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WO2001032816A1 - Compositions detergentes lessivielles prenant soin des tissus - Google Patents

Compositions detergentes lessivielles prenant soin des tissus Download PDF

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Publication number
WO2001032816A1
WO2001032816A1 PCT/US2000/028438 US0028438W WO0132816A1 WO 2001032816 A1 WO2001032816 A1 WO 2001032816A1 US 0028438 W US0028438 W US 0028438W WO 0132816 A1 WO0132816 A1 WO 0132816A1
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WIPO (PCT)
Prior art keywords
group
laundry detergent
alkyl
detergent composition
independently
Prior art date
Application number
PCT/US2000/028438
Other languages
English (en)
Inventor
Kemal Vatansever Catalan
Patrick Fimin August Delplancke
Axel Masschelein
Pramod Kakumanu Reddy
Diane Barbara Parry
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU10855/01A priority Critical patent/AU1085501A/en
Priority to US10/111,495 priority patent/US6956017B1/en
Priority to BR0015272-2A priority patent/BR0015272A/pt
Priority to JP2001535500A priority patent/JP2003514068A/ja
Priority to DE60032164T priority patent/DE60032164T2/de
Priority to EP00972156A priority patent/EP1224253B1/fr
Priority to MXPA02004216A priority patent/MXPA02004216A/es
Priority to CA002386914A priority patent/CA2386914C/fr
Publication of WO2001032816A1 publication Critical patent/WO2001032816A1/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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0089—Pearlescent compositions; Opacifying agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • 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
    • C11D1/755—Sulfoxides
    • 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
    • C11D1/79—Phosphine oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines

Definitions

  • the present invention relates to laundry detergent compositions comprising a semi-polar nonionic surfactant and certain cyclic amine based polymer, oligomer or copolymer materials.
  • Short fibers are dislodged from woven and knit fabric/textile structures by the mechanical action of laundering. These dislodged fibers may form lint, fuzz or "pills" which are visible on the surface of fabrics and diminish the appearance of newness of the fabric. Further, repeated laundering of fabrics and textiles, especially with bleach-containing laundry products, can remove dye from fabrics and textiles and impart a faded, worn out appearance as a result of diminished color intensity, and in many cases, as a result of changes in hues or shades of color.
  • the fabric care cationic cyclic amine based polymers are not highly compatible with the high levels of anionic surfactants usually formulated within the conventional laundry detergent compositions. It has been found further that those anionic surfactants significantly decrease the efficiency of such cyclic amine based compounds. Such high levels of anionic surfactants are generally used to provide good cleaning properties. Therefore, in order to formulate compositions with such cationic cyclic amine based polymers, detergent compositions have been formulated without anionic surfactants but with nonionic surfactants. However, it has been found that detergent compositions with a high level of nonionic surfactants do not provide the same cleaning performance as comparable high level of anionic surfactants and are more difficult to formulate, especially at high electrolyte content.
  • the object of the present invention is therefore to formulate a laundry detergent composition which provide excellent cleaning properties together with excellent fabric care benefits. It has been surprisingly found that the combination of a semi-polar nonionic surfactant with the above mentioned cationic cyclic amine based polymer provide both excellent cleaning properties together with excellent fabric care benefits. It has been further found that the combination of the semi-polar nonionic surfactants with the cyclic amine based polymers, of the present invention provide good dye transfer inhibition and antifading.
  • compositions of the present invention demonstrate high physical stability when formulated in a liquid form.
  • the present invention is directed to laundry detergent compositions comprising a semi-polar nonionic surfactant and a cyclic amine based polymer, oligomer or copolymer.
  • Such compositions provide good cleaning performance as well as the desired fabric appearance and integrity benefits.
  • the cyclic amine based polymer, oligomer or copolymer is characterized by the following formula as defined below.
  • the present invention relates to the laundering of fabrics and textiles in aqueous washing or treating solutions formed from effective amounts of the detergent compositions described herein, or formed from the individual components of such compositions.
  • Laundering of fabrics and textiles in such washing solutions, followed by rinsing and drying, imparts fabric cleaning as well as fabric appearance benefits to the fabric and textile articles so treated.
  • fabric care benefits can include improved overall appearance, pill/fuzz reduction, antifading, improved dye transfer inhibition, improved abrasion resistance, and/or enhanced softness.
  • the laundry detergent compositions of the present invention comprise a cyclic amine based polymer and an amine oxide surfactants and provide excellent cleaning properties together with excellent fabric care benefits.
  • the semi-polar nonionic surfactants by their chemical nature, introduce some 'hidden' anionic character. Therefore, those semi-polar nonionic surfactants so provide good cleaning properties while not interacting with the cationic polymers, thereby providing excellent fabric cleaning and fabric care properties.
  • semi-polar nonionic surfactants act as hydrotropes within compositions of the present invention, when formulated in the liquid form.
  • high levels of nonionic surfactants within liquid compositions lead to phase separation.
  • the semi-polar nonionic surfactants of the present invention act as hydrotropes and reduce greatly phase separation.
  • These semi-polar nonionic surfactants therefore are found to facilitate the formulation of high nonionic detergent compositions and to increase the physical stability of liquid products. This allows to formulate laundry detergent compositions comprising a high level of nonionic surfactants, which are perfectly fluid isotropic liquids.
  • the first essential element of the laundry detergent compositions of the present invention is the cyclic amine based polymer, oligomer or copolymer as described hereinafter :
  • the first essential component of the compositions of the present invention is one or more cyclic amine based polymer, oligomer or copolymer.
  • Such materials have been found to impart a number of appearance benefits to fabrics and textiles laundered in aqueous washing solutions formed from detergent compositions which contain such cyclic amine based fabric treatment materials.
  • Such fabric appearance benefits can include, for example, improved overall appearance of the laundered fabrics, reduction of the formation of pills and fuzz, improved dye transfer inhibition, protection against color fading, improved abrasion resistance, etc.
  • the combination of semi-polar nonionic surfactants with the cyclic amine based fabric treatment materials used in the compositions and methods according to the present invention can provide such fabric appearance benefits while maintaining good cleaning performance.
  • the cyclic amine based polymer, oligomer or copolymer component of the compositions herein may comprise combinations of these cyclic amine based materials.
  • a mixture of piperadine and epihalohydhn condensates can be combined with a mixture of morpholine and epihalohydhn condensates to achieve the desired fabric treatment results.
  • the molecular weight of cyclic amine based fabric treatment materials can vary within the mixture as is illustrated in the Examples below.
