[go: up one dir, main page]

EP0618290B1 - 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

Info

Publication number
EP0618290B1
EP0618290B1 EP93870059A EP93870059A EP0618290B1 EP 0618290 B1 EP0618290 B1 EP 0618290B1 EP 93870059 A EP93870059 A EP 93870059A EP 93870059 A EP93870059 A EP 93870059A EP 0618290 B1 EP0618290 B1 EP 0618290B1
Authority
EP
European Patent Office
Prior art keywords
nonionic surfactant
detergent
silica
sodium aluminosilicate
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP93870059A
Other languages
German (de)
English (en)
Other versions
EP0618290A1 (fr
Inventor
Paul Amaat Raymond Gerard France
Paul Van Dijk
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=8215331&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0618290(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP93870059A priority Critical patent/EP0618290B1/fr
Priority to DE69325014T priority patent/DE69325014T2/de
Priority to AT93870059T priority patent/ATE180274T1/de
Priority to CA002159179A priority patent/CA2159179C/fr
Priority to US08/532,554 priority patent/US5691294A/en
Priority to PCT/US1994/001915 priority patent/WO1994023001A1/fr
Priority to JP6522055A priority patent/JPH08508524A/ja
Publication of EP0618290A1 publication Critical patent/EP0618290A1/fr
Publication of EP0618290B1 publication Critical patent/EP0618290B1/fr
Application granted granted Critical
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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 100:1 to 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-A-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-A-0 351 937 published 24th January, 1990 and EP-A-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-A-0 513 824 published 19th November, 1992, describes a process for making nonionic detergent granules and the use of a surface coating having a particle size of less than 10 micrometers.
  • EP-A-0 477 974 published on 1st April, 1992, discloses nonionic powdery detergent compositions comprising 10 to 60% by weight of crystalline aluminosilicate and an oil absorbent carrier.
  • the oil absorbent carriers exemplified include mixtures Tokusil AL-1 (silica).
  • 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 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.
  • 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-A-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 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, and the like).
  • 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, magnesium, etc.), 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
  • 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 piperidinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine and mixtures thereof.
  • Exemplary surfactants are C 12 -C 18 alkyl polyethoxylate (1.0) sulfate, C 12 -C 18 E(1.0)M), C 12 -C 18 alkyl polyethoxylate (2.25) sulfate, C 12 -C 18 E(2.25)M), C 12 -C 18 alkyl polyethoxylate (3.0) sulfate C 12 -C 18 E(3.0), and C 12 -C 18 alkyl polyethoxylate (4.0) sulfate C 12 -C 18 E(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, 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 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 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 alkylpolyglucoside (the nonionic
  • 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. When included therein, 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, 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 : [R 2 (OR 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 from 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 %, 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 form 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 dimenthyl 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 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 [(AlO 2 ) z ⁇ (SiO 2 ) y ] ⁇ xH 2 O wherein z and y are at least 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 micrometers is preferred.
  • the aluminosilicate ion exchange builder materials herein are in hydrated form and contain from 10% 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 micrometer to 10 micrometers. Amorphous materials are often smaller, e.g., down to less than 0.01 micrometer.
  • Preferred ion exchange materials have a particle size diameter of from 0.2 micrometer to 4 micrometers.
  • 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 0.13 grams Ca + /litre/minute/gram/litre (2 grains Ca ++ /gallon/minute/gram/gallon) of aluminosilicate (anhydrous basis), and generally lies within the range of from 0.13 grams/litre/minute/gram/litre (2 grains/gallon/minute/gram/gallon) to 0.39 grams/litre/minute/gram/litre (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 0.26 grams/litre/minute/gram/litre (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 0.065 grams/litre/minute/gram/litre (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.
  • 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 (SiO2) 12 ] ⁇ xH 2 O wherein x is from 20 to 30, especially about 27 and has a particle size generally less than 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 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 having a molar ratio of SiO 2 to alkali metal oxide of from 0.5 to 4.0, preferably from 1.0 to 2.4.
  • powders normally used in detergents such as zeolite, carbonate, silica, silicate, citrate, phosphate or perborate 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 such process is to agglomerate by the following steps:
  • 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.
  • detergent granules are prepared by an agglomeration technique such as the fine dispersion mixing and granulation process described above, followed by spraying some or all of the nonionic surfactant onto detergent granules in 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 detergent agglomerates are then dry mixed with other optional ingredients.
  • the process is described in more details in the Applicant's WO-A-9 405 761.
  • 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 Layered silicate compacted granule 30 (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
  • 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) % by weight of product on sieve Tyler Sieve no microns 3 6 E 14 1180 22 21 25 20 850 52 48 53 35 425 95 97 92 65 212 99 99 97 100 150 100 100 100 Average particle size (microns) 782 762 797 Standard geometric deviation 0.553 0.521 0.634
  • 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.
  • 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.

