EP0929623A1 - Compositions detergentes - Google Patents

Compositions detergentes

Info

Publication number
EP0929623A1
EP0929623A1 EP97943528A EP97943528A EP0929623A1 EP 0929623 A1 EP0929623 A1 EP 0929623A1 EP 97943528 A EP97943528 A EP 97943528A EP 97943528 A EP97943528 A EP 97943528A EP 0929623 A1 EP0929623 A1 EP 0929623A1
Authority
EP
European Patent Office
Prior art keywords
group
detergent composition
cationic
alkyl
moiety
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97943528A
Other languages
German (de)
English (en)
Other versions
EP0929623A4 (fr
Inventor
Stuart Clive Askew
Graham Alexander Sorrie
Robin Gibson Hall
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0929623A1 publication Critical patent/EP0929623A1/fr
Publication of EP0929623A4 publication Critical patent/EP0929623A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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 granular detergent compositions or components thereof containing cationic compounds with particulate/clay-soil removal/anti-redeposition properties and a hydrophobic organic peroxyacid bleaching system for use in laundry and dish washing processes.
  • a particularly important property of a detergent composition is its ability to remove paniculate type soils from a variety of fabrics during laundering. Perhaps the most important paniculate soils are the clay- type soils. Clay soil particles generally comprise negatively charged layers of aluminosilicates and positively charged cations (e.g. calcium) which are positioned between and hold together the negatively charged layers.
  • positively charged cations e.g. calcium
  • a variety of models can be proposed for compounds which would have paniculate/ clay-soil removal properties.
  • One model requires that the compound have two distinct characteristics. The first is the ability of the compound to adsorb onto the negatively charged layers of the clay particle. The second is the ability of the compound, once adsorbed, to push apart (swell) the negatively charged layers so that the clay particle loses its cohesive force and can be removed in the wash water.
  • a model proposed for the anti-redeposition action of the positively charged anti-redeposition compounds is as follows. Adsorption of the positively charged molecule on the surface of clay particles in the wash water gives the particles the dispersancy properties of the molecule. As more and more of these compounds adsorb onto the suspended clay soil particles, the latter become encased within a hydrophilic layer provided by the attached ethoxy units. As such the hydrophilically encased soil is prevented from redepositing on fabrics, in particular hydrophobic fabrics such as polyester, during the laundering or dish washig cycle.
  • Another component traditionally used in detergent is bleach, to remove bleachable stains or soils from the fabric.
  • a disadvantage of the use of most bleaches is that various other detergent components are bleach sensitive and that they can be oxidised by the bleach, whereby their original properties can be diminished. Thus, not all detergent components are bleach- compatible.
  • cationic, (partially) quatemized ethoxylated (poly) amines which have clay-soil removal/anti- redeposition properties, are fully compatible with bleaches formulated therewith.
  • hydrophobic bleaches despite their tendency to migrate to the (hydrophobic) fabric surface, they do not necessarily interact fully with the bleachable stain or soil components. It has been found that the hydrophobic bleaches can be prevented from migration onto hydrophobic bleachable stains/soils by deposited clay-soil particulates on the fabric. Thereby, their bleaching performance can be diminished. This result in a lessening of the bleachable/ dingy soil cleaning performance of the hydrophobic bleach.
  • a detergent composition comprising a hydrophobic bleach. It has been found that in detergent compositions comprising both components the bleach efficacy of the hydrophobic organic peroxyacid bleaching system is enhanced. Thereby, the overall cleaning performance of the detergent is improved, which is especially noticeable on fabric stained with organic clay-soil particules, such as peat stains.
  • the present invention relates to granular detergent compositions or components thereof, which comprise a hydrophobic organic peroxyacid bleaching system, capable of providing a hydrophobic organic peroxyacid compound and one or more cationic compounds, which are cationic, (partially) quatemized ethoxylated (poly) amine compounds with paniculate/ clay-soil removal / anti-redeposition properties.
  • a hydrophobic organic peroxyacid bleaching system capable of providing a hydrophobic organic peroxyacid compound and one or more cationic compounds, which are cationic, (partially) quatemized ethoxylated (poly) amine compounds with paniculate/ clay-soil removal / anti-redeposition properties.
  • the present invention relates to granular detergent compositions or components thereof, which comprise
  • a water-soluble cationic compound having clay soil removal/anti-redeposition properties which is selected from the group consisting of:
  • M* is an N + or N group; each M ⁇ is an N+ or N group, and at least one M ⁇ is an N+ group;
  • R is H or C1-C4 alkyl or hydroxyalkyl
  • Rl is C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no 0-N bonds are formed
  • each R2 is C1-C4 alkyl or hydroxyalkyl, the moiety -L-X, or two R2 together form the moiety - (CH2) A 2 -(CH2 , wherein A 2 is -O- or -CH2-, r is 1 or 2, s is 1 or 2 and r + s is 3 or 4
  • each R3 is Cj-Cs alkyl or hydroxyalkyl, benzyl, the moiety L-X, or two R3 or one R 2 and one R- together form the moiety -(CH2) r -A 2 -(CH2) 5 -
  • R 4 is a substituted
  • hydrophobic organic peroxyacid bleaching system comprises (i) a hydrogen peroxide source and (ii) a hydrophobic organic peroxyacid bleach precursor compound.
  • An essential feature of the present invention is a water-soluble cationic compound which has particulate/ clay-soil removal/anti-redeposition properties and which is selected from the group consisting of cationic mono-di- and polyamines.
  • the water-soluble cationic compound is preferably present at a level of from 0.01 % to 30% , more preferably from 0.1 % to 15% , most preferably from 0.2% to 3.0% by weight of the detergent composition.
  • the water-soluble cationic compounds of the present invention useful in the granular detergent compositions or components thereof in accord with the present invention include ethoxylated cationic monoamines, ethoxylated cationic diamines and ethoxylated cationic polyamines as previously defined.
  • R* can be branched
  • Rl is preferably C2-C6 alkylene for the ethoxylated cationic diamines.
  • Each R2 is preferably methyl or the moiety -L-X; each R3 is preferably C1-C4 alkyl or hydroxyalkyl, and most preferably methyl.
  • the positive charge of the N+ groups is offset by the appropriate number of counter anions.
  • Suitable counter anions include C1-, Br-, SO3-2, PO4- 2 , MeOS ⁇ 3 ⁇ and the like.
  • Particularly preferred counter anions are Cl- and Br-.
  • X can be a nonionc group selected from hydrogen (H), C1-C4 alkyl or hydroxyalkyl ester or ether groups, or mixtures thereof.
  • Preferred esters or ethers are the acetate ester and methyl ether, respectively.
  • the particularly preferred nonionic groups are H and the methyl ether.
  • hydrophilic chain L usually consists entirely of the polyoxyalkylene moiety -[(R6 ⁇ ) w (CH2CH2-0,,)-].
  • the moieties - (R ⁇ O)m- and -(CH2CH2 ⁇ )n- of the polyoxyalkylene moiety can be mixed together or preferably form blocks of -(R ⁇ O),,,- and -(CH2CH2O),,- moieties.
  • R6 is preferably C3H6 (propylene);
  • m is preferably from 0 to about 5 and is most preferably 0, i.e. the polyoxyalkylene moiety consists entirely of the moiety -(CH2CH2O .
  • the moiety -(CH2CH2O preferably comprises at least about 85 % by weight of the polyoxyalkylene moiety and most preferably 100% by weight (m is O).
  • M and each M 2 are preferably an N + group for the cationic diamines and polyamines.
  • Preferred ethoxylated cationic monoamines and diamines have the formula:
  • a is from 0 to 20, preferably 0 to 4 (e.g. ethylene, propylene, hexamethylene)
  • b is l or 0.
  • n is preferably at least about 16, with a typical range of from about 20 to about 35.
  • n is at least about 12 with a typical range of from about 12 to about 42.
  • R4 linear, branched, or cyclic is preferably a substituted C3-C6 alkyl, hydroxyalkyl or aryl group; Al is preferably
  • n is preferably at least about 12, with a typical range of from about 12 to about 42; p is preferably from 3 to 6.
  • R 4 is a substituted aryl or alkaryl group
  • q is preferably 1 and R5 is preferably C2-C3 alkylene.
  • R 4 is a substituted alkyl, hydroxyalkyl, or alkenyl group, and when q is 0, R$ is preferably a C2-C3 oxyalkylene moiety; when q is 1, R ⁇ is preferably C2-C3 alkylene.
  • ethoxylated cationic polyamines can be derived from polyamino amides such as:
  • ethoxylated cationic polyamines can also be derived from polyaminopropyleneoxide derivatives such as:
  • each c is a number from 2 to about 20.
  • An essential feature of detergent compositions or components thereof in accord with the invention is a hydrophobic organic peroxyacid bleaching system, capable of providing a hydrophobic orgamc peroxyacid compound.
  • hydrophobic organic peroxyacid compound it is meant herein an organic peroxyacid whose parent carboxylic acid has a critical micelle concentration less than 0.5 moles/litre and wherein said critical micelle concentration is measured in aqueous solution at 20°-50°C.
  • the hydrophobic organic peroxyacid bleaching system comprises a hydrogen peroxide source and a hydrophobic organic peroxyacid bleach precursor compound.
  • the production of the hydrophobic organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
  • Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches.
  • the hydrophobic organic peroxyacid bleaching system comprises a preformed hydrophobic organic peroxyacid, which is incorporated directly into the composition.
  • Compositions containing mixtures of a hydrogen peroxide source and hydrophobic organic peroxyacid precursor in combination with a preformed hydrophobic organic peroxyacid are also envisaged.
  • the hydrophobic organic peroxyacid contains at least 7 carbon atoms, more preferably at least 9 carbon atoms, most preferably at least 11 carbon atoms.
  • the peroxyacid has an alkyl chain comprising at least 7 carbon atoms, more preferably at least 8 carbon atoms, most preferably at least 9 carbon atoms.
  • Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the form of the alkali metal, preferably sodium salt at a level of from 1 % to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5% to 25% by weight of the compositions.
  • inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts.
  • the inorganic perhydrate salts are normally the alkali metal salts.
  • the inorganic perhydrate salt may be included as the crystalline solid without additional protection.
  • the preferred executions of such granular compositions utilise a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.
  • Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.
  • Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaB ⁇ 2H2 ⁇ 2 or the tetrahydrate NaB ⁇ 2H2 ⁇ 2.3H2 ⁇ .
  • Alkali metal percarbonates particularly sodium percarbonate are preferred perhydrates herein.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C ⁇ 3.3H2 ⁇ 2, and is available commercially as a crystalline solid.
  • Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as
  • L is a leaving group and X is essentially any functionality, such that on perhydrolysis the structure of the peroxyacid produced is
  • X will thus contain at least 6 carbon atoms.
  • the hydrophobic peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.05% to 20% by weight, more preferably from 0.1 % to 15% by weight, most preferably from 0.2% to 10% by weight of the detergent compositions.
  • Suitable hydrophobic peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes.
  • Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms
  • R is an alkyl chain containing from 1 to 8 carbon atoms
  • R is H or R
  • R5 is an alkylene chain containing from 1 to 8 carbon atoms
  • Y is H or a solubilizing group.
  • Any of R , R and R may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups
  • the preferred solubilizing groups are -S0 3 ⁇ M , -C0 " M , -S0 4 " M + , -N + (R 3 ) 4 X " and 0 ⁇ -N(R 3 ) 3 and most preferably -SO 3 " M + and -C0 2 " M + wherein R is an ali yl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
  • Preferred peroxyacid precursors are amide substituted alkyl peroxyacid precursor compounds, including those of the following general formulae:
  • R is an aryl or alkaryl group with from about 1 to about 14 carbon atoms
  • R 2 is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms
  • R 5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • R 1 preferably contains from about 6 to 12 carbon atoms.
  • R 2 preferably contains from about 4 to 8 carbon atoms.
  • Rl may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 .
  • R2 can include alkyl, aryl, wherein said R 2 may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • R 1 and R 5 should not contain more than 18 carbon atoms total. Amide substimted bleach activator compounds of this type are described in EP-A-0170386.
  • bleach precursors of this type include amide substimted peroxyacid precursor compounds selected from (6- octanamido-caproyl)oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzene- sulfonate, and the highly preferred (6- nonanamidocaproyl)oxy benzene sulfonate, and mixtures thereof as described in EP-A-0170386.
  • precursor compounds of the benzoxazin- type as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
  • R j is an alkyl, alkaryl, aryl, or arylalkyl containing at least 5 carbon atoms.
  • Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
  • Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains at least 7 carbon atoms.
  • alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS) and sodium nonanoyloxybenzene sulfonate (NOBS).
  • Still another class of hydrophobic bleach activators are the N-acylated precursor compounds of the lactam class disclosed generally in GB-A- 955735.
  • Preferred materials of this class comprise the caprolactams.
  • Suitable caprolactam bleach precursors are of the formula:
  • R 1 is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6 to 12 carbon atoms.
  • Preferred hydrophobic N-acyl caprolactam bleach precursor materials are selected from benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam and mixtures thereof. A most preferred is nonanoyl caprolactam.
  • Suitable valero lactams have the formula:
  • R* is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6 to 12 carbon atoms. More preferably, R is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof.
  • the organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed hydrophobic organic peroxyacid , typically at a level of from 0.05% to 20% by weight, more preferably from 1 % to 10% by weight of the composition.
  • a preferred class of hydrophobic organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
  • R is an aryl or alkaryl group with from about 1 to about 14 carbon atoms
  • R2 is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
  • Rl preferably contains from about 6 to 12 carbon atoms.
  • R preferably contains from about 4 to 8 carbon atoms.
  • Rl may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2.
  • R2 can include alkyl, aryl, wherein said R2 may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R5 is preferably H or methyl.
  • Rl and R ⁇ should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • Suitable examples of this class of agents include (6-octylamino)-6-oxo-caproic acid, (6-nonylamino)-6-oxo- caproic acid, (6-decylamino)-6-oxo-caproic acid, 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. 4,483,781, U.S. 4,634,551, EP 0,133,354, U.S. 4,412,934 and EP 0, 170,386.
  • a preferred hydrophobic preformed peroxyacid bleach compound for the purpose of the invention is monononylamido peroxy carboxylic acid.
  • Suitable organic peroxyacids include diperoxyalkanedioc acids having more than 7 carbon atoms, such as diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • organic peroxyacids include diamino peroxyacids, which are disclosed in WO 95/ 03275, with the following general formula:
  • R is selected from the group consisting of C1-C12 alkylene, C5-C12 cycloalkylene, C6-C12 arylene and radical combinations thereof;
  • Rl and R2 are independently selected from the group consisting of H, Cj-Ci6 alkyl and C6-C12 aryl radicals and a radical that can form a C3-C12 ring together with R3 and both nitrogens;
  • R3 is selected from the group consisting of C1-C12 alkylene, C5-C12 cycloalkylene and C6-C12 arylene radicals;
  • n and n' each are an integer chosen such that the sum thereof is 1;
  • m and m' each are an integer chosen such that the sum thereof is 1 ; and
  • M is selected from the group consisting of H, alkali metal, alkaline earth metal, ammonium, alkanolammonium cations and radicals and combinations thereof.
  • Suitable organic peroxyacids are include the amido peroxyacids which are disclosed in WO 95/ 16673, with the following general structure:
  • X represents hydrogen or a compatible substituent
  • Ar is an aryl group
  • the substituent X on the benzene nucleus is preferably a hydrogen or a meta or para substituent, selected from the group comprising halogen, typically chlorine atom, or some other non- released non-interfering species such as an alkyl group, conveniently up to C6 for example a methyl, ethyl or propyl group.
  • X can represent a second amido-percarboxylic acid substituent of formula :-
  • R is selected from the group consisting of C1-C12 alkylene, C5-C12 cycloalkylene, Q3-C12 arylene and radical combinations thereof;
  • the detergent composition or component thereof can comprise additional polymeric cationic ethoxylated amine compounds with paniculate/ clay-soil removal/ anti-redeposition, selected from the group consisting of water-soluble cationic polymers.
