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WO1998013451A1 - Detergent compositions - Google Patents

Detergent compositions Download PDF

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Publication number
WO1998013451A1
WO1998013451A1 PCT/US1997/016697 US9716697W WO9813451A1 WO 1998013451 A1 WO1998013451 A1 WO 1998013451A1 US 9716697 W US9716697 W US 9716697W WO 9813451 A1 WO9813451 A1 WO 9813451A1
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WO
WIPO (PCT)
Prior art keywords
group
cationic
detergent composition
alkyl
component
Prior art date
Application number
PCT/US1997/016697
Other languages
French (fr)
Inventor
Alan Thomas Brooker
Michael Alan John Moss
Francisco Ramon Figueroa
Stuart Clive Askew
Graham Alexander Sorrie
Robin Gibson Hall
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB9619921A external-priority patent/GB2317392A/en
Priority claimed from GB9622679A external-priority patent/GB2318799A/en
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to CZ991018A priority Critical patent/CZ101899A3/en
Priority to EP97943396A priority patent/EP0929625A4/en
Priority to CA002265941A priority patent/CA2265941A1/en
Priority to BR9711535A priority patent/BR9711535A/en
Priority to CZ991020A priority patent/CZ102099A3/en
Priority to AU44878/97A priority patent/AU4487897A/en
Publication of WO1998013451A1 publication Critical patent/WO1998013451A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • C11D17/06—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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • 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

