GB2323384A - A detergent composition - Google Patents

A detergent composition Download PDF

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Publication number
GB2323384A
GB2323384A GB9705840A GB9705840A GB2323384A GB 2323384 A GB2323384 A GB 2323384A GB 9705840 A GB9705840 A GB 9705840A GB 9705840 A GB9705840 A GB 9705840A GB 2323384 A GB2323384 A GB 2323384A
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Prior art keywords
detergent
acid
particle
weight
particle according
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GB9705840A
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GB9705840D0 (en
Inventor
Gerard Marcel Baillely
Stuart Clive Askew
Graham Alexander Sorrie
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to GB9705840A priority Critical patent/GB2323384A/en
Publication of GB9705840D0 publication Critical patent/GB9705840D0/en
Priority to EP98200736A priority patent/EP0866118A3/en
Priority to CA 2232205 priority patent/CA2232205A1/en
Publication of GB2323384A publication Critical patent/GB2323384A/en
Withdrawn legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082Special 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
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2086Hydroxy carboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3942Inorganic per-compounds

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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)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

An agglomerate or extruded detergent particle, comprises a perborate component, an acid source and one or more surfactants, for use in detergent compositions which are suitable for use in laundry washing methods. The acid is preferably citric acid and acts to reduce the tendency of the composition to gel and thereby assists in dispersing.

Description

2323384 Detergent particle
Technical Field
The present invention relates to an agglomerated or extruded detergent particle, comprising perborate bleach, an acid source and one or more surfactants, for use in detergent compositions which are suitable for use in laundry washing methods. The invention also relates to a process for making the agglomerated or extruded detergent 10 particle.
CM1463F Backgiound to the Invention There is a trend amongst commercially available granular detergents towards higher bulk densities and towards granular detergent compositions which have a higher content of detergent active ingredients, such as bleach.,Such detergents ofTer greater convenience to the consumer and at the same time reduce the amount of packaging materials which will, ultimately, be disposed of However, traditional detergent formulations and processes to produce the final detergent powder are not always satisfactory or suitable for these detergents, with higher active ingredient concentration.
Amongst consumers there is also a need for detergents which provide improved bleachable stain removal. Therefore, in the recent past detergents have been developed which contain various types of bleaches, which can be incorporated at high levels.
The (high density) detergents, comprising high levels of bleach and surfactant can lead to poor solubility properties, arising from low rate of dissolution or the formation of gels, and thus to poor dispensing of the product, either from the dispensing drawer of a washing machine, or from a dosing device placed with the laundry inside the machine. This poor dispensing is often caused by gelling of particles, which have high levels of surfactant and/ or bleach, upon contact with water. The gel prevents a proportion of the detergent powder from being solubilized in the wash -.Yaterhich reduces the effectiveness of the powder. This is a particular problem IpWWater pressures and/or at lower washing temperature.
I 2 EP-A-0 639 637 discloses the replacement of perborate bleach with an alkali metal percarbonate to improve the dispensing profile and dissolution rate of a detergent.
Citrate or mixtures of citrate with sulphate or carbonate can be used to coat the percarbonate bleach.
EP-A-0 639 639 contains a similar disclosure in this respect.
Other ways to improve dispensing include the use of an effervescence system. If the detergent contains an effervescence system then the generation of a gas such as carbon dioxide pushes the particles of the detergent apart, and prevents them from gelling.
The use of effervescence to improve the dispensability of granular materials has been used extensively in pharmaceutical preparations. The most widely used effervescent system in this respect is citric acid in combination with bicarbonate. The use of this simple effervescent system has also been described for improving the dispersibility of pesticidal compositions for controlling water-borne pests, e.g. GB-A-2, 184,946.
EP-A-0 534 525 discloses the use of citric acid with a specified particle size range of 350 to 1500 microns.
US -A-5, 114,647 discloses a sanitising composition comprising granules of alkali metal carbonate and aliphatic carboxylic acid of a particle size of 150 to 2,000 microns.
EP-A-0 333 223 discloses a bathing preparation comprising furnaric acid having an average particle size of 50-500 microns.
The Applicants have found that one of the specific problems associated with poor dispensing of detergent compositions which contain bleaching agents and particularly perborate monohydrate bleach, is that localised high concentrations of bleach form which may contact the fabric and cause spot bleaching of coloured fabrics. Secondly, poorly dispensed surfactants tend to deposit on the fabric and the machine. This can lead to fabric damage. These problems can be encountered especially with detergent compositions comprising high levels of surfactants and perborate, especially petborate 3 (monohydrate). However, these high concentrations are often required for an optimal stain/soil removal and suspension and bleachable stain removal.
The Applicants now have found that this problem can be solved or reduced when an acid source is agglomerated with or extruded along with the surfactants, or a part thereof, and the perborate bleach to form an agglomerated or extruded detergent particle. In the detergent comprising this agglomerated or extruded particle, an alkali source should be present, capable of producing a gas when reaction with the acidic source. We have found that agglomerating or extruding of such an acid source with surfactant(s) and bleach, when there is an alkali source present in the detergent composition, improves the solubility and/or dispersion of the surfactant(s) and the perborate bleach in the wash water and eliminates or reduces the problems of fabric damage by high concentrate bleach and of solid detergent particles or surfactants remaining in the washing machine and on washed clothes. It is believed that the acid reacts rapidly with the alkali in the wash water to release the gas. This helps disperse the perborate bleach and the detergent in general surfactants and minimise the formation of high concentrations of bleach and of insoluble clumps.
The improved dispensing of the surfactant(s) and the perborate bleach can amount to an overall improved and more efficient performance.
Furthermore, the detergent residues in the dispensing drawer or dispensing device are reduced.
All documents cited in the present description are, in relevant part, incorporated herein by reference.
Summ@1y of the Invention According to the present invention there is provided an agglomerate or extruded detergent particle comprising a perborate component, one or more surfactants and an acid source. Optionafly other detergent ingredient can be present in the agglomerate or extrudate. The agglomerated or extruded detergent particle can be included in detergents comprising an alkali source capable of reacting with the acid source to produce a gas. According to the present invention there is also provided a process for making the agglomerate or extruded detergent particle.
4 Detailed Despplption of the Invention Agglomerate or extruded particl The agglomerate or extruded detergent particle of the present invention contains one or more surfactants and an acid source and a perborate component, which are described below.
The amount of each component in the agglomerate or extruded detergent particle can vary depending on the application of the particle and on the nature of the final detergent composition comprising the particle. For example, when the particle will be used in a detergent composition comprising one or more of the same ingredients as the particle, the level thereof in the particle can be reduced.
The level of surfactant in the particle is preferably from 15% to 95%, more preferably from 25% to 60%, most preferably from 30% to 50% by weight of the particle.
