WO2000078914A1 - Detergent particles and methods for making them - Google Patents

Detergent particles and methods for making them Download PDF

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Publication number
WO2000078914A1
WO2000078914A1 PCT/US2000/016920 US0016920W WO0078914A1 WO 2000078914 A1 WO2000078914 A1 WO 2000078914A1 US 0016920 W US0016920 W US 0016920W WO 0078914 A1 WO0078914 A1 WO 0078914A1
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WIPO (PCT)
Prior art keywords
detergent
particulate
components
component
geometric mean
Prior art date
Application number
PCT/US2000/016920
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English (en)
French (fr)
Inventor
Christopher Andrew Morrison
Scott John Donoghue
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU57512/00A priority Critical patent/AU5751200A/en
Priority to JP2001505659A priority patent/JP2003503549A/ja
Priority to US09/979,528 priority patent/US6579844B1/en
Priority to BR0011844-3A priority patent/BR0011844A/pt
Priority to EP00942968A priority patent/EP1187905A1/en
Priority to MXPA02000030A priority patent/MXPA02000030A/es
Priority to CA002375497A priority patent/CA2375497A1/en
Publication of WO2000078914A1 publication Critical patent/WO2000078914A1/en

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • 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
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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

Definitions

  • the present invention relates to particulate detergent compositions and methods for making them
  • Such detergent compositions may be used for any cleaning purposes, m particular for dish-washmg or laundry detergents They may be used directly in the form of particulate detergent compositions or alternatively, may be formed into tablets of detergent composition using any of the well known tablettmg methods such as compaction.
  • particulate detergents In order to meet the needs of the consumer, particulate detergents must meet several criteria in addition to providing good cleaning properties Such additional c ⁇ te ⁇ a include- good flow properties so that they can be easily delivered from the container to the washing machine or washing process; good solubility/dispensing so that they will be delivered into the wash effectively; and in addition, particulate detergents must appeal to the consumer aesthetically. Most particulate detergents comprise a primarily white or pale-coloured base with optional colour-contrasting speckles. It has been found that detergents where the base particles vary in hue are judged by the consumer to be undesirable and are even thought by the consumer to provide less effective cleaning.
  • detergent compositions generally comprise pre-processed detergent components such as agglomerates, blown powder produced by spray drying processes or extrudates, in addition to raw mate ⁇ als, and because the raw materials themselves vary so much m colour, size and or shape, significant efforts must be made to avoid non-uniformity. In order to address this, considerable efforts and high costs are required to provide detergent particulates with uniform properties. It would therefore be desirable to find a method for making detergents which enable use of a wider range of active detergent materials such as those with wide vanations of colour, shape and/or size, yet to produce detergent particles with good flow properties and good dispensing and dissolving properties in addition to good aesthetic properties.
  • a detergent particle compnsmg at least two particulate components, a first component of a first colour and a second component of a second colour, the first and second components being adhered to one another, the mean particle size of at least the first or second particulate component being no more than 50% of the mean particle size of the detergent particle
  • a detergent particle having a sphericity index no greater than 1 7 compnsmg at least two particulate components, a first component and a second component, at least one of the first and second components having a sphericity index greater than 1 7, the first and second components being adhered to one another substantially in the absence of pressure compaction.
  • a detergent particle having a geometric mean particle diameter greater than 500 microns, the detergent particle compnsmg a first particulate component and a second particulate component, the first and second particulate components being adhered to one another substantially in the absence of pressure compaction, the geometric mean particle size of at least one of the first and second components being no more than 50 % of the geometric mean particle size of the detergent particle.
  • the first and second particulate components has a span of at least 1.7.
  • a method for making the detergent particles described comprising contacting the first particulate component and the second particulate component, optionally in the presence of a binder in a moderate to low shear mixing step to adhere the first and second particulate components to one another and detergent composition comprising the claimed detergent particles.
  • the present inventors have found that by selecting a combination of first and second particulate detergent components and forming these into a single particle, the undesirable properties and lack of uniformity can be overcome. Furthermore, these benefits can be achieved without the intensive processing steps which have been used in the prior art, such as formation of particulates from pastes which require lengthy, energy intensive mixing such as high shear mechanical mixing and even extrusion, both of which use compaction pressure to form particulates and require energy intensive drying processes.
  • the first and second particulates are differently coloured from one another.
  • Colour difference refers to the ⁇ E value as measured using t ⁇ -stimulus colonmetry using a D25M Colorimeter manufactured by Hunter Laboratories.
  • L, a and b values are generated for a sample by directing incident light onto a sample of powder at a 45° angle. Incident light is reflected from the sample and collected by photo detectors which are set vertically above the powder sample at 0°. The detectors convert the light intensity into t ⁇ -stimulus values (X,Y,Z) as documented by Commission Internationale de l'Eclairage (CUE).
  • ⁇ E V( ⁇ L 2 + ⁇ a 2 + ⁇ b 2 ), where ⁇ L is the difference in L value between the first and second particulate components, ⁇ a is the difference in a value between the first and second particulate components and ⁇ b is the difference in b value between the first and second particulate components.
