EP1228188A1 - Detergent compositions - Google Patents

Detergent compositions

Info

Publication number
EP1228188A1
EP1228188A1 EP00977127A EP00977127A EP1228188A1 EP 1228188 A1 EP1228188 A1 EP 1228188A1 EP 00977127 A EP00977127 A EP 00977127A EP 00977127 A EP00977127 A EP 00977127A EP 1228188 A1 EP1228188 A1 EP 1228188A1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
percarbonate
weight
sodium
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00977127A
Other languages
German (de)
French (fr)
Inventor
Paul Anthony Gould
Nicola Ethel 15 The Wills Building DAVIDSON
Susan Judith Schamp
Koen Mariette Albert Schamp
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP1228188A1 publication Critical patent/EP1228188A1/en
Withdrawn legal-status Critical Current

Links

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
    • C11D3/395—Bleaching agents
    • C11D3/3955—Organic bleaching agents
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the present invention relates to bleach-containing detergents. This technology may find an application in laundry detergent compositions, soaking detergent compositions, or any other compositions for household applications or the like.
  • perborate As a source of available oxygen in granular bleach-containing detergent compositions for use in hot or humid environments.
  • the inclusion of a bleaching system in a granular detergent formulation helps to improve the cleaning performance of the detergent and is common practice in the laundry industry.
  • the inventors have found that in granular bleach-containing detergent compositions, it is the perborate that causes the increase in the mean particle size of the detergent composition during storage in conditions of high temperature and high relative humidity. Whilst not intending to be bound by theory, it is thought that in these conditions, sodium perborate monohydrate is hydrated to sodium perborate tetrahydrate. Sodium perborate tetrahydrate forms a gel that binds other detergent ingredients, thus forming detergent components of an irregular and increased size. This increase in the mean particle size of the detergent components results in a product that is of coarse appearance and not acceptable to the consumers.
  • the inventors have suprisingly found that when selected sodium percarbonate is used instead of sodium perborate as a source of available oxygen in a granular bleach- containing detergent composition with a bulk density of less than 570g/l, the problem of increasing particle sizes is alleviated. It has been found that when such products are stored under hot and/or humid conditions, for example, after being simultaneously exposed to 32°C and 80% relative humidity for 24 hours, the detergent composition retains its main particle size, in that it has a mean particle size of 100% to 130% of the original mean particle size. This results in a product that remains attractive to the consumer, which is of great benefit to the laundry industry and is especially applicable to handwash applications.
  • the inventors have found that, after storage in such, the detergent composition retains its bulk density, in that it has a bulk density of 90% to 100% of the original bulk density. This results in a product that can still be effectively and accurately dosed during the washing process.
  • detergent compositions namely sodium percarbonate which comprises less than 2% by weight chloride ions or sodium percarbonate prepared by a fluidised bed process
  • detergent compositions comprising said sodium percarbonate are particularly stable.
  • the invention provides a granular bleach-containing detergent composition with a bulk density of less than 570g/l, characterised in that the detergent composition comprises a percarbonate source, and that, after being openly exposed simultaneously to 32°C and 80%) relative humidity for 24 hours, the detergent composition has a mean particle size of 100% to 130%) of the original mean particle size.
  • the invention also provides a granular bleach-containing detergent composition with a bulk density of less than 570g/l comprising a percarbonate source and less than 0.06% by weight extractable suds suppressing silicone, where the percarbonate source comprises a salt of percarbonate, characterised in that percarbonate source comprises less than 2% by weight chloride ions.
  • the invention is applicable to detergent compositions that are stored in a climate comprising conditions of high temperature and high relative moisture content.
  • the granular bleach-containing detergent composition has a bulk density of less than 570g/l, preferably from 200g/l to 550g/l, more preferably from 300g/l to 550g/l, even more preferably from 400g/l to 500g/l.
  • the granular bleach-containing detergent composition comprises a percarbonate source that comprises a salt of percarbonate, preferably sodium percarbonate, although in addition other forms of percarbonate can also be comprised by the percarbonate source of the invention. Also, in addition to percarbonate, other sources of available oxygen known in the art, or a combination thereof, can be included in the granular detergent composition, although it is preferred that percarbonate is the only perhydrate component included in the granular detergent composition.
  • the mean particle size of the detergent composition is the mean particle size of all of the particles that the detergent composition comprises.
  • the granular detergent composition comprises a percarbonate source and optionally additional detergent ingredients.
  • the detergent composition When the granular detergent composition is exposed to conditions of 32°C and 80% relative humidity for 24 hours, after exposure to these conditions, the detergent composition has a mean particle size of 100% to 130%), preferably 100%> to 120%, more preferably 100% to 110% of the original mean particle size.
  • detergent composition comprising 20% by weight alkyl sulphate surfactant in a blown powder, less than 2% by weight other cationic or anionic, surfactants in a blown powder, 25%) by weight sodium tripolyphosphate surfactants in a blown powder, 6%> by weight 1.6 ratio silicate surfactants in a blown powder, 15% by weight carbonate surfactants in a blown powder, and 10%> by weight sodium percarbonate (for example, see examples, sodium percarbonate sample 1 and 2) was placed, on a petri dish with no external barrier, in an incubator with controlled ambient conditions of 32°C and 80% relative humidity. The detergent composition was exposed to these said conditions in the incubator for 24 hours.
  • the mean particle size is determined before and after the detergent composition was exposed to the said conditions.
  • the mean particle size of the detergent composition is measured using the method ISO 3118 (1976), where lOOg of product is used to determine the mean particle size, the sieve sizes that are used are 250, 425, 600, 850, 1180 and 2000 micrometers, and the time the product is allowed in the sieves before the mean particle size is measured is 5 minutes. See example 1.
  • the granular detergent composition comprises a blown powder, a percarbonate source, and additional detergent ingredients, and has a bulk density less than 570g/l.
  • the detergent composition is stored in conditions of 32°C and 80%) relative humidity for 8 weeks, after storage in these conditions, the detergent composition has a bulk density of 90% to 100%) of the original bulk density.
  • 1.5kg detergent composition comprising 20% by weight alkyl sulphate surfactant in a blown powder, less than 2%> by weight other cationic or anionic surfactants in a blown powder, 25 > by weight sodium tripolyphosphate in a blown powder, 6% by weight 1.6 ratio silicate in a blown powder, 15% by weight carbonate in a blown powder, and 10% by weight sodium percarbonate (for example, see examples, sodium percarbonate example 1 and 2) was stored, in packaging typical of laundry detergent products, in a room with controlled ambient conditions of 32°C and 80% relative humidity. The detergent composition was stored in these said conditions for 8 weeks.
  • the bulk density is determined before and after the detergent composition was stored in these said conditions.
  • the bulk density of the detergent composition is measured using the method ISO 3424 (1975), see example 2.
  • the detergent composition can comprise an alkali or earth metal salt of phosphate.
  • the alkali or earth metal salt of phosphate can be any known in the art, or combination thereof. Preferably this is sodium phosphate or sodium tripolyphosphate.
  • the detergent composition comprises less than 36%, preferably from 1 to 35%, more preferably from 10%) to 35%, even more preferably from 12%> to 30%, by weight an alkali or earth metal salt of phosphate.
  • Detergent compositions containing a low level of, or no, phosphate can also be used by this invention. Typical sources of phosphate that can be comprised by the composition of the invention are described hereinafter.
  • the detergent composition is preferably a high sudsing detergent formulation. These can be any high sudsing detergent formulations known in the art, or part thereof.
  • the detergent composition can comprise less than 5%, preferably less than 2%, more preferably less than 1 % by weight a suds suppresser.
  • the suds suppresser can be any known in the art, or combination thereof.
  • the suds suppresser is either a soap, paraffin, wax, or any combination thereof.
  • the detergent composition can comprise less than 0.06% by weight extractable suds suppressing silicone.
  • the extractable suds suppressing silicone can be any known in the art, or any combination thereof. Typical suds suppressers, including suds suppressing silicone are described hereinafter.
  • the detergent composition has a moisture content of less than 10%, preferably 6%> to 9%> by weight.
  • 'moisture content means for the purpose of the invention, any free water molecules present in the detergent composition or water molecules in the form of hydrates, such as present in sodium phosphate, usually this is sodium tripolyphosphate.
  • the reserve alkalinity gives a measure of the buffering capacity of the detergent. This is the amount of NaOH or detergent composition required to neutralise 0.2M hydrochloric acid to pH 7.5.
  • the granular detergent composition has a preferred reserve alkalinity of at least 6g NaOH per lOOg detergent composition, measured to a pH of 7.5.
  • the detergent composition comprises 0.05% to 2%, preferably 0.1% to 2%, more preferably 0.2% to 1.5%, even more preferably 0.5% to 1.0%, by weight a metal chelating agent.
  • the metal chelating agent can be any agent known in the art, or combination thereof, that chelates heavy metal ions, as described hereinafter. Bleaching System
  • the granular detergent composition of the invention comprises a source of percarbonate.
  • the percarbonate source acts as a source of available oxygen.
  • Other sources of available oxygen can also be comprised by the detergent composition of the invention, to form a bleaching system.
  • Typical bleaching systems comprised by the detergent composition are described hereinafter.
  • 'bleaching system means for the purpose of the invention any bleaching system known in the art that comprises the percarbonate source and an additional bleaching compound, preferably a peracid or precursor thereto.
  • 'percarbonate source means for the purpose of the invention, any source of percarbonate, typically comprising a salt of percarbonate, preferably the salt of percarbonate is sodium percarbonate.
  • the detergent composition comprises a percarbonate source at a level of from 0.01% to 12%, preferably from 2% to 10%>, more preferably from 3% to 7%, by weight of the detergent composition.
  • the percarbonate source of the invention can be prepared by any method known in the art, preferably a fluidised bed process.
  • the fluidised bed process can be any known in the art.
  • the percarbonate source preferably comprises less than 2%, preferably less than 1.5%, more preferably less than 1.2%, even more preferably less than 1% by weight chloride ions, or chloride containing compounds.
  • the detergent composition can comprise a coated source of percarbonate.
  • the source of percarbonate can be coated by any coating known in the art, or combination thereof.
  • the coating comprises one or more alkali metal salt, preferably this is sodium carbonate, sodium bicarbonate, sodium silicate, sodium sulphate, or any combination thereof.
  • the coated sodium percarbonate is formed by contacting the percarbonate source with the coating in such a way that the coating is present on the surface of the source of percarbonate.
  • the coating is present on the surface of the source of percarbonate in such a way as to either completely or partially coat the percarbonate source.
  • the coated source of percarbonate is prepared by a method comprising contacting the source of percarbonate with carbon dioxide to form a coating of sodium bicarbonate on the surface of the sodium percarbonate particle. Usually this is done in the presence of moisture.
  • the coated source of percarbonate particle comprises a coating present at a level of 0.01% to 20%, preferably 1% to 15%, more preferably 4% to 10%, by weight of the coated sodium percarbonate particle Any detergent components which comprise sodium percarbonate can also be coated in this manner.
  • the coated percarbonate can be prepared by a fluidised bed process and/or by spraying the coating onto the surface of the sodium percarbonate.
  • the source of percarbonate preferably has a mean particle size of 500 to 1000, preferably 500 to 850, more preferably 550 to 800 micrometers.
