WO1998013463A1 - Compositions detergentes comprenant des amines cationiques et des lipases - Google Patents

Compositions detergentes comprenant des amines cationiques et des lipases Download PDF

Info

Publication number
WO1998013463A1
WO1998013463A1 PCT/US1997/016716 US9716716W WO9813463A1 WO 1998013463 A1 WO1998013463 A1 WO 1998013463A1 US 9716716 W US9716716 W US 9716716W WO 9813463 A1 WO9813463 A1 WO 9813463A1
Authority
WO
WIPO (PCT)
Prior art keywords
detergent composition
cationic
group
alkyl
granular detergent
Prior art date
Application number
PCT/US1997/016716
Other languages
English (en)
Inventor
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
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to JP10515748A priority Critical patent/JP2000503712A/ja
Priority to EP97941712A priority patent/EP0929637A4/fr
Priority to AU43565/97A priority patent/AU4356597A/en
Priority to CA002265803A priority patent/CA2265803A1/fr
Priority to BR9713217-9A priority patent/BR9713217A/pt
Publication of WO1998013463A1 publication Critical patent/WO1998013463A1/fr

Links

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
    • C11D17/06—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
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase

Definitions

  • the present invention relates to granular detergent compositions or components thereof containing cationic compounds with paniculate/ clay-soil removal/anti-redeposition properties and a lipase enzyme 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 panicle. The second is the ability of the compound, once adsorbed, to push apart (swell) the negatively charged layers so that the clay particle loses its cohesive force and can be removed in the wash water.
  • a model proposed for the anti-redeposition action of the positively charged anti-redeposition compounds is as follows. Adsorption of the positively charged molecule on the surface of clay particles in the wash water gives the particles the dispersancy properties of the molecule. As more and more of these compounds adsorb onto the suspended clay soil particles, the latter become encased within a hydrophilic layer provided by the attached ethoxy units. As such the hydrophilically encased soil is prevented from redepositing on fabrics, in particular hydrophobic fabrics such as polyester, during the laundering or dish washig cycle.
  • lipase enzymes which are known to be used in detergent compositions to aid the removal of (greasy) stains, containing triglycerides or fatty esters.
  • WO 92/05249 discloses certain lipase enzyme variants for improved properties and methods of their production.
  • the stain removal performance of lipase enzymes is directly related to their concentration in the detergent composition, so that an increase in the amount of lipase enzyme increases the stain removal performance. It has however been observed that under stressed conditions, such as the use of short washing machine cycles, or at low temperatures or in the presence of highly stained substrates, the optimum performance of the lipase enzyme is achieved at a certain level. Increasing the level of lipase enzyme beyond this amount does not result in increased stain removal performance benefits.
  • lipase enzymes in a granular detergent composition (or components thereof), comprising cationic, (partially) quatemized ethoxylated (poly) amines which have clay-soil removal/anti- redeposition properties.
  • a granular detergent composition or components thereof
  • cationic, (partially) quatemized ethoxylated (poly) amines which have clay-soil removal/anti- redeposition properties.
  • Detergent compositions (or components thereof) employing both cationic quatemized ethoxylated (poly) amines and lipase enzyme have been shown to deliver a surprisingly better cleaning performance than that of detergent compositions employing either of the two components individually.
  • a further advantage of the present invention is that the stain/ soil removal benefits can even be observed after the completion of only one wash cycle.
  • the present invention relates to granular detergent compositions or components thereof, which comprise a lipolytic enzyme 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 a granular detergent composition or component thereof which comprises
  • a water-soluble cationic compound having clay soil removal/anti-redeposition properties which is selected from the group consisting of:
  • R 2 2) ethoxylated cationic diamines having the formula:
  • R is H or C1-C4 alkyl or hydroxyalkyl
  • R 1 is C2-C12 alkylene, hydroxy alkylene, 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 R 2 together form the moiety - (CH2) r A 2 -(CH2) J -, 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 Ci-Cs alkyl or hydroxyalkyl, benzyl, the moiety L-X, or two R3 or one R 2 and one R3 together form the moiety -(CH2) r -A 2 -(CH2),-
  • R 4 is a
  • R6 is C3-C4 alkylene or hydro yalkylene 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 2 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: and wherein the ratio of compound (a) to (b) is from 1 : 100 to 100: 1.
  • An essential feature of the present invention is a water-soluble cationic compound which has paniculate/ clay-soil removal/anti-redeposition properties and which is selected from the group consisting of cationic mono-di- and polyamines.
  • the ratio of lipolytic enzyme to water-soluble cationic compound is from 1: 100 to 100: 1, more preferably from 1;10 to 10: 1 , most preferably from 1:5 to 5: 1.
  • the water-soluble cationic compound is preferably present at a level of from 0.01 % to 30%, more preferably from 0.1 % to 15% , most preferably from 0.2% to 3.0% by weight of the detergent composition.
  • the water-soluble cationic compounds of the present invention useful in the granular detergent compositions or components thereof in accord with the present invention include ethoxylated cationic monoamines, ethoxylated cationic diamines and ethoxylated cationic polyamines as previously defined.
  • Rl can be branched
  • Rl is preferably C2-C6 alkylene for the ethoxylated cationic diamines.
  • Each R 2 is preferably methyl or the moiety -L-X; each R3 is preferably C1-C4 alkyl or hydroxyalkyl, and most preferably methyl.
  • the positive charge of the N+ groups is offset by the appropriate number of counter anions.
  • Suitable counter anions include C1-, Br-, SO3-2, PO4-2, MeOS ⁇ 3- and the like. Particularly preferred counter anions are Cl- and Br-.
  • X can be a nonionc group selected from hydrogen (H), C1-C4 alkyl or hydroxyalkyl ester or ether groups, or mixtures thereof.
