WO1998013453A1 - Detergent particle - Google Patents

Detergent particle Download PDF

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Publication number
WO1998013453A1
WO1998013453A1 PCT/US1997/016706 US9716706W WO9813453A1 WO 1998013453 A1 WO1998013453 A1 WO 1998013453A1 US 9716706 W US9716706 W US 9716706W WO 9813453 A1 WO9813453 A1 WO 9813453A1
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WO
WIPO (PCT)
Prior art keywords
cationic
group
alkyl
moiety
hydroxyalkyl
Prior art date
Application number
PCT/US1997/016706
Other languages
English (en)
French (fr)
Inventor
Scott Donoghue
Achille Doumen
Steven Ongena
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB9619921A external-priority patent/GB2317392A/en
Priority claimed from GB9623067A external-priority patent/GB2319038A/en
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU44883/97A priority Critical patent/AU4488397A/en
Priority to EP97943401A priority patent/EP0929627A4/en
Priority to CA002265891A priority patent/CA2265891A1/en
Priority to BR9714343-0A priority patent/BR9714343A/pt
Priority to JP51574798A priority patent/JP3773542B2/ja
Publication of WO1998013453A1 publication Critical patent/WO1998013453A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines

Definitions

  • the present invention relates to a particle containing cationic compounds with particulate/ clay-soil removal/anti-redeposition properties and a carrier material, for use in detergent compositions or components thereof and a process for making the particle.
  • Clay soil particles generally comprise negatively charged layers of aluminosilicates and positively charged cations (e.g. calcium) which are positioned between and hold together the negatively charged layers.
  • EP-B-1 1 1 965 discloses the use in detergents of cationic compounds, which have both clay-soil removal and anti-redeposition properties.
  • US 4.659,802 and US 4,664,848 describe quaternized amines which have clay-soil removal and anti-redeposition properties and which can be used in combination with anionic surfactants.
  • the Applicants have now found that these problems can be ameliorated by the use of a carefully chosen ratio of cationic compound to carrier material, or when a specific carrier material absorbs or encapsulates the cationic. (partially) quaternized ethoxylated (poly) amines (which have clay-soil removal/anti-redeposition properties).
  • the present invention therefor provides a particle in which the cationic compound is absorbed or bound or encapsulated in such a way that the particle formed is water-soluble, flowable and (temperature-) stable, and has an acceptable odour and colour in the final detergent.
  • carrier materials used herein are that they also have detergent properties, such as builder capacities.
  • Particles produced according to the preferred process for making the particle are found to be very effective, having particularly good flowability, stability and solubility, whilst overcoming malodour and discolouration problems.
  • compositions or components thereof, containing this particle are also envisaged herein.
  • the present invention relates to a particle comprising one or more cationic compounds, which are cationic, (partially) quaternized ethoxylated (poly) amine compounds with particulate/ clay-soil removal / anti-redeposition properties, and a carrier material and optionally other material. Furthermore the present invention relates to a process for making this particle and the use thereof in detergent compositions or components thereof.
  • the present invention relates to a particle comprising
  • a water-soluble cationic compound having clay soil removal/anti- redeposition properties which is selected from the group consisting of:
  • a 1 is— C — , — CO— , — NCN — , — CN — , — OCN— , R R R R R R R
  • R is H or C1 -C4 alkyl or hydroxyalkyl
  • R is C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2- 3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no O-N bonds are formed
  • each R ⁇ is C ⁇ - C ⁇ alkyl or hydroxyalkyl, the moiety -L-X, or two R ⁇ together form the moiety - (CH2) r -A2-(CH2).y-, wherein A ⁇ is -O- or -CH2-, r is 1 or 2, s is 1 or 2 and r + s is 3 or 4
  • each R ⁇ is Cj-Cg alkyl or hydroxyalkyl, benzyl, the moiety L-X, or two R- or one R2 and one R ⁇ together form the moiety -(CH2) r -A2-(CH2),s-;
  • R ⁇ is a
  • the invention also relates to a particle comprising:
  • the particle of the present invention comprises a water-soluble cationic compound and one or more powdered carrier materials, present in a ratio from 1 : 15 to 4: 1 by weight, more preferably from 1 :7 to 1 :1, most preferably from 1 :4 to 1 : 1.5 by weight.
  • the present invention provides a particle comprising a water-soluble cationic compound and one or more aluminosilicate carrier materials.
  • detergent ingredients can be present in the particle, preferably anionic surfactants and/ or polyethylene glycols (as described herein).
  • the particle size of the particles in accord with the present invention should preferably be such that no more of than 15% of the particles are greater than 1.8mm in diameter and no more than 15% of the particles are smaller than 0.25mm in diameter.
  • the mean particle size is such that 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.
  • An essential feature of the present invention is a water-soluble cationic compound which has particulate/ clay-soil removal/anti-redeposition properties and which is selected from the group consisting of cationic mono- di- and polyamines.
  • the ratio of cationic compound to the powdered carrier material and preferably to the aluminosilicate carrier material is from 1 :15 to 4: 1 by weight, more preferably from 1 :7 to 1 :1, most preferably from 1 :4 to 1 : 1.5 by weight.
  • the water-soluble cationic compound is preferably present in the detergent composition 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 cationic compound does not have a desirable colour, particularly when the compound is not white, the cationic compound can be discoloured before incorporation in the particle of the invention by any standard method.