  • the detergent composition typically comprises additional detergent ingredients. These detergent ingredients are described below.
  • the detergent composition comprises a surfactant, builder, chelant and a bleaching system.
  • any alkoxylated nonionic surfactants can also be comprised by the composition of the invention.
  • 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 surfactants being the condensation products of aliphatic alcohols with from 1 to 75 moles of alkylene oxide, in particular about 50 or from 1 to 15 moles, preferably to 1 1 moles, particularly ethylene oxide and/or propylene oxide, are highly preferred nonionic surfactant comprised in the anhydrous component of the particles of the invention.
  • 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 9 moles and in particular 3 or 5 moles, of ethylene oxide per mole of alcohol.
  • Polyhydroxy fatty acid amides are highly preferred nonionic surfactant comprised by the composition of the invention , in particular those having the structural formula wherein : Rl is H, Cj.jg, preferably C C 4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably Cj or C2 alkyl, most preferably C] alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 or C 7 -C 19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain Cj ] - C 7 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
  • a highly preferred nonionic polyhydroxy fatty acid amide surfactant for use herein is a Cl2" l4 > a C15-C17 and/or C]g-C]g alkyl N-methyl glucamide.
  • composition of the invention comprises a mixture of a C12-C18 alkyl N-methyl glucamide and condensation products of an alcohol having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 9 moles and in particular 3 or 5 moles, of ethylene oxide per mole of alcohol.
  • the polyhydroxy fatty acid amide can be prepared by any suitable process.
  • One particularly preferred process is described in detail in WO 9206984.
  • a product comprising about 95% by weight polyhydroxy fatty acid amide, low levels of undesired impurities such as fatty acid esters and cyclic amides, and which is molten typically above about 80°C, can be made by this process.
  • Fatty acid amide surfactants or alkoxylated fatty acid amides can also be comprised by the composition of the invention. They include those having the formula: R ⁇ CON(R ⁇ ) (R° ) wherein R" is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon or even 11 to 13 carbon atoms and R ⁇ ar >d R8 are each individually 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 11, preferably 1 to 7, more preferably form 1-5, whereby it may be preferred that R 7 is different to R 8 . one having x being 1 or 2, one having x being from 3 to 11 or preferably 5.
  • R ⁇ CON(R ⁇ ) (R° ) wherein R" is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon or even 11 to 13 carbon atoms and R ⁇ ar >d R8 are each
  • Alkyl esters of fatty acids can also be comprised in any material of the invention. They include those having the formula: R9COO(R! 0) wherein R ⁇ is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon or even 11 to 13 carbon atoms and RIO is a C1-C4 alkyl, C1-C4 hydroxyalkyl, or -(C2H4O) x H, where x is in the range of from 1 to
  • R*0 1S a methyl or ethyl group.
  • Alkylpolysaccharides can also be comprised by the composition of the invention, such as those disclosed in US 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 ⁇ 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.
  • composition of the invention may comprise polyethylene and/or propylene glycol, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
  • the detergent composition of the invention preferably comprises one or more anionic surfactants.
  • Any anionic surfactant useful for detersive purposes is suitable. Examples include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulphate, sulphonate, carboxylate and sarcosinate surfactants. Anionic sulphate surfactants are preferred.
  • 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, o monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C ⁇ -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 sulphate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulphates, alkyl ethoxysulphates, fatty oleoyl glycerol sulphates, alkyl phenol ethylene oxide ether sulphates, the C5-C17 acyl-N-(C ⁇ -C4 alkyl) and -N-(C]-C2 hydroxyalkyl) glucamine sulphates, and sulphates of alkylpolysaccharides such as the sulphates of alkylpolyglucoside (the nonionic non-sulphated compounds being described herein).
  • Alkyl sulphate surfactants are preferably selected from the linear and branched primary C9-C22 alkyl sulphates, more preferably the C ⁇ ⁇ -C ⁇ branched chain alkyl sulphates and the C]2-C]4 linear chain alkyl sulphates.
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C J Q-CI 8 alkyl sulphates which have been ethoxylated with from 0.5 to 50 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a Ci 1 - Cjg, most preferably C] ⁇ -C ⁇ alkyl sulphate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
  • Anionic sulphonate surfactants suitable for use herein include the salts of C5-C20 linear or branched alkylbenzene sulphonates, alkyl ester sulphonates, in particular methyl ester sulphonates, C6-C22 primary or secondary alkane sulphonates, C.5-C24 olefin sulphonates, sulphonated polycarboxylic acids, alkyl glycerol sulphonates, fatty acyl glycerol sulphonates, fatty oleyl glycerol sulphonates, 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-(CHRj-CHR2-O) ⁇ -R3 wherein R is a Cg to Cjg alkyl group, x is from 1 to 25, R ⁇ 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-l-nonanoic acid, 2- butyl-1-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressers.
  • alkali metal sarcosinates of formula R-CON (Rl) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, Rl is a C1-C4 alkyl group and M is an alkali metal ion.
  • R is a C5-C17 linear or branched alkyl or alkenyl group
  • Rl is a C1-C4 alkyl group
  • M is an alkali metal ion.
  • Another preferred optional ingredient of the detergent composition of the invention is a cationic surfactant, which may preferably be present at a level of from 0.1 % to 60% by weight of the composition or particle, more preferably from 0.4% to 20%>, most preferably from 0.5%) to 5% by weight of the composition.
  • the ratio of the anionic surfactant to the cationic surfactant is preferably from 25: 1 to 1 :3, more preferably from 15: 1 to 1 : 1. most preferably from 10:1 to 1 : 1
  • the ratio of cationic surfactant to the stabilising agent is preferably from 1:30 to 20:1, more preferably from 1 :20 to 10: 1.
  • the cationic surfactant is selected from the group consisting of cationic ester surfactants, cationic mono-alkoxylated amine surfactants, cationic bis-alkoxylated amine surfactants and mixtures thereof.
  • the optional cationic mono-alkoxylated amine surfactant for use herein has the general formula:
  • 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 11 carbon atoms;
  • R ⁇ and R ⁇ are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl;
  • R4 is selected from hydrogen (preferred), methyl and ethyl,
  • X" is an anion such as chloride, bromide, methyl sulphate, sulphate, or the like, to provide electrical neutrality;
  • A is selected from C1-C4 alkoxy, especially ethoxy (i.e., -CH2CH2O-), propoxy, butoxy and mixtures thereof; and
  • p is from 1 to about 30, preferably 1 to about 15, most preferably 1 to about 8.
  • R ⁇ is Cg-Cj hydrocarbyl and mixtures thereof, preferably Cg-C ⁇ , especially Cg-C ⁇ 1 alkyl, preferably Cg and C ⁇ Q alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
  • the cationic bis-alkoxylated amine surfactant for use herein has the general formula:
  • R* is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, more preferably 6 to about 11, most preferably from about 8 to about 10 carbon atoms
  • R ⁇ is an alkyl group containing from one to three carbon atoms, preferably methyl
  • R ⁇ and R ⁇ can vary independently and are selected from hydrogen (preferred), methyl and ethyl
  • X" is an anion such as chloride, bromide, methylsulphate, sulphate, or the like, sufficient to provide electrical neutrality.
  • a and A' can vary independently and are each selected from C ⁇ -C4 alkoxy, especially ethoxy, (i.e., -CH2CH2O-), propoxy, butoxy and mixtures thereof; p is from 1 to about
  • q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.
  • R ⁇ is Cg-Cjg hydrocarbyl and mixtures thereof, preferably C5, Cg, C ⁇ o > C ⁇ 2 > C ⁇ 4 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 Cg-Ci g hydrocarbyl, preferably Cg-C ⁇ alkyl, independently p is 1 to about 3 and q is 1 to about 3, R ⁇ is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
  • 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(OR4) X NO(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 R ⁇ is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are C ⁇ Q-Cig alkyl dimethylamine oxide, and C ⁇ o-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 comprised by the composition of 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 C -C ⁇ g hydrocarbyl group, each R ⁇ is typically C1-C3 alkyl, and R ⁇ is a C1 -C5 hydrocarbyl group.
  • Preferred betaines are C ⁇ 2- 18 dimethyl-ammonio hexanoate and the ClO-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • the detergent composition of the invention preferably comprises a water-soluble builder compound, typically present at a level of from 0%> to 36%> by weight, preferably from 1% to 35%) by weight, more preferably from 10% to 35%o, even more preferably from 12%> to 30% by weight of the composition or particle.
  • the water-soluble builder compound is an alkali or earth alkali metal salt of phosphate present at the level described above.
  • water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, phosphates, and mixtures of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfmyl carboxylates.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in US Patent No. 3,936,448, and the sulphonated 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.
  • 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.
  • the detergent composition of the invention may contain a partially soluble or insoluble builder compound.
  • Examples of largely water insoluble builders include the sodium aluminosilicates.
  • Suitable aluminosilicate zeolites have the unit cell formula Na z [(AlO2) z (SiO2)y]. H2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 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 Nagg [(Al ⁇ 2)86(Si ⁇ 2)l06J- 276 H 2 O.
  • Preferred crystalline layered silicates for use herein have the general formula:
  • M is sodium or hydrogen
  • x is a number from 1.9 to 4 and y is a number from 0 to 20.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043.
  • x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2.
  • the most preferred material is ⁇ -Na2Si2 ⁇ 5, available from Hoechst AG as NaSKS-6.
  • the detergent composition of the invention preferably comprises an organic peroxyacid precursor.
  • the production of the organic peroxyacid may occur by an in situ reaction of such a precursor with the percarbonate source.
  • a preformed organic peroxyacid is incorporated directly into the composition.
  • 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:
  • Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O- acyl groups, which precursors can be selected from a wide range of classes.
  • Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1 147871, 2143231 and EP-A-0170386.
  • 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
  • R 3 is an alkyl chain containing from 1 to 8 carbon atoms
  • R 4 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 ammonium groups.
  • the preferred solubilizing groups are -SO, ⁇ M , -CO- ' M , -SO M , -N (R ) .X " and
  • M is an alkyl chain containing from 1 to 4 carbon atoms
  • M is a cation which provides solubility to the bleach activator
  • 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
  • X is a halide, hydroxide, methylsulphate or acetate anion.
  • Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
  • Preferred precursors of this type provide peracetic acid on perhydrolysis.
  • Typical 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 sulphonate (iso-NOBS), sodium nonanoyloxybenzene sulphonate (NOBS), sodium acetoxybenzene sulphonate (ABS) and pentaacetyl glucose.
  • the detergent composition preferably comprises 0.1% to 2%, preferably 0.1% to 1%, more preferably 0.2% to 0.7%, even more preferably 0.25% to 0.6%, by weight TAED.
  • the detergent composition preferably comprises 0.1% to 4%, preferably 0.2% to 3%, more preferably 0.4% to 2%, even more preferably 0.7% to 1.9%, by weight NOBS.
  • the detergent composition can also comprise a combination of NOBS and TAED, present at the levels described hereinbefore.
  • Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
  • Rl is an alkyl group with from 1 to 14 carbon atoms
  • R ⁇ 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 Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulphonates, 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.
  • 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 organic peroxyacid bleaching system may contain a preformed organic peroxyacid.
  • a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae: R N — R' OOH R N R OOH
  • R is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
  • R ⁇ is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R ⁇ 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 detergent composition of the invention or any detergent component comprised by the detergent composition of the invention, preferably comprise as an optional detergent ingredient, a heavy metal ion sequestrant.