  • These polymers comprise a polymer backbone, at least 2M groups and at least one L-X group, wherein M is a cationic group attached to or integral with the backbone; X is a nonionic group selected from the group consisting of H, Cj -C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof; and L is a hydrophilic chain connecting groups M and X or connecting X to the polymer backbone.
  • the polymeric cationic ethoxylated amine compounds can be present in detergent compositions at a level of from 0.01 % to 30%, more preferably from 0.1 % to 15%, most preferably from 0.2% to 3% by weight of the detergent composition.
  • polymer backbone refers to the polymeric moiety to which groups M and L-X are attached or are integral with. Included within this term are oligomer backbones (2 to 4 units), and true polymer backbones (5 or more units).
  • attachment means that the group is pendent from the polymer backbone, examples of such attachment being represented by the following general structures A and B:
  • integral with means that the group forms part of the polymer backbone, examples of which are represented by the following general stmcmres C and D:
  • Any polymer backbone can be used as long as the cationic polymer formed is water-soluble and has clay soil removal/anti-redeposition properties.
  • Suitable polymer backbones can be derived from the polyurethanes, the polyesters, the polyethers, the poly amides, the polyimides and the like; the poly aery late s, the poly aery lamides, the polyvinylethers, the polyethylenes, the polypropylenes and like poly alky lenes, the polystyrenes and like polyalkarylenes, the poly alky leneamines, the polyalkyleneimmes, the polyvinylammes, the polyalylamines, the polydiallyl amines, the polyvinylpyridines, the polyaminotriazoles, polyvinyl alcohol, the aminopolyurey lenes, and mixtures thereof.
  • M can be any compatible cationic group which comprises an N+ (quarternary), positively charged center.
  • the quarternary positively charged center can be represented by the following general stmcmres E and F:
  • M groups are those containing a quarternary center represented by general structure E.
  • the cationic group is preferably positioned close to or integral with the polymer backbone.
  • counter anions include Cl", Br, SO32-, SO4 -, PO42-, MeOS ⁇ 3" and the like. Particularly preferred counter anions are Cl" and Br.
  • X can be a nonionic group selected from hydrogen (H), C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof.
  • the preferred ester or ether groups are the acetate ester and methyl ether, respectively;
  • the particularly preferred nonionic groups are H and the methyl ether.
  • the cationic polymers suitable for use in granular detergent compositions or components thereof in accord with the present inventions normally have a ratio of cationic groups M to nonionic groups X of from about 1:1 to about 1:2.
  • the ratio of cationic groups M to nonionic groups X can be varied.
  • the ratio of groups M to groups X can usually range from about 2:1 to about 1:10. In preferred cationic polymers, the ratio is from about 1:1 to about 1:5.
  • the polymers formed from such copolymenzation are typically random, i.e.
  • the units which contain groups M and groups L-X can comprise 100% of the cationic polymers of the present invention. However, inclusion of other units (preferably nonionic) in the polymers is also permissible. Examples of other units include acrylamides, vinyl ethers and those containing unquaternized tertiary amine groups (M*) containing an N centre. These other units can comprise from 0% to about 90% of the polymer (from about 10% to 100% of the polymer being units containing M and L-X groups, including Ml-L-X groups). Normally, these other units comprise from 0% to about 50% of the polymer (from about 50% to 100% of the polymer being units containing M and L-X groups).
  • the number of groups M and L-X each usually ranges from about 2 to about 200. Typically the number of groups M and L-X are each from about 3 to about 100. Preferably, the number of groups M and L-X are each from about 3 to about 40.
  • hydrophilic chain L usually consists entirely of the polyoxyalkylene moiety -[(R'0) m (CH2CH2 ⁇ ) contend]-.
  • the moieties -(R'0) m - and -(CH2CH2 ⁇ ) ⁇ - of the polyoxyalkylene moiety can be mixed together, or preferably form blocks of -(R'0) m - and - (CH2CH2O),,- moieties.
  • R' is preferably C3H6 (propylene);
  • m is preferably from 0 to about 5, and most preferably 0; i.e.
  • the polyoxyalkylene moiety consists entirely of the moiety -(CH2CH2O),,-.
  • the moiety -(CH2CH2O),,- preferably comprises at least about 85 % by weight of the polyoxyalkylene moiety, and most preferably 100% by weight (m is 0).
  • n is usually from about 3 to about 100.
  • n is from about 12 to about 42.
  • a plurality (2 or more) of moieties -L-X can also be hooked together and attached to group M or to the polymer backbone, examples of which are represented by the following general stmcmres G and H:
  • Stmcmres such as G and H can be formed, for example, by reacting glycidol with group M or with the polymer backbone, and ethoxylating the subsequently formed hydroxy groups.
  • cationic polymers of the present invention are as follows:
  • Suitable cationic polymers are derived from polyurethanes, polyesters, polyethers, polyamides and the like. These polymers comprise units selected from those having formulas I, II and HI:
  • X is 0 or 1; R is H or C1-C4 alkyl or hydroxyalkyl; R 1 is C2-C12 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to abut 20 oxyalkylene units provided that no 0-0 or 0-N bonds are formed with A ; when x is 1, R 2 is -R5- except when A* is O
  • NCR 5 — NCOR 5 — , — CNR 5 — , or OCNR 5
  • R3 is -R ⁇ -;
  • R4 is C1 -C4 alkyl or hydroxyalkyl, or the moiety - (R 5 )rl(C3H6 ⁇ ) ffl (CH2CH 2 0) ⁇ ]-X;
  • R5 is C ⁇ -C ⁇ 2 alkylene, hydroxyalkylene, alkenylene, arylene, or alkarylene;
  • each R6 is C ⁇ _ C4 alkyl or hydroxyalkyl, or the moiety -(CH2) r -A2-(CH2)s-, wherein A2 is -O- or -CH2-;
  • R 7 is H or R 4 ;
  • R 8 is C2-C3 alkylene or hydroxyalkylene;
  • X is H,
  • R ⁇ is C1 -C4 alkyl or hydoxyalkyl
  • k is 0 or 1
  • m and n are numbers such that the moiety -(CH2CH2O),,- comprises at least about 85% by weight of the moiety - [(C3H6 ⁇ ) m (CH2CH2 ⁇ ) tread]-
  • m is from 0 to about 5
  • n is at least about 3
  • r is 1 or 2
  • s is 1 or 2
  • r + s is 3 or 4
  • y is from 2 to about 20
  • the number of u, v and w are such that there are at least 2 N+ centers and at least 2 X groups.
  • Al is preferably
  • A2 is preferably -0-; x is preferably 1; and R is preferably H.
  • R* can be linear (e.g. -CH2-CH2-CH2-,
  • R 1 is preferably C2-C alkylene or phenylene, and most preferably C2-C6 alkylene (e.g. ethylene, propylene, hexamethylene).
  • R is preferably - OR5- or -(OR8) y -;
  • R3 is preferably -R5 ⁇ - or -(OR ⁇ -;
  • R and R6 are preferably methyl.
  • R5 can be linear or branched, and is preferably C2-C3 alkylene; R 7 is preferably H or C1-C3 alkyl; R8 is preferably ethylene; R ⁇ is preferably methyl; X is preferably H or methyl; k is preferably 0; m is preferably 0, r and s are each preferably 2; y is preferably from 2 to about 12.
  • n is preferably at least about 6 when the number of N + centers and X groups is 2 or 3; n is most preferably at least about 12, with a typical range of about 12 to about 42 for all ranges of u + v + w.
  • u is preferably from about 3 to about 20.
  • v and w are each preferably from about 3 to about 40.
  • Suitable cationic polymers are derived from polyacrylates, polyacrylamides, polyvinylethers and the like. These polymers comprise units selected from those having formulas IV, V and VI.
  • R is H or C1 -C4 alkyl or hydroxyalkyl;
  • Rl is substimted C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or C2- C3 oxyalkylene;
  • each R is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene;
  • each R3 is C1-C4 alkyl or hydroxyalkyl, the moiety -(R )*-[(C3H6 ⁇ ) OT (CH2CH2 ⁇ ) contend]-X, or together form the moiety -(CH2) r -A -(CH2) -, wherein A2 is -O- or CH2-;
  • each R4 is C1-C4 alkyl or hydroxyalkyl, or two R4 together form the moiety -(CH2) r -A2-(CH2)*-;
  • X is H, O
  • R ⁇ is C1-C4 alkyl or hydroxalkyl
  • j is 1 or 0
  • k is 1 or 0
  • m and n are numbers such that the moiety - (CH2CH2O),,- comprises at least about 85% by weight of the moiety - [(C3H 0) OT (CH2CH20) tread]-
  • m is from 0 to about 5
  • n is at least about 3
  • r is 1 or 2
  • s is 1 or 2 and r + s is 3 or 4
  • the number of u, v and w are such that there are at least 2N+ centres and at least 2 X groups.
  • A* is preferably
  • A2 is preferably -0-; R is preferably H. R* can be linear
  • CH 3 branched e.g. — CH 2 — C — , — CH 2 CH — ,
  • R* is preferably substimted C2-C6 alkylene or substimted C2-C3 oxyalkylene, and most preferably
  • Each R2 is preferably C2-C3 alkylene, each R3 and R4 are preferably methyl; R$ is preferably methyl; X is preferably H or methyl; j is preferably 1; k is preferably 0; m is preferably 0; r and s are each preferably 2.
  • n, u, v and w can be varied according to the n, u, v and w for the polyurethane and like polymers.