Landscapes

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

Claims (10)

  1. Composant ou composition détergente granulaire ayant une masse volumique apparente d'au moins 700 g/l, qui comprend :
    i) une poudre détergente qui comprend au moins un tensioactif non-ionique qui est un liquide à des températures inférieures à 40°C ; et
    il) de 0,5 à 15 % en poids d'un auxiliaire d'écoulement pulvérulent, caractérisé en ce que l'auxiliaire d'écoulement comprend de l'aluminosilicate de sodium et de la silice hydrophobe, où le rapport de l'aluminosilicate de sodium à la silice hydrophobe dans le composant il) est de 100:1 à 3:1.
  2. Composant ou composition détergente selon la revendication 1, qui comprend de 20 à 80 % en poids d'un ou plusieurs tensioactifs non-ioniques.
  3. Composant ou composition détergente selon l'une ou l'autre des revendications 1 ou 2, qui comprend au moins 10 % en poids d'au moins un tensioactif non-ionique qui est un liquide à des températures inférieures à 40°C.
  4. Composant ou composition détergente selon l'une quelconque des revendications précédentes, qui comprend au moins un tensioactif non-ionique choisi dans le groupe des alcools éthoxylés, et au moins un tensioactif non-ionique choisi dans le groupe des amides d'acides gras polyhydroxylés.
  5. Composant ou composition détergente selon la revendication 4, qui comprend au moins un tensioactif non-ionique choisi dans le groupe des alcools éthoxylés ayant un groupe alkyle ayant essentiellement de 9 à 15 atomes de carbone et en moyenne 2 à 10 groupes éthoxylés par molécule, et au moins un tensioactif non-ionique choisi dans le groupe des N-méthylglucamides, ayant un groupe alkyle ayant essentiellement de 12 à 18 atomes de carbone.
  6. Composant ou composition détergente selon l'une quelconque des revendications précédentes, dans lequel le rapport de l'aluminosilicate de sodium à la silice dans le composant il) est de 20:1 à 5:1 et de préférence d'environ 10:1.
  7. Composant ou composition détergente selon l'une quelconque des revendications précédentes, dans lequel la silice est une silice fumée hydrophobe ayant une granulométrie primaire moyenne de 7 à 25 nanomètres.
  8. Composant ou composition détergente selon l'une quelconque des revendications précédentes, dans lequel l'aluminosilicate de sodium est un aluminosilicate cristallin hydraté.
  9. Procédé pour préparer une poudre détergente à écoulement libre ayant une masse volumique apparente d'au moins 700 g/l, qui comprend les étapes consistant :
    i) à préparer un système tensioactif non-ionique qui comprend au moins un tensioactif non-ionique qui est un liquide à des températures inférieures à 40°C ;
    il) à préparer une poudre détergente granulaire ayant une masse volumique apparente d'au moins 650 g/l ;
    iii) à pulvériser tout ou partie du système tensioactif non-ionique de l'étape i) sur la poudre détergente granulaire de l'étape ii) ;
    iv) à mélanger le produit de l'étape iii) avec une poudre prémélangée, ladite poudre prémélangée comprenant de l'aluminosilicate de sodium et de la silice hydrophobe, où la poudre prémélangée est utilisée en une quantité de 3 à 15 % en poids par rapport au composant détergent fini ou à la composition détergente finie, et ayant une rapport de l'aluminosilicate de sodium à la silice hydrophobe de 100:1 à 3:1.
  10. Procédé selon la revendication 9, dans lequel le rapport de l'aluminosilicate de sodium à la silice hydrophobe dans la poudre prémélangée de l'étape iv) est de 20:1 à 5:1 et de préférence d'environ 10:1.
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
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
DE69325014T DE69325014T2 (de) 1993-03-30 1993-03-30 Natrium-Aluminiumsilikat und hydrophobe Kieselsäure enthaltende Fliesshilfe für Waschmittelpulver
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
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
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___________
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

