WO1996005283A1 - Composition detergente - Google Patents

Composition detergente Download PDF

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Publication number
WO1996005283A1
WO1996005283A1 PCT/US1995/009620 US9509620W WO9605283A1 WO 1996005283 A1 WO1996005283 A1 WO 1996005283A1 US 9509620 W US9509620 W US 9509620W WO 9605283 A1 WO9605283 A1 WO 9605283A1
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WO
WIPO (PCT)
Prior art keywords
detergent composition
alkyl
composition according
granular detergent
compositions
Prior art date
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PCT/US1995/009620
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English (en)
Inventor
Suzanne Powell
Christiaan Arthur Jacques Kamiel Thoen
Youssef Oubrahim
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The Procter & Gamble Company
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Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=26305438&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1996005283(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from GB9416224A external-priority patent/GB2292155A/en
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP95928210A priority Critical patent/EP0775191B1/fr
Priority to DE69532758T priority patent/DE69532758T2/de
Priority to AT95928210T priority patent/ATE262577T1/de
Priority to BR9509066A priority patent/BR9509066A/pt
Priority to MX9701084A priority patent/MX9701084A/es
Publication of WO1996005283A1 publication Critical patent/WO1996005283A1/fr

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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds

Definitions

  • the present invention relates to detergent compositions comprising a bleach, a builder system and a surfactant system having improved overall cleaning performance on a range of soils, particularly oily soils and bleachable soils.
  • Ingredients commonly employed in the detergent compositions for fabric washing are surfactants, detergency builders and bleaches.
  • Builders serve a number of functions such as assisting in the control of mineral hardness, peptization and pH control.
  • the level of builder required in granular compositions for example is typically in the range of from 10% to 90% by weight of the detergent composition and builders are commonly employed at levels up to 50% .
  • a bleach detergent composition comprising a builder system in combination with a surfactant system wherein the weight ratio of the surfactant system to the builder system differs from that conventionally employed and wherein the composition has a specific lower pH range.
  • One advantage of the present invention is that the performance of certain detergency enzymes is also improved thus resulting in an improvement of the removal performance of enzymatic stains.
  • Another advantage of the present invention is the overall improved bleaching performance of the hydrophobic peracids in the compositions of the present invention at pH 8 to 9.8, despite the reduction in the rate of perhydrolysis.
  • a further advantage is that the amount of soaps formed from hardness ions and soils containing fatty acids is reduced by the use of the compositions of the present invention.
  • EPO 313 143 describes non phosphate aluminosilicate built detergent bleach compositions having effective cleaning and stain removal performance at 40°C.
  • the compositions may additionally comprise 5-40% detergent active and are described as alkaline pH 8-10.5, preferably 8-9.
  • DE 42 42 185 relates to granular wash- and cleaning compositions having a high surfactant content and a high density.
  • the compositions comprise 20-55% anionic and nonionic surfactants and optionally soap and may optionally comprise builders, bleach and enzymes.
  • the pH value of the compositions are not disclosed.
  • EPO 219 314 relates to granular detergent compositions having improved solubility.
  • the compositions comprise 30-85% linear alkyl sulphonate (LAS) and alkyl sulphate (AS), alkali metal silicate, wherein the ratio of LAS/AS to silicate is 1.5:1 to 6:1, 15-60% sulphate and 0- 20% phosphate.
  • the compositions may comprise bleaching agents and other detergency builders.
  • the examples disclose compositions in which the ratio of total builder to surfactant is high. The pH of the compositions are not disclosed.
  • European Patent Application number 94914042.0 relates to layered silicate builders in combination with secondary alkyl sulphates to minimise deposition.
  • the compositions may additionally comprise 5-30% nonionics, percarbonate bleach and have a pH of 7.5-11.
  • WO 95/02673 discloses low pH (8-9) granular detergent compositions having improved biodegradability.
  • the compositions comprise 5-50% detergent surfactant, 5-50% non phosphorous builder and 0-5% enzymes. All the exemplified compositions contain a high builder to surfactant ratio.
  • European Patent Application number 91201057.6 also relates to low pH (7-9.3) granular detergent compositions comprising a low level of chlorine scavenger which minimises fading of fabric colours.
  • the composition comprises 15-25% linear alkyl sulphonate and alkyl sulphate, 20-30% alumino silicate, 1-3% alkali metal silicate, 4-10% citric acid and 5-20% alkali metal carbonate.
  • the compositions may also comprise 5-50% detergent surfactant and 5- 95% detergency builders. All of the exemplified compositions comprise high builder to surfactant ratios.
  • the present invention is a granular detergent composition
  • a granular detergent composition comprising a bleach system, a builder system and a surfactant system, wherein the ratio of said surfactant system to said builder system is 0.8:1.0 or greater, characterised in that the pH of a 1% solution of said composition at 20°C is from 8 to 9.8.
  • the detergent composition comprises as essential components a surfactant system.
  • surfactant system refers to a system which comprises at least one surfactant selected from anionic, nonionic, cationic, zwitterionic, amphoteric surfactants and any mixtures thereof.
  • the surfactant system is selected from anionic, nonionic, cationic surfactants and mixtures thereof, more preferably from anionic and nonionic surfactants.
  • said surfactant system is preferably a non soap surfactant system.
  • the detergent composition comprises at least 1 % of a surfactant system, preferably from 10% to 50%, more preferably from 15% to 35%, most preferably from 20% to 30% of a surfactant system.
  • Anionic surfactants useful herein include the conventional primary, branched-chain and random C10-C20 alkyl sulphates ("AS"), the ClO"Cl8 secondary (2,3) alkyl sulphates of the formula CH3(CH2) x (CHOS ⁇ 3 " M + ) CH3 and CH3(CH2) y (CHOS ⁇ 3 ⁇ M + ) CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulphates such as oleoyl sulphate, the C10-C1 alkyl alkoxy sulphates ("AE X S"; especially EO 1-7 ethoxy sulphates), Cio-Cjs alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), sulphated C10-C18 alkyl polyglycosides, and C12-C