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.
  • EP-B-1 11 965 discloses the use in detergents of cationic compounds, which have both clay-soil removal and anti-redeposition properties.
  • 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 washing 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.
  • the bleach-compatibility of the cationic, quatemized ethoxylated (poly) amines can be explained as follows.
  • the quatemization of the nitrogen groups of these molecules is believed to have a dual purpose. It provides a cationic charge on the molecule, improving adsorption onto clay particles either on the fabric surface or dispersed in wash water, and it removes the oxidisable lone pair on the nitrogen groups from attack by bleaching species, thus making the molecule stable in a bleach containing laundry detergents.
  • hydrophobic bleaches despite their tendency to migrate to the hydrophobic stains or soils on the fabric surface, they do not necessarily interact fully with these. 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 results in a lessening of the bleachable/ dingy soil cleaning performance of the hydrophobic bleach.
  • hydrophilic bleachable stains such as beverage stains
  • hydrophobic bleach it has also been found that the removal of certain hydrophilic bleachable stains (such as beverage stains) by hydrophobic bleach is not always satisfactory, which is believed to be due to the limited interaction between the hydrophilic stains and hydrophobic bleach.
  • these problems can be ameliorated by the inclusion of one or more compounds which have clay-soil removal/anti-redeposition properties (as mentioned above) in a detergent composition, comprising a hydrophobic bleach.
  • detergent compositions comprising both components the bleach efficacy of the hydrophobic organic peroxyacid bleaching system is enhanced.
  • the bleach efficacy can also or further be enhanced by inclusion of non-hydrophobic bleaches in the bleach system. In both situations the overall cleaning performance of the detergent is improved.
  • the interaction between the cationic compound and the anionic, hydrophobic (and also non-hydrophobic) bleach facilitates the migration and/ or interaction of the bleach to a negatively surface.
  • the interaction between the cationic compound and the (hydrophobic) bleach makes the bleach more hydrophilic, thus facilitating the migration or interaction of the bleach with hydrophilic, bleachable 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 particulate/ 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 particulate/ clay-soil removal / anti-redeposition properties.
  • 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
  • a water-soluble cationic compound having clay soil removal/anti-redeposition properties which is selected from the group consisting of:
  • Ml is an N+ or N group; each M ⁇ is an N+ or N group, and at least one M ⁇ is an N+ group;
  • a 1 is —NC — , --
  • 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 O-N bonds are formed
  • each R ⁇ is C]- C4 alkyl or hydroxyalkyl, the moiety -L-X, or two R ⁇ together form the moiety - (CH2) r -A2-(CH2) f -, wherein A2 is -0- or -CH2-, r is 1 or 2, s is 1 or 2 and r + s is 3 or 4
  • each R ⁇ is Cj-Cg alkyl or hydroxyalkyl.
  • R ⁇ is a substituted C3-C12 alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having p substitution sites;
  • R ⁇ is C ⁇ -C ⁇ 2 alkenyl, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no O-O or O-N bonds are formed;
  • X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof;
  • L is a hydrophilic chain which contains the polyoxyalkylene moiety
  • R 6 is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety
  • -(CH2CH2O), comprises at least about 50% by weight of said polyoxyalkylene moiety; d is 1 when M ⁇ is N+ and is 0 when M ⁇ is N; n is at least about 16 for said cationic monoamines, is at least about 6 for said cationic diamines and is at least about 3 for said cationic polyamines; p is from 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is 1 when q is 1.
  • said hydrophobic organic peroxyacid bleaching system comprises (i) a hydrogen peroxide source and (ii) a hydrophobic organic peroxyacid bleach precursor compound.
  • a non-hydrophobic bleaching system preferably comprising (i) a hydrogen peroxide source and (ii) a non-hydrophobic 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 ratio of the hydrophobic organic peroxyacid compound (provided by the hydrophobic organic peroxyacid bleaching) to the water-soluble cationic compound is preferably from 20: 1 to 1 :2, more preferably from 10: 1 to 1 :1 , most preferably from 7: 1 to 1 : 1.
  • 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 R z is preferably methyl or the moiety -L-X; each R ⁇ is preferably -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), C ⁇ -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 -[(R 6 O) m (CH2CH2-Oêt)-].
  • the moieties -(R 6 O)m- and - (CH2CH2 ⁇ )n- of the polyoxyalkylene moiety can be mixed together or preferably form blocks of -(R ⁇ O) m - and -(CH2CH2 ⁇ ) justify- moieties.
  • R ⁇ 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 -(CH2CH2 ⁇ ) horr-.
  • the moiety -(CH2CH2O) lake- preferably comprises at least about 85% by weight of the polyoxyalkylene moiety and most preferably 100% by weight (m is O).
  • l and each M ⁇ 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 1 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-C 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 ⁇ is a substituted aryl or alkaryl group
  • q is preferably 1 and R ⁇ is preferably C2-C3 alkylene.
  • R ⁇ is a substituted alkyl, hydroxyalkyl, or alkenyl group
  • 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: O
  • 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 organic 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 1 1 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.
  • the ratio of the hydrophobic organic peroxyacid compound (provided by the hydrophobic organic peroxyacid bleaching) to the water-soluble cationic compound is preferably from 20:1 to 1 :2, more preferably from 10:1 to 1 :1. most prferablv from 7:1 to 1 : 1.
  • 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 ⁇ 2H 2 O 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 3 is an alkyl chain containing from 1 to 8 carbon atoms.
  • R , R5 is an alkylene chain containing from 1 to 8 carbon atoms and Y is H or a solubilizing group.
  • Any of R 1 , R 3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups
  • the preferred solubilizing groups are -SO, " M , -CO ? " M , -SO M , -N (R J ) C and 0 ⁇ -N(R 3 )_ and most preferably -SO ⁇ M + and -CO " M + wherein R is an alkyl 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
  • 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
  • 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 and L can be essentially any leaving group
  • R! preferably contains from about 6 to 12 carbon atoms.
  • R ⁇ preferably contains from about 4 to 8 carbon atoms, R! 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 ⁇ .
  • R2 can include alkyl, aryl, wherein said R ⁇ may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • R 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.
  • bleach precursors of this type include amide substituted 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 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 hexanoyloxy benzene 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* is an alkyl, aryl, alkoxy aryl or alkaryl group containing from 6 to 12 carbon atoms.
  • Prefe ⁇ ed 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, Rl 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 1 carbon atoms
  • R 2 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.
  • R* 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 R ⁇ .
  • R can include alkyl, aryl, wherein said R2 may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ 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 peroxycarboxylic 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, 6" l2 arylene and radical combinations thereof;
  • Rl and R ⁇ are independently selected from the group consisting of H, Cj-Cjg alkyl and Cg-C 12 aryl radicals and a radical that can form a C3-C ⁇ 1 ring together with R ⁇ and both nitrogens;
  • R ⁇ is selected from the group consisting of C1-C12 alkylene, C5-
  • 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 ;
  • 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:
  • 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, Y, Z and n are as defined above.
  • Rl is selected from the group consisting of C] -Cj2 alkylene, C5-C]2 cycloalkylene, C(,-C ⁇ 2 arylene and radical combinations thereof;
  • a non-hydrophobic peroxyacid bleach precursor is present in the detergent compositions or components thereof.
  • This can be any peroxyacid bleach precursor, not being a hydrophobic peroxyacid bleach precursor as defined above.
  • the non-hydrophobic peroxyacid contains less than 7 carbon atoms, more preferably less than 5, most preferably 2.
  • peroxyacid bleach precursors are those, which can be a precursor for both hydrophobic and non-hydrophobic peroxyacids.
  • the non-hydrophobic peroxyacid bleach precursors are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight of the compositions.
  • the ratio of the non-hydrophobic peroxyacid bleach precursor to the cationic compound is preferably from 20:1 to 1:10. more preferably from 10:1 to 1;1. most preferably from 7:1 to 1 :1.
  • Suitable peroxyacid bleach precursors 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 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.
  • Preferred non-hydrophobic peroxyacid bleach precursors are alkyl fatty peroxyacid bleach precursors, perbenzoic acid precursor, perbenzoic acid derivative precursors and cationic peroxyacid precursors.
  • a highly preferred additional peroxyacid bleach precursor is an alkyl fatty peroxyacid bleach precursors.
  • Alkyl fatty peroxyacid bleach precursors form alkyl fatty peroxyacids on perhydrolysis.
  • Preferred precursors of this type give rise to peracetic acid on perhydrolysis.
  • Preferred alkyl fatty peroxyacid precursor compounds of the imide type include the N-,N,N 1N 1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains l, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.
  • TAED Tetraacetyl ethylene diamine
  • any perbenzoic acid precursors are suitable herein, including those of the N-acylated lactam class, which are preferred.
  • Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybenzene sulfonate:
  • benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents including for example:
  • Preferred perbenzoic acid precursor compounds of the imide type include N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas.
  • Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • Preferred perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the compound having the formula:
  • Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:
  • Suitable perbenzoic acid derivative precursors include any of the herein disclosed perbenzoic precursors in which the perbenzoic group is substituted by essentially any functional group including alkyl groups.
  • Cationic peroxyacid precursor compounds are also suitable herein.
  • cationic peroxyacid precursors are formed by substituting the peroxyacid part with an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group.
  • Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1.382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • a preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-(trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
  • a preferred cationically substituted alkyl oxybenzene sulfonate is the methyl ammonium derivative of 2,3,3 -tri-methyl hexanoyloxybenzene sulfonate.
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caprolactam:
  • Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.
  • 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-
  • T MILE 26 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, C ⁇ -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 structures 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 polyamides, the polyimides and the like, the polyacrylates, the polyacrylamides, the poly vinylethers, the polyethylenes, the polypropylenes and like polyalkylenes, the polystyrenes and like polyalkarylenes, the polyalkyleneamines, the polyalkyleneimines, the polyvinylamines, the polyalylamines, the polydiallylammes, the polyvinylpyridines, the polyaminotriazoles, polyvinyl alcohol, the aminopolyureylenes, and mixtures thereof.
  • M can be any compatible cationic group which comprises an N + (quartemary), positively charged center.
  • the quartemary positively charged center can be represented by the following general structures E and F:
  • M groups are those containing a quartemary center represented by general structure E.
  • the cationic group is preferably positioned close to or integral with the polymer backbone.
  • Suitable counter anions include Cl", Br, SO3 2 ", SO4 2 ", PO4 2 ", MeOSO3” and the like. Particularly preferred counter anions are Cl" and Br.
  • X can be a nonionic group selected from hydrogen (H), C ⁇ -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.
  • the ratio is from about 1 :1 to about 1 :5.
  • the polymers formed from such copolymerization are typically random, i.e. the cationic, nonionic and mixed cationc/nonionic monomers copolymerize in a nonrepeating sequence.
  • the units which contain groups M and groups L-X can comprise 100% of the cationic polymers of the present invention.
  • other units preferably nonionic
  • examples of other units include acrylamides, vinyl ethers and those containing unquatemized tertiary amine groups (Ml) containing an N centre.
  • Ml unquatemized tertiary amine groups
  • 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 M ⁇ -L-X groups).
  • 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'O) OT (CH2CH2O) n ]-.
  • the moieties -(R'O) m - and - (CH2CH 2 O) can be mixed together, or preferably form blocks of -(R'O) w - and -(C ⁇ CH ⁇ O),,- 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 -(CH2CH2 ⁇ ) rt -.
  • the moiety -(CH2CH2 ⁇ ) lake- 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 structures G and H:
  • Structures 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 III:
  • X is 0 or 1 ;
  • R is H or C1-C4 alkyl or hydroxyalkyl;
  • R 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 O-O or O-N bonds are formed with Al ; when x is 1 , R 2 is -R ⁇ - except when A ⁇ is 0
  • R 3 is -R ⁇ -;
  • R 4 is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R ⁇ ) ⁇ - [(C3H6 ⁇ ) OT (CH 2 CH2 ⁇ ) horr]-X;
  • R 5 is C1-C12 alkylene, hydroxyalkylene. alkenylene, arylene, or alkarylene; each R ⁇ is C1 4 alkyl or hydroxyalkyl. or the moiety - (CH 2 ) A 2 -(CH 2 )s-, wherein A 2 is -O- or -CH 2 -;
  • R 7 is H or R 4 ;
  • R 8 is C 2 -C 3 alkylene or hydroxyalkylene;
  • X is H,
  • R ⁇ is C ⁇ -C4 alkyl or hydoxyalkyl
  • k is 0 or 1
  • m and n are numbers such that the moiety -(CH2CH2 ⁇ ) rt - comprises at least about 85% by weight of the moiety -[(C3H6 ⁇ ) (CH2CH2 ⁇ ) M ]-
  • 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.
  • A is preferably
  • a 2 is preferably -O-; x is preferably 1; and R is preferably H.
  • R* can be linear (e.g. -CH 2 -CH 2 -CH 2 -,
  • R 2 is preferably -OR5- or -(OR 8 ) ⁇ -;