  • the water-soluble cationic compounds of the present invention which are useful in granular detergent compositions or components thereof, include ethoxylated cationic monoamines, ethoxylated cationic diamines and ethoxylated cationic polyamines as previously defined.
  • R ⁇ can be branched
  • Rl is preferably C2-C( j alkylene for the ethoxylated cationic diamines.
  • Each R ⁇ is preferably methyl or the moiety -L-X; each R ⁇ is preferably C ⁇ -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, MeOSO3- and the like. Particularly preferred counter anions are Cl- and Br-.
  • 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 O) (CH2CH2.O réelle ].
  • the moieties -(R 6 O)m- and - (CH2CH2 ⁇ )n- of the polyoxyalkylene moiety can be mixed together or preferably form blocks of -(R ⁇ ) m - and -(CH2CH2 ⁇ ) n - moieties.
  • R*> is preferably C3H6 (propylene);
  • m is preferably from 0 to about 5 and is most preferably 0, i.e. the polyoxyalkylene moiety consists entirely of the moiety -(CH2CH2O) n -.
  • the moiety -(CH2CH2 ⁇ ) ⁇ - preferably comprises at least about 85% by weight of the polyoxyalkylene moiety and most preferably 100% by weight (m is O).
  • M 1 and each M ⁇ are preferably an N+ group for the cationic diamines and polyamines.
  • Preferred ethoxylated cationic monoamines and diamines have the formula:
  • a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene)
  • b is 1 or 0.
  • n is preferably at least about 16, with a typical range of from about 20 to about 35.
  • n is at least about 12 with a typical range of from about 12 to about 42.
  • R4 linear, branched, or cyclic is preferably a substituted C3-C6 alkyl, hydroxyalkyl or aryl group; Al is preferably
  • n is preferably at least about 12, with a typical range of from about 12 to about 42; p is preferably from 3 to 6.
  • R ⁇ is a substituted aryl or alkaryl group
  • q is preferably 1 and R ⁇ is preferably C2-C alkylene.
  • R ⁇ is a substituted alkyl, hydroxyalkyl, or alkenyl group
  • R ⁇ is preferably a C2-C3 oxyalkylene moiety
  • R ⁇ is preferably C2-C3 alkylene.
  • ethoxylated cationic polyamines can be derived from polyamino amides such as:
  • ethoxylated cationic polyamines can also be derived from polyaminopropyleneoxide derivatives such as:
  • each c is a number from 2 to about 20.
  • Another essential component of the particle of the present invention is one or more powdered carrier materials.
  • the ratio of cationic compound to the powdered carrier material and preferably to the aluminosilicate carrier material is from 1 :15 to 2:1 by weight, more preferably from 1 :7 to 1 : 1 , most preferably from 1 :4 to 1 : 1.5 by weight.
  • the carrier material will preferably be a white, free-flowing material with a low water content, preferably less than 25%. more preferably less than 15%, most preferably less than 10% by weight of the carrier material.
  • the carrier material preferably has a porous or crystalline structure, providing thus a carrier material with a high surface area for a better interaction with the water-soluble cationic compound (and optionally other detergent ingredients).
  • Preferred carrier materials are certain inorganic and organic powders or salts, more preferably certain water-soluble and partially or largely water insoluble builder materials.
  • Suitable organic powders include alkyl or alkylene sulphates, borates or phosphates, preferably alkyl sulphates.
  • Preferred inorganic powdered carrier materials include carbonates, bicarbonates. silicates, sulphates and phosphates.
  • Suitable water-soluble builder materials include the water soluble monomeric polycarboxylates, or their acid forms.
  • a highly preferred carrier material is citrate or citric acid.
  • carrier materials which are largely water insoluble builder materials and which are essential in the second aspect of the invention, include the aluminosilicates, preferably sodium aluminosilicates.
  • Zeolites are highly preferred. Suitable aluminosilicate zeolites have the unit cell formula Na z [(AlO2) z (SiO2)y]- xH ? O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably such that no more than 25%, more preferably no more than 10%. most preferably no more than 5% structure bound water is present, by weight of the aluminosilicate zeolite.
  • the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials for use herein are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof.
  • zeolite MAP builder Another preferred aluminosilicate zeolite carrier material is zeolite MAP builder.
  • 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 alumino silicates especially zeolite MAP, have 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 d50 values are disclosed in EP 384070A.
  • the carrier material comprised in the particle of the present invention can comprise a single carrier material.
  • Preferred carrier materials are mentioned above.
  • Alumino silicate materials are particularly preferred.
  • one of the preferred carrier materials forms at least 50%, more preferably more than 70%, most preferably more than 80% by weight of the carrier material in the particle.
  • the particle can be made by mixing or spray drying of the carrier material and cationic compound, and optionally other ingredients.
  • the cationic compound is purified before formation of the particle.
  • a particularly preferred purification step can be the removal from the cationic compound of volatile compounds which can cause a malodour. by use of a steam stripping process, whereafter the cationic compound can be incorporated in a particle in accord with the present invention.
  • An example is disclosed in EP 1 1 1 965A.
  • the particle of the present invention is made via an agglomeration process.
