EP0767827B1 - Waschmittel - Google Patents

Waschmittel Download PDF

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Publication number
EP0767827B1
EP0767827B1 EP95923986A EP95923986A EP0767827B1 EP 0767827 B1 EP0767827 B1 EP 0767827B1 EP 95923986 A EP95923986 A EP 95923986A EP 95923986 A EP95923986 A EP 95923986A EP 0767827 B1 EP0767827 B1 EP 0767827B1
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EP
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Prior art keywords
alkyl
detergent composition
nonionic
surfactant
composition according
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EP95923986A
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English (en)
French (fr)
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EP0767827A1 (de
EP0767827A4 (de
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Nour-Eddine Guedira
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Procter and Gamble Co
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Procter and Gamble Co
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Priority claimed from JP6148881A external-priority patent/JP2849041B2/ja
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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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to granular detergent compositions comprising a builder system, nonionic polysaccharide ethers and a specific surfactant system for improved greasy soil and clay soil removal.
  • a common problem encountered during the laundering process of fabrics is mineral salt deposition.
  • Insoluble salts of calcium may be formed in the wash liquor and be deposited onto the fabric which results in the fabric gaining an undesirable grey and dull appearance.
  • Detergency builders are thus incorporated into detergent compositions in order to reduce this effect by aiding the suspension of such insoluble salts in the wash liquor.
  • Builders typically employed in detergent compositions include phosphates. However, in some locales a low phosphate formulation is required. In such circumstances the soil suspension of the formulation is reduced and the greying of fabrics is increased.
  • soil release polymers may be incorporated into the detergent composition. During laundering, the soil release agents are adsorbed onto the surface of the fabric, thereby reducing the hydrophobicity of the fabric surface. Once the fabric is treated with a soil release agent, the ease of removal of soils and stains from the surface of the fabric is considerably improved.
  • soil release agents incorporated into detergent compositions which provide benefits to primarily hydrophobic synthetic fabrics include synthetic soil release agents, preferably terephthalate based and polysaccharide ethers.
  • a surfactant system may affect the performance of the polysaccharide ether. Indeed it is known in the art that the performance of the nonionic polysaccharide ethers may be optimised in the presence of nonionic surfactants as the major surfactant species. Indeed, polysaccharide ethers such as cellulose ethers have been described for example in GB 1 534 641, which discloses nonionic surfactant detergent compositions comprising cellulose ether soil release agents such as alkyl and hydroxyalkyl cellulose ethers.
  • EPO 320296 relates to fabric softening additives for detergent compositions which soften natural fibres without causing redeposition problems on synthetics.
  • An intimate mixture of cellulose ethers and fabric softener at a ratio of 1:1 to 0.06:1 is disclosed.
  • Anionic, nonionic and mixtures of surfactants and phosphate builders are disclosed.
  • EPO 213730 relates to detergent compositions for treating fabrics which soften natural fibres without causing redeposition problems.
  • the compositions comprise nonionic cellulose ethers, a non-soap anionic detergent (2-50%) and a fabric softening agent.
  • Nonionic surfactants are also disclosed, as are phosphate builders.
  • EPO 213729 discloses detergent compositions comprising 5-50 % soap, 2-25% nonionic surfactants and 0.05-5% cellulose ether which exhibit improved low temperature solubility and low level soil redeposition.
  • the ratio of soap to nonionic surfactant is 1:1 to 10: 1.
  • EPO 256696 discloses a detergent composition for improved soil suspension comprising anionic surfactants (5-90%), vinyl pyrrolidone polymer and nonionic cellulose ether.
  • Optional ingredients include nonionic surfactants and phosphate builders.
  • EPO 054 325 discloses detergent compositions with reduced soil redeposition effect comprising a ternary mixture of CMC, carboxylate and cellulose ether with 5-50% detergent active.
  • the actives include anionic and nonionic surfactants and mixtures thereof, but no ratios are specified.
  • FR 2237960 discloses a detergent composition comprising a cellulose ether and a maleic anhydride copolymer.
  • Detergent actives including anionic and nonionic surfactants, soaps and builders including phosphates are disclosed.
  • nonionic polysaccharide ethers in a detergent formulation, where the surfactant system comprises substantially high levels of nonionic surfactants has been observed to detrimentally affect the soil release performance of the polysaccharides. This problem is further exacerbated in the presence of builder systems comprising reduced phosphate levels. It is believed that the presence of free cations resulting from the use of underbuilt detergent compositions encourage the absorption of the polysaccharide onto soil clay particles present in the aqueous wash liquor. Thus, the amount of polysaccharide available for soil release is reduced. Furthermore, the clay particles containing adsorbed polysaccharide ether readily deposit onto the fabric which results in poorer particulate/clay soil removal performance.
  • a granular detergent composition comprising a nonionic polysaccharide ether and a surfactant system having improved soil removal performance and reduced clay soil removal negatives.
  • a surfactant system comprising a non soap anionic surfactant and a nonionic surfactant at specific ratios. It is believed that the interference of the clay particles with the nonionic polysaccharide ethers may be reduced and the clay soil removal performance of the composition thus improved, by incorporating a specific amount of non soap anionic surfactant with respect to the nonionic surfactant.