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
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

Publications (2)

Publication Number Publication Date
EP0618290A1 EP0618290A1 (fr) 1994-10-05
EP0618290B1 true EP0618290B1 (fr) 1999-05-19

Family

ID=8215331

Family Applications (1)

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

Country Status (6)

Country Link
EP (1) EP0618290B1 (fr)
JP (1) JPH08508524A (fr)
AT (1) ATE180274T1 (fr)
CA (1) CA2159179C (fr)
DE (1) DE69325014T2 (fr)
WO (1) WO1994023001A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0643130B2 (fr) * 1993-09-13 2007-09-19 The Procter & Gamble Company Composition détergentes granulaires contenant un tensio-actif non-ionique et procédé de sa préparation
DE19524464C2 (de) * 1995-07-10 2000-08-24 Cognis Deutschland Gmbh Verfahren zur Herstellung von Zuckertensidgranulaten
TW370561B (en) 1996-03-15 1999-09-21 Kao Corp High-density granular detergent composition for clothes washing
CZ356398A3 (cs) * 1996-05-07 1999-04-14 The Procter & Gamble Company Postup pro přípravu aglomerovaných detergentních směsí majících zlepšenou tekutost
US5807817A (en) * 1996-10-15 1998-09-15 Church & Dwight Co., Inc. Free-flowing high bulk density granular detergent product
GB9711359D0 (en) 1997-05-30 1997-07-30 Unilever Plc Detergent powder composition
GB9711350D0 (en) * 1997-05-30 1997-07-30 Unilever Plc Granular detergent compositions and their production
WO1998054289A1 (fr) 1997-05-30 1998-12-03 Unilever Plc Compositions detergentes particulaires a ecoulement fluide
GB9711356D0 (en) 1997-05-30 1997-07-30 Unilever Plc Particulate detergent composition
DE19757216A1 (de) * 1997-12-22 1999-06-24 Henkel Kgaa Teilchenförmiges Wasch- und Reinigungsmittel
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

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA962158A (en) * 1971-03-11 1975-02-04 Unilever Limited Detergent compositions
US4666740A (en) * 1976-12-02 1987-05-19 The Colgate-Palmolive Co. Phosphate-free concentrated particulate heavy duty laundry detergent
EP0000216A1 (fr) * 1977-06-23 1979-01-10 THE PROCTER & GAMBLE COMPANY Composition détergente renfermant un système régulateur de mousse
US4406808A (en) * 1977-10-06 1983-09-27 Colgate-Palmolive Company High bulk density carbonate-zeolite built heavy duty nonionic laundry detergent
DE2900063A1 (de) * 1979-01-02 1980-07-17 Henkel Kgaa Waschmittel mit einem gehalt an schaumdaempfend wirkendem polydimethylsiloxan und verfahren zu dessen herstellung
DE3424987A1 (de) * 1984-07-06 1986-02-06 Unilever N.V., Rotterdam Verfahren zur herstellung eines pulverfoermigen waschmittels mit erhoehtem schuettgewicht
US4970017A (en) * 1985-04-25 1990-11-13 Lion Corporation Process for production of granular detergent composition having high bulk density
ES2020949B3 (es) * 1986-01-17 1991-10-16 Kao Corp Composicion detergente granular de alta densidad.
JPS62228000A (ja) * 1986-03-28 1987-10-06 花王株式会社 高密度粒状洗剤組成物
DE3805624A1 (de) * 1988-02-24 1989-08-31 Degussa Pulverfoermiger waschmittelentschaeumer
GB8810821D0 (en) * 1988-05-06 1988-06-08 Unilever Plc Detergent compositions & process for preparing them
DE69112970T2 (de) * 1990-09-28 1996-03-21 Kao Corp Nichtionische pulverförmige Detergentzusammensetzung.
JP3192469B2 (ja) * 1991-05-17 2001-07-30 花王株式会社 ノニオン洗剤粒子の製造方法