  • R3 is preferably -R 5 O- or -(OR 8 )y-;
  • R 4 and R 6 are preferably methyl.
  • R 5 can be linear or branched, and is preferably C2- C3 alkylene; R is preferably H or C1-C3 alkyl; R 8 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; R ⁇ is substituted C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or C2-C3 oxyalkylene; each R 2 is Cj-Cj2 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; each R ⁇ is C1-C4 alkyl or hydroxyalkyl, the moiety -(R 2 )*-[(C3H 6 O) m (CH2CH2 ⁇ ) contend]-X, or together form the moiety -(CH2) r -A 2 -(CH2).y-» wherein A 2 is -O- or -CH2-; each R 4
  • SUBSTITUTE SHEET (WILE 26) is C1-C4 alkyl or hydroxyalkyl, or two R ⁇ together form the moiety -(CH2)r ⁇ - (CH 2 V; X is H,
  • 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) M - comprises at least about 85% by weight of the moiety -[(C3H6 ⁇ ) (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 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.
  • Al is preferably
  • a 2 is preferably -O-; R is preferably H. Rl can be linear
  • S ⁇ BSTlTllTESH ⁇ (RULE26) substituted alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene;
  • Rl is preferably substituted C2-C ⁇ alkylene or substituted C2-C3 oxyalkylene, and most preferably
  • Each R 2 is preferably C2-C3 alkylene, each R 3 and R 4 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 polyalkyleneamines, polyalkyleneimines and the like. These polymers comprise units selected from those having formulas VII and VIII and IX.
  • R is C 2 -Ci2 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no O-N bonds are formed; each R 2 is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R 3 )jfc-[(C3H 6 O) m (CH2CH2 ⁇ ) contend]-X; R 3 is Cj-C ⁇ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; M' is an N+ or N centre; X is H,
  • R 4 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 -(CH2CH2 ⁇ ) w - comprises at least about 85% by weight of the moiety -[(C3H6 ⁇ ) w (CH2CH2 ⁇ ) tread]-;
  • m is from 0 to about 5;
  • R* can be varied like Rl of the polyurethene and like polymers; each R 2 is preferably methyl or the moiety -(R )#- [(C3H6 ⁇ ) m (CH2CH2 ⁇ ) tread]-X; R 3 is preferably C2-C3 alkylene; R 4 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 1 1 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 mixture 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 + 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 polyethyleneamines (PEA's) and polyethyleneimines (PEI's). These preferred cationic polymers comprise units having the general formula:
  • R 2 (preferably methyl), M', X, d, x, y, z and n are defined as before: a is 1 or O.
  • 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 mixture 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.
  • n is at least about 6.
  • 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 Esseimann 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
  • 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:
  • Rl is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R 2 )jt- [(C3H6 ⁇ ) m (CH2CH2 ⁇ ) utilizat]-X;
  • R 2 is Cj-C ⁇ alkylene, hydroxyalkylene, alkylene, arylene or alkarylene;
  • each R 3 is C1-C4 alkyl or hydroxyalkyl, or together form the moiety -(CH2) r -A-(CH2 , wherein A is -O- or -CH2-;
  • X is H,
  • R 4 is C1-C4 alkyl or hydroxyalkyl
  • k is 1 or 0
  • m and n are numbers such that the moiety -(CH2CH2 ⁇ ) ⁇ - comprises at least about 85% by weight of the moiety -[(C3H6 ⁇ ) OT (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
  • 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+ 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, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
  • 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 substituted 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 ⁇ -C, o monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C fi -C , . 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 oxide ether sulfates, the C5-C17 acyl-N-(C j -C4 alkyl) and -N-(C ⁇ -C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Alkyl sulfate surfactants are preferably selected from the linear and branched primary CjQ-Cj alkyl sulfates, more preferably the Cj 1-C15 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the Cjo-Cig alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C j j -C 1 g, most preferably C ⁇ ⁇ -C ⁇ 5 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
  • a particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
  • Anionic sulfonate surfactant Anionic sulfonate surfactant
  • Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, Cg-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates. fatty oleyl glycerol sulfonates, and any mixtures thereof.
  • Anionic carboxylate surfactant include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, Cg-C24 olefin sulfonates, sulfonated polycarboxylic acids, alky
  • Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates. the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
  • Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2 ⁇ ) x CH2C00"M + wherein R is a C ⁇ to Cjg 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-O)-R3 wherein R is a C6 to C ⁇ alkyl group, x is from 1 to 25, R ⁇ and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
  • Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid. 2-propyl- 1-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.
  • any 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 preferred 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.
  • Nonionic polvhvdroxy fatty acid amide surfactant Nonionic polvhvdroxy fatty acid amide surfactant
  • Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R CONRlZ wherein : Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl. ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably Cj or C2 alkyl, most preferably C] alkyl (i.e., methyl); and R2 is a C5- C31 hydrocarbyl, preferably straight-chain C5-C 19 alkyl or alkenyl. more preferably straight-chain C9-C j 7 alkyl or alkenyl.
  • 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.
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
  • Nonionic fattv acid amide surfactant Nonionic fattv acid amide surfactant
  • Suitable fatty acid amide surfactants include those having the formula: R6C0N(R7)2 wherein R" 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.
  • R6C0N(R7)2 R" 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
  • R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10. and x is from 1.3 to 8.
  • the glycosyl is preferably derived from glucose.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocar boxy lie acids.
  • Suitable amine oxides include those compounds having the formula R 3 (OR 4 ) X N0(R5)2 wherein R 3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each 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 C ⁇ Q-C ⁇ g alkyl dimethylamine oxide, and C] ⁇ _ ⁇ acylamido alkyl dimethylamine oxide.
  • a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ. Zwitterionic surfactant
  • 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 + R 2 COO" wherein R is a Cg-Ci g hydrocarbyl group, each Rl is typically C1-C3 alkyl. and R 2 is a C1-C5 hydrocarbyl group.
  • Preferred betaines are C]2-18 dimethyl-ammonio hexanoate and the C J O-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 C5- C)6, preferably C ⁇ -Cjo N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • cationic ester surfactants Another suitable group of 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 (i.e. -COO-) linkage and at least one cationically charged group.
  • 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 mixtures 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 mixtures 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 sulfinyl carboxylates.
  • Polycarboxylates containing three carboxy groups include, in particular, water- soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccina.es 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 mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
  • 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 [(AlO2) z (SiO2)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 mixtures thereof. Zeolite A has the formula
  • Zeolite X has the formula Nagg [(AlO 2 )86(SiO 2 )l06]- 276 H 2 O.
  • 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 d5o 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 d50 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 d5Q 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.
  • diethylene triamine penta methylene phosphonate
  • ethylene diamine tri methylene phosphonate
  • hexamethylene diamine tetra methylene phosphonate
  • hydroxy-ethylene 1 ,1 diphosphonate Preferred among the above species are diethylene triamine penta (methylene phosphonate).
  • 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.
  • Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2 -hydroxy ethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.
  • iminodiacetic acid-N-2- hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl- 3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
  • EP-A-476,257 describes suitable amino based sequestrants.
  • EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
  • EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2- phosphonobutane-l,2,4-tricarboxylic acid are alos suitable. 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.
  • Preferred examples of these catalysts include Mnl O) ⁇ (u-OAc)2(l,4,7-trimethyl-l,4,7-triazacyclononane)2-(Cl ⁇ 4)2, Mnl V 4(u- O)6(l,4,7-triazacyclononane) 4 -(Cl ⁇ 4)2, Mn ⁇ Mn IV 4(u-O) ⁇ (u-OAc)2-(l,4,7- trimethyl-1 ,4,7-triazacyclononane)2-(Cl ⁇ 4)3, and mixtures thereof. Others are described in European patent application publication no.
  • 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 mixtures thereof.
  • U.S. Pat. 5,1 14,61 1 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 substituted 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)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)2 ⁇ 2 ⁇ 4, Bis-(2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.
  • bleach catalysts include binuclear Mn complexed with tetra-N-dentate and bi-N- dentate ligands. including N4MnIH(u-O)2Mnl ⁇ N4) + and [Bipy2MnlH(u- O)2Mn Iv bipy ]-(ClO 4 )3.
  • Other 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 (metal lo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711 ,748 and European patent application, publication no.
  • 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 upases, 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
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries AS (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 AS.
  • 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 oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri AS, 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 thereofin 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.
  • 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.
  • Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcelluiose and hydroxyethylcellulose.
  • 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 mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
  • Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component.
  • silicone antifoam compounds 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 C ⁇ -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.
  • high molecular weight fatty esters e.g. fatty acid triglycerides
  • fatty acid esters of monovalent alcohols e.g. fatty acid esters of monovalent alcohols
  • 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 DCO544, commercially available from DOW Coming under the tradename DCO544;
  • an inert carrier fluid compound most preferably comprising a C ] g-C j g 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 mixture 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-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
  • the N-O group can be represented by the following general structures :
  • Rl, R2. and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.
  • the N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group.
  • 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-vinyipyrrolidone 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 polyvinyloxazolidones as polymeric dye transfer inhibiting agents.
  • Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.
  • the detergent compositions herein may also utilize polyvmylimidazole 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:
  • R ⁇ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • 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.
  • Rj is anilino
  • R2 is morphilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-mo hilino-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • 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 incorporated 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/polyoxyethylene terephthalate polyesters of U.S.
  • Gosselink et al. for example those produced by transesterification oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG").
  • 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 SMI 00 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 structures, 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 incorporated 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 composiiton.
  • the 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 drum 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.
  • 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 manufactured using any suitable compacting process, such as tabletting, briquetting or extrasion, preferably tabletting.
  • tablets for use in dish washing processes are manufactured using a standard rotary tabletting press using compression forces of from 5 to 13 KN/cm 2 , more preferably from 5 to 1 1 KN/cm 2 so that the compacted solid has a minimum hardness of 176N to 275N, preferably from 195N to 245N, measured by a C100 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 drum 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 drum before the commencement of the wash, before, simultaneously with or after the washing machine has been loaded with laundry.
  • water is introduced into the drum and the drum 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 drum 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 drum 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. WO94/11562.
  • 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 construction 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. 001 1500, 001 1501, 001 1502, and 001 1968.
  • 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 mixtures 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- 2 7H2 ⁇ 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
  • NOVO Industries AS Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries AS under the tradename
  • 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
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyry)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-l .3.5- triazin-2-yl)amino) stilbene-2:2'-disulfonate
  • HEDP 1,1-hydroxyethane diphosphonic acid EDDS Ethylenediamine-N, N'-disuccinic acid QEA1 bis((C2H5 ⁇ C 2 H4 ⁇ ) n ) (CH 3 ) -N + -C 6 H 12 -N+-
  • PEGX Polyethylene glycol with a molecular weight of x PEO Polyethylene oxide, with a molecular weight of
  • 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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Abstract