The level of acid source in the particle is preferably from 1% to 40%, more preferably from 3% to 30%, even more preferably from 5% to 25%, most preferably from 7% to 15% by weight of the particle The level of perborate component in the particle is preferably from 10% to 70%, more preferably from 15% to 50%, most preferably from 20% to 40% by weight of the particle.
Preferably, at least one anionic surfactant is present. In a preferred embodiment a nonionic surfactant and an anionic surfactant are present. In a further preferred embodiment an anionic and a cationic and optionally a nonionic surfactant are present. When a cationic surfactant is present, preferably a silicate or alumino silicate containing material is present.
Preferably, magnesium sulphate is present in the particle, preferably at a level of from 0. 1% to 8%, more preferably of from 0.2% to 5%, most preferably from 0.3% to 3% by weight of the particle.
Preferably, the particle does not comprise a bleach activator and/ or crystalline layered silicate.
The agglomerate or extruded particle can optionally comprise additional detergent ingredients. Preferred optional ingredients in the particle can be builders (alumino silicates, polymeric carboxylates), an source, bleach activators and bleach catalysts.
Surfactant The level of surfactant in the particle is preferably from 15% to 95%, more preferably from 25% to 60%, most preferably from 30% to 50% by weight of the particle.
When the particle is comprised in a detergent composition, the total level of surfactant in the detergent composition is preferably of from 1% to 90%, preferably 3% to 70%, more preferably 5% to 40%, even more preferably 10% to 30%, most preferably 12% to 25% by weight of the detergent composition.
The surfactant in the agglomerate or extruded particle is selected from anionic, nonionic and cationic surfactants and mixtures thereof.
Optionally, ampholytic, amphoteric and zwitterionic surfactants can be present in the particle.
A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, and species 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, 198 1.
6 Anionic surfactant The agglomerated or extruded detergent particle in accordance with the present invention preferably comprise one or more anionic surfactants. Essentially any 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 surfactants are preferred.
The level of anionic surfactant is preferably from 10% to 95%, more preferably from 20% to 60%, most preferably from 25% to 50% by weight of the particle.
In detergent compositions, comprising the particle, the total level of anionic surfactant is preferably from 2% to MYXo, more preferably from 4% to 30%, even more preferably from 5% to 25%, most preferably from 6% to 15% by weight of the composition.
Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulflasuccinate (especially saturated and unsaturated C 12-C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C 14 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 surfactant 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 17 acyl-N-(C I -C4 alkyl) and -N-(C I -C2 hYdr0XYalkYl) glucamine siffates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
7 Alkyl sulfate surfactants are preferably selected from the linear and branched primary C I O-C 18 alkyl sulfates, more preferably the C I I -C 15 branched chain alkyl sulfates and the C 12-C 14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C I O-C 18 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 C I I -C I g, most preferably C I I -C 15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from I to 5, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
Anionic suifonate surfactant Anionic sulfonate surfactants suitable for use herein include the salts Of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-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.
Anionic carbo2gylate surfactant Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('akl carboxyis'), especially certain secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)x CH2COO-M+ wherein R is a C6 to Cl 8 alkYl group, x ranges from 0 to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR 1 -CHR2-0)-R3 wherein R is a C6 to Cl 8 alkyl group, x is from 1 to 25, RI and R2 are selected from the group 35 consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of 8 hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl1 -undecanoic acid, 2-ethyl- 1 -decanoic acid, 2-propyl1 -nonanoic acid, 2-butyl- 1 -octanoic acid and 2-pentyl- 1 -heptanoic acid. Certain soaps may also be included as suds suppressors.
Alkali metal sarcosinate surfactant Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (R1) CH2 COOM, wherein R is a CS-C 17 linear or branched alkyl or alkenyl group, 15 RI is a Cl -C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and olcoyl methyl sarcosinates in the form of their sodium salts.
Cationic surfactants Another preferred surfactant of the invention is one or more cationic surfactants.
Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C6-C 16, preferably C6-C 10 N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Another preferred cationic surfactant is an C6-C IS alkyl or 25 alkenyl ester of an quaternary ammonium alcohol, such as quaternary choline esters.
The level of cationic surfactant is preferably from 1% to 20%, more preferably from 2% to 15%, most preferably from 4% to 10% by weight of the particle.
In detergent compositions, comprising the particle, the level of cationic surfactant is preferably from 0.2% to 20%, more preferably from 0. 5% to 15%, even more preferably from 1% to 10%, most preferably from 1% to 5% by weight of the composition.
9 Nonionic surfactant The detergent composition of the present invention preferably contains a nonionic surfactant. Essentially any nonionic surfactant can be used herein.
The level of nonionic surfactant is preferably from 5% to 60%, more preferably from 1 (Y?lo to 45%, most preferably from 15% to 3 5% by weight of the particle. In detergent compositions, comprising the particle, the level of nonionic surfactant is preferably from 1% to 30%, more preferably from 2% to 25%, even more preferably from 3% to 15%, most preferably from 4% to 12% by weight of the composition.
AlkoUlated nonionic surfactant Essentially any alkated nonionic surfactants are suitable herein. The ethoxylated 15 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.
Nonionic alkMlated alcohol surfactant The condensation products of aliphatic alcohols with from I to 25 moles of alkylene - oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein.
The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
Nonionic polyhydroU SM acid amide surfactant Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONR 1 Z wherein: R 1 is II, C 1 -C4 hydrocarbyl, 2-hydroxy ethyl, 2 hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable Cl -C4 alkyl, more preferably Cl or C2 alkyl, most preferably Cl alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C 5-C 19 alkyl or alkenyl, more preferably straight-chain C9-C 17 alkyl or alkenyl, most preferably straight-chain C I I -C 17 alkyl or alkenyl, or mixture thereof, 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.
Nonionic fiM acid an-dde surfactant Suitable fatty acid amide surfactants include those having the formula: R6CON(I7)2 wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R7 is selected from the group consisting of hydrogen, Cl - C4 alkyl, Cl -C4 hydroxyalkyl, and -W2H40)xH, where x is in the range of from 1 to 3.
Nonionic alkylpolysaccharide surfactant Suitable 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 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
Preferred alkylpolyglycosides have the formula R2O(CnH2riOXglYcOsY1)x wherein R2 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.
11 Qptional surfactants AWhoteric surfa Optional amphoteric surfactants for use in the particle or detergent compositions, comprising the particle, include the amine oxide surfactants and the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula R3(OR4)xNO(R5)2 wherein R3 is selected from an allcyl, hydroxyallcyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 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 R5 is an alkyl or hydroxyalkyl group containing from I to 3, or a polyethylene oxide group containing from I to 3 ethylene oxide groups. Preferred are C I O-C 18 alkyl dimethylamine oxide, and CIO-18 acylamido aflql dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Mranol(TM) C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic surfactant Optionally, zwitterionic surfactants can be incorporated into the particle or detergent compositions comprising the particle. 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 suifonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
Suitable betaines are those compounds having the formula RQU)2NR2C00wherein R is a C6-C 18 hydrocarbyl group, each R 1 is typically C 1 -C3 alkyl, and R2 is a C 1 C5 hydrocarbyl group. Preferred betaines are C 1218 dimethyl-ammonio hexanoate and the C 10- 18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.