  • Preferred esters or ethers are the acetate ester and methyl ether, respectively.
  • the particularly preferred nonionic groups are H and the methyl ether.
  • hydrophilic chain L usually consists entirely of the polyoxyalkylene moiety -[(R6 ⁇ ) OT (CH2CH2-O n )-].
  • the moieties - (R ⁇ O)m- and -(CH2CH2 ⁇ )n- of the polyoxyalkylene moiety can be mixed together or preferably form blocks of -(R°0) m - and -(CH2CH2O moieties.
  • R > is preferably C3H6 (propylene);
  • m is preferably from 0 to about 5 and is most preferably 0, i.e. the polyoxyalkylene moiety consists entirely of the moiety -(CH2CH2O .
  • the moiety -(CH2CH2O preferably comprises at least about 85% by weight of the polyoxyalkylene moiety and most preferably 100% by weight (m is O).
  • Ml and each M 2 are preferably an N+ group for the cationic diamines and polyamines.
  • Preferred ethoxylated cationic monoamines and diamines have the formula:
  • a is from 0 to 20, preferably from 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-C6 alkyl, hydroxyalkyl or aryl group; Al is preferably
  • n is preferably at least about 12, with a typical range of from about 12 to about 42; p is preferably from 3 to 6.
  • R4 is a substituted aryl or alkaryl group
  • q is preferably 1 and R ⁇ is preferably C2-C3 alkylene.
  • R ⁇ is preferably a C2-C3 oxyalkylene moiety; when q is 1, R5 is preferably C2-C3 alkylene.
  • ethoxylated cationic polyamines can be derived from polyamino amides such as:
  • ethoxylated cationic polyamines can also be derived from polyaminopropyleneoxide derivatives such as:
  • each c is a number from 2 to about 20.
  • Another essential component of the granular detergent compositions or component thereof in acoord with the present invention is a lipolytic or lipase enzyme.
  • the ratio of lipolytic enzyme to water-soluble cationic compound is from 1 :100 to 100:1, more preferably from 1: 10 to 10: 1 , most preferably from 1:5 to 5: 1.
  • the lipolytic or lipase enzym is preferably present at levels of from 0.01 % to 3% by weight, more preferably 0.03% to 1 % by weight, most preferably from 0.06% to 0.5% by weight of the compositions most preferably on a lOOKLU/gram basis.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also Upases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P. " Other commercial Upases include Amano-CES, Upases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum Upases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and Upases ex Pseudomonas gladioli.
  • the LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use herein.
  • Upases such as Ml Lipase ⁇ an d LipomaxR (Gist-Brocades) and Lipolase ⁇ and Lipolase Ultra ⁇ (Novo) which have found to be very effective when used in combination with the compositions of the present invention.
  • suitables are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever.
  • lipolytic enzymes such as cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely Upases which do not require interfacial activation.
  • cutinases EC 3.1.1.50
  • Upases which do not require interfacial activation.
  • Addition of cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever).
  • Another preferred lipase for use herein is D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa. Most preferably the Humicola lanuginosa strain DSM 4106 is used.
  • D96L lipolytic enzyme variant is meant the lipase variant as described in patent application WO 92/05249 viz. wherein the native lipase ex Humicola lanuginosa aspartic acid (D) residue at position 96 is changed to Leucine (L). According to this nomenclature said substitution of aspartic acid to Leucine in position 96 is shown as : D96L.
  • D96L the standard LU assay was used (Analytical method, internal Novo Nordisk number AF 95/6-GB 1991.02.07).
  • a substrate for D96L was prepared by emulsifying glycerine tributyrate (Merck) using gum-arabic as emulsifier. Lipase activity was assayed at pH 7 using pH stat. method.
  • the detergent composition or components 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 on L-X group, wherein M is a cationic group attached to or integral with the backbone; X is a nonionic group selected from the group consisting of H, 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 to or integral with. Included within this term are oligomer backbones (2 to 4 units), and true polymer backbones (5 or more units).
  • attachmented to M means that the group is pendent from the polymer backbone, examples of which are 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 poly aery lamides, the polyvinylethers, the polyethylenes, the polypropylenes and like polyalkylenes, the polystyrenes and like polyalkarylenes, the poly alky ieneamines, the polyalkyleneimines, the polyvinylamines, the polyalylamines, the polydiallylamines, the polyvinylpyridines, the polyaminotriazoles, polyvinyl alcohol, the aminopolyureylenes, and mixtures thereof.
  • M can be any compatible cationic group which comprises an N+ (quarternary), positively charged center.
  • the quarternary positively charged center can be represented by the following general structures E and F:
  • M groups are those containing a quarternary center represented by general structure E.
  • the cationic group is preferably positioned close to or integral with the polymer backbone.
  • counter anions include Cl", Br-, SO3 2 -, SO4 2 -, PO4 2 -, MeOS03" and the like. Particularly preferred counter anions are Cl' and Br".
  • X can be a nonionic group selected from hydrogen (H), C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof.
  • the preferred ester or ether groups are the acetate ester and methyl ether, respectively;
  • the particularly preferred nonionic groups are H and the methyl ether.
  • the cationic polymers suitable for use in granular detergent compositions 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.
  • inclusion of other units (preferably nonionic) in the polymers is also permissible.
  • other units include acrylamides, vinyl ethers and those containing unquaternized tertiary amine groups (M ) containing an N centre.
  • M unquaternized 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).
  • Normally, these other units comprise from 0% to about 50% of the polymer (from about 50% to 100% of the polymer being units containing M and L-X groups).
  • the number of groups M and L-X each usually ranges from about 2 to about 200. Typically the number of groups M and L-X are each from about 3 to about 100. Preferably, the number of groups M and L-X are each from about 3 to about 40.
