WO1999064558A1 - Cleaning compositions containing speckle particles - Google Patents

Cleaning compositions containing speckle particles Download PDF

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Publication number
WO1999064558A1
WO1999064558A1 PCT/US1998/012371 US9812371W WO9964558A1 WO 1999064558 A1 WO1999064558 A1 WO 1999064558A1 US 9812371 W US9812371 W US 9812371W WO 9964558 A1 WO9964558 A1 WO 9964558A1
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WO
WIPO (PCT)
Prior art keywords
particles
microns
speckle
particle size
acid
Prior art date
Application number
PCT/US1998/012371
Other languages
French (fr)
Inventor
Benjamin Edgar Chapman
Nour-Eddine Guedira
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to PCT/US1998/012371 priority Critical patent/WO1999064558A1/en
Priority to AU80720/98A priority patent/AU8072098A/en
Publication of WO1999064558A1 publication Critical patent/WO1999064558A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets

Definitions

  • the invention relates to cleaning compositions comprising speckle particles and other particles of selected mean particle sizes and present at selected levels.
  • detergents are often obtained by spraying-on an aqueous solution of a specific dye onto hygroscopic material or directly onto the final detergent base particles and subsequently drying the thus dyed materials or particles.
  • a problem associated with this method is that the hygroscopic material absorbs large amount of water which may result in caking and that introduction of water to the final detergent particles can result in caking of the product. This is particularly a problem when higher amounts of aqueous dye-solution need to be used, for example, when very diluted dye solutions are to be used, or strongly dyed particles are needed or the dye is absorbed by the material or particles which are to be dyed.
  • Another problem associated with detergents comprising large amounts of dye per particle can be that the dye can 'bleed' in the presence of water. This may be the case when the detergent is made by spraying on large amounts of aqueous dye solutions, or when the detergent comprises large amount of hygroscopic material or of course, when the detergents are introduced to the washing or cleaning liquid. This 'bleeding' may cause colour changes of the product and the packing material. Moreover, under certain conditions, the dye or the dye particles which may deposit on the fabrics, can 'bleed' on the fabrics and cause colour changes on the washed fabric.
  • the inventors have now found a means to introduce large amounts of dyed particles or speckles in a cleaning product without incurring any of the before mentioned problems.
  • the inventors have found that when only particles of a specific mean particle size are dyed, a larger number of particles can be present in the cleaning composition, without incurring any of the above problems. It has been found that the selection of particles of a specific particle size ensures a more efficient and controlled dyeing of the particles, which enables the effective use of small amounts of dye per particle whilst obtaining a homogeneously dyed particle.
  • the particles preferably have a relatively high density to reduce the absorption of the dye-solution.
  • the amount of dye required can be minimised, thus reducing the chance of bleeding of the dye or colouring of the fabrics in the washing or cleaning process. It has also been found that, depending on the specific particle size of the speckles and the other particle of the product and the colour intensity of the dye, an optimum colour appearance of the product can be obtained with a minimum amount of dye.
  • the other particles of the product are also of a specific particle size
  • a homogeneously distribution of the dye throughout the product can be obtained by reduction of segregation of the particles and thus a reduction of the formation of localised high concentrations of dye. This will also amount to a reduction of the chance of colour changes in the products, packaging material and moreover of the fabrics in the washing or cleaning process.
  • the present invention provides a cleaning composition comprising speckle particles and other particles, whereby the amount of speckled particles in percentage by weight of the composition (CP%) is:
  • Mncp is the mean particle size of the other particles and Mcp is the mean particle size of the speckle particles, provided that CP is from 2% to 10% by weight, Mncp is from 100 microns to 1100 microns and Mcp is from 100 microns to 1100 microns.
  • the particles in the composition are such that the colour difference of the speckled particles compared to the other particles ( ⁇ E) is from 15 to 40,
  • ⁇ E being V ( ⁇ L) 2 +( ⁇ a) 2 + ( ⁇ b) 2 ⁇ L being L (speckle particle) - L (othCTParticles >- , namely being the whiteness difference between the speckle particles and the other particles, ⁇ a being a (speclde particle) - a (other p " thsta) , namely being the greenness/redness difference between the speckled particles and the other particles, ⁇ b being b (spedde particles) - b (other vu&im) , namely being the blueness/ yellowness difference between the speckle particles and the other particles as defined by the Hunter colour analysis method.
  • compositions are preferably solid laundry or dish washing or hard-surface cleaning compositions.
  • the invention also relates to a process for making the compositions and the speckled particle thereof .
  • the invention also relates to the use of speckle particles at a level CP, as defined above, being between 2% and 10% by weight, in cleaning compositions comprising also other particles, having the specific particle sizes as defined above.
  • the colour or whiteness difference between the speckled particles and the other particles is preferably between 15 and 40, as defined above.
  • the speckled particles of the invention may have any colour or whiteness other than the colour or whiteness of the other particles of the compositions of the invention.
  • the at least one of the values ⁇ L, ⁇ a or ⁇ b, as defined herein, should not be O.
  • the speckle particle is preferably not white.
  • the speckled particle is dyed, preferably with an aqueous solution of a dyestuff as described hereinafter.
  • the compositions comprise the coloured particles at a level of from 2% to 10%.
  • the precise level of speckle particles present in the composition depends in particular on the particle size of the speckled particles and the other particles, as is defined by the formula above.
  • the particle size of the speckle particles and the other particles are selected such that more than 3% or even more than 3.8% or even more than 4.1% by weight of speckled particles are present.
  • the speckle particle has a mean particle size of 100 microns to 1100 microns, preferably from 250 microns to 850 microns, it may be preferred that the particle size is from 250 or 350 microns to 590 microns.
  • the particles preferably are such that 80% by weight of the particles has a particle size of more than 100 microns (more than 80% by weight of the particles on Tyler sieve mesh 100) and less than 10% by weight of the particles has a particle size of more than 1180 microns (through Tyler mesh sieve 14); or more preferably 80% by weight of the particles has an particle size of more than 250 microns and less than 10% by weight of the particles has a particle size of more than 850.
  • the speckled particle preferably comprises one or more ingredients, commonly employed in cleaning compositions, such as detergent actives, fillers, organic or inorganic builders, alkalinity or acid sources, including enzymes or enzyme prills, (poly) carboxylic acids or salts thereof, inorganic salts, including phosphates, sulphates, carbonates. It may be preferred that the particle is a base granule of the cleaning compositions, but it may be preferred that the particle comprises inorganic or organic salts, preferably carbonate, or acids, preferably citric acid.
  • the particle has a pore size which is at least 20 microns. It may be preferred that the density of the particle is at least 300 g/litre, preferably up to 2000 g/litre, more preferably from 420 g/litre to 1500g/litre.
  • the ratio of the mean particle size of the speckle particle to the mean particle size of the other particle is preferably from 1:2 to 2.5:1, or more preferably from 1:1 to 2:1.
  • the speckle particle preferably comprise a dye to provide the colouring, preferably present in low levels, preferably up to 2% or more preferably up to 1% or even up to 0.7% and it may be preferred that the dye is present a t a level of below 0.5% or even 0.2% or even 0.1% by weight of the speckle particle.
  • the speckle particles preferably have a colour intensity such that the colour difference of the speckle particles compared to the other particles ( ⁇ E) is from 15 to 40, or more preferably between 20 and 35, as defined by the formula
  • ⁇ L being the whiteness difference between the speckle particles and the non-speckle
  • other particles ⁇ a being the greenness/redness difference between the speckle particles and the other, non-speckle particles
  • ⁇ b being the blueness/yellowness difference between the speckle particles and the non-speckle particles as defined by the Hunter colour analysis method, as described in for example the 'Manual of Hunter analysis equipment' and in: 'Hunter, R.S. 'Photoelectric color difference meter', Journal of the Optical Society of America, Vol. 48, 1958, pp 985-995.
  • no UV-lens filter apparatus is used.
  • compositions of the invention comprise also other particles, not being the speckle particles of the invention, meaning for the purpose of the invention that they do not have the same colour or whiteness as the speckle particles. Therefore, at least one of the values ⁇ L, ⁇ a or ⁇ b between the other particles and the speckle particles should not be 0, as defined herein.
  • the other particles may comprises any ingredient or mixtures thereof commonly employed in cleaning compositions, as described herein after. It may be preferred that the other particles are detergent base particles, comprising for example one or more surfactants, organic and/or inorganic builders, bleach, perfumes, polymeric compounds, enzymes, suds suppressers or mixtures thereof.
  • the other particle has a mean particle size of 100 microns to 1100 microns, preferably from 250 microns to 850 microns, and it may be preferred that the mean particle size is from 250 or 350 microns to 590 microns.
  • the particles preferably are such that 80% by weight of the particles has a particle size of more than 100 microns (more than 80% by weight of the particles on Tyler sieve mesh 100) and less thanl0% by weight of the particles has a particle size of more than 1180 microns (through Tyler mesh sieve 14); or more preferably 80% by weight of the particles has an particle size of more than 250 microns and less than 10% by weight of the particles has a particle size of more than 850 microns.
  • the other particle of the invention may be prepared by any conventional method for making detergent particles, including agglomeration, extrusion, crutching, dry mixing, spray-drying.
  • the density of the other particle is at least 300 g/litre, preferably up to 1200g/litre, more preferably from 380 g/litre to 950 g/litre or even to 780 g/litre.
  • the speckle particles of the invention are preferably dyed particles.