12 Acid source In accordance with the present invention, an acid source, or source of acidity, is present in the agglomerate or extruded detergent particle. When comprised in a detergent composition, the detergent composition contains an alkali source, capable of reacting with the acid source to produce a gas. Optionally, the alkali source or part thereof can be comprised in the particle.
The level of the acid source in the particle is preferably from 1% to 40%, more preferably from 3% to 30%, even more preferably from 5% to 25%, most preferably from 7% to 15% by weight of the particle.
In detergent compositions comprising the particle, the level of the source of acidity is preferably present of from 0. 1% to 50%, more preferably from 0. 5% to 25%, even more preferably from 1% to 12%, most preferably from 1% to 7% weight of the composition.
Preferably, 80% or more of the acid source has a particle size in the range of from about 150 microns to about 710 microns, with at least about 37% by weight of the acid source having a particle size of about 3 5 0 microns or less. In a preferred embodiment 100% of the acid source has a particle size of about 710 microns or less. Alternatively, greater than about 3 8%, more preferably 3 8.7%, of the particulate acid source has a particle size of about 350 microns or less.
The particle size of the acid source is calculated by sieving a sample of the source of acidity on a series of Tyler sieves. For example, a Tyler sieve mesh 100 corresponds to an aperture size of 150 microns. The weight fractions thereby obtained are plotted against the aperture size of the sieves.
The acid source may be any suitable organic, mineral or inorganic acid, or a derivative thereof, or a mixture thereof The acid source may be a mono-, bi- or tri-protonic acid. Preferred derivatives include a salt or ester of the acid. The source of acidity is preferably non-hygroscopic, which can improve storage stability. However, monohydrates acids can also be useful herein. Organic acids and their derivatives are preferred. The acid is preferably water-soluble. Suitable acids include citric, glutaric, 13 succinic or adipic acid, monosodium phosphate, sodium hydrogen sulfate, boric acid, or a salt or an ester thereof Citric acid is especially preferred.
Perborate component Another essential ingredient of the agglomerate or extruded detergent particle of the present invention is a perborate component, which is capable of bleaching.
The level of perborate component in the particle is preferably from 10% to 70%, more preferably from 15% to 50%, most preferably from 20% to 40% by weight of the particle.
In detergent compositions comprising the particle, the perborate is preferably present at a level of from 1% to 4CP/o by weight, more preferably from 6% to 25% by weight, most preferably from 13% to 20% by weight of the compositions.
The perborate is preferably in the form of a salt, normally in the form of the alkali metal, preferably sodium salt.
The perborate bleach is preferably sodium perborate in the form of the monohydrate or tetrahydrate, which can be represented respectively with the nominal formula NaB02H202 and NaB02H202.3H20.
The perborate bleach may be included as the crystalline solid without additional protection. However, preferred executions of certain granular compositions utilize a coated form of the perborate bleach 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.
Source of Alkali In accordance with the present invention, when the agglomerate or extruded detergent particle is present in a detergent composition, an alkali source is generally present in the detergent composition such that it has the capacity to react with the acid source to 14 produce a gas. Preferably this gas is carbon dioxide, and therefore the alkali is a carbonate, or a suitable derivative thereof Optionally, the alkali source, or part thereof can be present in the particle.
The detergent composition comprising the particle of the present invention, preferably contains from about 2% to about 75%, preferably from about 5% to about WX), most preferably from about 10% to about 3 0% by weight of the alkali source. When the alkali source is present in the particle, the agglomerate or extrudate preferably contains from about 5% to about 60%, more preferably from 10% to 50%, most preferably from 15% to 3 5% of the alkali source.
In a preferred embodiment, the alkali source is a carbonate. Examples of preferred carbonates are the c earth and alkali metal carbonates, including sodium carbonate, bicarbonate and sesqui-carbonate and any mixtures thereof with ultra-fine calcium carbonate such as are disclosed in German Patent Application No. 2,3 2 1,001 published on November 15, 1973. Alkali metal percarbonate salts may also be included in the detergent compositions and are also suitable sources of carbonate species and are described below in more detail.
Other suitable sources will be known to those skilled in the art.
The alkah source may also comprise other components, such as a silicate. Suitable silicates include the water soluble sodium silicates with an Si02: Na20 ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and 2.0 ratio being most preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an Si02: Na20 ratio of 2.0 is the most preferred silicate.
Alkali metal persilicates are also suitable sources of silicate herein.
Process for making of the agglomerate particle The agglomerate detergent particle can be prepared via a process comprising the steps of i) admixing one or more detergent surfactants, the perborate component and an acid source and optionally other detergent ingredientsto form a mixture; and ii) agglomerating the mixture to form agglomerated particles.
Typically, such a process involves mixing an ciTective amount of powder, including the acid source, with a high active surfactant paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably in-fine mixers, preferably two, such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Preferably a high shear mixer is used, such as a Lodige CB (Trade Name). Most preferably, a high shear mixer is used in combination with a low shear mixer, such as a Lodige CB (Trade Name) and a Lodige KM (Trade name) or Schugi KM (Trade Name). Optionally, only one or more low shear mixer are used. Preferably, the agglomerates are thereafter dried and/ or cooled.
An other agglomeration process involves mixing of various components of the final agglornrate in diffierent stages, using an fluidised bed. For example, a preferred particle in accord with the present invention can be agglomerated by addition, preferably by spraying on, of nonionic, anionicsurfactants and optionally a wax, or mixtures thereof, to the acid source in powdered form and other optional ingredients. Then, additional components, including the perborate bleach and optinally the alkali source or part thereof, can be added and agglomerated in one or more stages, thus forming the final agglomerate particle.
Preferably, no bleach activator and/ or crystalline layered silicate is added to the agglomerate mix in the agglomeration process for making the particle of the invention.
The agglomerate particles may take the form of flakes, prills, marurnes, noodles, ribbons, but preferably take the form of granules. A preferred way to process the particles is by agglomerating powders (e.g. aluminosificate, carbonate) with high active surfactant pastes and to control the particle size of the resulting agglomerates within specified limits. Typical particle sizes are from 0. 10 mm to 5. 0 mm in diameter, preferably from 0.25 mm to 3.0 mm in diameter, most preferably from 0.40 mm to 1. 00 mm in diameter.
16 A high active surfactant paste comprising a mix of, typically, from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight of surfactant, and optionally it can contain an appropriate acid source. The paste may be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to avoid degradation of the anionic surfactants used. An operating temperature of the paste of WC to 80C is typical. Such pastes and methods for making and processing such pastes is for example described in WO 93/03128.