  • ⁇ E value of at least 3.
  • the invention is particularly useful for even larger colour differences such as ⁇ E values of at least 4, or even at least 6 or 8 or even at least 10.
  • a whiteness value of from 92 to 100 is preferred for the detergent particles of the invention.
  • the apparatus consists of a microscope connected to a video camera and computer
  • the sphencity index of the detergent particle is no greater than 1.7 and the sphencity index of at least one of the first and second particulate components is at least 1 7.
  • the standard deviation of the span of the detergent particles of the invention is less than 0.8, preferably less than 0.5 and most preferably below 0.2.
  • the sphericity index of the detergent particles according to the invention is preferably no greater than 1 5, more preferably no greater than 1.3 or even 1.2.
  • the sphe ⁇ city index of at least one of the first and second particulates is preferably greater than 1.9 or even greater than 2.1 or even greater than 2.5
  • the invention enables highly irregular components to be adhered together to form a highly regular detergent particle without the need for high energy compaction pressure processing via aqueous pastes or slurries such as m extrusion or high shear mixing processes.
  • the invention is even useful when both the first and second particulates comprise highly irregular particles, so that preferably, the sphericity index of both the first and second particulates is greater than 1.9 or even greater than 2.1 or 2.5 or even 3.
  • 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 m accordance with ISO 31 18 (1976).
  • a suitable device is the Ro-Tap testign sieve shaker Model B using 8" 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 g4 13 /D 50 ); See Gotoh et al, Powder Technology Handbook, pp. 6-11, Marcel Dekker 1997.
  • the geometric mean particle diameter of at least the detergent particle is at least 500 microns and the geometric particle diameter of at least one of the first and second particulate components is no more than 50% of the geometric mean particle diameter of the detergent particle, preferably no greater than 25% or even no greater than 10% or 5%.
  • the geometric mean particle diameter of both the first and second particulate components is as defined.
  • at least one of the first and second particulate components has a span (geometric standard deviation) of at least 1.7, or even at least 2 or 2.5 or at least 3 or at least 3.5 or even at least 4 or at least 5.
  • the span of both the first and second particulate components is as defined.
  • the invention is particularly useful for forming detergent particles having a span at least 0.3, preferably at least 0.4 or even at least 0.5 or greater, below the span of the first and/or second particulates.
  • the particle sizes of the first and second components can vary widely.
  • the invention has been found to be useful even where there is a difference in geometric mean particle diameter between the first and second particulate components of at least 200 microns or even of at least 250 or 300 or even at least 400 or even at least 500 microns.
  • one or both of the first and second particulates has a geometric mean particle diameter below 550 ⁇ m. It is particularly preferred that at least one of the first and second particulate components has a geometric mean particle diameter greater than 150 ⁇ m or even greater than 200 ⁇ m and preferably no greater than 450 ⁇ m or even no greater than 400 ⁇ m.
  • the ratio of the mean particle sizes of the first and second particulate components respectively will be at least 3.2, preferably at least 2:1 or even a high ratio of at least 5 : 1 or at least 10:1.
  • the ratio may be even higher such that the ratio is at least 20:1 or even at least 50:1.
  • the relatively smaller particulate component has a colour which is most desirable relative to the colour of the other particulate component. It may also be preferred that the smaller particle diameter particulate component the smaller sphericity index
  • the process of the present invention is suitable for forming detergent particles from first and second particulates each having a wide span of bulk densities and having bulk densities which vary significantly from one that of one another.
  • bulk density refers to the uncompressed, untapped powder bulk density, as measured by pounng 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 nm of the vessel, measu ⁇ ng the remaining mass of powder and dividing the mass by the volume of the vessel.
  • the bulk density of the first and second particulate components may differ by at least 25 g/1, or even by at least 75 g/1 or at least 100 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 700 g/1, preferably greater than 750 g/1 or even above 800 g/1.
  • the bulk density of the detergent particles of the invention will generally be from 400 to 1 lOOg/l, generally the bulk density will be above 550 g 1, preferably greater than 650 g/1 or even greater than 700 g/1
  • the invention may be particularly useful for prepa ⁇ ng detergent particles having bulk density below 550g/l, or even below 500 or below 450g/l.
  • Each of the first and second particulate components may compnse an individual detergent ingredient in particulate form or may comprise a pre-formed detergent particulate. As used herein, 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-drymg, agglomeration, marume ⁇ sation, extrusion or compaction process, all of which methods for combining detergent ingredients are well known m the art.
  • Particularly preferred pre-formed particulates are powders obtained from spray-drymg processes, agglomerates and extrudates Spray dned powders are particularly useful.
  • Suitable spray-drymg processes for forming such pre-formed particulates are descnbed 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 m 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 pnor 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 compnses a surfactant or mixture of surfactants. Suitable surfactants are descnbed 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 Where the pre-formed particulate component compnses 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 NT A, DTPA and succmic acid derivative chelants, as descnbed below. These components are preferably present in a pre-formed particulate component m 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. Where the particulate components are detergent raw materials, any particulate detergent ingredient is suitable.
