EP0643130B2 - Granulare Waschmittelzusammensetzungen mit nichtionischem Tensid und Verfahren zu ihrer Herstellung - Google Patents

Granulare Waschmittelzusammensetzungen mit nichtionischem Tensid und Verfahren zu ihrer Herstellung Download PDF

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EP0643130B2
EP0643130B2 EP94201094A EP94201094A EP0643130B2 EP 0643130 B2 EP0643130 B2 EP 0643130B2 EP 94201094 A EP94201094 A EP 94201094A EP 94201094 A EP94201094 A EP 94201094A EP 0643130 B2 EP0643130 B2 EP 0643130B2
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Prior art keywords
surfactant
surfactant system
weight
composition
softening point
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EP94201094A
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French (fr)
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EP0643130A1 (de
EP0643130B1 (de
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Paul Amaat Raymond Gerard France
John Christian Schmitt
Carole Patricia Denise Wilkinson
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Procter and Gamble Co
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Procter and Gamble Co
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Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to AT94201094T priority Critical patent/ATE188991T1/de
Priority to DE69422675T priority patent/DE69422675T3/de
Priority to EP94201094A priority patent/EP0643130B2/de
Priority to ES94201094T priority patent/ES2140498T3/es
Priority to CA002171528A priority patent/CA2171528C/en
Priority to CN94193891.3A priority patent/CN1133607A/zh
Priority to JP7509239A priority patent/JPH09502760A/ja
Priority to PCT/US1994/010062 priority patent/WO1995007968A1/en
Priority to US08/612,946 priority patent/US5698510A/en
Publication of EP0643130A1 publication Critical patent/EP0643130A1/de
Publication of EP0643130B1 publication Critical patent/EP0643130B1/de
Publication of EP0643130B2 publication Critical patent/EP0643130B2/de
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    • 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
    • C11D17/065—High-density particulate detergent compositions
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads

Definitions

  • the present invention is concerned with granular detergent components or compositions which are rich in high performance nonionic surfactants.
  • the compositions are based upon specified surfactant systems and of processes which make it possible to produce very high surfactant active components.
  • Nonionic surfactants are important components of current laundry detergent compositions. Present trends demand particulate components or compositions which have a high bulk density and which have a high level of nonionic surfactant. The particulate must have good physical characteristics and must deliver nonionic surfactant which have been selected for high performance in to the wash. Various prior art attempts have been described which approach these demands from different perspectives. For example :
  • EP-A-544492 published on 2nd June, 1993, discloses particulate high density detergent composition comprising 15 to 50% of a mixed anionic/nonionic surfactant system.
  • the nonionic surfactants chosen are ethoxylated alcohols having a peaked ethoxylation distribution with an average of about 3 to 6.5.
  • fatty acid soaps are suggested as suitable structurants which modify the surfactant viscosity profile the resulting granules where soap is used (in Examples 16 to 19, 24 to 29) have surfactant activities of 29 to 32.5%.
  • WO-A-9206160 published on 16th April, 1992, discloses high performing nonionic surfactant systems based on mixtures of glucose amides and ethoxylated nonionic surfactants.
  • a component is described which comprises a nonionic surfactant system which is a mixture of 20% Dobanol (Trade Name) EO3 and 80% N-methyl-glucose amide in aqueous solution.
  • EP618290-A filed on 30 march 1993 and published on 05.10.94. discloses in an example a mixture containing 35% nonionic surfactant, being a polyhydroxy fatty amide and an alcohol ethoxylate.
  • EP-A-364881 published on 25th April 1990, describes gels formed from polyglycol ether derivatives and water in ratios of from 5:1 to 12. The gels are formed into free-flowing granulates by mixing with finely divided solids.
  • the problem addressed by the present invention concerns the need to provide high density particulate laundry detergent which has a high nonionic surfactant content, and which does not cake or lump upon storage, even in hot. humid conditions, and which dissolves and disperses rapidly upon contact with water even cold water, to give a high detergency performance on the washing load.
  • the present invention provides a nonionic, or mixed nonionic/anionic, surfactant system having a specific viscosity profile which can be formed into a solid particulate which does not cake during storage, which dissolves rapidly and has an excellent performance profile.
  • the surfactant system has a softening point above ambient temperature, i.e. above 25°C, preferably above 40°C.
  • Good rates of solubility can be correlated with the softening point of the surfactant system.
  • Surfactant systems having a softening point of greater than 100°C e.g. "pure" C16 N-methyl glucosamide
  • the softening point of the surfactant system will be less than 80°C.
  • the surfactant system of the present invention has a softening point which lies within the ranged of from 40°C to 100°C, and furthermore that the surfactant system has a viscosity profile whereby the viscosity of the surfactant system is from 25000 to 50000 cps at a temperature of 10°C above the softening point.
  • Finished laundry detergent compositions may be prepared by mixing or blending the nonionic containing particles with:
  • the nonionic surfactant containing particles of the present invention may be prepared by:
  • the cooling step (b) is preferably performed using a high pressure scraped surface heat exchanger.
  • surfactant system means the defined mixture of surfactants comprising nonionic surfactants alone or a mixed anionic/nonionic surfactant system. Whilst other components such as water and solvents (e.g. short chain alcohols) may be present in the surfactant system these will generally be minimised and preferably excluded.
  • softening point as used herein means the temperature at which the surfactant system passes between the solid and mixed solid/liquid phases.
  • the softening point can be identified by using a differential scanning calorimetry (DSC) curve.
  • DSC differential scanning calorimetry
  • the curve is a plot of true specific heat capacity against temperature.
  • the softening point is the temperature at which enthalpy of melting is greater than zero. This is the temperature at which phase change begins to occur when the solid surfactant system is heated.
  • viscosity means the viscosity measured at a shear rate of 25s -1 .
  • the viscosity can be measured by rotational analysis (e.g. a rheometer). Suitable instruments for these measurements are manufactured by Physica Messtechnik, Germany, (supplied by Thermo instrument Systems of Breda, Netherlands).
  • high active refers to nonionic surfactant activities of at least 35% by weight of the particulate component or composition, preferably greater than 40% by weight, and more preferably about 50% by weight.
  • a surfactant system which fulfils all of the physical requirements (ie the viscosity profile) of the present invention, it will usually be necessary to blend two or more compatible nonionic surfactants to give the required properties.
  • a homogeneous mixture of a high melting point surfactant with a low melting point surfactant, in suitable proportions, will give a surfactant system having the desired softening point.
  • nonionic surfactant While any nonionic surfactant may be usefully employed in the present invention, two families of nonionics have been found to be particularly useful. These are nonionic surfactants based on alkoxylated (especially ethoxylated) alcohols, and those nonionic surfactants based on amidation products of fatty acid esters and N-alkyl polyhydroxy amine. The amidation products of the esters and the amines are generally referred to herein as polyhydroxy fatty acid amides. Particularly useful in the present invention are mixtures comprising two or more nonionic surfactacts wherein at least one nonionic surfactant is selected from each of the groups of alkoxylated alcohols and the polyhydroxy fatty acid amides.
  • Suitable nonionic surfactants include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
  • the length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • polyethylene oxide condensates of alkyl phenols e.g., the condensation products of alkyl phenols having an alkyl group containing from 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from 4 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with an average of up to 25 moles of ethylene oxide per more of alcohol.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 9 to 15 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide.
  • Polyhydroxy fatty acid amides may be produced by reacting a fatty acid ester and an N-alkyl polyhydroxy amine.
  • the preferred amine for use in the present invention is N-(R1)-CH2(CH2OH)4-CH2-OH, where R1 is typically a alkyl, e.g. methyl group; and the preferred ester is a C12-C20 fatty acid methyl ester.
  • Nonionic surfactant systems and granular detergents made from such systems have been described in WO 92 6160, published on 16th April, 1992.
  • This application describes (example 15) a granular detergent composition prepared by fine dispersion mixing in an Eirich RV02 mixer which comprises N-methyl glucosamide (10%), nonionic surfactant (10%).
  • the surfactant system may also comprise anionic surfactants, indeed the inclusion of such surfactants may be of considerable advantage in order to improve the rate of solubility of the granular surfactant.
  • the laundry detergent compositions of the present invention can contain, in addition to the nonionic surfactant system of the present invention, one or more anionic surfactants as described below.
  • Alkyl Ester sulfonate surfactants hereof include linear esters of C 8 -C 20 carboxylic acids (i.e. fatty acids) which are sulfonated with gaseous SO 3 according to "The Journal of the American oil Chemists Society'" 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
  • the preferred alkyl ester sulfonate surfactant comprises alkyl ester sulfonate surfactants of the structural formula: wherein R 3 is a C 8 -C 20 hydrocarbyl, preferably an alkyl, or combination thereof, R 4 is a C 1 -C 6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
  • Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine.
  • R 3 is C 10 -C 16 alkyl
  • R 4 is methyl, ethyl or isopropyl.
  • methyl ester sulfonates wherein R 3 is C 14 -C 16 alkyl.
  • Alkyl sulfate surfactants hereof are water soluble salts or acids or the formula ROSO 3 M wherein R preferably is a C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 20 alkyl component, more preferably a C 12 -C 18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quarternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof). Typically alkyl chains of C 12-16 are preferred
  • Alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m SO 3 M wherein R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C 20 alkyl or hydroxyalkyl, more preferably C 12 -C 18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between 0.5 and 6, more preferably between 0.5 and 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium or magnesium), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethylammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof.
  • Exemplary surfactants are C 12 -C 18 alkyl ether (1.0) sulfate, C 12 -C 18 alkyl ether (2.25) sulfate, C 12 -C 18 alkyl ether (3.0) sulfate, and C 12 -C 18 alkyl ether (4.0) sulfate, wherein the counterion is conveniently selected from sodium and potassium.
  • anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C 9 -C 20 linear alkylbenzenesulphonates, C 8 -C 22 primary or secondary alkanesulphonates, C 8 -C 24 olefinsulphonates, sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • C 9 -C 20 linear alkylbenzenesulphonates C 8 -C 22 primary or secondary alkanesulphonates
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); methyl ester sulphonates (MES); acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C 12 -C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C 14 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpoly
  • the laundry detergent compositions of the present invention typically comprise from 1 % to 40 % preferably from 3 % to 20 % by weight of such anionic surfactants.
  • the laundry detergent compositions of the present invention may also contain cationic, ampholytic, zwitterionic, and semi-polar surfactants which can be combined, as described below, with the described nonionic-containing particles.
  • Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-chain hydrocarbyl group.
  • cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula: [R 2 (0R 3 )y][R 4 (OR 3 )y] 2 R 5 N+X- wherein R2 is an alkyl or alkyl benzyl group having from 8 to 18 carbon atoms in the alkyl chain, each R 3 is selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -CH 2 CH(CH 2 OH)-, -CH 2 CH 2 CH 2 -, and mixtures thereof; each R 4 is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups, -CH 2 COH-
  • the laundry detergent compositions of the present invention typically comprise from 0 % to 25 %, preferably form 3 % to 15 % by weight of such cationic surfactants.
  • Ampholytic surfactants are also suitable for use in the laundry detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched chain.
  • One of the aliphatic substituents contains at least 8 carbon atoms, typically from 8 to 18 carbon atoms, and at least one contains an anionic water-solubilizing group e.g. carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35 for examples of ampholytic surfactants.
  • the laundry detergent compositions of the present invention typically comprise from 0 % to 15 96, preferably from 1 % to 10 % by weight of such ampholytic surfactants.
  • Zwitterionic surfactants are also suitable for use in laundry detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivates of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quarternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at columns 19, line 38 through column 22, line 48 for examples of zwitterionic surfactants.
  • the laundry detergent compositions of the present invention typically comprise from 0 % to 15 %, preferably from 1 % to 10 % by weight of such zwitterionic surfactants.
  • Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and 2 moieties selected from the group consisting af alkyl groups and hydrocyalkyl groups containing from 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms.
  • Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula : wherein R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from 8 to 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms or mixtures thereof; x is from 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • the R 5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • amine oxide surfactants in particular include C 10 -C 18 alkyl dimethyl amine oxides and C 8 -C 12 alkoxy ethyl dihydroxy ethyl amine oxides.
  • the laundry detergent compositions of the present invention typically comprise from 0 % to 15 %, preferably from 1 % to 10 % by weight of such semi-polar nonionic surfactants.
  • the granular components and compositions will also contain other optional ingredients, such as builders, chelants (including phosphonic acids, succinic acids and their salts), bleaches, bleach activators (such as tetraacetylethylene diamine), polymers and co-polymers.
  • chelants including phosphonic acids, succinic acids and their salts
  • bleaches such as tetraacetylethylene diamine
  • bleach activators such as tetraacetylethylene diamine
  • the detergent compositions herein can contain crystalline aluminosilicate ion exchange material of the formula Na z [(AlO 2 ) z ⁇ (SiO 2 ) y ] ⁇ xH 2 O wherein z and y are at about 6, the molar ratio of z to y is from 1.0 to 0.4 and z is from 10 to 264.
  • Amorphous hydrated aluminosilicate materials useful herein have the empirical formula M z (zAlO 2 ⁇ ySiO 2 ) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from 0.5 to 2 and y is 1, said material having a magnesium ion exchange capacity of at least 50 milligram equivalents of CaCO 3 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from 1 to 10 microns is preferred.
  • the aluminosilicate ion exchange builder materials herein are in hydrated form and contain from 5% to 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from 18% to 22% water in their crystal matrix.
  • the crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from 0.1 micron to 10 microns. Amorphous materials are often smaller, e.g., down to less than 0.01 micron.
  • Preferred ion exchange materials have a particle size diameter of from 0.2 micron to 4 microns.
  • particle size diameter herein represents the average particle size diameter by weight of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
  • the crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least 200 mg equivalent of CaCO 3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from 300 mg eq./g to 352 mg eq./g.
  • the aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least 129.7 x 10 -3 g/l/min/g/l (2 grains Ca ++ /gal-Ion/minute/gram/gallon) of aluminosilicate (anhydrous basis), and generally lies within the range of from 129.7 x 10 -3 to 389 x 10 -3 g/l/min/g/l (2 grains/gallon/minute/gram/gallon to 6 grains/gallon/minute/gram/gallon), based on calcium ion hardness.
  • Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least 259.4 x 10 -3 g/l/min/g/l (4 grains/gallon/minute/gram/gallon).
  • the amorphous aluminosilicate ion exchange materials usually have a Mg ++ exchange of at least 50 mg eq. CaCO 3 /g (12 mg Mg ++ /g) and a Mg ++ exchange rate of at least 64.84 g/l/min/g/l (1 grain/gallon/minute/gram/gallon). Amorphous materials do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units).
  • Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available.
  • aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally occurring minosi!icates or synthatically derived.
  • a method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat. No. 3,985,669, Krummel et al., issued Oct. 12, 1976.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B. and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ] ⁇ xH 2 O wherein x is from 20 to 30, especially 27 and has a particle size generally less than 5 microns.
  • the granular detergents of the present invention can contain neutral or alkaline salts which have a pH in solution of seven or greater, and can be either organic or inorganic in nature.
  • the builder salt assists in providing the desired density and bulk to the detergent granules herein. While some of the salts are inert, many of them also function as detergency builder materials in the laundering solution.
  • neutral water-soluble salts include the alkali metal, ammonium or substituted ammonium chlorides, fluorides and sulfates.
  • the alkali and alkaline earth metal, and especially sodium and magnesium, salts of the above are preferred.
  • Sodium sulfate is typically used in detergent granules and is a particularly preferred salt.
  • Citric acid and, in general, any other organic or inorganic acid may be incorporated into the granular detergents of the present invention as long as it is chemically compatible with the rest of the agglomerate composition.
  • water-soluble salts include the compounds commonly known as detergent builder materials.
  • Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, and polyhydroxysulfonates.
  • alkali metal especially sodium, salts of the above.
  • inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from 6 to 21, and orthophosphate.
  • polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid.
  • Other phosphorus builder compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148.
  • nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate.
  • Suitable silicates are those having an SiO 2 :Na 2 O ratio in the range from 1.6 to 3.4, the so-called amorphous silicates of SiO 2 : Na 2 O ratios from 2.0 to 2.8 being preferred. These materials can be added at various points of the manufacturing process, such as in the form of an aqueous solution serving as an agglomerating agent for other solid components, or, where the silicates are themselves in particulate form, as solids to the other particulate components of the composition.