  • the dye used for dyeing the particles as used herein can be a dye stuff or an aqueous solution of a dye stuff. It may be preferred that the dye is an aqueous solution comprising a dyestuff, at any level to obtain suitable dyeing of the particles, preferably such that levels of dye solution are obtained up to 2% by weight of the speckle particle, or more preferably up to 0.5% by weight, as described above.
  • the dye also comprising other ingredients such as organic binder materials.
  • the dyestuff can be any suitable dyestuff.
  • suitable dyestuff s include E104 - food yellow 13 (quinoline yellow), El 10 - food yellow 3 (sunset yellow FCF), El 31 - food blue 5 (patent blue V), Ultra Marine blue (trade name), E133 - food blue 2 (brilliant blue FCF), E140 - natural green 3 (chlorophyll and chlorphyllins), E141 and Pigment green 7 (chlorinated Cu phthalocyanine).
  • Preferred dyestuffs may be Monastral Blue BV paste (trade name) and/ or Pigmasol Green (trade name).
  • composition of the invention is preferably obtainable by a process comprising the steps of dyeing particles of a mean particle size of from 100 to 1100 microns, preferably 250 to 850 microns, with a dye, preferably an aqueous solution of a dyestuff, to obtain speckle particles and addition of the speckle particles to other particles, of a mean particle size of 100 to 1100 microns, preferably 250 to 850 microns.
  • the speckle particle of the invention are preferably prepared by spraying-on the dye, preferably an aqueous solution of a dyestuff.
  • This process preferably includes two steps namely a spraying-on step and a drying step. These may be carried out in stepwise fashion, or alternatively both steps may occur simultaneously.
  • the spraying-on step preferably comprises spraying an aqueous mixture comprising the dyestuff onto a particle.
  • This spraying-on can be achieved by any spraying process commonly known to the person skilled in the art.
  • the spraying-on is carried out whilst the particles are in motion, for example by agitation.
  • Suitable agitation means comprise drum mixers, KM Loedige (trade name) mixers, V blenders, spray granulators, fluidised beds, turbodisers (trade name) and Schugi (trade name) mixers.
  • the drying step involves drying the particles obtained from the first step. This drying process may be carried out using any known drying apparatus such as fluidised bed dryers and granulator dryers.
  • spraying-on and drying steps occur simultaneously, most preferably being carried out as a continuous process in a fluidised bed drier.
  • the finished particles preferably have a moisture content of from 0.1 % to 5 % , preferably from o.5% to 3.5% by weight of the finished particle.
  • the cleaning compositions of the invention are preferably solid laundry, dishwashing or hard-surface cleaning compositions, preferably in the form of granules, extrudates, flakes or tablets.
  • compositions in accord with the invention may also contain additional detergent components.
  • additional detergent components The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition or component, and the precise nature of the washing operation for which it is to be used.
  • compositions of the invention preferably contain one or more additional detergent components selected from surfactants, bleaches, bleach catalysts, alkalinity systems, builders, phosphate-containing builders, organic polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti- redeposition agents soil releasing agents, perfumes, brightners, photobleaching agents and additional corrosion inhibitors.
  • additional detergent components selected from surfactants, bleaches, bleach catalysts, alkalinity systems, builders, phosphate-containing builders, organic polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti- redeposition agents soil releasing agents, perfumes, brightners, photobleaching agents and additional corrosion inhibitors.
  • compositions in accord with the invention preferably contain one or more surfactants selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
  • ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
  • compositions in accord with the present invention preferably comprise an additional anionic surfactant.
  • anionic surfactants useful for detersive purposes can be comprised in the detergent composition. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.
  • Anionic sulfate and sulfonate surfactants are preferred.
  • surfactants systems comprising a sulfonate and a sulfate surfactant, preferably a linear or branched alkyl benzene sulfonate and alkyl ethoxylsulfates, as described herein, preferably combined with a cationic surfactants as described herein.
  • 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 sulfosuccinate (especially saturated and unsaturated C, ,-,-C 1 8 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C fi -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 surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(Cj-C4 alkyl) and -N-(Cj-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Alkyl sulfate surfactants are preferably selected from the linear and branched primary Cl ⁇ "Ci8 a lkyl sulfates, more preferably the C ⁇ ⁇ -C ⁇ branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the CiO"Cl8 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 ⁇ 1-C18, most preferably Ci ⁇ -C ⁇ 5 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
  • a particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124. Anionic Sulfonate Surfactant
  • Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, Cg-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
  • Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
  • Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2 ⁇ ) x
  • Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR ⁇ -CHR2-O)-R3 wherein R is a
  • Ri and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof
  • R3 is selected from the group consisting of 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-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl- 1-nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors. Alkali Metal Sarcosinate Surfactant
  • Suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON
  • R1 CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group
  • R! is a C1-C4 alkyl group and M is an alkali metal ion.
  • Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
  • any alkoxylated nonionic surfactants are suitable herein.
  • the ethoxylated and propoxylated nonionic surfactants are preferred.
  • Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
  • the condensation products of aliphatic alcohols with from 1 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.
  • Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R 2 CONR 1 Z wherein : Rl is H, Ci -C4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C ⁇ or C2 alkyl, most preferably C ⁇ alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C11-C1 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
  • Suitable fatty acid amide surfactants include those having the formula: R ⁇ CON R ⁇ )2 wherein R > is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R ⁇ is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4 ⁇ ) x H, where x is in the range of from 1 to 3.
  • 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 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
  • Preferred alkylpolyglycosides have the formula:
  • R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
  • the glycosyl is preferably derived from glucose.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula R3(OR ) X NO(R5)2 wherein R ⁇ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to
  • R ⁇ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are Cj ⁇ " i8 alkyl dimethylamine oxide, and CJQ-18 acylamido alkyl dimethylamine oxide.
  • a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.
  • Zwitterionic surfactants can also be incorporated into the detergent compositions in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable betaines are those compounds having the formula R(R')2N + R 2 COO" wherein R is a Cg-C ⁇ hydrocarbyl group, each Rl is typically C1-C3 alkyl, and R 2 is a C1-C5 hydrocarbyl group.
  • Preferred betaines are C12-I8 dimethyl-ammonio hexanoate and the CJQ-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein. Cationic Surfactants
  • Suitable cationic surfactants to be used in the detergent herein include the quaternary ammonium surfactants.
  • the quaternary ammonium surfactant is a mono
  • C6"Ci6 > preferably Cg-Cjo N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
  • cationic ester surfactants Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants.
  • the cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group.
  • Suitable cationic ester surfactants including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
  • ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms.
  • the atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain.
  • spacer groups having, for example, -O-O- (i.e.
  • spacer groups having, for example - CH2-O- CH2- and -CH2-NH-CH2- linkages are included.
  • the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.
  • cationic mono-alkoxylated amine surfactant preferably of the general formula I:
  • R is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about
  • R 2 and R ⁇ are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R 2 and R- are methyl groups; R ⁇ is selected from hydrogen (preferred), methyl and ethyl; X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.
  • Particularly preferred ApR 4 groups are — CH CH 2 OH, — CH 2 CH2CH OH, — CH CH(CH 3 )OH and — CH(CH 3 )CH 2 OH, with — CH 2 CH 2 OH being particularly preferred.
  • Preferred R! groups are linear alkyl groups. Linear R groups having from 8 to 14 carbon atoms are preferred.
  • Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula
  • R! is CjO' lS hydrocarbyl and mixtures thereof, especially CJQ' H alkyl, preferably CJO and Cj2 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
  • compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH(CH 3 )CH 2 O] and [CH2CH(CH3 ⁇ ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and or i-Pr units.
  • EO ethoxy
  • i-Pr isopropoxy units
  • Pr n-propoxy units
  • the levels of the cationic mono-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1% to 20%, more preferably from 0.2% to 7%, most preferably from 0.3% to 3.0% by weight of the composition.
  • the cationic bis-alkoxylated amine surfactant preferably has the general formula II:
  • R! is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms;
  • R 2 is an alkyl group containing from one to three carbon atoms, preferably methyl;
  • R- and R 4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl,
  • X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality.
  • a and A can vary independently and are each selected from Ci -C4 alkoxy, especially ethoxy,
  • p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.
  • R* is CI Q-CJS hydrocarbyl and mixtures thereof, preferably C ⁇ Q, Cj2 > C14 alkyl and mixtures thereof.
  • X is any convenient anion to provide charge balance, preferably chloride.
  • cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:
  • R* is C10-C18 hydrocarbyl, preferably C10-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3
  • R 2 is C1-C3 alkyl, preferably methyl
  • X is an anion, especially chloride or bromide.
  • Other compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH2O] and [CH2CH(CH3O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
  • compositions are a perhydrate bleach, such as metal perborates, metal percarbonates, particularly the sodium salts.
  • Perborate can be mono or tetra hydrated.
  • Sodium percarbonate has the formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid.
  • Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.
  • a preferred feature of the composition is an organic peroxyacid bleaching system.
  • 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.
  • 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.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as
  • L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is
  • 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 O-acyl groups, which precursors can be selected from a wide range of classes.
  • Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789.
  • Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms
  • R is an alkyl chain containing from 1 to 8 carbon atoms
  • R is
  • R 1 , R3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
  • the preferred solubilizing groups are -SO 3 " M + , -CO 2 " M + , -SO 4 " M + , -N + (R 3 ) 4 X "
  • M and -CO 2 M wherein R 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.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
  • Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
  • Preferred precursors of this type provide peracetic acid on perhydrolysis.