  • an oligomer is a molecule consisting of only a few monomer units while polymers comprise considerably more monomer units.
  • oligomers are defined as molecules having an average molecular weight below about 1 ,000 and polymers are molecules having an average molecular weight of greater than about 1 ,000.
  • Copolymers are polymers or oligomers wherein two or more dissimilar monomers have been simultaneously or sequentially polymerized.
  • Copolymers of the present invention can include, for example, polymers or oligomers polymerized from a mixture of a primary cyclic amine based monomer, e.g., piperadine, and a secondary cyclic amine monomer, e.g., morpholine.
  • the cyclic amine based fabric treatment component of the detergent compositions herein will generally be comprised at a level of from 0.01 % to 5% by the weight of the detergent composition, preferably at a level of from 0.1 % to 4% by weight, more preferably at a level of from 0.75% to 3%.
  • each T is independently selected from the group consisting of H, C ⁇ -C ⁇
  • W comprises at least one cyclic constituent selected from the group consisting of:
  • W may also comprise an aliphatic or substituted aliphatic moiety of the general structure
  • each B is independently C-
  • -each D is independently C 2 -C6 alkylene;
  • each Q is independently selected from the group consisting of hydroxy, C-
  • is independently selected from the group consisting of H, C-j-Cs alkyl and C-
  • each R 2 is independently selected from the group consisting of C-
  • each R 3 is independently selected from the group consisting of H, R 2 , O, C-j- C 2 Q hydroxyalkyl, C- ⁇ -C 2 o alkyl, substituted alkyl, C ⁇ -C-i i aryl, substituted aryl, C7-C-11 alkylaryl, C-
  • suitable cyclic amine based compounds of the present invention are those compounds wherein at least about 10 mole%, preferably at least about 20 mole%, more preferably at least about 30 mole%, and most preferably at least about 50 mole% of the R 3 groups are O, provided that O is only present on a tertiary N.
  • cyclic amine based compounds of the present invention are those compounds wherein :
  • T and R 3 groups are anionic moieties selected from the group consisting of
  • each R4 is independently selected from the group consisting of H, C-i-C 22 alkyl,
  • each R5 is independently selected from the group consisting of C 2 -Cs alkylene, C 2 -C8 alkyl substituted alkylene;
  • A is a compatible monovalent or di or polyvalent anion
  • These cyclic amine based polymers can be linear or branched. One specific type of branching can be introduced using a polyfunctional crosslinking agent. An example of such polymer is exemplified below.
  • Example section below contains numerous non-limiting examples of cyclic amine polymers according to the present invention.
  • a cyclic amine such as imidazole, alkyl imidazole, aminoalkyl imidazole, benzimidazole, piperazine, aminoalkyl piperazine, bis(N-aminoalkyl)piperazine, aminoalkyl morpholine, aminoalkyl pipe dine, and optionally an acyclic amine and mixtures thereof;
  • a cross linking agent selected from the group consisting of 1 ,2 dichloroethane, 1 ,2 dichloropropane, 1 ,3 dichloropropane, 1 ,3 dichloropronae-2-ol, 1 ,4 dichlorobutane, 1 ,6 dichlorohexane, epichlorohydrin, bisepoxybutane, bisglicedyl ether of 4,4'didihydroxydiphenyl-dimethylmethane, bishalohydrins of C2-C8 diols, bisglycidyl ethers C2-C18 diols, bisglycidyl ethers of polyalkyleneglycols and mixtures thereof
  • Preferred cyclic amine based compounds that fall within the above general structure include compounds:
  • -at least one W is selected from the group consisting of:
  • each R-j is H
  • -at least one W is selected from the group consisting of:
  • -at least one W is selected from the group consisting of:
  • Preferred compounds to be used as the linking group R 2 include, but are not limited to: polyepoxides, ethylenecarbonate, propylenecarbonate, urea, ⁇ , ⁇ - unsaturated carboxylic acids, esters of , ⁇ -unsaturated carboxylic acids, amides of ⁇ , ⁇ -unsaturated carboxylic acids, anhydrides of ⁇ , ⁇ -unsaturated carboxylic acids, di- or polycarboxylic acids, esters of di- or polycarboxylic acids, amides of di- or polycarboxylic acids, anhydrides of di- or polycarboxylic acids, glycidylhalogens, chloroformic esters, chloroacetic esters, derivatives of chloroformic esters, derivatives of chloroacetic esters, epihalohydhns, glycerol dichlorohydrins, bis-(halohydrins), polyetherdihalo-compounds, phosgene,
  • R 2 can also comprise a reaction product formed by reacting one or more of polyetherdiamines, alkylenediamines, polyalkylenepolyamines, alcohols, alkyleneglycols and polyalkyleneglycols with ⁇ , ⁇ -unsaturated carboxylic acids, esters of ⁇ , ⁇ -unsaturated carboxylic acids, amides of ⁇ , ⁇ - unsaturated carboxylic acids and anhydrides of ⁇ , ⁇ -unsaturated carboxylic acids provided that the reaction products contain at least two double bonds, two carboxylic groups, two amide groups or two ester groups.
  • cyclic amine based polymer, oligomer or copolymer materials for use herein include adducts of two or more compositions selected from the group consisting of piperazine, piperadine, imidazole, epichlorohydrin benzyl quat, epichlorohydrin methyl quat, morpholine and mixtures thereof.
  • the second essential element of the laundry detergent compositions of the present invention is a semi-polar nonionic surfactant, preferably an amine oxide surfactant.
  • Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 8 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 8 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 8 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
  • Preferred semi-polar nonionic detergent surfactants for the purpose of the present invention are the amine oxide surfactants having the formula : 0
  • R3(OR 4 ) X N(R5) 2 wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
  • the R ⁇ groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • amine oxide surfactants in particular include C ⁇ ⁇ o-C-
  • the laundry detergent compositions of the present invention typically comprise from 0.1 % to 20%, preferably from about 1 % to about 10%, more preferably from 2% to 7% by weight of such semi-polar nonionic surfactants.
  • Detergent components preferably from about 1 % to about 10%, more preferably from 2% to 7% by weight of such semi-polar nonionic surfactants.
  • the laundry detergent compositions of the present invention may contain additional detergent components.
  • additional detergent components The precise nature of these additional component, and levels of incorporation thereof will depend on the physical form of the composition, and the nature of the cleaning operation for which it is to be used.
  • the laundry detergent compositions of the present invention preferably further comprise a detergent ingredient selected from nonionic and/or cationic surfactants, a cellulosic based polymers or oligomers, dye transfer inhibiting polymers, a mannanase enzyme and/or mixtures thereof.