  • the present invention is a granular detergent composition having a density of 400-1200 g/l and comprising from 0.01% to 10% of a nonionic polysaccharide ether selected from ethyl hydroxyethyl cellulose ethers, methyl cellulose ethers, methylhydroxyethyl cellulose ethers or mixtures thereof, a builder system comprising less than 20% of a phosphate builder and at least 1% of a surfactant system, wherein said system comprises a non soap anionic surfactant and a nonionic surfactant at a ratio of from 0.6:1 to 10:1.
  • a nonionic polysaccharide ether selected from ethyl hydroxyethyl cellulose ethers, methyl cellulose ethers, methylhydroxyethyl cellulose ethers or mixtures thereof
  • a builder system comprising less than 20% of a phosphate builder and at least 1% of a surfactant system, wherein said system comprises a
  • the granular detergent composition comprises as essential components a nonionic polysaccharide ether, and a surfactant system comprising non-soap anionic surfactants and nonionic surfactants.
  • an essential component of the detergent composition is a nonionic polysaccharide ether selected from methylcellulose ether commercially available as Metolose (Shin Etsu), ethyl hydroxyethyl cellulose, commercially available as Bermocoll (Akzo/Nobel), methyl hydroxyethyl cellulose ether commercially available as Tylose MH300 (Hoechst) and mixtures thereof.
  • said polysaccharide ether preferably has a molecular weight from 10000 to 200000, most preferably from 30000 to 150000.
  • the weight average molecular weight is obtained by standard analytical methods as described in Polymer handbooks.
  • a preferred method is light scattering from polymer solutions as originally defined by Debye.
  • compositions of the present invention comprise from 0.01 % to 10%, preferably from 0.01 % to 3%, most preferably from 0.1% to 2% of said nonionic polysaccharide ethers.
  • the detergent composition comprises at least 1% of a surfactant system, preferably from 2% to 40 % of a surfactant system.
  • the surfactant system comprises as essential ingredients a non soap anionic surfactant and a nonionic surfactant.
  • Non soap anionic surfactants useful herein include the conventional primary, branched-chain and random C 10 -C 20 alkyl sulphates ("AS"), the C 10 -C 18 secondary (2,3) alkyl sulphates of the formula CH 3 (CH 2 ) x (CHOSO 3 - M + ) CH 3 and CH 3 (CH 2 ) y (CHOSO 3 - M + ) CH 2 CH 3 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 C 10 -C 18 alkyl alkoxy sulphates (“AE X S”; especially EO 1-7 ethoxy sulphates), C 10 -C 18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), sulphated C 10 -C 18 alkyl polyglycoside
  • suitable alkyl or hydroxyalkyl alkoxylated sulphates for use herein are of the formula RO(A) m SO 3 M, wherein R is an unsubstituted C 11 -C 24 alkyl or hydroxyalkyl component, preferably a C 12 -C 20 , alkyl or hydroxyalkyl, more preferably a C 12 -C 18 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 C 12 -C 18 alkyl polyethoxylate (2.25) sulphate, C 12 -C 18 alkyl polyethoxylate (3) sulphate and C 12 -C 18 alkyl polyethoxylate (4) sulphate wherein M is selected from sodium or potassium.
  • C 12 -C 14 alkyl sulphate which has been ethoxylated with an average of from 0.5 to 4 moles of ethylene oxide per molecule is especially preferred.
  • Suitable anionic surfactants for use herein include salts (e.g. alkali metal and ammonium salts) of C 11 -C 24 , preferably C 12 -C 20 linear alkylaryl sulphonates, particularly linear alkyl benzene sulphonates, primary or secondary alkane sulphonates, alkene sulphonates such as ⁇ -olefin sulphonates, ether sulphonates, sulphonated polycarboxylic acids, oxyalkane sulphonates (fatty acid isethionates), acylamino alkane sulphonates (taurides), alkyl and alkenyl sarcosinates, alkyl glycerol sulphonates, fatty acyl glycerol sulphonates, fatty oleyl glycerol sulphonates, and any mixtures thereof.
  • salts e.g. alkali metal and ammonium salt
  • compositions comprise from 1% to 80%, preferably from 2 % to 50%, most preferably from 3% to 25 % of a non soap anionic surfactant.
  • another essential 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 C 11 -C 15 linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C 12 -C 14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product of C 14 -C 15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-6.5 (the condensation product of C 12 -C 13 linear alcohol with 6.54 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C 14 -C 15 linear alcohol with 7 moles of ethylene oxide), NeodolTM 45-4 (the condensation product of C 14 -C 15 linear alcohol with 4 moles of ethylene oxide), NeodolTM23-3 (the condensation product of C 12 -C 13 linear alcohol with 3 moles of ethyene oxide) marketed by Shell Chemical Company, Kyr
  • 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 PluronicTM 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 R 2 O(C n H 2n O)t(glycosyl) x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, 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.
  • Suitable nonionic surfactants for use herein also the C 10 -C 18 N-alkyl polyhydroxy fatty acid amides. Typical examples include the C 12 -C 18 N-methylglucamides. See WO 9,206,154.
  • Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10 -C 18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C 12 -C 18 glucamides can be used for low sudsing.
  • compositions of the present invention comprise from 1% to 50%, preferably from 2% to 35%, more preferably from 2% to 30% of said nonionic surfactants.
  • Preferred surfactants for use herein are linear alkyl benzene sulphonate, alkyl sulphates, alkyl alkoxylated sulphates and alkyl alkoxylated nonionics and polyhydroxyfatty acid amides.
  • the anionic and nonionic surfactant are present in the detergent composition at a ratio of from 0.6:1 to 10:1, preferably from 0.6:1 to 8:1, more preferably from 0.8:1 to 6:1.