In an especially preferred embodiment of the present invention, the detergent composition has a density of greater than about 600 g/1 and is in the form of powder or a granulate.
Process for making the extruded particle Extruded particles can generally be prepared by mixing the various components, optionally addition of powdered components and/or slip additives, forcing the obtained mixture by pressure through the extruder holes of the required diameter or less, cutting of the extruded paste into extrudates (granules) of the required length and rounding the extrudates. WO 91/13678 and WO 91/02047 describe such processes.
In more detail the extruded particles can be made as follows. The detergent ingredients can be mixed into one paste. Preferably, the various detergent components are pre-mixed in different pastes, preferably two, whereby the acid source preferably is present in a different pre-mixed past than the alkali source if present in the particle, especially when the alkaline source is a carbonate or bicarbonate.
In a highly preferred embodiment, one pre-mixed paste comprises the perborate component and part of the surfactant, preferably the anionic surfactant if present, and additional components such as zeolite and cationic surfactant, and one pre-mixed paste comprises the acid source and part of the surfactant, preferably the nonionic surfactant. The premixed pastes will then be mixed to form one paste.
Optionally, water and additional detergent components, such as slip additives, 35 additional bleach, enzymes, optionally bleach activators, stabilisers and soap can be 17 added to the pre-mixed paste or pastes or to the paste as a whole, simultaneously with or shortly after the mixing process has started.
Preferably the paste obtained is coated with a slip material prior to or simultaneously with the introduction of the paste in the extruder. A variety of compounds are known to be useful herein as slip additives. Preferred slip additives are those compounds which also have a secondary detergent function, such as certain anionic and nonionic surfactants, polymeric polycarboxylates, polyvinyl alcohols.
Under pressure (20 bar or more) the paste or coated paste is then passed through the holes (of the extruder) of the required diameter or less, whereafter the extruded granules are cut in to granules of the required length (about 0. 1 mm to 2.0 mm, preferably about 0. 4 mm to 1. 0 mm).
Typical particle diameter sizes (width) are from 0. 10 mm to 5. 0 mm, preferably from 0.25 mm to 3.Omm, most preferably from 1.00 mm to 2.50.
The viscosity of the paste should be controlled to avoid cacking of the paste in the extruder or during mixing and to avoid the paste from blocking the extruder. By constant pressure, the viscosity is best controlled by heating and cooling the paste and/ or the extruder.
Optionally, the obtained extrudates are rounded, to obtain round or spherical particles.
Preferably, the thus obtained particles are dusted with a powder, preferably zeolite, and dried, to form equally shaped granules, and to avoid agglomeration of the granules.
Additional ingredients The agglomerate or extruded detergent particle and/ or the detergent compositions, comprising the particle of the invention, may also contain additional ingredients or components. The precise nature of these additional ingredients, and levels of 18 incorporation thereof will depend on the physical form of the final composition, and the precise nature of the washing operation for which it is to be used- The detergent particle preferably comprises as an additional ingredient one or more builders, preferably alumino silicates and/ or organic polycarboxylate polymers, alkali sources, bleach activators or bleach catalysts, or mixtures thereof The detergent compositions, comprising the particle of the invention, preferably contain one or more additional detergent components selected from surfactants as described above, additional acid sources, additional bleaches, builders, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
Water-soluble builder compound The particle and/ or the detergent compositions of the present invention can 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 70% by weight, most preferably from 20% to 60% by weight of the composition.
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, phosphates, 25 and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be monomeric or ofigomeric 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 cont i g two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycofic acid, tartaric acid, tartronic acid 35 and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, in particular, water-soluble 19 citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1, 3 79,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials 5 such as 2-oxa1, 1, 3 -propane tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1, 1,3,3-propane tetracarboxylates and 1, 1,2,3propane tetracarboxylates. Polycarboxylates containing suifo 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 15 molecule, more particularly citrates.
Borate builders, as well as buflders 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 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 2 1, and salts of phytic acid.
Partially soluble or insoluble builder compound The particle and/ or the detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present in the detergent composition at a level of from 1 % to 80% by weight, preferably from 101% to 70% by weight, most preferably from 20% to 60% weight of the composition.
In the particle, the partially soluble or insoluble builder compound is preferably present at a level of from 5% to 85% by weight, preferably from 15% to 60% by weight, most preferably from 20% to 500/6 weight of the particle.
Examples of largely water insoluble builders include the sodium alundnosificates.
Suitable aluminosificate zeofites have the unit cell formula Naj(A102MSi02M. xH20 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 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% 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 Zeofite A, Zeolite B, Zeofite P, Zeofite Y, Zeolite HS and mixtures thereof. Zeofite A has the formula Na 12 [A102) 12 (Si02)121. xH20 wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 1(A102)86(SiO2)1061. 276 H20.
Preferably, the particle of the invention does not comprise a crystalline layered silicate. However, preferred crystalline layered silicates for use in the detegrent compositions herein have the general formula NaMSix02x+lYH20 wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A 0 164514 and methods for their preparation are disclosed in DE-A-3417649 and DE A-3742043. Herein, x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2. The most preferred material is 8-Na2Si205, available from Hoechst AG as NaSKS-6.
Additional peLhydrate bleaches In addition to the perborate bleach, metal percarbonates, particularly sodium percarbonate is an optional perhydrate which can be incorporated into the particle or 21 detergent composition of the invention. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C03.3H202, and is available commercially as a crystalline solid.
Potassium peroxyinonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.
Organic peroU-a-cid bleaching system A preferred feature of detergent compositions of the invention is an organic peroxyacid bleaching system. In one preferred execution the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleach of the claimed invention. In an alternative preferred execution a preformed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
Peromyacid bleach precursor Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach 25 precursors may be represented as 0 11 X-C-1, where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is 0 11 X-C-00H 22 Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, most preferably from 1. 5% to 10% by weight of the detergent compositions.
Suitable peroxyacid bleach precursor compounds typically contain one or more N- or 0-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, 1147871, 2143231 and EP-A-0170386.
Leaving groups 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.
Y 3 3y 0 0 11 1 A 11 -N-C-R -N N -N-L-CH-R4 1 $ 1 1 1 R 3 Li 1k3Y 1 Y 23 R3 1 -u-(;ti=k;-CH=CH2 Y 1 9 0 11 M2-k; \ 4 11 U 0 Y 11 >-k; -N / I. NR4 -- c 1---1 11 U 0 1 1 3 1 -0-C=CHR4, and 0 Y 11 1 -N-S-CH-RI 1 11 1k3 U and mixtures thereof, wherein R 1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R 3 is an alkyl chain containing from 1 to 8 carbon atoms, R is H 3 1 3 or R, and Y is H or a solubilizing group. Any of R ' R and R4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, 10 halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
The preferred solubilizing groups are -S03-M + 1 -C02 - M + I-SO4 - M +, N + (R 3)4X and O<-N(R 3)3 and most preferably -SO 3 -M+ and -CO2-M+ wherein R 3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methyisulfate or acetate anion.