  • a detergent ingredient selected from nonionic and/or cationic surfactants, a cellulosic based polymers or oligomers, dye transfer inhibiting polymers, a mannanase enzyme and/or mixtures thereof.
  • compositions suitable for use in a laundry machine washing method preferably contain both a surfactant and a builder compound and additionally one or more detergent components preferably selected from organic polymeric compounds, bleaching agents, additional enzymes, suds suppressors, dispersants, lime-soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
  • Laundry compositions can also contain softening agents, as additional detergent components.
  • compositions of the invention can also be used as detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions.
  • the laundry detergent compositions according to the invention can be liquid, paste, gels, bars, tablets, spray, foam, powder or granular.
  • Granular compositions can also be in "compact” form and the liquid compositions can also be in a "concentrated” form.
  • the density of the laundry detergent compositions herein ranges from
  • compositions herein are best reflected by density and, in terms of composition, by the amount of inorganic filler salt; inorganic filler salts are conventional ingredients of detergent compositions in powder form; in conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition. In the compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the composition.
  • the inorganic filler salts, such as meant in the present compositions are selected from the alkali and alkaline-earth-metal salts of sulphates and chlorides. A preferred filler salt is sodium sulphate.
  • Liquid detergent compositions according to the present invention can also be in a "concentrated form", in such case, the liquid detergent compositions according the present invention will contain a lower amount of water, compared to conventional liquid detergents.
  • the water content of the concentrated liquid detergent is preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the detergent composition.
  • Suitable detergent compounds for use herein are selected from the group consisting of the below described compounds.
  • the laundry detergent compositions of the present invention can further comprise other detersive surfactants selected from anionic, nonionic, zwitterionic, ampholytic or cationic type or can comprise compatible mixtures of these types.
  • the laundry detergent compositions of the present invention will comprise a high level of nonionic surfactants - one or more- and a low level of anionic surfactants -one or more. More preferably the nonionic surfactants will be comprised within the laundry detergent composition of the present invention at a level of from 1 %-50%, most preferably at a level of from 5%-30%, even most preferably at a level of from 15%-25% by weight of the total composition. More preferably the anionic surfactants will be comprised within the laundry detergent compositions of the present invention at a level of from 0%-10%, most preferably at a level of from 0%-5%. Even most preferably, the laundry detergent compositions of the present invention will comprise no anionic surfactants.
  • Preferred nonionic surfactants for the laundry detergent compositions of the present invention are the condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, and/mixtures thereof.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • Preferred are the condensation products of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with from about 2 to about 10 moles of ethylene oxide per mole of alcohol. About 3 to about 9 moles of ethylene oxide and most preferably from 5 to 7 moles of ethylene oxide per mole of alcohol are present in said condensation products.
  • nonionic surfactants of this type include TergitofM 15-S-9 (the condensation product of C11-C15 linear alcohol with 9 moles ethylene oxide), TergitofM 24-L-6 NMW (the condensation product of C-
  • NeodofT 45.7 t e condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide
  • Neodol ⁇ M 45.5 the condensation product of C-14- C15 linear alcohol with 5 moles of ethylene oxide
  • Genapol LA O3O or O5O the condensation product of C ⁇
  • nonionic surfactant of the present invention are the alkylpolysaccharides 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.
  • 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 sacchahde containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally 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 ⁇ (C n H 2n O) t (glycosyl) x
  • R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is 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.
  • the glycosyl is preferably derived from glucose.
  • the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position).
  • the additional glycosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-, 3-, 4- and/or 6- position, preferably predominately the 2-position.
  • nonionic surfactants are the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
  • the hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility.
  • the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide.
  • Examples of compounds of this type include certain of the commercially-available Plurafac ⁇ M LF404 and Pluronic T M surfactants, marketed by BASF.
  • nonionic surfactant are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
  • This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11 ,000.
  • this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
  • nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula :
  • R2 _ c - N - Z, II I o R1 wherein R1 is H, or R " 1 is C-j_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is 05.31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R1 is methyl
  • R2 is a straight C-
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
  • Nonionic surfactants are Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include IgepalTM CO-630, marketed by the GAF Corporation; and TritonTM X- 45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
  • Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alkyltrimethylammonium halogenides, and those surfactants having the formula :
  • R2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R ⁇ 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 selected from the group consisting of C-1-C4 alkyl, C-1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups, - CH 2 CHOH-CHOHCOR 6 CHOHCH 2 OH wherein R 6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R5 is the same as R 4 or is an alkyl chain wherein the total number of carbon atoms in the alkyl chain, each R ⁇ is selected from the group consisting of -CH 2 CH 2 -,
  • Quaternary ammonium surfactant suitable for the present invention has the formula (I):
  • R1 is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the formula (II) :
  • y is 2-4, preferably 3.
  • R2 is H or a C1-C3 alkyl
  • x is 0-4, preferably 0-2, most preferably 0,
  • R3, R4 and R5 are either the same or different and can be either a short chain alkyl (C1-C3) or alkoxylated alkyl of the formula III, whereby X- is a counterion, preferably a halide, e.g. chloride or methylsulfate.
  • R6 is C- ⁇ -C-4 and z is 1 or 2.
  • Preferred quat ammonium surfactants are those as defined in formula I whereby R-
  • Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula : R 1 R 2 R 3 R N + X" (i)
  • is Cs-C-i ⁇ alkyl
  • each of R 2 , R 3 and R4 is independently C1-C4 alkyl, C-1-C4 hydroxy alkyl, benzyl, and -(C 2 H4Q) X H where x has a value from 2 to 5, and X is an anion.
  • R 2 , R 3 or R4 should be benzyl.
  • is C-
  • R 2 R 3 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 of formulae (i) for use herein are : coconut trimethyl ammonium chloride or bromide; coconut methyl dihydroxyethyl ammonium chloride or bromide; decyl thethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide;
  • cationic materials are the fabric softening components including the water- insoluble quaternary-ammonium fabric softening actives or their corresponding amine precursor, the most commonly used having been di-long alkyl chain ammonium chloride or methyl sulfate.
  • Preferred cationic softeners among these include the following:
  • DTDMAC ditallow dimethylammonium chloride
  • DSOEDMAC di(stearoyloxyethyl) dimethylammonium chloride
  • Biodegradable quaternary ammonium compounds have been presented as alternatives to the traditionally used di-long alkyl chain ammonium chlorides and methyl sulfates. Such quaternary ammonium compounds contain long chain alk(en)yl groups interrupted by functional groups such as carboxy groups. Said materials and fabric softening compositions containing them are disclosed in numerous publications such as EP-A-0,040,562, and EP-A-0,239,910.
