EP0618290A1 - Aides d'écoulement pour poudres détergents comprenant d'aluminosilicate de sodium et de la silice hydrophobe - Google Patents

Aides d'écoulement pour poudres détergents comprenant d'aluminosilicate de sodium et de la silice hydrophobe Download PDF

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Publication number
EP0618290A1
EP0618290A1 EP93870059A EP93870059A EP0618290A1 EP 0618290 A1 EP0618290 A1 EP 0618290A1 EP 93870059 A EP93870059 A EP 93870059A EP 93870059 A EP93870059 A EP 93870059A EP 0618290 A1 EP0618290 A1 EP 0618290A1
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EP
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Prior art keywords
nonionic surfactant
detergent
powder
silica
sodium aluminosilicate
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EP93870059A
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German (de)
English (en)
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EP0618290B1 (fr
Inventor
Paul Amaat Raymond Gerard France
Paul Van Dijk
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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 DE69325014T priority Critical patent/DE69325014T2/de
Priority to EP93870059A priority patent/EP0618290B1/fr
Priority to AT93870059T priority patent/ATE180274T1/de
Priority to PCT/US1994/001915 priority patent/WO1994023001A1/fr
Priority to US08/532,554 priority patent/US5691294A/en
Priority to CA002159179A priority patent/CA2159179C/fr
Priority to JP6522055A priority patent/JPH08508524A/ja
Publication of EP0618290A1 publication Critical patent/EP0618290A1/fr
Publication of EP0618290B1 publication Critical patent/EP0618290B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to the use of flow aids for granular products which comprise a mixture of sodium aluminosilicate and silica in a narrowly defined ratio.
  • the silica used is hydrophobic silica, preferably fumed hydrophobic silica.
  • the ratio of sodium aluminosilicate to silica is from about 100:1 to about 3:1, preferably from 20:1 to 5:1, and most preferably around 10:1.
  • the flow aid is used in the process of manufacturing high density granular detergent components or compositions which comprise nonionic surfactants. It is most useful in combination with nonionic surfactants which are liquid at ambient temperature, and are therefore mobile. Without a suitable flow aid, the nonionic surfactant tends to leak from the powder and soak into the cardboard container which forms an unsightly stain. Although it is possible to avoid this problem by using lower levels of nonionic surfactant in the composition, or by selecting nonionic surfactants which have a lower solidification temperature, this limits the flexibility of formulation.
  • flow aids in general which help to reduce the stickiness of detergent granules comprising nonionic surfactants, and which may help to increase bulk density is known, for example from the following prior art:
  • JP 61 069897 laid open 10th April, 1986 states that aluminosilicate, silicon dioxide, bentonite and clay having an average particle diameter of not more than 10 micrometers can be used as a surface modifier at a level of from 0.5% to 35%.
  • EP 0 351 937 published 24th January, 1990 and EP 0 352 135, published 24th January, 1990 disclose agglomeration processes carried out sequentially with high speed and low speed mixing. No finely divided particulate is present is the granulation step.
  • flow aids may be used, for example, aluminosilicates, precipitated silica and others are suitable.
  • EP 0 513 824 published 19th November, 1992, describes a process for making nonionic detergent granules and the use of a surface coating agent having a particle size of less than 10 micrometers.
  • the present invention is aimed at making nonionic detergent agglomerates having a high bulk density and which comprise higher levels of nonionic surfactant the those of the prior art, but do not have the same leakage problems.
  • Another problem which is associated with making detergent agglomerates having a high bulk density is that the bulk density tends to change during storage, especially during the first few hours or days after manufacture. This in turn gives rise to problems of quality control, especially on packaging lines. It is a feature of the products of the present invention that changes in bulk density during storage are greatly reduced, or even eliminated.
  • the present invention also addresses the problem of achieving more control over particle size distribution of the finished product.
  • One of the factors influencing particle size distribution is the effectiveness of the flow aid which is introduced near to the end of the manufacturing process.