  • hydrophilic chain L usually consists entirely of the polyoxyalkylene moiety -[(R'0) m (CH2CH2 ⁇ ) n ]-.
  • the moieties -(RO) m - and -(CH2CH2O),,- of the polyoxyalkylene moiety can be mixed together, or preferably form blocks of -(RO) m - and - (CH2CH2O),,- moieties.
  • R' is preferably C3H6 (propylene);
  • m is preferably from 0 to about 5, and most preferably 0; i.e.
  • the polyoxyalkylene moiety consists entirely of the moiety -(CH2CH2 ⁇ ) ⁇ -.
  • the moiety -(CH2CH2O),,- preferably comprises at least about 85 % by weight of the polyoxyalkylene moiety, and most preferably 100% by weight (m is 0).
  • n is usually from about 3 to about 100.
  • n is from about 12 to about 42.
  • a plurality (2 or more) of moieties -L-X can also be hooked together and attached to group M or to the polymer backbone, examples of which are represented by the following general 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 ethoxy lating 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;
  • Rl is C2-C12 alkylene, hydroxy alkylene, 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 A ; when x is 1, R 2 is -R5- except when Al is 0
  • NCR 5 — — NCOR 5 — , — CNR 5 , or OCNR 5
  • R3 is -R5-; R4 i s C1-C4 alkyl or hydroxyalkyl, or the moiety - (R 5 )r[(C3H6 ⁇ ) OT (CH 2 CH2 ⁇ ) ⁇ ]-X; R5 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene, or alkarylene; each R is Cj_ C4 alkyl or hydroxyalkyl, or the moiety -(CH2) r -A -(CH2)s-, wherein A 2 is -O- or -CH2-; R 7 is H or R 4 ; R8 is C2-C3 alkylene or hydroxyalkylene; X is H,
  • -R9 or a mixture thereof, wherein is C1-C4 alkyl or hydoxyalkyl; k is 0 or 1; m and n are numbers such that the moiety -(CH2CH2 ⁇ ) ⁇ - comprises at least about 85% by weight of the moiety - [(C3H6 ⁇ ) m (CH2CH2 ⁇ )J-; 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.
  • Al is preferably
  • a 2 is preferably -O-; x is preferably 1; and R is preferably H.
  • Rl can be linear (e.g. -CH2-CH2-CH2-,
  • R 2 is preferably - OR5- or -(OR8) y -;
  • R3 is preferably -R5 ⁇ - or -(OR°) ;
  • R and R6 are preferably methyl.
  • R$ can be linear or branched, and is preferably C2-C3 alkylene;
  • R? is preferably H or C1-C3 alkyl;
  • R° " is preferably ethylene;
  • R 9 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.
  • a 1 is — O — , — NC — , — NCO — , — CNC — , — CN — ,
  • R is H or C1-C4 alkyl or hydroxyalkyl; Rl is substituted C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or C2- C3 oxyalkylene; each R 2 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; each R ⁇ is C1-C4 alkyl or hydroxyalkyl, the moiety -(R )*-[(C3H6 ⁇ ) m (CH2CH2 ⁇ ) n ]-X, or together form the moiety -(CH2) r -A 2 -(CH2),s-, wherein A 2 is -O- or - CH2-; each R 4 is C1-C4 alkyl or hydroxyalkyl, or two R 4 together form the moiety -(CH2) r -A -(CH2 ; X is H, O
  • R5 is C1-C4 alkyl or hydroxalkyl
  • j is 1 or 0
  • k is 1 or 0
  • m and n are numbers such that the moiety - (CH2CH2O),,- comprises at least about 85% by weight of the moiety - [(C3H6 ⁇ ) m (CH2CH2 ⁇ )J-;
  • m is from 0 to about 5;
  • n is at least about 3;
  • r is 1 or 2, s is 1 or 2 and r + s is 3 or 4; the number of u, v and w are such that there are at least 2N-- centres and at least 2 X groups.
  • A is preferably
  • a 2 is preferably -0-; R is preferably H. Rl can be linear
  • Rl is preferably substituted C2-C6 alkylene or substituted C2-C3 oxyalkylene, and most preferably
  • Each R 2 is preferably C2-C3 alkylene, each R3 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.
  • Rl is C2-C12 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no O-N bonds are formed; each R 2 is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R3) [(C 3 H6 ⁇ ) (CH 2 CH2 ⁇ ) n ]-X; R3 is C1-C12 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 -(CH2CH2O),,- comprises at least about 85% by weight of the moiety -[(C3H6 ⁇ ) m (CH2CH2 ⁇ ) tread]-;
  • m is from 0 to about 5;
  • n is at least about 3; 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.
  • Rl can be varied like Rl of the polyurethene and like polymers; each R 2 is preferably methyl or the moiety -(R ⁇ )*- [(C3H6 ⁇ ) OT (CH2CH2 ⁇ ) tread]-X; R3 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 -I- z.
  • x + y + z is from 2 to about 40 and preferably from 2 to about 20.
  • x + y + z can range from 2 to 9 with from 2 to 9 N+ centres and from 2 to 11 X groups.
  • x + y + z is at least 10, with a preferred range of from 10 to about 42.
  • the M' groups are typically a 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) d ( R2 )d
  • R 2 (preferably methyl), M', X, d, x, y, z and n are defined as before; a is 1 or 0.
  • the PEAs used in preparing cationic polymers of the present invention have the following general formula:
  • x 4- y 4- 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 4- y 4- 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 trietliylenetetramine (TETA) and tetraethylenepentamine (TEPA).
  • TETA trietliylenetetramine
  • 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.
  • 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 4- z is 2 or 3, n is preferably at least about 6. Where y 4- z is from 4 to 9, suitable benefits are achieved when n is at least about 3.
  • n is at least about 12, with a typical range of about 12 to about 42.
  • the PEIs used in preparing the polymers of the present invention have a molecular weight of at least about 440 prior to ethoxylation, which represents at least about 10 units.
  • Preferred PEIs used in preparing these polymers have a molecular weight of from about 600 to about 1800.
  • the polymer backbone of these PEIs can be represented by the general formula:
  • x, y, and z represents a number of sufficient magnitude to yield a polymer having the molecular weights previously specified.
  • linear polymer backbones are possible, branch chains can also occur.
  • the relative proportions of primary, secondary and tertiary amine groups present in the polymer can vary, depending on the manner of preparation. The distribution of amine groups is typically as follows:
  • Each hydrogen atom attached to each nitrogen atom of the PEI represents an active site for subsequent ethoxylation.
  • These PEIs can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • Specific methods for preparing PEIs are disclosed in US Pat. No. 2,182,306 to Ulrich et al., issued Dec. 5, 1939; US Pat No. 3,033,746 to Mayle et al., issued May 8, 1962; US Pat. No. 2,208,095 to Esselmann et al., issued July 16, 1940; US Pat. No. 2,806,839 to Crowther, issued Sept. 17, 1957; and US Pat. No. 2,533,696 to Wilson, issued May 21, 1951 (all here