  • detergent particles themselves may contain all of the ingredients of a full formulated detergent or may be mixed with additional detergent components such as individual detergent ingredients in particulate form or pre-formed detergent particles as desc ⁇ bed above.
  • detergent compositions of the present invention comprise more than 30 wt%, more preferably more than 50 wt% or even as high as 80 or 90 wt% or even at least 95 wt% of the detergent particles according to the present invention.
  • 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 in the form of a solution or melt and will be added by spraying either directly mto the mixer or onto the particulate components as they travel mto 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 may be any conventional detergent binding agent, preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, polyethylene glycol, polyvmyl pyrrolidone, polyacrylates, organic acids or their salts such as citnc acid or citric salts, and mixtures thereof.
  • suitable binder materials including those listed herein are described m Beerse et al, US Patent number 5108646 (Procter and Gamble Company), the disclosure of which is incorporated herein by reference.
  • a first feed stream of first particulate component is fed into the mixer and in addition a second feed stream comprising the second particulate component is fed into the mixer and binder is also present in the mixer.
  • the binder may be fed directly via a third stream mto the mixer or it may be contacted with the first and/or second particulate component prior to one or both of these feed streams entering the mixer. Where the mixer is divided into different zones, the three components may be fed into the same zone or optionally may be fed into different zones.
  • the first and second particulate components will be pre -mixed prior to addition of the binder.
  • a further liquid component is applied to the outside of the particles produced.
  • This further coatmg may be the same chemical composition as the binder or may be any of the other coatmg materials or detergent ingredients descnbed below.
  • suitable moderate to low shear mixers 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 compnses 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 10 m/s, or even below 8m s or even lower.
  • the mean residence time of the vanous 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 with 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 descnbmg the degree of mixing occurring to particles m a piece of equipment such as the fluid bed.
  • the Stokes number is measured by the formula:
  • first and second particulate components can be added at the same or 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 increase uniformity of the shape of the detergent particles produced.
  • the bed is typically fluidized with heated air in order to dry or partially dry moisture such as any binder liquids from the ingredients m the fluid bed
  • the spraying is generally achieved via nozzles capable of delive ⁇ ng 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 particle size.
  • the solution or slurry rheology is 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 m 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.
  • an optional coating zone followed by a drying zone and a cooling zone.
  • Typical conditions within a fluid bed apparatus of the present mvention mclude: (l) a mean residence time from about 1 to about 20 minutes, (n) a depth of unfluidised bed of from about 100 to about 600 mm, (in) 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 micron, (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 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 coatmg 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 coatmg 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.
  • Any coatmg stage may take place either immediately after formation of the detergent particles of the mvention either before or after any drying step and optionally after the detergent particles have been mixed with additional detergent ingredients for forming a fully formulated detergent composition.
  • any such coating agent will also have detergent active properties.
  • a particularly preferred coating agent is a surfactant or aqueous solution of surfactant.
  • the detergent particles produced according to the present invention preferably have a geometric mean particle diameter of at least 500 microns or at least 600 or even at least 700 microns. Generally the mean particle diameter will be no greater than 3000 microns, preferably no greater than 2500 or even no greater than 1500 microns.
  • the sphe ⁇ city index of the detergent particles according to the present invention will preferably be no greater than 1.5 or even no greater than 1.4 or 1.3 or even no greater than 1.2.
  • the span of the detergent particles according to the mvention is generally from 1 to 1.8, preferably no greater than 1.7, most preferably no greater than 1.6 or even 1.4.
  • the weight percentage of the detergent particles derived from the first and second particulate components respectively may be in a ratio of from 100: 1 to 1 : 100.
  • the weight ratio will be low, but the number average of particles of the desirably coloured component in the detergent particle will generally be at least 50, preferably at least 100 or even 500 or 1000 times the number average of the undesirably coloured component in the detergent particle.
  • Detergent ingredients which are suitable as ingredients of the first particulate component or the second particulate component and/or as ingredients of any additional ingredients added to the detergent particles of the present invention to form the fully formulated detergent compositions of the invention, are descnbed below.
  • surfactant Suitable surfactants for use m 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 Heu ⁇ ng on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and TJ 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 compnsmg such particles comp ⁇ ses an additional anionic surfactant.
  • any anionic surfactants useful for detersive purposes can be comp ⁇ sed in the detergent composition.
  • These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and t ⁇ ethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosmate surfactants.
  • Anionic sulfate and sulfonate surfactants are preferred.
  • the anionic surfactants may be present in the detergent particle m amounts below 25 wt % or even below 20 wt % but m 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-l- undecanoic acid, 2-ethyl-l-decano ⁇ c acid, 2-propyl-l-nonano ⁇ c acid, 2-butyl-l-octano ⁇ c acid and 2-pentyl-l-heptano ⁇ c acid. Certain soaps may also be included as suds suppressors.