  • the surfactant system of the present invention may optionally comprise zwitterionic, amphoteric surfactants such as C 12 -C 18 betaines, sulphobetaines ("sultaines") and C 10 -C 18 amine oxides and cationic surfactants.
  • zwitterionic, amphoteric surfactants such as C 12 -C 18 betaines, sulphobetaines ("sultaines") and C 10 -C 18 amine oxides and cationic surfactants.
  • 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: [R 2 (OR 3 ) y ][R 4 (OR 3 ) y ] 2 R 5 N + X -
  • R 2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain
  • each R 3 is selected from the group consisting of CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -CH 2 CH(CH 2 OH)-, -CH 2 CH 2 CH 2 -, and mixtures thereof
  • each R 4 is selcted from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups, -CH 2 CHOH-
  • Preferred cationic surfactants are the water soluble quaternary amonium compounds useful in the present composition have the formula: R 1 R 2 R 3 R 4 N + X - wherein R 1 is a C 8 -C 16 alkyl, each of R 2 , R 3 and R 4 is independently C 1 -C 4 alkyl, C 1 -C 4 hydroxy alkyl, benzyl and (C 2 H 4 O) x H where x has a value of from 1 to 5 and X is an anion. Not more than one of the R 2 , R 3 or R 4 should be benzyl.
  • the preferred alkyl chain length for R 1 is from C 12 -C 15 , 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 R 2 R 3 and R 4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
  • quaternary ammonium compounds for use herein are:
  • the detegent composition comprises as an essential ingredient a builder system.
  • Said builder system comprises less than 20%, preferably less than 10%, more preferably less than 1% phosphate builder.
  • Most preferably the compositions of the present invention are substantially free of phosphate builder.
  • phosphate builders include the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, orthophosphates and glassy polymeric meta-phosphates) and phosphonates.
  • the builder system may comprise non phosphate builders to assist in controlling mineral hardness and the removal of particulate soils.
  • Inorganic as well as organic builders can be used.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form.
  • the compositions will typically comprise at least 1 % builder.
  • Liquid formulations typically comprise from 5% to 50%, more typically about 5% to 30%, by weight, of detergent builder.
  • Granular formulations typically comprise from 10% to 80%, more typically from 15% to 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • Inorganic detergent builders include, but are not limited to, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, 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 SiO 2 :Na 2 O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Hoechst commonly abbreviated herein as "SKS-6”
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na 2 Si 2 O 5 morphology form of layered silicate.
  • 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 O 2x+1 ⁇ yH 2 O 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.
  • delta-Na 2 Si 2 O 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.
  • carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • 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: M z [(SiO 2 ) w (zAlO 2 ) y ] ⁇ xH 2 O wherein w, z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
  • 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.
  • the crystalline aluminosilicate ion exchange material has the formula: Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ] ⁇ xH 2 O 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.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, 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 C 5 -C 20 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.
  • Fatty acids e.g., C 12 -C 18 monocarboxylic acids
  • the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • the detergent compositions may comprise a number of optional conventional detergent adjuncts such as builders, chelants, polymers, antiredeposition agents 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, polyfunctionally-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 ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, 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.
  • Polyfunctionally-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 1,2-dihydroxy-3,5-disulfobenzene.
  • EDDS ethylenediamine disuccinate
  • [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
  • these chelating agents will generally comprise from 0.1 % to 10% more preferably, from 0.1% to 3.0% by weight of such compositions.
  • Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles 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 fiber 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 C 4 -C 6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO 3 S(CH 2 ) n OCH 2 CH 2 O-, 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 copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like.
  • Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C 1 -C 6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vinyl ester) e.g., C 1 -C 6 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.
  • 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-1,2-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-1,2-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 stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • a crystalline-reducing stabilizer preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • the detergent compositions herein may optionally contain bleaching agents or bleaching compositions 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.
  • 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 bleaching agents 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, Bums 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 Burns 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. It has also been observed that the incorporation of nonanoyloxybenzene sulphonate in a nonionic polysaccharide ether containing composition (as illustrated in Example 4, II-III) provides an additional colour care performance benefit.
  • amido-derived bleach activators are those of the formulae: R 1 N(R 5 )C(O)R 2 C(O)L or R 1 C(O)N(R 5 )R 2 C(O)L wherein R 1 is an alkyl group containing from about 6 to about 12 carbon atoms, R 2 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-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551.
