WO1998013452A1 - Compositions detergentes ou composant de ces dernieres - Google Patents

Compositions detergentes ou composant de ces dernieres Download PDF

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Publication number
WO1998013452A1
WO1998013452A1 PCT/US1997/016705 US9716705W WO9813452A1 WO 1998013452 A1 WO1998013452 A1 WO 1998013452A1 US 9716705 W US9716705 W US 9716705W WO 9813452 A1 WO9813452 A1 WO 9813452A1
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WIPO (PCT)
Prior art keywords
cationic
moiety
alkyl
detergent
group
Prior art date
Application number
PCT/US1997/016705
Other languages
English (en)
Inventor
Jennifer Leupoin Caldarelli
Stuart Clive Askew
Graham Alexander Sorrie
Robin Gibson Hall
Tiffany Alice Hensman
Hossam Tantawy
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB9619928A external-priority patent/GB2317394A/en
Priority claimed from GBGB9713946.3A external-priority patent/GB9713946D0/en
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to JP10515746A priority Critical patent/JP2000506935A/ja
Priority to AU44882/97A priority patent/AU4488297A/en
Priority to BR9712839-2A priority patent/BR9712839A/pt
Priority to CA002265942A priority patent/CA2265942A1/fr
Priority to EP97943400A priority patent/EP0929626A4/fr
Publication of WO1998013452A1 publication Critical patent/WO1998013452A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/3715—Polyesters or polycarbonates
    • 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
    • C11D3/3719—Polyamides or polyimides
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the present invention relates to a detergent composition or component containing cationic compounds with clay-soil/ paniculate soil removal/anti-redeposition properties and one or more carboxylate-containing polyelectrolyte compounds, with builder or dispersant properties, for use in laundry and dish washing processes.
  • Clay soil panicles generally comprise negatively charged layers of aluminosilicates and positively charged cations (e.g. calcium) which are positioned between and hold together the negatively charged layers.
  • a variety of models can be proposed for compounds which have clay soil removal propenies.
  • 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; and 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.
  • clay soil removal there is a need to keep the removed soil in suspension during the laundering (or dish washing) cycle. Soil which is removed from the fabric and suspended in the wash water can redeposit on the surface of the fabric. This redeposited soil causes a dulling or "greying" effect which is especially noticeable on white fabrics.
  • anti-redeposition agents are also often included in detergent compositions.
  • detergent compounds traditionally employed in detergents are soil dispersants and anti-encrustation agent, such as carboxylate-containing polyelectrolyte compounds.
  • EP-B-111 965 discloses the use in detergents of cationic compounds, which have both clay-soil removal and anti-redeposition properties.
  • a model proposed for the anti-redeposition action of these compounds is as follows. Adsorption of the positively charged molecule on the surface of clay particles in the wash water gives the clay 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. As such the hydrophilically encased soil is prevented from redepositing on hydrophobic fabrics such as polyester, during the laundering or dish washing cycle.
  • Such detergent components or detergent compositions have now been found to deliver a surprisingly better clay/ soil removal and cleaning performance than that of detergent compositions employing either of the two components individually. It has also been found that specific ratios of the cationic quatemized ethoxylated (poly) amines to the carboxylate-containing polyelectrolyte compounds are particularly preferred and enable good performance benefits to be achieved even when using very low amounts of each component.
  • the cleaning performance benefits of the detergent compositions containing both carboxylate-containing polyelectrolyte compounds and cationic. (partially) quatemized ethoxylated (poly) amines are found to depend both on the amount of carboxylate-containing polyelectrolyte compound used and its properties (e.g. the molecular weight of the polymeric compound and the monomeric segments comprised in the polymeric compound). For example, in built conditions it has been found that co-polymeric polycarboxylic compounds, for example maleic/ acrylic co-polymers, have a better (calcium) builder/ dispersant performance than homo-polymeric polycarboxylic compounds of a similar molecular weight. Thus, lower levels of certain, preferred polymeric compounds are as effective as higher levels of others.
  • a further advantage of the present invention is that the clay/ soil removal benefits can even be observed after the completion of only one wash cycle.
  • a solid, preferably 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:
  • M* is an N + or N group; each M 2 is an N+ or N group, and at least one M 2 is an N+ group;
  • R is H or C1-C4 alkyl or hydroxyalkyl
  • R 1 is C2-C12 alkylene. hydroxy alky lene, alkenylene, arylene or alkarylene, or a C2-C3 oxyaikylene moiety having from 2 to about 20 oxyaikylene units provided that no O-N bonds are formed
  • each R 2 is -C4 alkyl or hydroxyalkyl, the moiety -L-X, or two R 2 together form the moiety -(CH2) r -A 2 -(CH2) ⁇ -, wherein A 2 is -O- or -CH2-, r is 1 or 2, s is 1 or 2 and r + s is 3 or 4
  • each R ⁇ is C ⁇ -Cg alkyl or hydroxyalkyl, benzyl, the moiety L-X, or two R 3 or one R 2 and one R 3 together form the moiety -(CP ⁇ r -A 2 - (CH2 ;
  • R 6 is C3-C4 alkylene or hydroxy alkylene and m and n are numbers such that the moiety
  • -(CH2CH2 ⁇ ) fl - comprises at least about 50% by weight of said polyoxyalkylene moiety; d is 1 when M 2 is N + and is 0 when M 2 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;
  • a preferred ratio of (a) to (b) is from 1 : 1 to 1 :6.
  • the detergent compositions but particularly the detergent components and especially the spray-dried panicles comprising the cationic quatemized ethoxylated (poly) amines and the carboxylate-containing polyelectrolyte compounds in the specific levels and ratios are crisp and free flowing and do not have the tendency to cake, and are capable of absorbing other detergent compounds when present, such as for example anionic, cationic and nonionic surfactants. This thus minimises caking of the compositions comprising the components or spray -dried particles.
  • a spray-dried particle or granule comprising compounds (a) and (b) as described above and with (a) and (b) in a referred ratio of from 1:1 to 1.10.
  • Preferred anionic counterions for the cationic water-soluble compounds are halides such as Cl" and Br", or most preferably MeS ⁇ 4".
  • An essential feature of the present invention is a water-soluble cationic compound which has paniculate soil/ clay-soil removal/anti-redeposition properties and which is selected from the group consisting of cationic mono-di- and polyamines.
  • the ratio in the composition or component thereof of the cationic compound to the carboxylate-containing polyelectrolyte compound is from 1:95 to 95: 1, more preferably from 1 :25 to 25: 1, most preferably from 1 :5 to 5: 1.
  • the ratio of the carboxylate- containing polyelectrolyte compound to the water-soluble cationic compound in the component is preferably from 1 : 1 to 1 : 10, more preferably from 1 : 1 to 1 :4, most preferably from 1 : 1 to 1 :2.
  • the water-soluble cationic compound is preferably present at a level of from 0.01 % to 30% , more preferably from 0.1 % to 15 % . most preferably from 0.2% to 3.0% by weight of the detergent composition.
  • the ratio of the carboxylate-containing polyelectrolyte compound to the water-soluble cationic compound in the component is from 1 : 1 to 1 : 10, more preferably from 1 : 1 to 1 :4, most preferably from 1 : 1 to 1:2.
  • the water-soluble cationic compound is preferably present at a level of from 0.1 % to 30%, more preferably from 0.5% to 15% , even more preferably from 0.5% to 7% , most preferably from 0.6% to 2% by weight of the spray-dried particle or detergent component.