  • This preferred agglomeration process comprises the following steps:
  • agglomeration techniques used for step (B) are described in more detail in the Applicants co-pending European Application EP-A-643130.
  • the melted compound of the present invention is intimately mixed with the powdered carrier material in a high shear mixer, such as a Loedige® CB unit.
  • the agglomerate particles may be finished in further mixing units, such as a Loedige® KM, or a fluidised bed.
  • the agglomerate particles are preferably cooled in a fluidised bed cooler by passing cool air.
  • Optional detergent ingredients can also be added in step (b). However, preferably optional detergent ingredients are added to the melted compound before step (b).
  • step (c) the agglomerate particle is dried before cooled, preferably by use of a fluid bed dryer by passing hot air.
  • Another technique for obtaining the particle of the present invention is by use of spray drying techniques. Suitable techniques for spraying the melted compound onto powdered carrier material(s) are described in the Applicants co-pending Patent Application WO9405761, published on 17th March 1994.
  • Optional ingredients can be comprised in the particle of the present invention, which can be selected from the additional detergent components described hereinafter. When comprised in the particle they are preferably present at a level of :rom 0.05% to 30%, more preferably from 0.5% to 20%, most preferably from 1.0% to 15% by weight of the particle.
  • Preferred optional detergent ingredients present in the particle of the present invention are anionic surfactants, preferably alkyl sulphates, alkyl benzene sulphonates or alkyl sulphates condensed with ethylene oxide and polyethylene glycols, preferably with a molecular weight of from 5000 to 10000.
  • Another preferred ingredient in the particles of the present invention is a cationic polymers, which has clay-soil removal/ anti-redeposition properties, as described in the next paragraph.
  • Detergent compositions or components thereof are cationic polymers, which has clay-soil removal/ anti-redeposition properties, as described in the next paragraph.
  • the particle of the present invention can be incorporated in detergent compositions (or be combined with components thereof).
  • the particle in accord with the invention is present in a detergent composition thereof, this will be done in such a manner that the water-soluble cationic compound is preferably present in the detergent composition 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 detergent compositions or components thereof preferably contain one or more additional detergent components selected from (additional) surfactants, (additional) builders, sequestrants, bleach, bleach precursors, bleach catalysts, organic polymeric compounds, additional enzymes, suds suppressors, lime soap dispersants, additional soil suspension and anti-redeposition agents soil releasing agents, perfumes and corrosion inhibitors.
  • additional detergent components selected from (additional) surfactants, (additional) builders, sequestrants, bleach, bleach precursors, bleach catalysts, organic polymeric compounds, additional enzymes, suds suppressors, lime soap dispersants, additional soil suspension and anti-redeposition agents soil releasing agents, perfumes and corrosion inhibitors.
  • the detergent compositions or components thereof preferably contain an (additional) surfactant selected from anionic, nonionic. cationic. ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
  • ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
  • the detergent compositions or components thereof 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 unsaturated Cp-C, dominant monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C ⁇ -C , . diesters), N-acyl sarcosinates.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
  • Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C]7 acyl-N-(C ⁇ -C4 alkyl) and -N-(Cj-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Alkyl sulfate surfactants are preferably selected from the linear and branched primary C i o- 18 alkyl sulfates, more preferably the C i ⁇ -C ⁇ 5 branched chain alkyl sulfates and the C ⁇ 2-C ] 4 linear chain alkyl sulfates.
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the Cio-C j g alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule.
  • the alkyl ethoxysulfate surfactant is a C j ⁇ -C i g, most preferably C ⁇ ⁇ -C ⁇ 5 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
  • a particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
  • Anionic sulfonate surfactant Anionic sulfonate surfactant
  • Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester suifonates, C5-C22 primary or secondary alkane sulfonates, Cg-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates. fatty oleyl glycerol sulfonates. and any mixtures thereof.
  • 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 CFbCOO'M " wherein R is a Cg to Cjg alkyl group, x ranges from O to 10. and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation.
  • Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRj-CHR2-O)-R3 wherein R is a Cg to C jg 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, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
  • Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl- 1 -undecanoic acid, 2-ethyl- 1 -decanoic acid, 2-propyl- 1-nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors.
  • alkali metal sarcosinates of formula R-CON (Ri) CH2 COOM, wherein R is a C5-CJ 7 linear or branched alkyl or alkenyl group, Ri is a C1-C4 alkyl group and M is an alkali metal ion.
  • R is a C5-CJ 7 linear or branched alkyl or alkenyl group
  • Ri is a C1-C4 alkyl group
  • M is an alkali metal ion.
  • any alkoxylated nonionic surfactants are suitable herein.
  • the ethoxylated and propoxylated nonionic surfactants are preferred.
  • Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxy late/propoxy late condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
  • condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
  • Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R 2 CONR 1 Z wherein : RI is H, C1-C4 hydrocarbyl. 2-hydroxy ethyl, 2- hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C ⁇ or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R2 is a C5- C31 hydrocarbyl, preferably straight-chain C5-C 19 alkyl or alkenyl, more preferably straight-chain C9-C ⁇ alkyl or alkenyl, most preferably straight-chain C ⁇ j-C 57 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Nonionic fattv acid amide surfactant Nonionic fattv acid amide surfactant
  • Suitable fatty acid amide surfactants include those having the formula: R ⁇ CON(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, C]-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4 ⁇ ) x H, where x is in the range of from 1 to 3.
  • Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565.647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
  • Preferred alkylpolyglycosides have the formula
  • R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
  • the glycosyl is preferably derived from glucose.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula R3(OR ) x N ⁇ (R5)2 wherein R- is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R ⁇ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are Cio-Cj g alkyl dimethylamine oxide, and CjQ-lg 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 heterocychc secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable betaines are those compounds having the formula R(R')2N + R2COO" wherein R is a Cg-Cjg hydrocarbyl group, each R is typically C1-C3 alkyl, and R 2 is a C1-C5 hydrocarbyl group.
  • Preferred betaines are C 12- 18 dimethyl-ammonio hexanoate and the C ⁇ Q.
  • Complex betaine surfactants are also suitable for use herein. Cationic surfactants
  • Suitable cationic surfactants to be used in the detergent compositions or components thereof, herein include the quaternary ammonium surfactants selected from mono Cg-C j 6, preferably C ⁇ -C ] Q N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • cationic surfactants which can be used in the detergent compositions or components thereof, for use herein are cationic ester surfactants.
  • the cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group.
  • Suitable cationic ester surfactants including choline ester surfactants, have for example been disclosed in US Patents Nos. 4228042, 4239660 and 4260529.
  • ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i.e. of three atoms chain length), preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms.
  • the atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain.
  • spacer groups having, for example, -O-O- (i.e. peroxide), - N-N-.
  • spacer groups having, for example - CFb-O- CH2- and -CH2-NH-CH2- linkages are included.
  • the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.
  • the detergent composition or components thereof can comprise additional polymeric cationic ethoxylated amine compounds with particulate/ clay-soil removal/ anti- redeposition, selected from the group consisting of water-soluble cationic polymers.
  • These polymers comprise a polymer backbone, at least 2M groups and at least on L- X group, wherein M is a cationic group attached to or integral with the backbone; X is a nonionic group selected from the group consisting of H, C ⁇ -CA alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof; and L is a hydrophilic chain connecting groups M and X or connecting X to the polymer backbone.
  • the polymeric cationic ethoxylated amine compounds can be present in detergent compositions at a level of from 0.01% to 30%, more preferably from 0.1% to 15%, most preferably from 0.2% to 3% by weight of the detergent composition.
  • polymer backbone refers to the polymeric moiety to which groups M and L-X are attached to or integral with. Included within this term are oligomer backbones (2 to 4 units), and true polymer backbones (5 or more units).
  • 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 polyethers, 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 mixtures thereof.
  • M can be any compatible cationic group which comprises an N + (quartemary), positively charged center.
  • the quartemary positively charged center can be represented by the following general structures E and F:
  • M groups are those containing a quartemary center represented by general structure E.
  • the cationic group is preferably positioned close to or integral with the polymer backbone.
  • the positive charge of the N + centres is offset by the appropriate number of counter anions.
  • Suitable counter anions include Cl", Br", SO32-, SO4-", PO42-, MeOSO3" and the like.
  • Particularly preferred counter anions are Cl" and Br.
  • X can be a nonionic group selected from hydrogen (H), C ] -C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof.
  • the preferred ester or ether groups are the acetate ester and methyl ether, respectively;
  • the particularly preferred nonionic groups are H and the methyl ether.
  • the cationic polymers suitable for use in granular detergent compositions 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 nonrepeating sequence.
  • the units which contain groups M and groups L-X can comprise 100% of the cationic polymers of the present invention.
  • inclusion of other units (preferably nonionic) in the polymers is also permissible.
  • other units include acrylamides, vinyl ethers and those containing unquaternized tertiary amine groups (M * ) containing an N centre.
  • M * unquaternized tertiary amine groups
  • These other units can comprise from 0% to about 90% of the polymer (from about 10% to 100% of the polymer being units containing M and L-X groups, including M ⁇ -L-X groups).
  • 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 -[(RO) m (CH2 c ⁇ 2°)n
  • the moieties -(R'O) TO - and - (CH2CH2 ⁇ ) w - of the polyoxyalkylene moiety can be mixed together, or preferably form blocks of -(R'O) - and -(CH2CH2 ⁇ ) ⁇ - moieties.
  • R' is preferably C3H6 (propylene); m is preferably from 0 to about 5, and most preferably 0; i.e. the polyoxyalkylene moiety consists entirely of the moiety -(CH2CH2O),,-.
  • the moiety -(CH2CH2 ⁇ ) n - 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:
  • One class of suitable cationic polymers are derived from polyurethanes, polyesters, polyethers, polyamides and the like. These polymers comprise units selected from those having formulas I, II and III:
  • R R X is 0 or 1 ;
  • R is H or C1-C4 alkyl or hydroxyalkyl;
  • Rl is C2-C12 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to abut 20 oxyalkylene units provided that no O-O or O-N bonds are formed with A ⁇ ; when x is 1, R 2 is -R 5 - except when A* is
  • R3 is -R 5 -;
  • R A is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R )fc- [(C3H6 ⁇ ) m (CH2CH2 ⁇ ) utilizat]-X;
  • R 5 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene, or alkarylene; each R° is C 1 4 alkyl or hydroxyalkyl, or the moiety - (CH 2 ) r -A -(CH2)s-, wherein A 2 is -O- or -CH2-;
  • R 7 is H or R 4 ;
  • R» is C 2 -C 3 alkylene or hydroxyalkylene;
  • X is H,
  • R ⁇ is C [ -C 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 -[(C3HgO) (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 about 20; the number of u, v and w are such that there are at least 2 N + centers and at least 2 X groups.
