EP0706560B1 - Process for the production of a detergent composition - Google Patents

Process for the production of a detergent composition Download PDF

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Publication number
EP0706560B1
EP0706560B1 EP94923685A EP94923685A EP0706560B1 EP 0706560 B1 EP0706560 B1 EP 0706560B1 EP 94923685 A EP94923685 A EP 94923685A EP 94923685 A EP94923685 A EP 94923685A EP 0706560 B1 EP0706560 B1 EP 0706560B1
Authority
EP
European Patent Office
Prior art keywords
hydrophobic material
detergent
premix
detergent composition
particulate
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
EP94923685A
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German (de)
English (en)
French (fr)
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EP0706560A1 (en
Inventor
Mark Phillip Houghton
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
Original Assignee
Unilever PLC
Unilever NV
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP94923685A priority Critical patent/EP0706560B1/en
Publication of EP0706560A1 publication Critical patent/EP0706560A1/en
Application granted granted Critical
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Anticipated expiration legal-status Critical
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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
    • 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
    • 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

Definitions

  • This invention relates to a process for the production of a detergent composition, in particular to a process for the production of a detergent composition having a high bulk density and which contains a hydrophobic material.
  • Spray-drying has been employed for many years in the production of detergent compositions.
  • an aqueous slurry of heat-stable components of the detergent composition is formed and fed to a spray-drying tower at elevated temperature in order to provide a substantially homogeneous mixture of the components.
  • the water in the slurry is then removed by evaporation in the spray-dry tower to produce a spray-dried detergent powder.
  • This powder may then be processed further and/or further components added as desired.
  • EP-A-337523 discloses a process in which a hydrophobic material is incorporated into a detergent composition produced by a spray-drying process in order to provide improved dispensing and powder properties.
  • the hydrophobic material may be incorporated either in the slurry which is to be spray-dried or it may be sprayed in liquefied form onto the spray-dried detergent composition powder.
  • the spray drying process has several drawbacks, in particular, it is very energy intensive and requires significant capital investment.
  • EP-A-492679 discloses a detergent composition containing a surfactant and a polyol additive which is completely esterified with fatty acids having an average of at least 14 carbon atoms per fatty acid residue.
  • the additive may be incorporated either in a slurry which is to be spray-dried or alternatively sprayed onto a detergent powder.
  • DE3617756 discloses a process for producing a granular detergent composition having a high bulk density comprising the steps of kneading detergent ingredients to form a kneaded mixture, disintegrating the solid mixture and then coating the disintegrated mixture with a water insoluble finely divided powder having a specified particle diameter.
  • JP-A-62228000 discloses a granular detergent composition which is coated with a) a fine aluminosilicate powder, and b) a hydrophobic fine pulverised powder wherein the ratio of a) to b) is 3:1 to 1:3 and a) and b) are present at a combined level of 1 to 5 weight percent.
  • the composition is said to provide improved solubility by preventing conglutination of detergent particles due to the coating of components a) and b).
  • Detergent compositions having a high bulk density may be produced without a spray-drying step, herein referred to as a non-tower process, by mixing together the components of the detergent composition in a mixing apparatus, densifying and optionally granulating the components to produce a high density detergent composition
  • EP-A-0367339 discloses a process for preparing a high bulk density granular detergent composition.
  • a first aspect of the invention provides a process for the production of a high bulk density detergent composition or a component therefore which contains a detergent active compound and a hydrophobic material and which comprises a particulate material, which is not the direct product of a spray-drying process, the process comprising forming a flowable premix comprising the hydrophobic material and a liquid component, mixing the premix with the particulate material, densifying the mixture of the particulate material and the premix during or subsequent to the said mixing and granulating the said mixture thereby to form a particulate high bulk density detergent composition or component therefor.
  • a composition produced by the present invention has a bulk density of at least 700g/l.
  • the process of the present invention may be a continuous or a batch process as desired.
  • the particulate material may comprise all of the components of the detergent composition excluding the hydrophobic material or alternatively the particulate material may comprise at least one of the said components and the other components may be incorporated into the composition during or subsequent to the mixing of the particulate material and the hydrophobic material.
  • the components of the detergent composition will be selected to provide the desired characteristics and will generally include a surfactant and a builder in addition to the hydrophobic material.
