EP0339707A2 - Encapsulated liquid detergent composition - Google Patents

Encapsulated liquid detergent composition Download PDF

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Publication number
EP0339707A2
EP0339707A2 EP19890200931 EP89200931A EP0339707A2 EP 0339707 A2 EP0339707 A2 EP 0339707A2 EP 19890200931 EP19890200931 EP 19890200931 EP 89200931 A EP89200931 A EP 89200931A EP 0339707 A2 EP0339707 A2 EP 0339707A2
Authority
EP
European Patent Office
Prior art keywords
encapsulated
detergent composition
liquid detergent
water
aqueous
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
EP19890200931
Other languages
German (de)
French (fr)
Other versions
EP0339707B1 (en
EP0339707B2 (en
EP0339707A3 (en
Inventor
Peter Willem Appel
Lucas Dominicus Maria Van Den Brekel
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
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
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0339707A2 publication Critical patent/EP0339707A2/en
Publication of EP0339707A3 publication Critical patent/EP0339707A3/en
Publication of EP0339707B1 publication Critical patent/EP0339707B1/en
Application granted granted Critical
Publication of EP0339707B2 publication Critical patent/EP0339707B2/en
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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles

Definitions

  • the present invention relates to an encapsulated, essentially non-aqueous liquid detergent composition.
  • non-aqueous liquid detergent compositions are dispersions comprising a non-aqueous liquid (solvent) phase which can be a liquid surfactant, an organic non-aqueous non-surfactant liquid or a mixture of such materials. Furthermore, they contain dispersed particulate solids. These are small (e.g. 10 microns) particles of solid material which are useful in cleaning, such as solid surfactants, builders, bleaches, enzymes or any other of such solids known in the art.
  • non-aqueous liquid detergent compositions are advantageous in that they constitute a very concentrated product form, the stability of the liquids leaves much to be desired. Furthermore, their handling and dispensing properties have proven to be problematic.
  • a product having an optimal viscosity is difficult to formulate because of conflicting requirements. If the viscosity of the liquid product is too high, substantial amounts thereof may remain in the dispenser of the washing machine. If, on the other hand, its viscosity is too low the liquid detergent may leak down the drain of the European type washing machines. Furthermore upon contact with water the non-aqueous liquids tend to form gels, which again causes dispensing problems. Moreover, as with all liquid detergent compositions, non-­aqueous liquid detergent compositions are difficult to dose from the point of view of administering the right amount of detergent as well as the messiness during handling of the liquid products. Therefore it would be desirable to provide a suitable unit dosing form for these kind of compositions.
  • liquid detergent compositions in a self-dissolving capsule.
  • the capsule which is usually made of gelatin, imposes considerable restrictions on the type of liquid detergent to be used therein, and the encapsulation has only been successful in a few occasions.
  • only essentially water-free or non-aqueous liquid detergent compositions can be used, as water tends to dissolve the gelatin capsule.
  • GB-A-2,192,404 (Scherer) relates to a foam bath product comprising 40-60% of amine salts of long chain alkyl ether sulphates, 25-35% low molecular weight polyethylene glycol and 2,5-7,5% glycerin encapsulated in soft elastic water-­soluble gelatin.
  • the US-patent 3,528,925 discloses an encapsulated synthetic liquid detergent composition consisting of 33-65% of an anionic surface active ingredient, 8-36,5% of a nonionic surface active ingredient and 20-59% of an alkanolamine or alkylamine.
  • the composition is therefore essentially a non-built light duty detergent composition. It contains less than 1% water and is encapsulated in gelatin.
  • One object of the present invention is to provide an encapsulated, heavy duty liquid detergent composition. Another object is to provide an essentially non-aqueous liquid detergent composition, suitable for use in such encapsulated detergent product.