  • n is at least about 3 for the cationic PEIs.
  • the minimum degree of ethoxylation required for suitable clay soil removal/anti-redeposition performance can increase as the molecular weight of th 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 )*- [(C 3 H 6 0) m (CH 2 CH2 ⁇ ) ⁇ ]-X;
  • R 2 is C1-C12 alkylene, hydroxyalkylene, alkylene, arylene or alkarylene;
  • each R3 is C1-C4 alkyl or hydroxyalkyl, or together form the moiety -(CH2) r -A-(CH2),-, wherein A is -O- or -CH2-;
  • X is H,
  • R 4 is C1-C4 alkyl or hydroxyalkyl; k is 1 or 0; m and n are numbers such that the moiety -(CH2CH2O),,- comprises at least about 85% by weight of the moiety - t(C3H6 ⁇ ) m (CH2CH2 ⁇ ) n ]-; 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 4- 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 2N4- centres and at least 2 X groups.
  • A is preferably -0-; Rl is preferably methyl; each R 2 is preferably C2-C3 alkylene; each R3 is preferably methyl; R 4 is preferably methyl; 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 N4- 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 4- 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 thereof, 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, builders, sequestrants, bleach, bleach precursors, bleach catalysts, organic polymeric compounds, additional 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, builders, sequestrants, bleach, bleach precursors, bleach catalysts, organic polymeric compounds, additional 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.
  • an additional surfactant selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
  • anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants is given in U.S. P. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch).
  • a list of suitable cationic surfactants is given in U.S. P. 4,259,217 issued to Murphy on March 31, 1981.
  • ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
  • the detergent compositions or components 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 ⁇ g monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C ⁇ -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 ethoxy sulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(C ⁇ -C4 alkyl) and -N-(Cj-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 Cjo-Cig alkyl sulfates, more preferably the C ⁇ - Cj5 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the Cjrj-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 Cj i-Cjg, most preferably C11-C15 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, C - C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated poly carboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
  • Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl poly ethoxy poly carboxylate 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 CH2COO-M + wherein R is a C to Cig 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 poly ethoxy polycarboxylate surfactants include those having the formula RO-(CHRj-CHR2-0)-R3 wherein R is a C to Ci 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, hydroxy succinic 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-1-undecanoic acid, 2-ethyl-l-decanoic acid, 2-pro ⁇ yl-l- nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors.
  • alkali metal sarcosinates of formula R-CON (Rl) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, Rl is a C1-C4 alkyl group and M is an alkali metal ion.
  • R is a C5-C17 linear or branched alkyl or alkenyl group
  • Rl is a C1-C4 alkyl group
  • M is an alkali metal ion.
  • alkoxy lated nonionic surfactants are suitable herein.
  • the ethoxylated and propoxy lated 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 ethoxy late/propoxy late 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.
  • Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R 2 CONRlZ wherein : Rl is H, -C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably Ci or C 2 alkyl, most preferably Cj alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain Ci 1-C17 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
  • Nonionic fatty acid amide surfactant Suitable fatty acid amide surfactants include those having the formula: R6CON(R7) 2 wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R? is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and - (C2H4 ⁇ ) x H, where x is in the range of from 1 to 3.
  • Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
  • Preferred alkylpolyglycosides have the formula
  • 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 amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula R3(OR 4 ) X NO(R 5 )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 R 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 CIO-CJS alkyl dimethylamine oxide, and CiO-18 acylamido alkyl dimethylamine oxide.
  • a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.
  • Zwitterionic surfactants can also be incorporated into the detergent compositions or components thereof in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable betaines are those compounds having the formula R(R')2N+R COO" wherein R is a C6-C18 hydrocarbyl group, each Rl is typically C1-C3 alkyl, and R 2 is a -C5 hydrocarbyl group.
  • Preferred betaines are C ⁇ 2- 18 dimethyl -ammonio hexanoate and the CJO-18 acylamidopropane (or ethane) dimethyl (or dietnyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • Suitable cationic surfactants to be used in the detergent compositions or components thereof, herein include the quaternary ammonium surfactants selected from mono C -C ⁇ , preferably C6-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, for use 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 carboxymethyloxysuccmates described in British Patent No.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2- ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
  • Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or 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 Partially soluble or insoluble builder compound
  • the detergent compositions or components thereof, of the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
  • Examples of largely water insoluble builders include the sodium aluminosilicates.
  • Suitable aluminosilicate zeolites have the unit cell formula Na z [(Al ⁇ 2)z(Si ⁇ 2)y]. H2O 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 Na 8 6 [(AlO 2 )86(SiO 2 )i06]- 16 H 2 0.
  • zeolite MAP builder Another preferred aluminosilicate zeolite is zeolite MAP builder.
