EP0150613A2 - Compositions détergentes - Google Patents

Compositions détergentes Download PDF

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Publication number
EP0150613A2
EP0150613A2 EP84308962A EP84308962A EP0150613A2 EP 0150613 A2 EP0150613 A2 EP 0150613A2 EP 84308962 A EP84308962 A EP 84308962A EP 84308962 A EP84308962 A EP 84308962A EP 0150613 A2 EP0150613 A2 EP 0150613A2
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EP
European Patent Office
Prior art keywords
granules
weight
aluminosilicate
sodium
parts
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.)
Granted
Application number
EP84308962A
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German (de)
English (en)
Other versions
EP0150613A3 (en
EP0150613B1 (fr
Inventor
Roger Brace
Ian Eric Niven
Andrew William Travill
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.)
Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority to AT84308962T priority Critical patent/ATE52537T1/de
Publication of EP0150613A2 publication Critical patent/EP0150613A2/fr
Publication of EP0150613A3 publication Critical patent/EP0150613A3/en
Application granted granted Critical
Publication of EP0150613B1 publication Critical patent/EP0150613B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • C11D3/39—Organic or inorganic per-compounds

Definitions

  • Granular detergent compositions invariably contain water. Most or all of this water is relatively loosely bound and is lost when the composition is heated to say 135°C. This loosely bound water is constituted by water of crystallisation of the components in the composition, and further water which is more loosely bound to ingredients such as detergent active materials.
  • moisture is the water which is lost from the composition when it is heated to 135°C.
  • compositions containing amorphous aluminosilicate and also in compositions containing NTA (sodium nitrilotriacetate) some water is not lost at 135°C. This more tightly bound water however adds to the total water content of the composition.
  • compositions containing amorphous aluminosilicate are dependent upon the moisture content of the composition rather than the total water content.
  • the critical factor in the ion-exchange properties of the composition is the moisture content of the base powder.
  • y preferably lies between 0.25 and 0.5. Otherwise, the preferred level for y is from 0.5 to 0.6.
  • compositions of the invention necessarily contain a synthetic detergent active material otherwise known as a detergent surfactant, preferably present at an overall level of between 2% and 60% by weight, especially about between 5% and 40% of the composition.
  • a synthetic detergent active material otherwise known as a detergent surfactant
  • Suitable detergent surfactants are well known and readily available, as described for example in "Surface Active Agents and Detergents", Volumes I and II by Schwartz, Perry and Berch.
  • Synthetic anionic detergent compounds which can be used are usually water soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating the higher (C 8 -C 18 ) alcohols produced by reducing the glycerides of tallow or coconut oil; sodium and potassium alkyl (C 9 -C 20 ) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 -C 15 ) benzene sulphonates, sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C 8 -C 18 ) fatty aclohol- alkylene oxide, particularly ethylene oxide, reaction products; the reaction of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and potassium salt
  • Nonionic detergent active compounds may alternatively or additionally be used.
  • nonionic detergent active compounds include the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C 6 -C 22 ) phenols, generally 5 to 25 EO; ie 5 to 25 units of ethylene oxide per molecule; the condensation products of aliphatic (C 8 -C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene- diamine.
  • Other so-called nonionic detergent active compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
  • compositions for example mixed anionic or mixed anionic and nonionic compounds, may be used in the detergent compositions, particularly to impart thereto controlled low sudsing properties. This is beneficial for compositions intended for use in suds-intolerant automatic washing machines.
  • amphoteric or zwitterionic detergent active compounds can also be used in the compositions of the invention but this is not normally desired due to their relatively high cost. If any amphoteric or zwitterionic detergent active compounds are used, especially sulphobetaines such as hexadecyl dimethyl ammoniopropane sulphonate, it is generally in small amounts in compositions based on the much more commonly used anionic and/or nonionic detergent active compositions.
  • Some soap can also be present in the compositions, especially in low sudsing compositions together with mixed synthetic and nonionic detergent compounds.
  • Such soaps are the sodium, or less desirably potassium, salts of C 12 - C 22 fatty acids, especially natural fatty acids derived from nut oils, such as coconut oil or palm kernel oil, or preferably tallow class fats, such as beef and mutton tallows, palm oil, lard, some vegetable butters and castor oil, or mixtures thereof.
  • tallow class soaps which are soaps of predominantly C 14 -C 20 (mainly C 18 ) fatty acids of which normally at least about 40% are saturated fatty acids
  • soaps from nut oils which are soaps of predominantly C 10 -C 14 (mainly C 12 ) fatty acids, of which normally at least about 75% are saturated fatty acids.