  • suitable alkyl or hydroxyalkyl alkoxy lated sulphates for use herein are of the formula RO(A) m S ⁇ 3M, wherein R is an unsubstituted C11-C24 alkyl or hydroxyalkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably a C12-C18 alkyl or hydroxyalkyl component, A is an ethoxy or propoxy group, m is from 1 to 15, more preferably from 1 to 10, and M is H or a cation which may be selected from metal cations such as sodium, potassium, lithium, calcium, magnesium, ammonium or substituted ammonium.
  • substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations such as tetramethyl-ammonium, dimethyl piperidium and cations derived from alkanolamines, e.g. monoethanolamine, diethanolamine and triethanolamine and mixtures thereof.
  • exemplary surfactants are C12- Ci8 alkyl polyethoxylate (2.25) sulphate, C12-C18 alkyl polyethoxylate (3) sulphate and C12-C1 alkyl polyethoxylate (4) sulphate wherein M is selected from sodium or potassium.
  • C12-C14 alkyl sulphate which has been ethoxylated with an average of from 0.5 to 4 moles of ethylene oxide per molecule is especially preferred.
  • anionic surfactants for use herein include salts (e.g. alkali metal and ammonium salts) of Cn-C24, preferably C 2-C20 alkyl sarcosinates, linear alkylaryl sulphonates, particularly linear alkyl benzene sulphonates, primary or secondary alkane sulphonates, alkene sulphonates such as ⁇ -olefin sulphonates, ether sulphonates, sulphonated poly carboxylic acids, oxyalkane sulphonates (fatty acid isethionates), acylamino alkane sulphonates (taurides), alkyl glycerol sulphonates and sulphates, fatty acyl glycerol sulphonates, fatty oleoyl glycerol sulphonates, and any mixtures thereof.
  • salts e.g. alkali metal and ammonium salts
  • anionic surfactants are fatty acids and the salts thereof, particularly monocarboxylic fatty acids and the salts thereof.
  • Preferred anionic surfactants for use herein are alkyl sulphates, alkyl alkoxy lated sulphates and mixtures thereof.
  • compositions comprise from 3% to 30%, preferably from 10% to 20%, most preferably from 12% to 18% of a anionic surfactant.
  • another component of the surfactant system is a nonionic surfactant.
  • polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use herein.
  • the polyethylene oxide condensates are preferred.
  • These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide.
  • the alkyl ethoxylate condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use herein.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.
  • Most preferred are the condensation products of alcohols having an alkyl group containing from 8 to 15 carbon atoms with from about 3 to about 9 moles of ethylene oxide per mole of alcohol.
  • nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of C11-C15 linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodo.TM 45.9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), Neodo.
  • NeodolTM 23-3 the condensation product of C12-C13 linear alcohol with 3 moles of ethyene oxide
  • Dobanol 91 and Dobanol 25 marketed by the Shell Chemical Company and Lial 111 marketed by Enichem.
  • condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein.
  • examples of compounds of this type include certain of the commercially-available Pluronic ⁇ surfactants, marketed by BASF.
  • condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein.
  • this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
  • Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21 , 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties.
  • the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • the preferred alkylpolyglycosides have the formula
  • R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, x is from 0 to 10 preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 and t is from 0 to 10.
  • the glycosyl is preferably derived from glucose.
  • Fatty acid amide surfactants suitable for use herein are those having the formula:
  • R is H or a C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl and R2 is a C5-C31 hydrocarbyl and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxy groups directly connected to the chain or an alkoxylated derivative thereof.
  • R is a methyl
  • R is a straight chain Cll- C15 alkyl or alkenyl such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose in a reductive amination reaction
  • polyhydroxy fatty acid amides suitable for use herein are gemini polyhydroxy fatty acid amides having the formula:
  • X is a bridging group having from about 2 to about 200 atoms
  • Z and Z' are the same or different alcohol-containing moieties having two or more hydroxyl groups (e.g., glycerol, and units derived from reducing sugars such as glucose, maltose and the like), or either one (but not both) of Z or Z' is hydrogen
  • R and R 1 are the same or different hydrocarbyl moieties having from about 1 to about 21 carbon atoms and can be saturated, branched or unsaturated (e.g., oleoyl) and mixtures thereof.
  • Preferred X groups are selected from substituted or unsubstituted, branched or linear alkyl, ether alkyl, amino alkyl, or amido alkyl moieties having from about 2 to about 15 carbon atoms.
  • Preferred alkyl moieties are unsubstituted, linear alkyl moieties having the formula -(CH2)rr > wherein n is an integer from 2 to about 15, preferably from 2 to about 10, and most preferably from 2 to about 6; and also unsubstituted, branched alkyl moieties having from 3 to about 15 carbon atoms, preferably from 3 to about 10 carbon atoms, and most preferably from 3 to about 6 carbon atoms.
  • ethylene and propylene (branched or linear) alkyl moieties are ethylene and propylene (branched or linear) alkyl moieties.
  • unsubstituted, branched or linear ether alkyl moieties having the formula -R2-(0-R2) m -, wherein each R2 is independently selected from C2-C8 branched or linear alkyl and/or aryl moieties (preferably ethyl, propyl or combinations thereof) and m is an integer from 1 to about 5.
  • X may also be unsubstituted, branched or linear amino and/or amido alkyl moieties having the formula -R2-(N(R3)-R2) m -, wherein each R* is independently selected from C2-C8 branched or linear alkyl and/or aryl moieties (preferably ethyl, propyl or combinations thereof), m is an integer from 1 to about 5, and R3 is selected from hydrogen, C1-C5 alkyl, and -C(0)R 4 -, wherein R 4 is C1-C21 alkyl, including -C(0)R.
  • the X moiety may be derived from commercially available amine compounds such as, for example, Jeffamines- (supplied by Texaco) such as JED600, JEDR148, JEDR192, JED230, JED2000, J-D230 and J-D400.
  • Jeffamines- supplied by Texaco
  • Preferred X moieties therefore include: -(CH2)2-, -( H2)3-, - (CH 2 ) 4 -, -(CH 2 )5-, -(CH 2 )6-, -CH 2 CH(CH 3 )(CH 2 )3-, -(CH 2 )2-0-(CH 2 )2- , -(CH 2 )3-0-(CH 2 )3-, -(CH 2 )2-0-(CH 2 )3-0-(CH2)2-, -(CH 2 )3-0-(CH2)2-0-(CH 2 )3-, -(CH 2 )2-0-(CH2)3-0-(CH2)2-, -(CH 2 )2- NH-(CH 2 )2-, -(CH 2 )3-NH-(CH 2 )3-, -(CH 2 )2-NH-(CH 2 )3-, -(CH 2 )2-NH-(CH 2 )3-, -(CH 2 )2-NH-(