  • Preferred alkyl percarboxylic precursor compounds of the imide type include the N-
  • TAED Tetraacetyl ethylene diamine
  • the TAED is preferably not present in the agglomerated particle of the present invention, but preferably present in the detergent composition, comprising the particle.
  • alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
  • Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
  • R* is an alkyl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-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 N- benzoyl substituted ureas.
  • Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole.
  • Other useful N-acyl group- containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
  • 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 halide ion.
  • the peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore.
  • 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; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
  • 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:
  • R is H, alkyl, alkaryl, aryl, or arylalkyl.
  • the detergent composition 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* is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A- 0170386.
  • organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • diacyl and tetraacylperoxides especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
  • the composition can contain a transition metal containing bleach catalyst.
  • One suitable type of bleach catalyst is a catalyst system comprising a transition 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 ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • a transition 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
  • a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • 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 Mnl ⁇ 2 ⁇ -0)3 ( 1 ,4,7-trimethyl- 1,4, 7-triazacyclononane)2-(PF6)2, MnH 2(u-
  • bleach catalysts useful herein may also be selected as appropriate for the present invention.
  • 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(l,4,7-trimethyl-l,4,7-triazacyclononane)(OCH3)3_(PF6).
  • Still another type of bleach catalyst 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.
  • Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.
  • U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand.
  • Said ligands are of the formula:
  • B is a bridging group selected from O, S.
  • R ⁇ , R ⁇ , and R ⁇ can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups.
  • Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2-bispyridylamine.
  • Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and -bispyridylamine complexes.
  • Highly preferred catalysts include Co(2,2 , -bispyridylamine)Cl2, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)2 ⁇ 2Cl ⁇ 4, Bis-(2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.
  • binuclear Mn complexed with tetra-N-dentate and bi-N- dentate ligands include [Bipy2MnH (u-
  • bleach catalysts are described, for example, in European patent application, publication 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 application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat.
  • the bleach catalyst is typically used in a catalytically effective amount in the compositions and processes herein.
  • catalytically effective amount is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance bleaching and removal of the stain or stains of interest from the target substrate.
  • the test conditions will vary, depending on the type of washing appliance used and the habits of the user. Some users elect to use very hot water; others use warm or even cold water in laundering operations. Of course, the catalytic performance of the bleach catalyst will be affected by such considerations, and the levels of bleach catalyst used in fully-formulated detergent and bleach compositions can be appropriately adjusted.
  • compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 1 ppm to about 200 ppm of the catalyst species in the wash liquor.
  • 3 micromolar manganese catalyst is effective at 40°C, pH 10 under European conditions using perborate and a bleach precursor. An increase in concentration of 3- 5 fold may be required under U.S. conditions to achieve the same results.
  • compositions in accord with the present invention preferably contain a water- soluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight, preferably from 10% to 60% by weight, most preferably from 15% to 40% by weight of the composition.
  • the detergent compositions of the invention preferably comprise phosphate- containing builder material. Preferably present at a level of from 0.5% to 60%, more preferably from 5% to 50%, more preferably from 8% to 40.
  • the phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.
  • Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
  • the most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of from 0.1% to 15%, more preferably from 0.5% to 8% by weight of the composition.
  • 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- ⁇ ropane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
  • Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
  • Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.
  • Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
  • compositions in accord with the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 0.5% to 60% by weight, preferably from 5% to 50% by weight, most preferably from 8% to 40% weight of the composition.
  • Examples of largely water insoluble builders include the sodium aluminosilicates.
  • Suitable aluminosilicate zeolites have the unit cell formula Na z [(AlO2) z (SiO2)y].
  • XH2O 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 Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:
  • Zeolite X has the formula Nag6 [(AlO 2 )86(Si ⁇ 2)l06]- 276 H 2 O.
  • zeolite MAP builder Another preferred aluminosilicate zeolite is zeolite MAP builder.
  • the zeolite MAP can be present at a level of from 1% to 80%, more preferably from 15% to 40% by weight of the compositions.
  • Zeolite MAP is described in EP 384070 A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
  • zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
  • the zeolite MAP detergent builder has a particle size, expressed as a dso value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.
  • the dso value indicates that 50% by weight of the particles have a diameter smaller than that figure.
  • the particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d5Q values are disclosed in EP 384070A. Heavy metal ion sequestrant
  • compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant.
  • 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 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most preferably from 0.3% to 2% by weight of the compositions or component
  • Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1- 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, 1,1 hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.
  • Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2- hydroxypropylenediamine disuccinic acid or any salts thereof.
  • 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.
  • iminodiacetic acid-N-2- hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl- 3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
  • EP-A-476,257 describes suitable amino based sequestrants.
  • EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
  • EP-A- 528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-l,2,4-tricarboxylic acid are alos suitable.
  • Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
  • diethylenetriamine pentacetic acid ethylenediamine- N,N-disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • EDDS ethylenediamine- N,N-disuccinic acid
  • 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • Another preferred ingredient useful in the compositions herein is one or more additional enzymes.
  • Preferred additional enzymatic materials include the commercially available Upases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
  • Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.
  • Preferred amylases include, for example, ⁇ -amylases 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, Duramyl and BAN by Novo Industries A/S.
  • Highly preferred amylase enzymes maybe those described in PCT/ US 9703635, and in WO95/26397 and WO96/23873.
  • Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight 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 ofHumicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein.
  • a preferred lipase is derived from Pseudomonas pseudoalcaligenes. which is described in Granted European Patent, EP-B-0218272.
  • Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
  • Organic polymeric compounds are preferred additional components of the compositions herein and are preferably present as components of any particulate components where they may act such as to bind the particulate component together.
  • organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, including quaternised ethoxylated (poly) amine clay-soil removal/ anti-redeposition agent in accord with the invention.
  • Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%, most preferably from 0.5% to 10% by weight of the compositions.
  • organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A-1,596,756.
  • salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.
  • polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
  • organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
  • organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
  • Highly preferred polymeric components herein are cotton and non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent 5,415,807, Gosselink et al., and in particular according to US application no.60/051517.
  • Another organic compound which is a preferred clay dispersant anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula:
  • X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof
  • a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene)
  • the detergent compositions of the invention when formulated for use in machine washing compositions, may comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to 3% by weight of the composition.
  • 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.
  • antifoam compound any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
  • Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a siUca component.
  • silicone antifoam compounds encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
  • Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
  • Other suitable antifoam 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 metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • Suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C1 -C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa- alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di- alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
  • high molecular weight fatty esters e.g. fatty acid triglycerides
  • fatty acid esters of monovalent alcohols e.g. fatty acid esters of monovalent alcohols
  • a preferred suds suppressing system comprises:
  • antifoam compound preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
  • silica at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound
  • silica/silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight;
  • a dispersant compound most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%, preferably 1% to 10% by weight;
  • a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544;
  • an inert carrier fluid compound most preferably comprising a Ci6-Ci8 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 EP-A-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-A-0210721 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.
  • suds suppressing systems comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxyhc polymers, such as copolymers of laic and acrylic acid.
  • compositions herein may also comprise from 0.01% 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 N-vinyUmidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.
  • 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:
  • Rj is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl;
  • R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
  • R ⁇ is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)- s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation.
  • Tinopal-CBS-X and Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • K ⁇ is anilino
  • R2 is N-2-hydroxyethyl-N-2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-(N-2- hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • R ⁇ is anilino
  • R2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid, sodium salt.
  • This particular brightener species are commercially marketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX by Ciba Geigy Corporation.
  • SRA Polymeric soil release agents, hereinafter "SRA" can optionally be employed in the present compositions. If utilized, SRA's will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the compositions.
  • Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.
  • Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide.
  • esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
  • Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1,2- ⁇ ropylene glycol (“PG”) in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water.
  • DMT dimethyl terephthalate
  • PG 1,2- ⁇ ropylene glycol
  • SRA's include the nonionic end-capped 1,2- propylene/polyoxyethylene terephthalate polyesters of U.S.
  • Gosselink et al. for example those produced by transesterification oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG").
  • SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6- dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S.
  • Gosselink for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S.
  • SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S.
  • methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution.
  • Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
  • SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage.
  • Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al..
  • Other classes include: (III) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.;
  • compositions of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
  • compositions contain from about 2% to about 10% by weight of an organic acid, preferably citric acid.
  • an organic acid preferably citric acid.
  • minor amounts e.g., less than about 20% by weight
  • neutralizing agents e.g., buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides and dyes, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25, 1981 (herein incorporated by reference), can be present.
  • composition of the invention can be made via a variety of methods, including dry-mixing, agglomerating, compaction, or spray-drying of the various compounds comprised in the detergent component, or mixtures of these techniques.
  • compositions herein can take a variety of physical forms including liquid, but preferably solid forms such as tablet, flake, pastille and bar, and preferably granular forms.
  • compositions in accord with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach.
  • Detergent compositions herein in particular laundry detergents, preferably have a bulk density of from 280 g/litre to 200 g/litre, or preferably from 300 g/litre or even 350g/litre or 420g/litre to 2000g litre or more preferably to 1500g/litre or 100 g/litre or even to 700g/litre.
  • the detergent compositions can include as an additional component a chlorine-based bleach.
  • a chlorine-based bleach since preferred detergent compositions of the invention are solid, most liquid chlorine-based bleaching will not be suitable for these detergent compositions and only granular or powder chlorine-based bleaches will be suitable.
  • the detergent compositions can be formulated such that they are chlorine-based bleach-compatible, thus ensuring that a chlorine based bleach can be added to the detergent composition by the user at the beginning or during the washing process.