  • suitable anionic surfactants are the alkali metal sarcosmates of formula R-CON (R*) CH2
  • R is a C5-C17 linear or branched alkyl or alkenyl group
  • R ⁇ is a Ci -C4 alkyl group
  • M is an alkali metal ion.
  • anionic surfactants include lsethionates such as the acyl lsethionates, N-acyl taurates, fatty acid amides of methyl taunde, alkyl succinates and sulfosuccinates, monoesters of sulfosuccmate (especially saturated and unsaturated C. -,-C, monoesters) diesters of sulfosuccmate (especially saturated and unsaturated C ⁇ -C, .
  • Resin acids and hydrogenated resm acids are also suitable, such as rosin, hydrogenated rosm, and res acids and hydrogenated resm acids present in or de ⁇ ved 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-C17 acyl-N-(Cj-C4 alkyl) and -N-(C ⁇ -C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccha ⁇ des 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 Ci Q-Cj g alkyl sulfates, more preferably the C ⁇ ⁇ -C ⁇ ⁇ branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the CI Q-CI g alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a Ci 1 -Cj g, most preferably
  • Ci 1 -Ci 5 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,
  • Cg-C24 olefin sulfonates Cg-C24 olefin sulfonates, sulfonated polycarboxy c 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, pnmary 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 2 CONR 1 Z wherem : 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 havmg 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 de ⁇ ved from a reducing sugar in a reductive animation reaction; more preferably Z is a glycityl.
  • Suitable alkylpolysaccha ⁇ des for use herein are disclosed U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccha ⁇ de, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccha ⁇ de units.
  • Preferred alkylpolyglycosides have the formula: R2 ⁇ (C n H 2n O)t(glycosyl) x
  • R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxy alky lphenyl, 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 de ⁇ ved from glucose.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxyhc acids.
  • Suitable amine oxides include those compounds having the formula 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 C10-C1 g alkyl dimefhylamme oxide, and Cjo-lS acylamido alkyl dimethylamme oxide.
  • Zwitterionic surfactants can also be incorporated into the detergent compositions in accord with the invention. These surfactants can be broadly desc ⁇ bed as de ⁇ vatives of secondary and tertiary amines, denvatives of heterocychc secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaines such as Ci 2_18 dimethyl-ammonio hexanoate and the CJO-18 acylamidopropane (or ethane) dimethyl (or diethyl) betames 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-Ci g, 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 am e surfactants preferably of the general formula I:
  • R ⁇ is CI Q-C I g hydrocarbyl and mixtures thereof, especially C10-C14 alkyl, preferably Ci 0 and C 12 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
  • the levels of the cationic mono-alkoxylated amme 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 amme surfactant such as
  • R* is C J O-CI g hydrocarbyl and mixtures thereof, preferably C J Q, C12,
  • X is any convenient anion to provide charge balance, preferably chloride.
  • the detergent particles or detergent compositions containing them preferably compnse a bleach activator, preferably compnsmg 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 1100 microns. More preferably, all of the activator are present in one or more particulate components having the specified weight average particle size
  • the bleach activator may be preferred that at least 80%, preferably at least 90% or even at least 95 % or even substantially 100% of the component or components compnsmg 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 compnse a compound having an oxy-benzene sulphonate group, preferably NOBS, DOBS, LOBS and or NACA-OBS.
  • Preferred hydrophilic peroxy acid bleach precursors preferably compnses 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
  • hydrophobic peroxyacid bleach precursors produce a peroxy acid of the formula above wherem 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 compnsmg 1 to 5 carbon atoms.
  • the leaving group hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur withm 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 1 , R3 and R 4 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 solubi zmg 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, and X is a ha de, hydroxide, methylsulfate or acetate anion.
  • Peroxyacid bleach precursor compounds are preferably mcorporated m 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, lmides, lactams and acylated de ⁇ vatives of lmidazoles and oximes. Examples of useful materials with these classes are disclosed in GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A- 0170386.
  • Alkyl percarboxyhc acid bleach precursors form percarboxyhc acids on perhydrolysis.
  • Preferred precursors of this type provide peracetic acid on perhydrolysis.
  • Preferred alkyl percarboxyhc precursor compounds of the lmide type mclude the N-,N,N*N* tetra acetylated alkylene diammes 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 diamme (TAED) is particularly preferred as hydrophilic peroxy acid bleach precursor.
  • alkyl percarboxyhc acid precursors include sodium 3,5,5-tn-methyl 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 2 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 1 preferably contains from about 6 to 12 carbon atoms.
  • R 2 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.
  • R2 can include alkyl, aryl, wherein said R 2 may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • Rl and R ⁇ should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described m EP-A-0170386. It can be preferred that
  • Rl and R ⁇ forms together with the nitrogen and carbon atom a nng structure.
  • bleach precursors of this type include amide substituted peroxyacid precursor compounds selected from (6-octanam ⁇ do-caproyl)oxybenzenesulfonate, (6- decanamido-caproyl) oxybenzene- sulfonate, and the highly preferred (6-nonanam ⁇ docaproyl)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 m 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.
  • Examples of preferred cationic peroxyacid precursors are desc ⁇ bed in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906.
  • 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 t ⁇ alkyl ammonium methylene benzoyl caprolactams and the t ⁇ alkyl 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.