  • A* is preferably
  • a 2 is preferably -O-; x is preferably 1 ; and R is preferably H.
  • Rl can be linear (e.g. -CH 2 -CH2-CH 2 -,
  • R 1 is preferably C2-C6 alkylene or phenylene, and most preferably C2-C6 alkylene (e.g. ethylene, propylene, hexamethylene).
  • R 2 is preferably -OR 5 - or -(OR 8 )y-;
  • R3 is preferably -R 5 O- or -(OR 8 ) ⁇ -;
  • 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 cationic polymers are derived from polyacrylates, polyacrylamides, polyvinylethers and the like. These polymers comprise units selected from those having formulas IV, V and VI.
  • R is H or C1-C4 alkyl or hydroxyalkyl; R* is substituted C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or C2-C3 oxyalkylene; each R 2 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; each R ⁇ is C1-C4 alkyl or hydroxyalkyl, the moiety -(R 2 )A-[(C3H6 ⁇ ) OT (CH 2 CH2 ⁇ ) n ]-X, or together form the moiety -(CH2) r -A 2 -(CH2 , wherein A 2 is -O- or -CH2-; each R 4 is C1-C4 alkyl or hydroxyalkyl, or two R 4 together form the moiety -(CH2V-A 2 - (CH2) r ; X is H, 0
  • R 5 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 ⁇ ) ⁇ - comprises at least about 85% by weight of the moiety -[(C3HgO), relief(CH 2 CH2 ⁇ ) admir]-
  • 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 Ms preferably
  • a 2 is preferably -O-; R is preferably H. R ⁇ can be linear
  • R* is preferably substituted C2-Cg alkylene or substituted C2-C3 oxyalkylene, and most preferably
  • Each R 2 is preferably C2-C3 alkylene, each R ⁇ 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.
  • 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 -C]2 alkylene, hydroxyalkylene, alkenylene, cycloalkylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no O-N bonds are formed; each R 2 is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R 3 )H(C3H6 ⁇ ) (CH2CH2 ⁇ ) harness]-X; R 3 is 1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene; M' is an N+ or N centre; X is H,
  • R 4 is C1-C4 alkyl or hydroxyalkyl
  • d is 1 when M' is N+ and is 0 when M' is N
  • e is 2 when M' is N+ and is 1 when M' is N
  • k is 1 or 0
  • m and n are numbers such that the moiety -(CH2CH2 ⁇ ) shadow- comprises at least about 85%) by weight of the moiety -[ ⁇ H ⁇ O ⁇ C ⁇ CHoO),,]-
  • 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.
  • R' can be varied like R ⁇ of the polyurethene and like polymers; each R 2 is preferably methyl or the moiety -(R 3 )jfc- [(C 3 H 6 O) OT (CH2CH 2 O) cramp]-X; R 3 is preferably C 2 -C 3 alkylene; R 4 is preferably methyl; X is preferably H; k is preferably 0; m is preferably 0.
  • n is preferably at least about 6 when the number of M' and X groups is 2 or 3; n is most preferably at least about 12, with a typical range of from about 12 to about 42 for all ranges of x + y + z.
  • x + y + z is from 2 to about 40 and preferably from 2 to about 20.
  • x + y + z can range from 2 to 9 with from 2 to 9 N+ centres and from 2 to 1 1 X groups.
  • x + y + 7. is at least 10, with a preferred range of from 10 to about 42.
  • the M' groups are typically a mixture of from about 50 to 100%) N+ centres and from 0 to about 50% N centres.
  • Preferred cationic polymers within this class are derived from the C2-C3 polyalkyleneamines (x + y + z is from 2 to 9) and polyalkyleneimines (x + y + z is at least 10. preferably from 10 to about 42).
  • Particularly preferred cationic polyalkyleneamines and polyalkyleneimines are the cationic polyethyleneamines (PEA's) and polyethyleneimines (PEI's). These preferred cationic polymers comprise units having the general formula:
  • R 2 (preferably methyl), M', X, d, x, y, z and n are defined as before; a is 1 or O.
  • the PEAs used in preparing cationic polymers of the present invention have the following general formula:
  • x + y + z is from 2 to 9, and a is 0 or 1 (molecular weight of from about 100 to about 400).
  • a is 0 or 1 (molecular weight of from about 100 to about 400).
  • Each hydrogen atom attached to each nitrogen atom represents an active site for subsequent ethoxylation.
  • x + y + z is from about 3 to about 7 (molecular weight is from about 140 to about 310).
  • These PEA's can be obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. The common PEA's obtained are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA).
  • TETA triethylenetetramine
  • TEPA tetraethylenepentamine
  • the cogenerically derived mixture does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can also be present cyclic amines with side chains in which nitrogen atoms appear. See US Pat. No. 2,792,372 to Dickson, issues May 14, 1957, which describes the preparation of PEAs.
  • n is at least about 6.
  • y + z is from 4 to 9, suitable benefits are achieved when n is at least about 3.