  • Preferred Z and Z' groups are independently selected from polyhydroxyhydrocarbyl moieties having a linear hydrocarbyl chain with at least 2 hydroxyls (in the case of glycerol) or at least 3 hydroxyls ( in the case of other sugars) directly connected to the chain, or an alkoxy lated derivative (preferably ethoxy lated or propoxylated) thereof.
  • Z and Z' preferably will be derived from a reducing sugar, more preferably Z and/or Z' is a glycityl moiety.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde.
  • high dextrose com syrup high fructose com syrup, and high maltose com syrup can be utilised as well as the individual sugars listed above. These com syrups may yield a mix of sugar components for Z and Z'. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z and/or Z' preferably will be selected from the group consisting of -CH2-(CHOH)-p-CH2 ⁇ H, - CH(CH2 ⁇ H)-(CHOH) p -i-CH2 ⁇ H, -CH2-(CHOH)2(CHORl)(CHOH)- CH2OH, where p is an integer from 1 to 5, inclusive, and Rl is H or a cyclic mono- or polysaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein p is 4, particularly -CH2-(CHOH)4- CH2OH.
  • R and R' groups are independently selected from C3-C21 hydrocarbyl moieties, preferably straight or branched chain C3-C13 alkyl or alkenyl, more preferably straight chain C5-C11 alkyl or alkenyl, most preferably straight chain C5-C9 alkyl or alkenyl, or mixtures thereof.
  • R- CO-N ⁇ and/or R'-CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • Examples of such compounds therefore include, but are not limited to: CH 3 (CH2)6C(0)N[CH2(CHOH)4CH 2 OH]-(CH2)2-
  • Preferred nonionic surfactant for use herein are polyhydroxyfatty acid amides, ethoxy lated alcohols, alkylpolyglucosides and mixtures thereof.
  • compositions of the present invention comprise from 1 % to 20%, preferably from 3% to 18%, more preferably from 5% to 15% of said nonionic surfactants.
  • the anionic and nonionic surfactant are present in the detergent composition at a ratio of from 1.0:9.0 to 1.0:0.25, preferably from 1.0:1.5 to 1.0:0.4 .
  • Cationic detersive surfactants suitable for use herein are those having one long chain hydrocarbyl group.
  • cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides and surfactants having the formula: 14 [R2(OR 3 )y][R (OR3) y ] 2 R5N+X-
  • R2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain
  • each R3 is selected from the group consisting of CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH2 ⁇ H)-, - CH2CH2CH2-, and mixtures thereof
  • each R 4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups, -CH2CHOH- CHOHCOR6CHOHCH2OH wherein R6 is any hexose or hexose polymer having a molecular weight less than about 1000 and hydrogen when y is not 0
  • R*5 is the same as R 4 or is an alkyl chain wherein the total number of carbon atoms of R ⁇ plus R ⁇ is not more than about 18
  • each y is from about 0 to about 10 and the sum of the y
  • Preferred cationic surfactants are the water soluble quaternary ammonium compounds useful in the present composition have the formula:
  • R1R2R3R4N+X- wherein Rj is a C8-C16 alkyl, each of R2, R3 and R4 is independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl and (C2H4 ⁇ ) x H where x has a value of from 1 to 5 and X is an anion. Not more than one of the R2, R3 or R4 should be benzyl.
  • the preferred alkyl chain length for Rj is from C12-C15, particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived from synthetically by olefin build up or OXO alcohols synthesis.
  • Preferred groups for the R2R3 and R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
  • Suitable quaternary ammonium compounds for use herein are: coconut trimethyl ammonium chloride or bromide; coconut methyl dihydroxyethyl ammonium chloride or bromide; decyl trimethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide; C12-C15 dimethyl hydroxyethyl ammonium chloride or bromide; coconut dimethyl hydroxyethyl ammonium chloride or bromide; myristyl trimethyl ammonium methyl sulphate; lauryl dimethyl benzyl ammonium chloride or bromide; lauryl dimethyl (ethoxy)4 ammonium chloride or bromide and choline esters.
  • the detergent composition may comprise from 0.1 % to 6%, preferably from 1.0% to 3.5% of a cationic surfactant.
  • the surfactant system of the present invention may also comprise zwitterionic and/or amphoteric surfactants such as C12-C18 betaines, sulphobetaines ("sultaines") and C10-C18 amine oxides.
  • zwitterionic and/or amphoteric surfactants such as C12-C18 betaines, sulphobetaines ("sultaines") and C10-C18 amine oxides.
  • the detergent composition comprises as an essential ingredient a builder system.
  • builder system refers to a system comprising at least one builder selected from the builders defined herein below and any mixtures thereof.
  • the builder system may comprise inorganic as well as organic builders and which are selected from the group consisting of alkali metal silicates, layered silicates, aluminosilicates, phosphates, citrates, succinates, hexadioates and mixtures thereof.
  • Suitable phosphate builders for use herein include the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, orthophosphates and glassy polymeric meta-phosphates) and phosphonates.
  • Inorganic detergent builders include, but are not limited to, phytic acid, silicates and aluminosilicates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) and the so- called “weak” builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt” situation that may occur with zeolite or layered silicate builders.
  • silicate builders are the alkali metal silicates, particularly those having a Si ⁇ 2:Na2 ⁇ ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminium. NaSKS-6 has the delta-Na2S-2 ⁇ 5 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3 ,417,649 and DE- A-3 ,742,043.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 ⁇ + l *yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • the delta-Na2S-2 ⁇ 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
  • x Na ⁇ 2 [(Al ⁇ 2)l2(Si ⁇ 2)l2]-xH 2 0 wherein x is from about 20 to about 30, especially about 27.
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are also useful as builders in the detergent compositions of the present invention, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2- dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • the builder system preferably comprises builders selected from alkali metal silicates, layered silicates, aluminosilicates, citrates, phosphates, succinates and mixtures thereof, more preferably selected from alkali metal silicates, layered silicates, aluminosilicates, citrates and mixtures thereof.
  • compositions will typically compri issee at least 1 % builder, preferably 5% to 50%, most preferably from 15% to 35%, more preferably 18% to 28% .