  • Such a spray-dried particle or such a component preferably is present in a granular detergent composition at a level of from 5% to 90% , more preferably from 20% to 60%, most preferably from 30% to 50% by weight of the composition.
  • Cationic amines preferably is present in a granular detergent composition at a level of from 5% to 90% , more preferably from 20% to 60%, most preferably from 30% to 50% by weight of the composition.
  • the water-soluble cationic compounds of the present invention useful in the detergent compositions or components in accord with the present invention include ethoxylated cationic monoamines, ethoxylated cationic diamines and ethoxylated cationic polyamines as previously defined.
  • Ri can be branched
  • R* is preferably C2-C6 alkylene for the ethoxylated cationic diamines.
  • Each R 2 is preferably methyl or the moiety -L-X; each R 3 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 , MeS ⁇ 4- and the like. Particularly preferred counter anions are Cl- and Br-, but most preferably MeS ⁇ 4-.
  • X can be a non-ionic 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 -[(R 6 0) (CH2CH2_O ⁇ )-].
  • the moieties -(R 6 0)m- and - (CH2CH2 ⁇ )n- of the polyoxyalkylene moiety can be mixed together or preferably form blocks of -(R 6 0) w - and -(CH2CH2 ⁇ ) justify- moieties.
  • R 6 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 -(CF ⁇ CFFjO), ! -.
  • the moiety (CH2CH2 ⁇ ) M - preferably comprises at least about 85% by weight of the polyoxyalkylene moiety and most preferably 100% by weight (m is O).
  • M* and each M 2 are preferably an N+ group for the cationic diamines and polyamines.
  • Preferred ethoxylated cationic monoamines and diamines have the formula:
  • 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;
  • A* is preferably O
  • n is preferably at least about 12, with a typical range of from about 12 to about 42; p is preferably from 3 to 6.
  • R 4 is a substituted aryl or alkaryl group
  • q is preferably 1 and R ⁇ is preferably C2-C3 alkylene.
  • R 4 is a substituted alkyl, hydroxyalkyl, or alkenyl group, and when q is 0, R ⁇ is preferably a C2-C3 oxyaikylene moiety; when q is 1, R ⁇ is preferably C2-C3 alkylene.
  • ethoxylated catiomc polyamines can be derived from polyamino amides such as:
  • ethoxylated cationic polyamines can also be derived from polyaminopropyleneoxide derivatives such as:
  • An essential component of the invention is one or more carboxylate-containing polyelectrolyte compounds, which have builder or dispersant properties.
  • these compounds are homo- or co-polymeric polycarboxylic compounds and most preferably co-polymeric polycarboxylic compounds in which the acid monomer of said polycarboxylic compound comprises at least two carboxyl groups separated by not more than two carbon atoms. Salts of these polycarboxylic compounds are also considered herein.
  • the polycarboxylic compounds of the present invention will comprise at least 12 carboxylate groups.
  • the carboxylate-containing polyelectrolyte compound is preferably present at a level of from 0.01 % to 40% , more preferably from 0.1 % to 10% , most preferably from 0.2% to 6% by weight of the detergent composition
  • the carboxylate- containing polyelectrolyte compound is preferably present at a level of from 0.05% to 30% , more preferably from 0.1% to 15% , more preferably from 0.15% to 7%, most preferably from 0.2% to 2.0% or more preferred to 1.2% by weight of the detergent component.
  • the carboxylate-containing polyelectrolyte compound is preferably present at a level from 0.2% to 2.0% or more preferred to 1.2% by weight of the spray-dried particle.
  • Such a spray-dried particle or such a component preferably is present in a granular detergent composition at a level of from 5% to 90%, more preferably from 20% to 60%, most preferably from 30% to 50% by weight of the composition.
  • the carboxylate-containing polyelectrolyte materials can be prepared by polymerising or copolymerizing suitable unsamrated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerised to form suitable polymeric polycarboxylates are selected from acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in these carboxylate-containing polyelectrolyte compounds herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than 40% by weight.
  • Carboxylate-containing materials can also optionally include further monomeric units such as nonionic spacing units.
  • suitable nonionic spacing units may include vinyl alcohol or vinyl acetate.
  • Particular preferred carboxylate-containing polyelectrolyte compounds are acrylic/maleic -based co-polymers.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid/ maleic anhydride.
  • the average molecular weight of such copolymers in the acid form preferably can range from 1,000 to 100,000, more preferably from 2,000 to 75,000 or even more preferred to 70,000, but most preferred are the co-polymers with a average molecular weight of from 2.500 to 20,000 or in another preferred embodiment from 60,000 to 75,000 or even 70,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from 30:1 to 1 :30, more preferably from 10: 1 to 1 : 1 , most preferably from 4: 1 to 7:3.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986.
  • carboxylate-containing polyelectrolyte compounds can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are for example the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such homo-polymers in the acid form preferably ranges from 1,800 to 100,000, more preferably from 2,000 to 10,000, most preferably from 3,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers or can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.
  • polyamino-based 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.
  • carboxylate-containing polyelectrolyte compounds suitable for the purpose of the invention include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
  • Terpolymers containing monomer units selected from maleic acid, acrylic acid and polyaspartic acid, particularly those having an average molecular weight of from 5.000 to 2 0,000, are also suitable herein.
  • carboxylate-containing polyelectrolyte compounds are the polyelectrolyte-containing glycols, particularly those of molecular weight 1.000- 10,000, more particularly 2,000 to 8,000 and most preferably about 4.000.
  • carboxylate-containing polyelectrolyte compounds are those which typically have a hydrophilic backbone and at least one hydrophobic side chain.
  • carboxylate-containing polyelectrolyte compounds have a molecular weight of between 500 and 100,000, more preferred from 1.000 to 70,000, especially preferred from 1,500 to 10,000, or in another preferred embodiment from 2,800 to 6,000.
  • Carboxylate-containing polyelectrolyte compounds for use herein may for example be prepared by using conventional aqueous polymerisation procedures, suitable methods are for example described in GB 89 24477, GB 89 24478 and GB 89 24479.
  • the hydrophilic backbone of the polymer is predominantly linear (the main chain of the backbone constitutes at least 50%, preferably more than 75% , most preferred more than 90% by weight of the backbone), suitable monomer constituents of the hydrophilic backbone are for example unsamrated C ⁇ -Cg acids, ethers, alcohols, aldehydes, ketones or esters, sugar units, alkoxy units, maleic anhydride and saturated polyalcohols such as glycerol.
  • the hydrophobic side groups are composed of alkoxy groups for example butylene oxide and/or propylene oxide and/or alkyl or alkenyl chains having from 5 to 24 carbon atoms.
  • the hydrophobic groups may be connected to the hydrophilic backbone via relatively hydrophilic bonds for example a poly ethoxy linkage.
  • Preferred carboxylate-containing polyelectrolyte compounds of this type are the polymers described in WO 91/ 08281.
  • Preferred counterions for the carboxylate-containing polyelectrolyte compounds are for example sodium, magnesium or calcium ions.
  • a preferred component according to the invention comprises a spray-dried particle can be used in a detergent composition.