  • crystalline layered sodium silicates of general formula NaMSi x O 2x+1 ⁇ yH 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043.
  • x in the general formula above has a value of 2, 3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred examples of this formula comprise the y and ⁇ forms of Na 2 Si 2 O 5 .
  • Crystalline layered silicates are incorporated either as dry mixed solids, or as solid components of agglomerates with other components.
  • powders normally used in detergents such as zeolite, carbonate, silica, silicate, citrate, phosphate, perborate or percarbonate and process acids such as starch and sugars, can be used in preferred embodiments of the present invention.
  • other components may be added at any one of the stages of the process of the present invention, or they may be mixed with or sprayed on to the granular detergents of the present invention.
  • Polymers which are particularly useful in the present invention include sodium carboxy-lower alkyl celluloses, sodium lower alkyl celluloses and sodium hydroxy-lower alkyl celluloses, such as sodium carboxymethyl cellulose, sodium methyl cellulose and sodium hydroxypropyl cellulose, polyvinyl alcohols (which often also include some polyvinyl acetate), polyvinyl pyrrolidone, polyethylene glycol, polyaspartate, polyacrylamides, polyacrylates and various copolymers, such as those of maleic and acrylic acids. Molecular weights for such polymers vary widely but most are within the range of 2,000 to 100,000.
  • polymeric polycarboxyate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967.
  • Such materials include the water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
  • Another optional detergent composition ingredient is a suds suppressor, exemplified by silicones, and silica-silicone mixtures.
  • Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms, exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent-impermeable carrier.
  • the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.
  • useful silicone suds controlling agents can comprise a mixture of an alkylated siloxane, of the type referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica.
  • a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethyl-silanated) silica having a particle size in the range from 10 nanometers to 20 nanometers and a specific surface area above 50 m 2 /g, intimately admixed with dimethyl silicone fluid having a molecular weight in the range from 500 to 200,000 at a weight ratio of silicone to silanated silica of from 1:1 to 1:2.
  • a preferred silicone suds controlling agent is disclosed in Bartollota et al. US Patent 3,933,672.
  • Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent Application DTOS 2,646,126 published April 28, 1977.
  • An example of such a compound is DC0544, commercially available from Dow Corning, which is a siloxane/glycol copolymer.
  • the suds suppressors described above are normally employed at levels of from 0.001% to 0.5% by weight of the composition, preferably from 0.01% to 0.1% by weight.
  • the preferred methods of incorporation comprise either application of the suds suppressors in liquid form by spray-on to one or more of the major components of the composition or alternatively the formation of the suds suppressors into separate particulates that can then be mixed with the other solid components of the composition.
  • the incorporation of the suds modifiers as separate particulates also permits the inclusion therein of other suds controlling materials such as C 20 -C 24 fatty acids, microcrystalline waxes and high MWt copolymers of ethylene oxide and propylene oxide which would otherwise adversely affect the dispersibility of the matrix. Techniques for forming such suds modifying particulates are disclosed in the previously mentioned Bartolotta et al US Patent No. 3,933,672.
  • Another optional ingredient useful in the present invention is one or more enzymes.
  • Preferred enzymatic materials include the commercially available amylases, neutral and alkaline proteases, lipases, esterases and cellulases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • the nonionic containing particles of the present invention can be effectively combined with other ingredients to form a multi-purpose granular detergent.
  • the finished detergent composition should include detergent ingredients such as those described above.
  • the nonionic surfactant particles can be simply mixed with the rest of the ingredients that are in particulate form or in turn may be subjected to further process steps of spraying liquids and coating with fine powders.
  • the modular approach is based on the manufacturing of particles highly specific in one or at most two ingredients of the formulation which are then mixed at the desired ratios to form the finished products.
  • These particles being highly specific in the ingredient they are to deliver, can be used in a wide range of products without need to be modified.
  • These particles can be prepared with an optimal combination of ingredients that maximize their properties independent!y of full finished product formulations.
  • the nonionic surfactant particles described in the present invention can be suitably complemented with one high activity anionic surfactant particle and at least one builder particle.
  • the ability to manufacture high activity nonionic and anionic particles separately allows their use at different ratios in different formulations.
  • the high activity of these particles allow their preparation with a minimum amount of process aids, which are typically inorganic builders such as zeolites, carbonates, silicates, etc. Therefore, in a typical household granular detergent composition, there is room to be able to incorporate one or more highly specific builder particles by dry mixing.
  • the presence of builder particles that dissolve independently from the surfactants, and which preferably have a more rapid rate of solution than the principle particles which contain the surfactants, is preferred. This improves the rate of alkalinity release to the wash and reduces the potential precipitation of the surfactants with salts of calcium or magnesium present in hard water.
  • the nonionic surfactant containing particles of the present invention may be prepared by:
  • the surfactant system may be pumped using any conventional pumping means.
  • one preferred means of pumping is to use an extruder.
  • the extruder fulfils the functions of pumping and mixing the surfactant system on a continuous basis.
  • a basic extruder consists of a barrel with a smooth inner cylindrical surface. Mounted within this barrel is the extruder screw. There is an inlet port for the surfactant system which, when the screw is rotated, causes the surfactant system to be moved along the length of the barrel.
  • the detailed design of the extruder allows various functions to be carried out. Additional ports in the barrel may allow other ingredients, including co-surfactants and/or chemical structuring agents to be added directly into the barrel.
  • Secondly means for heating or cooling may be installed in the wall of the barrel for temperature control.
  • a preferred extruder is the twin screw extruder. This type of extruder has two screws mounted in parallel within the same barrel, which are made to rotate either in the same direction (co-rotation) or in opposite directions (counter-rotation).
  • the co-rotating twin screw extruder is the most preferred piece of equipment for use in this invention.
  • An extruder is particularly useful in this invention because the paste can be effectively cooled by adding liquid nitrogen or solid carbon dioxide into the barrel and at the same time pumps the increasingly viscous (colder) paste out of the extruder.
  • Suitable twin screw extruders for use in the present invention include those supplied by : APV Baker, (CP series); Werner and Pfleiderer, (Continua Series); Wenger, (TF Series); Leistritz, (ZSE Series); and Buss, (LR Series).
  • the surfactant system is transferred from the pumping means into a cooling means.
  • the means for cooling may be any type of conventional heat exchanger.
  • the surfactant system is introduced into the heat exchanger at a temperature above its softening point, and then cooled to a temperature close to, or even below its softening point with a resulting sharp increase in viscosity.
  • the cooling step (b) is preferably performed using a high pressure scraped surface heat exchanger.
  • a piece of equipment is the Chemetator (Trade Name), manufactured by Crown Chemtech Ltd., Reading, England; and the Fryma (Trade Name), manufactured by Fryma Maschinen AG, Reinfelden, Switzerland.
  • shock cooling or supercooling can be achieved. In this way the paste stays in a liquid form even at temperatures below its softening point for a short period of time. The allows very high active agglomerates to be produced.
  • the viscous surfactant system is then granulated with suitable powders (step (c)).
  • suitable powders Many processes for granulating surfactant pastes are known to the man skilled in the art.
  • a process which is suited to the present invention is that of fine dispersion mixing or agglomeration. In this process a finely dispersed viscous surfactant system is contacted with a finely divided powder which causes the powder to stick together (or agglomerate). Normally a blend of powders is present in the granulation step, in which case not all of the powders need to be finely divided.