  • the zeolite MAP can be present at a level of from 1 % to 80%, more preferably from 15% to 40% by weight of the compositions.
  • Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
  • zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
  • the zeolite MAP detergent builder has a particle size, expressed as a d50 value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.
  • the 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 d50 values are disclosed in EP 384070A.
  • the detergent compositions or components thereof in accord with the invention preferably contain as an optional component a heavy metal ion sequestrant.
  • heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
  • Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1 % to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5% by weight of the compositions.
  • Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1, 1 diphosphonate.
  • Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2- hydroxypropylenediamine disuccinic acid or any salts thereof.
  • Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A- 399,133.
  • iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
  • EP-A-509,382 The ⁇ -alanine-N,N' -diacetic acid, aspartic acid-N,N' -diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.
  • EP-A-476,257 describes suitable amino based sequestrants.
  • EP-A- 510,331 describes suitable sequestrants derived from collagen, keratin or casein.
  • EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane- 1,2,4- tricarboxylic acid are alos suitable.
  • Glycinamide-N,N' -disuccinic acid Glycinamide-N,N' -disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2- hydroxypropylenediamine-N-N' -disuccinic acid (HPDDS) are also suitable.
  • a preferred feature of detergent compositions or component thereof in accord with the invention is an organic peroxyacid bleaching system.
  • the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
  • the production of the 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.
  • a preformed organic peroxyacid is incorporated directly into the composition.
  • Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
  • 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 utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.
  • Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.
  • Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaB ⁇ 2H2 ⁇ 2 or the tetrahydrate NaB ⁇ 2H2 ⁇ 2-3H2 ⁇ .
  • Alkali metal percarbonates particularly sodium percarbonate are preferred perhydrates herein.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C ⁇ 3.3H2 ⁇ 2, and is available commercially as a crystalline solid.
  • Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as O i i
  • L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is
  • Peroxyacid bleach precursor compounds 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 detergent compositions.
  • Suitable 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 acy lated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB- A-1586789.
  • Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms
  • R is an alkyl chain containing from 1 to 8 carbon atoms
  • R is H or R
  • R ⁇ is an alkenyl chain containing from 1 to 8 carbon atoms
  • Y is H or a solubilizing group.
  • Any of R , R and R may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups
  • the preferred solubilizing groups are -S0 3 " M , -C0 ' M , -S0 4 " M + , -N + (R 3 ) 4 X " and 0 ⁇ --N(R 3 ) 3 and most preferably -S0 3 " M + and -C0 " 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, and X is a halide, hydroxide, methylsulfate or acetate anion.
  • Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
  • Preferred precursors of this type provide peracetic acid 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 from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 , 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.
  • TAED Tetraacetyl ethylene diamine
  • alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
  • Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
  • Rl is an alkyl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene group containing from 1 to 14 carbon atoms
  • R5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-acy lated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxy benzene sulfonates, and the benzoy lation products of sorbitol, glucose, and all saccharides with benzoy lating agents, and those of the imide type including 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.
  • Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • Cationic peroxyacid precursor compounds produce cationic peroxy acids on perhydrolysis.
  • cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group.
  • Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.
  • the peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore.
  • the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter
  • 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-acy lated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • Preferred cationic peroxyacid precursors of the N-acy lated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
  • precursor compounds of the benzoxazin-type as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
  • R j is H, alkyl, alkaryl, aryl, or arylalkyl.
  • the organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1 % to 15% by weight, more preferably from 1 % to 10% by weight of the composition.
  • a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
  • Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
  • Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.
  • organic peroxy acids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • diacyl and tetraacylperoxides especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
  • 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 cellulases, endolases, cutinases, amylases, neutral and alkaline proteases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
  • Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001 % to 4% active enzyme by weight of the composition.
  • Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B licheniformis, described in more detail in GB- 1,269,839 (Novo).
  • Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist- Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S.
  • Amylase enzyme may be inco ⁇ orated into the composition in accordance with the invention at a level of from 0.0001 % to 2% active enzyme by weight of the composition.