  • the ratio of said surfactant system to said builder system is 0.8:1.0 or more, preferably 0.9:1.0 to 4.0:1.0, more preferably from 0.95:1.0 to 3.0:1.0, most preferably from 1.0:1.0 to 2.0:1.0.
  • the detergent compositions herein comprise as an essential ingredient a bleach system.
  • bleach system refers to a system containing a bleaching agent and one or more bleach activators.
  • Bleaching agents will typically be at levels of from 1 % to 40%, more typically from 5% to 30%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from 0.1 % to 60%, more typically from 0.5% to 40% of the bleaching composition comprising the bleaching agent-plus- bleach activator.
  • the bleach system used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate” bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
  • a preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
  • the percarbonate can be coated with silicate, borate or water- soluble surfactants. Preferred coatings are based on carbonate/sulphate mixtures.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
  • bleaching, agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof.
  • Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Bums et al.
  • bleaching agents can also be used.
  • Peroxygen bleaching agents, the perborates, e.g., sodium perborate (e.g., mono- or tetra-hydrate) , the percarbonates, etc. are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
  • bleach activators e.g., sodium perborate (e.g., mono- or tetra-hydrate)
  • bleach activators e.g., sodium perborate (e.g., mono- or tetra-hydrate)
  • bleach activators e.g., sodium perborate (e.g., mono- or tetra-hydrate)
  • bleach activators e.g., mono- or tetra-hydrate
  • nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.
  • RlN(R5)C(0)R2c(0)L or RlC(0)N(R5)R2c(0)L wherein Rl is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R-5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group.
  • a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydroxyl anion.
  • a preferred leaving group is phenol sulfonate.
  • bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6- nonanamidocaproyl)- oxybenzenesulfonate, (6-decanamido- caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551 , incorporated herein by reference.
  • Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference.
  • a highly preferred activator of the benzoxazin-type is:
  • Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams, acyl pyrolidone and acyl valerolactams of the formulae:
  • R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.
  • Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5- trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, adsorbed into sodium perborate.
  • Other preferred activators are
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilised herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminium phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from 0.025% to 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • the bleaching compounds can be catalysed by means of a manganese compound.
  • a manganese compound Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621 , U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos.
  • Preferred examples of these catalysts include Mnr v 2( u - )3(1 ,4,7-trimethyl-l ,4,7-triazacyclononane)2(PF6)2, Mn- ⁇ 2(u-0) ⁇ (u-OAc)2(l ,4,7-trimethyl-l ,4,7-triazacyclononane)2- (Cl ⁇ 4)2, MnIV 4 ( u -0)6(l ,4,7-triazacyclononane)4(Cl ⁇ 4)4, Mn ⁇ Mn ⁇ (u-0) ⁇ (u-OAc)2-(l ,4,7-trimethyl-l,4,7-triazacyclononane)2(Cl ⁇ 4)3, Mn IV (l,4,7-trimethyl-l,4,7-triazacyclononane)- (OCH3)3(PF6), and mixtures thereof.
  • metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611.
  • the use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084.
  • the performance of the composition is improved by the use of specific pH values.
  • the compositions have a pH of from 8 to 9.8, preferably from 8.5 to 9.8, more preferably from 9 to 9.8, measured at 20°C at 1 % concentration.
  • the required pH value of the compositions of the present invention may be achieved by methods known in the art such as modification of the buffer system and/or incorporation of acidic species.
  • the buffer system is based on carbonate, bicarbonates, protonic acids and/ or coordinatively unsaturated metals or non metals.
  • the detergent composition may comprise any number of optional ingredients commonly employed in detergent compositions such as chelants, soil release agents, enzymes, suds suppressors, softeners and brighteners and the like.
  • the detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, poly functionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethy lenediaminetetracetates , N-hydroxyethy lethylenediaminetriacetates , nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetra- aminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Poly functionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as l,2-dihydroxy-3,5- disulfobenzene.
  • a preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins. If utilised, these chelating agents will generally comprise from 0.1 % to 10% more preferably, from 0.1 % to 3.0% by weight of such compositions.
  • EDDS ethylenediamine disuccinate
  • Polymeric soil release agents are characterised by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibres, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibres and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • the polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fibre surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
  • Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as M ⁇ 3S(CH2)nOCH2CH2 ⁇ -, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
  • Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.
  • Soil release agents characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Ci-C ⁇ vinyl esters, preferably poly (vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vinyl ester) e.g., Ci-C ⁇ vinyl esters
  • poly (vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
  • Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters. If utilised, soil release agents will generally comprise from about 0.01 % to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1 % to about 5%, preferably from about 0.2% to about 3.0%.
  • Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-l,2-propylene units.
  • the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end- caps.
  • a particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-l ,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
  • Said soil release agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing stabiliser, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • a crystalline-reducing stabiliser preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.
  • Polymeric dispersing agents can advantageously be utilised at levels from 0.1 % to 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders.
  • Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders by crystal growth inhibition, paniculate soil release peptization, and anti-redeposition.
  • Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerised to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerised acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued march 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 90,000, most preferably from about 7,000 to 80,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1: 1, more preferably from about 70:30 to 30:70.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
  • Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate.
  • Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol or acetate terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
  • PEG polyethylene glycol
  • PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent.
  • Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1 ,000 to about 50,000, more preferably from about 1,500 to about 10,000.
  • Polyamino acid dispersing agents such as polyaspartate and polyglutamate may also be used, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antire- deposition properties.
  • Granular detergent compositions which contain these compounds typically contain from about 0.01 % to about 10.0% by weight of the water-soluble ethoxylated amines.
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986.
  • Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
  • Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S.
  • CMC carboxy methyl cellulose
  • compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
  • dye transfer inhibiting agents include poly vinyl pyrrolidone polymers, polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from 0.01 % to 10% by weight of the composition, preferably from 0.01 % to 5%, and more preferably from 0.05% to 2%.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the N-0 group can be represented by the following general structures:
  • R ⁇ , R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1 ; and the nitrogen of the N-0 group can be attached or form part of any of the aforementioned groups.
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are poly vinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.
  • polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000.
  • the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization.
  • the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
  • poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
  • Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferred for use herein.
  • the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis. Vol 113.
  • the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N- vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched. It has also been observed that additional dye transfer inhibition benefits are provided by compositions comprising nonionic polysaccharide ethers and dye transfer inhibitors such as PVNO and PVPVI such as illustrated in Example 1 , reference B and formulation B. It is believed that a synergic effect due to the combination of polysaccharides and dye transfer inhibitors provides the unexpected whiteness maintenance performance benefits to white fabrics which have been subjected to repetitive washing.
  • compositions also may employ a polyvmylpyrrolidone (“PVP”) having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000.
  • PVP's are known to persons skilled in the detergent field; see, for example, EP- A-262,897 and EP-A-256,696, incorporated herein by reference.
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from about 500 to about 100,000, preferably from about 1 ,000 to about 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
  • the detergent compositions herein may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from 0.01 % to 1 % by weight of such optical brighteners.
  • hydrophilic optical brighteners useful in the present invention are those having the structural formula:
  • Et S SOO 33 MM SSOO33MM R wherein Ri 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.
  • 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 preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • 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.
  • Rj 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.
  • the specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents herein before described.
  • the combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics.
  • the extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient".
  • the exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
  • Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration.
  • the enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof.
  • Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • Enzymes are normally incorporated at levels sufficient to provide from O.Olmg to 5 mg by weight of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from about 0.001 % to about 5%, preferably 0.01 %-l % by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
  • AU Anson units
  • proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo.
  • protealytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio- Synthetics, Inc. (The Netherlands).
  • proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985).
  • Amylases include, for example, ⁇ -amylases described in British Patent Specification No. 1 ,296,839 (Novo), RAPID ASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.
  • bacterial amylases are present so as to provide from 0.001KNU to 1000KNU, preferably from 0.01KNU to 100KNU activity per gram of detergent composition.
  • Fungal amylases if present in the compositions of the present invention preferably provide from 0.01 FAU to 10000FAU, more preferably from 0.1 FAU to 1000FAU (Fungal alpha amylase units) per gram of detergent composition.
  • the cellulase usable in the present invention include both bacterial or • fungal cellulase.
  • Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander).
  • Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
  • cellulase enzyems are present in the detergent composition from 0.0001 % to 2%, preferably from 0.01 % to 1 % as 1000CEVU active cellulase.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1 ,372,034. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P.” Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • the LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use herein.
  • the lipase enzymes are present at from 0.001 LU to 100LU, preferably from 0.005LU to 10LU per milligram of detergent composition.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase- containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.
  • the enzymes employed herein are stabilised by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes.
  • Calcium ions are generally somewhat more effective than magnesium ions and are preferred herein if only one type of cation is being used.