  • the detergent composition may consist essentially of such particles, but preferably the detergent composition comprises the particles and other components, having a different chemical composition.
  • the spray -dried particle of the invention are formed by a process, which includes a spray -drying step.
  • the spray-drying step produces a spray -dried particle, generally having a free-moisture content below 10% by weight, preferably less than 7%, or more preferably less than 6% .
  • free -moisture content is determined by placing 2 grams of a sample of base detergent granules in for example a petri dish, placing the sample in a heating chamber up to 160°C for 10 minutes, followed by measurement of the weight loss due to water evaporation.
  • the particles of the invention are formed in a process whereby a paste or slurry or crutcher mix comprising the cationic compound and the carboxylate- containing polyelectrolytes, is formed into particles and dried in a spray-drying process as known in the art.
  • the process for manufacturing the spray-dried particles comprises preparing an aqueous solution-dispersion, commonly referred to as a paste or slurry or crutcher mix, comprising the components of the final particle.
  • the cationic compound and the carboxylate-containing polyelectrolyte can be mixed together prior to addition to the other ingredients of the crutcher mix, which will be comprised in the spray-dried particle.
  • the cationic compound and the carboxylate-containing polyelectrolyte can be mixed with other organic compounds, which will be comprised in the final spray -dried particle, prior to addition to the other ingredients of the crutcher mix (which will be comprised in the final spray-dried particle).
  • the cationic compound and the carboxylate-containing polyelectrolyte can be added to the crutcher or crutcher mix at the same time as the other ingredients, which will be comprised in the final spray -dried particle.
  • the crutcher mix will usually be of as high a solids content as feasible, e.g., 40% to 80% , with the balance, e.g. 10% to 60% , being water. More water may be used but then energy demands are increased, tower throughput are diminished, products resulting may be tackier and poorer flowing g and often the desired low density base and final detergent composition particles will not be obtained.
  • the crutcher mix preferably has a temperature of from 50°C to 100°C, typically 80°C prior to the drying step.
  • the crutcher mix is then sprayed at an elevated pressure (usually from 40 to 100 bar, preferably 70 to 90 bar, typically at about 80 bar) through one or more spray nozzles into a drying tower, through which drying air, passes to dry the resulting droplets of crutcher mix to globular the particles.
  • an elevated pressure usually from 40 to 100 bar, preferably 70 to 90 bar, typically at about 80 bar
  • spray nozzles equivalent atomisers of other designs may also be used.
  • the preferred spray tower design is counter-current, the height of the tower usually being from 5 to 25 meters and the entering hot air, usually the gaseous products of combustion of oil or gas, being at a temperature in the range of from 150° to 400°C and the outlet air usually at a temperature in the range of from 50° to 160°C.
  • Concurrent tower designs may also be employed wherein similar inlet and outlet air temperatures obtain.
  • the nozzle size for producing droplets of crutcher mix will be chosen such particles of the preferred particle size are formed, preferably of from 0.1 mm to 3.0 mm. Preferably, substantially all the particles are within this range when removed from the spray tower, but any off-size particles can be removed by screening, may be size-reduced to the desired size range or may be recycled in the same or a subsequent crutcher mix.
  • Preferred additional ingredient of the crutcher mix can be anionic surfactants, cationic softeners or cationic surfactants, nonionic, sulphate and carbonate salts, and hydrotropes.
  • additional detergent compounds or components can be added to the particles, preferably by melting the compound or component and spraying the molten compound or component, which may be in concentrated aqueous solution but preferably is free of water, onto the surfaces of the tumbling base particles in an inclined drum, through which the particles progress from an elevation feed end to the discharge end.
  • the particle can be introduced to a detergent composition by any method, known in the art.
  • the particles are dry-added to the other detergent ingredients.
  • the detergent compositions or components in accordance with the invention may also contain additional detergent ingredients.
  • additional detergent ingredients and levels of incorporation thereof will depend on the physical form of the component, and the precise nature of the washing operation for which it is to be used.
  • the components or the detergent compositions in accordance with the invention preferably contain one or more additional detergent components selected from surfactants, additional builders, sequestrants, bleach, bleach precursors, bleach catalysts, additional organic polymeric compounds, enzymes, suds suppressors, additional lime soap dispersants, additional soil suspension and anti-redeposition agents soil releasing agents, perfumes and corrosion inhibitors.
  • additional detergent components selected from surfactants, additional builders, sequestrants, bleach, bleach precursors, bleach catalysts, additional organic polymeric compounds, enzymes, suds suppressors, additional lime soap dispersants, additional soil suspension and anti-redeposition agents soil releasing agents, perfumes and corrosion inhibitors.
  • a preferred additional component can be additional polymeric cationic ethoxylated amine compounds with paniculate soil/clay-soil removal/ anti-redeposition, selected from the group consisting of water-soluble cationic polymers.
  • These polymers comprise a polymer backbone, at least 2M groups and at least one L-X group, wherein M is a cationic group attached to or integral with the backbone; X is a nonionic group selected from the group consisting of H, C ⁇ -C4 alkyl or hydroxyalkyl ester or ether groups, and mixmres thereof; and L is a hydrophilic chain connecting groups M and X or connecting X to the polymer backbone.
  • 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).
  • 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: -- M - M —
  • 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 poly ethers, the polyamides, the polyimides and the like, the polyacrylates, the polyacrylamides, the polyvinylethers, the polyethylenes, the polypropylenes and like polyalkylenes, the polystyrenes and like polyalkarylenes, the polyalkyleneamines, the polyalkyleneimines, the polyvinylamines, the polyalylamines, the polydiallylamines, the polyvinylpyridines, the polyaminotriazoles, polyvinyl alcohol, the aminopolyureylenes, and mixmres thereof.
  • M can be any compatible cationic group which comprises an N+ (quartemary). positively charged center.
  • the quartemary positively charged center can be represented by the following general structures E and F:
  • M groups are those containing a quarternary center represented by general structure E.
  • the cationic group is preferably positioned close to or integral with the polymer backbone.
  • the positive charge of the N + centres is offset by the appropriate number of counter anions.
  • Suitable counter anions include Cl", Br, SO3 2 ", SO4 2” , PO4 2 ", MeOS ⁇ 3” and the like.
  • Particularly preferred counter anions are Cl " and Br".
  • X can be a nonionic group selected from hydrogen (H), C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof.
  • the preferred ester or ether groups are the acetate ester and methyl ether, respectively;
  • the particularly preferred nonionic groups are H and the methyl ether.
  • the cationic polymers suitable for use in granular detergent components 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 cationic/nonionic monomers copolymerize in a non repeating sequence.