  • Organic polymeric compounds are preferred additional components of the detergent compositions or components thereof in accord with the invention, and are preferably present as components of any paniculate components where they may act such as to bind the paniculate 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 inco ⁇ orated 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.
  • Te ⁇ olymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
  • organic polymeric compounds suitable for inco ⁇ oration in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxy methylcellulose, hydroxypropylmethy .cellulose 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 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.
  • 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 C18-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 (a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
  • silica at a level of from 1 % to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;
  • silica/silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight;
  • a dispersant compound most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72- 78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%, preferably 1 % to 10% by weight;
  • a particularly preferred silicone glycol rake copolymer of this type is DC0544, commercially available from DOW Corning under the tradename DC0544;
  • an inert carrier fluid compound most preferably comprising a Ci6-Ci8 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 are 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
  • 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 poly amine 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-0 group is part of these groups.
  • the N-0 group can be represented by the following general structures : O
  • Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group forms part of these groups.
  • the N-0 group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
  • One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-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- vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000.
  • the preferred copolymers have a molar ratio of N- vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.
  • the detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000.
  • PVP polyvinylpyrrolidone
  • Suitable polyvinylpyrrolidones are commercially vailable from ISP Co ⁇ oration, 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 Co ⁇ oration.
  • 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 polvvinylimidazole 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:
  • Ri is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2- hydroxyethyl-N-methylamino, mo ⁇ hilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • Rj is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino- 6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Co ⁇ oration. 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 Co ⁇ oration.
  • Rj is anilino
  • R2 is mo ⁇ hilino
  • 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 Co ⁇ oration.
  • SRA polymeric soil release agents
  • SRA's will generally comprise from 0.01 % to 10.0%, typically from 0.1 % to 5%, preferably from 0.2% to 3.0% by weight, of the compositions.
  • Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.
  • Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide.
  • esters may be made using additional monomers capable of being inco ⁇ orated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
  • Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate (“DMT”) and 1,2-propylene glycol (“PG”) in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water.
  • DMT dimethyl terephthalate
  • PG 1,2-propylene glycol
  • SRA's include the nonionic end-capped 1,2-propylene/polyoxy ethylene terephthalate polyesters of U.S.
  • 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 SM100 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.
  • 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.
  • 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, poly acids, suds regulants, opacifiers, anti-oxidants, bactericides, dyes, perfumes and brighteners, such as those described in US Patent 4,285,841 to Barrat et al., issued August 25, 1981 (herein inco ⁇ orated by reference).
  • the detergent component of the invention can be made via a variety of methods, including dry-mixing and agglomerating of the various compounds comprised in the detergent component.
  • the detergent component preferably forms part of a detergent composiiton.
  • 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 extrusion, 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 11 KN/cm 2 so that the compacted solid has a minimum hardness of 176N to 275N, preferably from 195N to 245N, measured by a C 100 hardness test as supplied by I. Holland instruments.
  • This process may be used to prepare homogeneous or layered tablets of any size or shape.
  • 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. W094/11562.
  • Especially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070.
  • the latter Application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium.
  • the support ring is provided with a masking arrangemnt to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration, or a similar structure in which the walls have a helical form.
  • the dispensing device may be a flexible container, such as a bag or pouch.
  • the bag may be of fibrous 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. 0011500, 0011501, 0011502, and 0011968.
  • a convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.
  • a preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware, silverware and cutlery and 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.
  • Citric acid Anhydrous citric acid Borate Sodium borate Carbonate Anydrous sodium carbonate with a particle size between 200 ⁇ m and 900 ⁇ m
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m
  • Silicate Amo ⁇ hous Sodium Silicate (Si ⁇ 2:Na2 ⁇ 2.0:1)
  • DTPA Diethylene triamine pentaacetic acid
  • DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename Dequest 2060
  • Brightener 1 Disodium 4,4' -bis(2-sulphostyry)biphenyl
  • Brightener 2 Disodium 4,4' -bis(4-anilino-6-mo ⁇ holino-
  • PEO Polyethylene oxide with a molecular weight of 50,000
  • SRP 1 Sulfobenzoyl and capped esters with oxyethylene oxy and terephtaloyl backbone
  • SRP 2 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
  • 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
  • laundry bar detergent compositions were prepared in accord with the invention.
  • Paraffin Paraffin oil sold under the tradename Winog 70 by Wintershall.