Alkyl jperearbogylic acid bleach precurso A1kyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis.
Preferred alkyl percarboxyfic precursor compounds of the imide type include the N,N,NIN1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group 24 contains 1, 2 and 6 carbon atoms. Tetruacetyl ethylene diamine (TAED) is particularly preferred, The TAED is preferably not present in the agglomerated particle of the present invention, but preferably present in the detergent composition, comprising the particle.
Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5tri-methyl hexanoyloxybenzene suifonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
An-dde substituted &k cyacid precursors yl peroL Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
R' - C - N - R2 - C - L R' -N-C-R2-C-1- 11 5 11! 5 11 1 is 0 R 0 or R 0 0 wherein RI is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl group containing 1 to carbon atoms and L can be essentially any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0 1703 86.
Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable 0-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the Nbenzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl in-ddazole and N-benzoyl benzinfidazole. Other useful N-acyl groupcontaining perbenzoic acid precursors include Nbenzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
Cationic peronacid precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
Typicafly, cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a hafide ion.
The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter.
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4, 751,015) 4,988,45 1; 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 described 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, Nacylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl pero)ijdes. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
Benzoxazin organic perQxyacid precursors Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
26 11 k; 111 0 1 CO W U-K1 0 wherein R, is H, alkyl, alkaryl, aryl, or arylalkyl.
Preformed organic peroU-a-c-id The organic peroxyacid bleaching system 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 1 % to 15% by weight, more preferably from 1 % to 10% by weight of the composition.
A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
R' -C-N-R2-C-OOH H 5 U R I 1 U or R' -N-C-R2- C -OOH 1 5 11 11 R 0 0 wherein RI is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl, ary], or 1 group containing 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A0170386.
Other organic peroxyacids include 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.
27 Bleach catalyst The particle and/ or the compositions optionally contain a transition metal containing bleach catalyst. One suitable type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediarninetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof Such catalysts are disclosed in U.S. Pat. 4, 430,243.
Other types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include MnIV2(u-0)3 (1,4,7-trimethyl1,4,7-triazacyclononane)2-(PF6)2, MnlH2(u 0)1(ti-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(CI04)2, MnIV 4(u 0)6(1,4,7-triazacyclononane)4-(CI04)2, MnIIIMnIV4(u-0) I (u-OAc)2-(1,4,7 trimethyl-1,4,7-triazacyclononane)2-(CI04)3, and mixtures thereof Othersare described in European patent application publication no. 549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl 1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7tetramethyl-1,4,7 triazacyclononane, and mixtures thereof For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat.
5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(1,4,7-tfimethyl-1,4,7-triazacyclononane)(OCH3)3- (PF6). Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble complex of manganese (III), and/or (IV) with a ligand which is a non- carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N- dentate ligands, including N4Mn1II(U-0)2MnIVN4)+and [BiPY2MnII1(U-O)2Mn1V biPY21 (CI04)3- Further suitable bleach catalysts are described, for example, in European patent application No. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent 28 application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U. S. 4,601,84 5 (aluminosilicate support with manganese and zinc or magnesium salt), U. S. 4,626,3 73 (manganeselligand catalyst), U. S. 4,119,5 5 7 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S. 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts).
Heg:vy metal ion sequestrant The particle and or the detergent compositions, comprising the particle of the invention preferably contain as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant herein components 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.
Heavy metal ion sequestrants are generally present at a level of from 0. 005% to 20%, preferably from 0. 1% to 10%, more preferably from 0.25% to 7.5% and most 20 preferably from 0.5% to 5% by weight of the compositions.
Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane I hydroxy disphosphonates and nitrilo trimethylene phosphonates.
Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyarainocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2hydroxypropylenediamine disuccinic acid or any salts thereof. Especially preferred is ethylenediamine-N,N-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
29 Other suitable heavy metal ion sequestrants for use herein are 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. The iminodiacetic acid-N-2- hydroxypropyl sufflonic acid and aspartic acid N-carboxymethyl N-2- hydroxypropyl-3sulfonic 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-Nmonoacetic 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 2phosphonobutane-1,2,4-tricarboxylic acid are also suitable. Glycinamide-NN'15 disuccinic acid (GADS), ethylenediamine-N-Ndiglutaric acid (EDDG) and 2hydroxypropylenediaminc-N-N-disuccinic acid (HPDDS) are also suitable.
ELnzym Another preferred ingredient useful in the detergent compositions, comprising the particle, is one or more additional enzymes. Optionally, the enzymes or part thereof cam be present in the agglomerated or extruded particle of the invention.
Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions.
Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred commercially available 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, ot-amylases obtained from a special strain of B licheniformis, 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 and BAN by Novo Industries A/S. 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 of the composition.
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 of the compositions.
The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., ThermoLnyces 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 pseudoalcaliRenes, which is described in Granted European Patent, EP-B0218272.
Another preferred lipase herein is obtained by cloning the gene fromHurnicola lanu,ginos and expressing the gene in Aspermillu o!Lz 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.
Organic polyineric compound Organic polymeric compounds are preferred additional components of the particle and/ or the detergent compositions, comprising the particle in accord with the invention, and are preferably present as components of any particulate components where they may act such as to bind the particulate component together. By 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.
31 Organic polymeric compound is typicafly incorporated in the detergent compositions of the invention at a level of from 0. 1% to 30%, preferably from 0.5% to 15%, most preferably from 1 % to 1 G5/o by weight of the compositions.
Examples of organic polymeric compounds include the water soluble organic homoor 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. Examples of such salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.
The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EPA-351629.
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.
Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropyimethylcellulose 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.
Another organic compound, which is a preferred clay dispersant/ antiredeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula.
32 X -(- OCH2CH2)n - CH3 CH3 N±CH2-CH2-f-CH2)a- N±CH2CH20nX (CH2CH20_)n-X (C H2 C H2 0 t X wherein X is a nonionic group selected from the group consisting of H, Cl -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) b is 1 or 0; for cationic monoamines (b=O), n is at least 16, with a typical range of from 20 to 35; for cationic diamines (b=l), n is at least about 12 with a typical range of from about 12 to about 42.
Other dispersants/ anti-redeposition agents for use herein are described in EP-B011965 and US 4,659,802 and US 4,664,848.
Suds suppressing Vstern The detergent compositions, when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0. 1% to 5% by weight of the composition.
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.
By antifoam compound it is meant herein 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 antifoarn compound including a silicone component.
Such silicone antifoam compounds also typically contain a silica component. The term "silicone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and 33 hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsdoxanes having trimethylsilyl end blocking units.
Other suitable antifoarn compounds include the monocarboxylic fatty acids and soluble salts thereof These materials are described in US Patent 2, 954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali 10 metal salts such as sodium, potassium, and lithium salts, and arnmonium and alkanolammonium salts.
Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g. stearone) Nalkylated amino triazines such as tri- to hexaalkylmelamines or di- to tetra alkyldiarnine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing I to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl dialkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
A preferred suds suppressing system comprises (a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoarn compound comprising in combination (i) polydirnethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight of the silicone antifoarn compound; and (ii) 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 5 0%, preferably 10% to 40% by weight; (b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to 34 propylene oxide ratio of from 1: 0. 9 to 1: 1. 1, at a level of from 0. 5% to 10%, preferably 1% to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DC0544, commercially available from DOW Coming under the tradename DC0544; (c) an inert carrier fluid compound, most preferably comprising a C 16-C 18 ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight; A highly preferred particulate suds suppressing system is described in EPA-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50'C to 85'C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45'C to 80'C.
Clay softening system The particle and/ or the detergent compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.
The clay mineral compound is preferably a smectite clay compound. Smectite clays are disclosed in the US Patents Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647.
European Patents Nos. EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents, PoLymeric dye transfer inhibiting agents The particle, but preferably the detergent compositions may also comprise from 0.0 1 % to 10 %, preferably from 0.05% to 0. 5% by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and Nvinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof a) Polyamine N-oxide polymers Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula:
p 1 (1) Ax tx wherein P is a polymerisable unit, and 00 0 Ii i l A is NC, CO, C, -0-, -S-, N-; x is 0 or 1; R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N- 0 group can be attached or wherein the nitrogen of the N-0 group is part of these groups.
The N-O group can be represented by the following general structures:
0 A (.Ill-. 1 4-(R2)y (R3)z 0 or W(R1)x wherein RI, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or I and wherein the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group forms 36 part of these groups. The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-0 group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-0 group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof Other suitable polyamine N-oxides are the polyamine oxides whereto the N- 0 group is attached to the polymerisable unit. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (1) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof The polyamine N-oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired watersolubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000.
b) Copolymers of N-vinylpyr[olidone and N-viLiylimidazole Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000. The preferred copolymers have a molar ratio of N-vinylimidazole to N- vinylpyrrolidone from 1 to 0.2.
c) PolysdLiyljpyirolidone The detergent compositions herein may also utilize polyvinylpyrrolidone ('WP,') having an average molecular weight of from 2,500 to 400,000. Suitable polyvinylpyrrolidones are commercially valuable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K- 15 (viscosity molecular 37 weight of 10, 000), PVP K-3 0 (average molecular weight of 40, 000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HIP 165 and Sokalan 1HP 12.
d) Pol3Linyloxazolidone The detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazohdones have an average molecular weight of from 2,500 to 400,000.
e) Pol3Ldnylimidazole The detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.
Optical brightener The detergent compositions herein also optionally contain from about 0. 005% to 5% by weight of certain types of hydrophilic optical brighteners.
Hydrophilic optical brighteners useful herein include those having the structural formula:
RI R2 N H H N N O-N-- C=C- N-ON 1 R N S03M 1 S03M H Ni RI wherein RI is selected from anifino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylanlino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
38 When in the above formula, RI is anifino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anifino-6-(N2-bis-hydroxyethyl)s-triazine-2-yl)amino]-2,2'-stflbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal- UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, RI is anilino, R2 is N-2-hydroxyethyl-N-2methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6- (N-2hydroxyethyl-N-methylamino)-s-triazine-2-yl)anno]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
When in the above formula, RI is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilinos-triazine-2-yl)aniino]2,2'stilbenedisuifonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
Cationic fabric softening aggnts Cationic fabric softening agents can also be incorporated into the particle and/or the compositions. Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340.
Cationic fabric softening agents are typically incorporated at total levels of from 0.5% to 15% by weight, normally from 1% to 5% by weight.
Other optional ingredients Other optional ingredients suitable for inclusion in the particle and the detergent compositions include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
39 pH of the compositions The final detergent compositions preferably have a pH measured as a 1% solution in distilled water of at least 10. 0, preferably from 10. 0 to 12.5, most preferably from 10.5 to 12.0.
Form of the agglomerated or extruded particle and detergent compositions thereof Surfactant agglomerate particles The particles may take the form of flakes, prifis, marumes, noodles, ribbons, but preferably take the form of granules. The most preferred way to process the particles, as described above, is by agglomerating or mixing and extruding powders (e.g. aluminosilicate, optionally carbonate) with high active surfactant pastes and to control the particle size of the resultant particles within specified limits.
Form of the compositions The compositions, comprising the particle, can take a variety of physical forms including granular, tablet and bar. The compositions can be of the form of the socalled concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.
The mean particle size of the base composition of granular compositions in accordance with the invention can be from 0. 1 mm to 5.0 mm, but it should preferably be such that no more that 5% of particles are greater than 1.7mm in diameter and not more than 5% of particles are less than 0. 15mm in diameter.
The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.
The bulk density of granular detergent compositions is typically of at least 500 g/litre, more preferably from 650 g/litre to 1200 g/litre. Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the 5 funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base. The cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 nil.
To carry out a measurement, the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup. The filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge. The filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.
Laundly 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. By an effective amount of the detergent composition it is meant from 40g 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.
In a preferred use aspect a dispensing device is employed in the washing method. The dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the commencement of the wash cycle. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.
Once the washing machine has been loaded with laundry the dispensing device containing the detergent product is placed inside the drum. At the commencement of 41 the wash cycle of the washing machine water is introduced into the drum and the drum periodically rotates. The design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.
To allow for release of the detergent product during the wash the device may possess a number of openings through which the product may pass. Alternatively, the device may be made of a material which is permeable to liquid but impermeable to the solid product, which will allow release of dissolved product. Preferably, the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle.
Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle. Especially preferred dispensing devices for use with the composition of the invention have been described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EPA0288346. An article by J.Bland published in Manufacturing Chemist, November 1989, pages 41-46 also describes especially preferred dispensing devices for use with granular laundry products which are of a type commonly know as the "granulette". Another preferred dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No. W094/11562.
Especially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070. The latter Application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to adrnit to the bag sufficient product for one washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium. The support ring is provided with a masking arrangement to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration, or a similar structure in which the walls have a helical form.
42 Alternatively, the dispensing device may be a flexible container, such as a bag or pouch. The bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 00 18678. Alternatively it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501, 0011502, and 0011968. A convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.
Packaging for the compositions Conunercially marketed executions of the bleaching compositions can be packaged in any suitable container including those constructed from paper, cardboard, plastic materials and any suitable laminates. A preferred packaging execution is described in European Application No. 94921505.7.