  • the flow aids of the present invention have been found to be more efficient in this regard.
  • the present invention relates to detergent components or compositions having a bulk density of at least 700 g/l which comprises a nonionic surfactant system which includes at least one nonionic surfactant which is a liquid at temperatures below 40°C, and from 0.5% to 15% by weight of the component or composition of a flow aid which is a premixed powder comprising sodium aluminosilicate and hydrophobic silica in the ratio of from 100:1 to 3:1
  • a flow aid which is a premixed powder comprising sodium aluminosilicate and hydrophobic silica in the ratio of from 100:1 to 3:1
  • the invention also relates to a process for making such detergent components or compositions.
  • the present invention comprises two essential components; a granular detergent which comprises a nonionic surfactant which is a liquid at temperatures below 40°C, and a flow aid which is a premixed powder comprising sodium aluminosilicate and silica. Both of these components will now be described in more detail
  • Granular Detergent comprising Nonionic Surfactant
  • 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.
  • nonionic surfactants such as the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from about 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 about 9 to 15 carbon atoms with from about 2 to 10 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide.
  • At least one of the nonionic surfactants used is a liquid at temperatures below 40°C.
  • the nonionic surfactant system as a whole may have a higher solidification temperature.
  • the nonionic surfactant system also includes a polyhydroxy fatty acid amide component.
  • 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 and the preferred ester is a C12-C20 fatty acid methyl ester. Most preferred is the reaction product of N-methyl glucamine with 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 glucamide (10%), nonionic surfactant (10%).
  • the present invention provides a method of making a granular detergent component which comprises an ethoxylated nonionic surfactant at a level of from 1% to 50% by weight of the component.
  • the particular benefits of the invention will be even more evident when the ethoxylated nonionic surfactant is at a level of from 10% to 50% by weight of the detergent component or composition, preferably from 12% to 30% by weight, and even more preferably from 15% to 20% by weight.
  • the polyhydroxy fatty acid amide may be present in compositions of the present invention at a level of from 0% to 50% by weight of the detergent component or composition, preferably from 5% to 40% by weight, even more preferably from 10% to 30% by weight.
  • 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 C8-C20 carboxylic acids (i.e. fatty acids) which are sulfonated with gaseous SO3 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 R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a C1-C6 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.
  • R3 is C10-C16 alkyl
  • R4 is methyl, ethyl or isopropyl.
  • methyl ester sulfonates wherein R3 is C14-C16 alkyl.
  • Alkyl sulfate surfactants hereof are water soluble salts or acids or the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C18 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, and the like).
  • alkyl chains of C12-16 are
  • Alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate, C12-C18E(1.0)M), C12-C18 alkyl polyethoxylate (2.25) sulfate, C12-C18E(2.25)M), C12-C18 alkyl polyethoxylate (3.0) sulfate C12-C18E(3.0), and C12-C18 alkyl polyethoxylate (4.0) sulfate C12-C18E(4.0)M), wherein M 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, C9-C20 linear alkylbenzenesulphonates, C8-C22 primary or secondary alkanesulphonates, C8-C24 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.
  • alkylpolyglycolethersulfates containing up to 10 moles of ehtylene oxide
  • 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 C12-C18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsul
  • 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 tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference). When included therein, the laundry detergent compositions of the present invention typically comprise from about 1 % to about 40 %, preferably from about 3 % to about 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, as well as nonionic surfactants other than those already described herein, including the semi-polar nonionic amine oxides described below.
  • 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 : [R2(0R3)y][R4(OR3)y]2R5N+X - wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2-, and mixtures thereof; each R4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R4 groups, -CH2COH-CHOHCOR6CHOHCH2
  • the laundry detergent compositions of the present invention typically comprise from 0 % to about 25 %, preferably form about 3 % to about 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 about 8 to about 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 (herein incorporated by reference) for examples of ampholytic surfactants.