  • the quaternary ammonium compounds and amine precursors herein have the formula (I) or (II), below :
  • Q is selected from -O-C(O)-, -C(O)-O-, -O-C(O)-O-, -NR 4 -C(O)-, -C(O)-
  • R 1 is (CH 2 ) n -Q-T2 0 r T3;
  • R2 is (CH 2 ) m -Q-T 4 or T ⁇ or R3;
  • R3 is C1-C4 alkyl or C1-C4 hydroxyalkyl or H;
  • R 4 is H or C-1 -C4 alkyl or C1-C4 hydroxyalkyl
  • T 1 , T 2 , T3, T 4 , T ⁇ are independently C «
  • softener-compatible anions include chloride or methyl sulfate.
  • the alkyl, or alkenyl, chain T 1 , T 2 , ⁇ 3, T 4 , T ⁇ must contain at least 11 carbon atoms, preferably at least 16 carbon atoms.
  • the chain may be straight or branched.
  • Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl material.
  • the compounds wherein T ⁇ , T 2 , ⁇ 3, T 4 , T ⁇ represents the mixture of long chain materials typical for tallow are particularly preferred.
  • quaternary ammonium compounds suitable for use in the aqueous fabric softening compositions herein include :
  • N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride; N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium chloride; N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium chloride;
  • the laundry detergent compositions of the present invention typically comprise from 0.2% to about 25%, preferably from about 1 % to about 8% by weight of such cationic surfactants.
  • water-soluble salts of the higher fatty acids i.e., "soaps" are useful anionic surfactants in the compositions herein.
  • Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
  • Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • non-soap anionic surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of acyl groups.
  • this group of synthetic surfactants are a) the sodium, potassium and ammonium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-C-
  • Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C-
  • surfactants for use in the laundry detergent compositions described herein are amine based surfactants of the general formula:
  • is a C6-C ⁇ 2 alkyl group
  • n is from about 2 to about 4
  • X is a bridging group which is selected from NH, CONH, COO, or O or X can be absent; and R 3 and R4 are individually selected from H, C-1-C4 alkyl, or (CH 2 -CH 2 -O(Rs)) wherein R5 is H or methyl.
  • Especially preferred amines based surfactants include the following:
  • Particularly preferred amines for use in the surfactants defined above include those selected from the group consisting of octyl amine, hexyl amine, decyl amine, dodecyl amine, Cs- C ⁇
  • the amine based surfactant is described by the formula: R-
  • the laundry detergent compositions of the present invention can further comprise one or more cellulosic based polymer or oligomer.
  • Such materials have been found to impart a number of appearance benefits to fabrics and textiles laundered in aqueous washing solutions formed from detergent compositions which contain such cellulosic based fabric treatment materials.
  • Such fabric appearance benefits can include, for example, improved overall appearance of the laundered fabrics, reduction of the formation of pills and fuzz, protection against color fading, improved abrasion resistance, etc.
  • One suitable type of cellulosic based polymer or oligomer fabric treatment material for use herein has an average molecular weight of from about 5,000 to about 2,000,000, preferably from about 50,000 to about 1 ,000,000.
  • cellulosic based compounds will generally be comprised at a level of from 0.1 % to 5%, more preferably at a level of from 0.5% to 4%, more preferably at a level of from 0.75% to 3% by the weight of the detergent composition.
  • each R is selected from the group consisting of R 2 , Re, and
  • each R 2 is independently selected from the group consisting of H and C1-C4 alkyl;
  • each R c is -( CH 2 )y-C-OZ wherein each Z is independently selected from the group consisting of M, R , Re, and R H ;
  • each R H is independently selected from the group consisting of C5 -C 2 Q alkyl
  • each R4 is independently selected from the group consisting of H, C-j-C o alkyl, C5-C7 cycloalkyl, C7-C 2 Q alkylaryl, C7-C 2 Q arylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl;
  • each R5 is independently selected from the group consisting of H, C-] -C 2 o alkyl, C5-C7 cycloalkyl, C7-C 2 o alkylaryl, C7-C 2 o arylalkyl, substituted alkyl, hydroxyalkyl, (R4) 2 N-alkyl, and (R4)3 N-alkyl; wherein:
  • M is a suitable cation selected from the group consisting of Na, K, 1/2Ca, and 1/2Mg; each x is from 0 to about 5; each y is from about 1 to about 5; and provided that:
  • the Degree of Substitution for group R H is between about 0.001 and 0.1 , more preferably between about 0.005 and 0.05, and most preferably between about 0.01 and 0.05;
  • DSR H Degree of Substitution
  • the "Degree of Substitution" for group R c which is sometimes abbreviated herein "DSRC" means the number of moles of group Re components, wherein Z is H or M, that are substituted per anhydrous glucose unit, wherein an anhydrous glucose unit is a six membered ring as shown in the repeating unit of the general structure above.
  • Z is H or M
  • the requirement that Z be H or M is necessary to insure that there are a sufficient number of carboxy methyl groups such that the resulting polymer is soluble. It is understood that in addition to the required number of R c components wherein Z is H or M, there can be, and most preferably are, additional Re components wherein Z is a group other than H or M.
  • the laundry detergent compositions herein may also further comprise from 0.1 % to 80% by weight of a detergent builder.
  • a detergent builder Preferably such compositions in liquid form will comprise from about 1 % to 10% by weight of the builder component.
  • compositions in granular form will comprise from about 1 % to 50% by weight of the builder component.
  • Detergent builders are well known in the art and can comprise, for example, phosphate salts as well as various organic and inorganic nonphosphorus builders.
  • Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates.
  • polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
  • Other suitable polycarboxylates for use herein are the polyacetal carboxylates described in U.S.
  • Particularly preferred polycarboxylate builders are the oxydisuccinates and the ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate described in U.S. Patent 4,663,071 , Bush et al., issued May 5, 1987, the disclosure of which is incorporated herein by reference.
  • nonphosphorus, inorganic builders include the silicates, aluminosilicates, borates and carbonates. Particularly preferred are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of SiO to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. Also preferred are aluminosilicates including zeolites. Such materials and their use as detergent builders are more fully discussed in Corkill et al., U. S. Patent No. 4,605,509, the disclosure of which is incorporated herein by reference. Also discussed in U. S. Patent No. 4,605,509 are crystalline layered silicates which are suitable for use in the detergent compositions of this invention.