  • the particulate material comprises an adjunct, that is, a particle comprising at least 2 components of the composition. Components of the detergent composition which are liquid may be added to the particulate material during or subsequent to the mixing step or incorporated by means of an adjunct as desired.
  • the hydrophobic material is incorporated into the particulate material for example as a melt, solution, suspension, or a slurry.
  • the hydrophobic material is in the liquid phase when it is mixed with the particulate material, thus if the hydrophobic material is solid at ambient temperature, it is suitably heated to a temperature above its melting point and then mixed with the particulate material.
  • the hydrophobic material is suitably mixed with the particulate material at a rate sufficient to permit efficient mixing between the two components.
  • the hydrophobic material has a viscosity of no more than 1000mPa and preferably no more than 500mPa at a shear rate of 200 s -1 at the temperature at which it is mixed with the base material.
  • the hydrophobic material is sprayed onto the particulate material to provide an even distribution of the flowable material over the particulate material during the mixing step.
  • the hydrophobic material is mixed in the liquid phase with a liquid component, preferably a surfactant and more preferably a non-ionic surfactant to form the flowable premix prior to mixing with the base material.
  • a liquid component preferably a surfactant and more preferably a non-ionic surfactant to form the flowable premix prior to mixing with the base material.
  • the hydrophobic material may be a substantially pure material or may be a mixture of different materials.
  • the hydrophobic material is substantially insoluble in water and has a contact angle to water of at least 75° and preferably at least 85°.
  • the hydrophobic material is suitably solid at ambient temperature and preferably has a melting point in the range 25 to 110°C, more preferably in the range 30 to 80°C, especially 35 to 60°C and optimally 35 to 50°C. It is particularly preferred that the hydrophobic material is solid at ambient temperature for ease of handling but has a melting point below the wash temperature as this reduces undesirable deposition of the material.
  • Suitable hydrophobic materials include silicone oils; long chain esters preferably having at least 9 carbon atoms in both the acid and the alcohol parts thereof for example stearyl stearate; and preferably hydrocarbon waxes.
  • the hydrophobic material is present in an amount of up to 5 %, preferably from 0.1 to 3%, more preferably from 0.2 to 2%, especially 0.4 to 1.8% by weight based on the detergent composition.
  • the amount of hydrophobic material which may be present in the premix may be limited in order to ensure that the premix is sufficiently mobile to allow for an even distribution of the hydrophobic material during mixing with the particulate material.
  • the mixing and densification steps may be carried out simultaneously using a high speed mixer, suitable examples include a Shugi (trademark) Granulator, a Drais (trade mark) K-TTP 80 Granulator and the Lodige (trade mark) CB30 recycler.
  • the residence time in the mixing step is suitably about 5 to 30 seconds and the rate of mixing in the apparatus is suitably in the range 100 to 2500rpm depending upon the degree of densification and the particle size required.
  • the granulation step if present may be carried out using a lower speed mixer for example, the Drais (trade mark) K-T 160 and the Lodige (trade mark) KM300 mixer.
  • the residence time in the granulation step is suitably about 1 to 10 minutes and the rate of mixing in the apparatus is about 40 to 160 rpm.
  • the present invention further provides a particulate detergent composition or component therefor obtainable by a non tower process having a high bulk density comprising a detergent active compound, a detergency builder and a hydrophobic material dispersed substantially uniformly within the particles, wherein a flowable liquid premix of the hydrophobic material and a liquid component is formed and the premix is mixed with the said detergent active compound or builder prior to or whilst the detergent active and builder are mixed whereby a substantially uniform dispersion of the said material within the particles is obtained.
  • the detergent composition is produced by a non-tower process in which the hydrophobic material is mixed with a liquid surfactant, preferably a nonionic surfactant, to produce a solution.
  • a liquid surfactant preferably a nonionic surfactant
  • the hydrophobic material is preferably melted to aid formation of a solution with the surfactant.
  • compositions produced according to the present invention will generally contain detergent-active compounds and detergency builders, and may optionally contain bleaching components and other active ingredients to enhance performance and properties.
  • the detergent-active compounds may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof.
  • Many suitable detergent-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
  • the preferred detergent-active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds.
  • Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 ; primary and secondary alkyl sulphates, particularly C 12 -C 15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • Sodium salts are generally preferred.
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C 8 -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Non-ethoxylated nonionic surfactants include alkylpolyglycosides also glycerol monoethers, and polyhydroxyamides (glucamide).
  • detergent-active compound surfactant