  • the chlorine-based bleach is such that a hypochlorite species is formed in aqueous solution.
  • the hypochlorite ion is chemically represented by the formula OCT.
  • Those bleaching agents which yield a hypochlorite species in aqueous solution include alkali metal and alkaline earth metal hypochlorites, hypochlorite addition products, chloramines, chlorimines, chloramides, and chlorimides.
  • Specific examples of compounds of this type include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, l,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dichloramine T, chloramine B and Dichloramine B.
  • a preferred bleaching agent for use in the compositions of the instant invention is sodium hypochlorite, potassium hypochlorite, or a mixture thereof.
  • hypochlorite-yielding bleaching agents are available in solid or concentrated form and are dissolved in water during preparation of the compositions of the instant invention. Some of the above materials are available as aqueous solutions.
  • Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention.
  • an effective amount of the detergent composition it is meant from lOg to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
  • the composition is formulated such that it is suitable for hard-surface cleaning or hand washing.
  • the detergent composition is a pre-treatment or soaking composition, to be used to pre-treat or soak soiled and stained fabrics.
  • speckle particle is a preferred speckle particle of the invention.
  • Sodium carbonate particles having 75% of particles having a particle size of from 600 microns to 850 microns and 25 % of particles having a particle size of from 425 microns to 600 microns are obtained by agglomerating and sieving sodium carbonate powder. The thus obtained particles are sprayed with a Monastral blue BV paste solution and subsequently dried, obtaining speckle particles comprising lOOOppm of dye.
  • speckle particle is another preferred speckle particle of the invention.
  • Detergent base particles are obtained by mixing anionic surfactant, nonionic surfactant, phosphate or zeolite, carbonate, PEG 4000 and water, to obtain after drying a particle which comprises 20% anionic surfactants, 5% nonionic surfactants, 45% phosphate or zeolite A, 20% carbonate, 5% PEG 4000 and a balance of water.
  • the thus obtained particles are sieved and screened, thus obtaining particles which have 75% of particles having a particle size of from 600 microns to 850 microns and 25 % of particles having a particle size of from 425 microns to 600 microns.
  • the thus obtained particles are sprayed with a Pigmasol Green solution and subsequently dried, obtaining speckle particles comprising lOOOppm of dye.
  • Nai2( lO2SiO2)i2-27H2O having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis)
  • Citric acid Anhydrous citric acid
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m
  • MA/AA Copolymer of 4:6 maleic/acrylic acid, average molecular weight about 10,000
  • Protease Proteolytic enzyme having 3.3% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Savinase
  • Protease I Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591, sold by Genencor Int. Inc.
  • Alcalase Proteolytic enzyme having 5.3% by weight of active enzyme, sold by NOVO Industries A/S
  • Amylase Amylolytic enzyme having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T
  • Amylase II Amylolytic enzyme as disclosed in PCT/ US9703635 Lipase Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase
  • Lipolytic enzyme having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Ultra
  • Endolase Endoglucanase enzyme having 1.5% by weight of active enzyme, sold by NOVO Industries A/S
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino- 1.3.5- triazin-2-yl)amino) stilbene-2:2'-disulfonate
  • HEDP 1,1 -hydroxyethane diphosphonic acid PEGx Polyethylene glycol with a molecular weight of x (typically 4,000) PEO Polyethylene oxide, with an average molecular weight of 50,000
  • PVNO Polyvinylpyridine N-oxide polymer with an average molecular weight of 50,000
  • PVP VI Copolymer of polyvinylpyrolidone and vinyUmidazole with an average molecular weight of 20,000
  • SRP 1 Anionically end capped poly esters
  • SRP 2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer
  • PEI Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen
  • Opacifier Water based monostyrene latex mixture, sold by
  • compositions are pre-treatment compositions in accordance with the invention.
  • Non-cotton soil release polymer according to U.S. Patent 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995.
  • Non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., issued November 6, 1990.

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Abstract

The present invention provides a cleaning composition comprising speckle particles and other particles, whereby the amount of speckled particles is determined in particular by the mean particle size of the speckle particle Mncp and the mean particle size of the other particle and Mcp, provided that the level of the speckle particle is from 2 % to 10 % by weight, Mncp is from 100 microns to 1100 microns and Mcp is from 100 microns to 1100 microns.

Description

Cleaning Compositions Containing Speckle Particles
Technical Field
The invention relates to cleaning compositions comprising speckle particles and other particles of selected mean particle sizes and present at selected levels.
Background to the Invention
In recent years, detergent manufacturers have introduced in their products small amounts of coloured or dyed particles or speckles. It has been found that the detergent users associate the coloured product with improved cleaning that the consumer acceptance of product comprising coloured particles is normally higher than product not comprising such coloured particles.
These detergents are often obtained by spraying-on an aqueous solution of a specific dye onto hygroscopic material or directly onto the final detergent base particles and subsequently drying the thus dyed materials or particles. A problem associated with this method is that the hygroscopic material absorbs large amount of water which may result in caking and that introduction of water to the final detergent particles can result in caking of the product. This is particularly a problem when higher amounts of aqueous dye-solution need to be used, for example, when very diluted dye solutions are to be used, or strongly dyed particles are needed or the dye is absorbed by the material or particles which are to be dyed.
Another problem associated with detergents comprising large amounts of dye per particle can be that the dye can 'bleed' in the presence of water. This may be the case when the detergent is made by spraying on large amounts of aqueous dye solutions, or when the detergent comprises large amount of hygroscopic material or of course, when the detergents are introduced to the washing or cleaning liquid. This 'bleeding' may cause colour changes of the product and the packing material. Moreover, under certain conditions, the dye or the dye particles which may deposit on the fabrics, can 'bleed' on the fabrics and cause colour changes on the washed fabric.
Also, it has now been found to be essential that the dye in the product is evenly applied at the surface of the particles and throughout the product, to avoid localised high concentrations of dye, which may amount to any of the above problems.
However, despite the problems related to the presence of large amounts of dye in the products, it may be desirable to have a high level of coloured particles present in the product.
The inventors have now found a means to introduce large amounts of dyed particles or speckles in a cleaning product without incurring any of the before mentioned problems. Firstly, the inventors have found that when only particles of a specific mean particle size are dyed, a larger number of particles can be present in the cleaning composition, without incurring any of the above problems. It has been found that the selection of particles of a specific particle size ensures a more efficient and controlled dyeing of the particles, which enables the effective use of small amounts of dye per particle whilst obtaining a homogeneously dyed particle. Secondly, the particles preferably have a relatively high density to reduce the absorption of the dye-solution. Hereby, the amount of dye required can be minimised, thus reducing the chance of bleeding of the dye or colouring of the fabrics in the washing or cleaning process. It has also been found that, depending on the specific particle size of the speckles and the other particle of the product and the colour intensity of the dye, an optimum colour appearance of the product can be obtained with a minimum amount of dye.
Furthermore, when the other particles of the product are also of a specific particle size, a homogeneously distribution of the dye throughout the product can be obtained by reduction of segregation of the particles and thus a reduction of the formation of localised high concentrations of dye. This will also amount to a reduction of the chance of colour changes in the products, packaging material and moreover of the fabrics in the washing or cleaning process.
Furthermore, it has been found that when the particles are dyed, then being speckles, and optionally dried prior to addition to the other particles, a product is obtained which has a reduced risk of caking. Furthermore, more homogeneously dyed particles are obtained by this method, which allows introduction of higher amounts of dyed particles in the products.
Summary of the invention
The present invention provides a cleaning composition comprising speckle particles and other particles, whereby the amount of speckled particles in percentage by weight of the composition (CP%) is:
2
2 xf 1.5 Mncp - Mcp CP (%) - 10 β >■ 1.5 Mncp J
wherein Mncp is the mean particle size of the other particles and Mcp is the mean particle size of the speckle particles, provided that CP is from 2% to 10% by weight, Mncp is from 100 microns to 1100 microns and Mcp is from 100 microns to 1100 microns.
In a preferred embodiment the particles in the composition are such that the colour difference of the speckled particles compared to the other particles (ΔE) is from 15 to 40,
ΔE being V (ΔL)2+(Δa)2+ (Δb)2 ΔL being L(speckle particle) - L(othCTParticles>- , namely being the whiteness difference between the speckle particles and the other particles, Δa being a(speclde particle) - a(other p"thsta) , namely being the greenness/redness difference between the speckled particles and the other particles, Δb being b(spedde particles) - b(other vu&im) , namely being the blueness/ yellowness difference between the speckle particles and the other particles as defined by the Hunter colour analysis method.
The compositions are preferably solid laundry or dish washing or hard-surface cleaning compositions.
The invention also relates to a process for making the compositions and the speckled particle thereof .
The invention also relates to the use of speckle particles at a level CP, as defined above, being between 2% and 10% by weight, in cleaning compositions comprising also other particles, having the specific particle sizes as defined above. Hereby, the colour or whiteness difference between the speckled particles and the other particles is preferably between 15 and 40, as defined above.
Detailed description of the invention
Speckle particles
The speckled particles of the invention may have any colour or whiteness other than the colour or whiteness of the other particles of the compositions of the invention.
Therefore, the at least one of the values ΔL, Δa or Δb, as defined herein, should not be O.
The speckle particle is preferably not white. Preferably, the speckled particle is dyed, preferably with an aqueous solution of a dyestuff as described hereinafter. The compositions comprise the coloured particles at a level of from 2% to 10%. In accord with the invention, the precise level of speckle particles present in the composition depends in particular on the particle size of the speckled particles and the other particles, as is defined by the formula above.