  • the units which contain groups M and groups L-X can comprise 100% of the cationic polymers of the present invention.
  • other units preferably nonionic
  • examples of other units include acryiamides, vinyl ethers and those containing unquaternized tertiary amine groups (Ml) containing an N centre.
  • Ml 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).
  • 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) TO (CH2CH2 ⁇ ) ⁇ ]-.
  • the moieties -(R'0) m - and - (CH2CH2 ⁇ ) ⁇ - of the polyoxyalkylene moiety can be mixed together, or preferably form blocks of -(R'0) - 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 -(CH2CH2 ⁇ ) ⁇ - preferably comprises at least about 85% by weight of the polyoxyalkylene moiety, and most preferably 100% by weight (m is 0).
  • n is usually from about 3 to about 100.
  • n is from about 12 to about 42.
  • a plurality (2 or more) of moieties -L-X can also be hooked together and attached to group M or to the polymer backbone, examples of which are represented by the following general structures G and H:
  • Structures such as G and H can be formed, for example, by reacting glycidol with group M or with the polymer backbone, and ethoxylating the subsequently formed hydroxy groups.
  • cationic polymers of the present invention are as follows:
  • Suitable cationic polymers are derived from polyurethanes, polyesters, polyethers, polyamides and the like. These polymers comprise units selected from those having formulas I, II and III:
  • X is 0 or 1; R is H or C1-C4 alkyl or hydroxyalkyl; R is C2-C12 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C2-C3 oxyaikylene moiety having from 2 to abut 20 oxyaikylene units provided that no O- O or O-N bonds are formed with A* ; when x is 1 , R 2 is -R ⁇ - except when A* is
  • R3 is -R ⁇ -;
  • R4 is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R )#- [(C3H6 ⁇ ) m (CH2CH2 ⁇ ) utilizat]-X;
  • R 5 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene, or alkarylene; each R6 is C1.C4 alkyl or hydroxyalkyl, or the moiety -(CH2) A 2 -(CH2)s-, wherein A 2 is -0- or -CH2-;
  • R 7 is H or R 4 ;
  • R 8 is C2-C3 alkylene or hydroxyalkylene;
  • X is H,
  • R ⁇ is C1-C4 alkyl or hydoxyalkyl
  • k is 0 or 1
  • m and n are numbers such that the moiety -(CH2CH2 ⁇ ) ⁇ - comprises at least about 85% by weight of the moiety -[(C3H6 ⁇ ) m (CH2CH2 ⁇ ) ⁇ ]-;
  • 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
  • SOBS ⁇ iT SHEET PILE 26
  • the number of u, v and w are such that there are at least 2 N + centers and at least 2 X groups.
  • A* is preferably
  • a 2 is preferably -0-; x is preferably 1; and R is preferably H.
  • R* can be linear (e.g. -CH2-CH2-CH2-,
  • R 1 is preferably C2-Cg alkylene or phenylene, and most preferably C2-C6 alkylene (e.g. ethylene, propylene, hexamethylene).
  • R 2 is preferably -OR 5 - or -(OR ,-;
  • R3 is preferably -R 5 0- or - (OR 8 )y-;
  • R 4 and R 6 are preferably methyl.
  • R 5 can be linear or branched, and is preferably C2-C3 alkylene; R 7 is preferably H or C1-C3 alkyl; R 8 is preferably ethylene; R ⁇ is preferably methyl; X is preferably H or methyl; k is preferably 0; m is preferably 0, r and s are each preferably 2; y is preferably from 2 to about 12.
  • n is preferably at least about 6 when the number of N+ centers and X groups is 2 or 3; n is most preferably at least about 12, with a typical range of about 12 to about 42 for all ranges of u + v + w.
  • u is preferably from about 3 to about 20.
  • v and w are each preferably from about 3 to about 40.
  • Suitable catiomc 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 — ,
  • R is H or Ci -C4 alkyl or hydroxyalkyl;
  • R 1 is substituted C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or C2-C3 oxyaikylene;
  • R 2 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene;
  • R 3 is C1-C4 alkyl or hydroxyalkyl, the moiety -(R 2 )*-[(C3H6 ⁇ ) (CH2CH2 ⁇ ) contend]- X, or together form the moiety -(CH2) A -(CH2)j-, wherein A 2 is -O- or -CH2-; each R 4 is C1-C4 alkyl or hydroxyalkyl, or two R 4 together form the moiety - (CH 2 )rA 2 -(CH 2 ) ir ; X is H,
  • R ⁇ is C1-C4 alkyl or hydroxalkyl
  • j is 1 or 0
  • k is 1 or 0
  • m and n are numbers such that the moiety -(CH2CH2 ⁇ ) n - comprises at least about 85% by weight of the moiety -[ ⁇ H ⁇ O ⁇ C ⁇ C ⁇ O),,]-
  • 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 s preferably
  • a 2 is preferably -0-; R is preferably H. R* can be linear
  • SWST ⁇ UTE SHEET (e.g. — CH 2 — CH— or
  • R* is preferably substituted C 2 -C6 alkylene or substituted C2-C3 oxyaikylene, and most preferably
  • Each R 2 is preferably C2-C3 alkylene, each R 3 and R 4 are preferably methyl; R 5 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.
  • SWST ⁇ UTE SHEET (RULE 26) Another class of suitable cationic polymers are derived from polyalkyleneamines, polyalkyleneimines and the like. These polymers comprise units selected from those having formulas VII and VIII and IX.
  • R* is C 2 -Ci2 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C2-C3 oxyaikylene moiety having from 2 to about 20 oxyaikylene units provided that no O-N bonds are formed; each R 2 is C1-C4 alkyl or hydroxyalicyl, or the moiety -(R ) ⁇ -[(C3H6 ⁇ ) m (CH2CH2 ⁇ ) n ]-X; R 3 is Ci- 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-l- 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 -(C ⁇ C ⁇ O) ⁇ - comprises at least about 85% by weight of the moiety -[(C3H6 ⁇ ) (CH2CH2 ⁇ ) ⁇ ]-
  • 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 R* of the polyurethene and like polymers; each R 2 is preferably methyl or the moiety -(R 3 ) - [(C3H6 ⁇ ) (CH2CH2 ⁇ ) tread]-X; R 3 is preferably C2-C3 alkylene; R 4 is preferably methyl; X is preferably H; k is preferably 0; m is preferably 0.
  • n is preferably at least about 6 when the number of M' and X groups is 2 or 3; n is most preferably at least about 12, with a typical range of from about 12 to about 42 for all ranges of x + y + z.
  • x + y + z is from 2 to about 40 and preferably from 2 to about 20.
  • x + y + z can range from 2 to 9 with from 2 to 9 N+ centres and from 2 to 11 X groups.
  • x + y + z is at least 10, with a preferred range of from 10 to about 42.
  • the M' groups are typically a mixmre of from about 50 to 100% N -t- 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 (R 2 ) 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 + y + z is from 2 to 9, and a is 0 or 1 (molecular weight of from about 100 to about 400).
  • a is 0 or 1 (molecular weight of from about 100 to about 400).
  • Each hydrogen atom attached to each mtrogen atom represents an active site for subsequent ethoxylation.
  • x -I- y - z is from about 3 to about 7 (molecular weight is from about 140 to about 310).
  • These PEA's can be obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. The common PEA's obtained are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA).
  • the cogenerically derived mixmre does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can also be present cyclic amines with side chains in which nitrogen atoms appear. See US Pat. No. 2,792,372 to Dickson, issues May 14, 1957, which describes the preparation of PEAs.
  • n is at least about 6.
  • y + z is from 4 to 9, suitable benefits are achieved when n is at least about 3.
  • n is at least about 12, with a typical range of about 12 to about 42.
  • the PEIs used in preparing the polymers of the present invention have a molecular weight of at least about 440 prior to ethoxylation, which represents at least about 10 units.
  • Preferred PEIs used in preparing these polymers have a molecular weight of from about 600 to about 1800.
  • the polymer backbone of these PEIs can be represented by the general formula:
  • x, y, and z represents a number of sufficient magnimde 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 mtrogen atom of the PEI represents an active site for subsequent ethoxylation.
  • These PEIs can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing PEIs are disclosed in US Pat. No. 2,182,306 to Ulrich et al., issued Dec. 5, 1939; US Pat No. 3,033,746 to Mayle et al. , issued May 8, 1962; US Pat. No. 2,208,095 to 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 herein incorporated by reference).