  • amount present will depend on the intended use of the detergent composition. For example, for machine dishwashing a relatively low level of a low-foaming nonionic surfactant is generally preferred. In fabric washing compositions, different surfactant systems may be chosen, as is well known to the skilled formulator, for handwashing products and for products intended for use in different types of washing machine.
  • the total amount of surfactant present will also depend on the intended end use and may be as low as 0.5 wt%, for example, in a machine dishwashing composition, or as high as 60 wt%, for example, in a composition for washing fabrics by hand. In compositions for machine washing of fabrics, an amount of from 5 to 40 wt% is generally appropriate.
  • Detergent compositions suitable for use in most automatic fabric washing machines generally contain anionic non-soap surfactant, or nonionic surfactant, or combinations of the two in any ratio, optionally together with soap.
  • the detergent compositions of the invention will generally also contain one or more detergency builders.
  • the total amount of detergency builder in the compositions will suitably range from 10 to 80 wt%, preferably from 15 to 60 wt%.
  • Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever); crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1 473 201 (Henkel), amorphous aluminosilicates as disclosed in GB 1 473 202 (Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250 (Procter & Gamble); and layered silicates as disclosed in EP 164 514B (Hoechst).
  • Inorganic phosphate builders for example, sodium orthophosphate, pyrophosphate and tripolyphosphate, may also be present, but on environmental grounds those are no longer preferred.
  • Zeolite builders may suitably be present in amounts of from 10 to 45 wt%, amounts of from 15 to 35 wt% being especially suitable for (machine) fabric washing compositions.
  • the zeolite used in most commercial particulate detergent compositions is zeolite A.
  • maximum aluminium zeolite P zeolite MAP
  • Zeolite MAP is an alkali metal aluminosilicate of the P type having a silicon to aluminium ratio not exceeding 1.33, preferably not exceeding 1.15, and more preferably not exceeding 1.07.
  • Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
  • polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates
  • monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates,
  • Especially preferred organic builders are citrates, nitrolotriacetic acid and oxydisuccinate and are suitably used in amounts of from 5 to 30 wt%, preferably from 10 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%.
  • Builders both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
  • Detergent compositions according to the invention may also suitably contain a bleach system.
  • Machine dishwashing compositions may suitably contain a chlorine bleach system, while fabric washing compositions may more desirably contain peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
  • peroxy bleach compounds for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
  • Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates.
  • organic peroxides such as urea peroxide
  • inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates.
  • Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.
  • sodium percarbonate having a protective coating against destabilisation by moisture Especially preferred is sodium percarbonate having a protective coating against destabilisation by moisture.
  • Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao).
  • the peroxy bleach compound is suitably present in an amount of from 5 to 35 wt%, preferably from 10 to 25 wt%.
  • the peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures.
  • the bleach precursor is suitably present in an amount of from 1 to 8 wt%, preferably from 2 to 5 wt%.
  • Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors.
  • An especially preferred bleach precursor suitable for use in the present invention is N,N,N',N'-tetracetyl ethylenediamine (TAED).
  • novel quaternary ammonium and phosphonium bleach precursors disclosed in US 4 751 015 and US 4 818 426 (Lever Brothers Company) and EP 402 971A (Unilever) are also of great interest.
  • peroxycarbonic acid precursors in particular cholyl-4-sulphophenyl carbonate.
  • peroxybenzoic acid precursors in particular, N,N,N-trimethylammonium toluoyloxy benzene sulphonate; and the cationic bleach precursors disclosed in EP 284 292A and EP 303 520A (Kao).
  • a bleach stabiliser may also be present.
  • Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA) and the polyphosphonates such as Dequest (Trade Mark), EDTMP.
  • An especially preferred bleach system comprises a peroxy bleach compound (preferably sodium percarbonate optionally together with a bleach activator), and a transition metal bleach catalyst as described and claimed in EP 458 397A, EP 458 398A and EP 509 787A (Unilever).
  • a peroxy bleach compound preferably sodium percarbonate optionally together with a bleach activator
  • a transition metal bleach catalyst as described and claimed in EP 458 397A, EP 458 398A and EP 509 787A (Unilever).
  • Fluorescer is preferably present in an amount within the range of from 0.02 to 0.8 wt%, more preferably from 0.03 to 0.5 wt%.
  • compositions of the invention may contain alkali metal, preferably sodium, carbonate, in order to increase detergency and ease processing.
  • Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%.
  • compositions containing little or no sodium carbonate are also within the scope of the invention.
  • Powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate polymer, or sodium silicate.
  • a powder structurant for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleate polymer, or sodium silicate.