  • the amount of soap can be varied widely from about 0.5% to about 20% by weight of the composition, but is normally from about 1% to about 5% if present for lather control purposes. Higher amounts of soap can be used as a supplementary detergent active compound.
  • compositions of the invention necessarily contain an amorphous aluminosilicate builder material, preferably present at a level of from 10% to 60% by weight, especially 12.5% to 50% by weight of the composition.
  • Amorphous aluminosilicate builder materials are described in detail in GB 1 473 202 (HENKEL).
  • amorphous aluminosilicates described therein have one significant defect, namely that they react with sodium silicate, which is an important constituent of most detergent compositions.
  • the mechanism of the reaction between amorphous aluminosilicate and sodium silicate is not fully understood, but its effect is to lessen the effectiveness of the aluminosilicate as a detergent builder in that it slows down the removal of hardness ions and may also reduce the capacity of the aluminosilicate for such ions.
  • an amorphous aluminosilicate which can be used in the preparation of detergent compositions, using orthodox spray-drying equipment and not requiring special techniques to prevent the interaction between the sodium silicate and amorphous sodium aluminosilicate.
  • This amorphous aluminosilicate can be produced in a particle size which is such that it can be used in detergent compositions without further size reduction and, also, in a sufficiently high solids content that excessive quantities of water do not have to be removed from the aluminosilicate and, hence, from a detergent slurry composition containing the aluminosilicate, making it commercially less attractive.
  • a stable slurry of the aluminosilicate can be prepared in the presence of suitable dispersing agents and size reduced aluminosilicate by grinding or milling a slurry of aluminosilicate and dispersing agent.
  • the preferred amorphous hydrated sodium aluminosilicate is characterised by a chemical composition calculated on an anhydrous basis: 0.8-1.4 Na 2 O:Al 2 O 3 :2.2-3.6 SiO 2 , and has, calculated on a dry basis, a calcium ion-exchange capacity greater than 100 mg CaO/g, a magnesium capacity greater than 50 mg MgO/g, an average particle size in the range 2 to 20 ⁇ m, and the ability to form a filter cake having a solids content in the range 35-50%, in a filter press with a closing pressure of 5.62 kg/cm 2 , which filter cake can be converted into a pumpable slurry in said solids range, and has a silicate resistance (as hereinafter defined) such that the second order rate constant k for the calcium exchange process is greater than 0.2 °H -1 min -1 and a residual water hardness after 10 minutes of less than 1.5 °H and which after drying at 50°C to 80% solids has a rate constant k
  • the amorphous hydrated sodium aluminosilicate has a chemical composition of: 0.8-1.4 Na 2 O:Al 2 O 3 :2.4-3.2 Si0 2 and may optionally contain an inert soluble salt such as sodium sulphate.
  • the calcium and magnesium ion-exchange capacities are determined as follows.
  • Sodium aluminosilicate (equivalent to 1.00 g anhydrous solids determined as the residue after heating to constant weight at 700°C) is added to 1 litre of 5.0 x 10 -3 M CaCl 2 solution and stirred for 15 minutes at 20°C.
  • the aluminosilicate is then removed by Millipore membrane filtration and the residual calcium concentration ( Z x 10 M) of the filtrate is determined by complexometric titration or atomic absorption spectrophotometry.
  • the calcium exchange capacity is calculated as 56(5.0-Z) mg CaO/g aluminosilicate.
  • Magnesium ion-exchange capacity is measured in a similar fashion using a 5 x 10 -3 M MgCl 2 stock solution and a pH in the range 9.5-10.5.
  • the test is designed to simulate some of the conditions which prevail when sodium aluminosilicate is used in a detergent system.
  • the response of a Radiometer calcium ion specific electrode is determined by the addition of aliquots (0-20 mls) of calcium chloride (3 x 10 -2 M) to a solution of 5 mls M NaCl in 175 mls of water at 50°C. The resulting solution is 0.025 M in Na + and 3 x 10 -3 M in Ca ++ . To this is added sufficient aluminosilicate to give 2.5 g/litre (anhydrous basis) and stirring is maintained throughout the water softening measurement. The electrode response is measured over the next 10 minutes and, using the calibration data, is calculated as Ca concentration (°H) versus time. Water softening may be conveniently summarised by the hardness remaining after 1 and 10 minutes.
  • the electrode test is applied to filter cake, dried powders and to the slurries produced by the silicate resistance test.
  • the test may still be performed provided allowance is made when weighing samples for the ion-exchange measurement.
  • the water softening kinetics involved in the determination of the rate constant k involve the use of data obtained using the calcium ion specific electrode as described above.
  • the equilibrium hardness is determined from:
  • the most effective sodium aluminosilicates for use according to this invention have a rate constant k s greater than 2 and an equilibrium calcium concentration (Ca ) less than 1 °H after silicate treatment.