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) quaternized ethoxylated (poly) amine compounds with clay-soil removal/anti-redeposition properties, for use in laundry and dish washing processes. Preferably, also a non-hydrophobic bleach system is present.

Description

Detergent Compositions
Technical Field
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.
Background to the Invention
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.
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.
In addition to clay soil removal, there is a need to keep the removed soil in suspension during the laundering (or dish washing) cycle. Soil which is removed from the fabric and suspended in the wash water can redeposit on the surface of the fabric. This redeposited soil causes a dulling or "greying" effect which is especially noticeable on white fabrics. To minimise this problem, anti-redeposition agents can be included in the detergent composition.
For example EP-B-1 11 965 discloses the use in detergents of cationic compounds, which have both clay-soil removal and anti-redeposition properties.
US 4.659,802 and US 4,664,848 describe quatemized amines which have clay-soil removal and anti-redeposition properties and which can be used in combination with anionic surfactants.
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 washing 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.
The Applicants have found that cationic, (partially) quatemized ethoxylated (poly) amines which have clay-soil removal/anti-redeposition properties, are fully compatible with bleaches formulated therewith.
It also has been found that the use in detergent compositions (or components thereof) of (oxygen-releasing) bleach in combination with fully quaternised ethoxylated (poly) amines provides a better improvement in cleaning or whiteness maintenance than the use of (oxygen releasing) bleach in combination with partially quaternised ethoxylated (poly) amines. However, even the partially quaternised ethoxylated (poly) amines provide an improvement in cleaning or whiteness maintenance in combination with bleach.
Without wishing to be bound by theory, the bleach-compatibility of the cationic, quatemized ethoxylated (poly) amines can be explained as follows. The quatemization of the nitrogen groups of these molecules is believed to have a dual purpose. It provides a cationic charge on the molecule, improving adsorption onto clay particles either on the fabric surface or dispersed in wash water, and it removes the oxidisable lone pair on the nitrogen groups from attack by bleaching species, thus making the molecule stable in a bleach containing laundry detergents.
Recently developed bleach species are bleaching systems based on hydrophobic peroxyacids.
It has been found that one problem with hydrophobic bleaches is that despite their tendency to migrate to the hydrophobic stains or soils on the fabric surface, they do not necessarily interact fully with these. 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 results in a lessening of the bleachable/ dingy soil cleaning performance of the hydrophobic bleach.
It also has been found that the removal of bleachable stains or soils on negatively charged fabric (such as fabric at high pH, cotton fabric or fabric surfaces containing negatively charged particles/ compounds, such as anionic surfactants) by hydrophobic bleaches is not always satisfactory. This is thought to be due to a lessened tendency of negatively charged hydrophobic bleaches to migrate to negatively charged fabric surfaces.
It has also been found that the removal of certain hydrophilic bleachable stains (such as beverage stains) by hydrophobic bleach is not always satisfactory, which is believed to be due to the limited interaction between the hydrophilic stains and hydrophobic bleach. The Applicants have found that these problems can be ameliorated by the inclusion of one or more compounds which have clay-soil removal/anti-redeposition properties (as mentioned above) in 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. Furthermore it has been found that the bleach efficacy can also or further be enhanced by inclusion of non-hydrophobic bleaches in the bleach system. In both situations the overall cleaning performance of the detergent is improved.
The following mechanisms are believed to be responsible therefor. Firstly, it is believed that the interaction between the cationic compound and the anionic, hydrophobic (and also non-hydrophobic) bleach facilitates the migration and/ or interaction of the bleach to a negatively surface. Secondly, the interaction between the cationic compound and the (hydrophobic) bleach makes the bleach more hydrophilic, thus facilitating the migration or interaction of the bleach with hydrophilic, bleachable stains.
All documents cited in the present description are, in relevant part, incorporated herein by reference.
Summary of the invention
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 particulate/ clay-soil removal / anti-redeposition properties.
In more detail, the present invention relates to granular detergent compositions or components thereof, which comprise
(a) a hydrophobic organic peroxyacid bleaching system, capable of providing a hydrophobic organic peroxyacid compound; and (b) a water-soluble cationic compound having clay soil removal/anti-redeposition properties, which is selected from the group consisting of:
1 ) ethoxylated cationic monoamines having the formula:
R"
R" - + L— X
R
2) ethoxylated cationic diamines having the formula:
(R3)d R3 (R3)d R3
X L M1 R1 "- L— X or R3 - M1 R1 4"— R or L L L L L
X X X X X
(R3)d R3
(X — L )2 M2 R1 M2 R2
R2
wherein Ml is an N+ or N group; each M^ is an N+ or N group, and at least one M^ is an N+ group;
3) ethoxylated cationic polyamines having the formula:
Figure imgf000007_0001
R2 4) mixtures thereof;
0 wherein A1 is —NC — , --
R
Figure imgf000008_0001
O O 0 0 0
— CO — , — 000- , OC— , CNC or — O— ,
R
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 O-N bonds are formed; each R^ is C]- C4 alkyl or hydroxyalkyl, the moiety -L-X, or two R^ together form the moiety - (CH2)r-A2-(CH2)f-, wherein A2 is -0- or -CH2-, r is 1 or 2, s is 1 or 2 and r + s is 3 or 4; each R^ is Cj-Cg alkyl or hydroxyalkyl. benzyl, the moiety L-X, or two R^ or one R2 and one R^ together form the moiety -(CH2)r-A2-(CH2)5-; R^ is a substituted C3-C12 alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having p substitution sites; R^ is C\-C\2 alkenyl, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no O-O or O-N bonds are formed; X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof; L is a hydrophilic chain which contains the polyoxyalkylene moiety
-[(R6O)OT(CH2CH2O)„]-; wherein R6 is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety
-(CH2CH2O),,- comprises at least about 50% by weight of said polyoxyalkylene moiety; d is 1 when M^ is N+ and is 0 when M^ is N; n is at least about 16 for said cationic monoamines, is at least about 6 for said cationic diamines and is at least about 3 for said cationic polyamines; p is from 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is 1 when q is 1. In a preferred aspect said hydrophobic organic peroxyacid bleaching system comprises (i) a hydrogen peroxide source and (ii) a hydrophobic organic peroxyacid bleach precursor compound.
In another preferred embodiment a non-hydrophobic bleaching system is present, preferably comprising (i) a hydrogen peroxide source and (ii) a non-hydrophobic bleach precursor compound.
Detailed description of the invention
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.
In detergent compositions, 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 ratio of the hydrophobic organic peroxyacid compound (provided by the hydrophobic organic peroxyacid bleaching) to the water-soluble cationic compound is preferably from 20: 1 to 1 :2, more preferably from 10: 1 to 1 :1 , most preferably from 7: 1 to 1 : 1.
Cationic amines
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.
In the preceding formulas for the cationic amines, R* can be branched
(e.g- CH3
CB- CH — CH? CH" );
cyclic (e.g. - — ),
or most preferably linear
(e.g. CH2CH2 - , — CH2CH2CH2 — )
alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene. Rl is preferably C2-C6 alkylene for the ethoxylated cationic diamines. Each Rz is preferably methyl or the moiety -L-X; each R^ is preferably -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, MeOSθ3- and the like. Particularly preferred counter anions are Cl - and Br-.
X can be a nonionc group selected from hydrogen (H), C \ -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.
In the preceding formulas, hydrophilic chain L usually consists entirely of the polyoxyalkylene moiety -[(R6O)m(CH2CH2-O„)-]. The moieties -(R6O)m- and - (CH2CH2θ)n- of the polyoxyalkylene moiety can be mixed together or preferably form blocks of -(R^O)m- and -(CH2CH2θ)„- moieties. R^ 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 -(CH2CH2θ)„-. The moiety -(CH2CH2O)„- preferably comprises at least about 85% by weight of the polyoxyalkylene moiety and most preferably 100% by weight (m is O).
In the preceding formulas, l and each M^ are preferably an N+ group for the cationic diamines and polyamines.
Preferred ethoxylated cationic monoamines and diamines have the formula:
Figure imgf000011_0001
wherein X and n are defined as before, a is from 0 to 20, preferably 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0. For preferred cationic monoamines (b=0), n is preferably at least about 16, with a typical range of from about 20 to about 35. For preferred cationic diamines (b=l), n is at least about 12 with a typical range of from about 12 to about 42.
In the preceding formula for the ethoxylated cationic polyamines. R4 (linear, branched, or cyclic) is preferably a substituted C3-C alkyl, hydroxyalkyl or aryl group; Al is preferably
O
- - CN- - ;
H
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. When R^ is a substituted aryl or alkaryl group, q is preferably 1 and R^ is preferably C2-C3 alkylene. When R^ 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.
These ethoxylated cationic polyamines can be derived from polyamino amides such as: O
HO
Figure imgf000012_0001
These ethoxylated cationic polyamines can also be derived from polyaminopropyleneoxide derivatives such as:
(OC3H6)c NH2
CH3 ~(OC3H6)c NH2
OC3H6)c NH2
wherein each c is a number from 2 to about 20.
Hydrophobic organic peroxyacid bleaching system
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 organic peroxyacid compound. By 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.
Preferably 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. In an alternative preferred execution 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.
Preferably, the hydrophobic organic peroxyacid contains at least 7 carbon atoms, more preferably at least 9 carbon atoms, most preferably at least 1 1 carbon atoms. In a preferred aspect 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.
The ratio of the hydrophobic organic peroxyacid compound (provided by the hydrophobic organic peroxyacid bleaching) to the water-soluble cationic compound is preferably from 20:1 to 1 :2, more preferably from 10:1 to 1 :1. most prferablv from 7:1 to 1 : 1.
Inorganic perhydrate bleaches
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.
Examples of 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. For certain perhydrate salts however, 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 NaBθ2H2θ2 or the tetrahydrate NaBθ2H2O2.3H2θ.
Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2Cθ3.3H2θ2, and is available commercially as a crystalline solid.
Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.
Peroxyacid bleach precursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as
O X C L
where L is a leaving group and X is essentially any functionality, such that on perhydrolysis the structure of the peroxyacid produced is
O X C OOH
For the purposes of the present invention 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.
Leaving groups
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:
Figure imgf000015_0001
O O ■ Y and O
Figure imgf000015_0002
Figure imgf000016_0001
Figure imgf000016_0002
and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R 3 is an alkyl chain containing from 1 to 8 carbon atoms. R 4 i •s
H or R , R5 is an alkylene chain containing from 1 to 8 carbon atoms and Y is H or a solubilizing group. Any of R 1 , R 3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups
The preferred solubilizing groups are -SO,"M , -CO? "M , -SO M , -N (RJ) C and 0<-N(R3)_ and most preferably -SO ~M+ and -CO "M+ wherein R is an alkyl 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. Preferably, 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.
Amide substituted alkyl peroxyacid precursors
Preferred peroxyacid precursors are amide substituted alkyl peroxyacid precursor compounds, including those of the following general formulae:
R1 — C __ N __ R2 — c — L R1 N c — R2__ . C __ L
O R5 O or R5 0 0
wherein 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, and R^ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group, R! preferably contains from about 6 to 12 carbon atoms. R^ preferably contains from about 4 to 8 carbon atoms, R! 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^. R2 can include alkyl, aryl, wherein said R^ may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R^ is preferably H or methyl. R 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.
Preferred examples of bleach precursors of this type include amide substituted 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.
Benzoxazin organic peroxyacid precursors
Also suitable are 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:
Figure imgf000017_0001
wherein R, is an alkyl, alkaryl, aryl, or arylalkyl containing at least 5 carbon atoms.
Alkyl percarboxylic acid bleach precursors
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.
Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxy benzene sulfonate (iso-NOBS) and sodium nonanoyloxybenzene sulfonate (NOBS).
N-acylated lactam precursors
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:
c — CH - CH .
CH-
CH- CH .