  • One preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt%.
  • detergent compositions of the invention include sodium silicate and sodium metasilicate; antiredeposition agents such as cellulosic polymers; fluorescers; inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; proteolytic and lipolytic enzymes; dyes; coloured speckles; perfumes; foam controllers; and fabric softening compounds. This list is not intended to be exhaustive.
  • a particulate detergent composition was prepared by feeding a particulate material and a flowable premix to a Lodige CB30 recycler high speed mixer/densifier.
  • the flowable premix comprised the wax and nonionic surfactant components listed in Table 1.
  • the particulate material comprised particles of the other solid components listed in Table 1.
  • the hydrocarbon wax was melted prior to mixing with the nonionic surfactant to provide a sprayable solution.
  • the premix was introduced to the mixer and the components mixed and densified for 15 seconds at about 1400rpm.
  • the mixture was then fed to a Lodige Ploughshare granulator operated at about 120 rpm for granulation to form granules of the detergent composition.
  • the residence time was about 2 minutes.
  • compositions not according to the invention as listed in Table 1 were produced by the same method as in Examples 1 to 4 except that hydrophobic material was not included in the formulation.
  • Table 1 Example A 1 B 2 C 3 D 4 a PAS Na 18.8 18.6 19 18.9 0 0 9.48 9.48 b LAS Na 0 0 0 0 27.5 27.5 0 0 A24 Zeolite 49.6 49.2 49.0 48.8 45.2 45.0 55.2 55.2 Carbonate 3.3 3.3 3.3 3.3 4.8 4.8 1.62 1.62 c Nonionic 3 EO 8.27 8.3 0 0 4.78 4.75 11.96 11.85 7 EO 10.5 10.5 19.8 19.8 8.87 8.93 9.48 9.4 Soap 0 0 0 0 0 0 3.3 3.3 d SCMC 0.99 0.99 0.99 0.99 1.49 1.49 e Wax 0 0.62 0 0.51 0 0.49 0 1 Water/Salts to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100 to 100
  • compositions A to D and 1 to 4 were subjected to the following tests to assess the delivery into the wash, dispersion and dissolution characteristics. The results are shown below in Table 2.
  • Test 1 cage test
  • a 50 g powder sample was introduced into the cylindrical vessel which was then closed.
  • the vessel was attached to the agitator arm which was then moved down to a position such that the top of the cylindrical vessel was just below the surface of the water. After a 10 second delay, the apparatus was operated for 15 rotation/rest cycles.
  • the cylindrical vessel and handle were removed from the water and the vessel detached from the handle. Surface water was carefully poured off, and any powder residues transferred to a preweighed container and dried for 24 hours at 100°C. The weight of dried residue as a percentage of the initial powder weight (50 g) was then calculated.
  • Test 2 delivery device test
  • the delivery device was attached in an upright position (opening uppermost) to an agitator arm positioned above water.
  • the device could be moved vertically up and down through a distance of 30 cm, the lowest 5 cm of this travel being under water.
  • Each up or down journey had a duration of 2 seconds, the device being allowed to rest 5 cm under water for 4 seconds at the lowest position, and at the highest position being rotated through 100° and allowed to rest in the resulting tilted orientation for 2 seconds before redescending. 5 litres of water at a temperature of 20°C were used.
  • a preweighed powder sample was introduced into the device in its highest position, and the apparatus then allowed to operate for six cycles and stopped when the device was again in its highest position. Surface water was carefully poured off, and any powder residues transferred to a preweighed container. The container was then dried at 100°C for 24 hours, and the weight of dried residue as a percentage of the initial powder weight calculated.
  • Test 3 black pillowcase test
  • a washing machine test was also used to determine the extent that insoluble residues were deposited on washed articles.
  • the machine used was a Siemens Siwamat (TradeMark) Plus 3700 front-loading automatic washer.
  • a 100 g dose of powder was placed in a flexible delivery device as described previously.
  • the delivery device was placed inside a black cotton pillowcase having dimensions of 30 cm by 60 cm, taking care to keep it upright, and then pillowcase was then closed by means of a zip fastener.
  • the pillowcase containing the (upright) delivery device was then placed on top of a 3.5 kg dry cotton washload in the drum of the washing machine.
  • the machine was operated on the "heavy duty cycle" at a wash temperature of 40°C, using water of 15° French hardness and an inlet temperature of 20°C/
  • the pillowcase was removed, opened and turned inside out, and the level of powder residues on its inside surfaces determined by visual assessment using a scoring system of 1 to 5: a score of 5 corresponds to a residue of approximately 75 wt% of the powder, while 1 indicates no residue.
  • a panel of five assessors was used to judge each pillowcases and allot a score. With each powder the wash process was carried out ten times and the scores were averaged over the ten repeats.
  • dispensing is assessed by means of a standard procedure using a test rig based on the main wash compartment of the dispenser drawer of the Philips (Trade Mark) AWB 126/7 washing machine.
  • This drawer design provides an especially stringent test of dispensing characteristics especially when used under conditions of low temperature, low water pressure and low rate of water flow.
  • a 100 g dose of powder is placed in a heap at the front end of the main compartment of the drawer, and subjected to a water fill of 5 litres at 10°C and an inlet pressure of 50 kPa, flowing in over a period of 1 minute.