  • Additional stability can be provided by the presence of various other art-disclosed stabilisers, especially borate species: see Severson, U.S. 4,537,706.
  • the level of calcium or magnesium ions should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, fatty acids, etc., in the composition.
  • any water-soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the corresponding magnesium salts.
  • a small amount of calcium ion generally from about 0.05 to about 0.4 millimoles per litre, is often also present in the composition due to calcium in the enzyme slurry and formula water.
  • the formulation may include a sufficient quantity of a water-soluble calcium ion source to provide from 1 to 30, preferably from 2 to 20 millimoles per litre in the laundry liquor. In the alternative, natural water hardness may suffice.
  • compositions herein will typically comprise from about 0.05% to about 2% by weight of a water-soluble source of calcium or magnesium ions, or both.
  • the amount can vary, of course, with the amount and type of enzyme employed in the composition.
  • compositions herein may also optionally, but preferably, contain various additional stabilisers, especially borate-type stabilisers.
  • additional stabilisers will be used at levels in the compositions from about 0.25% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 3%, by weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid).
  • Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable.
  • Substituted boric acids e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid
  • compositions of the present invention may also be incorporated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" and in front-loading European-style washing machines.
  • suds suppressors A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopaedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
  • One category of compounds which may be employed for suds suppressing benefits is fatty acids and the salts thereof, see U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John. However, whilst such compounds may assist in suds suppression, for the purposes of the present invention such compounds are to be considered as components of the surfactant system.
  • the detergent compositions herein may also contain non-surfactant suds suppressors.
  • non-surfactant suds suppressors include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g., stearone), etc.
  • suds inhibitors include N-alky lated 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, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilised in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 50°C, and a minimum boiling point not less than about 110°C (atmospheric pressure). It is also known to utilise waxy hydrocarbons, preferably having a melting point below about 100°C.
  • the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al.
  • the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms.
  • the term "paraffin,” as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Non-surfactant suds suppressors comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
  • Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
  • silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526.
  • Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
  • polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1,500 cs. at 25 °C;
  • siloxane resin composed of (CH3)3SiO ⁇ /2 units of Si ⁇ 2 units in a ratio of from (CH3)3 SiOj/2 units and to Si ⁇ 2 units of from about 0.6:1 to about 1.2:1;
  • the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol.
  • the primary silicone suds suppressor is branched/crossl inked and preferably not linear.
  • the silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800.
  • the polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight % , preferably more than about 5 weight % .
  • the preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol: copolymer of polyethylene-polypropylene glycol .
  • the preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
  • suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872.
  • the secondary alcohols include the C ⁇ -C ⁇ alkyl alcohols having a C1-C16 chain.
  • a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
  • Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
  • Mixed suds suppressors typically comprise mixtures of alcohol -I- silicone at a weight ratio of 1:5 to 5:1.
  • suds should not form to the extent that they overflow the washing machine.
  • Suds suppressors when utilized, are preferably present in a "suds suppressing amount.
  • Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
  • compositions herein will generally comprise from 0.01 % to about 5% of suds suppressor.
  • Silicone suds suppressors are typically utilised in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimised and effectiveness of lower amounts for effectively controlling sudsing.
  • Preferably from about 0.01 % to about 1 % of silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%.
  • these weight percentage values include any silica that may be utilised in combination with polyorganosiloxane, as well as any adjunct materials that may be utilised.
  • Monostearyl phosphate suds suppressors are generally utilised in amounts ranging from about 0.1 % to about 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically utilised in amounts ranging from about 0.01 % to about 5.0%, although higher levels can be used. The alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.
  • compositions of the present invention may be used in laundry detergent compositions, fabric treatment compositions and fabric softening compositions.
  • the compositions of the present invention find particular utility in automatic laundry washing machines.
  • the compositions may be formulated as conventional granules, bars, pastes or powders.
  • the detergent compositions are manufactured in conventional manner, for example in the case of powdered detergent compositions, spray drying, agglomeration or spray mixing processes may be utilised.
  • Preferably granular detergent compositions according to the present invention have a density of from 400g/l to 1200g/l, more preferably from 500g/l to lOOOg/1, most preferably from 600g/l to lOOOg/1.
  • XYEZ A C ⁇ - Ciy predominantly linear primary alcohol condensed with an average of Z moles of ethylene oxide
  • XYEZS C ⁇ - C ⁇ sodium alkyl sulphate condensed with an average of Z moles of ethylene oxide per mole
  • TFAA C 16-C is alkyl N-methyl glucamide.
  • Silicate Amo ⁇ hous Sodium Silicate (Si ⁇ 2:Na2 ⁇ ratio 2.0)
  • DETPMP Diethylene triamine penta (Methylene phosphonic acid), marketed by Monsanto under the Tradename Dequest 2060
  • compositions of the present invention were prepared by combining the listed ingredients in the given amounts.
  • All of the exemplified compositions above have a pH value of from 8 to 9.8 measured as a 1% solution at 20°C.