  • Suitable cationic polymers are derived from poly alky leneamines, polyalkyleneimines and the like. These polymers comprise units selected from those having formulas VII and VIII and
  • Rl is C2-C12 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no 0-N bonds are formed; each R2 is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R3) [(C 3 H ⁇ ) ffl (CH2CH2 ⁇ ) ⁇ ]-X; R3 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; M' is an N+ or N centre; X is H,
  • R4 is C1-C4 alkyl or hydroxyalkyl
  • d is 1 when M' is N+ and is 0 when M' is N
  • e is 2 when M' is N+ and is 1 when M' is N
  • k is 1 or 0
  • m and n are numbers such that the moiety
  • Rl can be varied like R* of the polyurethene and like polymers; each R2 is preferably methyl or the moiety -(R 3 )*- [(C3H6 ⁇ ) m (CH2CH2 ⁇ )J-X; R3 is preferably C2-C3 alkylene; R4 is preferably methyl; X is preferably H; k is preferably 0; m is preferably 0.
  • n is preferably at least about 6 when the number of M' and X groups is 2 or 3; n is most preferably at least about 12, with a typical range of from about 12 to about 42 for all ranges of x + y + z.
  • x + y + z is from 2 to about 40 and preferably from 2 to about 20.
  • x - - y + z can range from 2 to 9 with from 2 to 9 N + centres and from 2 to 11 X groups.
  • x + y - - z is at least 10, with a preferred range of from 10 to about 42.
  • the M' groups are typically a mixmre of from about 50 to 100% N+ centres and from 0 to about 50% N centres.
  • Preferred cationic polymers within this class are derived from the C2- C3 polyalkyleneamines (x -f- y + z is from 2 to 9) and polyalkyleneimines (x + y + z is at least 10, preferably from 10 to about 42).
  • Particularly preferred cationic polyalkyleneamines and polyalkyleneimines are the cationic polyethy leneamines (PEA's) and polyethyleneimines (PEI's). These preferred cationic polymers comprise units having the general formula: (R 2 ) d (R 2 ) d
  • R preferably methyl
  • M', X, d, x, y, z and n are defined as before; a is 1 or 0.
  • the PEAs used in preparing cationic polymers of the present invention have the following general formula:
  • x + y + z is from 2 to 9, and a is 0 or 1 (molecular weight of from about 100 to about 400).
  • a is 0 or 1 (molecular weight of from about 100 to about 400).
  • Each hydrogen atom attached to each nitrogen atom represents an active site for subsequent ethoxylation.
  • x + y + z is from about 3 to about 7 (molecular weight is from about 140 to about 310).
  • These PEA's can be obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. The common PEA's obtained are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA).
  • TETA triethylenetetramine
  • TEPA tetraethylenepentamine
  • the cogenerically derived mixmre does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can also be present cyclic amines with side chains in which nitrogen atoms appear. See US Pat. No. 2,792,372 to Dickson, issues May 14, 1957, which describes the preparation of PEAs.
  • the minimum degree of ethoxylation required for preferred clay soil removal/anti-redeposition performance can vary depending upon the number of units in the PEA. Where y + z is 2 or 3, n is preferably at least about 6. Where y + z is from 4 to 9, suitable benefits are achieved when n is at least about 3.
  • n is at least about 12, with a typical range of about 12 to about 42.
  • the PEIs used in preparing the polymers of the present invention have a molecular weight of at least about 440 prior to ethoxylation, which represents at least about 10 units.
  • Preferred PEIs used in preparing these polymers have a molecular weight of from about 600 to about 1800.
  • the polymer backbone of these PEIs can be represented by the general formula:
  • x, y, and z represents a number of sufficient magnitude to yield a polymer having the molecular weights previously specified.
  • linear polymer backbones are possible, branch chains can also occur.
  • the relative proportions of primary, secondary and tertiary amine groups present in the polymer can vary, depending on the manner of preparation. The distribution of amine groups is typically as follows:
  • Each hydrogen atom attached to each nitrogen atom of the PEI represents an active site for subsequent ethoxylation.
  • These PEIs can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • Specific methods for preparing PEIs are disclosed in US Pat. No. 2, 182,306 to Ulrich et al., issued Dec. 5, 1939; US Pat No. 3,033,746 to Mayle et al., issued May 8, 1962; US Pat. No. 2,208,095 to Esselmann et al., issued July 16, 1940; US Pat. No. 2,806,839 to Crowther, issued Sept. 17, 1957; and US Pat. No. 2,533,696 to Wilson, issued May 21, 1951 (all here
  • n is at least about 3 for the cationic PEIs.
  • the minimum degree of ethoxylation required for suitable clay soil removal/anti-redeposition performance can increase as the molecular weight of the PEI increases, especially much beyond about 1800.
  • the degree of ethoxyalation for preferred polymers increases as the molecular weight of the PEI increases.
  • n is preferably at least about 12, with a typical range of from about 12 to about 42.
  • n is preferably at least about 24, with a typical range of from about 24 to about 42.
  • Suitable cationic polymers are those derived from the diallylamines. These polymers comprise units selected from those having formulas X and XI:
  • R is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R 2 )*- [(C 3 H 6 0) ffI (CH2CH2 ⁇ ) ⁇ ]-X;
  • R 2 is -C12 alkylene, hydroxyalkylene, alkylene, arylene or alkarylene;
  • each R3 is C1-C4 alkyl or hydroxyalkyl, or together form the moiety -(CH2) r -A-(CH2) » wherein A is -O- or -CH2-;
  • X is H,
  • R4 is C1-C4 alkyl or hydroxyalkyl
  • k is 1 or 0
  • m and n are numbers such that the moiety -(CH2CH2 ⁇ ) structuri- comprises at least about 85% by weight of the moiety - [(C3H6 ⁇ ) m (CH2CH2 ⁇ ) canal]-;
  • m is from 0 to about 5;
  • n is at least about 3;
  • r is 1 or 2, s is 1 or 2, and r + s is 3 or 4;
  • x is 1 or 0;
  • y is 1 when x is 0 and 0 when x is 1 ; the number of u and v are such that there are at least 2N+ centres and at least 2 X groups.
  • A is preferably -O-;
  • X is preferably H;
  • k is preferably 0;
  • m is preferably 0;
  • r and s are each preferably 2.
  • n is preferably at least about 6 when the number of N-l- centres and X groups are each 2 or 3, n is preferably at least 12, with a typical range of from about 12 to about 42 for all range of u + v.
  • v is 0, and u is from 2 to about 40, and preferably from 2 to about 20.
  • the detergent compositions or components thereof in accord with the invention may also contain additional detergent components.
  • additional detergent components and levels of incorporation thereof will depend on the physical form of the composition or component, and the precise nature of the washing operation for which it is to be used.
  • compositions or components thereof, of the invention preferably contain one or more additional detergent components selected from additional surfactants, additional bleaches, bleach catalysts, alkalinity systems, builders, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, additional soil suspension and anti- redeposition agents soil releasing agents, perfumes and corrosion inhibitors.
  • additional detergent components selected from additional surfactants, additional bleaches, bleach catalysts, alkalinity systems, builders, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, additional soil suspension and anti- redeposition agents soil releasing agents, perfumes and corrosion inhibitors.
  • the detergent compositions or components thereof in accord with the invention preferably contain an additional surfactant selected from anionic, nonionic, catiomc, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
  • anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants is given in U.S. P. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch).
  • a list of suitable cationic surfactants is given in U.S. P. 4,259,217 issued to Murphy on March 31, 1981.
  • ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
  • the detergent compositions or compositions thereof in accord with the present invention preferably comprise an additional anionic surfactant.
  • any anionic surfactants useful for detersive purposes can be comprised in the detergent composition. These can include salts (including, for example, sodium, potassium, ammonium, and substimted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.
  • Anionic sulfate surfactants are preferred.
  • anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C ⁇ 2 -C j monoesters) diesters of sulfosuccinate (especially saturated and unsaturated --C14 diesters), N-acyl sarcosinates.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
  • Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene NOT FURNISHED AT TIME OF PUBLICA ⁇ ON
  • soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
  • Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2 ⁇ ) x CH2COO-M+ wherein R is a C to C18 alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation.
  • Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR ⁇ -CHR2 ⁇ 0)-R3 wherein R is a C to Ci8 alkyl group, x is from 1 to 25, Ri and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substimted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
  • Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2- methyl-1-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l- nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors.
  • alkali metal sarcosinates of formula R-CON (Rl) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, Rl is a C1-C4 alkyl group and M is an alkali metal ion.
  • R is a C5-C17 linear or branched alkyl or alkenyl group
  • Rl is a C1-C4 alkyl group
  • M is an alkali metal ion.
  • alkoxylated nonionic surfactants are suitable herein.
  • the ethoxylated and propoxylated nonionic surfactants are preferred.
  • Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
  • the condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene 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 prefened are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
  • Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R 2 CONR!Z wherein : Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixmre thereof, preferable C1-C4 alkyl, more preferably C ⁇ or C2 alkyl, most preferably C ⁇ alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C11 -C17 alkyl or alkenyl, or mixmre thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof
  • Nonionic fattv acid amide surfactant Suitable fatty acid amide surfactants include those having the formula: R6cON(R7)2 wherein R6 is an alkyl group containing from 7 to 21 , preferably from 9 to 17 carbon atoms and each R? is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and - (C2H4 ⁇ ) x H, where x is in the range of from 1 to 3.
  • 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 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
  • Preferred alkylpolyglycosides have the formula
  • R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixmres thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
  • the glycosyl is preferably derived from glucose.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula R3(OR4) X N°(R 5 )2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixmres thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixmres thereof; x is from 0 to 5, preferably from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are C10-C18 alkyl dimethylamine oxide, and C ⁇ rj-18 acylamido alkyl dimethylamine oxide.
  • a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.
  • Zwitterionic surfactants can also be incorporated into the detergent compositions or components thereof in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable betaines are those compounds having the formula R(R')2N + R2C00" wherein R is a C ⁇ -Cis hydrocarbyl group, each Rl is typically C1-C3 alkyl, and R is a C1-C5 hydrocarbyl group.
  • Preferred betaines are C12-I8 dimethyl-ammonio hexanoate and the Cio-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • Suitable cationic surfactants to be used in the detergent compositions or components thereof herein include the quaternary ammonium surfactants selected from mono C ⁇ -Cjg, preferably C ⁇ -Cio N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substimted by methyl, hydroxyethyl or hydroxypropyl groups.
  • cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants.
  • the cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising at least one ester
  • Suitable cationic ester surfactants including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
  • ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms.
  • the atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixmres thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain.
  • spacer groups having, for example, -O-O- (i.e.
  • spacer groups having, for example -CH2- O- CH2- and -CH2-NH-CH2- linkages are included.
  • the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.
  • the detergent compositions or components thereof in accord with the present invention preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.
  • Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, phosphates, and mixmres of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water- soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfmyl carboxylates.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccmates described in British Patent No.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1 ,261 ,829, 1, 1 ,2,2- ethane tetracarboxylates, 1 , 1,3,3-propane tetracarboxylates and 1 , 1 ,2 , 3-propane tetracarboxylates .
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1 ,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
  • Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixmres thereof with their salts e.g. citric acid or citrate/citric acid mixmres are also contemplated as useful builder components.
  • Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.
  • Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
  • Partially soluble or insoluble builder compound Partially soluble or insoluble builder compound
  • the detergent compositions or compositions thereof in accord with the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
  • Examples of largely water insoluble builders include the sodium aluminosilicates.
  • Suitable aluminosilicate zeolites have the unit cell formula Na z [(Al ⁇ 2)z(Si ⁇ 2)y] . XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixmres thereof. Zeolite A has the formula
  • Zeolite X has the formula Na 8 6 [(Al ⁇ 2)86(Si ⁇ 2)l06l- 276 H 2 0.
  • zeolite MAP builder Another preferred aluminosilicate zeolite is zeolite MAP builder.
  • the zeolite MAP can be present at a level of from 1 % to 80% , more preferably from 15% to 40% by weight of the compositions.
  • Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
  • zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
  • the zeolite MAP detergent builder has a particle size, expressed as a d50 value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.
  • the d5o value indicates that 50% by weight of the particles have a diameter smaller than that figure.
  • the particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d50 values are disclosed in EP 384070A.
  • the detergent compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant.
  • heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
  • Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1 % to 10% , more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5 % by weight of the compositions.
  • Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
  • Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2- hydroxypropylenediamine disuccinic acid or any salts thereof.
  • EDDS ethylenediamine-N,N' -disuccinic acid
  • Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A- 399, 133.
  • iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
  • EP-A-509,382 The ⁇ -alanine-N,N' -diacetic acid, aspartic acid-N,N * -diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.
  • EP-A-476,257 describes suitable amino based sequestrants.
  • EP-A- 510,331 describes suitable sequestrants derived from collagen, keratin or casein.
  • EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane- 1,2,4- tricarboxylic acid are alos suitable.
  • Glycinamide-N,N' -disuccinic acid Glycinamide-N,N' -disuccinic acid (GADS), ethylenediamine-N-N * -diglutaric acid (EDDG) and 2- hydroxypropylenediamine-N-N' -disuccinic acid (HPDDS) are also suitable.
  • the oxygen-releasing bleach system can contain a transition metal containing bleach catalyst.
  • One suitable type of bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • a transition metal cation of defined bleach catalytic activity such as copper, iron or manganese cations
  • an auxiliary metal cation having little or no bleach catalytic activity such as zinc or aluminum cations
  • a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Prefened examples of these catalysts include Mn ⁇ V2(u-0)3(l ,4,7-trimethyl-
  • ligands suitable for use herein include 1,5,9-trimethyl- 1 ,5,9-triazacyclododecane, 2-methyl-l ,4,7-triazacyclononane, 2- methyl-1 ,4,7-triazacyclononane, 1 ,2,4,7-tetramethyl-l ,4,7- triazacyclononane, and mixmres thereof.
  • the bleach catalysts useful herein may also be selected as appropriate for the present invention.
  • suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(l ,4,7-trimethyl-l ,4,7-triazacyclononane)(OCH3)3_(PF6).
  • Still another type of bleach catalyst is a water-soluble complex of manganese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
  • Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixmres thereof.
  • U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)- cyclic ligand.
  • Said ligands are of the formula:
  • Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
  • said rings may be substimted with substituents such as alkyl, aryl, alkoxy, halide, and nitro.
  • substituents such as alkyl, aryl, alkoxy, halide, and nitro.
  • Particularly preferred is the ligand 2,2'-bispyridylamine.
  • Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and - bispyridylamine complexes.