  • the laundry detergent compositions of the present invention typically comprise form 0 % to about 15 %, preferably from about 1 % to about 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 (herein incorporated by reference) for examples of zwitterionic surfactants.
  • the laundry detergent compositions of the present invention typically comprise form 0 % to about 15 %, preferably from about 1 % to about 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 about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting af alkyl groups and hydrocyalkyl groups containing form about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of form about 10 to about 18 carbon atoms and 2 moieties selected form the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms.
  • Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula : wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is form 0 to about 3; and each R5 is an alkyl or hydroxyalkyl group containing form about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
  • the R5 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 C10-C18 alkyl dimenthyl amine oxides and C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
  • the laundry detergent compositions of the present invention typically comprise form 0 % to about 15 %, preferably from about 1 % to about 10 % by weight of such semi-polar nonionic surfactants.
  • the granular detergent will also contain other optional ingredients.
  • examples of such ingredients which are commonly used in detergents are given in more detail hereinbelow
  • the other essential feature of the present invention is the flow aid which comprises sodium aluminosilicate and silica.
  • Sodium aluminosilicate may take many forms.
  • One example is crystalline aluminosilicate ion exchange material of the formula Na z [(AlO2) z ⁇ (SiO2)y] ⁇ xH2O wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0.4 and z is from about 10 to about 264.
  • Amorphous hydrated aluminosilicate materials useful herein have the empirical formula M z (zAlO2 ⁇ ySiO2) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO3 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from about 1 to 10 microns is preferred.
  • the aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 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 about 18% to about 22% water in their crystal matrix.
  • the crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron.
  • Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 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 about 200 mg equivalent of CaCO3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg eq./g to about 352 mg eq./g.
  • the aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca++/gallon/minute/gram/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/gallon/minute/gram/gallon to about 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 about 4 grains/gallon/minute/gram/gallon.
  • the amorphous aluminosilicate ion exchange materials usually have a Mg++ exchange of at least about 50 mg eq. CaCO3/g (12 mg Mg++/g) and a Mg++ exchange rate of at least about 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.
  • the aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetically 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, incorporated herein by reference.
  • 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 Na12[(AlO2)12(SiO2)12] ⁇ xH2O wherein x is from about 20 to about 30, especially about 27 and has a particle size generally less than about 5 microns.
  • Silica is a highly dispersed amorphous silicon dioxide. It is commercially available in many forms. Most commonly silica has a tapped density of from 50 g/l to 120 g/l. The specific surface area of the particles ranges from 25 square metres per gram to 800 square metres per gram. The surface of silica particles can be chemically modified to change their behaviour with respect to water. For example,silica particles may be treated with organosilanes to make the particles predominantly hydrophobic. It has been found that silicas must be hydrophobised to be useful in the present invention.
  • silica is usually prepared by one of two techniques; either by precipitation or by high temperature flame hydrolysis.
  • Precipitated silicas generally have an agglomerate size of from 3 micrometers to 100 micrometers
  • fumed silicas made by flame hydrolysis
  • fumed silicas usually have primary particles which are generally spherical and have an average diameter of from 7nm to 40nm. Fumed silicas having an average primary particle size of from 7 to 25 nanometers are preferred in the present invention.
  • This silica is a hydrophobic, fumed silica which has a specific surface area of about 110 square metres per gram and an average primary particle size of 16 nanometers.
  • the sodium aluminosilicate and the silica must be premixed in a ratio of from 100:1 to 3:1. Preferably the ratio will be from 20:1 to 5:1, and most preferably around 10:1.
  • the resulting premix is a free-flowing powder which is much easier to handle than either the zeolite power on its own, or the silica powder on its own.
  • Sodium aluminosilicate powder alone is usually sticky and does not flow well.
  • Silica powder on its own is very dusty, due to the very small particle size and low bulk density.
  • the flow aids of the present invention are a free-flowing, non-dusty powder.