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

Abstract

L'invention concerne des compositions détergentes de blanchiment présentant des caractéristiques de nettoyage améliorées et comprenant un adjuvant, ainsi qu'un système tensioactif, présents selon des rapports spécifiques supérieurs à ceux qu'on utilise habituellement, ladite composition détergente présentant une plage de valeur de pH inférieure spécifiée.
PCT/US1995/009620 1994-08-11 1995-08-01 Composition detergente WO1996005283A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP95928210A EP0775191B1 (fr) 1994-08-11 1995-08-01 Composition detergente
DE69532758T DE69532758T2 (de) 1994-08-11 1995-08-01 Waschmittel
AT95928210T ATE262577T1 (de) 1994-08-11 1995-08-01 Waschmittel
BR9509066A BR9509066A (pt) 1994-08-11 1995-08-01 Composiçao detergente
MX9701084A MX9701084A (es) 1994-08-11 1995-08-01 Composiciones detergentes.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9416224.5 1994-08-11
GB9416224A GB2292155A (en) 1994-08-11 1994-08-11 Handwash laundry detergent composition comprising three surfactants
GB9511601.8 1995-06-08
GB9511601A GB2292564A (en) 1994-08-11 1995-06-08 Detergent Composition

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Publication Number Publication Date
WO1996005283A1 true WO1996005283A1 (fr) 1996-02-22

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EP (1) EP0775191B1 (fr)
AT (1) ATE262577T1 (fr)
BR (1) BR9509066A (fr)
CA (1) CA2196423A1 (fr)
DE (1) DE69532758T2 (fr)
ES (1) ES2218550T3 (fr)
MX (1) MX9701084A (fr)
WO (1) WO1996005283A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0830445A1 (fr) * 1995-06-08 1998-03-25 The Procter & Gamble Company Compositions detergentes
GB2353800A (en) * 1999-09-02 2001-03-07 Procter & Gamble Antibacterial detergent compositions
US7445644B2 (en) 2005-10-28 2008-11-04 The Procter & Gamble Company Compositions containing anionically modified catechol and soil suspending polymers
US7585376B2 (en) 2005-10-28 2009-09-08 The Procter & Gamble Company Composition containing an esterified substituted benzene sulfonate
US7892362B2 (en) 2005-10-28 2011-02-22 The Procter & Gamble Company Composition containing an esterified substituted benzene sulfonate
US8173587B2 (en) 2006-08-04 2012-05-08 Reckitt Benckiser N.V. Detergent composition
EP2737042B1 (fr) 2011-07-29 2018-03-14 Henkel AG & Co. KGaA Lessive ou produit de nettoyage présentant un composé médiateur activable électrochimiquement