  • the result is a granular composition which generally has a particle size distribution in the range of 250 to 1200 micrometers and has a bulk density of at least 650 g/l.
  • the viscous surfactant system is used as the paste which is finely dispersed with an effective amount of powder in a suitable mixer.
  • suitable mixers for carrying out the fine dispersion mixing are described in more detail below.
  • Any suitable powder may be chosen by mixing one or more of the ingredients listed above which may be conveniently handled in powder form. Powders comprising zeolite, carbonate, silica, silicate,sulphate, phosphate, citrate, citric acid and mixtures of these are particularly preferred.
  • the transfer of the viscous surfactant system from the heat exchanger into the mixer can be done in many ways, from simply pouring to high pressure pumping through small holes at the end of the pipe, before the entrance to the mixer. While all these ways are viable to manufacture agglomerates with good physical properties, it has been found that in a preferred embodiment of the present invention the extrusion of the paste through a die results in a better distribution in the mixer which improves the yield of particles with the desired size.
  • Preferred operating temperatures should also be as low as possible since this leads to a higher surfactant concentration in the finished particle.
  • the temperature during the agglomeration is less than 80°C, more preferably between 0°C and 70°C, even more preferably between 10 and 60°C and most preferably between 20 and 50°C.
  • Lower operating temperatures useful in the process of the present invention may be achieved by a variety of methods known in the art such as nitrogen cooling, cold water jacketing of the equipment or addition of solid CO2; with a preferred method being solid CO2, and a most preferred method being nitrogen cooling.
  • Suitable pieces of equipment in which to carry out the fine dispersion mixing or granulation of the present invention are mixers of the Fukae R FS-G series manufactured by Fukae Powtech Kogyo Co., Japan; this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall.
  • the stirrer and cutter may be operated independently of one another and at separately variable speeds.
  • the vessel can be fitted with a cooling jacket or, if necessary, a cryogenic unit.
  • mixers found to be suitable for use in the process of the invention include Diosna R V series ex Dierks & Söhne, Germany; and the Pharma Matrix R ex T K Fielder Ltd., England.
  • Other mixers believed to be suitable for use in the process of the invention are the Fuji R VG-C series ex Fuji Sangyo Co., Japan; and the Roto R ex Zanchetta & Co srl, Italy.
  • Other preferred suitable equipment can include Eirich R , series RV, manufactured by Gustau Eirich Hardheim, Germany; Lödige R , series FM for batch mixing, series Baud KM for continuous mixing/agglomeration, manufactured by Lödige Machinenbau GmbH, Paderborn Germany; Drais R T160 series, manufactured by Drais Werke GmbH, Mannheim Germany; and Winkworth R RT 25 series, manufactured by Winkworth Machinery Ltd., Berkshire, England.
  • the Littleford Mixer, Model #FM-130-D-12, with internal chopping blades and the Cuisinart Food Processor, Model #DCX-Plus, with 7.75 inch (19.7 cm) blades are two examples of suitable mixers. Any other mixer with fine dispersion mixing and granulation capability and having a residence time in the order of 0.1 to 10 minutes can be used.
  • the "turbine-type" impeller mixer, having several blades on an axis of rotation, is preferred.
  • the invention can be practiced as a batch or a continuous process.
  • the granulated surfactant particles are then allowed to cool to ambient temperatures. This may be most effectively achieved in a fluid bed cooler.
  • the granular components or compositions described above may be suitable for use directly, or they may be treated by additional process steps. Commonly used process steps include drying, cooling and/or dusting the granules with a finely divided flow aid. In addition the granules may be blended with other components in order to provide a composition suitable for the desired end use as has been described above. Any type of mixer or dryer (such as fluid bed dryers) may be found to be suitable for this purpose.
  • the finely divided flow aid if used, may be chosen from a wide variety of suitable ingredients such as zeolite, silica, talc, clay or mixtures of these.
  • High active nonionic surfactant particulate compositions were prepared in batch mode using a pilot plant scale high shear mixer, an Eirich RVO2.
  • the mixer was first charged with a mixture of powders, namely, Zeolite A , Alkyl Sulphate powder (having a carbon chain length distribution of C12 to C18), finely divided sodium carbonate and PEG4000.
  • a surfactant system in the form of a nonionic surfactant paste consisting of a homogeneous mixture of 1 part ethoxylated nonionic surfactant and 1 part polyhydroxy fatty acid amide (Palm Glucosamide), was then added on top of the powder mixture while the mixer was being operated at 1600rpm.
  • Paste was added until discrete granules were formed in the mixer.
  • the agglomerates where then transferred to a rotating drum mixer and dusted for 1-2 minutes with a flow aid at a level of 3 % by weight of the granular detergent.
  • the flow aid was a blend of 30 parts zeolite with 1 part hydrophobic silica.
  • Table 1 The compositions of the agglomerates are given below in Table 1.
  • the resulting agglomerates were made with a total surfactant activity of 54% and 58% respectively and showed good cake strength and compression values, and dissolved rapidly in water.
  • Example 2 The process of example 1 was repeated to provide the following composition (see table 2): Table 2 % by weight Polyhydroxy fatty acid amide 20 Nonionic surfactant (C25E3) 20 Sodium Carbonate 30 Zeolite 27 Flow aid (Zeolite/Hydrophobic silica) 3
  • the resulting agglomerates were made with a total surfactant activity of 40% and showed good cake strength and compression value. Although the rate of dissolution in water was still acceptable, it was not as rapid as the composition of example 1 under comparable conditions.
  • This example describes the process in batch mode in a pilot plant scale high shear mixer as used in example 1.
  • the mixer was first charged with a mixture of powders namely Zeolite A and finely divided sodium carbonate.
  • a surfactant system in the form of a nonionic surfactant paste consisting of a homogeneous mixture of 1 part ethoxylated nonionic surfactant and 3 parts of polyhydroxy fatty acid amides (Tallow Glucosamide), was then added on top of the powder mixture while the mixer was being operated at 1600rpm.
  • the surfactant system has a high softening point, greater than 100°C.
  • Table 3 % by weight Polyhydroxy fatty acid amide 30
  • This example describes the process in batch mode in a pilot plant scale high shear mixer as used in example 1.
  • the mixer was first charged with a mixture of powders to be used, namely Zeolite A and finely divided sodium carbonate.
  • a surfactant system in the form of a nonionic surfactant paste consisting of a homogeneous mixture of 3 parts ethoxylated nonionic surfactant and 1 part polyhydroxy fatty acid amides (Tallow Glucosamide), was then added on top of the powder mixture while the mixer was being operated at 1600rpm.
  • the surfactant system had a softening point of 40°C and a viscosity of only 13000 cps at a temperature just above that softening point (viscosity measured at a shear rate of 25s -1 ).
  • the following composition was made (see table 4): Table 4 % by weight Polyhydroxy fatty acid amide 7 Nonionic surfactant (C25E3) 21 Sodium Carbonate 35 Zeolite 34 Flow aid (Zeolite/Hydrophobic silica) 3
  • the resulting agglomerates were made with a total surfactant activity of 28% and showed higher cake strength and compression values. Although this composition has a rapid rate of dissolution, the total surfactant activity achieved is lower than either of examples 1 or 2.
  • This example describes the process in batch mode in a pilot plant scale high shear mixer as used in example 1.
  • the mixer was first filled with a mixture of powders to be used, in this particular case Zeolite A and fine sodium carbonate.
  • a nonionic surfactant paste of polyhydroxy fatty acid amides (Tallow Glucosamide) with a softening point of 148°C (in this case the softening point is a true melting point), was then added on top of the powder mixture while the mixer was being operated at 1600rpm.
  • the following composition was made (see table 5): Table 5 % by weight Polyhydroxy fatty acid amide 40 Sodium Carbonate 30 Zeolite 27 Flow aid (Zeolite/Hydrophobic silica) 3
  • This example describes the process in batch mode in a pilot plant scale high shear mixer as used in example 1.
  • the mixer was first charged with a mixture of powders to be used, namely Zeolite A, finely divided citrate and finely divided sodium carbonate.
  • Anionic surfactant agglomerates were separately prepared by granulating a 78% active surfactant paste (4 parts alkyl sulphate, C14-C15 and 1 part alkyl ether sulphate, C13-C15 with an average of 3 ether groups per molecule) with a powder mixture of zeolite, carbonate, CMC, acrylic-maleic co-polymer.