  • organic peroxyacid compounds are the amide substituted compounds as descnbed in EP-A-0170386.
  • Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid Mono- and diperazelaic acid, mono- and diperbrassyhc acid and N-phfhaloylaminoperoxicaproic acid are also suitable herein.
  • Inorganic perhydrate salts are a preferred source of peroxide Preferably 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 matenal which provides better storage stability for the perhydrate salt the granular product. Suitable coatings compnse inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic matenals 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 herem.
  • 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 ammo alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nit ⁇ lo tnmethylene phosphonates, preferably, diethylene tnamme penta (methylene phosphonate), ethylene diamine t ⁇ (methylene phosphonate) hexamethylene diamine terra (methylene phosphonate) and hydroxy- ethylene 1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphomc acid
  • suitable chelants for use herein include mt ⁇ lot ⁇ acetic acid and polyammocarboxyhc acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine digluta ⁇ c acid, 2-hydroxypropylened ⁇ amme disuccinic acid or any salts thereof, and lminodiacetic acid derivatives such as 2-hydroxy
  • EP-A-516,102 The lminodiacetic ac ⁇ d-N-2- hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3 -sulfonic acid sequestrants desc ⁇ bed in EP-A-516,102 are also suitable herein
  • the ⁇ -alanme-N,N'-d ⁇ acet ⁇ c acid, aspartic ac ⁇ d-N,N'-d ⁇ acet ⁇ c acid, aspartic acid-N-monoacetic acid and lmmodisuccmic acid sequestrants described m EP-A-509,382 are also suitable.
  • EP-A-476,257 describes suitable ammo based sequestrants.
  • EP-A-510,331 desc ⁇ bes suitable sequestrants denved from collagen, keratm or casein.
  • EP-A-528,859 descnbes a suitable alkyl lminodiacetic acid sequestrant.
  • Glycmamide- N,N'-d ⁇ succm ⁇ c acid Glycmamide- N,N'-d ⁇ succm ⁇ c acid (GADS), ethylenediamine-N-N'-diglutanc acid (EDDG) and 2- hydroxypropylenediamme-N-N'-disuccinic acid (HPDDS) are also suitable.
  • diethylenet ⁇ am e pentacetic acid ethylened ⁇ am ⁇ ne-N,N'-d ⁇ succm ⁇ c 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 ethylened ⁇ am ⁇ ne-N,N'-d ⁇ succm ⁇ c acid
  • the chelating agents compnsmg a amino or amine group can be bleach-sensitive and are suitable in the compositions of the invention.
  • the component or compositions herem 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% 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 compnses tetrasodium pyrophosphate or even more preferably anhydrous sodium t ⁇ polyphosphate.
  • Suitable water-soluble builder compounds include the water soluble monome ⁇ c polycarboxylates, or their acid forms, homo or copolyme ⁇ c polycarboxyhc acids or their salts in which the polycarboxyhc acid compnses 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 momome ⁇ c or ohgomenc type although monome ⁇ c polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycohc acid and ether derivatives thereof
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succmic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglyco c acid, tartaric acid, tartronic acid and fumanc 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 succmate derivatives such as the carboxymethyloxysuccmates descnbed in B ⁇ tish Patent No.
  • Polycarboxylates containing sulfo substituents include the sulfosuccmate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and m U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates descnbed in B ⁇ tish 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 monomenc or ohgomenc polycarboxylate chelatmg agents or mixtures thereof with their salts e.g. citnc acid or citrate/citnc acid mixtures are also contemplated as useful builder components.
  • Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.
  • Suitable examples of water-soluble phosphate builders are the alkali metal t ⁇ polyphosphates, 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-polyme ⁇ c polycarboxyhc acids or their salts in which the polycarboxyhc acid compnses 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 anhydnde, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.
  • polyam o compounds are useful herein including those denved 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 aluminosihcates.
  • Suitable alummosilicate zeolites have the unit cell formula Na z [(Al ⁇ 2) z (S ⁇ 2)y]. xFFjO wherem 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 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the alummosilicate matenal are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • the alummosilicate zeolites can be naturally occurnng mate ⁇ als, but are preferably synthetically de ⁇ ved. Synthetic crystalline alummosilicate ion exchange mate ⁇ als are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:
  • zeolite MAP builder Another preferred alummosilicate 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-sihcate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably withm the range from 0.9 to 1.33 and more preferably withm the range of from 0.9 to 1.2. Of particular interest is 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 d5 Q 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 d5o 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, descnbed herein. Other methods of establishing d5Q values are disclosed in EP 384070A Other Detergent Ingredients
  • a preferred ingredients 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 dye g 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 desc ⁇ bed above.
  • the dye may also be mixed with a non-aqueous earner mate ⁇ al, such as non-aquous liquid mate ⁇ als including nonionic surfactants.
  • the dye also comprising other ingredients such as organic binder matenals, which may also be a non-aqueous liquid.
  • the dyestuff can be any suitable dyestuff. Specific examples of suitable dyestuffs mclude
  • E104 - food yellow 13 quinohne yellow
  • El 10 - food yellow 3 unsunset yellow FCF
  • E131 - food blue 5 patent blue V
  • Ultra Marine blue trade name
  • El 33 - food blue 2 bnl ant blue FCF
  • E140 - natural green 3 chlororophyll and chlorphyl ns
  • E141 and Pigment green 7 chlormated Cu phthalocyanme
  • Preferred dyestuffs may be Monastral Blue BV paste (trade name) and or Pigmasol Green (trade name).
  • perfume or perfume compositions of the invention 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 compnses an oxygen-containmg functional group
  • Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or mixtures thereof