  • Amorphous aluminosilicates which will yield, economically, a filter cake of relatively high solids content containing an aluminosilicate at a particle size suitable for inclusion in detergent compositions according to the invention and having the benefits of silicate resistance previously spelt out, may be prepared by a process in which aqueous sodium silicate, having a composition Na 2 0 2-4 Si0 2 and a concentration in the range 1-4 moles/litre SiO 2 ; an aqueous aluminate having a composition 1-2 Na 2 0 Al 2 O 3 and a concentration in the range 0.5 to 2.0 moles/litre A1203, are intimately mixed together at a temperature of up to 45°C in a mixing device to produce a sodium aluminosilicate composition which is immediately subjected to high shear in a disintegrator to produce a particle size of aluminosilicate less than 20 ⁇ m and subsequently aged.
  • aqueous sodium silicate having a composition Na 2 0 2-4 Si0 2
  • aluminate and silicate solutions can conveniently be achieved using a mixer such as that described in Handbook of Chemical Engineering by Perry & Chilton, 5th Edition, Chapter 21, ref 21-4, under the heading "Jet Mixers”.
  • the objective of such mixers is to ensure a rapid and intimate mixing of the two solutions.
  • Suitable disintegrators for use in reducing the particle size of the sodium aluminosilicate include devices designed to impart high shear, such as the Waring (Trade Mark) blender supplied by Waring Products Division, Dynamics Corporation of America, New Hartford, Connecticut, USA, and Greaves SM (Trade Mark) mixer, as supplied by Joshua Greaves & Sons Limited, Ramsbottom, Lancashire, England.
  • Waring Trade Mark
  • Greaves SM Trade Mark
  • Various other devices can be used but it is believed that where the shear is provided by rotation of a stirrer blade in the reaction mixture, no such device will be satisfactory unless the tip speed of the rotor exceeds 300 m/min.
  • the tip speed is in the range 1000-3000 m/min.
  • the processing subsequent to the high shear treatment can comprise an ageing step for the free-flowing slurry which typically extends for a period of 1-2 hours, but can be longer.
  • the precipitate formation and ageing can take place in the presence of an inert salt such as sodium sulphate.
  • the aged slurry can also be treated with a dilute mineral acid such as sulphuric acid to reduce its pH to about 10.0 or 11.0 prior to washing and filtering.
  • compositions of the invention necessarily contain a peroxygen bleach compound, preferably at a level of between 5% and 50% by weight of the composition, especially between 8% and 32% by weight.
  • Suitable peroxygen bleaches include sodium perborate (for example as the tetrahydrate) and sodium percarbonate.
  • compositions of the invention may include an alkaline salt selected from alkalimetal silicates, carbonates and phosphates.
  • the amount of sodium silicate used can vary widely according to the type of composition involved, that is from a minimum of about 0.1% to about 50% by weight of the resultant detergent composition. Normally, however, amounts in the range of from about 0.5% to about 20%, especially about 1% to about 15%, are used for conventional purposes, that is for corrosion inhibition, pH buffer control and powder structuring properties. Amounts of sodium silicate in excess of this up to about 40% are sometimes used for supplementary detergency building properties in fabric washing compositions. Still higher levels of sodium silicate can be present in other types of powdered detergent compositions, for example for dishwashing or industrial purposes in which high alkalinity is usual.
  • any normal type of sodium silicate can be used, preferably with a sodium oxide to silica ratio of from about 2:1 to about 1:4, for example sodium alkaline silicate (Na 2 0.2Si0 2 ) sodium neutral silicate (Na20.3.3Si02), sodium metasilicate (Na 2 0.Si0 2 ) or sodium orthosilicate (2Na 2 O.SiO 2 ), or mixtures thereof, the less alkaline silicates (Na 2 0.1-4SiO 2 ) being preferred.
  • sodium alkaline silicate Na 2 0.2Si0 2
  • sodium neutral silicate Na20.3.3Si02
  • sodium metasilicate Na 2 0.Si0 2
  • sodium orthosilicate 2Na 2 O.SiO 2
  • the less alkaline silicates Na 2 0.1-4SiO 2
  • alkaline materials examples include sodium carbonate, sodium tripolyphosphate, sodium orthophosphate and sodium pyrophosphate. These alkaline materials will also add to the building capacity of the compositions.
  • the use of sodium pyrophosphate may lead to unacceptably high levels of inorganic deposition on the fabrics and it is therefore preferred to include less than 5% pyrophosphate in the compositions, most preferably substantially no pyrophosphates.
  • the detergent compositions made according to the invention can contain any of the conventional additives in the amounts in which such additives are normally employed in fabric washing detergent compositions.
  • these additives include lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, powder flow aids such as finely divided silicas and other aluminosilicates, lather depressants, antiredeposition agents such as sodium carboxymethyl- cellulose, per-acid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid and alkali metal salts of dichloroisocyanuric acid, fabric softening agents such as clays of the smectite and illite types, anti-ashing aids, starches, soap scum dispersants, inorganic salts such as sodium sulphate, and usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases and amylases, germicides and colourants.
  • slurry stabilisers such as copoly- ethylene-maleic anhydride and copolyvinylmethylether- maleic anhydride, usually in salt form.