Landscapes

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

Abstract

Des compositions détergentes granulaires ou des constituants de ces dernières contiennent une lipase et un ou plusieurs composés cationiques qui sont des composés cationiques de (poly)amine éthoxylés (partiellement) quaternisés dotés de propriétés d'élimination des taches de terre et d'argile et d'anti-redéposition. Ces compositions détergentes ou leurs constituants sont destinés à être utilisés dans des procédés de lavage du linge ou de la vaisselle.
PCT/US1997/016716 1996-09-24 1997-09-22 Compositions detergentes comprenant des amines cationiques et des lipases WO1998013463A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP10515748A JP2000503712A (ja) 1996-09-24 1997-09-22 カチオン性アミンおよびリパーゼ酵素を含んでなる洗剤組成物
EP97941712A EP0929637A4 (fr) 1996-09-24 1997-09-22 Compositions detergentes comprenant des amines cationiques et des lipases
AU43565/97A AU4356597A (en) 1996-09-24 1997-09-22 A detergent composition comprising cationic amines and lipase enzymes
CA002265803A CA2265803A1 (fr) 1996-09-24 1997-09-22 Compositions detergentes comprenant des amines cationiques et des lipases
BR9713217-9A BR9713217A (pt) 1996-09-24 1997-09-22 Uma composição detergente compreendendo aminas catiÈnicas e enzimas lipases

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9619927.8 1996-09-24
GB9619927A GB2317393A (en) 1996-09-24 1996-09-24 Detergent compositions

Publications (1)

Publication Number Publication Date
WO1998013463A1 true WO1998013463A1 (fr) 1998-04-02

Family

ID=10800426

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/016716 WO1998013463A1 (fr) 1996-09-24 1997-09-22 Compositions detergentes comprenant des amines cationiques et des lipases

Country Status (9)

Country Link
EP (1) EP0929637A4 (fr)
JP (1) JP2000503712A (fr)
CN (1) CN1238802A (fr)
AR (1) AR010475A1 (fr)
AU (1) AU4356597A (fr)
BR (1) BR9713217A (fr)
CA (1) CA2265803A1 (fr)
GB (1) GB2317393A (fr)
WO (1) WO1998013463A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016004617A1 (fr) * 2014-07-11 2016-01-14 The Procter & Gamble Company Particules structurées comprenant une polyalkylène-imine alcoxylée, et détergent granulaire pour la lessive comprenant ces particules

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000018877A1 (fr) * 1998-09-25 2000-04-06 The Procter & Gamble Company Compositions de detergent granulaires comportant des particules homogenes et procede de production de celles-ci
US6906022B1 (en) 1998-09-25 2005-06-14 The Procter & Gamble Company Granular detergent compositions having homogenous particles and process for producing same
GB0810881D0 (en) 2008-06-16 2008-07-23 Unilever Plc Improvements relating to fabric cleaning
WO2009153184A1 (fr) * 2008-06-16 2009-12-23 Unilever Plc Perfectionnements relatifs au nettoyage de tissus
EP2767579B1 (fr) * 2013-02-19 2018-07-18 The Procter and Gamble Company Procédé de lavage d'un textile

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101457A (en) * 1975-11-28 1978-07-18 The Procter & Gamble Company Enzyme-containing automatic dishwashing composition
US4659802A (en) * 1982-12-23 1987-04-21 The Procter & Gamble Company Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions
US4664848A (en) * 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
US4711730A (en) * 1986-04-15 1987-12-08 The Procter & Gamble Company Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents
US4713194A (en) * 1986-04-15 1987-12-15 The Procter & Gamble Company Block polyester and like compounds having branched hydrophilic capping groups useful as soil release agents in detergent compositions
US4861502A (en) * 1988-02-08 1989-08-29 The Procter & Gamble Company Conditioning agent containing amine ion-pair complexes and composiitons thereof
US4861512A (en) * 1984-12-21 1989-08-29 The Procter & Gamble Company Sulfonated block polyesters useful as soil release agents in detergent compositions