  • n is at least about 3 for the cationic PEIs.
  • the minimum degree of ethoxylation required for suitable clay soil removal/anti-redeposition performance can increase as the molecular weight of the PEI increases, especially much beyond about 1800.
  • the degree of ethoxyalation for preferred polymers increases as the molecular weight of the PEI increases.
  • n is preferably at least about 12, with a typical range of from about 12 to about 42.
  • n is preferably at least about 24, with a typical range of from about 24 to about 42.
  • Suitable cationic polymers are those derived from the diallylamines. These polymers comprise units selected from those having formulas X and XI:
  • R ⁇ is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R 2 )fc- [(C3H6 ⁇ ) m (CH2CH2 ⁇ ) ⁇ ]-X;
  • R 2 is alkylene, hydroxyalkylene, alkylene, arylene or alkarylene; each R 3 is C1 -C4 alkyl or hydroxyalkyl, or together form the moiety -(C ⁇ ⁇ MC ⁇ , 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 -(C ⁇ C ⁇ O) ⁇ - comprises at least about 85% by weight of the moiety -[(C3H6 ⁇ ) (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
  • r + s is 3 or 4
  • x is 1 or 0
  • y is 1 when x is 0 and 0 when x is 1 ; the number of u and v are such that there are at least 2N+ centres and at least 2 X groups.
  • A is preferably -0-; R is preferably methyl; each R 2 is preferably C2-C3 alkylene; each R 3 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 N + centres and X groups are each 2 or 3, n is preferably at least 12, with a typical range of from about 12 to about 42 for all range of u + v.
  • v is 0, and u is from 2 to about 40, and preferably from 2 to about 20.
  • the detergent compositions or components preferably contain an additional surfactant selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixmres thereof.
  • ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
  • the detergent compositions or components preferably comprise an additional anionic surfactant.
  • 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 unsamrated C, 2-C, n monoesters) diesters of sulfosuccinate (especially saturated and unsamrated C fi -C « 4 diesters), N-acyl sarcosinates.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
  • Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(C ⁇ -C4 alkyl) and -N-(C ⁇ -C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Alkyl sulfate surfactants are preferably selected from the linear and branched primary C10-C18 alkyl sulfates, more preferably the C11-C15 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
  • Alkyl ethoxy sulfate surfactants are preferably selected from the group consisting of the C10-C18 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 Cii-Cig. most preferably Ci 1-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 mixmres of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixmres have been disclosed in PCT Patent Application No. WO 93/18124.
  • Anionic sulfonate surfactant Anionic sulfonate surfactant
  • Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixmres thereof.
  • Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
  • Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2 ⁇ ) x CH2C00"M + wherein R is a C to Ci alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation.
  • Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR ⁇ -CHR2- 0)-R3 wherein R is a C to Ci g alkyl group, x is from 1 to 25, K ⁇ and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxy succinic acid radical, and mixmres thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixmres 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-methyI-l-undecanoic acid, 2-ethyl-l- decanoic acid, 2-propyl-l-nonanoic acid, 2-butyl-l -octanoic acid and 2-pentyl-l- heptanoic acid. Certain soaps may also be included as suds suppressors.
  • alkali metal sarcosinates of formula R- CON (R 1 ) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, R 1 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
  • R 1 is a C1 -C4 alkyl group
  • M is an alkali metal ion.
  • any alkoxylated nonionic surfactants are suitable herein.
  • the ethoxylated and propoxylated nonionic surfactants are preferred.
  • Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxy lated/propoxylated fatty alcohols, nonionic ethoxy late/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
  • the condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
  • Nonionic polvhvdroxy fatty acid amide surfactant Nonionic polvhvdroxy fatty acid amide surfactant
  • Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R 2 CONR*Z wherein : RI is H, C1 -C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixmre thereof, preferable C1-C4 alkyl, more preferably Ci or C2 alkyl, most preferably C alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C 9 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight- chain Ci 1 -C17 alkyl or alkenyl, or mixmre thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Nonionic fatty acid amide surfactant Nonionic fatty acid amide surfactant
  • Suitable fatty acid amide surfactants include those having the formula: R6C0N(R )2 wherein R ⁇ is an alkyl group containing from 7 to 21 , preferably from 9 to 17 carbon atoms and each R ⁇ is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4 ⁇ ) x H, where x is in the range of from 1 to 3.
  • 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 mixmres thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
  • the glycosyl is preferably derived from glucose.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula R 3 (OR ) x N°(R 5 )2 wherein R 3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixmres thereof, containing from 8 to 26 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixmres thereof; x is from 0 to 5, preferably from 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are C ⁇ o _ i8 alkyl dimethylamine oxide, and C ⁇ o-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. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable betaines are those compounds having the formula R(R')2N + R 2 COO ⁇ wherein R is a C fj -Ci hydrocarbyl group, each R* is typically C -C3 alkyl, and R 2 is a C1-C5 hydrocarbyl group.
  • Preferred betaines are C12-I8 dimethyl- ammonio hexanoate and the C Q-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein. Cationic surfactants
  • the cationic surfactant is selected from the group consisting of catiomc mono-alkoxylated amine surfactants, cationic bis-alkoxylated amine surfactants and mixmres thereof.
  • the catiomc surfactant is preferably present at a level of from 0.1 % to 20% , more preferably from 0.4% to 7%, most preferably from 0.5% to 3 % by weight of the detergent composition.
  • the cationic surfactant can be a cationic mono-alkoxylated amine surfactant, which has the general formula I:
  • Rl is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms;
  • R 2 and R 3 are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R 2 and R 3 are methyl groups;
  • R 4 is selected from hydrogen (preferred), methyl and ethyl;
  • X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality;
  • A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and
  • p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8, with the proviso that if A is ethoxy and R4 is hydrogen and p is 1, R is not a C12-C14 alkyl group.
  • Particularly preferred ApR 4 groups are — CH2CH2OH, — CH2CH2CH2OH, — CH 2 CH(CH 3 )OH and — CH(CH3)CH OH, with — H 2 CH 2 OH being particularly preferred.
  • Preferred R* groups have no greater than 10 carbon atoms, or even no greater than 8 or 9 carbon atoms.
  • Preferred R* groups are linear alkyl groups.
  • Linear R 1 groups having from 8 to 11 carbon atoms, or from 8 to 10 carbon atoms are preferred.
  • Such a catiomc surfactant which is highly preferred has a formula wherein Ri is a Cg-Ci ⁇ alkyl group, p is 1, A is ethoxy and R2 and R3 are methyl groups.
  • Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula
  • R* is C10-C1 hydrocarbyl and mixmres thereof, especially C10-C14 alkyl, preferably C Q and C 2 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