  • n is at least about 12, with a typical range of about 12 to about 42.
  • the PEIs used in preparing the polymers of the present invention have a molecular weight of at least about 440 prior to ethoxylation, which represents at least about 10 units.
  • Preferred PEIs used in preparing these polymers have a molecular weight of from about 600 to about 1800.
  • the polymer backbone of these PEIs can be represented by the general formula:
  • x, y, and z represents a number of sufficient magnitude to yield a polymer having the molecular weights previously specified.
  • linear polymer backbones are possible, branch chains can also occur.
  • the relative proportions of primary, secondary and tertiary amine groups present in the polymer can vary, depending on the manner of preparation. The distribution of amine groups is typically as follows:
  • Each hydrogen atom attached to each nitrogen atom of the PEI represents an active site for subsequent ethoxylation.
  • These PEIs can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • Specific methods for preparing PEIs are disclosed in US Pat. No. 2,182,306 to Ulrich et al., issued Dec. 5, 1939; US Pat No. 3,033,746 to Mayle et al., issued May 8, 1962; US Pat. No. 2,208,095 to Esselmann et al., issued July 16, 1940; US Pat. No. 2,806,839 to Crowther, issued Sept. 17, 1957; and US Pat. No. 2,533,696 to Wilson, issued May 21, 1951 (all here
  • n is at least about 3 for the cationic PEIs.
  • the minimum degree of ethoxylation required for suitable clay soil removal/anti-redeposition performance can increase as the molecular weight of the PEI increases, especially much beyond about 1800.
  • the degree of ethoxylation for preferred polymers increases as the molecular weight of the PEI increases.
  • n is preferably at least about 12, with a typical range of from about 12 to about 42.
  • n is preferably at least about 24, with a typical range of from about 24 to about 42.
  • Suitable cationic polymers are those derived from the diallylamines. These polymers comprise units selected from those having formulas X and XI:
  • R ⁇ is C1-C4 alkyl or hydroxyalkyl, or the moiety -(R 2 ) - [(C 3 H6 ⁇ ), negligence(CH2CH2 ⁇ ) admir]-X;
  • R 2 is C1-C12 alkylene, hydroxyalkylene. alkylene, arylene or alkarylene; each R3 is C1-C4 alkyl or hydroxyalkyl. or together form the moiety -(CH2 - A-(CH2) , wherein A is -O- or -CH2-;
  • X is H.
  • R 4 is C1-C4 alkyl or hydroxyalkyl; k is 1 or 0; m and n are numbers such that the moiety -(C ⁇ C ⁇ O),,- comprises at least about 85% by weight of the moiety -[(C3H6 ⁇ ) w (CH2CH2 ⁇ ) rt ]-; m is from 0 to about 5; n is at least about 3; r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; x is 1 or 0; y is 1 when x is 0 and 0 when x is 1 ; the number of u and v are such that there are at least 2N+ centres and at least 2 X groups.
  • A is preferably -O-; R ⁇ is preferably methyl; each R- 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 thereof preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.
  • Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates. or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, phosphates, and mixtures of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Polycarboxylates containing three carboxy groups include, in particular, water- soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1, 3, 3 -propane tetracarboxylates and 1 ,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
  • Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
  • Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium poiymeta/phosphate in which the degree of polymerization ranges from about 6 to 21 , and salts of phytic acid.
  • Partially soluble or insoluble builder compound Partially soluble or insoluble builder compound
  • the detergent compositions or components thereof, of the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
  • Preferred largely insoluble builder compounds are aluminosilicate ion exchange materials, preferably zeolite A and zeolite MAP, as described above.
  • the detergent compositions or components thereof preferably contain as an optional component a heavy metal ion sequestrant.
  • heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
  • Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5% by weight of the compositions.
  • Suitable heavy metal ion sequestrants for use herein include organic phosphonates. such as the amino alkylene poly (alkylene phosphonates). alkali metal ethane 1 - hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • diethylene triamine penta methylene phosphonate
  • ethylene diamine tri methylene phosphonate
  • hexamethylene diamine tetra methylene phosphonate
  • hydroxy-ethylene 1,1 diphosphonate Preferred among the above species are diethylene triamine penta (methylene phosphonate).
  • Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.
  • ethylenediaminotetracetic acid such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.
  • EDDS ethyienediamine-N,N'-disuccinic acid
  • Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2 -hydroxy ethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.
  • iminodiacetic acid-N-2- hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl- 3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
  • EP-A-476,257 describes suitable amino based sequestrants.
  • EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
  • EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2- phosphonobutane-1.2,4-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.
  • a preferred feature of detergent compositions or component thereof is an organic peroxyacid bleaching system.
  • the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
  • the production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
  • Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches.
  • a preformed organic peroxyacid is incorporated directly into the composition.
  • Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
  • Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the form of the alkali metal, preferably sodium salt at a level of from 1% to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5% to 25% by weight of the compositions. Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection.
  • Suitable executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.
  • Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.
  • Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaB ⁇ 2H2 ⁇ 2 or the tetrahydrate NaBO 2 H2 ⁇ 2.3H O.
  • Alkali metal percarbonates particularly sodium percarbonate are preferred perhydrates herein.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid.
  • Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as
  • L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is O
  • 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 cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms
  • R 3 is an alkyl chain contai •ning from 1 to 8 carbon atoms.