  • zeolites crystalline aluminosilicates
  • the invention necessarily requires that the base powder granules be made by spray-drying.
  • the slurry making and spray drying steps in the process of the present invention may be accomplished using conventional equipment for this purpose, for example in crutcher, paddle or turbo mixers and spray drying towers.
  • Normal temperatures may be used for these operations, for example from about 30°C to about 100°C, preferably about 70°C to 90°C for the slurry making and about 200°C to 450°C for the drying gas inlet in the spray drying process, with higher temperatures within this range being generally preferred for economic reasons.
  • the base powder necessarily contains the detergent surfactant and the amorphous aluminosilicate.
  • the peroxybleach, together with any other heat sensitive ingredients may be subsequently mixed with the base powder granules.
  • the alkaline salt if present, may be included in the granules, mixed therewith subsequently or both. Where sodium silicate is the alkaline salt, it may be advantageous to add it subsequently to further reduce the risk of interaction with the sodium aluminosilicate in the slurry. It is preferred that any subsequently added materials be in their fully hydrated forms.
  • the filter cake was processed so as to produce a stable, pumpable aqueous suspension by incorporating a suitable dispersing agent and reducing the particle size of the aluminosilicate to between 4.0 and 6.0 microns by milling or grinding the aluminosilicate in an aqueous medium containing the said dispersing agent, all in accordance with the teaching of British Patent Specification No 1 051 336 (MOBIL OIL CORPORATION).
  • the filter cake, or the suspension as prepared above can be converted into dry powder form by a variety of drying techniques.
  • the residual moisture content (loss on ignition) of the aluminosilicate is not less than about 20% by weight.
  • Filter cakes can be conveniently dried in an oven at a temperature of 50°C for the purpose of testing the preservation of the ion exchange properties and the determination of the k d value.
  • the mixer used was a Greaves SM mixer, having a high speed impeller rotating at about 3000 rpm with a tip speed of 1975 m/min.
  • Intense stirring is required to (a) prevent gelation which would lead to low solids content filter cakes and (b) control the particle size of the aluminosilicate.
  • a Waring blender (Model CB 6 "1 gallon capacity") having a high speed impeller, about 13000 rpm, producing a tip speed of about 2800 m/min may be used.
  • Ion exchange performance - Ca electrode method (°HCa)
  • particulate detergent compositions were prepared by spray-drying a base powder and adding thereto a number of post-dosed ingredients.
  • the base powders had the following formulations, in parts by weight expressed as anhydrous material.
  • the ion exchange properties of these powders after storage was determined by washing the powders with de-ionised water on a filter cake to extract the insoluble aluminosilicate material and drying. 0.5g of the dried material was then added to 200 ml of water having a hardness of 30°FH (equivalent to a calcium ion concentration of 3 x 10- 3 molar). The free calcium ion concentration was measured after 1 minute.
  • the powders were stored for 6 weeks at 37°C and 70% relative humidity (Examples 4, 4A and 4B) or for 12 weeks at 28°C and 70% relative humidity (Examples 1, 2, 2A, 3 and 3A). In the same manner, the ion exchange properties of the base powders were measured immediately after spray drying. The results were as follows:
  • Example 1 to 4 The powders of Examples 1 to 4 were stored under various conditions after which the percentage of perborate which had decomposed was measured. Similar powders were produced in which the amorphous aluminosilicate was replaced by Zeolite-4A, of similar particle size, to provide control Examples. With the zeolite containing powders the moisture content was lower, namely between about 4.5% and 8% of the base powders. Moisture contents identical to Examples 1 to 4 lead to poor powder properties and even more perborate decomposition on storage. The results were as follows:
  • Example 5 and 6 After storage at 37°C and 70% relative humidity for 4 weeks, 39% and 28% of the sodium perborate in Example 5 and 6 respectively had decomposed.
  • zeolite 4A of similar particle size
  • a base powder was spray dried having a composition identical to Example 4, but in which no sodium silicate was included.
  • the water level was 9.7 parts and the total base powder weight was 53.4 parts.
  • the moisture content was 7.1 parts (13.3%), giving a value of y equal to 0.42.
  • a number of detergent compositions was prepared by spray-drying an aqueous slurry containing the following ingredients: Miscellaneous minor ingredients 1.4
  • Example B The powders of Examples B and 10 were stored for 12 weeks at 28°C and 70% relative humidity. After this storage the ion-exchange rate was again measured. In the case of Example B the time taken to reach 3.3° FH was greater than 10 minutes and in the case of Example 10, 0.9 minutes.
  • Example 10 shows improved bleach stability over the comparison composition, Example B.
  • Example B approximates to that disclosed in Example 1 of British Patent Specification GB 2 013 707.
  • the detergent actives used in the foregoing examples were approximately:

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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  • Inorganic Chemistry (AREA)
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EP84308962A 1983-12-21 1984-12-20 Compositions détergentes Expired - Lifetime EP0150613B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84308962T ATE52537T1 (de) 1983-12-21 1984-12-20 Reinigungsmittelzusammensetzungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8334017 1983-12-21
GB838334017A GB8334017D0 (en) 1983-12-21 1983-12-21 Detergent composition

Publications (3)

Publication Number Publication Date
EP0150613A2 true EP0150613A2 (fr) 1985-08-07
EP0150613A3 EP0150613A3 (en) 1987-08-05
EP0150613B1 EP0150613B1 (fr) 1990-05-09

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP84308962A Expired - Lifetime EP0150613B1 (fr) 1983-12-21 1984-12-20 Compositions détergentes

Country Status (10)

Country Link
EP (1) EP0150613B1 (fr)
JP (1) JPS60155296A (fr)
AT (1) ATE52537T1 (fr)
AU (1) AU560739B2 (fr)
CA (1) CA1227100A (fr)
DE (1) DE3482190D1 (fr)
ES (1) ES8608037A1 (fr)
GB (1) GB8334017D0 (fr)
NO (1) NO163140C (fr)
ZA (1) ZA849950B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0451894A1 (fr) * 1990-04-09 1991-10-16 Unilever N.V. Compositions détergentes granulaires à haute densité apparente et leur procédé de préparation
EP0461428A2 (fr) * 1990-06-13 1991-12-18 Leuna-Werke Ag Composition détergente
DE4031910A1 (de) * 1990-10-08 1992-04-09 Henkel Kgaa Percarbonathaltiges waschmittel
WO1992015663A1 (fr) * 1991-03-05 1992-09-17 Henkel Kommanditgesellschaft Auf Aktien Detergents
EP0518576A2 (fr) * 1991-06-10 1992-12-16 Unilever Plc Compositions détergentes granulaires à haute densité apparente
EP0572288A1 (fr) * 1992-05-26 1993-12-01 Rhone-Poulenc Chimie Utilisation de silico-aluminate amorphe en tant que capteurs de précipités calciques