It may be preferred that the particle size of the speckle particles and the other particles are selected such that more than 3% or even more than 3.8% or even more than 4.1% by weight of speckled particles are present.
The speckle particle has a mean particle size of 100 microns to 1100 microns, preferably from 250 microns to 850 microns, it may be preferred that the particle size is from 250 or 350 microns to 590 microns.
The particles preferably are such that 80% by weight of the particles has a particle size of more than 100 microns (more than 80% by weight of the particles on Tyler sieve mesh 100) and less than 10% by weight of the particles has a particle size of more than 1180 microns (through Tyler mesh sieve 14); or more preferably 80% by weight of the particles has an particle size of more than 250 microns and less than 10% by weight of the particles has a particle size of more than 850.
The speckled particle preferably comprises one or more ingredients, commonly employed in cleaning compositions, such as detergent actives, fillers, organic or inorganic builders, alkalinity or acid sources, including enzymes or enzyme prills, (poly) carboxylic acids or salts thereof, inorganic salts, including phosphates, sulphates, carbonates. It may be preferred that the particle is a base granule of the cleaning compositions, but it may be preferred that the particle comprises inorganic or organic salts, preferably carbonate, or acids, preferably citric acid.
It may be preferred that the particle has a pore size which is at least 20 microns. It may be preferred that the density of the particle is at least 300 g/litre, preferably up to 2000 g/litre, more preferably from 420 g/litre to 1500g/litre.
The ratio of the mean particle size of the speckle particle to the mean particle size of the other particle is preferably from 1:2 to 2.5:1, or more preferably from 1:1 to 2:1.
The speckle particle preferably comprise a dye to provide the colouring, preferably present in low levels, preferably up to 2% or more preferably up to 1% or even up to 0.7% and it may be preferred that the dye is present a t a level of below 0.5% or even 0.2% or even 0.1% by weight of the speckle particle.
The speckle particles preferably have a colour intensity such that the colour difference of the speckle particles compared to the other particles (ΔE) is from 15 to 40, or more preferably between 20 and 35, as defined by the formula
ΔE being V (ΔL)2+(Δa)2+ (Δb)2
ΔL being the whiteness difference between the speckle particles and the non-speckle, other particles, Δa being the greenness/redness difference between the speckle particles and the other, non-speckle particles, Δb being the blueness/yellowness difference between the speckle particles and the non-speckle particles as defined by the Hunter colour analysis method, as described in for example the 'Manual of Hunter analysis equipment' and in: 'Hunter, R.S. 'Photoelectric color difference meter', Journal of the Optical Society of America, Vol. 48, 1958, pp 985-995. In the Hunter analysis method used herein, no UV-lens filter apparatus is used.
The other particle of the composition
The compositions of the invention comprise also other particles, not being the speckle particles of the invention, meaning for the purpose of the invention that they do not have the same colour or whiteness as the speckle particles. Therefore, at least one of the values ΔL, Δa or Δb between the other particles and the speckle particles should not be 0, as defined herein. The other particles may comprises any ingredient or mixtures thereof commonly employed in cleaning compositions, as described herein after. It may be preferred that the other particles are detergent base particles, comprising for example one or more surfactants, organic and/or inorganic builders, bleach, perfumes, polymeric compounds, enzymes, suds suppressers or mixtures thereof. The other particle has a mean particle size of 100 microns to 1100 microns, preferably from 250 microns to 850 microns, and it may be preferred that the mean particle size is from 250 or 350 microns to 590 microns.
The particles preferably are such that 80% by weight of the particles has a particle size of more than 100 microns (more than 80% by weight of the particles on Tyler sieve mesh 100) and less thanl0% by weight of the particles has a particle size of more than 1180 microns (through Tyler mesh sieve 14); or more preferably 80% by weight of the particles has an particle size of more than 250 microns and less than 10% by weight of the particles has a particle size of more than 850 microns.
The other particle of the invention may be prepared by any conventional method for making detergent particles, including agglomeration, extrusion, crutching, dry mixing, spray-drying.
It may be preferred that the density of the other particle is at least 300 g/litre, preferably up to 1200g/litre, more preferably from 380 g/litre to 950 g/litre or even to 780 g/litre.
Dye
The speckle particles of the invention are preferably dyed particles. The dye used for dyeing the particles as used herein can be a dye stuff or an aqueous solution of a dye stuff. It may be preferred that the dye is an aqueous solution comprising a dyestuff, at any level to obtain suitable dyeing of the particles, preferably such that levels of dye solution are obtained up to 2% by weight of the speckle particle, or more preferably up to 0.5% by weight, as described above. Optionally, the dye also comprising other ingredients such as organic binder materials.
The dyestuff can be any suitable dyestuff. Specific examples of suitable dyestuff s include E104 - food yellow 13 (quinoline yellow), El 10 - food yellow 3 (sunset yellow FCF), El 31 - food blue 5 (patent blue V), Ultra Marine blue (trade name), E133 - food blue 2 (brilliant blue FCF), E140 - natural green 3 (chlorophyll and chlorphyllins), E141 and Pigment green 7 (chlorinated Cu phthalocyanine). Preferred dyestuffs may be Monastral Blue BV paste (trade name) and/ or Pigmasol Green (trade name).
Making process
The composition of the invention is preferably obtainable by a process comprising the steps of dyeing particles of a mean particle size of from 100 to 1100 microns, preferably 250 to 850 microns, with a dye, preferably an aqueous solution of a dyestuff, to obtain speckle particles and addition of the speckle particles to other particles, of a mean particle size of 100 to 1100 microns, preferably 250 to 850 microns.
The speckle particle of the invention are preferably prepared by spraying-on the dye, preferably an aqueous solution of a dyestuff. This process preferably includes two steps namely a spraying-on step and a drying step. These may be carried out in stepwise fashion, or alternatively both steps may occur simultaneously.
The spraying-on step preferably comprises spraying an aqueous mixture comprising the dyestuff onto a particle. This spraying-on can be achieved by any spraying process commonly known to the person skilled in the art.
Preferably, the spraying-on is carried out whilst the particles are in motion, for example by agitation. Suitable agitation means comprise drum mixers, KM Loedige (trade name) mixers, V blenders, spray granulators, fluidised beds, turbodisers (trade name) and Schugi (trade name) mixers.
The drying step involves drying the particles obtained from the first step. This drying process may be carried out using any known drying apparatus such as fluidised bed dryers and granulator dryers.
It may be preferred that the spraying-on and drying steps occur simultaneously, most preferably being carried out as a continuous process in a fluidised bed drier.
The finished particles preferably have a moisture content of from 0.1 % to 5 % , preferably from o.5% to 3.5% by weight of the finished particle.
Cleaning Compositions
The cleaning compositions of the invention are preferably solid laundry, dishwashing or hard-surface cleaning compositions, preferably in the form of granules, extrudates, flakes or tablets.
The compositions in accord with the invention may also contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition or component, and the precise nature of the washing operation for which it is to be used.
The compositions of the invention preferably contain one or more additional detergent components selected from surfactants, bleaches, bleach catalysts, alkalinity systems, builders, phosphate-containing builders, organic polymeric compounds, enzymes, suds suppressors, lime soap, dispersants, soil suspension and anti- redeposition agents soil releasing agents, perfumes, brightners, photobleaching agents and additional corrosion inhibitors. Surfactant
The compositions in accord with the invention preferably contain one or more surfactants selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
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, 1981.
Where present, ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
Anionic Surfactant
The compositions in accord with the present invention preferably comprise an additional anionic surfactant. 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 and sulfonate surfactants are preferred.
Highly preferred are surfactants systems comprising a sulfonate and a sulfate surfactant, preferably a linear or branched alkyl benzene sulfonate and alkyl ethoxylsulfates, as described herein, preferably combined with a cationic surfactants as described herein.
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 sulfosuccinate (especially saturated and unsaturated C, ,-,-C1 8 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated Cfi-C14 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-C17 acyl-N-(Cj-C4 alkyl) and -N-(Cj-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
Alkyl sulfate surfactants are preferably selected from the linear and branched primary Clθ"Ci8 alkyl sulfates, more preferably the C\ \-C\ζ branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the CiO"Cl8 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\ 1-C18, most preferably Ci \-C\ 5 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124. Anionic Sulfonate Surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, Cg-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
Anionic Carboxylate Surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2θ)x
CH2C00"M+ wherein R is a Cg to Cjg alkyl group, x ranges from O 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-(CHRι -CHR2-O)-R3 wherein R is a
C6 to Cjg alkyl group, x is from 1 to 25, Ri and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of 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-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl- 1-nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-l-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 C5-C17 linear or branched alkyl or alkenyl group,
R! is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
Alkoxylated Nonionic Surfactant
Essentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.
Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
Nonionic Alkoxylated Alcohol Surfactant
The condensation products of aliphatic alcohols with from 1 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 Polyhydroxy Fatty Acid Amide Surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONR1Z wherein : Rl is H, Ci -C4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C\ or C2 alkyl, most preferably C\ alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C11-C1 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 Fatty Acid Amide Surfactant
Suitable fatty acid amide surfactants include those having the formula: R^CON R^)2 wherein R > is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R^ is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4θ)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 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
Preferred alkylpolyglycosides have the formula:
R2θ(CnH2nO)t(glycosyl)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. Amphoteric Surfactant
Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula R3(OR )XNO(R5)2 wherein R^ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to
26 carbon atoms; R^ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are Cjθ" i8 alkyl dimethylamine oxide, and CJQ-18 acylamido alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic Surfactant
Zwitterionic surfactants can also be incorporated into the detergent compositions in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
Suitable betaines are those compounds having the formula R(R')2N+R2COO" wherein R is a Cg-C^ hydrocarbyl group, each Rl is typically C1-C3 alkyl, and R2 is a C1-C5 hydrocarbyl group. Preferred betaines are C12-I8 dimethyl-ammonio hexanoate and the CJQ-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein. Cationic Surfactants
Suitable cationic surfactants to be used in the detergent herein include the quaternary ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono
C6"Ci6> preferably Cg-Cjo N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants. The cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group.
Suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
In one preferred aspect the ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms. The atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain. Thus spacer groups having, for example, -O-O- (i.e. peroxide), - N-N-, and -N-O- linkages are excluded, whilst spacer groups having, for example - CH2-O- CH2- and -CH2-NH-CH2- linkages are included. In a preferred aspect the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain. Cationic mono-alkoxylated amine surfactants
Highly preferred herein are cationic mono-alkoxylated amine surfactant preferably of the general formula I:
Figure imgf000019_0001
wherein R is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about
14 carbon atoms; R2 and R^ are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R2 and R- are methyl groups; R^ is selected from hydrogen (preferred), methyl and ethyl; X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.
Preferably the ApR4 group in formula I has p=l and is a hydroxyalkyl group, having no greater than 6 carbon atoms whereby the — OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred ApR4 groups are — CH CH2OH, — CH2CH2CH OH, — CH CH(CH3)OH and — CH(CH3)CH2OH, with — CH2CH2OH being particularly preferred. Preferred R! groups are linear alkyl groups. Linear R groups having from 8 to 14 carbon atoms are preferred. Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula
Figure imgf000020_0001
wherein R! is CjO' lS hydrocarbyl and mixtures thereof, especially CJQ' H alkyl, preferably CJO and Cj2 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
As noted, compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH2O] and [CH2CH(CH3θ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and or i-Pr units.
The levels of the cationic mono-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1% to 20%, more preferably from 0.2% to 7%, most preferably from 0.3% to 3.0% by weight of the composition.
Cationic bis-alkoxylated amine surfactant
The cationic bis-alkoxylated amine surfactant preferably has the general formula II:
Figure imgf000020_0002
wherein R! is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms; R2 is an alkyl group containing from one to three carbon atoms, preferably methyl; R- and R4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl, X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality. A and A can vary independently and are each selected from Ci -C4 alkoxy, especially ethoxy,
(i.e., -CH2CH2O-), propoxy, butoxy and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.
Highly preferred cationic bis-alkoxylated amine surfactants for use herein are of the formula
Figure imgf000021_0001
wherein R* is CI Q-CJS hydrocarbyl and mixtures thereof, preferably C\Q, Cj2> C14 alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general cationic bis-alkoxylated amine structure noted above, since in a preferred compound Rl is derived from (coconut) Cl2"Cl4 alkyl fraction fatty acids, R2 is methyl and ApR^ and A'qR4 are each monoethoxy.
Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:
Figure imgf000021_0002
wherein R* is C10-C18 hydrocarbyl, preferably C10-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R2 is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide. Other compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH2O] and [CH2CH(CH3O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
Perhydrate Bleaches
An preferred additional components of the compositions is a perhydrate bleach, such as metal perborates, metal percarbonates, particularly the sodium salts. Perborate can be mono or tetra hydrated. Sodium percarbonate has the formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid.
Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.
Organic Peroxyacid Bleaching System
A preferred feature of the composition 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. Peroxyacid Bleach Precursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as
O X-C-L
where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is
O X-C-OOH
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 O-acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 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:
Figure imgf000024_0001
O N Λ O
-N-C-R1 - N — N-C-CH— R4
R3 R3 Y
I U
Y
R3 I -O-CH=C-CH=CH2 -O-CH=C-CH=CH2
Figure imgf000024_0002
and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R is an alkyl chain containing from 1 to 8 carbon atoms, R is
H or R 3 , and Y is H or a solubilizing group. Any of R 1 , R3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
The preferred solubilizing groups are -SO3 "M+, -CO2 "M+, -SO4 "M+, -N+(R3)4X"
3 - + - + 3 and O<~N(R ) and most preferably -SO., M and -CO2 M wherein R 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, methylsulfate or acetate anion.
Alkyl Percarboxylic Acid Bleach Precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis.
Preferred alkyl percarboxylic precursor compounds of the 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 contains 1, 2 and 6 carbon atoms. Tetraacetyl 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 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide Substituted Plkyl Peroxyacid Precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
R 1 N — R< R 1 N Rz
O R5 O or R5 O O
wherein R* is an alkyl group with from 1 to 14 carbon atoms, R2 is an alkylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
Perbenzoic Acid Precursor
Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable O-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 N- benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl group- containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid. Cationic Peroxyacid Precursors
Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
Typically, 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 halide 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; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
Examples of preferred cationic peroxyacid precursors are 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, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
Benzoxazin Organic Peroxyacid 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:
Figure imgf000028_0001
wherein R, is H, alkyl, alkaryl, aryl, or arylalkyl.
Preformed Organic Peroxyacid
The detergent composition 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:
Figure imgf000028_0002
wherein R* 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, aryl, or alkaryl group containing 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A- 0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
Bleach Catalyst
The composition can contain a transition metal containing bleach catalyst.
One suitable type of bleach catalyst is a catalyst system comprising a transition 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 ethylenediaminetetraacetic 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 Mnl ^2^-0)3 ( 1 ,4,7-trimethyl- 1,4, 7-triazacyclononane)2-(PF6)2, MnH 2(u-
O)ι(u-OAc)2(l,4,7-trimethyl-l,4,7-triazacyclononane)2-(Clθ4)2, MnΪV4(u-
O)6(l,4,7-triazacyclononane) -(Clθ4)2, MnIIlMnIV 4(u-O)ι(u-OAc)2.(l,4,7- trimethyl-l,4,7-triazacyclononane)2-(Clθ4)3, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include l,5,9-trimethyl-l,5,9-triazacyclododecane, 2-methyl- 1,4,7-triazacyclononane, 2-methyl-l,4,7-triazacyclononane, 1,2,4,7-tetramethyl- 1,4,7-triazacyclononane, and mixtures thereof.
The bleach catalysts useful herein may also be selected as appropriate for the present invention. 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(l,4,7-trimethyl-l,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. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands are of the formula:
R2 R3
R1-N=C-B-C=N-R4
wherein R , R2, R- , and R4 can each be selected from H, substituted alkyl and aryl groups such that each R!-N=C-R2 and R3-C=N-R form a five or six-membered ring. Said ring can further be substituted. B is a bridging group selected from O, S.
CR5R , NR and C=O, wherein R^, R^, and R^ can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2-bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co(2,2,-bispyridylamine)Cl2, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)2θ2Clθ4, Bis-(2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.
Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N- dentate ligands, including
Figure imgf000031_0001
[Bipy2MnH (u-
O)2MnIVbipy2]-(ClO4)3.
Other bleach catalysts are described, for example, in European patent application, publication 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 application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (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).
The bleach catalyst is typically used in a catalytically effective amount in the compositions and processes herein. By "catalytically effective amount" is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance bleaching and removal of the stain or stains of interest from the target substrate. The test conditions will vary, depending on the type of washing appliance used and the habits of the user. Some users elect to use very hot water; others use warm or even cold water in laundering operations. Of course, the catalytic performance of the bleach catalyst will be affected by such considerations, and the levels of bleach catalyst used in fully-formulated detergent and bleach compositions can be appropriately adjusted. As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 1 ppm to about 200 ppm of the catalyst species in the wash liquor. To illustrate this point further, on the order of 3 micromolar manganese catalyst is effective at 40°C, pH 10 under European conditions using perborate and a bleach precursor. An increase in concentration of 3- 5 fold may be required under U.S. conditions to achieve the same results.
Water-Soluble Builder Compound
The compositions in accord with the present invention preferably contain a water- soluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight, preferably from 10% to 60% by weight, most preferably from 15% to 40% by weight of the composition.
The detergent compositions of the invention preferably comprise phosphate- containing builder material. Preferably present at a level of from 0.5% to 60%, more preferably from 5% to 50%, more preferably from 8% to 40.
The phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.
Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing. The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa- 1,1, 3 -propane tricarboxylates described in British Patent No. 1,387,447. The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of from 0.1% to 15%, more preferably from 0.5% to 8% by weight of the composition.
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-ρropane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components. Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.
Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
Partially Soluble or Insoluble Builder Compound
The compositions in accord with the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 0.5% to 60% by weight, preferably from 5% to 50% by weight, most preferably from 8% to 40% weight of the composition.
Examples of largely water insoluble builders include the sodium aluminosilicates.
Suitable aluminosilicate zeolites have the unit cell formula Naz[(AlO2)z(SiO2)y].
XH2O 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 Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:
Na 12 [AlO2) 12 (SiO2)ι2]. xH2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6 [(AlO2)86(Siθ2)l06]- 276 H2O.
Another preferred aluminosilicate zeolite is zeolite MAP builder.
The zeolite MAP can be present at a level of from 1% to 80%, more preferably from 15% to 40% by weight of the compositions.
Zeolite MAP is described in EP 384070 A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
In a preferred aspect the zeolite MAP detergent builder has a particle size, expressed as a dso value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.
The dso value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d5Q values are disclosed in EP 384070A. Heavy metal ion sequestrant
The compositions 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 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most preferably from 0.3% to 2% by weight of the compositions or component
Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1- 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, 1,1 hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.
Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2- hydroxypropylenediamine disuccinic acid or any salts thereof.
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 sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl- 3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The β-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N- monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.
EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A- 528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-l,2,4-tricarboxylic acid are alos suitable. Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine- N,N-disuccinic acid (EDDS) and 1,1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
Enzyme
Another preferred ingredient useful in the compositions herein is one or more additional enzymes.
Preferred additional enzymatic materials include the commercially available Upases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
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, α-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, Duramyl and BAN by Novo Industries A/S. Highly preferred amylase enzymes maybe those described in PCT/ US 9703635, and in WO95/26397 and WO96/23873.
Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight 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 ofHumicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes. which is described in Granted European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
Organic Polymeric Compound
Organic polymeric compounds are preferred additional components of the compositions herein 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, including quaternised ethoxylated (poly) amine clay-soil removal/ anti-redeposition agent in accord with the invention.
Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%, most preferably from 0.5% to 10% by weight of the compositions.
Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.
The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629. 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, hydroxypropylmethylcellulose and hydroxyethylcellulose.
Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
Highly preferred polymeric components herein are cotton and non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent 5,415,807, Gosselink et al., and in particular according to US application no.60/051517.
Another organic compound, which is a preferred clay dispersant anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula:
Figure imgf000040_0001
wherein X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0; for cationic monoamines (b=0), 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-B- 011965 and US 4,659,802 and US 4,664,848.
Suds Suppressing System
The detergent compositions of the invention, when formulated for use in machine washing compositions, may comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to 3% by weight of the composition.
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 antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a siUca 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 hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units. Other suitable antifoam 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 metal salts such as sodium, potassium, and lithium salts, and ammonium 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 C1 -C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa- alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di- alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
A preferred suds suppressing system comprises:
(a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
(i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam 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 50%, 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 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 DCO544, commercially available from DOW Corning under the tradename DCO544;
(c) an inert carrier fluid compound, most preferably comprising a Ci6-Ci8 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 EP-A-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-A-0210721 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.
Other highly preferred suds suppressing systems comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxyhc polymers, such as copolymers of laic and acrylic acid.
Polymeric Dye Transfer Inhibiting Agents
The compositions herein may also comprise from 0.01% 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 N-vinyUmidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.
Optical Brightener
The 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:
Figure imgf000044_0001
wherein Rj is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl;
R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, R\ is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)- s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-CBS-X and Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein. When in the above formula, K\ is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2- hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]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, R\ is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid, sodium salt. This particular brightener species are commercially marketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX by Ciba Geigy Corporation.
Polymeric Soil Release Agent
Polymeric soil release agents, hereinafter "SRA", can optionally be employed in the present compositions. If utilized, SRA's will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the compositions.
Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.
Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide. Such esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-ρropylene glycol ("PG") in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the nonionic end-capped 1,2- propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711,730, December 8, 1987 to Gosselink et al., for example those produced by transesterification oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6- dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al., the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400.
SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. 4,000,093, December 28, 1976 to Nicol, et al.; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution. Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
Additional classes of SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al.. Other classes include: (III) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.;
Other Optional Ingredients
Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
Highly preferred compositions contain from about 2% to about 10% by weight of an organic acid, preferably citric acid. Also, preferably combined with a carbonate salt, minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides and dyes, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25, 1981 (herein incorporated by reference), can be present.
Form of the Compositions
The composition of the invention can be made via a variety of methods, including dry-mixing, agglomerating, compaction, or spray-drying of the various compounds comprised in the detergent component, or mixtures of these techniques.
The compositions herein can take a variety of physical forms including liquid, but preferably solid forms such as tablet, flake, pastille and bar, and preferably granular forms.
The compositions in accord with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach.
Detergent compositions herein, in particular laundry detergents, preferably have a bulk density of from 280 g/litre to 200 g/litre, or preferably from 300 g/litre or even 350g/litre or 420g/litre to 2000g litre or more preferably to 1500g/litre or 100 g/litre or even to 700g/litre.
Chlorine-Based Bleach
The detergent compositions can include as an additional component a chlorine-based bleach. However, since preferred detergent compositions of the invention are solid, most liquid chlorine-based bleaching will not be suitable for these detergent compositions and only granular or powder chlorine-based bleaches will be suitable. Alternatively, the detergent compositions can be formulated such that they are chlorine-based bleach-compatible, thus ensuring that a chlorine based bleach can be added to the detergent composition by the user at the beginning or during the washing process.
The chlorine-based bleachis such that a hypochlorite species is formed in aqueous solution. The hypochlorite ion is chemically represented by the formula OCT.
Those bleaching agents which yield a hypochlorite species in aqueous solution include alkali metal and alkaline earth metal hypochlorites, hypochlorite addition products, chloramines, chlorimines, chloramides, and chlorimides. Specific examples of compounds of this type include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, l,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dichloramine T, chloramine B and Dichloramine B. A preferred bleaching agent for use in the compositions of the instant invention is sodium hypochlorite, potassium hypochlorite, or a mixture thereof. A preferred chlorine-based bleach can be Triclosan (trade name).
Most of the above-described hypochlorite-yielding bleaching agents are available in solid or concentrated form and are dissolved in water during preparation of the compositions of the instant invention. Some of the above materials are available as aqueous solutions.
Laundry Washing Method
Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from lOg to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
In a preferred use aspect the composition is formulated such that it is suitable for hard-surface cleaning or hand washing. In another preferred aspect the detergent composition is a pre-treatment or soaking composition, to be used to pre-treat or soak soiled and stained fabrics.
Example I
The following speckle particle is a preferred speckle particle of the invention. Sodium carbonate particles, having 75% of particles having a particle size of from 600 microns to 850 microns and 25 % of particles having a particle size of from 425 microns to 600 microns are obtained by agglomerating and sieving sodium carbonate powder. The thus obtained particles are sprayed with a Monastral blue BV paste solution and subsequently dried, obtaining speckle particles comprising lOOOppm of dye.
Example II
The following speckle particle is another preferred speckle particle of the invention.
Detergent base particles are obtained by mixing anionic surfactant, nonionic surfactant, phosphate or zeolite, carbonate, PEG 4000 and water, to obtain after drying a particle which comprises 20% anionic surfactants, 5% nonionic surfactants, 45% phosphate or zeolite A, 20% carbonate, 5% PEG 4000 and a balance of water. The thus obtained particles are sieved and screened, thus obtaining particles which have 75% of particles having a particle size of from 600 microns to 850 microns and 25 % of particles having a particle size of from 425 microns to 600 microns. The thus obtained particles are sprayed with a Pigmasol Green solution and subsequently dried, obtaining speckle particles comprising lOOOppm of dye.
Abbreviations used in Examples
In the detergent compositions, the abbreviated component identifications have the following meanings:
LAS Sodium linear Cj ι_i3 alkyl benzene sulfonate
TAS Sodium tallow alkyl sulfate CxyAS Sodium C}x - Ciy alkyl sulfate
C46SAS Sodium Cj4 - Cj6 secondary (2,3) alkyl sulfate
CxyEzS Sodium Cjx-Ciy alkyl sulfate condensed with z moles of ethylene oxide
CxyEz Clχ-Ciy predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide
QAS R2.N+(CH3)2(C2H4OH) with R2 = Cι2 - CM
QAS 1 R2.N+(CH3)2(C2H4OH) with R2 = C8 - Ci i SADS Sodium Cι4-C22 alkyl disulfate of formula 2-(R).C4
H7.-l,4-(SO4-)2 where R = Cι0_C18
SADE2S Sodium Cι4-C22 alkyl disulfate of formula 2-(R).C
H7.-l,4-(SO4-)2 where R = C10-C18, condensed with z moles of ethylene oxide
MES x-sulpho methylester of Cig fatty acid APA Cg - CI Q amido propyl dimethyl amine Soap Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut fatty acids
STS Sodium toluene sulphonate CFAA C12-C14 (coco) alkyl N-methyl glucamide
TFAA Cl6" l8 lkyl N-methyl glucamide
TPKFA Cl6- l8 topped whole cut fatty acids
STPP Anhydrous sodium tripolyphosphate TSPP Tetrasodium pyrophosphate
Zeolite A Hydrated sodium aluminosilicate of formula
Nai2( lO2SiO2)i2-27H2O having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis)
NaSKS-6 Crystalline layered silicate of formula δ- Na2Si2θ5
Citric acid Anhydrous citric acid
Borate Sodium borate
Carbonate Anydrous sodium carbonate with a particle size between 200μm and 900μm
Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm
Silicate Amorphous sodium silicate (SiO2:Na2O = 2.0:1)
Sulfate Anhydrous sodium sulfate Mg sulfate Anhydrous magnesium sulfate Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425 μm and 850μm
MA/AA Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 70,000
MA/AA (1) Copolymer of 4:6 maleic/acrylic acid, average molecular weight about 10,000
AA Sodium polyacrylate polymer of average molecular weight 4,500 CMC Sodium carboxymethyl cellulose
Cellulose ether Methyl cellulose ether with a degree of polymerization of 650 available from Shin Etsu Chemicals
Protease Proteolytic enzyme, having 3.3% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Savinase
Protease I Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591, sold by Genencor Int. Inc.