  • the laundry detergent compositions of the present invention can also include any number of additional optional ingredients.
  • additional optional ingredients include conventional detergent composition components such as enzymes and enzyme stabilizing agents, suds boosters or suds suppressers, anti-tarnish and anticorrosion agents, bleaching agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, organic and inorganic fillers, solvents, hydrotropes, optical brighteners, dye transfer inhibition agents, dyes and perfumes.
  • pH adjusting agents may be necessary in certain applications where the pH of the wash solution is greater than about 10.0 because the fabric integrity benefits of the defined compositions begin to diminish at a higher pH.
  • a pH adjuster should be used to reduce the pH of the washing solution to below about 10.0, preferably to a pH of below about 9.5 and most preferably below about 7.5. Suitable pH adjusters will be known to those skilled in the art.
  • a preferred optional ingredients for incorporation into the detergent compositions herein comprises a bleaching agent, e.g., a peroxygen bleach.
  • a bleaching agent e.g., a peroxygen bleach.
  • peroxygen bleaching agents may be organic or inorganic in nature. Inorganic peroxygen bleaching agents are frequently utilized in combination with a bleach activator.
  • Useful organic peroxygen bleaching agents include 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-oxoperoxybutyhc acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781 , Hartman, Issued November 20, 1984; European Patent Application EP-A-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 (NAPAA) as described in U.S. Patent 4,634,551 , Issued January 6, 1987 to Burns et al.
  • NAPAA 6-nonylamino-6-oxoperoxycapro
  • Inorganic peroxygen bleaching agents may also be used, generally in particulate form, in the detergent compositions herein.
  • Inorganic bleaching agents are in fact preferred.
  • Such inorganic peroxygen compounds include alkali metal perborate and percarbonate materials.
  • sodium perborate e.g. mono- or tetra-hydrate
  • Suitable inorganic bleaching agents can also include sodium or potassium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
  • Persulfate bleach e.g., OXONE, manufactured commercially by DuPont
  • OXONE manufactured commercially by DuPont
  • inorganic peroxygen bleaches will be coated with silicate, borate, sulfate or water-soluble surfactants.
  • coated percarbonate particles are available from various commercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa.
  • Inorganic peroxygen bleaching agents e.g., the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during use of the compositions herein for fabric laundering/bleaching) of the peroxy acid corresponding to the bleach activator.
  • activators are disclosed in U.S.
  • NOBS nonanoyloxybenzene sulfonate
  • TAED tetraacetyl ethylene diamine
  • Rl N(R5)C(O)R 2 C(O)L or R1 C(O)N(R5)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, R5 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 perhydrolysis anion.
  • a preferred leaving group is phenol sulfonate.
  • bleach activators of the above formulae include (6- octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzene- sul-fonate, (6-decanamido-caproyl)oxybenzenesulfonate and mixtures thereof as described in the hereinbefore referenced U.S. Patent 4,634,551.
  • Another class of useful 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 useful bleach activators includes the acyl lactam activators, especially acyl caprolactams 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 caproiactam, nonanoyl caproiactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, nonanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof.
  • peroxygen bleaching agent will generally comprise from about
  • peroxygen bleaching agent will comprise from about 2% to 20% by weight of the compositions. Most preferably, peroxygen bleaching agent will be present to the extent of from about 3% to 15% by weight of the compositions herein.
  • bleach activators can comprise from about 2% to 10% by weight of the detergent compositions herein. Frequently, activators are employed such that the molar ratio of bleaching agent to activator ranges from about 1 :1 to 10:1 , more preferably from about 1.5:1 to 5: 1.
  • a detersive enzyme component Another highly preferred optional ingredient in the detergent compositions herein is a detersive enzyme component.
  • Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein- based, carbohydrate-based, or triglyceride-based stains from substrates, for the prevention of refugee dye transfer in fabric laundering, and for fabric restoration.
  • Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, mannanases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability, optimal thermostability, and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • Detersive enzyme means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry detergent composition.
  • Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases, amylases and peroxidases.
  • Enzymes are normally incorporated into detergent compositions at levels sufficient to provide a "cleaning-effective amount".
  • cleaning-effective amount refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics.
  • typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition.
  • the compositions herein will typically comprise from 0.001 % to 5%, preferably 0.01 %-1 % 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.
  • proteases are the subtilisins which are obtained from particular strains of B. subtilis and S. licheniformis.
  • One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1 ,243,784 to Novo.
  • proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo.
  • proteases include those of WO 9510591 A to Procter & Gamble.
  • a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble.
  • a recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo.
  • Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 10.
  • U.S. 4,435,307, Barbesgoard et al., March 6, 1984 discloses suitable fungal cellulases from Humicola insolens or 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. CAREZYME® and CELLUZYME® (Novo) are especially useful. See also WO 9117243 to Novo.
  • Amylases can be included for removal of carbohydrate-based stains.
  • WO94/02597 Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutant amylases. See also WO95/10603, Novo Nordisk A/S, published April 20, 1995.
  • Other amylases known for use in cleaning compositions include both ⁇ - and ⁇ -amylases.
  • ⁇ - Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341 ; and British Patent specification no. 1 ,296,839 (Novo).
  • amylases are stability-enhanced amylases described in WO94/18314, published August 18, 1994 and WO96/05295, Genencor, published February 22, 1996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95.
  • Examples of commercial ⁇ -amylases products are Purafect Ox Am® from Genencor and Termamyl®, Ban® ,Fungamyl® and Duramyl®, all available from Novo Nordisk A/S Denmark.
  • WO95/26397 describes other suitable amylases : ⁇ -amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® ⁇ -amylase activity assay. Suitable are variants of the above enzymes, described in WO96/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in WO95/35382.
  • 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 GB 1 ,372,034. See also, the lipase in Japanese Patent Application 53,20487, laid open Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” or "Amano-P.”
  • Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • Preferred enzyme for the compositions of the present invention is a mannanase enzyme.
  • a mannans-degrading enzyme EC 3.2.1.25 : ⁇ -mannosidase
  • EC 3.2.1.78 Endo-1 ,4- ⁇ -mannosidase, referred therein after as "mannanase”
  • EC 3.2.1.100 1 ,4- ⁇ -mannobiosidase (IUPAC Classification- Enzyme nomenclature, 1992 ISBN 0-12-227165-3 Academic Press).
  • the detergent compositions of the present invention comprise a ⁇ -1 ,4-Mannosidase (E.C. 3.2.1.78) referred to as "Mannanase”.