  • a level of the flow aid of from 0.5% to 15% by weight of the detergent composition is then mixed to coat the surfaces of the granules.
  • the level of the flow aid is from 3% to 12% by weight, and most preferably about 10% by weight.
  • ingredients which are known for use in detergent compositions may also be used as optional ingredients in the present invention.
  • builders other than aluminosilicates and silicas which have been described hereinabove
  • chelants and polymers are included here in more detail.
  • 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 examples include the alkali metal, ammonium or substituted ammonium chlorides, fluorides and sulfates.
  • the alkali metal, and especially sodium, 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 polyhyroxysulfonates.
  • 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 about 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, incorporated herein by reference.
  • nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of SiO2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
  • powders normally used in detergents such as zeolite, carbonate, silica, silicate, citrate, phosphate, perborate, etc. and process acids such as starch, can be used in preferred embodiments of the present invention.
  • organic polymers are also useful as builders to improve detergency. Included among such polymers may be mentioned 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), 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 polycarboxylate 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.
  • compositions of the present invention can be included in the compositions of the present invention. These include color speckles, bleaching agents and bleach activators, suds boosters or suds suppressors, antitarnish and anticorrosion agents, soil suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, pH adjusting agents, nonbuilder alkalinity sources, hydrotropes, enzymes, enzyme-stabilizing agents, and perfumes.
  • Granular detergent components which comprise nonionic surfactants may be made by many methods which are known to the man skilled in the art including spray drying, absorption of nonionic surfactants into porous carrier particles and various types of granulation, or combinations of these techniques.
  • One particularly useful method of granulation is known as agglomeration.
  • the term agglomeration is taken herein to mean the build-up of small particles to form the granular detergent having the required particle size.
  • Particles suitable for use in an agglomeration process may be in the form of powders of sodium aluminosilicate, carbonate, sulphate, citrate, silica, or mixtures of these, and the agglomeration may be effected in the presence of some or all of the nonionic surfactant system.
  • One method of doing this is by combining the powders with a liquid or pasty component which may comprise nonionic surfactant in a fine dispersion mixer or granulator.
  • One particularly preferred process is to agglomerate one or more powders comprising a premix of sodium aluminosilicate and silica.
  • the following steps are suitable:
  • 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.
  • One particularly preferred process method is to prepare the detergent granules by an agglomeration techniques such as the fine dispersion mixing and granulation process described above, and to spray some or all of the nonionic surfactant on to detergent granules in one a suitable mixer or rotating drum. Any of the mixers described above may be found to be suitable for this.
  • the granular detergent powder in step ii) is preferably made by agglomeration of detergent pastes, most preferably using a process of fine dispersion mixing or granulation.
  • the flow aids of the present invention will be added towards the end of the process and will help to prevent further agglomeration of the components which could lead to oversized particle distribution.
  • the flow aid may be incorporated by any suitable means, a rotating drum or mixer of the ploughshare type are most preferred.
  • a mixture of granular raw materials was prepared according to the following composition: % by weight Anionic surfactant agglomerate* 30 Layered silicate compacted granule (supplied by Hoechst under trade name SKS-6) 18 Percarbonate (supplied by Interox) 25 TAED agglomerate 9 Suds suppressor agglomerate 2 Perfume encapsulate 0.2 Granular dense soda ash 8.4 Granular acrylic-maleic copolymer 3.2 Enzymes 3.6 Granular soil release polymer 0.6 100 ⁇ *Anionic surfactant agglomerates were made from a 78% active surfactant paste which comprises C45AS/C35AE3S in the ratio of 80:20.
  • the paste was agglomerated with a powder mixture according to the process described in EPA510746.
  • the resulting anionic surfactant granule had a composition of 30% C45AS, 7.5% C35AE3S, 24% zeolite, 20% carbonate, 2.5% CMC, 12% acrylic-maleic co-polymer, and the balance of moisture.