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8525269D0 (en) * 1985-10-14 1985-11-20 Unilever Plc Detergent composition
GB8603667D0 (en) * 1986-02-14 1986-03-19 Unilever Plc Detergent composition
GB8810193D0 (en) * 1988-04-29 1988-06-02 Unilever Plc Detergent compositions & process for preparing them
JP4385981B2 (ja) 2005-03-30 2009-12-16 オンキヨー株式会社 動電型スピーカー

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2237839A1 (fr) * 1973-07-16 1975-02-14 Procter & Gamble
GB2013707A (en) * 1978-02-01 1979-08-15 Unilever Ltd Preparation of Spray-Dryed Detergent Compositions
US4180485A (en) * 1977-11-02 1979-12-25 The Procter & Gamble Company Spray-dried detergent compositions
EP0070079A2 (fr) * 1981-07-15 1983-01-19 Unilever N.V. Composition détergente
EP0098108A1 (fr) * 1982-06-25 1984-01-11 Unilever Plc Composition détergente

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO148854C (no) * 1973-04-13 1985-05-29 Henkel Kgaa Pulverformet til kornet vaske- eller blekemiddelblanding, uten eller med redusert fosfatinnhold
JPS5416521B2 (fr) * 1973-07-05 1979-06-22
BE874420A (fr) * 1978-03-02 1979-08-23 Unilever Nv Procede de production de compositions detergentes
JPS5821497A (ja) * 1981-07-31 1983-02-08 ライオン株式会社 嵩密度の小さい洗剤用添加物の製造法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2237839A1 (fr) * 1973-07-16 1975-02-14 Procter & Gamble
US4180485A (en) * 1977-11-02 1979-12-25 The Procter & Gamble Company Spray-dried detergent compositions
GB2013707A (en) * 1978-02-01 1979-08-15 Unilever Ltd Preparation of Spray-Dryed Detergent Compositions
EP0070079A2 (fr) * 1981-07-15 1983-01-19 Unilever N.V. Composition détergente
EP0098108A1 (fr) * 1982-06-25 1984-01-11 Unilever Plc Composition détergente

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0451894A1 (fr) * 1990-04-09 1991-10-16 Unilever N.V. Compositions détergentes granulaires à haute densité apparente et leur procédé de préparation
EP0461428A2 (fr) * 1990-06-13 1991-12-18 Leuna-Werke Ag Composition détergente
EP0461428A3 (en) * 1990-06-13 1992-06-17 Leuna-Werke Ag Cleaning composition
DE4031910A1 (de) * 1990-10-08 1992-04-09 Henkel Kgaa Percarbonathaltiges waschmittel
WO1992015663A1 (fr) * 1991-03-05 1992-09-17 Henkel Kommanditgesellschaft Auf Aktien Detergents
EP0518576A2 (fr) * 1991-06-10 1992-12-16 Unilever Plc Compositions détergentes granulaires à haute densité apparente
EP0518576A3 (en) * 1991-06-10 1993-08-04 Unilever Plc High bulk density granular detergent compositions
EP0572288A1 (fr) * 1992-05-26 1993-12-01 Rhone-Poulenc Chimie Utilisation de silico-aluminate amorphe en tant que capteurs de précipités calciques
FR2691715A1 (fr) * 1992-05-26 1993-12-03 Rhone Poulenc Chimie Utilisation de silico-aluminate amorphe en tant que capteurs de précipités calciques.
US5700294A (en) * 1992-05-26 1997-12-23 Rhone-Poulenc Chimie Method of washing with detergent compositions comprising amorphous silicoaluminate scavengers of calcium precipitates

Also Published As

Publication number Publication date
JPS60155296A (ja) 1985-08-15
GB8334017D0 (en) 1984-02-01
NO163140B (no) 1990-01-02
NO163140C (no) 1990-04-11
ATE52537T1 (de) 1990-05-15
AU560739B2 (en) 1987-04-16
EP0150613A3 (en) 1987-08-05
ZA849950B (en) 1986-08-27
AU3688984A (en) 1985-07-04
DE3482190D1 (de) 1990-06-13
EP0150613B1 (fr) 1990-05-09
NO845109L (no) 1985-06-24
CA1227100A (fr) 1987-09-22
ES8608037A1 (es) 1986-06-01
ES538769A0 (es) 1986-06-01
JPH0457718B2 (fr) 1992-09-14

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