  • a 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 0.05%> to 2%, preferably from 0.1 % to 1.5%, more preferably from 0.25% to 1.2% and most preferably from 0.5%) to 1% by weight of the composition.
  • 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.
  • 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.
  • Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethyl enetriamine pentacetic 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- 1,2,4-tricarboxylic acid are also suitable.
  • Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'- disuccinic acid (HPDDS) are also suitable.
  • Another preferred optional detergent ingredient useful in the detergent composition of the invention, or any detergent component comprised by the detergent composition of the invention, is one or more additional enzymes.
  • Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist- Brocades, those sold by Genencor International, and those sold under the tradename
  • 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 and BAN by Novo Industries A S.
  • Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001%> to 2% active enzyme by weight of the composition.
  • Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001%> to 10%) by weight of the particle, preferably 0.001% to 3% by weight of the composition, most preferably from 0.001%> to 0.5%> by weight of the compositions.
  • the lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., 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 detergent ingredients of the detergent composition of the invention, or any detergent component comprised by the detergent composition of the invention, 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.
  • Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1% to 50% by weight of the particle, preferably from 0.5%) to 25%o, most preferably from l%o to 15% 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 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.
  • the polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and 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.
  • organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
  • 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, C]-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 composition preferably comprises a suds suppresser at a level less than 5%, preferably 0.01% to 5%, preferably from 0.05% to 4%, most preferably from 0.1% to 3%, by weight of the composition
  • the suds suppresser is either a soap, paraffin, wax, or any combination thereof. If the suds suppresser is a suds suppressing silicone, then the detergent composition preferably comprises less than 0.06%> by weight extractable suds suppressing silicone.
  • 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 silica component.
  • silicone antifoam compounds are the siloxanes, particularly the polydime hylsiloxanes having trimethylsilyl end blocking units.
  • the composition comprises less than 0.6% by weight extractable suds suppressing silicone.
  • 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 suppresser 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 l8*- 40 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.
  • aliphatic l8*- 40 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
  • 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 antifoam compound
  • silica/silicone antifoam compound is incorporated at a level of less than 5%>, preferably 0.01% to 5%, more preferably 0.05%o to 4%, even more preferably 0.1% to 3%, 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 less than 5%, preferably 0.01% to 5%, more preferably 0.05% to 4%, even more preferably 0.1% to 3%, 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 C ⁇ -C ⁇ g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of less than 5%, preferably 0.01% to 5%, more preferably 0.05% to 4%o, even more preferably 0.1% to 3%, 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.
  • the detergent composition of the invention may comprise a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.
  • the clay mineral compound is preferably a smectite clay compound.
  • Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647.
  • European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents.
  • the detergent composition of the invention 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-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
  • Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula :
  • A is NC, CO, C, -O-, -S-, -N-; x is O or 1 ;
  • R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
  • the N-O group can be represented by the following general structures :
  • Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.
  • the N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group.
  • Prefe ⁇ ed polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, py ⁇ ole, imidazole, py ⁇ olidine, piperidine, quinoline, acridine and derivatives thereof.
  • polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit.
  • a preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
  • the polyamine N-oxides can be obtained in almost any degree of polymerisation.
  • the degree of polymerisation is not critical provided the material has the desired water- solubility and dye-suspending power.
  • the average molecular weight is within the range of 500 to 1000,000.
  • Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000.
  • the preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.
  • the detergent composition of the invention may also utilize polyvinylpy ⁇ olidone ("PVP") having an average molecular weight of from 2,500 to 400,000.
  • PVP polyvinylpy ⁇ olidone
  • Suitable polyvinylpy ⁇ olidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000).
  • PVP K-15 is also available from ISP Corporation.
  • Other suitable polyvinylpy ⁇ olidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
  • the detergent composition of the invention may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents.
  • Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.
  • the detergent composition of the invention may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
  • Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.
  • the detergent composition of the invention may also optionally comprise from 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
  • 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-UNPA-GX is the prefe ⁇ ed hydrophilic optical brightener useful in the detergent compositions herein.
  • R ⁇ 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 is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • Cationic fabric softening agents can also be incorporated into the detergent composition of the invention or in compositions containing the detergent component in accordance with the present invention.
  • Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 01 1 340.
  • Cationic fabric softening agents are typically incorporated at total levels of from 0.5% to 15%) by weight, normally from 1% to 5% by weight.
  • compositions or detergent component of the invention include highly preferably perfumes, colours and filler salts, with sodium sulphate being a prefe ⁇ ed filler salt.
  • the detergent composition of the invention can be made by a variety of methods, including dry-mixing, extruding, compacting and agglomerating of the various compounds comprised in the detergent composition.
  • the particles can be present in the compositions as a separate component of the composition, or can be added to other components or compounds of the composition.
  • the granular detergent composition of the invention can take a variety of physical forms including granular, flakes or extrudate.
  • Laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution for washing by machine or for washing by hand, having dissolved or dispensed therein an effective amount of a laundry composition.
  • an effective amount of the detergent composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 1 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional laundry methods.
  • Other laundry washing processes known in the art can also be used.
  • LAS Sodium linear Cl 1-13 alkyl benzene sulfonate LAS (I) Potassium linear or branched C 11 - 13 alkyl benzene sulfonate TAS Sodium tallow alkyl sulfate CxyAS Sodium Clx - Cly alkyl sulfate C46SAS Sodium C14 - C16 secondary (2,3) alkyl sulfate CxyEzS Sodium Clx-Cly alkyl sulfate condensed with z moles of ethylene oxide CxyEz Clx-Cly predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide
  • Nal2(AlO2SiO2)12.27H2O having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis)
  • Citric acid II Anhydrous or monohydrate citric acid, 80%) having a particle size of from 15 microns to 40 microns, having a volume average particle size of 25 microns
  • Malic acid Anhydrous malic acid, 80% having a particle size of from 50 microns to 100 microns, having a volume median particle size of
  • Maleic acid Anhydrous maleic acid, 80% having a particle size of from 5 microns to 30 microns, having a volume median particle size of 15 microns
  • Tartaric acid Anhydrous tartaric acid 80%> having a particle size of from 25 microns to 75 microns, having a volume median particle size of 50 microns
  • Carbonate I Anydrous sodium carbonate having 80%) by volume of particles with a particle size from 50 microns to 150 microns with a volume median particle size of 100 microns
  • Carbonate II Anydrous sodium carbonate having 80%> by volume of particles with a particle size from 35 microns to 75 microns, having a volume median particle size of 55 microns
  • Bicarbonate II Anhydrous sodium bicarbonate having 80%> by volume of particles with a particle size from 100 microns to 200 microns with a volume median particle size of 150 microns
  • Bicarbonate I Anydrous sodium bicarbonate having 80%o by volume of particles with a particle size from 15 microns to 40 microns, having a volume median particle size of 25 microns
  • 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%o 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
  • 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 Particle containing sodium perborate tetrahydrate of nominal formula NaBO2.3H2 O the particles having a weight average particle size of 950 microns, 85% particles having a particle size of from 850 microns to 950 microns
  • PB1 Particle containing anhydrous sodium perborate bleach of nominal formula NaBO2.H 202 the particles having a weight average particle size of 800 microns, 85%> particles having a particle size of from 750 microns to 950 microns
  • Coated percarbonate The coated sodium percarbonate source of the invention, as described hereinbefore (see detailed description of the invention, percarbonate source), as described hereinafter, with 4.5% by weight coating comprising sodium bicarbonate and/or sodium sulphate and prepared by a fluidised bed process (percarbonate sample 2) or with 4.5% by weight sodium carbonate and/or sodium sulphate and prepared by a crystalline/classification process, ex
  • NOBS Particle comprising nonanoyloxybenzene sulfonate in the form of the sodium salt, the particles having a weight average particle size of 750 microns to 900 microns
  • NAC-OBS Particle comprising (6-nonamidocaproyl) oxybenzene sulfonate, the particles having a weight average particle size of from 825 microns to 875 microns
  • TAED I Particle containing tetraacetylethylenediamme the particles having a weight average particle size of from 700 microns to 1000 microns
  • DTPA Diethylene triamine pentaacetic acid
  • DTPMP Diethylene triamine penta (methylene phosphonate), marketed by
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino- 1.3.5-triazin-2- yl)amino) stilbene-2:2'-disulfonate
  • PEGx Polyethylene glycol, with a molecular weight of x (typically 4,000)
  • PEO Polyethylene oxide with an average molecular weight of 50,000
  • PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole with an average molecular weight of 20,000
  • SRP 1 Anionically end capped poly esters SRP2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer
  • PEI Polyefhyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen
  • Silicone antifoam Polydimefhylsiloxane 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
  • the mean particle size of the detergent composition was determined by the method described hereinbefore (see detailed description of the invention, mean particle size).
  • a detergent composition used to determine the mean particle size is described hereinbefore (see detailed description of the invention, mean particle size).
  • the mean particle size of a detergent composition comprising 10%> by weight sodium perborate monohydrate (sodium perborate sample) is also shown, along with two detergent compositions comprising 10%) by weight sodium percarbonate (sodium percarbonate sample 1 and 2, see below for a more detailed description) before (Oh) and after exposure for 24 hours (24h) to conditions of 32°C and 80%> relative humidity by the method described hereinbefore (see detailed description of the invention, mean particle size).
  • the sodium percarbonate sample 1 comprises a coated sodium percarbonate comprising or with 4.5%) by weight sodium carbonate and/or sodium sulphate and prepared by a crystalline/classification process, ex Solvay.
  • the sodium percarbonate sample 2 comprises a coated sodium percarbonate comprising 4.5%) by weight a coating comprising sodium bicarbonate and/or sodium sulphate and the coated sodium percarbonate is prepared by a fluidised bed process
  • compositions are in accordance with the invention.