Abbreviations used in following Examples In the detergent compositions, the abbreviated component identifications have the following meanings:
LAS TAS C45AS CxyEzS C45E7 C25E3 C25E5 Sodium linear C 12 alkyl benzene sulfonate Sodium tallow alkyl sulfate Sodium C 14-C 15 linear alkyl sulfate Sodium C I X-C I y branched alkyl sulfate condensed with z moles of ethylene oxide A C 14-15 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide A C12-15 branched primary alcohol condensed with an average of 3 moles of ethylene oxide A C 12-15 branched primary alcohol condensed with an average of 5 moles of ethylene oxide CEQ QAS Soap TFAA TWA STPP Zeolite A NaSKS-6 Citric acid Carbonate Bicarbonate Silicate Sodium sulfate Citrate MA/AA cmc Protease Alcalase Cellulase Arnylase 43 R I COOCH2CH2.N+(CH3)3 with RI -- C I I -C 13 R2.N+(CH3)2(C2H40H) with R2:-- C12 - C14 Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils. C16-C18 alkylN-methylglucamide C 12-C 14 topped whole cut fatty acids Anhydrous sodium tripolyphosphate Hydrated Sodium Aluminosilicate of formula Nal2(AI02SiO2)12. 27H20 having a primary particle size in the range from 0. 1 to 10 micrometers Crystalline layered silicate of formula 5 -Na2Si205 Anhydrous citric acid Anhydrous sodium carbonate with a particle size between 200 pm and 900pm Anhydrous sodium bicarbonate with a particle size distribution between 400pm and 1200pm Amorphous Sodium Silicate (Si02:Na2O; 2.0 ratio) Anhydrous sodium sulfate Tri-sodium citrate dihydrate of activity 86. 4%with a particle size distribution between 4254m and 850pm Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 70,000. Sodium carboxymethyl cellulose Proteolytic enzyme of activity 4KNPU/g sold by NOVO Industries A/S under the tradename Savinase Proteolytic enzyme of activity 3AU/g sold by NOVO Industries A/S Cellulytic: enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the tradename Carezyme Amylolytic; enzyme of activity 60KNU/g sold by NOVO Industries A/S under the tradename Termamy160T 44 Lipase Endolase PB4 PB1 Percarbonate NOBS TAED DTPMEP:
Photoactivated Brightener 1 Brightener 2 HEDP PVNO PI SRP 1 SRP 2 Silicone antifoarn:
Alkalinity Lipolytic enzyme of activity 1 0OkLU/g sold by NOVO Industries A/S under the tradename Lipolase Endoglunase enzyme of activity 3000 CEW/g sold by NOVO Industries A/S Sodium perborate tetrahydrate of nominal formula NaB02.3H2OR202 Anhydrous sodium perborate monohydrate bleach of nominal formula NaB02R202 Sodium Percarbonate of nominal formula 2Na2C03.3H202 Nonanoyloxybenzene suifonate in the form of the sodium salt. Tetraacetylethylenediamine Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest 2060 Sufflonated Zinc Phthlocyanine encapsulated in bleach dextrin soluble polymer Disodium 4,4'-bis(2-sulphostyryl)biphenyl Disodium 4,4'-bis(4anilino-6-morpholino-1.3.5triazin-2-y1)amino) stilbene-2:2'-disuifonate. 1, 1 -hydroxyethane diphosphonic acid Polyvinylpyridine N-oxide Copolymer of polyvinylpyrolidone and vinylimidazole Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone Diethoxylated poly (1, 2 propylene terephtalate) short block polymer Polydimethylsiloxane: foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10: 1 to 100: 1. % weight equivalent of NaOH, as obtained using the alkalinity release test method described herein.
In the following Examples all levels are quoted as % by weight of the composition:
Example- 1
The following detergent formulations according to the present invention were prepared:
A B Blown Powder Zeolite A 15.0 Sodium sulfate - LAS 3.0 - CEQ 2.0 1.3 DTPW 0.4 - CMC 0.4 MA/AA 4.0 - Agglomerates PB1 15.0 10.0 C45AS - 11.0 LAS 6.0 - TAS 3.0 Silicate 4.0 - Zeolite A 10.0 13.0 CMC - 0.5 MA/AA - 2.0 Citric Acid 4.0 3.0 Spray On Perfume 0.3 0.5 C45E7 4.0 4.0 C25E3 2.0 2,0 Dry additives TAED 4.0 2.0 MA/AA - 3.0 NaSKS-6 12.0 46 Bicarbonate 7.0 5.0 Carbonate 17.0 14.0 PVPVI/PVNO 0.5 0.5 Alcalase 0.5 0.9 Lipase 0.4 0.4 Amylase 0.6 0.6 Cellulase 0.6 0.6 Silicone antifoam 5.0 5.0 Dry additives Sodium sulfate 0.0 2.0 Balance (Moisture and Nfiscellaneous) 100.0 100.0 Density (g/litre) 700 700 47 Example 2
The following high density and bleach-containing detergent formulations, according to the present invention were prepared:
C D Blown Powder Zeolite A 15.0 15.0 Sodium sulfate 0.0 0.0 LAS 3.0 3.0 QAS - 1.5 CEQ 2.0 2.0 DTPNV 0.4 0.4 CMC 0.4 0.4 MA/AA 4.0 2.0 Agglomerates PBI 15.0 15.0 LAS 4.0 4.0 TAS 2.0 1.0 C24E5 2.0 2.0 Silicate 3.0 4.0 Citric Acid 2.0 3.0 Zeolite A 8.0 8.0 Carbonate - 6.0 Magnesium sulphate 0.3 0.4 Spray on Perfume 0.3 0.3 C45E7 2.0 2.0 Dry additives Citrate 5.0 2.0 Bicarbonate - - Carbonate 16.0 10.0 TAED 6.0 5.
Polyethylene oxide of NM 5,000,000 - 0.2 48 Bentonite clay 10.0 Protease 1.0 1.0 Lipase 0.4 0.4 Amylase 0.6 0.6 Cellulase 0.6 0.6 Silicone antifoam 5.0 5.0 Dry additives Sodium sulfate 0.0 0.0 Balance (Moisture and NEscellaneous) 100.0 100.0 Density (Mitre) 850 850 49 Example 3
The following high density detergent formulations, according to the present invention were prepared:
E F Agglomerate LAS 7.5 PBI 12.0 - PB4 - 15.0 C45AS 14.0 CEQ - 3.5 Zeolite A 15.0 - citric acid 1.5 2.0 Carbonate 4.0 MA/AA 4.0 2.0 CMC 0.5 0.5 DTPNT 0.4 0.4 C24E5 5.0 5.0 Spray On Perfume 0.5 0.5 Dry Additives Zeolite - 6.0 HEDP 0.5 0.3 SKS 6 13.0 10.0 Citrate 3.0 1.0 TAED 5.0 7.0 Percarbonate 20.0 20.0 SRP 1 0.3 0.3 Protease 1.4 1.4 Lipase 0.4 0.4 Cellulase 0.6 0.6 Arnylase 0.6 0.6 Silicone antifoam 5.0 5.0 Brightener 1 0.2 0.2 Brightener2 0.2 - Balance (Moisture and 100 100 Miscellaneous) Density (g/litre) 850 850 51

Claims (21)

  1. Claims 1. An agglomerate or extruded detergent particle comprising one or
    more surfactants, an acid source and a perborate component.