  • the nonionic surfactant paste consisting of 1 part ethoxylated nonionic surfactant and 1 part polyhydroxy fatty acid amides (Palm Stearine Glucosamide).
  • the nonionic surfactant paste was cooled from 70 to 55 °C and extruded from a high pressure scraped surface heat exchanger.
  • the following composition was made (see table 6): Table 6 % by weight Polyhydroxy fatty acid amide 19 Nonionic surfactant (C25E3) 19 Sodium Carbonate 13 Zeolite 13 Citrate 13 Fine anionic agglomerates 20 Flow aid (Zeolite/Hydrophobic silica) 3
  • the agglomerates show excellent handling properties and rate of surfactant release.
  • a surfactant system was prepared by thorough mixing of two nonionic surfactants; namely, 50% by weight palm stearine (C16-C18) glucosamide (GA) with 50% by weight of C12-C15 alkyl ether (having an average of 3 ether groups per mole), C25E3.
  • the surfactant system had a softening point at 50°C, and viscosities of 25000 cps at 60°C, and 100 cps at 70°C.
  • Example 7 was repeated replacing the palm stearine glucosamide by tallow stearine glucosamide.
  • the surfactant system had a softening point at 65°C, and viscosities of 25000 cps at 75°C, and 100 cps at 85°C.
  • the surfactant system was cooled from 85°C to 45°C using a high pressure scraped surface heat exchanger.
  • the short residence time (10 seconds) in the heat exchanger results in the surfactant system remaining liquid for a short period of time even below the solidification point.
  • Granulation was then carried out with a mixture of particulate materials in a Braun food processor to give the following compositions: Ex. 8A % by weight Ex. 88 % by weight Nonionic surfactant (GA/C25E3) 50 50 C12-C28 alkyl sulphate powder - 15 Zeolite A 25 20 Carbonate 25 15
  • Example 8 The process of example 8 was repeated using a die at he outlet of the heat exchanger to form noodles or extrudates of the surfactant system.
  • the following composition was produced: % by weight Nonionic surfactant (GA/C25E3) 60 C12-C28 alkyl sulphate powder 20 Zeolite A 10 Carbonate 10
  • compositions of examples 7 to 9 showed good cake strength and compression values, and dissolved rapidly in water.
  • a finished laundry detergent was put together by blending the following components: % by weight a) Nonionic surfactant agglomerate 13.4 b) Anionic surfactant agglomerate 32.5 c) Layered Silicate compacted granule 10.1 d) Granular Percarbonate 22.7 e)portaacetylethylene diamine agglomerate 7.8 f) Suds Suppressor Agglomerate 6.5 g) Perfume encapsulate 0.1 h) Granular Soil Release Polymer 0.4 i) Granular Sodium Citrate dihydrate 3.5 j) Enzymes 3.0
  • Component a was prepared according to the composition and process described in Example 1 A above.
  • Component b) was prepared from an anionic surfactant paste having the following composition, the separate ingredients being mixed in aqueous form and subsequently dried to the required water level: alkyl sulphate (C14-C15) 57.2 alkyl ether sulphate (C13-C15 with 3EO) 14.3 acrylic-maleic copolymer 16 sodium ethylenediamine-N,N'-disuccinic acid 1.5 water 11
  • the anionic surfactant paste was maintained at 60°C and added to an Eirich RV02 mixer, operating at 1600 rpm with the following powder composition: zeolite A 14 light soda ash 75 Carboxymethyl cellulose 4 Magnesium sulphate 4 Water 3
  • the final particulate composition of component b) contained 53% anionic surfactant and had a bulk density of 710 g/l.
  • Component c the layered silicate compact granule, was prepared from powder layered silicate 2.0 ratio (SKS-6 trade name ex Hoechst), powder citric acid and ethoxylated tallow alcohol, TAE50 (average of 50 ether groups).
  • SKS-6 and the citric acid both with an average particle size of about 150 microns were mixed together while sprayed with TAE50 in a rotating spray drum at the following composition:
  • the mixture was then passed to the feed hopper of a roll compactor and was compacted into a flake.
  • the flake was ground up to 600 microns average particle size.
  • the oversize fraction was recycled back to the grinder and the fines fraction back to the compactor.
  • the particle prepared via this process reaches its maximum calcium exchange capacity at the pH of the wash in less than 2 minutes.
  • Components d) to j) were obtained from the following commercially available sources: d) supplied by Interox; e) supplied by Warwick International; f) prepared according to US-A-3,933,672; g) supplied by Haarman & Reimer; h) supplied by Hoechst; i) supplied by Jungbunzlauer; j) supplied by Novo Nordisk.
  • the finished composition was made by placing components a) to j) in a 120 litre rotating drum operating at 15 rpm.
  • a mixture of nonionic surfactant and a 20% aqueous solution of optical brightener at ratios of 14:1 were sprayed at 55°C on to the granular mixture to a level of 5% by weight of the finished product.
  • the nonionic surfactant used consisted of a mixture of 7 parts of nonionic surfactant (C25E3) with 3 parts of palm stearine glucosamide.
  • the finished composition had a bulk density of 850 g/l.
  • the particle size distribution was: Tyler Sieve no. Micrometers % by weight of product on sieve 14 1180 17 20 850 39 35 425 88 65 212 99 100 150 99.5
  • the mean particle size of the finished product composition was about 720 micrometers.
  • the product prepared according to this example exhibits very high rates of dissolution of both anionic and nonionic surfactants. Furthermore the rate of alkalinity release (principally due to component c) was excellent.
  • a homogeneous mixture of 2 parts polyhydroxy fatty acid amide (Palm Stearine Glucosamide) with 3 parts ethoxylated nonionic surfactant (C25E5) at 85°C was mixed with a copolymer of acrylic-maleic acid.
  • the paste was then cooled from 85 to 45 °C using a high pressure scraped surface heat exchanger. The viscosity of the cooled paste was greater than 20 000 cps.
  • the cooled paste was immediately agglomerated with detergent powders in a Braun food processor. In this example the powders were alkyl sulphate, sodium carbonate and zeolite A.
  • the resulting agglomerates had the following composition: % by weight Polyhydroxy fatty acid amide 16 Nonionic surfactant 24 Zeolite A (hydrated) 20 Carbonate 15 Sodium alkyl sulphate 15 Copolymer of acrylic-maleic acid 10
  • composition shows good cake strength and compression values and a high rate of surfactant release in water.
  • This example describes the same process as used in example 13 but a cooled twin screw extruder was used to premix the alkyl sulphate with the nonionic surfactant instead of a scraped surface heat exchanger.
  • This example describes the process in batch mode in a pilot plant scale high shear mixer, an Eirich RVO2, to produce high active nonionic detergent agglomerates.
  • the mixer was first charged with a mixture of powders to be used, in this example Zeolite A , Alkyl Sulphate (C28AS), fine citrate and fine sodium carbonate.
  • agglomerates were then transferred to a rotating drum mixer and dusted for 1-2 minutes with a flow aid at a level of 3 % by weight of the granular detergent.
  • the composition of the agglomerates is given below. % by weight Polyhydroxy fatty acid amide 12 Nonionic surfactant (C25E5) 24 Alkyl Sulphate 20 Sodium Carbonate 14 Zeolite A 10 Fine citrate 10 Polyethyleneoxide 7 Flow aid (ZeoliteA /Zeolite DAY) 3
  • the resulting agglomerates were made with a total surfactant activity of 57 % and showed good cake strength and compression values.
  • the rate of nonionic surfactant release in water is comparable to example 12.
  • a homogeneous mixture of 1 part Palm Stearine Glucosamide with 1 part ethoxylated nonionic surfactant (C25E5) at 90°C was mixed with a molten Palmitic Acid, PEG 4000 and zeolite in a jacketed tank fitted with a mixing screw.
  • the resultant mixture was fed into a continuous belt cooler and produced into flakes.
  • the flakes had the following composition: % by weight Polyhydroxy fatty acid amide 20 Nonionic surfactant 20 Palmitic Acid 10 Zeolite 30 PEG 4000 10 Alkyl Sulphate 10
  • the resulting flakes were ground up to average particle size of 200 microns in a pin disk mill using 5 % zeoliteA as a flow aid.
  • the resulting powders showed good cake strength and compression values.
  • the rate of nonionic surfactant release in water is comparable to example 12.
  • a homogeneous mixture of 3 parts Palm stearine Glucoseamide and 7 parts ethoxylated nonionic surfactant (C25E5) was cooled in a Scraped Wall Cooler (Chemitator ® ) to 45°C and mixed with powdered Alkyl Polyglucoside in a twin screw extruder.
  • the resulting mixture had a viscosity of greater than 20.000 cps.
  • the mixture was the agglomerated in batch mode in a pilot plant scale high shear mixer, an Eirich RVO2.
  • the mixer was first charged with a mixture of powders to be used, in this particular case Zeolite P, fine citrate and water as a binder, and then the surfactant mixture was added to the mixture to produce nonionic detergent agglomerates.
  • % by weight Polyhydroxy fatty acid amide 10
  • the resulting agglomerates were made with a total detergent activity of 45% and showed good cake strength and compression values.
  • the rate of nonionic surfactant release in water is comparable to example 12.