  • Another highly preferred ingredient useful m the particles or compositions herein is one or more additional enzymes
  • Preferred additional enzymatic materials include the commercially available hpases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions.
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, P ⁇ mase, Durazym, and Esperase by Novo Industnes 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 mto 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 Indust ⁇ es A/S.
  • Highly preferred amylase enzymes maybe those descnbed in PCT/ US 9703635, and m W095/26397 and W096/23873.
  • 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 hpolytic 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 , Thermomvces sp. or Pseudomonas sp. including Pseudomonas pseudoalcahgenes or Pseudomas fluorescens.
  • Lipase from chemically or genetically modified mutants of these strains are also useful herein.
  • a preferred lipase is de ⁇ ved from Pseudomonas pseudoalcaligenes, which is descnbed in Granted European Patent, EP-B-0218272.
  • Another preferred lipase herem is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza. as host, as desc ⁇ bed m European Patent Application, EP-A-0258 068, which is commercially available from Novo Indust ⁇ A/S,
  • the component or compositions herein also preferably contain from about 0.005% to 5% by weight of certain types of hydrophilic optical b ⁇ ghteners, as mentioned above.
  • examples are Tmopal-UNPA-GXTM and Tmopal-CBS-XTM by Ciba-Geigy Corporation.
  • Tinopal 5BM-GXTM Tinopal-DMS-XTM
  • Tinopal AMS-GXTM Tinopal AMS-GXTM
  • Photo-bleaching agents are preferred ingredients of the compositions or components herein.
  • Preferred photo-bleachmg agent herein comprise a compounds having a porphm or porphynn structure.
  • Porphm and porphynn in the literature, are used as synonyms, but conventionally porphm stands for the simplest porphynn without any substituents; wherem porphynn is a subclass of porphm.
  • the references to porphm in this application will include porphynn.
  • the porphm 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 nng systems such as py ⁇ dyl, py ⁇ dyl-N-oxide, phenyl, naphthyl and anthracyl moieties.
  • substituents selected from alkyl groups such as methyl, ethyl, propyl, t-butyl group and aromatic nng systems such as py ⁇ dyl, py ⁇ dyl-N-oxide, phenyl, naphthyl and anthracyl moieties.
  • the photo-bleachmg compound or component can have solubi zmg groups as substituents.
  • the photo-bleachmg agent can compnse a polymenc component capable of solubihzmg the photo-bleachmg compound, for example PVP, PVNP, PVI or co-polymers thereof or mixtures thereof.
  • Highly preferred photo-bleachmg compounds are compounds having a phthalocyanme structure, which preferably have the metal elements or cations desc ⁇ bed above.
  • the phthalocyanmes can be substituted for example the phthalocyanme structures which are substituted at one or more of the 1-4, 6, 8-11, 13, 15-18, 20, 22-25, 27 atom positions
  • Organic Polymenc 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) amme 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 vmyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
  • organic polymenc compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Further useful organic polymenc compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
  • Highly preferred polymenc components herem 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, Gosselmk et al., and in particular according to US apphcation no.60/051517.
  • Another organic compound which is a preferred clay dispersant/ anti-redeposition agent, for use herein, can be the ethoxylated cationic monoammes and diammes 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)
  • Other dispersants/ anti-redeposition agents for use herein are descnbed m EP-B-011965 and US 4,659,802 and US 4,664,848
  • the components and detergent compositions herein when formulated for use in machine washing compositions, may compnse 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 compnse 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 sudsmg 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.
  • silicone antifoam compounds encompasses a va ⁇ ety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of va ⁇ ous types.
  • Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having t ⁇ methylsilyl end blocking units.
  • Suitable antifoam compounds mclude the monocarboxyhc 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 t ⁇ glyce ⁇ des), fatty acid esters of monovalent alcohols, aliphatic Ci -C4Q ketones (e.g.
  • N-alkylated ammo triazmes such as t ⁇ - to hexa-alkylmelammes or di- to terra alkyldiamine chlort ⁇ azines formed as products of cyanu ⁇ c chlo ⁇ de with two or three moles of a pnmary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis steanc acid amide and monostearyl di-alkah metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
  • a pnmary or secondary amine containing 1 to 24 carbon atoms propylene oxide
  • bis steanc acid amide monostearyl di-alkah metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
  • a preferred suds suppressing system compnses antifoam compound, preferably compnsmg 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/sihca antifoam compound wherem said sihca/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 DC0544, commercially available from DOW Corning, and an inert carrier fluid compound, most preferably comprising a C ] g-C ⁇ g ethoxyl
  • EP-A-0210731 discloses other preferred particulate suds suppressing systems.
  • Other highly preferred suds suppressing systems compnse polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, alummosilicate and polycarboxyhc 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-vinylpyrrohdone and N-vmyhmidazole, polyv ylpyrrohdonepolymers 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 nnsing 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 ohgomenc terephthalate esters, typically prepared by processes involving at least one transeste ⁇ fication/oligome ⁇ zation, often with a metal catalyst such as a t ⁇ tamum(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.
  • SRAs include the nonionic end-capped 1,2- propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711,730, December 8, 1987 to Gosselmk et al.
  • SRA's include: the partly- and fully- amonic-end-capped ohgomenc esters of U.S 4,721,580, January 26, 1988 to Gosselmk; the noniomc-capped block polyester ohgomenc compounds of U.S.
  • SRAs also include: simple copolymenc 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 havmg 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 Shm-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.