  • R 4 is
  • R 5 is an alkenyl chain containing from 1 to 8 carbon atoms and Y is H or a solubilizing group.
  • Any of R 1 , R 3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups
  • 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*Nl tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 , 2 and 6 carbon atoms.
  • Tetraacetyl ethylene diamine (TAED) is particularly preferred.
  • alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyioxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
  • Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
  • R ⁇ 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.
  • Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-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.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
  • precursor compounds of the benzoxazin-type as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
  • R. 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 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 5 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.
  • Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
  • Another preferred ingredient useful in the detergent compositions or components thereof is one or more additional enzymes.
  • Preferred additional enzymatic materials include the commercially available cellulases, endolases, cutinases, amylases, lipases, 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, ct-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. (Additional) Organic polymeric compound
  • Organic polymeric compounds are preferred additional components of the detergent compositions or components thereof and are preferably present as components of any particulate components where they may act such as to bind the particulate component together.
  • organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, not being an quatemised ethoxylated (poly) amine clay-soil removal/ anti- redeposition agent in accord with the invention.
  • Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%. most preferably from 1% to 10% by weight of the compositions.
  • organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A- 1,596,756.
  • salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100.000, especially 40,000 to 80,000.
  • polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
  • Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
  • organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Further useful organic polymeric compounds are (additional) the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
  • the detergent 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 mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
  • Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component.
  • silicone antifoam compounds as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
  • Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
  • Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids, and salts thereof for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g.
  • fatty acid triglycerides fatty acid esters of monovalent alcohols
  • aliphatic C i g-C4Q 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.
  • aliphatic C i g-C4Q ketones e.g. stearone
  • N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuri
  • a preferred suds suppressing system comprises
  • antifoam compound preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
  • silica at a level of from 1 % to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;
  • silica silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight;
  • a dispersant compound most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1 :0.9 to 1 : 1.1 , at a level of from 0.5% to 10%, preferably 1% to 10% by weight;
  • a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW
  • an inert carrier fluid compound most preferably comprising a C ⁇ g-C i g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
  • a highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms.
  • EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C.
  • the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C.
  • the detergent compositions herein may also comprise from 0.01% to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
  • the polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can be cross-linked polymers.
  • Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula :
  • the N-O group can be represented by the following general structures :
  • RI, R2, and R3 are aliphatic groups, aromatic, heterocychc or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.
  • the N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
  • Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocychc groups.
  • R is selected from aliphatic, aromatic, alicyclic or heterocychc 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 heterocychc 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 aromaticheterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • R is an aromaticheterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
  • examples of these classes are polyamine oxides wherein R is a heterocychc compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
  • the polyamine N-oxides can be obtained in almost any degree of polymerisation.
  • the degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power.
  • the average molecular weight is within the range of 500 to 1000,000.
  • Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000.
  • the preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.
  • the detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000.
  • PVP polyvinylpyrrolidone
  • Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-l 5 (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-l 5 is also available from ISP Corporation.
  • Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
  • the detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents.
  • Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.
  • the detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
  • Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.
  • the detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.
  • Hydrophilic optical brighteners useful herein include those having the structural formula:
  • Rj is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino.
  • M is a salt-forming cation such as sodium or potassium.
  • Rj is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename
  • Tinopal-UNPA-GX by Ciba-Geigy Co ⁇ oration. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R] is anilino
  • R2 is N-2-hydroxyethyl-N-2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-aniiino-6-(N-2- hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Co ⁇ oration.
  • R ⁇ is anilino.
  • R2 is mo ⁇ hilino and M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-aniIino-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. Gosseiink.
  • 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.
  • Gosseiink 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 Gosseiink, 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.
  • Gosseiink 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 CJ-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-1 inked variety, see U.S. 4,201,824. Violland et al.;
  • the particle of the present invention can be introduced in the detergent component via a variety of methods, including dry-mixing and agglomerating of the various compounds comprised in the detergent component.
  • the detergent compositions or components thereof can have a variety of physical forms including granular, tablet, flake, pastille and bar forms.
  • the compositions are particularly the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.
  • the bulk density of granular detergent compositions in accordance with the present invention typically have a bulk density of at least 600 g/litre, more preferably from 650 g/litre to 1200 g/litre.
  • Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel.
  • the funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base.
  • the cup has an overall height of 90 mm.
  • the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup.
  • the filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge.
  • the filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.
  • Compacted solids may be manufactured using any suitable compacting process, such as tabletting, briquetting or extrusion, preferably tabletting.
  • tablets for use in dish washing processes are manufactured using a standard rotary tabletting press using compression forces of from 5 to 13 KN/cm 2 , more preferably from 5 to 1 1 KN/cm-'- 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.