  • the cationic surfactant can also be a cationic bis-alkoxylated amine surfactant, which has the general formula II:
  • R 1 is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms;
  • R 2 is an alkyl group containing from one to three carbon atoms, preferably methyl;
  • R 3 and R 4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl,
  • X " is an anion such as chloride, bromide, ethylsulfate, sulfate, or the like, sufficient to provide electrical neutrality.
  • a and A' can vary independently and are each selected from C -C4 alkoxy, especially ethoxy, (i.e., -CH2CH2O-), propoxy, butoxy and mixmres thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.
  • R* is Ci ⁇ -C g hydrocarbyl and mixmres thereof, preferably C10, C12, C 4 alkyl and mixmres thereof.
  • X is any convenient anion to provide charge balance, preferably chloride.
  • cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula:
  • Rl is i ⁇ -Cig hydrocarbyl, preferably C10- 14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R 2 is C -C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
  • the detergent components or compositions can contain additional water-soluble builder compounds.
  • Suitable water-soluble builder compounds include carboxylate materials, borates, phosphates, and mixmres of any of the foregoing.
  • 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.
  • the carboxylate builder suitable for use in the detergent composition or components thereof can be monomeric or oligomeric (containing up to four carboxylate groups) in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable, additional carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Carboxylates 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 umaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Carboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
  • Carboxylates 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.
  • Carboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent 5 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 additional carboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or dimeric polycarboxylate chelating agents or mixmres thereof with their salts e.g. citric acid or citrate/citric acid mixmres are also contemplated as useful builder components.
  • Partially soluble or insoluble builder compound Partially soluble or insoluble builder compound
  • the detergent component or compositions may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
  • Examples of largely water insoluble builders include the sodium aluminosilicates.
  • Suitable aluminosilicate zeolites have the unit cell formula Na z [(Al ⁇ 2) z (Si ⁇ 2)y] . XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 25 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 namrally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixmres thereof. Zeolite A has the formula
  • Zeolite X has the formula Na86 [(AlO 2 )86(Si ⁇ 2)l06]- 2 76 H 2 O.
  • zeolite MAP builder Another preferred aluminosilicate zeolite is zeolite MAP builder.
  • the zeolite MAP can be present at a level of from 1 % to 80% , more preferably from 15% to 40% by weight of the compositions.
  • Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
  • zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
  • the zeolite MAP detergent builder has a particle size, expressed as a d5Q value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.
  • the d5o value indicates that 50% by weight of the particles have a diameter smaller than that figure.
  • the particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d5Q values are disclosed in EP 384070A.
  • the detergent components or compositions 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.
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.
  • iminodiacetic acid-N-2- hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2- hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
  • EP-A-476,257 describes suitable amino based sequestrants.
  • EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
  • EP-A- 528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-l,2,4-tricarboxylic acid are also suitable.
  • Glycinamide- N.N' -disuccinic acid (GADS), ethylenediamine-N-N' -diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N' -disuccinic acid (HPDDS) are also suitable.
  • Organic peroxyacid bleaching system is also suitable.
  • a preferred feature of detergent compositions or components 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 mixmres 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 mixmres 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 NaB0 2 H 2 ⁇ 2.3H2 ⁇ .
  • Alkali metal percarbonates particularly sodium percarbonate are preferred perhydrates herein.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na 2 C ⁇ 3.3H2 2, and is available commercially as a crystalline solid.
  • Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions or components thereof.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as
  • L is a leaving group and X is essentially any functionality, such that on 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 acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789.
  • Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash
  • Preferred L groups are selected from the group consisting of:
  • R .1 is an alkyl, aryl, or alkaryl group containing
  • R is an alkyl chain containing from 1 to 8 carbon atoms
  • R 4 is H or R 3
  • R 3 ⁇ is an alkenyl chain containing from 1 to 8 carbon atoms
  • Y is H or a solubilizing group.
  • Any of R 1 , R3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups
  • the preferred solubilizing groups are -S0 3 " M + , -C0 2 " M + , -SO ⁇ ' M “1” , -N + (R 3 ) 4 X " and 0 ⁇ N(R 3 ) 3 and most preferably -S0 3 " M + and -C0 2 " M +
  • SWSTmiTE SUET (RULE 26) 3 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,N NI tetra acetylated alkylene diamines wherein d e 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 nonanoyloxy benzene 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:
  • R 1 is an alkyl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene group containing from 1 to 14 carbon atoms
  • R 5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating 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 peroxyacids 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.
  • Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammomum substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammomum methylene benzoyl caprolactams and the trialkyl ammomum 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 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: R 1 — C - N — R 2 — C — OOH
  • Ri 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 peroxyacids 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 is one or more additional enzymes.
  • Preferred additional enzymatic materials include the commercially available cellulases, endolases, cutinases, lipases, 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 incorporated into the composition in accordance with the invention at a level of from 0.0001 % to 2% active enzyme by weight of the composition.
  • Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001 % to 2% by weight, preferably 0.001 % to 1 % by weight, most preferably from 0.001 % to 0.5% by weight of the compositions.
  • the lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp. , Thermomvces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein.
  • a preferred lipase is derived from Pseudomonas pseudoalcaligenes. which is described in Granted European Patent, EP-B-0218272.
  • Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
  • the detergent components or compositions when formulated for use in machine washing compositions preferably comprise a suds suppressing system present at a level of from 0.01 % to 15%, preferably from 0.05% to 10% . most preferably from 0.1 % to 5 % by weight of the composition.
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
  • antifoam compound any compound or mixmres of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
  • Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component.
  • silicone antifoam compounds as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
  • Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
  • Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • Suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic 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 Cjg-C g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70% , by weight;
  • a highly preferred particulate suds suppressing system is described in EP-A- 0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50 °C to 85 °C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms.
  • EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixmre thereof, with a melting point of from 45 °C to 80°C.
  • Polymeric dve transfer inhibiting agents may also comprise from 0.01 % to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
  • the polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.
  • Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula :
  • A is NC, CO, C, -O-, -S-, -N-; x is O or 1 ;
  • R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group is part of these groups.
  • the N-0 group can be represented by the following general structures : O
  • RI, 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-0 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 die N-O functional group is part of said R group.
  • R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of die 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 components or 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 available from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000).
  • PVP K-15 is also available from ISP Corporation.
  • Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
  • the detergent components or 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 components or compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
  • Said polyvinylimidazoles preferably have an average molecular weight of from 2.500 to 400,000.
  • the detergent components or 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-hydroxy ethyl 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.
  • R is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • the brightener is 4,4'-bis[(4- amlino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • R is anilino
  • R2 is mo ⁇ hilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-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/polyoxyethylene terephthalate polyesters of U.S.
  • Gosselink et al. for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG").
  • SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721 ,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic -capped block polyester oligomeric compounds of U.S.
  • Gosselink for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5- sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S.
  • SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the C -C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S.
  • methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution.
  • Such materials are available as METOLOSE SMI 00 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.
  • SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 Lagasse et al. ; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage.
  • Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al..
  • Other classes include: (III) anionic terephthalate- based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al.;
  • optional ingredients include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
  • the detergent components and particularly the detergent compositions comprising the components 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 components or 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 reguiants, hydrotropes, such as salts of toluene sulphonate, xylene sulphonate or cumene sulphonate, enzyme stabilizing agents, suds reguiants, 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).
  • neutralizing agents e.g., buffering agents, phase reguiants, hydrotropes, such as salts of toluene sulphonate, xylene sulphonate or cumene sulphonate
  • enzyme stabilizing agents such as salts of toluene sulphonate,
  • the detergent component of the invention can be made via a variety of methods, including agglomeration or extrusion of a mixmre of the various compounds comprised, or to be comprised in the detergent component, but preferably via spray-drying of a mixmre or slurry comprising the water-soluble cationics and the carboxylate-containing polyelectrolyte compounds. This can be done via any method of spray-drying, known in the art.
  • the detergent component is preferably a spray-dried granule or particle or powder.
  • the cationic water-soluble compound is preferably combined with a carrier material.
  • the detergent component preferably forms part of a detergent composition.
  • the compositions in accordance with the invention can take a variety of physical forms including granular, tablet, flake, pastille and bar forms.
  • the compositions are particularly the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.
  • compositions can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach.
  • 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 40% or preferably not more than 15% of the particles are greater than 1.8mm in diameter and not more than 40% or preferably 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 typically is of at least 500 g/litre, more preferably from 600 g/litre to 1200 g/litre, preferably .
  • a lower bulk density of the composition containing the component is preferred.
  • 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 ⁇ , more preferably from 5 to llKN/cm 2 so that the compacted solid has a minimum hardness of 176N to 275N, preferably from 195N to 245N, measured by a C100 hardness test as supplied by I. Holland instruments.
  • This process may be used to prepare homogeneous or layered tablets of any size or shape.
  • Preferably tablets are symmetrical to ensure the uniform dissolution of the tablet in the wash solution.
  • Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent component but preferably a composition comprising the component 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
  • the dispensing device containing the detergent product is placed inside the drum before the commencement of the wash, either before, or 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 arrangement 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 mixmres thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of a machine dishwashing component or preferably composition, comprising the component 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.
  • Protease Proteolytic enzyme having 3.3% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Savinase
  • Protease I Proteolytic enzyme having 4% by weight of active enzyme, as described in WO 95/10591 , sold by Genencor Int. Inc.
  • Alcalase Proteolytic enzyme having 5.3% by weight of active enzyme, sold by NOVO Industries A/S
  • Amylase Amylolytic enzyme having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T
  • Lipase Lipolytic enzyme having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Lipase (1) Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Ultra
  • Endoglucanase enzyme having 1.5% by weight of active enzyme, sold by NOVO Industries A/S
  • Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename Dequest
  • PEO Polyethylene oxide with an average molecular weight of 50,000
  • SRP 1 Anionically end capped poly esters
  • SRP 2 Diethoxylated poly (1, 2 propylene terephtalate) short block polymer
  • PEI Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen
  • Example 1 In the following examples all levels are quoted as % by weight of the composition: Example 1
  • compositions M to O of bulk density 750 g/litre are compositions according to the invention:
  • laundry bar detergent compositions are examples in accord with the invention.
  • Nonionic C13-C15 mixed ethoxy lated/propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5 sold under the tradename Plurafac LF404 by BASF GmbH