  • 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.
  • 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: wherein R 6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.
  • 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, which discloses acyl caprolactams, adsorbed into sodium perborate. Other preferred activators are cationic bleach activators.
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum 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 catalyzed 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 Mn IV 2 (u-O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF 6 ) 2 , Mn III 2 (u-O) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 -(ClO 4 ) 2 , Mn IV 4 (u-O) 6 (1,4,7-triazacyclononane) 4 (ClO 4 ) 4 , Mn III Mn IV 4 (u-O) 1 (u-OAc) 2- (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO 4 ) 3 , Mn IV (1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH 3 ) 3 (PF 6 ), 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;
  • Polymeric dispersing agents can advantageously be utilized 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 (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate 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 polymerized 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 polymerized 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 antiredeposition properties.
  • Granular detergent compositions which contain these compounds typically contain from about 0.01 % to about 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain about 0.01 % to about 5%.
  • 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 polyvinyl 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-O group can be represented by the following general structures: wherein R 1 , R 2 , R 3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O 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.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These 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. However, 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. Typically, 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 maintainance performance benefits to white fabrics which have been subjected to repetitive washing.
  • compositions also may employ a polyvinylpyrrolidone (“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: wherein R 1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
  • R 1 is anilino
  • R 2 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 preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R 1 is anilino
  • R 2 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 1 is anilino
  • R 2 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 hereinbefore 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.
  • the detergent composition may comprise any other ingredients commonly employed in conventional detergent compositions such as suds suppressors, softeners, brighteners, additional enzymes and enzyme stabilisers.
  • compositions of the present invention may be used in laundry detergent compositions, fabric treatment compositions and fabric softening compositions in addition to hard surface cleaners.
  • 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 1000g/l, most preferably from 600g/l to 1000g/l.
  • the mean particle size of the components in accordance with the invention should preferably be such that no more than 5% of the particles are greater than 1.7mm in diameter and not more than 5% are less than 0.15mm in diameter.
  • the combination of the mix of the polysaccharide ether and anionic and nonionic surfactant are present at at least 10ppm in the aqueous wash solution having a pH of from 7 to 11, preferably from 9 to 10.5.
  • the present invention also relates to a method of laundering fabrics which comprises contacting said fabric with an aqueous laundry liquor formed from the granular composition and containing conventional detersive ingredients described herein in addition to the nonionic polysaccharide ether and nonionic and anionic surfactants of the present invention.
  • aqueous laundry liquor formed from the granular composition and containing conventional detersive ingredients described herein in addition to the nonionic polysaccharide ether and nonionic and anionic surfactants of the present invention.
  • polyester and polyester-cotton blends fabrics are used.
  • the abbreviated component identifications have the following meanings: XYAS Sodium C 1X - C 1Y alkyl sulphate 25EY A C 12-15 predominantly linear primary alcohol condensed with an average of Y moles of ethylene oxide XYEZ A C 1x - C 1y predominantly linear primary alcohol condensed with an average of Z moles of ethylene oxide XYEZS C 1X - C 1Y sodium alkyl sulphate condensed with an average of Z moles of ethylene oxide per mole TFAA C 16 -C 18 alkyl N-methyl glucamide.
  • Silicate Amorphous Sodium Silicate (SiO 2 :Na 2 O ratio 2.0) NaSKS-6 Crystalline layered silicate of formula ⁇ -Na 2 Si 2 O 5 Carbonate Anhydrous sodium carbonate MA/AA Copolymer of 30:70 maleic/acrylic acid, average molecular weight about 70,000. Zeolite A Hydrated Sodium Aluminosilicate of formula Na 12 (AlO 2 SiO 2 ) 12 .
  • Soil removal testing was conducted in a Hotpoint washing machine, short cycle, at 40°C, Newcastle city water with hardness of 12dH, using 75g of the detergent composition.
  • the cotton and polycotton fabrics were first pretreated with each one of the compositions described above and using the condition outlined above.
  • the staining mixtures were evenly spread over the fabric with a brush and left to dry on a bench overnight. The fabrics were then washed using the same formulation.
  • Example 2 Granular detergent compositions of the present invention
  • composition I II III Blown Powder Zeolite A 30.0 22.0 6.0 Sulphate 19.0 10.0 7.0 MA/AA 3.0 3.0 6.0 LAS 11.0 10.0 22.0 45AS 5.0 5.0 7.0 Silicate 1.0 5.0 Brightener 0.2 0.2 0.2 Carbonate 8.0 16.0 20.0 DETPMP 0.4 0.4 Spray On AE7 3.0 3.0 3.0 AE3 Dry additives PVP 0.5 0.5 0.5 Savinase protease TM (4.0 KNPU / g) 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0