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Claims (10)

  1. Granuläre Waschmittelzusammensetzung oder -komponente mit einer Schüttdichte von mindestens 650 g/l, umfassend ein Tensidsystem, wobei die Zusammensetzung oder Komponente 40 bis 85 Gew.-% nichtionisches Tensid umfaßt, welches eine Mischung aus Polyhydroxyfettsäureamid und einem ethoxylierten nichtionischen Tensid in einem Verhältnis von 3:7 bis 7:3 umfaßt, dadurch gekennzeichnet, daß das Tensidsystem bei Temperaturen von 25°C und darunter im wesentlichen in der festen Phase vorliegt, und daß das Tensidsystem einen Erweichungspunkt innerhalb des Bereichs von oberhalb 25°C bis 100°C aufweist, und wobei das Tensidsystem ein Viskositätsprofil aufweist, bei dem die Viskosität des Tensidsystems mindestens 20.000 cps bei einer Temperatur von 10°C über dem Erweichungspunkt, und weniger als 10.000 cps bei einer Temperatur von 30°C über dem Erweichungspunkt beträgt, wobei sämtliche Viskositäten bei einer Scherrate von 25 s-1 gemessen sind.
  2. Zusammensetzung oder Komponente nach Anspruch 1, wobei das Tensidsystem einen Erweichungspunkt aufweist, welcher innerhalb des Bereichs von 40°C bis 100°C liegt.
  3. Zusammensetzung oder Komponente nach Anspruch 1 oder 2, wobei das Tensidsystem ein Viskositätsprofil aufweist, bei dem die Viskosität des Tensidsystems 25.000 bis 50.000 cps bei einer Temperatur von 10°C über dem Erweichungspunkt beträgt.
  4. Zusammensetzung oder Komponente nach mindestens einem der Ansprüche 1 bis 3, wobei die Zusammensetzung oder Komponente mehr als 50 Gew.-% nichtionisches Tensid umfaßt.
  5. Granuläre Waschmittelzusammensetzung oder -komponente mit einer Schüttdichte von mindestens 650 g/l, umfassend ein Tensidsystem, wobei die Zusammensetzung oder Komponente 35 bis 85 Gew.-% nichtionisches Tensid, welches eine Mischung aus Polyhydroxyfettsäureamid und einem ethoxylierten nichtionischen Tensid in einem Verhältnis von 3:7 bis 7:3 umfaßt, und ein anionisches Tensid umfaßt, wobei das Gewichtsverhältnis des anionischen Tensids zu dem nichtionischen Tensid 1:100 bis 1:1 1 beträgt, dadurch gekennzeichnet, daß das Tensidsystem bei Temperaturen von 25°C und darunter im wesentlichen in der festen Phase vorliegt, und daß das Tensidsystem einen Erweichungspunkt innerhalb des Bereichs von oberhalb 25°C bis 100°C aufweist, und wobei das Tensidsystem ein Viskositätsprofil aufweist, bei dem die Viskosität des Tensidsystems mindestens 20.000 cps bei einer Temperatur von 10°C über dem Erweichungspunkt, und weniger als 10.000 cps bei einer Temperatur von 30°C über dem Erweichungspunkt beträgt, wobei sämtliche Viskositäten bei einer Scherrate von 25 s-1 gemessen sind.
  6. Zusammensetzung oder Komponente nach mindestens einem der Ansprüche 1 bis 5, wobei das Tensidsystem einen Wassergehalt von weniger als 15, vorzugsweise weniger als 10 Gew.-% des Tensidsystems aufweist.
  7. Zusammensetzung, umfassend eine oder mehrere Komponenten gemäß Anspruch 1, und umfassend weiterhin:
    a) eine Komponente, welche mindestens 40 Gew.-% anionisches Tensid umfaßt; und
    b) eine Komponente, welche mindestens 70 Gew.-% eines Buildermaterials umfaßt.
  8. Zusammensetzung nach Anspruch 7, wobei die Zusammensetzung 3 bis 40 Gew.-% einer Komponente gemäß Anspruch 1; und
    3 bis 40 Gew.-% einer Komponente, welche mindestens 40 Gew.-% anionisches Tensid umfaßt; und
    3 bis 20 Gew.-% einer Komponente, welche mindestens 70 Gew.-% Buildermaterial umfaßt; und
    wahlweise weitere Waschmittelkomponenten umfaßt.
  9. Verfahren zur Herstellung granulärer Waschmittelzusammensetzungen oder -komponenten nach den Ansprüchen 1 bis 8 aus einem Tensidsystem, das bei Temperaturen von 25°C und darunter im wesentlichen in der festen Phase vorliegt, wobei das Tensidsystem einen Erweichungspunkt innerhalb des Bereichs von oberhalb 25°C bis 100°C aufweist, und wobei das Tensidsystem ein Viskositätsprofil aufweist, wobei die Viskosität des Tensidsystems mindestens 20.000 cps bei einer Temperatur von 10°C über dem Erweichungspunkt, und weniger als 10.000 cps bei einer Temperatur von 30°C über dem Erweichungspunkt beträgt, wobei sämtliche Viskositäten bei einer Scherrate von 25 s-1 gemessen sind, wobei das Verfahren die Schritte umfaßt:
    a) Pumpen eines Tensidsystems in dessen Zustand mit geringer Viskosität;
    b) Kühlen des Tensidsystems auf eine Temperatur, bei der seine Viskosität auf mindestens 20.000 cps erhöht ist;
    c) Granulieren des Tensids in Gegenwart eines fein verteilten Pulvers;
    d) Kühlen der Agglomerate.
  10. Verfahren nach Anspruch 9, wobei der Kühlschritt (b) unter Verwendung eines Wärmeaustauschers mit unter Hochdruck abgeschabter Oberfläche durchgeführt wird.
EP94201094A 1993-09-13 1994-04-21 Granulare Waschmittelzusammensetzungen mit nichtionischem Tensid und Verfahren zu ihrer Herstellung Expired - Lifetime EP0643130B2 (de)