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

Abstract

Cette invention concerne des compositions détergentes solides ou granulaires, des composants de ces dernières ou, encore, des particules séchées par vaporisation, lesquels comprennent un ou plusieurs composés poly-électrolytes contenant un carboxylate. Ces compositions comprennent également un adjuvant ou possèdent des propriétés dispersantes. Elles comprennent en outre un ou plusieurs composés cationiques, lesquels consistent en des composés de (poly)amine éthoxylés, (partiellement) quaternisés et cationiques qui possèdent des propriétés d'élimination/d'anti-redéposition d'argile et de terre. Ces compositions peuvent être utilisées dans des machines à laver ou des lave-vaisselle.
PCT/US1997/016705 1996-09-24 1997-09-22 Compositions detergentes ou composant de ces dernieres WO1998013452A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP10515746A JP2000506935A (ja) 1996-09-24 1997-09-22 洗剤組成物または成分
AU44882/97A AU4488297A (en) 1996-09-24 1997-09-22 Detergent composition or component
BR9712839-2A BR9712839A (pt) 1996-09-24 1997-09-22 Composição ou componente detergente
CA002265942A CA2265942A1 (fr) 1996-09-24 1997-09-22 Compositions detergentes ou composant de ces dernieres
EP97943400A EP0929626A4 (fr) 1996-09-24 1997-09-22 Compositions detergentes ou composant de ces dernieres

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9619928A GB2317394A (en) 1996-09-24 1996-09-24 Detergent compositions
GB9619928.6 1996-09-24
GBGB9713946.3A GB9713946D0 (en) 1997-07-02 1997-07-02 Detergent composition or component
GB9713946.3 1997-07-02

Publications (1)

Publication Number Publication Date
WO1998013452A1 true WO1998013452A1 (fr) 1998-04-02

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EP (1) EP0929626A4 (fr)
JP (1) JP2000506935A (fr)
CN (1) CN1238801A (fr)
AR (1) AR010477A1 (fr)
AU (1) AU4488297A (fr)
BR (1) BR9712839A (fr)
CA (1) CA2265942A1 (fr)
WO (1) WO1998013452A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005052105A1 (fr) * 2003-11-21 2005-06-09 Henkel Kommanditgesellschaft Auf Aktien Systeme adjuvant soluble
US7041633B2 (en) * 2000-10-12 2006-05-09 The Procter & Gamble Company Process for preparing tablets
US7348303B2 (en) 2002-12-04 2008-03-25 Clariant International, Ltd. Quaternary ammonium composition

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5013758B2 (ja) * 2005-06-14 2012-08-29 ライオン株式会社 自動食器洗い乾燥機用洗浄剤組成物
JP5225543B2 (ja) * 2005-06-29 2013-07-03 株式会社Ａｄｅｋａ 自動食器洗浄機用洗浄剤組成物
SG173230A1 (en) * 2010-01-25 2011-08-29 Rohm & Haas Laundry detergent bar composition
JP5723655B2 (ja) * 2011-04-01 2015-05-27 ライオン株式会社 食器洗浄機用洗剤
JP2018104705A (ja) * 2016-12-27 2018-07-05 花王株式会社 繊維製品用粉末洗浄剤組成物
WO2018124090A1 (fr) * 2016-12-27 2018-07-05 花王株式会社 Composition détergente en poudre pour article textile
KR20230009905A (ko) * 2020-05-13 2023-01-17 그라파이트 이노베이션 앤드 테크놀로지스 인크. 코팅용 조성물, 코팅 및 이의 방법

Citations (1)

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Publication number Priority date Publication date Assignee Title
US4664848A (en) * 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties

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Publication number Priority date Publication date Assignee Title
CA2255011A1 (fr) * 1996-05-17 1997-11-27 Stuart Clive Askew Composition detergente

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Publication number Priority date Publication date Assignee Title
US4664848A (en) * 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties

Non-Patent Citations (1)

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Title
See also references of EP0929626A4 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7041633B2 (en) * 2000-10-12 2006-05-09 The Procter & Gamble Company Process for preparing tablets
US7348303B2 (en) 2002-12-04 2008-03-25 Clariant International, Ltd. Quaternary ammonium composition
EP2423180A1 (fr) 2002-12-04 2012-02-29 Clariant Finance (BV) Limited Composition d'ammonium quaternaire
WO2005052105A1 (fr) * 2003-11-21 2005-06-09 Henkel Kommanditgesellschaft Auf Aktien Systeme adjuvant soluble

Also Published As

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BR9712839A (pt) 1999-11-16
CA2265942A1 (fr) 1998-04-02
AU4488297A (en) 1998-04-17
CN1238801A (zh) 1999-12-15
EP0929626A1 (fr) 1999-07-21
AR010477A1 (es) 2000-06-28
EP0929626A4 (fr) 2000-01-05
JP2000506935A (ja) 2000-06-06

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