  • Mannanase a ⁇ -1 ,4-Mannosidase
  • the compositions of the present invention comprising further a mannanase enzyme, provide excellent color care while maintaining superior cleaning performance.
  • the mannanase enzyme will be an alkaline mannanase as defined below, more preferably, a mannanase originating from a bacterial source.
  • the compositions of the present invention will comprise an alkaline mannanase selected from the mannanase from the strain Bacillus agaradhaerens NICMB 40482; the mannanase from Bacillus subtilis strain 168, gene yght; the mannanase from Bacillus sp. I633; the mannanase from Bacillus sp. AAI12 and/or the mannanase from the strain Bacillus halodurans.
  • mannanase for the inclusion in the detergent compositions of the present invention is the mannanase enzyme originating from Bacillus sp. I633 as described in WO 99/64619.
  • alkaline mannanase enzyme is meant to encompass an enzyme having an enzymatic activity of at least 10%, preferably at least 25%, more preferably at least 40% of its maximum activity at a given pH ranging from 7 to 12, preferably 7.5 to 10.5.
  • a first more preferred mannanase for use in the present invention is the alkaline mannanase from Bacillus agaradhaerens NICMB 40482 which is described in WO 99/64619. More specifically, this mannanase is: i) a polypeptide produced by Bacillus agaradhaerens, NCIMB 40482; or ii) a polypeptide comprising an amino acid sequence as shown in positions 32-344 of SEQ ID NO:6 as shown in WO 99/64619; or iii) an analogue of the polypeptide defined in i) or ii) which is at least
  • polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 70% identical to the amino acid sequence of SEQ ID NO: 6 from amino acid residue 32 to amino acid residue 344 as shown in WO 99/64619;
  • the plasmid pSJ1678 comprising the polynucleotide molecule (the DNA sequence) encoding said mannanase has been transformed into a strain of the Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure at the Deutsche Sammlung von Mikroorganismen und Zelikulturen GmbH, Mascheroder Weg 1 b, D-38124 Braunschweig, Federal Republic of Germany, on 18 May 1998 under the deposition number DSM 12180.
  • a second more preferred enzyme is the mannanase from the Bacillus subtilis strain 168, which is described in U.S. Patent No. 6,060,299. More specifically, this mannanase is: i) is encoded by the coding part of the DNA sequence shown in SEQ
  • polypeptide comprising an amino acid sequence as shown SEQ ID NO:6 shown in the U.S. Patent No. 6,060,299; or iii) an analogue of the polypeptide defined in ii) which is at least 70% homologous with said polypeptide, or is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or is immunologically reactive with a polyclonal antibody raised against said polypeptide in purified form. Also encompassed in the corresponding isolated polypeptide having mannanase activity selected from the group consisting of:
  • polynucleotide molecules encoding a polypeptide having mannanase activity and comprising a sequence of nucleotides as shown in SEQ ID NO:5 as shown in the U.S. Patent No. 6,060,299
  • species homologs of (a) polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 70% identical to the amino acid sequence of SEQ ID NO: 6 as shown in U.S. Patent No. 6,060,299;
  • a third more preferred mannanase is described in WO 99/64619. More specifically, this mannanase is: i) a polypeptide produced by Bacillus sp. 1633; ii) a polypeptide comprising an amino acid sequence as shown in positions 31-330 of SEQ ID NO:2 as shown in WO 99/64619; or iii) an analogue of the polypeptide defined in i) or ii) which is at least 65% homologous with said polypeptide, is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or is immunologically reactive with a polyclonal antibody raised against said polypeptide in purified form.
  • isolated polynucleotide molecule selected from the group consisting of: (a) polynucleotide molecules encoding a polypeptide having mannanase activity and comprising a sequence of nucleotides as shown in SEQ ID NO: 1 from nucleotide 94 to nucleotide 990 in WO 99/64619; (b) species homologs of (a); (c) polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 65% identical to the amino acid sequence of SEQ ID NO: 2 from amino acid residue 31 to amino acid residue 330 in WO 99/64619;
  • the plasmid pBXM3 comprising the polynucleotide molecule (the DNA sequence) encoding a mannanase of the present invention has been transformed into a strain of the Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure at the Deutsche Sammlung von Mikroorganismen und Zelikulturen GmbH, Mascheroder Weg 1 b, D-38124 Braunschweig, Federal Republic of Germany, on 29 May 1998 under the deposition number DSM 12197.
  • a fourth more preferred mannanase is described in WO 99/64619. More specifically, this mannanase is: i) a polypeptide produced by Bacillus sp. AAI 12; ii) a polypeptide comprising an amino acid sequence as shown in positions 32-362 of SEQ ID NO:10 as shown in WO 99/64619; or iii) an analogue of the polypeptide defined in i) or ii) which is at least
  • 65% homologous with said polypeptide is derived from said polypeptide by substitution, deletion or addition of one or several amino acids, or is immunologically reactive with a polyclonal antibody raised against said polypeptide in purified form. Also encompassed is the corresponding isolated polynucleotide molecule selected from the group consisting of
  • polynucleotide molecules encoding a polypeptide having mannanase activity and comprising a sequence of nucleotides as shown in SEQ ID NO: 9 from nucleotide 94 to nucleotide 1086 as shown in WO 99/64619;
  • polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 65% identical to the amino acid sequence of SEQ ID NO: 10 from amino acid residue 32 to amino acid residue 362 as shown in WO 99/64619;
  • the plasmid pBXM1 comprising the polynucleotide molecule (the DNA sequence) encoding a mannanase of the present invention has been transformed into a strain of the Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure at the Deutsche Sammlung von Mikroorganismen und Zelikulturen GmbH, Mascheroder Weg 1 b, D-38124 Braunschweig, Federal Republic of Germany, on 7 October 1998 under the deposition number DSM 12433.
  • a fifth more preferred mannanase is described in WO 99/64619. More specifically, this mannanase is : i) a polypeptide produced by Bacillus halodurans, ii) a polypeptide comprising an amino acid sequence as shown in positions
  • polynucleotide molecules that encode a polypeptide having mannanase activity that is at least 65% identical to the amino acid sequence of SEQ
  • ID NO: 12 from amino acid residue 33 to amino acid residue 331 as shown in WO 99/64619; d) molecules complementary to (a), (b) or (c); and e) degenerate nucleotide sequences of (a), (b), (c) or (d).