  • an encapsulated essentially non-aqueous liquid detergent composition which is characterized in that it comprises a non-aqueous organic solvent and particles of a solid material dispersed therein, encapsulated in a water dispersible substance.
  • liquid detergent compositions preferably the liquid cleaning products are used which are described in the co-­pending European patent application 87.309568.1 which is incorporated herein by reference.
  • This European patent application relates to non-aqueous liquid cleaning products which are formulated by dispersing particulate solids in an organic solvent by using a structurant or deflocculant which causes a viscosity reduction at low shear rates in that solids/solvent system or an equivalent system in which the solids volume fraction is sufficiently high to raise the viscosity of the solvent.
  • the organic solvent may be a liquid surfactant.
  • the solids are particles of a solid material which is useful in cleaning, such as surfactants, builders, bleaches, enzymes, etc.
  • the structurant is any acid, salt or base which fulfills the aforementioned test.
  • the solid material which dispersed in the organic solvent is preferably a builder such as a zeolite or sodium tripolyphosphate (STP).
  • a builder such as a zeolite or sodium tripolyphosphate (STP).
  • the encapsulating material is a water-dispersible substance.
  • it comprises a water-soluble substance, e.g. gelatin, polyvinyl alcohol (PVA) or polyethylene glycol.
  • PVA polyvinyl alcohol
  • encapsulating material is gelatin.
  • the liquid detergent composition inside the capsule may additionally contain one or more proteolytic enzymes, although it would be expected that these would digest the gelatine capsule.
  • the essentially non-aqueous liquid detergent compositions can be prepared as described in the above mentioned European patent application. They can be encapsulated in accordance with methods which are known to the man skilled in the art. For instance, the US-patent 3.528.925 describes the encapsulation in gelatin of a non-aqueous liquid detergent composition by means of two continuous ribbons of a melted gelatin mass.
  • NAL'S non-aqueous detergent compositions
  • compositions were encapsulated into soft gelatin capsules by means of the rotary die process.
  • rotary die process two continuous ribbons of gelatin are formed and subsequently pressed together between two rotating drums having dies on their surfaces, whereby the liquid is added between the ribbons.
  • Round capsules were produced containing approximately 7.5g liquid detergent. The properties of these capsules were evaluated with regard to release, storage stability and performance.
  • the release rates and total delivery of the capsules were measured in a modified AEG drum-type washing machine, of which the front walls of both inner and outer drum were replaced by transparent plastic plates.
  • the release of the capsule contents was registered by means of on-line conductivity in a 40°C heat-up cycle with a water intake of 15 l of tap water and a wash load of 1 kg of mixed cotton.
  • a number of capsules was dosed corresponding to approximately 30 g of NAL.
  • the possible occurrence of mechanical loss was checked by recirculating the suds via the machine drain at the end of each experiment.
  • Spherical capsules containing non-aqueous liquid including l % savinase were stored under various conditions.
  • the samples which were stored in closed cups at 37°C showed a remaining activity after four weeks of 75 %, which figure is comparable with normal proteolytic enzyme stability in current non-aqueous liquids. No degradation of the polypeptide gelatine capsule wall was observed under these conditions.
  • the performance of the encapsulated NAL was compared with the performance of standard NAL on various test cloths.
  • the test was carried out in a top loading drum-­type washing machine, main wash only (40°C, 30 min), a water hardness of 15° FH and 3 kg of standard soiled load.
  • the performance of six spherical capsules (correponding to 45 g of NAL), with and without Savinase, was compared to the performance of 45 g non-encapsulated NAL, without savinase, as a control.
  • the products were dosed in the drum between the load.