Landscapes

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

Abstract

The present invention provides a detergent composition with a bulk density of less than 570g/1, characterised in that the percarbonate source comprises a salt of percarbonate, and that, after being exposed simultaneously to 32°C and 80% relative humidity for 24 hours, the detergent composition has a mean particle size of 100% to 130% of the original mean particle size. The present invention also provides a granular bleach-containing detergent composition with a bulk density of less than 570g/1 comprising a percarbonate source and less than 0.06% by weight extractable suds suppressing silicone, where the percarbonate source comprises a salt of percarbonate, characterized in that percarbonate source comprises less than 2% by weight chloride ions. The detergent composition is particularly applicable for use in climates comprising conditions of high temperature and high relative humidity.

Description

Detergent Compositions
Technical Field
The present invention relates to bleach-containing detergents. This technology may find an application in laundry detergent compositions, soaking detergent compositions, or any other compositions for household applications or the like.
Background of the Invention
When detergent products are stored in a geographical location that has a hot and/or humid climate, an industrial environment, a household environment, or any combination thereof, where a high temperature and a high relative humidity are prevalent, it has been found that the mean particle size of the detergent composition increases during storage of the product. This increase in mean particle size, gives the product a coarse appearance of an aged product, which is not acceptable to the consumers, especially when the product is of a hand-wash application.
For many years, the laundry industry have been trying to determine the cause of this mean particle size increase of the detergent composition, with little success. However, the inventors have now successfully identified the cause of this mean particle size increase of the detergent composition during storage.
The laundry industry have been using perborate as a source of available oxygen in granular bleach-containing detergent compositions for use in hot or humid environments. The inclusion of a bleaching system in a granular detergent formulation helps to improve the cleaning performance of the detergent and is common practice in the laundry industry. The inventors have found that in granular bleach-containing detergent compositions, it is the perborate that causes the increase in the mean particle size of the detergent composition during storage in conditions of high temperature and high relative humidity. Whilst not intending to be bound by theory, it is thought that in these conditions, sodium perborate monohydrate is hydrated to sodium perborate tetrahydrate. Sodium perborate tetrahydrate forms a gel that binds other detergent ingredients, thus forming detergent components of an irregular and increased size. This increase in the mean particle size of the detergent components results in a product that is of coarse appearance and not acceptable to the consumers.
The inventors have suprisingly found that when selected sodium percarbonate is used instead of sodium perborate as a source of available oxygen in a granular bleach- containing detergent composition with a bulk density of less than 570g/l, the problem of increasing particle sizes is alleviated. It has been found that when such products are stored under hot and/or humid conditions, for example, after being simultaneously exposed to 32°C and 80% relative humidity for 24 hours, the detergent composition retains its main particle size, in that it has a mean particle size of 100% to 130% of the original mean particle size. This results in a product that remains attractive to the consumer, which is of great benefit to the laundry industry and is especially applicable to handwash applications.
Also, the inventors have found that, after storage in such, the detergent composition retains its bulk density, in that it has a bulk density of 90% to 100% of the original bulk density. This results in a product that can still be effectively and accurately dosed during the washing process.
By using specifically selected sodium percarbonate in detergent compositions, namely sodium percarbonate which comprises less than 2% by weight chloride ions or sodium percarbonate prepared by a fluidised bed process, the inventors have found that detergent compositions comprising said sodium percarbonate are particularly stable.
Summary of the Invention Summary of the Invention
The invention provides a granular bleach-containing detergent composition with a bulk density of less than 570g/l, characterised in that the detergent composition comprises a percarbonate source, and that, after being openly exposed simultaneously to 32°C and 80%) relative humidity for 24 hours, the detergent composition has a mean particle size of 100% to 130%) of the original mean particle size.
The invention also provides a granular bleach-containing detergent composition with a bulk density of less than 570g/l comprising a percarbonate source and less than 0.06% by weight extractable suds suppressing silicone, where the percarbonate source comprises a salt of percarbonate, characterised in that percarbonate source comprises less than 2% by weight chloride ions.
The invention is applicable to detergent compositions that are stored in a climate comprising conditions of high temperature and high relative moisture content.
Detailed Description of the Invention
Detergent Composition
The granular bleach-containing detergent composition has a bulk density of less than 570g/l, preferably from 200g/l to 550g/l, more preferably from 300g/l to 550g/l, even more preferably from 400g/l to 500g/l.
The granular bleach-containing detergent composition comprises a percarbonate source that comprises a salt of percarbonate, preferably sodium percarbonate, although in addition other forms of percarbonate can also be comprised by the percarbonate source of the invention. Also, in addition to percarbonate, other sources of available oxygen known in the art, or a combination thereof, can be included in the granular detergent composition, although it is preferred that percarbonate is the only perhydrate component included in the granular detergent composition.
Mean particle size
The mean particle size of the detergent composition is the mean particle size of all of the particles that the detergent composition comprises.
The granular detergent composition comprises a percarbonate source and optionally additional detergent ingredients. When the granular detergent composition is exposed to conditions of 32°C and 80% relative humidity for 24 hours, after exposure to these conditions, the detergent composition has a mean particle size of 100% to 130%), preferably 100%> to 120%, more preferably 100% to 110% of the original mean particle size.
For the purpose of this invention, this is determined by the following:
1 OOg of detergent composition comprising 20% by weight alkyl sulphate surfactant in a blown powder, less than 2% by weight other cationic or anionic, surfactants in a blown powder, 25%) by weight sodium tripolyphosphate surfactants in a blown powder, 6%> by weight 1.6 ratio silicate surfactants in a blown powder, 15% by weight carbonate surfactants in a blown powder, and 10%> by weight sodium percarbonate (for example, see examples, sodium percarbonate sample 1 and 2) was placed, on a petri dish with no external barrier, in an incubator with controlled ambient conditions of 32°C and 80% relative humidity. The detergent composition was exposed to these said conditions in the incubator for 24 hours.
The mean particle size is determined before and after the detergent composition was exposed to the said conditions. The mean particle size of the detergent composition is measured using the method ISO 3118 (1976), where lOOg of product is used to determine the mean particle size, the sieve sizes that are used are 250, 425, 600, 850, 1180 and 2000 micrometers, and the time the product is allowed in the sieves before the mean particle size is measured is 5 minutes. See example 1.
Bulk density
The granular detergent composition comprises a blown powder, a percarbonate source, and additional detergent ingredients, and has a bulk density less than 570g/l. When the detergent composition is stored in conditions of 32°C and 80%) relative humidity for 8 weeks, after storage in these conditions, the detergent composition has a bulk density of 90% to 100%) of the original bulk density.
For the purpose of this invention, this is determined by the following
1.5kg detergent composition comprising 20% by weight alkyl sulphate surfactant in a blown powder, less than 2%> by weight other cationic or anionic surfactants in a blown powder, 25 > by weight sodium tripolyphosphate in a blown powder, 6% by weight 1.6 ratio silicate in a blown powder, 15% by weight carbonate in a blown powder, and 10% by weight sodium percarbonate (for example, see examples, sodium percarbonate example 1 and 2) was stored, in packaging typical of laundry detergent products, in a room with controlled ambient conditions of 32°C and 80% relative humidity. The detergent composition was stored in these said conditions for 8 weeks.
The bulk density is determined before and after the detergent composition was stored in these said conditions. The bulk density of the detergent composition is measured using the method ISO 3424 (1975), see example 2.
Other preferred components of the detergent composition
The detergent composition can comprise an alkali or earth metal salt of phosphate. The alkali or earth metal salt of phosphate can be any known in the art, or combination thereof. Preferably this is sodium phosphate or sodium tripolyphosphate. The detergent composition comprises less than 36%, preferably from 1 to 35%, more preferably from 10%) to 35%, even more preferably from 12%> to 30%, by weight an alkali or earth metal salt of phosphate. Detergent compositions containing a low level of, or no, phosphate can also be used by this invention. Typical sources of phosphate that can be comprised by the composition of the invention are described hereinafter.
The detergent composition is preferably a high sudsing detergent formulation. These can be any high sudsing detergent formulations known in the art, or part thereof. The detergent composition can comprise less than 5%, preferably less than 2%, more preferably less than 1 % by weight a suds suppresser. The suds suppresser can be any known in the art, or combination thereof. Preferably the suds suppresser is either a soap, paraffin, wax, or any combination thereof. Also, the detergent composition can comprise less than 0.06% by weight extractable suds suppressing silicone. The extractable suds suppressing silicone can be any known in the art, or any combination thereof. Typical suds suppressers, including suds suppressing silicone are described hereinafter.
The detergent composition has a moisture content of less than 10%, preferably 6%> to 9%> by weight.
When used herein, 'moisture content' means for the purpose of the invention, any free water molecules present in the detergent composition or water molecules in the form of hydrates, such as present in sodium phosphate, usually this is sodium tripolyphosphate.
The reserve alkalinity gives a measure of the buffering capacity of the detergent. This is the amount of NaOH or detergent composition required to neutralise 0.2M hydrochloric acid to pH 7.5. The granular detergent composition has a preferred reserve alkalinity of at least 6g NaOH per lOOg detergent composition, measured to a pH of 7.5.
The detergent composition comprises 0.05% to 2%, preferably 0.1% to 2%, more preferably 0.2% to 1.5%, even more preferably 0.5% to 1.0%, by weight a metal chelating agent. The metal chelating agent can be any agent known in the art, or combination thereof, that chelates heavy metal ions, as described hereinafter. Bleaching System