Also Published As

Publication number Publication date
JPH08508524A (ja) 1996-09-10
DE69325014T2 (de) 2000-01-20
CA2159179C (fr) 1999-07-06
ATE180274T1 (de) 1999-06-15
CA2159179A1 (fr) 1994-10-13
DE69325014D1 (de) 1999-06-24
EP0618290A1 (fr) 1994-10-05
WO1994023001A1 (fr) 1994-10-13

Similar Documents

Publication Publication Date Title
EP0862611B1 (fr) Procede de production de granules de silicate de metal alcalin cristallin et detergent granulaire d'une densite elevee
CA2160662C (fr) Structuration de surfactifs liquides non ioniques avant le procede de granulation
EP0643130B1 (fr) Composition détergentes granulaires contenant un tensio-actif non-ionique et procédé de sa préparation
EP0618290B1 (fr) Aides d'écoulement pour poudres détergents comprenant d'aluminosilicate de sodium et de la silice hydrophobe
US5691294A (en) Flow aids for detergent powders comprising sodium aluminosilicate and hydrophobic silica
EP0578871B1 (fr) Procédé et compositions pour détergents sous forme compacte
US5698510A (en) Process for making granular detergent compositions comprising nonionic surfactant
WO1996003482A1 (fr) Procede de production de detergents granulaires et compositions de detergents comprenant un agent tensioactif non ionique
CA2143628C (fr) Procede pour l'obtention de detergent granulaire haute densite; compositions ainsi obtenues
US5610131A (en) Structuring liquid nonionic surfactants prior to granulation process
JPH09502468A (ja) 界面活性剤と消泡成分とを含む粒状洗剤組成物
CA2167158C (fr) Compositions detergentes renfermant du percarbonate et methodes de preparation
CA2231577C (fr) Procede de fabrication de detergents granulaires
JP3008266B2 (ja) 結晶性アルカリ金属ケイ酸塩顆粒の製造方法及び衣料用の高嵩密度粒状洗剤組成物
EP0627484A1 (fr) Agglomérats d'argiles revêtus des matériaux particulaires finement divisés
EP0660873B2 (fr) Detergent en poudre de haute densite
KR100267274B1 (ko) 고농축 비이온성 과립형 세제조성물 및 그 제조방법
EP1390461B1 (fr) Composition detergente granulaire

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU NL PT SE

17P Request for examination filed

Effective date: 19950323

17Q First examination report despatched

Effective date: 19970520

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19990519

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990519

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990519

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990519

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19990519

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990519

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990519

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990519

REF Corresponds to:

Ref document number: 180274

Country of ref document: AT

Date of ref document: 19990615

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69325014

Country of ref document: DE

Date of ref document: 19990624

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990819

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990819

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000330

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000330

26 Opposition filed

Opponent name: HENKEL KGAA

Effective date: 20000218

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PLBO Opposition rejected

Free format text: ORIGINAL CODE: EPIDOS REJO

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

APAA Appeal reference recorded

Free format text: ORIGINAL CODE: EPIDOS REFN

PLAY Examination report in opposition despatched + time limit

Free format text: ORIGINAL CODE: EPIDOSNORE2

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20050302

Year of fee payment: 13

PLAT Information related to reply to examination report in opposition deleted

Free format text: ORIGINAL CODE: EPIDOSDORE3

PLBC Reply to examination report in opposition received

Free format text: ORIGINAL CODE: EPIDOSNORE3

PLBC Reply to examination report in opposition received

Free format text: ORIGINAL CODE: EPIDOSNORE3

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20060206

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20060330

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20060331

Year of fee payment: 14

PLAY Examination report in opposition despatched + time limit

Free format text: ORIGINAL CODE: EPIDOSNORE2

PLBC Reply to examination report in opposition received

Free format text: ORIGINAL CODE: EPIDOSNORE3

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20070330

27W Patent revoked

Effective date: 20070720

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070330

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20060331