alkyl benzene sulphonate and 40 wt% water is continuously fed into the Lodige KM at a rate of 10%> of the powder feed on a solids weight basis.
  • Detergent agglomerates result and are dried in a conventional fluidised bed dryer after they exit the Lodige KM mixer, to obtain the high density granular dgetergents producted by the process.
  • the process is repeated using different proportions of spray dried powder and agglomerate according to example 1 B.
  • the bulk densities of the finished granular detergents obtained are also reported in Table 1 above.
  • Example 2 The bulk densities of the finished granular detergents obtained are also reported in Table 1 above.
  • the starting detergent ingredients which are continuously passed into a Lodige KM (Ploughshare) 600 have a mean residence time in the mixer of about 5 to 10 minutes.
  • a binder comprising 60 wt% C 9 . 13 alkyl benzene sulphonate and 40 wt%> water is continuously fed into the Lodige KM at a rate of 10% of the powder feed on a solids weight basis.
  • the resulting detergent agglomerates are fed to a fluid bed dryer.
  • An aqueous solution of PEG 4000 (30 wt% active) is sprayed onto the mixture in the fluid bed dryer in an amount to generate a 4wt% concentration of PEG in the final agglomerate.
  • the resulting product is screened to collect the particles in the finished detergent agglomerates with particle size in the range of about 600 to 1 lOO ⁇ m.
  • the fines were recycled to the Lodige KM and the large particles are ground and recycled to the fluid bed dryer.
  • the bulk density of the finished agglomerates is reported in Table 2 above.
  • Enzymes (lipase, protease, cellulase and/or amylase) 15
  • the relative proportions of the feed streams into the fluid bed and the bulk density of the finished agglomerates is given in Table 4 below.
  • the composition of the spray dried powder and the agglomerates fed into the fluid bed dryer is as defined in example 1 above.
  • the composition of the minors feedstream is given below. Ingredients in the feed stream Minors (wt%) Silicone suds supressor particle 20 TAED 30
  • Enzymes (lipase, protease, cellulase and/or amylase) 10
  • Table 5 sets out examples of fully formulated detergents in accordance with the invention. Table 5

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un procédé permettant de réguler la densité apparente de particules détergentes au cours de leur fabrication, ce procédé consistant tout d'abord à fournir à un mélangeur, dans des conditions de cisaillement faible ou modéré, un premier flux d'alimentation d'une première substance particulaire, ce fluxontenant une substance particulaire préalablement formée d'une première densité apparente. Ce procédé consiste ensuite à amener un deuxième flux d'alimentation d'une seconde substance particulaire choisie parmi des matières brutes détergentes particulaires et des substances particulaires préalablement formées d'une seconde densité apparente, et enfin éventuellement à introduire un troisième flux d'alimentation renfermant un liant. Ce procédé consiste ensuite à définir la vitesse d'alimentation respective du premier et du second flux d'alimentation, afin de réguler la densité apparente desdites particules détergentes, le diamètre géométrique moyen des particules de la première et de la seconde substances particulaires atteignant au moins 50νm.
PCT/US1999/024685 1998-10-26 1999-10-21 Particules detergentes et leurs procedes de fabrication WO2000024859A1 (fr)

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US60/105,576 1998-10-26
US14008099P 1999-06-21 1999-06-21
US60/140,080 1999-06-21

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000078914A1 (fr) * 1999-06-21 2000-12-28 The Procter & Gamble Company Particules de detergent et procede de fabrication desdites particules
US6579844B1 (en) 2000-06-20 2003-06-17 The Procter & Gamble Co. Detergent particles and methods for making them
WO2007124371A1 (fr) * 2006-04-20 2007-11-01 The Procter & Gamble Company Composition de détergent à lessive particulaire solide comprenant des particules de parfum
US7727947B2 (en) 2008-05-14 2010-06-01 The Procter & Gamble Company Process for the preparation of a solid laundry detergent composition comprising light density silicate salt
JP2012197342A (ja) * 2011-03-18 2012-10-18 Lion Corp 粒状洗剤組成物

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2190921A (en) * 1986-05-27 1987-12-02 Unilever Plc Granular detergent composition
EP0367339A2 (fr) * 1988-11-02 1990-05-09 Unilever N.V. Procédé de préparation d'une composition détergente granulaire ayant une haute densité apparente
DE4243704A1 (de) * 1992-12-23 1994-06-30 Henkel Kgaa Granulare Wasch- und/oder Reinigungsmittel
EP0643129A1 (fr) * 1993-09-07 1995-03-15 The Procter & Gamble Company Procédé de préparation de compositions détergentes
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
EP0866118A2 (fr) * 1997-03-20 1998-09-23 The Procter & Gamble Company Particule de détergent

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2190921A (en) * 1986-05-27 1987-12-02 Unilever Plc Granular detergent composition
EP0367339A2 (fr) * 1988-11-02 1990-05-09 Unilever N.V. Procédé de préparation d'une composition détergente granulaire ayant une haute densité apparente
DE4243704A1 (de) * 1992-12-23 1994-06-30 Henkel Kgaa Granulare Wasch- und/oder Reinigungsmittel
EP0643129A1 (fr) * 1993-09-07 1995-03-15 The Procter & Gamble Company Procédé de préparation de compositions détergentes
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
EP0866118A2 (fr) * 1997-03-20 1998-09-23 The Procter & Gamble Company Particule de détergent

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000078914A1 (fr) * 1999-06-21 2000-12-28 The Procter & Gamble Company Particules de detergent et procede de fabrication desdites particules
US6579844B1 (en) 2000-06-20 2003-06-17 The Procter & Gamble Co. Detergent particles and methods for making them
WO2007124371A1 (fr) * 2006-04-20 2007-11-01 The Procter & Gamble Company Composition de détergent à lessive particulaire solide comprenant des particules de parfum
US7727947B2 (en) 2008-05-14 2010-06-01 The Procter & Gamble Company Process for the preparation of a solid laundry detergent composition comprising light density silicate salt
US7732394B2 (en) 2008-05-14 2010-06-08 The Procter & Gamble Company Solid laundry detergent composition comprising light density silicate salt
JP2012197342A (ja) * 2011-03-18 2012-10-18 Lion Corp 粒状洗剤組成物

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