The granular detergent composition of the invention comprises a source of percarbonate. The percarbonate source acts as a source of available oxygen. Other sources of available oxygen can also be comprised by the detergent composition of the invention, to form a bleaching system. Typical bleaching systems comprised by the detergent composition are described hereinafter.
When used herein, 'bleaching system' means for the purpose of the invention any bleaching system known in the art that comprises the percarbonate source and an additional bleaching compound, preferably a peracid or precursor thereto.
Percarbonate Source
When used herein, 'percarbonate source' means for the purpose of the invention, any source of percarbonate, typically comprising a salt of percarbonate, preferably the salt of percarbonate is sodium percarbonate.
The detergent composition comprises a percarbonate source at a level of from 0.01% to 12%, preferably from 2% to 10%>, more preferably from 3% to 7%, by weight of the detergent composition.
The percarbonate source of the invention can be prepared by any method known in the art, preferably a fluidised bed process. The fluidised bed process can be any known in the art.
The percarbonate source preferably comprises less than 2%, preferably less than 1.5%, more preferably less than 1.2%, even more preferably less than 1% by weight chloride ions, or chloride containing compounds. The detergent composition can comprise a coated source of percarbonate. The source of percarbonate can be coated by any coating known in the art, or combination thereof. Preferably, the coating comprises one or more alkali metal salt, preferably this is sodium carbonate, sodium bicarbonate, sodium silicate, sodium sulphate, or any combination thereof. The coated sodium percarbonate is formed by contacting the percarbonate source with the coating in such a way that the coating is present on the surface of the source of percarbonate. The coating is present on the surface of the source of percarbonate in such a way as to either completely or partially coat the percarbonate source.
The coated source of percarbonate is prepared by a method comprising contacting the source of percarbonate with carbon dioxide to form a coating of sodium bicarbonate on the surface of the sodium percarbonate particle. Usually this is done in the presence of moisture.
The coated source of percarbonate particle comprises a coating present at a level of 0.01% to 20%, preferably 1% to 15%, more preferably 4% to 10%, by weight of the coated sodium percarbonate particle Any detergent components which comprise sodium percarbonate can also be coated in this manner.
The coated percarbonate can be prepared by a fluidised bed process and/or by spraying the coating onto the surface of the sodium percarbonate.
The source of percarbonate preferably has a mean particle size of 500 to 1000, preferably 500 to 850, more preferably 550 to 800 micrometers.
Additional detergent ingredients
The detergent composition typically comprises additional detergent ingredients. These detergent ingredients are described below. Preferably the detergent composition comprises a surfactant, builder, chelant and a bleaching system. Surfactants
Nonionic Alkoxylated Surfactant
Essentially any alkoxylated nonionic surfactants can also be comprised by the composition of the invention. 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.
Highly preferred are nonionic alkoxylated alcohol surfactants, being the condensation products of aliphatic alcohols with from 1 to 75 moles of alkylene oxide, in particular about 50 or from 1 to 15 moles, preferably to 1 1 moles, particularly ethylene oxide and/or propylene oxide, are highly preferred nonionic surfactant comprised in the anhydrous component of the particles of the invention. 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 9 moles and in particular 3 or 5 moles, of ethylene oxide per mole of alcohol.
Nonionic Polyhydroxy Fatty Acid Amide Surfactant
Polyhydroxy fatty acid amides are highly preferred nonionic surfactant comprised by the composition of the invention , in particular those having the structural formula wherein : Rl is H, Cj.jg, preferably C C4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably Cj or C2 alkyl, most preferably C] alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 or C7-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain Cj ] - C 7 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 animation reaction; more preferably Z is a glycityl.
A highly preferred nonionic polyhydroxy fatty acid amide surfactant for use herein is a Cl2" l4 > a C15-C17 and/or C]g-C]g alkyl N-methyl glucamide.
It may be particularly preferred that the composition of the invention comprises a mixture of a C12-C18 alkyl N-methyl glucamide and condensation products of an alcohol having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 9 moles and in particular 3 or 5 moles, of ethylene oxide per mole of alcohol.
The polyhydroxy fatty acid amide can be prepared by any suitable process. One particularly preferred process is described in detail in WO 9206984. A product comprising about 95% by weight polyhydroxy fatty acid amide, low levels of undesired impurities such as fatty acid esters and cyclic amides, and which is molten typically above about 80°C, can be made by this process.
Nonionic Fatty Acid Amide Surfactant
Fatty acid amide surfactants or alkoxylated fatty acid amides can also be comprised by the composition of the invention. They include those having the formula: R^CON(R^) (R° ) wherein R" is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon or even 11 to 13 carbon atoms and R^ ar>d R8 are each individually 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 11, preferably 1 to 7, more preferably form 1-5, whereby it may be preferred that R7 is different to R8. one having x being 1 or 2, one having x being from 3 to 11 or preferably 5. Nonionic Alkyl Esters of Fatty Acid Surfactant
Alkyl esters of fatty acids can also be comprised in any material of the invention. They include those having the formula: R9COO(R! 0) wherein R^ is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon or even 11 to 13 carbon atoms and RIO is a C1-C4 alkyl, C1-C4 hydroxyalkyl, or -(C2H4O)xH, where x is in the range of from 1 to
11, preferably 1 to 7, more preferably form 1-5, whereby it may be preferred that R*0 1S a methyl or ethyl group.
Nonionic Alkylpolysaccharide Surfactant
Alkylpolysaccharides can also be comprised by the composition of the invention, such as those disclosed in US 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 R^ is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.
Polyethylene/ Propylene Glycols
The composition of the invention may comprise polyethylene and/or propylene glycol, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
Anionic Surfactant
The detergent composition of the invention, preferably comprises one or more anionic surfactants. Any anionic surfactant useful for detersive purposes is suitable. Examples include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulphate, sulphonate, carboxylate and sarcosinate surfactants. Anionic sulphate surfactants are preferred.
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, ,-,-C, o monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C^-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 Sulphate Surfactant
Anionic sulphate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulphates, alkyl ethoxysulphates, fatty oleoyl glycerol sulphates, alkyl phenol ethylene oxide ether sulphates, the C5-C17 acyl-N-(Cι-C4 alkyl) and -N-(C]-C2 hydroxyalkyl) glucamine sulphates, and sulphates of alkylpolysaccharides such as the sulphates of alkylpolyglucoside (the nonionic non-sulphated compounds being described herein).
Alkyl sulphate surfactants are preferably selected from the linear and branched primary C9-C22 alkyl sulphates, more preferably the C^ \-C\ζ branched chain alkyl sulphates and the C]2-C]4 linear chain alkyl sulphates.
Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C J Q-CI 8 alkyl sulphates which have been ethoxylated with from 0.5 to 50 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a Ci 1 - Cjg, most preferably C] \-C\ζ alkyl sulphate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
Anionic Sulphonate Surfactant
Anionic sulphonate surfactants suitable for use herein include the salts of C5-C20 linear or branched alkylbenzene sulphonates, alkyl ester sulphonates, in particular methyl ester sulphonates, C6-C22 primary or secondary alkane sulphonates, C.5-C24 olefin sulphonates, sulphonated polycarboxylic acids, alkyl glycerol sulphonates, fatty acyl glycerol sulphonates, fatty oleyl glycerol sulphonates, 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 C to Cj 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-(CHRj-CHR2-O)χ-R3 wherein R is a Cg to Cjg alkyl group, x is from 1 to 25, R\ 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-l-nonanoic acid, 2- butyl-1-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressers.
Alkali Metal Sarcosinate Surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (Rl) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, Rl 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. Cationic Surfactant
Another preferred optional ingredient of the detergent composition of the invention, is a cationic surfactant, which may preferably be present at a level of from 0.1 % to 60% by weight of the composition or particle, more preferably from 0.4% to 20%>, most preferably from 0.5%) to 5% by weight of the composition.
When present, the ratio of the anionic surfactant to the cationic surfactant is preferably from 25: 1 to 1 :3, more preferably from 15: 1 to 1 : 1. most preferably from 10:1 to 1 : 1 The ratio of cationic surfactant to the stabilising agent is preferably from 1:30 to 20:1, more preferably from 1 :20 to 10: 1.
Preferably the cationic surfactant is selected from the group consisting of cationic ester surfactants, cationic mono-alkoxylated amine surfactants, cationic bis-alkoxylated amine surfactants and mixtures thereof.
Cationic Mono-Alkoxylated Amine Surfactants
The optional cationic mono-alkoxylated amine surfactant for use herein, has the general formula:
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 11 carbon atoms; R^ and R^ are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl; R4 is selected from hydrogen (preferred), methyl and ethyl, X" is an anion such as chloride, bromide, methyl sulphate, sulphate, or the like, to provide electrical neutrality; A is selected from C1-C4 alkoxy, especially ethoxy (i.e., -CH2CH2O-), propoxy, butoxy and mixtures thereof; and p is from 1 to about 30, preferably 1 to about 15, most preferably 1 to about 8.
Highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula:
wherein R^ is Cg-Cj hydrocarbyl and mixtures thereof, preferably Cg-C^, especially Cg-C} 1 alkyl, preferably Cg and C \ Q 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)CH2θ] and
[CH2CH(CH3θ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
Cationic Bis- Alkoxylated Amine Surfactant
The cationic bis-alkoxylated amine surfactant for use herein, has the general formula:
wherein R* is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, more preferably 6 to about 11, most preferably from about 8 to about 10 carbon atoms; R^ is an alkyl group containing from one to three carbon atoms, preferably methyl; R^ and R^ can vary independently and are selected from hydrogen (preferred), methyl and ethyl, X" is an anion such as chloride, bromide, methylsulphate, sulphate, or the like, sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C \ -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:
wherein R^ is Cg-Cjg hydrocarbyl and mixtures thereof, preferably C5, Cg, Cιo> C\2> C\4 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 R is derived from (coconut) C12- Cj4 alkyl fraction fatty acids, R^ is methyl and ApR^ and A'qR^ are each monoethoxy.
Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:
wherein R is Cg-Ci g hydrocarbyl, preferably Cg-C^ alkyl, independently p is 1 to about 3 and q is 1 to about 3, R^ 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)CH2θ] and [CH2CH(CH3θ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
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(OR4)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 R^ is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are C^Q-Cig alkyl dimethylamine oxide, and Cιo-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 comprised by the composition of 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 C -Cιg hydrocarbyl group, each R^ is typically C1-C3 alkyl, and R^ is a C1 -C5 hydrocarbyl group. Preferred betaines are C\ 2- 18 dimethyl-ammonio hexanoate and the ClO-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.
Water-Soluble Builder Compound
The detergent composition of the invention preferably comprises a water-soluble builder compound, typically present at a level of from 0%> to 36%> by weight, preferably from 1% to 35%) by weight, more preferably from 10% to 35%o, even more preferably from 12%> to 30% by weight of the composition or particle. Preferably, the water-soluble builder compound is an alkali or earth alkali metal salt of phosphate present at the level described above.
Other typical water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, phosphates, and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfmyl carboxylates. Polycarboxylates 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-l,l,3-propane tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in US Patent No. 3,936,448, and the sulphonated 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.
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 detergent composition of the invention, or any detergent component comprised by the detergent composition of the invention, may contain a partially soluble or insoluble builder compound.
Examples of largely water insoluble builders include the sodium aluminosilicates.
Suitable aluminosilicate zeolites have the unit cell formula Naz[(AlO2)z(SiO2)y]. H2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 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 [Alθ2) l2 (Siθ2)i2]. xH2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nagg [(Alθ2)86(Siθ2)l06J- 276 H2O.
Preferred crystalline layered silicates for use herein have the general formula:
NaMSixO2x+ι .yH2O
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. Herein, x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2. The most preferred material is δ-Na2Si2θ5, available from Hoechst AG as NaSKS-6.
Organic Peroxyacid Bleaching System
The detergent composition of the invention preferably comprises an organic peroxyacid precursor. The production of the organic peroxyacid may occur by an in situ reaction of such a precursor with the percarbonate source. In an alternative preferred execution a preformed organic peroxyacid is incorporated directly into the composition.
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
Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O- acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1 147871, 2143231 and EP-A-0170386.
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:
O Λ 0
-N— C— R — N N — N— C ιι-CH— R4
R3 U ■ R U3 Y i
I
Y
R3 Y I I -O-CH=C— CH=CH2 -O-CH=C-CH=CH2
-O-
R3 O Y
11 i
-O-C=CHR4 , and — N— S— CH— R4 II R3 O
and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from 1 to
14 carbon atoms, R 3 is an alkyl chain containing from 1 to 8 carbon atoms, R 4 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 ammonium groups.
The preferred solubilizing groups are -SO,~M , -CO-'M , -SO M , -N (R ) .X" and
3 - + - + 3 O<— N(R )τ and most preferably -SO, M and -CO- 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, methylsulphate 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.
Typical alkyl percarboxylic precursor compounds of the imide type include the N-
,N,N^N^ 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 alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulphonate (iso-NOBS), sodium nonanoyloxybenzene sulphonate (NOBS), sodium acetoxybenzene sulphonate (ABS) and pentaacetyl glucose.
The detergent composition preferably comprises 0.1% to 2%, preferably 0.1% to 1%, more preferably 0.2% to 0.7%, even more preferably 0.25% to 0.6%, by weight TAED.
The detergent composition preferably comprises 0.1% to 4%, preferably 0.2% to 3%, more preferably 0.4% to 2%, even more preferably 0.7% to 1.9%, by weight NOBS.
The detergent composition can also comprise a combination of NOBS and TAED, present at the levels described hereinbefore.
Amide Substituted Alkyl Peroxyacid Precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
wherein Rl is an alkyl group with from 1 to 14 carbon atoms, R^ 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 sulphonates, 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.
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:
wherein R. is H, alkyl, alkaryl, aryl, or arylalkyl.
Preformed Organic Peroxyacid
The organic peroxyacid bleaching system may contain a preformed organic peroxyacid.
A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae: R N — R' OOH R N R OOH
O R^ O or R5 O O
wherein R is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R^ is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R^ 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.
Heavy Metal Ion Sequestrant
The detergent composition of the invention, or any detergent component comprised by the detergent composition of the invention, preferably comprise as an optional detergent ingredient, 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 0.05%> to 2%, preferably from 0.1 % to 1.5%, more preferably from 0.25% to 1.2% and most preferably from 0.5%) to 1% by weight of the composition.
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.
Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethyl enetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2- hydroxypropylenediamine disuccinic acid or any salts thereof. Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
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- 1,2,4-tricarboxylic acid are also suitable. Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'- disuccinic acid (HPDDS) are also suitable.
Enzyme
Another preferred optional detergent ingredient useful in the detergent composition of the invention, or any detergent component comprised by the detergent composition of the invention, is one or more additional enzymes. Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist- Brocades, those sold by Genencor International, and those sold under the tradename
Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001%> to 4% active enzyme by weight of the composition.
Preferred amylases include, for example, 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 and BAN by Novo Industries A S. Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001%> to 2% active enzyme by weight of the composition.
Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001%> to 10%) by weight of the particle, preferably 0.001% to 3% by weight of the composition, most preferably from 0.001%> to 0.5%> by weight of the compositions.
The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., 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 detergent ingredients of the detergent composition of the invention, or any detergent component comprised by the detergent composition of the invention, and are preferably present as components of any particulate components where they may act such as to bind the particulate component together. By organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.
Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1% to 50% by weight of the particle, preferably from 0.5%) to 25%o, most preferably from l%o to 15% 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 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000. The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and 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.
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:
wherein X is a nonionic group selected from the group consisting of H, C]-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-01 1965 and US 4,659,802 and US 4,664,848.
Suds Suppressing System
The detergent composition preferably comprises a suds suppresser at a level less than 5%, preferably 0.01% to 5%, preferably from 0.05% to 4%, most preferably from 0.1% to 3%, by weight of the composition Preferably the suds suppresser is either a soap, paraffin, wax, or any combination thereof. If the suds suppresser is a suds suppressing silicone, then the detergent composition preferably comprises less than 0.06%> by weight extractable suds suppressing silicone.
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 silica component. The term "silicone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydime hylsiloxanes having trimethylsilyl end blocking units. Preferably the composition comprises less than 0.6% by weight extractable suds suppressing silicone.
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 suppresser 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 l8*- 40 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%o 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 antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level of less than 5%>, preferably 0.01% to 5%, more preferably 0.05%o to 4%, even more preferably 0.1% to 3%, 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 less than 5%, preferably 0.01% to 5%, more preferably 0.05% to 4%, even more preferably 0.1% to 3%, 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 C \ -C \ g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of less than 5%, preferably 0.01% to 5%, more preferably 0.05% to 4%o, even more preferably 0.1% to 3%, 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.
Clay Softening System
The detergent composition of the invention may comprise a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.
The clay mineral compound is preferably a smectite clay compound. Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents.
Polymeric Dye Transfer Inhibiting Agents
The detergent composition of the invention 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-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
a) Polyamine N-oxide polymers
Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula :
P
(I) Ax
R
wherein P is a polymerisable unit, and
O O O
A is NC, CO, C, -O-, -S-, -N-; x is O or 1 ;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
The N-O group can be represented by the following general structures :
O
wherein Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups. The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. Prefeπed polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyπole, imidazole, pyπolidine, piperidine, quinoline, acridine and derivatives thereof.
Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
The polyamine N-oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water- solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000.
b) Copolymers ofN-vinylpyrrolidone and N-vinylimidazole
Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000. The preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2. c) Polyvinylpyπolidone
The detergent composition of the invention may also utilize polyvinylpyπolidone ("PVP") having an average molecular weight of from 2,500 to 400,000. Suitable polyvinylpyπolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyπolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
d) Polvvinyloxazolidone
The detergent composition of the invention may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.
e) Polyvinylimidazole
The detergent composition of the invention may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.
Optical Brightener
The detergent composition of the invention may also optionally comprise from 0.005% to 5%> by weight of certain types of hydrophilic optical brighteners.