  • the plasmid pBXM5 comprising the polynucleotide molecule (the DNA sequence) encoding a mannanase of the present invention has been transformed into a strain of the Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure at the Deutsche Sammlung von Mikroorganismen und Zelikulturen GmbH, Mascheroder Weg 1 b, D-38124 Braunschweig, Federal Republic of Germany, on 9 October 1998 under the deposition number DSM 12441.
  • the enzyme-containing compositions herein may optionally also comprise from about 0.001 % to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01 % to about 6%, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes.
  • Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.
  • the laundry detergent compositions of the present invention can also include compounds for inhibiting dye transfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics. These are generally comprised in the laundry detergent compositions of the present invention at a level of from 0.001 % to 10 %, preferably from 0.01 % to 2%, more preferably from 0.05% to 1 % by weight.
  • Polymeric dye transfer inhibiting agents are used to inhibit the transfer of dyes from colored fabrics onto fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to become attached to other articles in the wash.
  • polymeric dye transfer inhibiting agents are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.
  • polyamine N-oxide polymers suitable for use contain units having the following structure formula : P
  • R wherein P is a polymerisable unit, whereto the R-N-O group can be attached to or wherein the R-N-O group forms part of the polymerisable unit or a combination of both.
  • II II II A is NC, CO, C, -O-,-S-, -N- ; x is O or 1 ;
  • R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
  • the N-O group can be represented by the following general structures :
  • R1 , R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.
  • the N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • polyamine N-oxides comprises the group of polyamine N- oxides wherein the nitrogen of the N-O group forms part of the R-group.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
  • Another class of said polyamine N-oxides comprises the group of polyamine N- oxides wherein the nitrogen of the N-O group is attached to the R-group.
  • Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit.
  • Preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
  • Another preferred class of polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is attached to said R groups. Examples of these classes are polyamine oxides wherein R groups can be aromatic such as phenyl.
  • 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.
  • the amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of 10:1 to 1 :1000000.
  • the amount of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by appropriate degree of N-oxidation.
  • the ratio of amine to amine N-oxide is from 2:3 to 1 :1000000. More preferably from 1 :4 to 1 :1000000, most preferably from 1 :7 to 1 :1000000.
  • the polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or not.
  • the amine oxide unit of the polyamine N-oxides has a PKa ⁇ 10, preferably PKa ⁇ 7, more preferred PKa ⁇ 6.
  • the polyamine oxides can be obtained in almost any degree of polymerisation.
  • the degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
  • the average molecular weight is within the range of 500 to 1000,000; preferably from 1 ,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
  • N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention have an average molecular weight range from 5,000-1 ,000,000, preferably from
  • Highly preferred polymers for use in the laundry detergent compositions according to the present invention comprise a polymer selected from N- vinylimidazole N-vinylpyrrolidone copolymers wherein said polymer has an average molecular weight range from 5,000 to 50,000 more preferably from
  • the average molecular weight range was determined by light scattering as described in Barth H.G. and Mays J.W. Chemical Analysis Vol 1 13, "Modern
  • N-vinylimidazole N-vinylpyrrolidone copolymers have an average molecular weight range from 5,000 to 50,000; more preferably from 8,000 to
  • the N-vinylimidazole N-vinylpyrrolidone copolymers characterized by having said average molecular weight range provide excellent dye transfer inhibiting properties while not adversely affecting the cleaning performance of detergent compositions formulated therewith.
  • the N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4 .
  • the laundry detergent compositions of the present invention may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
  • PVP polyvinylpyrrolidone
  • Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000).
  • polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones known to persons skilled in the detergent field (see for example EP-A-262,897 and EP-A- 256,696).
  • Polyvinyloxazolidone The laundry detergent compositions of the present invention may also utilize polyvinyloxazolidone as a polymeric dye transfer inhibiting agent.
  • Said polyvinyloxazolidones have an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
  • the laundry detergent compositions of the present invention may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
  • Said polyvinylimidazoles have an average about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
  • Cross-linked polymers are polymers whose backbone are interconnected to a certain degree; these links can be of chemical or physical nature, possibly with active groups n the backbone or on branches; cross-linked polymers have been described in the Journal of Polymer Science, volume 22, pages 1035-1039.
  • the cross-linked polymers are made in such a way that they form a three-dimensional rigid structure, which can entrap dyes in the pores formed by the three-dimensional structure.
  • the cross- linked polymers entrap the dyes by swelling.
  • Such cross-linked polymers are described in US5,912,221.
  • the laundry detergent composition of the present invention can optionally comprise a pearlescing agent to improve the aesthetic appearance of the product.
  • Suitable pearlescing agents are those well known in the art to provide pearlescing effects in surfactant compositions.
  • pearl lustre mica pigments such Iriodin ex Merck or equivalent e.g. Mearlin Magnapearl from the Meare Corp.
  • organic compounds having the property to crystallise as pearlescent needles in the product Typical compounds having this property are polyol esters such as ethylene glycol mono- (EGMS) or di-stearate (EGDS), or polyethyleneglycol mono- (PGMS) or distearate (PGDS).
  • EGMS ethylene glycol mono-
  • PGMS polyethyleneglycol mono-
  • PGDS polyethyleneglycol mono-
  • Suitable pearlescing agents can be found in WO 99/09944.” It is known in the art to further add to pearleacent agent-containing liquid products, a pearlescent crystallization enhancer. Suitable enhancers are the acids, salts, alcohols and esters having a hydrophobic moiety with at least 16C, pref. at least 18C; as described EP 520 551 B. It has been surprisingly found that the semi-polar nonionic surfactants of the present invention and preferably the amine oxide compounds, can function as a crystallization enhancer for organic pearlescent agents. Liquid detergent compositions comprising an organic pearlescent agent and a semi-polar nonionic surfactant, preferably an amine oxide, demonstrate a very attractive pearlescent appearance. It has been further found that liquid laundry detergent compositions comprising the surfactant system of the present invention demonstrate a particularly attractive pearleascent effect.
  • the laundry detergent compositions according to the present invention can be prepared by combining the essential and optional components in the requisite concentrations in any suitable order and by any conventional means.
  • Granular compositions are generally made by combining base granule ingredients, e.g., surfactants, builders, water, etc., as a slurry, and spray drying the resulting slurry to a low level of residual moisture (5-12%).
  • base granule ingredients e.g., surfactants, builders, water, etc.
  • the remaining dry ingredients e.g., granules of the essential cyclic amine based fabric treatment materials
  • the liquid ingredients e.g., solutions of the essential cyclic amine based fabric treatment materials, enzymes, binders and perfumes, can be sprayed onto the resulting granules to form the finished detergent composition.
  • Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations.
  • Liquid compositions according to the present invention can also be in "compact form", in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents. Addition of the cyclic amine based polymer, oligomer or copolymer materials to liquid detergent or other aqueous compositions of this invention may be accomplished by simply mixing into the liquid solutions the desired cyclic amine based fabric treatment materials.
  • the present invention also provides a method for laundering fabrics in a manner which imparts fabric cleaning and fabric appearance benefits provided by the combination of the semi-polar nonionic surfactant and the cyclic amine based polymer, oligomer or copolymer materials used herein.
  • Such a method employs contacting these fabrics with an aqueous washing solution formed from an effective amount of the detergent compositions hereinbefore described or formed from the individual components of such compositions. Contacting of fabrics with washing solution will generally occur under conditions of agitation although the compositions of the present invention may also be used to form aqueous unagitated soaking solutions for fabric cleaning and treatment.
  • the washing solution have a pH of less than about 10.0, preferably it has a pH of about 9.5 and most preferably it has a pH of about 7.5.
  • Agitation is preferably provided in a washing machine for good cleaning. Washing is preferably followed by drying the wet fabric in a conventional clothes dryer.
  • An effective amount of a high density liquid or granular detergent composition in the aqueous wash solution in the washing machine is preferably from about 500 to about 7000 ppm, more preferably from about 1000 to about 3000 ppm.
  • the polycationic condensate is prepared by reacting imidazole and epichlorohydrin. To a round bottomed flask equipped with a magnatic stirrer, condenser and a thermometer are added imidazole (0.68 moles) and 95 mL water. The solution is heated to 50°C followed by dropwise addition of epichlorohydrin (0.68 moles). After all the epichlorohydrin is added, the temperature is raised to 80°C until all the alkylating agent is consumed. The condensate produced had molecular weight of about 12,500.
  • the solution had a pH of 6.97 and contained 50.3% of water, 0.06% of glycolic acid and less than 0.05% of 2-chloroacetic acid.
  • the solution had a pH of 7.82 and contained 53.4% of water, 0.2% of glycolic acid and less than 0.05% of 2-chloroacetic acid.
  • Example 8 was repeated with the exceptions that 71.5 g (1.05 moles) of imidazole dissolved in 116.3 g of water, 40.8 g (0.34 moles) of the sodium salt of 2-chloroacetic acid dissolved in 100 g of water, 27.2 g (0.24 moles) of a 50% strength by weight solution of sodium hydroxide and 76.8 g (0.83 moles) of epichlorohydrin were reacted. 427.6 g of a yellow aqueous solution of an amphoteric amine based polymer having a net cationic charge of 3.7 mequiv/g and a K value of 9.5 were obtained.
  • the solution had a pH of 11.62 and contained 54.2% of water, 0.3% of glycolic acid and less than 0.05% of 2- chloroacetic acid.
  • Dispersant polymer 2.5 2.0 2.5 2.5 3.0
  • the cyclic amine based polymer is selected from one or more compound(s) illustrated in the table below
  • the chelant is selected from Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its sodium salt and/or Diethylene triamine pentaacetic acid.
  • the enzymes are selected from the conventional protease, amylase, lipase and/or cellulase enzymes as described above.
  • Mannanase is the mannanase enzyme sold by Novo Nordisk A/S under the tradename Mannaway.
  • the dispersant polymer is a poly(ethyleneimine) ethoxylated polymer of a molecular weight between 200 and 3000 and an EO between 7 and 30
  • Level of Modification DSR H about 0.001 to about 0.1
  • cyclic base amine polymer/oligomer are selected from one or more of the compounds below.
  • the chemical structures shown in the examples below are idealized structures. Side reactions expected to occur during the condensation are not shown.

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Abstract

L'invention concerne des compositions détergentes lessivielles comprenant un agent tensioactif non-ionique semi-polaire et un polymère, un oligomère ou un copolymère à base d'amine cyclique. Lesdites compositions présentent des bonnes propriétés nettoyantes, donnent aux tissus l'aspect voulu et ne l'abîment pas.
PCT/US2000/028438 1999-10-29 2000-10-13 Compositions detergentes lessivielles prenant soin des tissus WO2001032816A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
AU10855/01A AU1085501A (en) 1999-10-29 2000-10-13 Laundry detergent compositions with fabric care
US10/111,495 US6956017B1 (en) 1999-10-29 2000-10-13 Laundry detergent compositions with fabric care
BR0015272-2A BR0015272A (pt) 1999-10-29 2000-10-13 Composições detergentes para lavanderia com proteção de tecido
JP2001535500A JP2003514068A (ja) 1999-10-29 2000-10-13 布帛ケア効果を有する洗濯洗剤組成物
DE60032164T DE60032164T2 (de) 1999-10-29 2000-10-13 Waschmittelzusatz mit wäscheschutz
EP00972156A EP1224253B1 (fr) 1999-10-29 2000-10-13 Compositions detergentes lessivielles prenant soin des tissus
MXPA02004216A MXPA02004216A (es) 1999-10-29 2000-10-13 Composiciones detergentes para lavanderia con cuidado de telas.
CA002386914A CA2386914C (fr) 1999-10-29 2000-10-13 Compositions detergentes lessivielles prenant soin des tissus

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USPCT/US99/25393 1999-10-29
PCT/US1999/025393 WO2001032815A1 (fr) 1999-10-29 1999-10-29 Compositions detergentes de blanchissage avec entretien des textiles

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JP7506257B2 (ja) 2020-09-28 2024-06-25 ザ プロクター アンド ギャンブル カンパニー 染料固着剤及びアミンオキシドを含有する洗濯洗剤組成物

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US9365805B2 (en) 2014-05-15 2016-06-14 Ecolab Usa Inc. Bio-based pot and pan pre-soak
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BR0015272A (pt) 2002-11-26
CA2386914C (fr) 2008-01-29
DE60032164D1 (de) 2007-01-11
MXPA02004216A (es) 2002-10-17
AU1085501A (en) 2001-05-14
EP1224253B1 (fr) 2006-11-29
WO2001032815A1 (fr) 2001-05-10
JP2003514068A (ja) 2003-04-15
CN1387559A (zh) 2002-12-25
DE60032164T2 (de) 2007-09-27
EP1224253A1 (fr) 2002-07-24
CA2386914A1 (fr) 2001-05-10
AR026262A1 (es) 2003-02-05
AU1906500A (en) 2001-05-14

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