wherein R* is an alkyl, aryl, alkoxy aryl or alkaryl group containing from 6 to 12 carbon atoms. Prefeπed 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:
C H . CH .
N
CH . CH . wherein R! is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6 to 12 carbon atoms. More preferably, Rl is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof.
Mixtures of any of the peroxyacid bleach precursor, herein before described, may also be used.
Preformed organic peroxyacid
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:
R1 C — N — R2 — C — OOH
O R5 O or
R1 N — C — R2 — C — OOH
R5 O O
wherein R! is an aryl or alkaryl group with from about 1 to about 1 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms, and R^ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. R* 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 R^. R can include alkyl, aryl, wherein said R2 may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R^ 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 peroxycarboxylic acid.
Other suitable organic peroxyacids include diperoxyalkanedioc acids having more than 7 carbon atoms, such as diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
Other suitable organic peroxyacids include diamino peroxyacids, which are disclosed in WO 95/ 03275, with the following general formula:
O O O O
MOCR- R1N)n- C (NR2)n' R3 (R2N)m- C (NR1)m RCOOM wherein:
R is selected from the group consisting of C1-C12 alkylene, C5-C12 cycloalkylene, 6" l2 arylene and radical combinations thereof;
Rl and R^ are independently selected from the group consisting of H, Cj-Cjg alkyl and Cg-C 12 aryl radicals and a radical that can form a C3-C \ 1 ring together with R^ and both nitrogens; R^ is selected from the group consisting of C1-C12 alkylene, C5-
C_2 cycloalkylene and Cg-C^ 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.
Other suitable organic peroxyacids are include the amido peroxyacids which are disclosed in WO 95/ 16673, with the following general structure:
X -Ar - CO — NY— R(Z) — CO OOH in which X represents hydrogen or a compatible substituent, Ar is an aryl group, R represents (CH2)n >n which n = 2 or 3, and Y and Z each represent independently a substituent selected from hydrogen or an alkyl or aryl or alkaryl group or an aryl group substituted by a compatible substituent provided that at least one of Y and Z is not hydrogen if n = 3. 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. Alternatively, X can represent a second amido-percarboxylic acid substituent of formula:-
— CO NY - R(Z) - CO — OOH
in which R, Y, Z and n are as defined above.
MOOC-R 1 CO-NR2-R3-NR4-CO-R5COOOM
wherein Rlis selected from the group consisting of C] -Cj2 alkylene, C5-C]2 cycloalkylene, C(,-C\2 arylene and radical combinations thereof; R
Non-hvdrophobic peroxyacid bleach precursor
Preferably a non-hydrophobic peroxyacid bleach precursor is present in the detergent compositions or components thereof. This can be any peroxyacid bleach precursor, not being a hydrophobic peroxyacid bleach precursor as defined above. Preferably the non-hydrophobic peroxyacid contains less than 7 carbon atoms, more preferably less than 5, most preferably 2.
Other peroxyacid bleach precursors are those, which can be a precursor for both hydrophobic and non-hydrophobic peroxyacids.
The non-hydrophobic peroxyacid bleach precursors are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight of the compositions. The ratio of the non-hydrophobic peroxyacid bleach precursor to the cationic compound is preferably from 20:1 to 1:10. more preferably from 10:1 to 1;1. most preferably from 7:1 to 1 :1.
Suitable peroxyacid bleach precursors 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 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.
Preferred non-hydrophobic peroxyacid bleach precursors are alkyl fatty peroxyacid bleach precursors, perbenzoic acid precursor, perbenzoic acid derivative precursors and cationic peroxyacid precursors.
Alkyl fattv peroxyacid bleach precursors
A highly preferred additional peroxyacid bleach precursor is an alkyl fatty peroxyacid bleach precursors. Alkyl fatty peroxyacid bleach precursors form alkyl fatty peroxyacids on perhydrolysis. Preferred precursors of this type give rise to peracetic acid on perhydrolysis.
Preferred alkyl fatty peroxyacid precursor compounds of the imide type include the N-,N,N 1N 1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains l, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.
Perbenzoic acid precursor
Essentially any perbenzoic acid precursors are suitable herein, including those of the N-acylated lactam class, which are preferred. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybenzene sulfonate:
Figure imgf000023_0001
Also suitable are the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, including for example:
Figure imgf000023_0002
Ac = COCH3; Bz = Benzoyl
Preferred perbenzoic acid precursor compounds of the imide type include N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
Preferred perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the compound having the formula:
Figure imgf000024_0001
Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:
Figure imgf000024_0002
Perbenzoic acid derivative precursors
Suitable perbenzoic acid derivative precursors include any of the herein disclosed perbenzoic precursors in which the perbenzoic group is substituted by essentially any functional group including alkyl groups.
Cationic peroxyacid precursors
Cationic peroxyacid precursor compounds are also suitable herein. Typically such cationic peroxyacid precursors are formed by substituting the peroxyacid part with an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group.
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1.382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906. Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
A preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-(trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
Figure imgf000025_0001
A preferred cationically substituted alkyl oxybenzene sulfonate is the methyl ammonium derivative of 2,3,3 -tri-methyl hexanoyloxybenzene sulfonate.
Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caprolactam:
Figure imgf000025_0002
Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.
Cationic polymers
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-
T MILE 26 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, C\ -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.
As used herein, the term "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).
As used herein, the term "attached to " means that the group is pendent from the polymer backbone, examples of such attachment being represented by the following general structures A and B:
Figure imgf000026_0001
I I L X
X
A B
As used herein, the term "integral with" means that the group forms part of the polymer backbone, examples of which are represented by the following general structures C and D:
Figure imgf000027_0002
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 polyamides, the polyimides and the like, the polyacrylates, the polyacrylamides, the poly vinylethers, the polyethylenes, the polypropylenes and like polyalkylenes, the polystyrenes and like polyalkarylenes, the polyalkyleneamines, the polyalkyleneimines, the polyvinylamines, the polyalylamines, the polydiallylammes, the polyvinylpyridines, the polyaminotriazoles, polyvinyl alcohol, the aminopolyureylenes, and mixtures thereof.
M can be any compatible cationic group which comprises an N+ (quartemary), positively charged center. The quartemary positively charged center can be represented by the following general structures E and F:
Figure imgf000027_0001
Particularly preferred M groups are those containing a quartemary center represented by general structure E. The cationic group is preferably positioned close to or integral with the polymer backbone.
The positive charge of the N+ centres is offset by the appropriate number of counter anions. Suitable counter anions include Cl", Br, SO32", SO42", PO42", MeOSO3" and the like. Particularly preferred counter anions are Cl" and Br. X can be a nonionic group selected from hydrogen (H), C \ -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. However, for example, by appropriate copolymerization of cationic. nonionic (i.e. containing the group L-X), and mixed cationic/nonionic monomers, 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 copolymerization are typically random, i.e. the cationic, nonionic and mixed cationc/nonionic monomers copolymerize in a nonrepeating sequence.
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 unquatemized tertiary amine groups (Ml) 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 M^-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.
Other than moieties for connecting groups M and X, or for attachment to the polymer backbone, hydrophilic chain L usually consists entirely of the polyoxyalkylene moiety -[(R'O)OT(CH2CH2O)n]-. The moieties -(R'O)m- and - (CH2CH2O)„- of the polyoxyalkylene moiety can be mixed together, or preferably form blocks of -(R'O)w- and -(C^CH^O),,- 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 -(CH2CH2θ)rt-. The moiety -(CH2CH2θ)„- preferably comprises at least about 85% by weight of the polyoxyalkylene moiety, and most preferably 100% by weight (m is 0). For the moiety -(CH2CH2O)n-, n is usually from about 3 to about 100. Preferably, 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 structures G and H:
M
Figure imgf000029_0001
G H
Structures 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.
Representative classes of cationic polymers of the present invention are as follows:
A. Polyurethane, Polyester, Polyether, Polyamide or like Polymers.
One class of 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 III:
Figure imgf000030_0001
(*6ιX
(A1 — R1 A1^— R2 — ΪSΓ1"— R3 π
Figure imgf000030_0002
Figure imgf000030_0003
[(C3H60)m(CH2CH20)n] - X
wherein A is
O O o o O
-NC— , — CN- CO OC — or
R R
X is 0 or 1 ; R is H or C1-C4 alkyl or hydroxyalkyl; R 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 O-O or O-N bonds are formed with Al ; when x is 1 , R2 is -R^- except when A^ is 0
— C — ,
or is -(OR8)y- or -OR^- provided that no O-O or N-O bonds are formed with A^ , and R3 is -R5- except when A is
o — c— ,
or is -(R°O)- > or -R^O- provided that no O-O or O-N bonds are formed with A^ ; when x is 0, R2 is
(OR8)y— , -OR5- , - COR5 , - OCR5— , - OCR5,
O O O
NCR5 ,~ NCOR5- , — CNR5- ,or — OCNR5 -, RO RO OR OR
and R3 is -R^-; R4 is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R^)^- [(C3H6θ)OT(CH2CH2θ)„]-X; R5 is C1-C12 alkylene, hydroxyalkylene. alkenylene, arylene, or alkarylene; each R^ is C1 4 alkyl or hydroxyalkyl. or the moiety - (CH2) A2-(CH2)s-, wherein A2 is -O- or -CH2-; R7 is H or R4; R8 is C2-C3 alkylene or hydroxyalkylene; X is H,
O
— CR9,
-R9 or a mixture thereof, wherein R^ is C \ -C4 alkyl or hydoxyalkyl; k is 0 or 1 ; m and n are numbers such that the moiety -(CH2CH2θ)rt- comprises at least about 85% by weight of the moiety -[(C3H6θ) (CH2CH2θ)M]-; 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; 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.
In the above formulas, A is preferably
o o NC or CN — ;
R R
A2 is preferably -O-; x is preferably 1; and R is preferably H. R* can be linear (e.g. -CH2-CH2-CH2-,
CH2
Figure imgf000032_0001
alkylene, hydroxyalkylene, alkenylene, cycloalkylene, alkarylene or oxyalkylene; when Rl is a C2-C3 oxyalkylene moiety, the number of oxyalkylene units is preferably from about 2 to about 12; Rl is preferably C2-C.5 alkylene or phenylene, and most preferably C2-C6 alkylene (e.g. ethylene, propylene, hexamethylene). R2 is preferably -OR5- or -(OR8)^-; R3 is preferably -R5O- or -(OR8)y-; R4 and R6 are preferably methyl. Like Rl , R5 can be linear or branched, and is preferably C2- C3 alkylene; R 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.
In the above formulas, 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. For homopolymers (v and w are 0), u is preferably from about 3 to about 20. For random compolymers (u is at least 1 or preferably 0), v and w are each preferably from about 3 to about 40.
B. Polyacrylate, Poly aery lamide, Polyvinylether or Like Polymers
Another class of 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.
Figure imgf000033_0001
IV
Figure imgf000033_0002
VI
O O O O O
Ii I! II I! II wherein A1 is — O NC- NCO- CNC- -CN-
I I R R R R
O O O O O
II II II II OCN — ^OC — , — OCO — , — CO — ,or — NCN-;
R R R
R is H or C1-C4 alkyl or hydroxyalkyl; R^ is substituted C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or C2-C3 oxyalkylene; each R2 is Cj-Cj2 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; each R^ is C1-C4 alkyl or hydroxyalkyl, the moiety -(R2)*-[(C3H6O)m(CH2CH2θ)„]-X, or together form the moiety -(CH2)r-A2-(CH2).y-» wherein A2 is -O- or -CH2-; each R4
SUBSTITUTE SHEET (WILE 26) is C1-C4 alkyl or hydroxyalkyl, or two R^ together form the moiety -(CH2)r~ - (CH2V; X is H,
O
1 1 <. CR5,
-Rβ or mixture thereof, wherein 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)M- comprises at least about 85% by weight of the moiety -[(C3H6θ) (CH2CH2θ)„]-; 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.
In the above formulas, Al is preferably
o o
-CN- co or O
R
A2 is preferably -O-; R is preferably H. Rl can be linear
Figure imgf000034_0001
SϋBSTlTllTESHπ (RULE26) substituted alkylene, hydroxyalkylene, alkenylene, alkarylene or oxyalkylene; Rl is preferably substituted C2-C^ alkylene or substituted C2-C3 oxyalkylene, and most preferably
Figure imgf000035_0001
-CH2CH— or — CH
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.
In the above formulas, n, u, v and w can be varied according to the n, u, v and w for the polyurethane and like polymers.
C. Polyalkyleneamine, Polyalkyleneimine or like polymers.
Another class of suitable cationic polymers are derived from polyalkyleneamines, polyalkyleneimines and the like. These polymers comprise units selected from those having formulas VII and VIII and IX.
Figure imgf000036_0001
Figure imgf000036_0002
(R ,3J)k - [(C3H60)m(CH2CH20)n) — X
Figure imgf000036_0003
(R3)k [(C3H60)m(CH2CH20)n] — X