Priority Applications (9)

Application Number Priority Date Filing Date Title
AT94201094T ATE188991T1 (de) 1993-09-13 1994-04-21 Granulare waschmittelzusammensetzungen mit nichtionischem tensid und verfahren zu ihrer herstellung
DE69422675T DE69422675T3 (de) 1993-09-13 1994-04-21 Granuläre Waschmittelzusammensetzungen, umfassend nichtionisches Tensid, und Verfahren zur Herstellung solcher Zusammensetzungen
EP94201094A EP0643130B2 (de) 1993-09-13 1994-04-21 Granulare Waschmittelzusammensetzungen mit nichtionischem Tensid und Verfahren zu ihrer Herstellung
ES94201094T ES2140498T3 (es) 1993-09-13 1994-04-21 Composiciones detergentes granulares que comprenden un tensioactivo no ionico y procedimiento para preparar tales composiciones.
JP7509239A JPH09502760A (ja) 1993-09-13 1994-09-01 非イオン界面活性剤を含む粒状洗剤組成物およびこのような組成物の製法
CN94193891.3A CN1133607A (zh) 1993-09-13 1994-09-01 含有非离子表面活性剂的粒状洗涤剂组合物和制备该组合物的方法
CA002171528A CA2171528C (en) 1993-09-13 1994-09-01 Granular detergent compositions comprising nonionic surfactant and process for making such compositions
PCT/US1994/010062 WO1995007968A1 (en) 1993-09-13 1994-09-01 Granular detergent compositions comprising nonionic surfactant and process for making such compositions
US08/612,946 US5698510A (en) 1993-09-13 1994-09-01 Process for making granular detergent compositions comprising nonionic surfactant

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP93870187 1993-09-13
EP93870187 1993-09-13
EP94201094A EP0643130B2 (de) 1993-09-13 1994-04-21 Granulare Waschmittelzusammensetzungen mit nichtionischem Tensid und Verfahren zu ihrer Herstellung

Publications (3)

Publication Number Publication Date
EP0643130A1 EP0643130A1 (de) 1995-03-15
EP0643130B1 EP0643130B1 (de) 2000-01-19
EP0643130B2 true EP0643130B2 (de) 2007-09-19

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Family Applications (1)

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EP94201094A Expired - Lifetime EP0643130B2 (de) 1993-09-13 1994-04-21 Granulare Waschmittelzusammensetzungen mit nichtionischem Tensid und Verfahren zu ihrer Herstellung

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Country Link
EP (1) EP0643130B2 (de)
JP (1) JPH09502760A (de)
CN (1) CN1133607A (de)
AT (1) ATE188991T1 (de)
CA (1) CA2171528C (de)
DE (1) DE69422675T3 (de)
ES (1) ES2140498T3 (de)
WO (1) WO1995007968A1 (de)

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GB9424444D0 (en) * 1994-12-02 1995-01-18 Unilever Plc Detergent compositions
BR9606932A (pt) * 1995-01-26 1997-11-11 Procter & Gamble Processo para a manufatura de composições detergentes granulares compreendendo tensoativos não-iônico
US5858957A (en) * 1995-01-26 1999-01-12 The Procter & Gamble Company Process for the manufacture of granular detergent compositions comprising nonionic surfactant
ATE174954T1 (de) * 1995-04-27 1999-01-15 Procter & Gamble Verfahren zur herstellung von granularen waschmittelkomponenten oder waschmittelzusammensetzungen
DE69617035T2 (de) * 1995-09-04 2002-04-18 Unilever Plc Waschmittelzusammensetzungen und verfahren zu ihrer herstellung
DE19603760A1 (de) * 1996-02-02 1997-08-07 Henkel Kgaa Feste Reinigungsmittelzubereitungen
TW370561B (en) 1996-03-15 1999-09-21 Kao Corp High-density granular detergent composition for clothes washing
EP0798230A3 (de) * 1996-03-28 1998-05-13 The Procter & Gamble Company Standbeutel-Verpackungseinheit
GB9606913D0 (en) 1996-04-02 1996-06-05 Unilever Plc Surfactant blends processes for preparing them and particulate detergent compositions containing them
GB9711359D0 (en) 1997-05-30 1997-07-30 Unilever Plc Detergent powder composition
GB9711356D0 (en) 1997-05-30 1997-07-30 Unilever Plc Particulate detergent composition
ID29296A (id) 1997-05-30 2001-08-16 Unilever Nv Komposisi deterjen butiran lembut yang bebas mengalir
GB9711350D0 (en) * 1997-05-30 1997-07-30 Unilever Plc Granular detergent compositions and their production
DE19722767A1 (de) * 1997-06-02 1998-12-03 Henkel Kgaa Wasch- oder Reinigungsmittel mit erhöhter Reinigungsleistung
DE69825487T2 (de) * 1998-01-13 2005-08-18 The Procter & Gamble Company, Cincinnati Granuläre zusammensetzungen mit verbesserter auflösung
US6294512B1 (en) 1998-01-13 2001-09-25 The Procter & Gamble Company Granular compositions having improved dissolution
GB9825563D0 (en) * 1998-11-20 1999-01-13 Unilever Plc Particulate laundry detergent compositions containing anionic surfactant granules
GB9825560D0 (en) 1998-11-20 1999-01-13 Unilever Plc Particulate laundry detergent compositons containing nonionic surfactant granules
DE102004011087A1 (de) * 2004-03-06 2005-09-22 Henkel Kgaa Partikel umfassend diskrete, feinpartikuläre Tensidpartikel
DE102005018925A1 (de) * 2005-04-22 2006-10-26 Henkel Kgaa Wasch- oder Reinigungsmittel

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Also Published As

Publication number Publication date
ATE188991T1 (de) 2000-02-15
JPH09502760A (ja) 1997-03-18
DE69422675T3 (de) 2008-05-21
ES2140498T3 (es) 2000-03-01
CA2171528A1 (en) 1995-03-23
CA2171528C (en) 1999-12-14
EP0643130A1 (de) 1995-03-15
WO1995007968A1 (en) 1995-03-23
DE69422675T2 (de) 2000-08-10
EP0643130B1 (de) 2000-01-19
DE69422675D1 (de) 2000-02-24
CN1133607A (zh) 1996-10-16

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