  • Nai2(A102SiO2)i2- 7 H2O having a primary particle size in the range from 0.1 to 10 micrometers Zeolite A (dry) Zeolite A with a moisture content of lee than 10% by weight
  • DTPA Diethylene triamine pentaacetic acid
  • DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename Dequest
  • Brightener 1 Disodium 4,4'-bis(2-sulphostyry)biphenyl
  • Brightener 2 Disodium 4,4'-bis(4-anilino-6-mo ⁇ holino-l .3.5-triazin-2- yl)amino) stilbene-2:2'-disulfonate HEDP 1 , 1 -hydroxyethane diphosphonic acid EDDS Ethylenediamine-N, N'-disuccinic acid QEA1 bis((C 2 H5 ⁇ )(C 2 H4 ⁇ ) n ) (CH 3 ) -N+-C 6 H 12 -N + -(CH 3 ) bis((C2H5O)-(C2H 4 O) n ), wherein n-from 20 to 30
  • PEO Polyethylene oxide with a molecular weight of 50,000
  • Example 1 In the following examples all levels are quoted as % by weight of the composition: Example 1

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999011749A1 (en) * 1997-08-28 1999-03-11 The Procter & Gamble Company Agglomeration process for producing a particulate modifier polyamine detergent admix
EP0971030A1 (en) * 1998-07-10 2000-01-12 The Procter & Gamble Company Surfactant agglomerates
WO2000044874A1 (en) * 1999-02-01 2000-08-03 The Procter & Gamble Company Cationic particle and a process for making thereof
WO2001059048A1 (en) * 2000-02-07 2001-08-16 Unilever Plc Detergent compositions
WO2002103105A3 (de) * 2001-06-15 2003-05-01 Basf Ag Verfahren zur schmutzablösungsfördernden behandlung von oberflächen textiler und nicht-textiler materialien
EP1188817A3 (de) * 2000-09-08 2003-06-11 Cognis Deutschland GmbH & Co. KG Waschmittel
EP1191094A3 (de) * 2000-09-08 2003-06-11 Cognis Deutschland GmbH & Co. KG Waschmittel
US6627596B1 (en) 1999-02-01 2003-09-30 The Procter & Gamble Company Cationic particle and a process for making thereof
EP2423180A1 (en) 2002-12-04 2012-02-29 Clariant Finance (BV) Limited Quaternary ammonium composition
US11655436B2 (en) 2018-01-26 2023-05-23 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier
US12006488B2 (en) 2018-01-26 2024-06-11 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a carrier

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5903340B2 (ja) * 2012-06-25 2016-04-13 ライオン株式会社 粒状洗浄剤
EP4421156A1 (en) * 2018-01-26 2024-08-28 Ecolab USA Inc. Solidifying liquid anionic surfactants

Citations (1)

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

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5880398A (ja) * 1981-11-09 1983-05-14 小林製薬株式会社 カ−ペツト処理用組成物
US5211870A (en) * 1992-03-11 1993-05-18 The Procter & Gamble Company Malodor-free cleansing bar composition containing zeolite odor controlling agent
EP0906382A4 (en) * 1996-05-17 1999-11-24 Procter & Gamble DETERGENT COMPOSITION

Patent Citations (1)

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

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999011749A1 (en) * 1997-08-28 1999-03-11 The Procter & Gamble Company Agglomeration process for producing a particulate modifier polyamine detergent admix
EP0971030A1 (en) * 1998-07-10 2000-01-12 The Procter & Gamble Company Surfactant agglomerates
WO2000002995A1 (en) * 1998-07-10 2000-01-20 The Procter & Gamble Company Surfactant agglomerates
WO2000044874A1 (en) * 1999-02-01 2000-08-03 The Procter & Gamble Company Cationic particle and a process for making thereof
US6627596B1 (en) 1999-02-01 2003-09-30 The Procter & Gamble Company Cationic particle and a process for making thereof
WO2001059048A1 (en) * 2000-02-07 2001-08-16 Unilever Plc Detergent compositions
US6555513B2 (en) 2000-02-07 2003-04-29 Unilever Home & Personal Care Usa Division Of Conopco Inc. Detergent compositions
US6608016B2 (en) 2000-02-07 2003-08-19 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent compositions
EP1191094A3 (de) * 2000-09-08 2003-06-11 Cognis Deutschland GmbH & Co. KG Waschmittel
EP1188817A3 (de) * 2000-09-08 2003-06-11 Cognis Deutschland GmbH & Co. KG Waschmittel
WO2002103105A3 (de) * 2001-06-15 2003-05-01 Basf Ag Verfahren zur schmutzablösungsfördernden behandlung von oberflächen textiler und nicht-textiler materialien
US7074750B2 (en) 2001-06-15 2006-07-11 Basf Aktiengesellschaft Treatment method, which promotes the removal of dirt, for the surfaces of textiles and non-textiles
EP2423180A1 (en) 2002-12-04 2012-02-29 Clariant Finance (BV) Limited Quaternary ammonium composition
US11655436B2 (en) 2018-01-26 2023-05-23 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier
US11976255B2 (en) 2018-01-26 2024-05-07 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier
US12006488B2 (en) 2018-01-26 2024-06-11 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a carrier

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EP0929627A4 (en) 2000-01-05
AU4488397A (en) 1998-04-17
JP3773542B2 (ja) 2006-05-10
JP2000506936A (ja) 2000-06-06
CN1237999A (zh) 1999-12-08
CZ102199A3 (cs) 1999-07-14
EP0929627A1 (en) 1999-07-21
CN1113953C (zh) 2003-07-09
BR9714343A (pt) 2000-04-11
TR199900653T2 (xx) 1999-06-21
AR010223A1 (es) 2000-06-07
CA2265891A1 (en) 1998-04-02

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