Alcalase Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVO Industries A/S
Cellulase Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Carezyme
Amylase Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T
Amylase II Amylolytic enzyme, as disclosed in PCT/ US9703635 Lipase Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase
Lipase (1) Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Ultra
Endolase Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries A/S
PB4 Sodium perborate tetrahydrate of nominal formula NaBθ2.3H2O.H2θ2
PB1 Anhydrous sodium perborate bleach of nominal formula NaBθ2-H2θ2 Percarbonate Sodium percarbonate of nominal formula 2Na2CO3.3H2O2
DOBS Decanoyl oxybenzene sulfonate in the form of the sodium salt
DPDA Diperoxydodecanedioc acid NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt
NACA-OBS (6-nonamidocaproyl) oxybenzene sulfonate LOBS Dodecanoyl oxybenzene sulfonate in the form of the sodium salt
DOBS Decanoyl oxybenzene sulfonate in the form of the sodium salt
DOBA Decanoyl oxybenzoic acid TAED Tetraacetylethylenediamine DTPA Diethylene triamine pentaacetic acid DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename Dequest 2060
EDDS Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its sodium salt.
Photoactivated Sulfonated zinc phthlocyanine encapsulated in bleach (1) dextrin soluble polymer
Photoactivated Sulfonated alumino phthlocyanine encapsulated in bleach (2) dextrin soluble polymer
Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino- 1.3.5- triazin-2-yl)amino) stilbene-2:2'-disulfonate
HEDP 1,1 -hydroxyethane diphosphonic acid PEGx Polyethylene glycol, with a molecular weight of x (typically 4,000) PEO Polyethylene oxide, with an average molecular weight of 50,000
TEPAE Tetraethylenepentaamine ethoxylate PVI Polyvinyl imidosole, with an average molecular weight of 20,000
PVP Polyvinylpyrolidone polymer, with an average molecular weight of 60,000
PVNO Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000
PVP VI Copolymer of polyvinylpyrolidone and vinyUmidazole, with an average molecular weight of 20,000
QEA bis((C2H5O)(C2H4O)n)(CH3) -N+-C6H12-N+-
(CH3) bis((C2H5O)-(C2H O))n, wherein n = from 20 to 30
SRP 1 Anionically end capped poly esters SRP 2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer
PEI Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen
Silicone antifoam Polydimethylsiloxane foam controller with siloxane- oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1
Opacifier Water based monostyrene latex mixture, sold by
BASF Aktiengesellschaft under the tradename Lytron
621
Wax Paraffin wax Speckle I as described in the example I above Speckle II as described in the example II above In the following examples all levels are quoted as % by weight of the composition:
Example 1
The following detergent formulations are in accord with the invention.
Figure imgf000056_0001
Figure imgf000057_0001
Example 2
The following granular detergent formulations are in accord with the invention.
Figure imgf000057_0002
Figure imgf000058_0001
Figure imgf000059_0001
Example 3
The following granular detergent formulations are in accord with the invention.
Figure imgf000060_0001
Figure imgf000061_0001
Example 4
The following compositions are pre-treatment compositions in accordance with the invention
Figure imgf000061_0002
Figure imgf000062_0001
Figure imgf000062_0002
Figure imgf000063_0001
Figure imgf000064_0001
1. Non-cotton soil release polymer according to U.S. Patent 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995.
2. Non-cotton soil release polymer according to US application no.60/051517
Example 6
CC DD EE FF
Figure imgf000064_0002
Figure imgf000065_0001
Figure imgf000066_0001
1. Non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., issued November 6, 1990.
2. Non-cotton soil release polymer according to US application no.60/051517

Claims

Claims
1. A cleaning composition comprising speckle particles and other particles, whereby the amount of speckle particles in percentage by weight of the composition (CP%) is:
2 Xf 1.5 Mncp - Mcp ] CP (%) = 10 ╬▓ L 1.5 Mncp J
wherein Mncp is the mean particle size of the speckle particle and Mcp is the mean particle size of the other particle, provided that CP is from 2% to 10% by weight, Mncp is from 100 microns to 1100 microns and Mcp is from 100 microns to 1100 microns.
2. A cleaning composition according to Claim 1, wherein the colour difference of speckle particles compared to the other particles (ΔE) is from 15 to 40, preferably
Figure imgf000067_0001
ΔE being V (ΔL)2+(Δa )2+ (Δb)2
ΔL being L(spcclde tHύsk) - L(otherpartie,es)- , being the whiteness difference between the speckle particles and the other particles, Δa being ^'v^) _ a«>t er particles) ^ being the greenness/redness difference between the speckled particles and the other particles, Δb being b(speclde VK&M> - b(oher ""^ , being the blueness/ yellowness difference between the speckle particles and the other particles.
3. A composition according to Claim 1 or 2, whereby the Mcp is from 250 microns to 850 microns, more preferably from 350 microns to 590 microns.
4. A composition according to any preceding claim wherein the ratio of Mcp to Mncp is from 1:2 to 2.5:1, preferably from 1:1 to 2:1.
5. A composition according to any preceding Claim 1, whereby the speckle partic is a dyed particle.
6. A composition according to Claim 4, obtainable by a process comprising the steps of dyeing particles of a mean particle size of from 100 to 1100 microns, preferably 250 to 850 microns, with a dye to obtain speckle particles and addition of the speckle particles to other particles of a mean particle size of 10 to 1100 microns, preferably 250 to 850 microns.
7. A composition according to Claim 6, whereby the speckle particles are sieved and optionally dried prior to addition to the other particles to obtain speckle particles of mean particle size of from 100 to 1100 microns, preferably from 25 to 850 microns.
8. A composition according to any claim, being a solid laundry or dishwashing detergent composition, preferably in the form of granules, extrudates or a table whereby the speckle particles comprise detergent actives or detergent adjunct materials, preferably acids or salts, including carboxylic acid or salts thereof, phosphate-containing builders, silicate-containing builders, sulphates, carbonat bicarbonates, which preferably having a density of from 300g/litre to 2,000 g/litre, more preferably from 350 g/litre to 1500 g/litre.
9. A process for preparation of a cleaning composition according to any precedin claim, preferably a solid laundry or dishwashing composition, comprising the steps of dyeing particles of a mean particle size of from 100 to 1100 microns preferably from 250 to 850 microns, with a dye to obtain speckle particles, preferably subsequently or simultaneously drying of the speckle particles and addition of the speckle particles to other particles of mean particle size of from 100 to 1100 microns, preferably of from 250 to 850 microns.
10. Use in a cleaning composition comprising other particles, preferably a solid laundry or dishwashing, of speckle particles at a level of CP %, being
2
2 xf 1.5 Mncp - Mcp ] CP (%) = 10 ╬▓ ΓûáΓûá , .5 Mncp J
wherein Mncp is the mean particle size of the other particles and Mcp is the mean particle size of the speckle particle, provided that CP is from 2% to 10% by weight, Mncp is from 100 microns to 1100 microns and Mcp is from 100 microns to 1100 microns, wherein the colour difference of the speckle particles compared to the other particles (ΔE) is from 15 to 40,
ΔE being V (ΔL)2+ (Δa )2+ (Δb)2
ΔL being L(speckle particle) - L(otherpartic,es)' , being the whiteness difference between the speckle particles and the other particles, Δa being a (s cckle article) . a (other -"**«) , being the greenness/redness difference between the speckled particles and the other particles, Δb being b(speclde particles) - b(other particles) , being the blueness/ yellowness difference between the speckle particles and the other particles.
PCT/US1998/012371 1998-06-12 1998-06-12 Cleaning compositions containing speckle particles WO1999064558A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US1998/012371 WO1999064558A1 (en) 1998-06-12 1998-06-12 Cleaning compositions containing speckle particles
AU80720/98A AU8072098A (en) 1998-06-12 1998-06-12 Cleaning compositions containing speckle particles

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003018738A1 (en) * 2001-08-20 2003-03-06 Unilever Plc Photobleach speckle and laundry detergent compositions containing it
US7018971B2 (en) 2001-10-25 2006-03-28 Unilever Home And Personal Care Usa Division Of Conopco, Inc. Process for the production of detergent granules
US7018972B2 (en) 2001-10-25 2006-03-28 Unilever Home and Personal Care USA a division of Conopco, Inc. Process for the production of detergent granules
EP2084256B1 (en) † 2006-11-10 2013-12-18 The Procter and Gamble Company Fabric treatment composition with a fabric substantive dye

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB808668A (en) * 1956-04-23 1959-02-11 Hedley Thomas & Co Ltd Detergent compositions
GB1248994A (en) * 1968-05-31 1971-10-06 Colgate Palmolive Co Laundry products
GB2199338A (en) * 1986-12-30 1988-07-06 Unilever Plc Coloured detergent particles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB808668A (en) * 1956-04-23 1959-02-11 Hedley Thomas & Co Ltd Detergent compositions
GB1248994A (en) * 1968-05-31 1971-10-06 Colgate Palmolive Co Laundry products
GB2199338A (en) * 1986-12-30 1988-07-06 Unilever Plc Coloured detergent particles

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003018738A1 (en) * 2001-08-20 2003-03-06 Unilever Plc Photobleach speckle and laundry detergent compositions containing it
US7018971B2 (en) 2001-10-25 2006-03-28 Unilever Home And Personal Care Usa Division Of Conopco, Inc. Process for the production of detergent granules
US7018972B2 (en) 2001-10-25 2006-03-28 Unilever Home and Personal Care USA a division of Conopco, Inc. Process for the production of detergent granules
EP2084256B1 (en) † 2006-11-10 2013-12-18 The Procter and Gamble Company Fabric treatment composition with a fabric substantive dye
EP2084256B2 (en) † 2006-11-10 2017-03-29 The Procter and Gamble Company Fabric treatment composition with a fabric substantive dye

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