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

Claims (11)

  1. Granuläre Detergenszusammensetzung mit einer Dichte von 400-1.200 g/l, umfassend 0,01% bis 10% eines nichtionischen Polysaccharidethers, gewählt aus Ethylhydroxyethylcelluloseethern, Methylcelluloseethern, Methylhydroxyethylcelluloseethern oder Mischungen hiervon, ein Buildersystem, umfassend weniger als 20% eines Phosphatbuilders, und mindestens 1% eines Tensidsystems, wobei das Tensidsystem ein anionisches Nichtseifentensid und ein nichtionisches Tensid in einem Verhältnis von 0,6:1 bis 10:1 umfasst.
  2. Detergenszusammensetzung nach mindestens einem der vorangehenden Ansprüche, wobei das Verhältnis von anionischem Tensid zu nichtionischem Tensid 0,6:1 bis 8:1 beträgt.
  3. Detergenszusammensetzung nach mindestens einem der vorangehenden Ansprüche, wobei das Verhältnis von anionischem Tensid zu nichtionischem Tensid 0,8:1 bis 6:1 beträgt.
  4. Detergenszusammensetzung nach mindestens einem der vorangehenden Ansprüche, wobei die Zusammensetzung im Wesentlichen frei an dem Phosphatbuilder ist.
  5. Detergenszusammensetzung nach mindestens einem der vorangehenden Ansprüche, wobei das Buildersystem weiterhin 10% bis 80% eines Nichtphosphatbuilders umfasst, gewählt aus Silicaten, Polycarboxylaten, Carbonaten und Mischungen hiervon, bezogen auf Gewicht der Detergenszusammensetzung.
  6. Detergenszusammensetzung nach mindestens einem der vorangehenden Ansprüche, wobei der nichtionische Polysaccharidether ein Molekulargewicht von 10.000 bis 200.000 besitzt.
  7. Detergenszusammensetzung nach mindestens einem der vorangehenden Ansprüche, umfassend 0,01% bis 3% des nichtionischen Polysaccharidethers.
  8. Detergenszusammensetzung nach mindestens einem der vorangehenden Ansprüche, wobei das anionische Tensid gewählt ist aus Alkylsulfonaten, Alkylsulfaten, alkoxylierten Alkylsulfaten, Alkylsarcosinaten, Alkylalkoxycarboxylaten, sulfatierten Alkylpolyglucosiden, alpha-sulfonierten Alkylfettsäureestern und Mischungen hiervon.
  9. Detergenszusammensetzung nach mindestens einem der vorangehenden Ansprüche, umfassend 3% bis 25% des anionischen Tensids.
  10. Detergenszusammensetzung nach mindestens einem der vorangehenden Ansprüche, wobei das nichtionische Tensid gewählt ist auch Polyhydroxyfettsäureamiden, ethoxylierten Alkoholen, Alkylpolyglucosiden und Mischungen hiervon.
  11. Detergenszusammensetzung nach mindestens einem der vorangehenden Ansprüche, umfassend 2% bis 20% des nichtionischen Tensids.
EP95923986A 1994-06-30 1995-06-19 Waschmittel Expired - Lifetime EP0767827B1 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP148881/94 1994-06-30
JP14888194 1994-06-30
JP6148881A JP2849041B2 (ja) 1994-06-30 1994-06-30 洗剤組成物
GB9505030 1995-03-13
GB9505030A GB2290798A (en) 1994-06-30 1995-03-13 Detegent compositions
PCT/US1995/007795 WO1996000771A1 (en) 1994-06-30 1995-06-19 Detergent compositions