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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)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP94923685A 1993-07-02 1994-06-23 Process for the production of a detergent composition Revoked EP0706560B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP94923685A EP0706560B1 (en) 1993-07-02 1994-06-23 Process for the production of a detergent composition

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP93305236 1993-07-02
EP93305236 1993-07-02
PCT/EP1994/002064 WO1995001418A1 (en) 1993-07-02 1994-06-23 Process for the production of a detergent composition
EP94923685A EP0706560B1 (en) 1993-07-02 1994-06-23 Process for the production of a detergent composition

Publications (2)

Publication Number Publication Date
EP0706560A1 EP0706560A1 (en) 1996-04-17
EP0706560B1 true EP0706560B1 (en) 1997-08-27

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ID=8214463

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94923685A Revoked EP0706560B1 (en) 1993-07-02 1994-06-23 Process for the production of a detergent composition

Country Status (10)

Country Link
EP (1) EP0706560B1 (es)
JP (1) JPH08512072A (es)
AU (1) AU699818B2 (es)
CZ (1) CZ286742B6 (es)
DE (1) DE69405238T2 (es)
ES (1) ES2106557T3 (es)
HU (1) HU219207B (es)
PL (1) PL176757B1 (es)
WO (1) WO1995001418A1 (es)
ZA (1) ZA944679B (es)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9601920D0 (en) * 1996-01-31 1996-04-03 Unilever Plc Process for the production of a detergent composition

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3617756C2 (de) * 1985-05-29 1995-01-19 Lion Corp Verfahren zum Herstellen einer granularen Detergentien-Zusammensetzung mit hoher Schüttdichte
JPS62228000A (ja) * 1986-03-28 1987-10-06 花王株式会社 高密度粒状洗剤組成物
GB8806702D0 (en) * 1988-03-21 1988-04-20 Unilever Plc Detergent powders & processes for preparing them
GB9025673D0 (en) * 1990-11-26 1991-01-09 Unilever Plc Detergent powders and process for preparing them

Also Published As

Publication number Publication date
HUT74077A (en) 1996-10-28
WO1995001418A1 (en) 1995-01-12
CZ286742B6 (en) 2000-06-14
ZA944679B (en) 1995-12-29
AU699818B2 (en) 1998-12-17
JPH08512072A (ja) 1996-12-17
HU219207B (en) 2001-03-28
PL176757B1 (pl) 1999-07-30
PL312420A1 (en) 1996-04-15
EP0706560A1 (en) 1996-04-17
AU7383294A (en) 1995-01-24
DE69405238D1 (de) 1997-10-02
DE69405238T2 (de) 1998-01-02
HU9503926D0 (en) 1996-03-28
CZ496A3 (en) 1996-06-12
ES2106557T3 (es) 1997-11-01

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