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0111965B1 (fr) * 1982-12-23 1989-07-26 THE PROCTER & GAMBLE COMPANY Compositions détergentes contenant de composés cationiques ayant des propriétés pour enlever des taches et la contre-redéposition
CA2191314C (fr) * 1994-06-01 2000-06-27 Ronald A. Ii Swift Composition de detergent contenant du sarcosinate d'oleolyle et des tensioactifs anioniques dans des rapports optimaux
EP0906382A4 (fr) * 1996-05-17 1999-11-24 Procter & Gamble Composition detergente

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101457A (en) * 1975-11-28 1978-07-18 The Procter & Gamble Company Enzyme-containing automatic dishwashing composition
US4659802A (en) * 1982-12-23 1987-04-21 The Procter & Gamble Company Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions
US4664848A (en) * 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
US4861512A (en) * 1984-12-21 1989-08-29 The Procter & Gamble Company Sulfonated block polyesters useful as soil release agents in detergent compositions
US4711730A (en) * 1986-04-15 1987-12-08 The Procter & Gamble Company Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents
US4713194A (en) * 1986-04-15 1987-12-15 The Procter & Gamble Company Block polyester and like compounds having branched hydrophilic capping groups useful as soil release agents in detergent compositions
US4861502A (en) * 1988-02-08 1989-08-29 The Procter & Gamble Company Conditioning agent containing amine ion-pair complexes and composiitons thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0929637A4 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016004617A1 (fr) * 2014-07-11 2016-01-14 The Procter & Gamble Company Particules structurées comprenant une polyalkylène-imine alcoxylée, et détergent granulaire pour la lessive comprenant ces particules
US20160010033A1 (en) * 2014-07-11 2016-01-14 The Procter & Gamble Company Structured particles comprising an alkoxylated polyalkyleneimine, and granular laundry detergent comprising the same
US9487737B2 (en) 2014-07-11 2016-11-08 The Procter & Gamble Company Structured particles comprising an alkoxylated polyalkyleneimine, and granular laundry detergent comprising the same
CN106488977A (zh) * 2014-07-11 2017-03-08 宝洁公司 包含烷氧基化的聚亚烷基亚胺的结构化颗粒和包含该结构化颗粒的颗粒状衣物洗涤剂
CN106488977B (zh) * 2014-07-11 2019-04-16 宝洁公司 包含烷氧基化的聚亚烷基亚胺的结构化颗粒和包含该结构化颗粒的颗粒状衣物洗涤剂

Also Published As

Publication number Publication date
JP2000503712A (ja) 2000-03-28
AU4356597A (en) 1998-04-17
EP0929637A4 (fr) 2000-01-05
GB2317393A (en) 1998-03-25
CA2265803A1 (fr) 1998-04-02
CN1238802A (zh) 1999-12-15
GB9619927D0 (en) 1996-11-06
EP0929637A1 (fr) 1999-07-21
BR9713217A (pt) 2000-12-05
AR010475A1 (es) 2000-06-28

Similar Documents

Publication Publication Date Title
EP0934389A1 (fr) Compositions detergentes
WO1998017758A1 (fr) Compositions detergentes
EP0843714A1 (fr) Procede pour laver du linge
EP0906382A1 (fr) Composition detergente
WO1998013453A1 (fr) Particulate pour detergent
EP0929626A1 (fr) Compositions detergentes ou composant de ces dernieres
EP0934378A1 (fr) Compositions detergentes comprenant un melange de tensioactifs cationiques, anioniques et non ioniques
WO1998017759A1 (fr) Composition detergentes comprenant un melange d'un tensioactif cationique quaternaire et d'un tensioactif anionique d'alkyle sulfate
EP0929637A1 (fr) Compositions detergentes comprenant des amines cationiques et des lipases
GB2317390A (en) Detergent compositions
EP0929622A1 (fr) Compositions detergentes
WO1998013448A9 (fr) Compositions detergentes
EP0929623A1 (fr) Compositions detergentes
GB2317394A (en) Detergent compositions
EP0929643A1 (fr) Composition detergente a base d'amines cationiques et d'enzymes cellulases
EP0968269A1 (fr) Compositions detergentes
WO1998017751A1 (fr) Compositions de detergents
WO1998017777A1 (fr) Compostions detergentes
EP0929625A1 (fr) Compositions detergentes
GB2323385A (en) Detergent compositions
EP0934377A1 (fr) Compositions detergentes
WO1998017768A1 (fr) Composition detergente comprenant une enzyme lipase et un tensioactif cationique
WO1998017766A1 (fr) Compositions detergentes
WO1998017753A1 (fr) Composition detergente contenant un alkyle polysaccharide et des tensioactifs cationiques
GB2319038A (en) Detergent particle

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 97199989.9

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH KE LS MW SD SZ UG ZW AT BE CH DE DK ES FI FR GB GR IE IT LU MC

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2265803

Country of ref document: CA

Ref document number: 2265803

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1997941712

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: PA/a/1999/002818

Country of ref document: MX

Ref document number: 09269325

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 1997941712

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWW Wipo information: withdrawn in national office

Ref document number: 1997941712

Country of ref document: EP