WO2001036580A1 - Detergent compositions - Google Patents

Detergent compositions Download PDF

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Publication number
WO2001036580A1
WO2001036580A1 PCT/US2000/030870 US0030870W WO0136580A1 WO 2001036580 A1 WO2001036580 A1 WO 2001036580A1 US 0030870 W US0030870 W US 0030870W WO 0136580 A1 WO0136580 A1 WO 0136580A1
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WO
WIPO (PCT)
Prior art keywords
detergent composition
percarbonate
weight
sodium
composition according
Prior art date
Application number
PCT/US2000/030870
Other languages
English (en)
French (fr)
Inventor
Paul Anthony Gould
Nicola Ethel Davidson
Susan Judith Schamp
Koen Mariette Albert Schamp
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU14809/01A priority Critical patent/AU1480901A/en
Priority to JP2001539058A priority patent/JP2003527465A/ja
Priority to KR1020027006135A priority patent/KR20020059724A/ko
Priority to HU0204153A priority patent/HUP0204153A3/hu
Priority to CA002388838A priority patent/CA2388838A1/en
Priority to BRPI0015541-1A priority patent/BR0015541A/pt
Priority to MXPA02004788A priority patent/MXPA02004788A/es
Priority to EP00977127A priority patent/EP1228188A1/en
Publication of WO2001036580A1 publication Critical patent/WO2001036580A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—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.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
PCT/US2000/030870 1999-11-13 2000-11-10 Detergent compositions WO2001036580A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
AU14809/01A AU1480901A (en) 1999-11-13 2000-11-10 Detergent compositions
JP2001539058A JP2003527465A (ja) 1999-11-13 2000-11-10 洗剤組成物
KR1020027006135A KR20020059724A (ko) 1999-11-13 2000-11-10 세제 조성물
HU0204153A HUP0204153A3 (en) 1999-11-13 2000-11-10 Detergent compositions
CA002388838A CA2388838A1 (en) 1999-11-13 2000-11-10 Detergent compositions
BRPI0015541-1A BR0015541A (pt) 1999-11-13 2000-11-10 composições detergentes
MXPA02004788A MXPA02004788A (es) 1999-11-13 2000-11-10 Composiciones detergentes.
EP00977127A EP1228188A1 (en) 1999-11-13 2000-11-10 Detergent compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9926799A GB2356201A (en) 1999-11-13 1999-11-13 Detergent compositions
GB9926799.9 1999-11-13

Publications (1)

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WO2001036580A1 true WO2001036580A1 (en) 2001-05-25

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KR (1) KR20020059724A (ja)
CN (1) CN1423690A (ja)
AR (1) AR033657A1 (ja)
AU (1) AU1480901A (ja)
BR (1) BR0015541A (ja)
CA (1) CA2388838A1 (ja)
CZ (1) CZ20021639A3 (ja)
GB (1) GB2356201A (ja)
HU (1) HUP0204153A3 (ja)
MA (1) MA25877A1 (ja)
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EP1867707B1 (en) * 2006-06-16 2011-09-07 The Procter & Gamble Company Detergent compositions
JP5386285B2 (ja) * 2008-12-15 2014-01-15 花王株式会社 自動食器洗浄機用液体洗浄剤組成物
JP2011026456A (ja) * 2009-07-27 2011-02-10 Diversey Co Ltd 酸素系粉末洗浄剤組成物
JP5700469B2 (ja) * 2012-12-28 2015-04-15 花王株式会社 衣料用粉末洗剤組成物
CN106811336A (zh) * 2015-11-30 2017-06-09 常州西品科技有限公司 家用清洁剂

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
GB1466799A (en) * 1973-04-20 1977-03-09 Interox Particulate peroxygen compounds
GB1538893A (en) * 1975-05-23 1979-01-24 Interox Stabilisation of persalt compounds
EP0623553A1 (en) * 1993-05-06 1994-11-09 Mitsubishi Gas Chemical Company, Inc. 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
EP0970917A1 (de) * 1998-07-10 2000-01-12 Degussa-Hüls Aktiengesellschaft Verfahren zur Herstellung von beschichteten Persauerstoffverbindungen

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1553505A (en) * 1975-05-13 1979-09-26 Interox Chemicals Ltd Sonduim percarbonate
FR2323631A1 (fr) * 1975-09-15 1977-04-08 Ugine Kuhlmann Persels mixtes stables en melange lixiviel
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
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

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1466799A (en) * 1973-04-20 1977-03-09 Interox Particulate peroxygen compounds
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
GB1538893A (en) * 1975-05-23 1979-01-24 Interox Stabilisation of persalt compounds
EP0623553A1 (en) * 1993-05-06 1994-11-09 Mitsubishi Gas Chemical Company, Inc. 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
EP0970917A1 (de) * 1998-07-10 2000-01-12 Degussa-Hüls Aktiengesellschaft Verfahren zur Herstellung von beschichteten Persauerstoffverbindungen

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BR0015541A (pt) 2006-03-01
AR033657A1 (es) 2004-01-07
GB2356201A (en) 2001-05-16
CZ20021639A3 (cs) 2002-11-13
JP2003527465A (ja) 2003-09-16
MXPA02004788A (es) 2002-08-30
HUP0204153A3 (en) 2005-04-28
CN1423690A (zh) 2003-06-11
AU1480901A (en) 2001-05-30
HUP0204153A2 (hu) 2003-03-28
KR20020059724A (ko) 2002-07-13
MA25877A1 (fr) 2003-10-01
CA2388838A1 (en) 2001-05-25
EP1228188A1 (en) 2002-08-07

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