  • Highly preferred catalysts include Co(2 ,2 ' -bispyridylamine)Cl2 , Di(isothiocyanato)bispy ridylamine- cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2- bis ⁇ yridylamine)2 ⁇ 2Cl ⁇ 4, Bis-(2,2' -bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixmres thereof.
  • binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands including N4MnHI(u-0)2MnIVN4)+and [Bipy2MnHI(u-0)2MnIVbipy2]-(Cl ⁇ 4)3.
  • bleach catalysts are described, for example, in European patent application, publication no. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4, 119,557 (ferric complex catalyst), German Pat.
  • the bleach catalyst is typically used in a catalytically effective amount in the compositions and processes herein.
  • catalytically effective amount is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance bleaching and removal of the stain or stains of interest from the target substrate.
  • the test conditions will vary, depending on the type of washing appliance used and the habits of the user. Some users elect to use very hot water; others use warm or even cold water in laundering operations. Of course, the catalytic performance of the bleach catalyst will be affected by such considerations, and the levels of bleach catalyst used in fully- formulated detergent and bleach compositions can be appropriately adjusted.
  • compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 1 ppm to about 200 ppm of the catalyst species in the wash liquor.
  • 3 micromolar manganese catalyst is effective at 40° C, pH 10 under European conditions using perborate and a bleach precursor. An increase in concentration of 3-5 fold may be required under U.S. conditions to achieve the same results.
  • Another preferred ingredient useful in the detergent compositions or components thereof is one or more additional enzymes.
  • Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
  • Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001 % to 4% active enzyme by weight of the composition.
  • Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B licheniformis, described in more detail in GB- 1,269,839 (Novo).
  • Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist- Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S.
  • Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001 % to 2% active enzyme by weight of the composition.
  • Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001 % to 2% by weight, preferably 0.001 % to 1 % by weight, most preferably from 0.001 % to 0.5% by weight of the compositions.
  • the lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp.. Thermomvces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein.
  • a preferred lipase is derived from Pseudomonas pseudoalcaligenes . which is described in Granted European Patent, EP-B-0218272.
  • Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus orvza. as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
  • Organic polymeric compounds are preferred additional components of the detergent compositions or components thereofm accord with the invention, and are preferably present as components of any particulate components where they may act such as to bind the particulate component together.
  • organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, not being an quaternised ethoxylated (poly) amine clay-soil removal/ anti-redeposition agent in accord with the invention.
  • Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1 % to 30% , preferably from 0.5% to 15%, most preferably from 1 % to 10% by weight of the compositions.
  • organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A- 1,596, 756. Examples of such salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.
  • polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A- 305283 and EP-A-351629.
  • Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
  • organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methy lcellulose , carboxymethy lcellulose , hydroxypropylmethylcellulose and hydroxyethy lcellulose.
  • organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
  • the detergent compositions of the invention when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01 % to 15% , preferably from 0.05% to 10% , most preferably from 0.1 % to 5 % by weight of the composition.
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
  • antifoam compound any compound or mixmres of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
  • Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component.
  • silicone antifoam compounds as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
  • Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
  • Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • Suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C1 -C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa- alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
  • a preferred suds suppressing system comprises
  • antifoam compound preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
  • silica at a level of from 1 % to 50%, preferably 5% to 25 % by weight of the silicone/silica antifoam compound
  • silica/silicone antifoam compound is incorporated at a level of from 5 % to 50% , preferably 10% to 40% by weight;
  • a dispersant compound most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72- 78 % and an ethylene oxide to propylene oxide ratio of from 1 :0.9 to 1 : 1.1, at a level of from 0.5 % to 10% , preferably 1 % to 10% by weight;
  • a particularly preferred silicone glycol rake copolymer of this type is DC0544, commercially available from DOW Corning under the tradename DC0544;
  • an inert carrier fluid compound most preferably comprising a Cj6-Ci 8 ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80% , preferably 10% to 70% , by weight;
  • a highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50 °C to 85 °C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms.
  • EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixmre thereof, with a melting point of from 45 °C to 80 °C.
  • the detergent compositions herein may also comprise from 0.01 % to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
  • the polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.
  • Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula :
  • A is NC, CO, C, -O-, -S-, -N-; x is O or 1 ;
  • R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group is part of these groups.
  • the N-0 group can be represented by the following general stmcmres : O
  • Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-0 group forms part of these groups.
  • the N-0 group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-0 group forms part of the R-group.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
  • polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit.
  • a preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
  • the polyamine N-oxides can be obtained in almost any degree of polymerisation.
  • the degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
  • the average molecular weight is within the range of 500 to 1000,000.
  • Suitable herein are coploymers of N-vinylimidazole and N- vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000.
  • the preferred copolymers have a molar ratio of N- vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.
  • the detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000.
  • 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).
  • PVP K-15 is also available from ISP Corporation.
  • Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
  • the detergent compositions herein may also utilize polyvinyloxazohdones as polymeric dye transfer inhibiting agents.
  • Said polyvinyloxazohdones have an average molecular weight of from 2,500 to 400,000.
  • the detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
  • Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.
  • the detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.
  • Hydrophilic optical brighteners useful herein include those having the structural formula:
  • Rj is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl
  • R2 is selected from N-2-bis-hydroxy ethyl, N-2- hydroxyethyl-N-methylamino, morphilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • Rj is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4' ,-bis[(4-anilino- 6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R ⁇ is anilino
  • R2 is N-2-hydroxyethyl-N- 2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • R ⁇ is anilino
  • R2 is mo ⁇ hilino
  • 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 Co ⁇ oration.
  • SRA polymeric soil release agents
  • SRA's will generally comprise from 0.01 % to 10.0%, typically from 0.1 % to 5 % , preferably from 0.2% to 3.0% by weight, of the compositions.
  • Preferred SRA's typically have 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, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.
  • Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide.
  • esters may be made using additional monomers capable of being inco ⁇ orated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
  • Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1 ,2-propylene glycol (“PG”) in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water.
  • DMT dimethyl terephthalate
  • PG 1,2-propylene glycol
  • SRA's include the nonionic end-capped 1,2-propylene/polyoxy ethylene terephthalate polyesters of U.S.
  • SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa- 8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S.
  • Gosselink for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S.
  • SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C1-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S.
  • methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution.
  • Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin- etsu Kagaku Kogyo KK.
  • SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester stmcmres, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al. ; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage.
  • Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al..
  • Other classes include: (III) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.;
  • compositions of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
  • the detergent compositions of the present invention are operative within a wide range of wash pHs (e.g. from about 5 to about 12), they are particularly suitable when formulated to provide a near neutral wash pH, i.e. an initial pH of from about 7.0 to about 10.5 at a concentration of from about 0.1 to about 2% by weight in water at 20 °C.
  • Near neutral wash pH formulations are better for enzyme stability and for preventing stains from setting.
  • the wash pH is preferably from about 7.0 to about 10.5, more preferably from about 8.0 to about 10.5, most preferably from 8.0 to 9.0.
  • Preferred near neutral wash pH detergent formulations are disclosed to European Patent Application 83.200688.6, filed May 16, 1983, J.H.M. Wertz and P.C.E. Goffinet.
  • compositions of this type also preferably contain from about 2 to about 10% by weight of citric acid and minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzymes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides, dyes, perfumes and brighteners, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25, 1981 (herein inco ⁇ orated by reference).
  • the detergent component of the invention can be made via a variety of methods, including dry-mixing and agglomerating of the various compounds comprised in the detergent component.
  • the detergent component preferably forms part of a detergent composition.
  • compositions in accordance with the invention can take a variety of physical forms including granular, tablet, flake, pastille and bar forms.
  • the compositions are particularly the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine dmm with the soiled fabric load.
  • compositions in accord with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach.
  • granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation.
  • the quaternised clay-soil removal/ anti-redeposition agent in accord with the present invention can be added to the other detergent components by dry- mixing, agglomeration (preferably combined with a carrier material) or as a spray-dried component.
  • the mean particle size of the components of granular compositions in accordance with the invention, comprising the water-soluble cationic clay-soil removal/anti-redeposition compounds, should preferably be such that no more that 15% of the particles are greater than 1.8mm in diameter and not more than 15% of the particles are less than 0.25mm in diameter.
  • the mean particle size is such that from 10% to 50% of the particles has a particle size of from 0.2mm to 0.7mm in diameter.
  • the term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of sieves, preferably Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.
  • the bulk density of granular detergent compositions in accordance with the present invention typically have a bulk density of at least 600 g/litre, more preferably from 650 g/litre to 1200 g/litre.
  • Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel.
  • the funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base.
  • the cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
  • the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup.
  • the filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge.
  • the filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.
  • Compacted solids may be manufacmred using any suitable compacting process, such as tabletting, briquetting or extmsion, preferably tabletting.
  • tablets for use in dish washing processes are manufacmred using a standard rotary tabletting press using compression forces of from 5 to 13 KN/cm 2 , more preferably from 5 to 11 KN/cm 2 so that the compacted solid has a minimum hardness of 176N to 275N, preferably from 195N to 245N, measured by a C 100 hardness test as supplied by I. Holland instruments.
  • This process may be used to prepare homogeneous or layered tablets of any size or shape.
  • Preferably tablets are symmetrical to ensure the uniform dissolution of the tablet in the wash solution.
  • Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention.
  • an effective amount of the detergent composition it is meant from lOg to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
  • a dispensing device is employed in the washing method.
  • the dispensing device is charged with the detergent product, and is used to introduce the product directly into the dmm of the washing machine before the commencement of the wash cycle.
  • Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.
  • the dispensing device containing the detergent product is placed inside the dmm before the commencement of the wash, before, simultaneously with or after the washing machine has been loaded with laundry.
  • water is introduced into the dmm and the dmm periodically rotates.
  • the design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the dmm rotates and also as a result of its contact with the wash water.
  • the device may possess a number of openings through which the product may pass.
  • the device may be made of a material which is permeable to liquid but impermeable to the solid product, which will allow release of dissolved product.
  • the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the dmm of the washing machine at this stage of the wash cycle.
  • Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle.
  • Especially preferred dispensing devices for use with the composition of the invention have been described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A- 0201376, EP-A-0288345 and EP-A-0288346.
  • An article by J.Bland published in Manufacturing Chemist, November 1989, pages 41-46 also describes especially preferred dispensing devices for use with granular laundry products which are of a type commonly know as the "granulette”.
  • Another preferred dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No. W094/11562.
  • Especially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070.
  • the latter Application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium.
  • the support ring is provided with a masking arrangemnt to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration, or a similar structure in which the walls have a helical form.
  • the dispensing device may be a flexible container, such as a bag or pouch.
  • the bag may be of fibrous constmction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678.
  • it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501 , 0011502, and 0011968.
  • a convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.
  • a preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware, silverware and cutlery and mixmres thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of a machine dishwashing composition in accord with the invention.
  • an effective amount of the machine dishwashing composition it is meant from 8g to 60g of product dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine dishwashing methods.
  • Naj2(A102Si ⁇ 2)i2-27H2 ⁇ having a primary particle size in the range from 0.1 to 10 micrometers
  • Citric acid Anhydrous citric acid
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m
  • Silicate Amo ⁇ hous Sodium Silicate (Si ⁇ 2:Na2 ⁇ 2.0: 1) Sodium sulfate Anhydrous sodium sulfate Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between
  • NAC-OBS Nonanamido caproyl oxybenzene sulfonate in the form of the sodium salt.
  • NACA 6 nonylamino - 6 oxo - capronic acid NACA 6 nonylamino - 6 oxo - capronic acid.
  • NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt
  • DTPA Diethylene triamine pentaacetic acid
  • DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename Dequest 2060
  • PEO Polyethylene oxide with a molecular weight of 50,000
  • Formulation N is particularly suitable for usage under Japanese machine wash conditions.
  • Formulations O to S are particularly suitable for use under US machine wash conditions.
  • Formulations W and X are of particular utility under US machine wash conditions.
  • Y is of particular utility under Japanese machine wash conditions