Hydrophilic optical brighteners useful herein include those having the structural formula:
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-UNPA-GX is the prefeπed hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, R\ 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 is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
Cationic Fabric Softening Agents
Cationic fabric softening agents can also be incorporated into the detergent composition of the invention or in compositions containing the detergent component in accordance with the present invention. Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 01 1 340.
Cationic fabric softening agents are typically incorporated at total levels of from 0.5% to 15%) by weight, normally from 1% to 5% by weight.
Other Optional Ingredients
Other optional detergent ingredients suitable for inclusion in the compositions or detergent component of the invention include highly preferably perfumes, colours and filler salts, with sodium sulphate being a prefeπed filler salt.
Form of Composition
The detergent composition of the invention can be made by a variety of methods, including dry-mixing, extruding, compacting and agglomerating of the various compounds comprised in the detergent composition. The particles can be present in the compositions as a separate component of the composition, or can be added to other components or compounds of the composition. The granular detergent composition of the invention can take a variety of physical forms including granular, flakes or extrudate.
Laundry Washing Method
Laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution for washing by machine or for washing by hand, having dissolved or dispensed therein an effective amount of a laundry composition. By an effective amount of the detergent composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 1 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional laundry methods. Other laundry washing processes known in the art can also be used.
Packaging for the Compositions
Commercially marketed executions of the bleaching compositions can be packaged in any suitable container including those constructed from paper, cardboard, plastic materials and any suitable laminates. A prefeπed packaging execution is described in European Application No. 94921505.7.
Examples
Abbreviations used in examples
In the detergent compositions, the abbreviated component identifications have the following meaning:
LAS Sodium linear Cl 1-13 alkyl benzene sulfonate LAS (I) Potassium linear or branched C 11 - 13 alkyl benzene sulfonate TAS Sodium tallow alkyl sulfate CxyAS Sodium Clx - Cly alkyl sulfate C46SAS Sodium C14 - C16 secondary (2,3) alkyl sulfate CxyEzS Sodium Clx-Cly alkyl sulfate condensed with z moles of ethylene oxide CxyEz Clx-Cly predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide
QAS R2.N+(CH3)2(C2H4OH) with R2 = C12 - C14 QAS 1 R2.N+(CH3)2(C2H4OH) with R2 = C8 - C 11 APA C8 - CIO 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 C16-C18 alkyl N-methyl glucamide
TPKFA C12-C14 topped whole cut fatty acids
STPP Anhydrous sodium tripolyphosphate
TSPP Tetrasodium pyrophosphate
Zeolite A Hydrated sodium aluminosilicate of formula
Nal2(AlO2SiO2)12.27H2O having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis) NaSKS-6 Crystalline layered silicate of formula d- Na2Si2O5 Citric acid I Anhydrous citric acid, 80% having a particle size of from 40 microns to 70 microns, and having a volume median particle size of 55 microns
Citric acid II Anhydrous or monohydrate citric acid, 80%) having a particle size of from 15 microns to 40 microns, having a volume average particle size of 25 microns
Malic acid Anhydrous malic acid, 80% having a particle size of from 50 microns to 100 microns, having a volume median particle size of
75 microns
Maleic acid Anhydrous maleic acid, 80% having a particle size of from 5 microns to 30 microns, having a volume median particle size of 15 microns
Tartaric acid Anhydrous tartaric acid, 80%> having a particle size of from 25 microns to 75 microns, having a volume median particle size of 50 microns
Carbonate I Anydrous sodium carbonate having 80%) by volume of particles with a particle size from 50 microns to 150 microns with a volume median particle size of 100 microns Carbonate II Anydrous sodium carbonate having 80%> by volume of particles with a particle size from 35 microns to 75 microns, having a volume median particle size of 55 microns
Bicarbonate II: Anhydrous sodium bicarbonate having 80%> by volume of particles with a particle size from 100 microns to 200 microns with a volume median particle size of 150 microns
Bicarbonate I Anydrous sodium bicarbonate having 80%o by volume of particles with a particle size from 15 microns to 40 microns, having a volume median particle size of 25 microns
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 425μm and 850μm
MA AA Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 70,000 MA AA (1) Copolymer of 4:6 maleic/acrylic acid, average molecular weight about 10,000
AA Sodium polyacrylate polymer of average molecular weight 4,500
CMC Sodium carboxymethyl cellulose
Cellulose ether Methyl cellulose ether with a degree of polymerization of 650 available from Shin Etsu Chemicals
Protease Proteolytic enzyme, having 3.3%> by weight of active enzyme, sold by NOVO Industries A S under the tradename Savinase
Protease I Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591, sold by Genencor Int. Inc. Alcalase Proteolytic enzyme, having 5.3%o by weight of active enzyme, sold by NOVO Industries A/S
Cellulase Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Carezyme
Amylase Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T
Lipase Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase
Lipase (1) Lipolytic enzyme, having 2.0%) by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Ultra Endolase Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries A/S
PB4 Particle containing sodium perborate tetrahydrate of nominal formula NaBO2.3H2 O, the particles having a weight average particle size of 950 microns, 85% particles having a particle size of from 850 microns to 950 microns
PB1 Particle containing anhydrous sodium perborate bleach of nominal formula NaBO2.H 202, the particles having a weight average particle size of 800 microns, 85%> particles having a particle size of from 750 microns to 950 microns
Percarbonate The sodium percarbonate source of the invention as described hereinbefore (see detailed description of the invention, percarbonate source)
Coated percarbonate: The coated sodium percarbonate source of the invention, as described hereinbefore (see detailed description of the invention, percarbonate source), as described hereinafter, with 4.5% by weight coating comprising sodium bicarbonate and/or sodium sulphate and prepared by a fluidised bed process (percarbonate sample 2) or with 4.5% by weight sodium carbonate and/or sodium sulphate and prepared by a crystalline/classification process, ex
Solvay
NOBS Particle comprising nonanoyloxybenzene sulfonate in the form of the sodium salt, the particles having a weight average particle size of 750 microns to 900 microns
NAC-OBS Particle comprising (6-nonamidocaproyl) oxybenzene sulfonate, the particles having a weight average particle size of from 825 microns to 875 microns
TAED I Particle containing tetraacetylethylenediamme, the particles having a weight average particle size of from 700 microns to 1000 microns TAED II Tetraacetylethylenediamine of a particle size from 150 microns to
600 microns
DTPA Diethylene triamine pentaacetic acid DTPMP Diethylene triamine penta (methylene phosphonate), marketed by
Monsanto under the Tradename Dequest 2060 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
EDDS Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its sodium salt.
HEDP 1,1-hydroxyethane diphosphonic acid
PEGx Polyethylene glycol, with a molecular weight of x (typically 4,000)
PEO Polyethylene oxide, with an average molecular weight of 50,000
TEPAE Tetraethylenepentaamine ethoxylate
PVI Polyvinyl imidosole, with an average molecular weight of 20,000
PVP Polyvinylpyrolidone polymer, with an average molecular weight of
60,000 PVNO Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000
PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole, with an average molecular weight of 20,000
QEA bis((C2H5O)(C2H4O)n)(CH3) -N+-C6H 12-N+-(CH3) bis((C2H5O)-(C2H4 O))n, wherein n = from 20 to 30
SRP 1 Anionically end capped poly esters SRP2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer
PEI Polyefhyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen
Silicone antifoam : Polydimefhylsiloxane 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
Example 1
The mean particle size of the detergent composition was determined by the method described hereinbefore (see detailed description of the invention, mean particle size).
A detergent composition used to determine the mean particle size (MPS) is described hereinbefore (see detailed description of the invention, mean particle size). The mean particle size of a detergent composition comprising 10%> by weight sodium perborate monohydrate (sodium perborate sample) is also shown, along with two detergent compositions comprising 10%) by weight sodium percarbonate (sodium percarbonate sample 1 and 2, see below for a more detailed description) before (Oh) and after exposure for 24 hours (24h) to conditions of 32°C and 80%> relative humidity by the method described hereinbefore (see detailed description of the invention, mean particle size).
The sodium percarbonate sample 1 comprises a coated sodium percarbonate comprising or with 4.5%) by weight sodium carbonate and/or sodium sulphate and prepared by a crystalline/classification process, ex Solvay.
The sodium percarbonate sample 2 comprises a coated sodium percarbonate comprising 4.5%) by weight a coating comprising sodium bicarbonate and/or sodium sulphate and the coated sodium percarbonate is prepared by a fluidised bed process
Results
The particle size distribution(PSD)s of the said detergent compositions are shown below. Particle Size Sodium perborate sample Sodium percarbonate sample 1
(Sieve size) PSD (Oh) PSD (24h) PSD (Oh) PSD (24h)
2000 0 0.16 0.02 0.58
180 2.95 10.89 5.19 7.23
850 6.71 18.84 11.13 14.01
600 1 1.12 21.29 16.3 18.56
425 16.88 20.16 15.83 25.02
250 37.32 30.85 29.54 34.14
Pan 44.82 26.24 41.95 26.2
MPS (μm) 311 473 346 437
Particle Size Sodium percarbonate sample 2
(Sieve size) PSD (Oh) PSD (24h)
2000 0 0.01
180 4.45 3.98
850 9.31 9.52
600 19.6 20.92
425 16.75 21.73
250 28.62 37.89
Pan 41.02 32.67
MPS (μm) 351 386
Perborate Percarbonate Percarbonate sample samp] e l sampl e 2
Time Oh 24h Oh 24h Oh 24h
MPS (μm) 387 593 456 540 452 467
Increase in MPS (μm) 206 84 5
Increase in MPS
(% of origi nal MPS) 52% 26% 10% These data show that when selected sodium percarbonate, as opposed to sodium perborate is comprised by a detergent composition, the detergent composition has, after being exposed simultaneously to 32°C and 80%o relative humidity for 24 hours by the method described hereinbefore (see detailed description of the invention, mean particle size), a mean particle size of 100% to 130% of the original mean particle size.
Example 2
Perborate Percarbonate Percarbonate sample sample 1 sample 2 wkO wk8 wkO wk8 wkO wk8
Bulk density (g/1) 485 423 475 436 475 446
Bulk density
(% of original) 100 87 100 92 100 94
These data show that when selected sodium percarbonate, as opposed to sodium perborate is comprised by a detergent composition, the detergent composition has, after being stored in conditions of 32°C and 80%) relative humidity for 24 hours by the method described hereinbefore (see detailed description of the invention, mean particle size), a bulk density of 90%> to 100% of the original mean particle size.
Example 3
Table I
The following compositions are in accordance with the invention.
Table II
The following compositions are in accordance with the invention.^