Publications (3)

Publication Number Publication Date
EP0767827A1 EP0767827A1 (de) 1997-04-16
EP0767827A4 EP0767827A4 (de) 1999-01-27
EP0767827B1 true EP0767827B1 (de) 2004-04-28

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DE (1) DE69532955T2 (de)
IL (1) IL114339A0 (de)
MA (1) MA23594A1 (de)
MX (1) MX9700231A (de)
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GB9426458D0 (en) * 1994-12-31 1995-03-01 Procter & Gamble A detergent compositions comprising cellulytic enzyme
US6150851A (en) * 1997-06-06 2000-11-21 Tadahiro Ohmi Charge transfer amplifier circuit, voltage comparator, and sense amplifier
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles
DE102015224954A1 (de) * 2015-12-11 2017-06-14 Henkel Ag & Co. Kgaa Reinigungsverstärkende Celluloseether

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Publication number Priority date Publication date Assignee Title
DE2613790A1 (de) * 1975-04-02 1976-10-14 Procter & Gamble Waschmittel
US4174305A (en) * 1975-04-02 1979-11-13 The Procter & Gamble Company Alkyl benzene sulfonate detergent compositions containing cellulose ether soil release agents
US4136038A (en) * 1976-02-02 1979-01-23 The Procter & Gamble Company Fabric conditioning compositions containing methyl cellulose ether
US4048433A (en) * 1976-02-02 1977-09-13 The Procter & Gamble Company Cellulose ethers having a low molecular weight and a high degree of methyl substitution
ATE39126T1 (de) * 1982-07-27 1988-12-15 Procter & Gamble Fluessige reinigungsmittelzusammensetzungen, eine koazervatmischung aus alkylcellulose enthaltend und carboxymethylcellulose und verfahren zu deren herstellung.
US4532067A (en) * 1984-01-11 1985-07-30 Lever Brothers Company Liquid detergent compositions containing hydroxypropyl methylcellulose
US4566993A (en) * 1984-06-15 1986-01-28 O'donnell & Associates, Inc. Liquid detergents containing cellulose ethers stabilized by glycerol
US4564463A (en) * 1984-06-15 1986-01-14 Lever Brothers Company Liquid laundry detergents with improved soil release properties
GB8519047D0 (en) * 1985-07-29 1985-09-04 Unilever Plc Detergent composition
GB8618635D0 (en) * 1986-07-30 1986-09-10 Unilever Plc Detergent composition
GB8728958D0 (en) * 1987-12-11 1988-01-27 Unilever Plc Fabric softening additive for detergent compositions

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EP0767827A1 (de) 1997-04-16
BR9508160A (pt) 1997-08-12
DE69532955T2 (de) 2005-02-10
IL114339A0 (en) 1996-01-19
DE69532955D1 (de) 2004-06-03
EP0767827A4 (de) 1999-01-27
WO1996000771A1 (en) 1996-01-11
CA2194157C (en) 2000-11-14
CA2194157A1 (en) 1996-01-11
MX9700231A (es) 1997-04-30
MA23594A1 (fr) 1995-12-31
AU2867095A (en) 1996-01-25
TR199500795A2 (tr) 1996-06-21
ATE265517T1 (de) 2004-05-15

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