wherein R is C2-Ci2 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no O-N bonds are formed; each R2 is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R3)jfc-[(C3H6O)m(CH2CH2θ)„]-X; R3 is Cj-C^ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; M' is an N+ or N centre; X is H,
CR'
O
-R4 or mixture thereof, wherein 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 -(CH2CH2θ)w- comprises at least about 85% by weight of the moiety -[(C3H6θ)w(CH2CH2θ)„]-; m is from 0 to about 5; n is at least about 3; the number of x, y and z are such that there are at least 2M' groups, at least 2N+ centres and at least 2 X groups.
In the above formulas, R* can be varied like Rl of the polyurethene and like polymers; each R2 is preferably methyl or the moiety -(R )#- [(C3H6θ)m(CH2CH2θ)„]-X; R3 is preferably C2-C3 alkylene; R4 is preferably methyl; X is preferably H; k is preferably 0; m is preferably 0.
In the above formulas, 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. Typically, x + y + z is from 2 to about 40 and preferably from 2 to about 20. For short chain length polymers, x + y + z can range from 2 to 9 with from 2 to 9 N+ centres and from 2 to 1 1 X groups. For long chain length polymers, x + y + z is at least 10, with a preferred range of from 10 to about 42. For the short and long chain length polymers, the M' groups are typically a mixture 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 + 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 polyethyleneamines (PEA's) and polyethyleneimines (PEI's). These preferred cationic polymers comprise units having the general formula:
Figure imgf000038_0003
Figure imgf000038_0001
Figure imgf000038_0004
wherein R2 (preferably methyl), M', X, d, x, y, z and n are defined as before: a is 1 or O.
Prior to ethoxylation, the PEAs used in preparing cationic polymers of the present invention have the following general formula:
Figure imgf000038_0002
H wherein x + y + z is from 2 to 9, and 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. For preferred PEAs, 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). Above the pentamines, i.e., the hexamines, heptamines, octamines and possibly nonamines, the cogenerically derived mixture 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. For preferred cationic PEAs, 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:
H
H2N f-CH2CH2Ni^ -[ CH^H^ ^ - CH2CH2NH2]Z
wherein the sum of x, y, and z represents a number of sufficient magnitude to yield a polymer having the molecular weights previously specified. Although 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:
CH2CH2 — NH2 30%
CH2CH2 — NH— 40°/ oc
CH2CH2 — N 30°/c
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. 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 Esseimann 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 herein incorporated by reference).
As defined in the preceding formulas, n is at least about 3 for the cationic PEIs. However, it should be noted that 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. Also, the degree of ethoxyalation for preferred polymers increases as the molecular weight of the PEI increases. For PEIs having a molecular weight of at least about 600, n is preferably at least about 12, with a typical range of from about 12 to about 42. For PEIs having a molecular weight of at least 1800, n is preferably at least about 24, with a typical range of from about 24 to about 42.
D. Diallylamine Polymers
Another class of suitable cationic polymers are those derived from the diallylamines. These polymers comprise units selected from those having formulas X and XI:
Figure imgf000040_0001
Figure imgf000040_0002
wherein Rl is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R2)jt- [(C3H6θ)m(CH2CH2θ)„]-X; R2 is Cj-Cπ 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,
CR4,
I I
O
-R4 or mixture thereof, wherein R4 is C1-C4 alkyl or hydroxyalkyl; k is 1 or 0; m and n are numbers such that the moiety -(CH2CH2θ)π- comprises at least about 85% by weight of the moiety -[(C3H6θ)OT(CH2CH2θ)„]-; 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.
In the above formulas, A is preferably -O-; Rl is preferably methyl; each R2 is preferably C2-C3 alkylene; each R3 is preferably methyl; R4 is preferably methyl; X is preferably H; k is preferably 0; m is preferably 0; r and s are each preferably 2.
In the above formulas, n is preferably at least about 6 when the number of N+ 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. Typically, v is 0, and u is from 2 to about 40, and preferably from 2 to about 20.
Additional detergent components
The detergent compositions or components thereof in accord with the invention may also contain additional detergent components. The precise nature of these additional 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.
The 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 surfactant
The detergent compositions or components thereof in accord with the invention preferably contain an additional surfactant selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
A typical listing of 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.
Where present, ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
Anionic surfactant
The detergent compositions or compositions thereof in accord with the present invention preferably comprise an additional anionic surfactant. Essentially 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 substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.
Other anionic surfactants include the isethionates such as the acyl isethionates, N- acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C^-C, o monoesters) diesters of sulfosuccinate (especially saturated and unsaturated Cfi-C , . 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 surfactant
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 oxide ether sulfates, the C5-C17 acyl-N-(C j -C4 alkyl) and -N-(Cι-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
Alkyl sulfate surfactants are preferably selected from the linear and branched primary CjQ-Cj alkyl sulfates, more preferably the Cj 1-C15 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the Cjo-Cig alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C j j -C 1 g, most preferably C \ \ -C \ 5 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
Anionic sulfonate surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, Cg-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates. fatty oleyl glycerol sulfonates, and any mixtures thereof. Anionic carboxylate surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates. the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2θ)x CH2C00"M+ wherein R is a C^ to Cjg 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-(CHRι-CHR2-O)-R3 wherein R is a C6 to C\ alkyl group, x is from 1 to 25, R\ and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid. 2-propyl- 1-nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors.
Alkali metal sarcosinate surfactant
Other suitable anionic surfactants are the 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. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
Alkoxylated nonionic surfactant
Essentially any 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.
Nonionic alkoxylated alcohol surfactant
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 preferred 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.
Nonionic polvhvdroxy fatty acid amide surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R CONRlZ wherein : Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl. ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably Cj or C2 alkyl, most preferably C] alkyl (i.e., methyl); and R2 is a C5- C31 hydrocarbyl, preferably straight-chain C5-C 19 alkyl or alkenyl. more preferably straight-chain C9-C j 7 alkyl or alkenyl. most preferably straight-chain C \ \ -C 7 alkyl or alkenyl. or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
Nonionic fattv acid amide surfactant
Suitable fatty acid amide surfactants include those having the formula: R6C0N(R7)2 wherein R" 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 -(C2H4θ)xH, where x is in the range of from 1 to 3. Nonionic alkylpolvsaccharide surfactant
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
R2O(CnH2nO)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 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.
Amphoteric surfactant
Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocar boxy lie acids.
Suitable amine oxides include those compounds having the formula R3(OR4)XN0(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each 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 C \ Q-C \ g alkyl dimethylamine oxide, and C]θ_ι acylamido alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ. Zwitterionic surfactant
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+R2COO" wherein R is a Cg-Ci g hydrocarbyl group, each Rl is typically C1-C3 alkyl. and R2 is a C1-C5 hydrocarbyl group. Preferred betaines are C]2-18 dimethyl-ammonio hexanoate and the C J O-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.
Cationic surfactants
Suitable cationic surfactants to be used in the detergent compositions or components thereof herein include the quaternary ammonium surfactants selected from mono C5- C)6, preferably Cβ-Cjo N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
Another suitable group of 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 (i.e. -COO-) linkage and at least one cationically charged group.
Suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
In one preferred aspect the 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 mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain. Thus spacer groups having, for example, -O-O- (i.e. peroxide), - N-N-, and -N-O- linkages are excluded, whilst spacer groups having, for example - CH2-O- CH2- and -CH2-NH-CH2- linkages are included. In a preferred aspect the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.
Water-soluble builder compound
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 mixtures 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 sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, in particular, water- soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccina.es described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosucci nates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l,l,3-propane tricarboxylates described in British Patent No. 1,387,447.
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 mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures 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
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 Naz[(AlO2)z(SiO2)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 mixtures thereof. Zeolite A has the formula
Na 12 [AlO2) 12 (Siθ2)l2_- xH2°
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nagg [(AlO2)86(SiO2)l06]- 276 H2O.
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.
Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
In a preferred aspect the zeolite MAP detergent builder has a particle size, expressed as a d5o 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 d50 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 d5Q values are disclosed in EP 384070A.
Heavy metal ion sequestrant
The detergent compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant. By 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.
Other 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. Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2 -hydroxy ethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The 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. The β-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-l,2,4-tricarboxylic acid are alos suitable. Glycinamide-N,N'- disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2- hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
Bleach catalyst
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. Such catalysts are disclosed in U.S. Pat. 4,430.243.
Other types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include Mnl
Figure imgf000052_0001
O)ι(u-OAc)2(l,4,7-trimethyl-l,4,7-triazacyclononane)2-(Clθ4)2, MnlV4(u- O)6(l,4,7-triazacyclononane)4-(Clθ4)2, Mnι MnIV4(u-O)ι(u-OAc)2-(l,4,7- trimethyl-1 ,4,7-triazacyclononane)2-(Clθ4)3, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include l,5,9-trimethyl-l,5,9-triazacyclododecane, 2-methyl- 1,4.7-triazacyclononane, 2-methyl-l ,4,7-triazacyclononane, 1,2,4,7-tetramethyl- 1.4,7-triazacyclononane, and mixtures thereof. The bleach catalysts useful herein may also be selected as appropriate for the present invention. For examples of 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, as disclosed in U.S. Pat. 5,1 14,606, 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 mixtures thereof.
U.S. Pat. 5,1 14,61 1 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:
R2 R3
R1-N=C-B-C=N-R4
wherein R' , R2, R3, and R4 can each be selected from H, substituted alkyl and aryl groups such that each Rl-N=C-R2 and R3-C=N-R4 form a five or six-membered ring. Said ring can further be substituted. B is a bridging group selected from O, S. CR^RO, NR7 and C=O, wherein R^, R >, and R? can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with 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)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)2θ2θθ4, Bis-(2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.
Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N- dentate ligands. including N4MnIH(u-O)2Mnl ^N4)+and [Bipy2MnlH(u- O)2MnIvbipy ]-(ClO4)3. Other 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 (metal lo-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. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S. 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts).
The bleach catalyst is typically used in a catalytically effective amount in the compositions and processes herein. By "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. As a practical matter, and not by way of limitation, the 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. To illustrate this point further, on the order of 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.
Enzvme
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 upases, 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.
Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries AS (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, α-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 AS. 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 oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri AS, 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 compound
Organic polymeric compounds are preferred additional components of the detergent compositions or components thereofin 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. By 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.
Examples of 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.
The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein. Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcelluiose and hydroxyethylcellulose.
Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
Suds suppressing system
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.
By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term "silicone" 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.
Other 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.
Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C \ -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
(a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
(i) polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and
(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight;
(b) 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 DCO544, commercially available from DOW Coming under the tradename DCO544; (c) an inert carrier fluid compound, most preferably comprising a C ] g-C j g 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 mixture thereof, with a melting point of from 45°C to 80°C.
Polymeric dye transfer inhibiting agents
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.
a) Polvamine N-oxide polymers
Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula :
(I) Ax
wherein P is a polymerisable unit, and O O O
A is NC, CO, C, -O-, -S-, -N-; x is O or 1 ;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
The N-O group can be represented by the following general structures :
O
O
Figure imgf000060_0001
(R3)2 or - --- N-(R.,)x
wherein Rl, R2. and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups. The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
Other suitable 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. 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. Typically, the average molecular weight is within the range of 500 to 1000,000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole
Suitable herein are coploymers of N-vinylimidazole and N-vinyipyrrolidone 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.
c) Polvvinylpyrrolidone
The detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000. 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.
d) Polvvinyloxazolidone
The detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000. e) Polwinylimidazole
The detergent compositions herein may also utilize polyvmylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.
Optical brightener
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:
Figure imgf000062_0001
wherein R\ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, R| is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, R\ is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and 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.
When in the above formula, Rj is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-mo hilino-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
Polymeric Soil Release Agent
Known polymeric soil release agents, hereinafter "SRA", can optionally be employed in the present detergent compositions. If utilized, 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. Such esters may be made using additional monomers capable of being incorporated 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. Such 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. Other SRA's include the nonionic end-capped 1,2- propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711,730, December 8, 1987 to Gosselink et al., for example those produced by transesterification oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other examples of 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. 4,702,857, October 27, 1987 to 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. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al., the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400.
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. 4,000,093, December 28, 1976 to Nicol, et al.; and the 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 SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
Additional classes of SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, 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.;
Other optional ingredients
Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
Near neutral wash pH dergent formulation
While 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. In such formulations, 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.
Highly preferred 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 incorporated by reference). Form of the compositions
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 composiiton. The 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 drum with the soiled fabric load.
The compositions in accord with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach.
In general, 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. Preferably 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.
To carry out a measurement, 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 manufactured using any suitable compacting process, such as tabletting, briquetting or extrasion, preferably tabletting. Preferably tablets for use in dish washing processes, are manufactured using a standard rotary tabletting press using compression forces of from 5 to 13 KN/cm2, more preferably from 5 to 1 1 KN/cm2 so that the compacted solid has a minimum hardness of 176N to 275N, preferably from 195N to 245N, measured by a C100 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.
Laundry washing method
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. By 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.
In a preferred use aspect 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 drum 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 drum before the commencement of the wash, before, simultaneously with or after the washing machine has been loaded with laundry. At the commencement of the wash cycle of the washing machine water is introduced into the drum and the drum 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 drum rotates and also as a result of its contact with the wash water.
To allow for release of the detergent product during the wash the device may possess a number of openings through which the product may pass. Alternatively, 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. Preferably, the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum 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. WO94/11562.
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.
Alternatively, the dispensing device may be a flexible container, such as a bag or pouch. The bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678. Alternatively 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. 001 1500, 001 1501, 001 1502, and 001 1968. 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.
Machine dishwashing method
Any suitable methods for machine dishwashing or cleaning soiled tableware, particularly soiled silverware are envisaged.
A preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware, silverware and cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of a machine dishwashing composition in accord with the invention. By 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.
Packaging for the compositions
Commercially marketed executions of the bleaching compositions can be packaged in any suitable container including those constructed from paper, cardboard, plastic materials and any suitable laminates. A preferred packaging execution is described in European Application No. 94921505.7.
Abbreviations used in Examples
In the detergent compositions, the abbreviated component identifications have the following meanings:
LAS Sodium linear C 12 lk l benzene sulfonate
TAS Sodium tallow alkyl sulfate
CxyAS Sodium Cjx - Ciy alkyl sulfate
C46SAS Sodium C]4 - Cj secondary (2,3) alkyl sulfate
CxyEzS Sodium Cjx-Ciy alkyl sulfate condensed with z moles of ethylene oxide
CxyEz C j X-C j y predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide
QAS R2.N+(CH3)2(C2H4OH) with R = Cι2 - C] 4 Soap Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils
CFAA C12-C14 (coco) alkyl N-methyl glucamide
TFAA l6" l 8 alkyl N-methyl glucamide
TPKFA Ci2-C]4 topped whole cut fatty acids
STPP Anhydrous sodium tripolyphosphate
TSPP Tetrasodium pyrophosphate
Zeolite A Hydrated Sodium Aluminosilicate of formula
Naj2(A102Siθ2)i2-27H2θ having a primary particle size in the range from 0.1 to 10 micrometers
Zeolite MAP Hydrated sodium aluminosilicate zeolite MAP having a silicon to aluminium ratio of 1.07 NaSKS-6 Crystalline layered silicate of formula δ-
Na2Si2O5
Citric acid Anhydrous citric acid
Borate Sodium borate
Carbonate Anydrous sodium carbonate with a particle size between 200μm and 900μm
Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm
Silicate Amorphous Sodium Silicate (SiO2:Na2O = 2.0: 1 )
Sodium sulfate Anhydrous sodium sulfate Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425 μm and 850μm
MAAA Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 70.000
AA Sodium polyacrylate polymer of average molecular weight 4,500
CMC Sodium carboxymethyl cellulose Cellulose ether Methyl cellulose ether with a degree of polymerization of 650 available from Shin Etsu
Chemicals
Protease Proteolytic enzyme of activity 4KNPU/g sold by
NOVO Industries AS under the tradename
Savinase
Alcalase Proteolytic enzyme of activity 3AU/g sold by
NOVO Industries AS Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries AS under the tradename
Carezyme
Amvlase Amylolytic enzyme of activity 120KNU/g sold by
NOVO Industries AS under the tradename
Termamyl 120T Lipase Lipolytic enzyme of activity lOOKLU/g sold by NOVO Industries AS under the tradename
Lipolase
Endolase Endoglucanase enzyme of activity 3000 CEVU/g sold by NOVO Industries AS
PB4 Sodium perborate tetrahydrate of nominal formula
NaBO2.3H O.H2θ2
PB1 Anhudrous sodium perborate bleach of nominal formula NaBθ2-H2θ2
Percarbonate Sodium percarbonate of nominal formula
2Na CO .3H2θ2
NAC-OBS (Nonanamido caproyl) oxybenzene sulfonate in the form of the sodium salt.
NACA 6 nonylamino - 6 oxo - capronic acid. NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt
TAED Tetraacetylethylenediamine Mn catalyst MnIV (m-O)3(l,4,7-trimethyl- 1,4,7- triazacyclononane)2(PF6)2. as described in U.S. Pat. Nos.
5,246,621 and 5,244,594.
DTPA Diethylene triamine pentaacetic acid DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the
Tradename Dequest 2060
Photoactivated Sulfonated Zinc Phthlocyanine encapsulated in bleach dextrin soluble polymer
Brightener 1 Disodium 4,4'-bis(2-sulphostyry)biphenyl Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-l .3.5- triazin-2-yl)amino) stilbene-2:2'-disulfonate
HEDP 1,1-hydroxyethane diphosphonic acid EDDS Ethylenediamine-N, N'-disuccinic acid QEA1 bis((C2H5θχC2H4θ)n) (CH3) -N+-C6H12-N+-
(CH3) bis((C2H5O)-(C2H4θ)n), wherein n=from
20 to 30
QEA2 bis((C2H5O)-(C2H4θ)n) (CH3) N+ Rj, wherein
R\ is C4-CJ2 alkyl group and n=from 20 to 30 QEA3 tri{(bis((C2H5θ)-(C2H4θ)n)(CH3)-N+)-
(CONC3H6)}-C3H6O, wherein n=from
20 to 26
PEGX Polyethylene glycol, with a molecular weight of x PEO Polyethylene oxide, with a molecular weight of
50,000
TEPAE Tetraethylenepentaamine ethoxylate PVP Polyvinylpyrolidone polymer PVNO Polyvinylpyridine N-oxide PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole
SRPl Sulfobenzoyl and capped esters with oxyethylene oxy and terephtaloyl backbone
SRP2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer
Silicone antifoam Polydimethylsiloxane foam controller with siloxane oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10: 1 to
100: 1
Wax Paraffin wax
In the following examples all levels are quoted as % by weight of the composition:
Example 1
The following high density granular laundry detergent compositions A to F of particular utility under European machine wash conditions were prepared in accord with the invention:
Figure imgf000074_0001
Figure imgf000075_0001
Example 2
The following granular laundry detergent compositions G to I of particular utility under European machine wash conditions were prepared in accord with the invention:
Figure imgf000076_0001
Figure imgf000077_0001
Example 3
The following detergent formulations of particular utility under European machine wash conditions were prepared in accord with the invention.
Figure imgf000078_0001
Figure imgf000079_0001
Example 4
The following granular detergent formulations were prepared in accord with the invention. 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.
Figure imgf000080_0001
Figure imgf000081_0001
Example 5
The following granular detergent formulations were prepared in accord with the invention. Formulations W and X are of particular utility under US machine wash conditions. Y is of particular utility under Japanese machine wash conditions
Figure imgf000082_0001
Example 6
The following granular detergent compositions of particular utility under European wash conditions were prepared in accord with the invention.
Figure imgf000083_0001
Figure imgf000084_0001
Example 7
The following detergent compositions, according to the present invention were prepared:
Figure imgf000085_0001
Figure imgf000086_0001
Example 8
The following detergent formulations, according to the present invention were prepared:
Figure imgf000087_0001
Figure imgf000088_0001
Example 9
The following high density granular laundry detergent compositions FF to KK were prepared in accord with the invention:
Figure imgf000089_0001
Figure imgf000090_0001
Example 10
The following detergent compositions, according to the present invention were prepared:
Figure imgf000091_0001
Figure imgf000092_0001