  2. 2. A detergent particle according to claim 1 wherein said acid source is present at a level of from 3% to 30% by weight of the particle.
  3. 3. A detergent particle according to claim 1 wherein said acid source is present 10 at a level of from 7% to 15% by weight of the particle.
  4. 4 A detergent particle according to any preceding claim wherein said surfactant is present at a level of from 25% to 60% by weight of the particle.
  5. 5. A detergent particle according to any preceding claim wherein said perborate bleach is present at a level of from 15% to 50% by weight of the particle.
  6. 6. A detergent particle according to any preceding claim wherein said perborate bleach is in the form of a monohydrate.
  7. 7. A detergent particle according to any preceding claim wherein said perborate bleach is in the form of a tetrahydrate.
  8. 8. A detergent particle according to any preceding claim wherein the surfactant 25 comprises one or more anionic and nonionic surfactants
  9. 9. A detergent particle according to any preceding claim wherein said acid source comprises an organic acid.
  10. 10. A detergent particle according to any preceding claim wherein the acid source is citric acid.
  11. 11. A detergent particle according to any preceding claim which is substantially free from bleach activator and which contains alkaline crystalline layered silicate.
  12. 12. A detergent particle according to any preceding claim wherein magnesium sulphate is present at a level of from 0.3% to 3% by weight of the particle.
    52
  13. 13. A detergent composition comprising the detergent particle according to any preceding claim and an alkali source.
  14. 14. A detergent composition according to claim 13 wherein said alkali source comprises an alkaline salt selected from an alkali metal or alkaline earth metal carbonate, bicarbonate or sesqui-carbonate.
  15. 15. A detergent composition according to claim 13 or 14 wherein the alkali source is present in an amount of from about 2% to about 75% by weight of the 10 composition.
  16. 16. A detergent composition according to any of claims 13 to 15 wherein the alkali source is present in an amount of from about 101/6 to about 30% by weight of the composition.
  17. 17. A process for making an agglomerated detergent particle according to any of claims 1 to 10 comprising the steps of..
    i) admixing one or more detergent surfactants, the perborate bleach and an acid source to form a mixture; and ii) agglomerating the mixture to form agglomerated particles.
  18. 18. A process according to Claim 17 for making an agglomerated detergent particle according to any of claims 1 to 10, wherein in step i) the acid source and one or more surfactants are mixed prior to addition of the perborate bleach.
  19. 19. A process for making the extruded detergent particle according to any of claims 1 to 10 by extrusion, the process comprising forcing a paste, comprising the acid source, surfactant and perborate component under pressure through holes of an extruder, whereafter the extruded paste is cut into particles.
  20. 20. A process according to claim 19 whereby said paste comprises at least two pre-mixed pastes, comprising a first pre-mixed paste which comprises the acid source and a second pre-mixed paste whicho comprises the perborate component.
    53
  21. 21. A method of washing laundry in a domestic washing machine comprising, introducing into a dispensing device which is placed in the drum of the washing machine, or introducing into the dispensing drawer of a washing machine, an effective amount of a detergent composition of any one of claims 13 to 16.
GB9705840A 1997-03-20 1997-03-20 A detergent composition Withdrawn GB2323384A (en)

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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU1449100A (en) * 1998-10-26 2000-05-15 Procter & Gamble Company, The Detergent particles and processes for making them
DE19854083A1 (en) * 1998-11-24 2000-05-25 Henkel Kgaa Detergent containing citric acid
EP1048715A1 (en) * 1999-04-30 2000-11-02 The Procter & Gamble Company Method of dispensing a detergent composition
EP1048714A1 (en) * 1999-04-30 2000-11-02 The Procter & Gamble Company Method of dispensing a detergent composition
EP1048712A1 (en) * 1999-04-30 2000-11-02 The Procter & Gamble Company A process of treating fabrics with a laundry detergent additive tablet
US6491947B2 (en) 2000-11-03 2002-12-10 Chemlink Laboratories, Llc Expanded perborate salt, use, and method of production
US6541439B1 (en) * 2001-11-16 2003-04-01 Colgate-Palmolive Company Cleaning system including a powdered cleaning composition disposed in a water soluble container
WO2005001009A2 (en) * 2003-05-30 2005-01-06 Orange Glo International, Inc. Detergent formulations containing alkaline peroxide salts and organic acids
DE102007008655A1 (en) 2007-02-20 2008-08-21 Henkel Ag & Co. Kgaa Siderophore-metal complexes as bleach catalysts
GB0805908D0 (en) * 2008-04-01 2008-05-07 Reckitt Benckiser Inc Laundry treatment compositions

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4540504A (en) * 1983-04-22 1985-09-10 Warner-Lambert Company Denture cleaner having improved dissolution time and clarity and method of preparation

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4252664A (en) * 1978-10-30 1981-02-24 Colgate-Palmolive Company Effervescent granules
JPS63199796A (en) * 1987-02-16 1988-08-18 花王株式会社 High density granular detergent composition
EP0296813A1 (en) * 1987-06-24 1988-12-28 Imperial Chemical Industries Plc Powder compositions and detergent compositions
EP0483413B1 (en) * 1990-10-30 1996-01-31 The Procter & Gamble Company Improving the colour of surfactant agglomerates by admixing a solid bleaching agent
HUT65887A (en) * 1991-04-19 1994-07-28 Procter & Gamble Granular laundry detergent compositions having improved solubility and process for preparing the compositions
GB9120657D0 (en) * 1991-09-27 1991-11-06 Unilever Plc Detergent powders and process for preparing them
CA2141587A1 (en) * 1992-08-01 1994-02-17 Anthony Dovey Low gelling detergent compositions and a process for making such compositions
WO1995027774A1 (en) * 1994-04-07 1995-10-19 The Procter & Gamble Company Bleach compositions comprising metal-containing bleach catalysts and antioxidants
DE19509752A1 (en) * 1995-03-17 1996-09-19 Henkel Kgaa Compressed washing and cleaning agents with high powder density
GB2315761A (en) * 1996-07-31 1998-02-11 Procter & Gamble Detergent composition comprising a particulate acid source and an alkaline source
CA2261349C (en) * 1996-07-31 2002-10-15 The Procter & Gamble Company A detergent composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4540504A (en) * 1983-04-22 1985-09-10 Warner-Lambert Company Denture cleaner having improved dissolution time and clarity and method of preparation

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EP0866118A2 (en) 1998-09-23
GB9705840D0 (en) 1997-05-07
EP0866118A3 (en) 1998-12-16
CA2232205A1 (en) 1998-09-20

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