  • the mixture of granular ingredients listed above was placed inside a 140 litre rotating drum that operates at 25 rpm. While operating the drum a mixture of nonionic surfactant (C25E3) and a 20% aqueous solution of optical brightener at ratios of 14: 1 were sprayed onto the granular mixture to a level of 7% by weight of the granular components. The spraying time was about 1-2 minutes. Immediately afterwards, perfume was sprayed on, at a level of 0.5% by weight of the granular components, while rotating the drum. Then, without stopping the rotation of the drum, a flow aid was slowly added to the mixer, taking about 30 seconds. The level and type of flow aids used is given below in Table 1.
  • Examples 1 to 7 were made using flow aids of the present invention.
  • Examples A to F are comparative examples.
  • the different flow aids were tested in a Hosokawa Powder Characteristics tester type PT-E for flowability and floodability. The results are listed in Table 2, given below.
  • the data in Table 2 indicates that the flowability of zeolites is significantly improved by adding small amounts of hydrophobic silica Aerosil R 972. No improvement was found by using hydrophilic silica , eg. Sipernat 22S (Trade name) from Degussa.
  • the floodability index gives an indication of the behavior of a bulk material when it changes from a resting to a moving state. An increasing floodability index indicates easier bulk handling of the flow aid.
  • Table 4 shows that a narrower particle size distribution is obtained (as indicated by a smaller standard geometric deviation) from the products of the invention (examples 3 and 6) than from a 100% zeolite flow aid (comparative example E)
  • the nonionic surfactant leaking from the powder into the cardboard container, has been checked for all the products, by visual inspection of the inside wetting of the boxes.
  • flow aids comprising hydrophobic silica significantly reduced the nonionic leaking. No improvement with a 100% Zeolite flow aid was observed.
  • a mixture of granular raw materials was prepared according to the composition given in examples 1-7.
  • the mixture of granular ingredients described above was placed inside a 140 litre rotating drum that operates at 25 rpm. While operating the drum a mixture of nonionic surfactants (C25E3) and a 20% aqueous solution of optical brightener at ratios of 14: 1 were sprayed onto the granular mixture to a level of 7% by weight of the granular composition. The spraying time was about 1-2 minutes. Immediately afterwards, perfume is sprayed on, at a level of 0.5% by weight of the granular composition while rotating the drum.
  • C25E3 nonionic surfactants
  • optical brightener at ratios of 14: 1
  • This example describes the process in batch mode in a pilot plant scale high shear mixer, an Eirich RV02, to produce high active nonionic detergent agglomerates without nonionic leakage problems.
  • the mixer was filled first with a mixture of powders to be used, in this particular case zeolite A and fine sodium carbonate.
  • the agglomerates are then transferred to a rotating drum mixer and dusted for 1-2 minutes with a flow aid at a level of 5 or 10% by weight of the granular detergent.
  • the composition of the agglomerates was given below in Table 6.
  • Table 6 Product 9 A % by weight
  • Product 9 B % by weight
  • Alcohol Ethoxylate nonionic 26.25 21.0 Sodium alkyl sulphate - 7.0 Sodium carbonate 32.5 32.5 Zeolite 26.0 26.0 Misc/water 6.5 6.5
  • the resulting agglomerates were made with a detergent activity of 35% and a density of 700g/L.
  • the dusted agglomerates were packed into cardboard containers and checked for nonionic leaking.
  • Flow aids % flow aid nonionic leakage (9A & 9B) 100 % Zeolite 5 grade 5 10 grade 5 90% Zeolite / 10 % Silica 5 grade 3 10 grade 1
  • Example 10 is similar to Example 9.
  • a Lodige FM mixer fitted with internal ploughs and high speed choppers with cutter blades, was used as an agglomerator.
  • the mixer was filled first with a mixture of powders to be used and a mixture of surfactant paste was added on top.
  • the composition of the agglomerates is given below in Table 7.
  • the mixer is then started until granulation is achieved.