  • Other optional ingredients suitable for inclusion in the 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 citnc acid. Also, preferably combined with a carbonate salt, minor amounts (e.g., less than about 20%) by weight) of neutralizing agents, buffe ⁇ ng agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti- oxidants, bacte ⁇ cides 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 chlo ⁇ ne-based bleach.
  • a chlo ⁇ ne-based bleach since the detergent compositions of the invention are solid, most liquid chlo ⁇ ne-based bleaching will not be suitable for these detergent compositions and only granular or powder chlo ⁇ ne-based bleaches will be suitable.
  • a chlonne based bleach can be added to the detergent composition by the user at the beginning or du ⁇ ng the washing process.
  • the chlo ⁇ ne-based bleach is such that a hypochlonte species is formed in aqueous solution.
  • the hypochlo ⁇ te ion is chemically represented by the formula OCI .
  • hypochlonte species aqueous solution Those bleaching agents which yield a hypochlonte species aqueous solution mclude alkali metal and alkaline earth metal hypochlo ⁇ tes, hypochlo ⁇ te addition products, chloram es, chlo ⁇ mmes, chloramides, and chlonmides.
  • a preferred bleaching agent for use m the compositions of the instant invention is sodium hypochlonte, potassium hypochlonte, or a mixture thereof.
  • a preferred chlorine-based bleach can be Triclosan (trade name).
  • hypochlo ⁇ te-yielding bleaching agents are available in solid or concentrated form and are dissolved water dunng 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 fab ⁇ cs.
  • 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 tnpolyphosphate TSPP Tetrasodium pyrophosphate Zeolite A Hydrated sodium alummosilicate of formula
  • Nal2(A102S ⁇ 02)12.27H20 having a primary particle size m the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis) NaSKS-6 Crystalline layered silicate of formula d- Na2S ⁇ 205 Citric acid Anhydrous cit ⁇ c acid Borate Sodium borate Carbonate Anydrous sodium carbonate: particle size 200 ⁇ m to 900 ⁇ m Bicarbonate Anhydrous sodium bicarbonate with a particle size dist ⁇ bution between
  • 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 NOVO Industnes A/S
  • NAC-OBS (6-nonam ⁇ docaproyl) oxybenzene sulfonate
  • 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
  • PVNO Polyvinylpy ⁇ dme N-oxide polymer with an av. m. wt. of 50,000
  • SRP1 Aniomcally end capped poly esters SRP2 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 Silicone antifoam :Polyd ⁇ mefhyls ⁇ loxane 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
  • This Example illustrates a process according to this invention which produces uniform free flowing, good dispensing and dissolving detergent particles with uniformity of colour and particle shape.
  • Multiple detergent starting ingredients are dry mixed in an orbital vertical screw mixer of 200kg batch size, and several batches prepared. This premix is conveyed at 500kg/hr into a horizontal plate fluidised bed drier with outlet weir to maintain a constant static bed depth of 20cm. Fluidismg mlet air at 120°C is blown into the bed to maintain a fluidisation velocity of typically 2.0 ms-1. Fines are elut ⁇ ated from the top of the bed, are collected in a hopper and recycled back to the bed.
  • Air atomised spray nozzles are installed in the bed in a specific arrangement - typically 2 manifolds each with 3 nozzles aligned along the ho ⁇ zontal axis of the bed, positioned above the surface of the static bed.
  • Bmder is made by weighing PEG 4000 into an agitated hot water jacketed tank of water at 60°C, to create a 30% PEG solution.
  • Binder is pumped to the spray nozzle at 100 kg hr and atomised with 3 bar air withm the fluid bed
  • Product is collected from the fluid bed and is screened on Mogensen vibratory screening units using three decks with 1250 ⁇ m, 710 ⁇ m and 425 ⁇ m screens installed Oversize particles are ground and recycle to the fluid bed with the fines stream.
  • Collected product (yield between the 1250 ⁇ m and 425 ⁇ m screens) is of density 445 g/L and mean particle size 570 ⁇ m.
  • the sphericity index is 1 4 with a standard deviation of 0.4.
  • Other standard detergent matenals are post dry- added to the product in a mixing drum - including enzymes, perfume and dyed carbonate speckles. Spray -on materials such as perfume or nonionic surfactant may also be added at this stage to make a fully formulated detergent product.
  • the finished detergent has the following composition Component % Weight of Total Feed
  • Silicone based antifoam 4.0% as agglomerate Sodium carbonate 3.1% Polymeric soil release agent 0.5%
  • Na2S ⁇ 205 layered silicate (SKS-6) 5.8% Binder, sprayed onto the premix in the fluid bed
  • Example II This Example also illustrates the process of the invention and incorporates the parameters of Example I.
  • a premix of dry detergent mate ⁇ als is prepared as in example 1, of composition as listed below.
  • the mix is fed mto a continuous Lodige KM 600 plough-share mixer, which is a ho ⁇ zontally-positioned moderate speed mixer, at 200kg/hr feedrate.
  • the rotational speed of the shaft the mixer is about 100 rpm and the rotational speed of the cutters is about 3000 rpm
  • Water, at 60°C, is pumped from a hot water jacketed tank, as binder at 20 kg/hr
  • the water is atomised using air atomised nozzles positioned withm the Lodige KM.
  • Product from the Lodige KM is fed continuously mto a horizontal plate fluidised bed dner, which reduces the free moisture content to about 6% (Mettler mfra-red oven method).
  • Product is collected from the fluid bed and is screened on Mogensen vibratory screening units using three decks with 1180 ⁇ m, 710 ⁇ m and 500 ⁇ m screens installed Oversize particles are ground and recycled to the fluid bed with the fines stream Collected product (yield between the 1180 ⁇ m and
  • 500 ⁇ m screens is of density 620 g/L and mean particle size 610 ⁇ m
  • Other standard detergent mate ⁇ als are post dry -added to the product in a mixing drum - including enzymes, perfume and dyed carbonate speckles. Spray -on materials such as perfume or nonionic surfactant may also be added at this stage to form a fully formulated detergent.
  • Binder sprayed onto the premix in the Lodige KM
  • compositions In the following examples all levels are quoted as % by weight of the composition: TABLE
  • compositions are in accordance with the invention.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
PCT/US2000/016920 1999-06-21 2000-06-20 Detergent particles and methods for making them WO2000078914A1 (en)