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0810881D0 (en) 2008-06-16 2008-07-23 Unilever Plc Improvements relating to fabric cleaning

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US4681695A (en) * 1984-09-01 1987-07-21 The Procter & Gamble Company Bleach compositions
US4686062A (en) * 1985-02-23 1987-08-11 The Procter & Gamble Company Detergent composition
US4687592A (en) * 1985-02-19 1987-08-18 The Procter & Gamble Company Detergency builder system
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US5002691A (en) * 1986-11-06 1991-03-26 The Clorox Company Oxidant detergent containing stable bleach activator granules
US5019292A (en) * 1987-06-30 1991-05-28 The Procter & Gamble Company Detergent compositions
US5019280A (en) * 1986-11-14 1991-05-28 The Procter & Gamble Company Ion-pair complex conditioning agent with benzene sulfonate/alkyl benzene sulfonate anionic component and compositions containing same

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JP3194610B2 (ja) * 1991-12-26 2001-07-30 ライオン株式会社 高嵩密度粒状漂白洗剤組成物
US5283009A (en) * 1992-03-10 1994-02-01 The Procter & Gamble Co. Process for preparing polyhydroxy fatty acid amide compositions
AU7602994A (en) * 1993-09-09 1995-03-27 Procter & Gamble Company, The Granular detergent with n-alkoxy or n-aryloxy polyhydroxy fatty acid amide surfactant

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US5002682A (en) * 1983-04-29 1991-03-26 The Procter & Gamble Company Bleach compositions, their manufacture and use in bleach and laundry compositions
US4671891A (en) * 1983-09-16 1987-06-09 The Procter & Gamble Company Bleaching compositions
US4681695A (en) * 1984-09-01 1987-07-21 The Procter & Gamble Company Bleach compositions
US4687592A (en) * 1985-02-19 1987-08-18 The Procter & Gamble Company Detergency builder system
US4686062A (en) * 1985-02-23 1987-08-11 The Procter & Gamble Company Detergent composition
US5002691A (en) * 1986-11-06 1991-03-26 The Clorox Company Oxidant detergent containing stable bleach activator granules
US5019280A (en) * 1986-11-14 1991-05-28 The Procter & Gamble Company Ion-pair complex conditioning agent with benzene sulfonate/alkyl benzene sulfonate anionic component and compositions containing same
US5019292A (en) * 1987-06-30 1991-05-28 The Procter & Gamble Company Detergent compositions

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0830445A1 (fr) * 1995-06-08 1998-03-25 The Procter & Gamble Company Compositions detergentes
EP0830445A4 (fr) * 1995-06-08 2000-03-22 Procter & Gamble Compositions detergentes
GB2353800A (en) * 1999-09-02 2001-03-07 Procter & Gamble Antibacterial detergent compositions
US7445644B2 (en) 2005-10-28 2008-11-04 The Procter & Gamble Company Compositions containing anionically modified catechol and soil suspending polymers
US7585376B2 (en) 2005-10-28 2009-09-08 The Procter & Gamble Company Composition containing an esterified substituted benzene sulfonate
US7892362B2 (en) 2005-10-28 2011-02-22 The Procter & Gamble Company Composition containing an esterified substituted benzene sulfonate
US8119586B2 (en) 2005-10-28 2012-02-21 The Procter And Gamble Company Composition containing an esterified substituted benzene sulfonate
US8173587B2 (en) 2006-08-04 2012-05-08 Reckitt Benckiser N.V. Detergent composition
EP2737042B1 (fr) 2011-07-29 2018-03-14 Henkel AG & Co. KGaA Lessive ou produit de nettoyage présentant un composé médiateur activable électrochimiquement
EP2737042B2 (fr) † 2011-07-29 2022-04-06 Henkel AG & Co. KGaA Procédé de lavage ou de nettoyage avec un composé médiateur activable électrochimiquement

Also Published As

Publication number Publication date
BR9509066A (pt) 1998-07-21
DE69532758T2 (de) 2005-03-10
EP0775191B1 (fr) 2004-03-24
ES2218550T3 (es) 2004-11-16
EP0775191A1 (fr) 1997-05-28
DE69532758D1 (de) 2004-04-29
EP0775191A4 (fr) 1999-06-30
MX9701084A (es) 1997-05-31
CA2196423A1 (fr) 1996-02-22
ATE262577T1 (de) 2004-04-15

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