  • the agglomerates are then dusted for 1-2 minutes with a flow aid at a level of 5 or 10 % by weight of the granular detergent in a low shear KM Lodige mixer or a rotating drum mixer.
  • a high active agglomerate is made with reduced stickiness and no nonionic leakage when coated with a mixture of 80% Zeolite and 20% Hydrophobic Silica Aerosil R972.

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EP93870059A 1993-03-30 1993-03-30 Aides d'écoulement pour poudres détergents comprenant d'aluminosilicate de sodium et de la silice hydrophobe Revoked EP0618290B1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
DE69325014T DE69325014T2 (de) 1993-03-30 1993-03-30 Natrium-Aluminiumsilikat und hydrophobe Kieselsäure enthaltende Fliesshilfe für Waschmittelpulver
EP93870059A EP0618290B1 (fr) 1993-03-30 1993-03-30 Aides d'écoulement pour poudres détergents comprenant d'aluminosilicate de sodium et de la silice hydrophobe
AT93870059T ATE180274T1 (de) 1993-03-30 1993-03-30 Natrium-aluminiumsilikat und hydrophobe kieselsäure enthaltende fliesshilfe für waschmittelpulver
US08/532,554 US5691294A (en) 1993-03-30 1994-02-23 Flow aids for detergent powders comprising sodium aluminosilicate and hydrophobic silica
PCT/US1994/001915 WO1994023001A1 (fr) 1993-03-30 1994-02-23 Auxiliaires d'ecoulement pour poudres detergentes contenant de l'aluminosilicate de sodium et de la silice hydrophobe___________
CA002159179A CA2159179C (fr) 1993-03-30 1994-02-23 Substances facilitant l'ecoulement de detergents en poudre, qui contiennent de l'aluminosilicate de sodium et de la silice hydrophobe
JP6522055A JPH08508524A (ja) 1993-03-30 1994-02-23 アルミノケイ酸ナトリウムと疎水性シリカとを含む洗剤粉末用流動助剤

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EP93870059A EP0618290B1 (fr) 1993-03-30 1993-03-30 Aides d'écoulement pour poudres détergents comprenant d'aluminosilicate de sodium et de la silice hydrophobe

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EP0618290B1 EP0618290B1 (fr) 1999-05-19

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WO (1) WO1994023001A1 (fr)

Cited By (11)

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WO1997003165A1 (fr) * 1995-07-10 1997-01-30 Henkel Kommanditgesellschaft Auf Aktien Procede de preparation de granules tensioactifs de saccharose
WO1997042300A1 (fr) * 1996-05-07 1997-11-13 The Procter & Gamble Company Procede de fabrication de compositions detergentes agglomerees presentant une aptitude a l'ecoulement amelioree
EP0892043A1 (fr) * 1996-03-15 1999-01-20 Kao Corporation Composition detergente granulaire a haute densite pour vetements
WO1999032591A1 (fr) * 1997-12-22 1999-07-01 Henkel Kommanditgesellschaft Auf Aktien Detergent et nettoyant particulaire
EP0643130B1 (fr) * 1993-09-13 2000-01-19 The Procter & Gamble Company Composition détergentes granulaires contenant un tensio-actif non-ionique et procédé de sa préparation
US6069124A (en) * 1997-05-30 2000-05-30 Lever Brothers Company Division Of Conopco, Inc. Granular detergent compositions and their production
US6191095B1 (en) 1997-05-30 2001-02-20 Lever Brothers Company, A Division Of Conopco, Inc. Detergent compositions
US6221831B1 (en) 1997-05-30 2001-04-24 Lever Brothers Company, Division Of Conopco, Inc. Free flowing detergent composition containing high levels of surfactant
WO2001046375A1 (fr) * 1999-12-17 2001-06-28 Henkel Kommanditgesellschaft Auf Aktien Procede de production de granules de tensioactifs de sucre