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

Abstract

Compositions détergentes granuleuses, ou leurs constituants, comprenant un système de blanchiment peroxyacide organique hydrophobe. Ce système peut fournir un composé peroxyacide organique hydrophobe et un ou plusieurs composés cationiques, qui sont des composés (poly)amine cationiques éthoxylés (partiellement) quaternarisés ayant les propriétés suivantes: élimination de salissure argileuse/antiredéposition. On utilise les produits en question pour la lessive et la vaisselle.
EP97943528A 1996-09-24 1997-09-22 Compositions detergentes Withdrawn EP0929623A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9619921A GB2317392A (en) 1996-09-24 1996-09-24 Detergent compositions
GB9619921 1996-09-24
PCT/US1997/017077 WO1998013449A1 (fr) 1996-09-24 1997-09-22 Compositions detergentes

Publications (2)

Publication Number Publication Date
EP0929623A1 true EP0929623A1 (fr) 1999-07-21
EP0929623A4 EP0929623A4 (fr) 2000-01-05

Family

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Application Number Title Priority Date Filing Date
EP97943528A Withdrawn EP0929623A4 (fr) 1996-09-24 1997-09-22 Compositions detergentes

Country Status (11)

Country Link
EP (1) EP0929623A4 (fr)
JP (1) JP2000507642A (fr)
CN (1) CN1237997A (fr)
AU (1) AU4497997A (fr)
BR (1) BR9713471A (fr)
CA (1) CA2265899A1 (fr)
CZ (1) CZ102099A3 (fr)
GB (1) GB2317392A (fr)
HU (1) HUP9904683A3 (fr)
TR (1) TR199900654T2 (fr)
WO (1) WO1998013449A1 (fr)

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DE10160993A1 (de) 2001-12-12 2003-06-18 Basf Ag Stickstoffhaltige Polymere umfassende Reinigungsmittelzusammensetzungen
ES2391263T3 (es) 2002-12-04 2012-11-22 Clariant Finance (Bvi) Limited Procedimiento para preparar una composición de amonio cuaternario
US7521412B2 (en) * 2007-05-25 2009-04-21 Ecolab Inc. Dimensionally stable solid rinse aid
GB201403550D0 (en) * 2014-02-28 2014-04-16 Reckitt Benckiser Brands Ltd Composition
CN104818156B (zh) * 2015-04-10 2018-08-07 广州立白企业集团有限公司 一种改善低温油污清洁效果的餐具浸泡粉组合物
CN109926385B (zh) * 2017-12-19 2022-02-15 蓝思科技（长沙）有限公司 一种手机玻璃的清洗方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4664848A (en) * 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
GB2268879A (en) * 1992-07-24 1994-01-26 Laporte Esd Ltd Disinfectant compositions
GB2292564A (en) * 1994-08-11 1996-02-28 Procter & Gamble Detergent Composition
WO1997044417A1 (fr) * 1996-05-17 1997-11-27 The Procter & Gamble Company Composition detergente

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0111965B1 (fr) * 1982-12-23 1989-07-26 THE PROCTER & GAMBLE COMPANY Compositions détergentes contenant de composés cationiques ayant des propriétés pour enlever des taches et la contre-redéposition
US4659802A (en) * 1982-12-23 1987-04-21 The Procter & Gamble Company Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions
US4741842A (en) * 1986-01-27 1988-05-03 Colgate-Palmolive Company Particulate detergent softener compositions comprising a mixture of cationic softener and ethoxylated amine

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4664848A (en) * 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
GB2268879A (en) * 1992-07-24 1994-01-26 Laporte Esd Ltd Disinfectant compositions
GB2292564A (en) * 1994-08-11 1996-02-28 Procter & Gamble Detergent Composition
WO1997044417A1 (fr) * 1996-05-17 1997-11-27 The Procter & Gamble Company Composition detergente

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9813449A1 *

Also Published As

Publication number Publication date
TR199900654T2 (xx) 1999-06-21
GB9619921D0 (en) 1996-11-06
WO1998013449A1 (fr) 1998-04-02
HUP9904683A3 (en) 2001-02-28
CA2265899A1 (fr) 1998-04-02
CN1237997A (zh) 1999-12-08
HUP9904683A2 (hu) 2000-05-28
JP2000507642A (ja) 2000-06-20
GB2317392A (en) 1998-03-25
BR9713471A (pt) 2000-10-17
AU4497997A (en) 1998-04-17
CZ102099A3 (cs) 1999-08-11
EP0929623A4 (fr) 2000-01-05

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