Claims

What is claimed is:
1. A granular bleach-containing detergent composition with a bulk density of less than 570g/l, characterised in that the detergent composition comprises a percarbonate source, where the percarbonate source comprises a salt of percarbonate, and that, after being exposed simultaneously to 32°C and 80% relative humidity for 24 hours, the detergent composition has a mean particle size of 100%> to 130% of the original mean particle size.
2. A detergent composition according to claim 1, characterised in that, after being stored in conditions of 32°C and 80%> relative humidity for 8 weeks, the detergent composition has a bulk density of 90 to 100% of the original bulk density.
3. A detergent composition according to any preceding claim, characterised in that, after being exposed simultaneously to 32°C and 80% relative humidity for 24 hours, the detergent composition has a mean particle of 100% to 120%, preferably 100%) to 1 10%), of the original mean particle size.
4. A granular bleach-containing detergent composition with a bulk density of less than 570g/l comprising a percarbonate source and less than 0.06%> by weight extractable suds suppressing silicone, where the percarbonate source comprises a salt of percarbonate comprising less than 2% by weight chloride ions, or chloride-containing compounds.
5. A detergent composition according to any preceding claim, whereby the percarbonate source is prepared by a fluidised bed process.
6. A detergent composition according to any preceding claim, whereby the percarbonate source comprises less than 2% by weight chloride ions.
7. A detergent composition according to any preceding claim, whereby the detergent composition comprises less than 36%, preferably from 1%> to 35%, more preferably from 10%) to 35%, even more preferably 12% to 30%, by weight an alkali or earth alkali metal salt of phosphate.
8. A detergent composition according to any preceding claim, whereby the detergent composition comprises less than 5% by weight a suds suppresser, where the suds suppresser is either a soap, paraffin, wax, or any combination thereof.
9. A detergent composition according to any preceding claim, whereby the detergent composition comprises less than 0.06% by weight extractable suds suppressing silicone.
10. A detergent composition according to any preceding claim, whereby the detergent composition has a moisture content of less than 10% by weight.
11. A detergent composition according to any preceding claim, whereby the detergent composition has a reserve alkalinity greater than 6g NaOH per 1 OOg detergent composition, measured to a pH of 7.5.
12. A detergent composition according to any preceding claim, whereby the percarbonate source is present at a level from 0.01% to 12%>, preferably from 2% to 10%, more preferably from 3% to 7%, by weight.
13. A detergent composition according to any preceding claim, whereby the detergent composition comprises 0.05% to 2% by weight a metal chelating agent.
14. A detergent composition according to any preceding claim, whereby the detergent composition comprises a coated salt of percarbonate particle, characterised in that the coating comprises one or more alkali metal salt, preferably sodium carbonate, sodium bicarbonate, sodium silicate, sodium sulphate, or any combination thereof.
5. A detergent composition according to claim 13, whereby the coated salt of percarbonate particle comprises a coating present at a level of 0.01 % to 20%, preferably 4 to 15%, more preferably 4% to 10%>, by weight of the coated salt of percarbonate particle.
EP00977127A 1999-11-13 2000-11-10 Detergent compositions Withdrawn EP1228188A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9926799 1999-11-13
GB9926799A GB2356201A (en) 1999-11-13 1999-11-13 Detergent compositions
PCT/US2000/030870 WO2001036580A1 (en) 1999-11-13 2000-11-10 Detergent compositions

Publications (1)

Publication Number Publication Date
EP1228188A1 true EP1228188A1 (en) 2002-08-07

Family

ID=10864418

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00977127A Withdrawn EP1228188A1 (en) 1999-11-13 2000-11-10 Detergent compositions

Country Status (14)

Country Link
EP (1) EP1228188A1 (en)
JP (1) JP2003527465A (en)
KR (1) KR20020059724A (en)
CN (1) CN1423690A (en)
AR (1) AR033657A1 (en)
AU (1) AU1480901A (en)
BR (1) BR0015541A (en)
CA (1) CA2388838A1 (en)
CZ (1) CZ20021639A3 (en)
GB (1) GB2356201A (en)
HU (1) HUP0204153A3 (en)
MA (1) MA25877A1 (en)
MX (1) MXPA02004788A (en)
WO (1) WO2001036580A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1867707B1 (en) * 2006-06-16 2011-09-07 The Procter & Gamble Company Detergent compositions
JP5386285B2 (en) * 2008-12-15 2014-01-15 花王株式会社 Liquid detergent composition for automatic dishwashers
JP2011026456A (en) * 2009-07-27 2011-02-10 Diversey Co Ltd Oxygen-based powdered detergent composition
JP5700469B2 (en) * 2012-12-28 2015-04-15 花王株式会社 Powder detergent composition for clothing
CN106811336A (en) * 2015-11-30 2017-06-09 常州西品科技有限公司 household cleaners

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2226460B1 (en) * 1973-04-20 1976-12-17 Interox
US3951838A (en) * 1973-10-10 1976-04-20 E. I. Du Pont De Nemours And Company Silica sol stabilizers for improving the stability of sodium percarbonate in solid bleaches and detergents
GB1553505A (en) * 1975-05-13 1979-09-26 Interox Chemicals Ltd Sonduim percarbonate
LU72575A1 (en) * 1975-05-23 1977-02-10
FR2323631A1 (en) * 1975-09-15 1977-04-08 Ugine Kuhlmann MIXED STAFF STABLE IN LIXIVIEL MIXTURE
US4260508A (en) * 1979-08-15 1981-04-07 The Clorox Company Stabilized alkali metal percarbonate powder bleach
GB9007999D0 (en) * 1990-04-09 1990-06-06 Unilever Plc Particulate bleaching detergent composition
US5462804A (en) * 1993-05-06 1995-10-31 Mitsubishi Gas Chemical Co., Ltd. Stabilized particle of sodium percarbonate
US5902682A (en) * 1993-07-17 1999-05-11 Degussa Aktiengesellschaft Coated sodium percarbonate particles, a process for their preparation and their use
EP0653481A1 (en) * 1993-11-11 1995-05-17 The Procter & Gamble Company Granular detergent composition
EP0889849A1 (en) * 1996-03-27 1999-01-13 SOLVAY INTEROX (Société Anonyme) Process for producing a percarbonate
DE19830946A1 (en) * 1998-07-10 2000-01-13 Degussa Process for the preparation of coated peroxygen compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0136580A1 *

Also Published As

Publication number Publication date
GB9926799D0 (en) 2000-01-12
BR0015541A (en) 2006-03-01
AR033657A1 (en) 2004-01-07
GB2356201A (en) 2001-05-16
CZ20021639A3 (en) 2002-11-13
JP2003527465A (en) 2003-09-16
MXPA02004788A (en) 2002-08-30
HUP0204153A3 (en) 2005-04-28
CN1423690A (en) 2003-06-11
AU1480901A (en) 2001-05-30
HUP0204153A2 (en) 2003-03-28
KR20020059724A (en) 2002-07-13
MA25877A1 (en) 2003-10-01
CA2388838A1 (en) 2001-05-25
WO2001036580A1 (en) 2001-05-25

Similar Documents

Publication Publication Date Title
EP1121406B1 (en) Detergent compositions or components
WO1998035004A1 (en) Solid detergent compositions
WO1998035002A1 (en) Cleaning compositions
EP0975722A1 (en) Detergent particle
WO2000034422A2 (en) Effervescence components
EP1119604A1 (en) Foaming system and detergent compositions containing the same
EP0975723A1 (en) Foaming component
WO1999013040A1 (en) Detergent compositions
WO2001068794A1 (en) Detergent compositions
WO1999058632A1 (en) Effervescence particle
WO2001036580A1 (en) Detergent compositions
WO1998042811A1 (en) Detergent granule
WO1998044084A1 (en) Detergent particle
WO1998044084A9 (en) Detergent particle
WO1999058444A2 (en) Effervescence component
EP1019467B1 (en) granular DETERGENT COMPOSITION
WO1998017760A1 (en) A detergent composition
EP1319059B1 (en) Detergent compositions
WO2000053709A1 (en) Detergent compositions
WO1998017766A1 (en) Detergent compositions
GB2347681A (en) Detergent compositions or components

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20020524

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17Q First examination report despatched

Effective date: 20050304

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20050715