Claims

Claims
A granular detergent composition or component thereof comprising
(a) a hydrophobic organic peroxyacid bleaching system, capable of providing a hydrophobic organic peroxyacid compound; and
(b) a water-soluble cationic compound having clay soil removal/anti- redeposition properties, which is selected from the group consisting of:
1 ) ethoxylated cationic monoamines having the formula:
R^
R -N + L
R^
2) ethoxylated cationic diamines having the formula:
(R3)d R3 (R3)d R3
X- L— M1 — R1 - N+— L- - X or R3 — M1 — R1 — t — R or
/
L L L L L
X X X X X
Figure imgf000093_0001
(X— L — )2— M2— R1 — M2— R2
R2 wherein M* is an N+ or N group; each M2 is an N+ or N group, and at least one M2 is an N+ group;
3) ethoxylated cationic polyamines having the formula:
(R3)d
Figure imgf000094_0001
R2
4) mixtures thereof;
O O O O O wherein A1 is— NC — , NCO— , — NCN , CN - , -OCN- , R R R R R R
O O O O O CO— , — OCO— , — OC , — CNC - or -0 - ,
R
R is H or C1-C4 alkyl or hydroxyalkyl, Rl is C2-Ci2 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no O-N bonds are formed; each R2 is C1-C4 alkyl or hydroxyalkyl, the moiety -L-X, or two R2 together form the moiety -(CH2)r-A2-(CH2)s-, wherein A2 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-Cg alkyl or hydroxyalkyl, benzyl, the moiety L-X, or two R3 or one R2 and one R3 together form the moiety -(CH2)r-A2-(CH2 ; R is a substituted C3-C12 alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having p substitution sites; is C1-C12 alkenyl, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no O-O or O-N bonds are formed; X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof; L is a hydrophilic chain which contains the polyoxyalkylene moiety
-[(R6O)m(CH2CH2θ)„]-; wherein R6 is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety -(CH2CH2θ)w- comprises at least about 50% by weight of said polyoxyalkylene moiety; d is 1 when M2 is N+ and is 0 when M2 is N; n is at least about 16 for said cationic monoamines, is at least about 6 for said cationic diamines and is at least about 3 for said cationic polyamines; p is from 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is 1 when q is 1.
2. A granular detergent composition according to Claim 1 wherein the ratio of said hydrophobic organic peroxyacid compound to said water-soluble cationic compound is from 20: 1 to 1 :2.
3. A granular detergent composition according to Claim 1 or 2 wherein said cationic compound is present at a level of from 0.01% to 30% by weight of the detergent composition.
4. A granular detergent composition according to any of Claims 1 to 3 wherein the cationic compound is present at a level of from 0.2% to 3% by weight of the detergent composition.
5. A granular detergent composition or component thereof according to any of Claims 1 to 4 wherein said cationic compound is an ethoxylated cationic monoamine and is characterized in that one R2 is methyl, two R2 are the moiety L-X, m is 0 and n is at least about 20.
6. A granular detergent composition or component thereof according to any of Claims 1 to 4 wherein said cationic compound is an ethoxylated cationic diamine and is characterized in that R* is a C2-C6 alkylene.
7. A granular detergent composition or component thereof according to Claim 6 wherein said ethoxylated cationic diamine is characterized in that Rl is hexamethylene.
8. A granular detergent composition or component thereof according to Claim 6 or 7, wherein the cationic compounds is characterized in that each R2 is methyl or the moiety -L-X, each R3 is methyl and M^ and each M2 are an N+ group.
9. A granular detergent composition or component thereof according to any of Claims 6 to 8 wherein m is 0 and n is at least 12.
10. A detergent composition or component thereof according to any of Claims 1 to 4 wherein said cationic compound is an ethoxylated cationic polyamine and is characterized in that R4 is a substituted C3-C6 alkyl, hydroxyalkyl or aryl group; Al is
o
— CN —
H
and p is from 3 to 6.
11. A granular detergent composition or component thereof according to any of Claims 6 to 8 wherein m is 0 and n is at least 20.
12. A granular detergent composition or component thereof according to any of Claims 1 to 11 wherein a cationic clay-soil removal/ anti-redeposition polymer is present characterised in that it has a 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 and contains an N+ positively charged centre; and L connects groups M and X or connects group X to the polymer backbone; X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof; and L is a hydrophilic chain which contains the polyoxyalkylene moiety -
Figure imgf000096_0001
13. A granular detergent composition or component thereof according to Claim 12 wherein said cationic polymer is an ethoxylated cationic polymer which has a backbone, selected from the group consisting of the polyurethanes, the polyesters, the polyethers, the polyimides, the polyalkyleneimines and mixtures thereof.
14. A detergent composition or component thereof according to any of Claims 1 to 13 wherein said hydrophobic organic peroxyacid compound has at least 7 carbon atoms.
15. A detergent composition or component thereof according to any of Claims 1 or 14 wherein said hydrophobic organic peroxyacid bleaching system comprises a hydrogen peroxide source and a hydrophobic organic peroxyacid precursor.
16. A detergent composition according to Claim 15 wherein said hydrophobic organic peroxyacid precursor is present at a level of from 0.2% to 10% by weight of the detergent composition.
17. A detergent composition or component thereof according to either of Claims 15 or 16 wherein the organic peroxyacid precursor compound is an amide substituted alkyl peroxyacid precursor compound selected from the group consisting of
R N R N — C _ D2 _
O R O and R5 O O
wherein L can be essentially any leaving group, Rl is an aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms such that Rl and R^ in total not contain more than 18 carbon.
18. A detergent composition or component thereof according to any of Claims 1 or 13 wherein said hydrophobic organic peroxyacid bleaching system comprises a preformed organic peroxyacid.
19. A detergent composition according to Claim 18 wherein said preformed organic peroxyacid is present at a level of from 1% to 10% by weight of the detergent composition.
20. A detergent composition or component thereof according to either of Claims 18 or 19 wherein the preformed organic peroxyacid is selected from the group consisting of:
R1 — C - N - R2 C — OOH
O R5 O
and
R1 — N C R2 - C - OOH
R° O O
wherein Rl 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, and R^ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms such that R* and R^ not contain more than 18 carbon atoms total.
21. A granular detegrent composition or component thereof according to any of Claims 1 to 20, wherein a non-hydrophobic bleach precursor compound is present.
22. A granular detegrent composition according to Claim 21 wherein the ratio of said non-hydrophobic bleach precursor compound to the water-soluble cationic compound is from 10:1 to 1:1.
23. A granular detegrent composition according to Claim 21 or 22 wherein the non-hydrophobic bleach precursor compound is a N, N, N*, Nl"tetra acetylated alkylene diamine.
24. A granular detergent composition according to any of Claims 1 to 23 wherein the composition is formulated in such a manner as to provide a wash pH offrom 8.0 to 10.5.
25. A detergent composition according to any of Claims 1 to 24 wherein a heavy metal ion sequestrant is present at a level of from 0.1% to 10% by weight of the detergent composition.
26. A granular detergent composition or component thereof according to any of Claims 1 to 25 wherein a surfactant is present, selected from the group consisting of anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
27. A method of washing laundry in a domestic washing machine wherein an effective amount of a granular detergent composition according to any of Claims 1 to 26 is introduced into the drum of the washing machine, preferably before the commencement of the wash by use of a dispensing device which permits progressive release of said granular detergent composition into the wash liquor during the wash.
PCT/US1997/016697 1996-09-24 1997-09-22 Detergent compositions WO1998013451A1 (en)

Priority Applications (6)

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CZ991018A CZ101899A3 (en) 1996-09-24 1997-09-22 Detergents
EP97943396A EP0929625A4 (en) 1996-09-24 1997-09-22 Detergent compositions
CA002265941A CA2265941A1 (en) 1996-09-24 1997-09-22 Detergent compositions
BR9711535A BR9711535A (en) 1996-09-24 1997-09-22 Detergent compositions
CZ991020A CZ102099A3 (en) 1996-09-24 1997-09-22 Detergents
AU44878/97A AU4487897A (en) 1996-09-24 1997-09-22 Detergent compositions

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GB9619921A GB2317392A (en) 1996-09-24 1996-09-24 Detergent compositions
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GB9622679A GB2318799A (en) 1996-10-31 1996-10-31 Detergent compositions

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2423180A1 (en) 2002-12-04 2012-02-29 Clariant Finance (BV) Limited Quaternary ammonium composition
WO2020182521A1 (en) 2019-03-08 2020-09-17 Basf Se Cationic surfactant and its use in laundry detergent compositions

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105121617A (en) * 2012-11-28 2015-12-02 艺康美国股份有限公司 Perfume systems

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0111965A2 (en) * 1982-12-23 1984-06-27 THE PROCTER &amp; GAMBLE COMPANY Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
US4741842A (en) * 1986-01-27 1988-05-03 Colgate-Palmolive Company Particulate detergent softener compositions comprising a mixture of cationic softener and ethoxylated amine
GB2268879A (en) * 1992-07-24 1994-01-26 Laporte Esd Ltd Disinfectant compositions

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2292155A (en) * 1994-08-11 1996-02-14 Procter & Gamble Handwash laundry detergent composition comprising three surfactants
HUP9902631A3 (en) * 1996-05-17 2001-11-28 Procter & Gamble Detergent composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0111965A2 (en) * 1982-12-23 1984-06-27 THE PROCTER &amp; GAMBLE COMPANY Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
US4741842A (en) * 1986-01-27 1988-05-03 Colgate-Palmolive Company Particulate detergent softener compositions comprising a mixture of cationic softener and ethoxylated amine
GB2268879A (en) * 1992-07-24 1994-01-26 Laporte Esd Ltd Disinfectant compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0929625A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2423180A1 (en) 2002-12-04 2012-02-29 Clariant Finance (BV) Limited Quaternary ammonium composition
WO2020182521A1 (en) 2019-03-08 2020-09-17 Basf Se Cationic surfactant and its use in laundry detergent compositions

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CA2265941A1 (en) 1998-04-02
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CN1238800A (en) 1999-12-15
TR199900652T2 (en) 1999-08-23

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