US6303558B1 (en) 1997-05-30 2001-10-16 Lever Brothers Co., Division Of Conopco Detergent composition containing at least two granular components
WO2014015090A1 (fr) * 2012-07-20 2014-01-23 The Procter & Gamble Company Poche hydrosoluble revêtue avec une composition comprenant un fluidifiant de silice

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US5807817A (en) * 1996-10-15 1998-09-15 Church & Dwight Co., Inc. Free-flowing high bulk density granular detergent product

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EP0013028A1 (fr) * 1979-01-02 1980-07-09 Henkel Kommanditgesellschaft auf Aktien Produit de lavage contenant du polydiméthylsiloxane antimoussant et procédé pour sa fabrication
EP0329842A2 (fr) * 1988-02-24 1989-08-30 Degussa Aktiengesellschaft Produit antimousse pulvérulent pour détergents
EP0477974A2 (fr) * 1990-09-28 1992-04-01 Kao Corporation Composition détergente non-ionique pulvérulente
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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0643130B1 (fr) * 1993-09-13 2000-01-19 The Procter & Gamble Company Composition détergentes granulaires contenant un tensio-actif non-ionique et procédé de sa préparation
US6030937A (en) * 1995-07-10 2000-02-29 Henkel Kommanditgesellschaft Auf Aktien Method of preparing saccharose surfactant granulates
WO1997003165A1 (fr) * 1995-07-10 1997-01-30 Henkel Kommanditgesellschaft Auf Aktien Procede de preparation de granules tensioactifs de saccharose
EP0892043A4 (fr) * 1996-03-15 2001-01-10 Kao Corp Composition detergente granulaire a haute densite pour vetements
EP0892043A1 (fr) * 1996-03-15 1999-01-20 Kao Corporation Composition detergente granulaire a haute densite pour vetements
US6284722B1 (en) 1996-03-15 2001-09-04 Kao Corporation High-density granulated detergent composition for clothes
WO1997042300A1 (fr) * 1996-05-07 1997-11-13 The Procter & Gamble Company Procede de fabrication de compositions detergentes agglomerees presentant une aptitude a l'ecoulement amelioree
US6191095B1 (en) 1997-05-30 2001-02-20 Lever Brothers Company, A Division Of Conopco, Inc. Detergent compositions
US6069124A (en) * 1997-05-30 2000-05-30 Lever Brothers Company Division Of Conopco, Inc. Granular detergent compositions and their production
US6221831B1 (en) 1997-05-30 2001-04-24 Lever Brothers Company, Division Of Conopco, Inc. Free flowing detergent composition containing high levels of surfactant
US6303558B1 (en) 1997-05-30 2001-10-16 Lever Brothers Co., Division Of Conopco Detergent composition containing at least two granular components
WO1999032591A1 (fr) * 1997-12-22 1999-07-01 Henkel Kommanditgesellschaft Auf Aktien Detergent et nettoyant particulaire
WO2001046375A1 (fr) * 1999-12-17 2001-06-28 Henkel Kommanditgesellschaft Auf Aktien Procede de production de granules de tensioactifs de sucre
DE19961333B4 (de) * 1999-12-17 2006-12-14 Henkel Kgaa Verfahren zur Herstellung von Zuckertensidgranulaten
WO2014015090A1 (fr) * 2012-07-20 2014-01-23 The Procter & Gamble Company Poche hydrosoluble revêtue avec une composition comprenant un fluidifiant de silice
US9290727B2 (en) 2012-07-20 2016-03-22 The Procter & Gamble Company Water-soluble pouch coated with a composition comprising silica flow aid

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DE69325014D1 (de) 1999-06-24
EP0618290B1 (fr) 1999-05-19
ATE180274T1 (de) 1999-06-15
WO1994023001A1 (fr) 1994-10-13
CA2159179C (fr) 1999-07-06
CA2159179A1 (fr) 1994-10-13
JPH08508524A (ja) 1996-09-10

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