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Application Number Priority Date Filing Date Title
AU57512/00A AU5751200A (en) 1999-06-21 2000-06-20 Detergent particles and methods for making them
JP2001505659A JP2003503549A (ja) 1999-06-21 2000-06-20 洗剤粒子およびその製造方法
US09/979,528 US6579844B1 (en) 2000-06-20 2000-06-20 Detergent particles and methods for making them
BR0011844-3A BR0011844A (pt) 1999-06-21 2000-06-20 Partìculas de detergente e métodos para produzi-las
EP00942968A EP1187905A1 (en) 1999-06-21 2000-06-20 Detergent particles and methods for making them
MXPA02000030A MXPA02000030A (es) 1999-06-21 2000-06-20 Particulas de detergentes y procedimientos para elaborarlas.
CA002375497A CA2375497A1 (en) 1999-06-21 2000-06-20 Detergent particles and methods for making them

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3259207A4 (en) * 2015-02-18 2018-10-17 Henkel IP & Holding GmbH Solid state detergent in a transparent container
WO2022000468A1 (en) * 2020-07-03 2022-01-06 The Procter & Gamble Company Particulate laundry composition

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0718532D0 (en) * 2007-09-22 2007-10-31 Unilever Plc Improvements relating to fabric treatment compositions

Citations (4)

* 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
DE4243704A1 (de) * 1992-12-23 1994-06-30 Henkel Kgaa Granulare Wasch- und/oder Reinigungsmittel
EP0889116A1 (en) * 1996-03-19 1999-01-07 Kao Corporation High-density granular detergent composition
WO2000024859A1 (en) * 1998-10-26 2000-05-04 The Procter & Gamble Company Detergent particles and processes for making them

Patent Citations (4)

* 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
DE4243704A1 (de) * 1992-12-23 1994-06-30 Henkel Kgaa Granulare Wasch- und/oder Reinigungsmittel
EP0889116A1 (en) * 1996-03-19 1999-01-07 Kao Corporation High-density granular detergent composition
WO2000024859A1 (en) * 1998-10-26 2000-05-04 The Procter & Gamble Company Detergent particles and processes for making them

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3259207A4 (en) * 2015-02-18 2018-10-17 Henkel IP & Holding GmbH Solid state detergent in a transparent container
WO2022000468A1 (en) * 2020-07-03 2022-01-06 The Procter & Gamble Company Particulate laundry composition

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EP1187905A1 (en) 2002-03-20
AR024427A1 (es) 2002-10-02

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