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)
  • Detergent Compositions (AREA)

Abstract

Encapsulated, essentially non-aqueous liquid detergent composition, wherein the liquid detergent component comprises a non-aqueous organic solvent and particles of a solid material dispersed therein, encapsulated in a water-­dispersible substance. Preferably, the solid material comprises a builder.

Description

  • The present invention relates to an encapsulated, essentially non-aqueous liquid detergent composition.
  • In recent years, much effort has been put into developing essentially non-aqueous liquid detergent compositions. Such compositions are dispersions comprising a non-aqueous liquid (solvent) phase which can be a liquid surfactant, an organic non-aqueous non-surfactant liquid or a mixture of such materials. Furthermore, they contain dispersed particulate solids. These are small (e.g. 10 microns) particles of solid material which are useful in cleaning, such as solid surfactants, builders, bleaches, enzymes or any other of such solids known in the art.
    Although such non-aqueous liquid detergent compositions are advantageous in that they constitute a very concentrated product form, the stability of the liquids leaves much to be desired. Furthermore, their handling and dispensing properties have proven to be problematic. A product having an optimal viscosity is difficult to formulate because of conflicting requirements. If the viscosity of the liquid product is too high, substantial amounts thereof may remain in the dispenser of the washing machine. If, on the other hand, its viscosity is too low the liquid detergent may leak down the drain of the European type washing machines. Furthermore upon contact with water the non-aqueous liquids tend to form gels, which again causes dispensing problems. Moreover, as with all liquid detergent compositions, non-­aqueous liquid detergent compositions are difficult to dose from the point of view of administering the right amount of detergent as well as the messiness during handling of the liquid products. Therefore it would be desirable to provide a suitable unit dosing form for these kind of compositions.
  • In order to obviate some of these problems, it has been proposed to encapsulate liquid detergent compositions in a self-dissolving capsule. The capsule, which is usually made of gelatin, imposes considerable restrictions on the type of liquid detergent to be used therein, and the encapsulation has only been successful in a few occasions. In particular, only essentially water-free or non-aqueous liquid detergent compositions can be used, as water tends to dissolve the gelatin capsule.
  • GB-A-2,192,404 (Scherer) relates to a foam bath product comprising 40-60% of amine salts of long chain alkyl ether sulphates, 25-35% low molecular weight polyethylene glycol and 2,5-7,5% glycerin encapsulated in soft elastic water-­soluble gelatin.
  • The US-patent 3,528,925 (Chapuis) discloses an encapsulated synthetic liquid detergent composition consisting of 33-65% of an anionic surface active ingredient, 8-36,5% of a nonionic surface active ingredient and 20-59% of an alkanolamine or alkylamine. The composition is therefore essentially a non-built light duty detergent composition. It contains less than 1% water and is encapsulated in gelatin.
  • The wash performance of the encapsulated liquid detergent compositions such as described in said US-patent is unsatisfactory. The necessity of using essentially water-free detergent compositions in view of the stability of the gelatine capsule evidently constitutes a serious limitation to the detergent composition at the expense of its detergency properties. For example, there are restrictions as to the pH of the content of the capsule. The US-patent 3,528,925 teaches the need of using a weak organic base, such as alkyl- or alkanolamines, in order to keep the pH below 8, although it is known that this pH is too low for an optimal landry process. Furthermore, there is no builder present, probably to avoid unfavorable interactions with the other components, as well as stability- and or viscosity problems.
  • One object of the present invention is to provide an encapsulated, heavy duty liquid detergent composition. Another object is to provide an essentially non-aqueous liquid detergent composition, suitable for use in such encapsulated detergent product.
  • We have now found that these and other objectives can be achieved by the essentially non-aqueous encapsulated liquid detergent compositions according to the present invention.
  • In accordance with the first aspect of the present invention there is provided an encapsulated essentially non-aqueous liquid detergent composition, which is characterized in that it comprises a non-aqueous organic solvent and particles of a solid material dispersed therein, encapsulated in a water dispersible substance.
    As liquid detergent compositions, preferably the liquid cleaning products are used which are described in the co-­pending European patent application 87.309568.1 which is incorporated herein by reference.
  • This European patent application relates to non-aqueous liquid cleaning products which are formulated by dispersing particulate solids in an organic solvent by using a structurant or deflocculant which causes a viscosity reduction at low shear rates in that solids/solvent system or an equivalent system in which the solids volume fraction is sufficiently high to raise the viscosity of the solvent. The organic solvent may be a liquid surfactant. The solids are particles of a solid material which is useful in cleaning, such as surfactants, builders, bleaches, enzymes, etc. The structurant is any acid, salt or base which fulfills the aforementioned test.
  • According to the present invention, the solid material which dispersed in the organic solvent is preferably a builder such as a zeolite or sodium tripolyphosphate (STP).
  • The encapsulating material is a water-dispersible substance. Preferably it comprises a water-soluble substance, e.g. gelatin, polyvinyl alcohol (PVA) or polyethylene glycol. Especially preferred as encapsulating material is gelatin. In this case it was surprisingly found that the liquid detergent composition inside the capsule may additionally contain one or more proteolytic enzymes, although it would be expected that these would digest the gelatine capsule.
  • The essentially non-aqueous liquid detergent compositions can be prepared as described in the above mentioned European patent application. They can be encapsulated in accordance with methods which are known to the man skilled in the art. For instance, the US-patent 3.528.925 describes the encapsulation in gelatin of a non-aqueous liquid detergent composition by means of two continuous ribbons of a melted gelatin mass.
  • The invention will now be further illustrated by the following examples.
    • Examples 1 - 2
  • The following non-aqueous detergent compositions (NAL'S) were used for encapsulation (the amounts are given as % by weight):
    1 2
    Plurafac RA 30 29.7 30.0
    Marlon 3 3
    Glycerol triacetate 5 5
    STP. 0aq 51.1 51.7
    Soda ash 10.2 10.3
    Savinase 1.0 --
  • These compositions were encapsulated into soft gelatin capsules by means of the rotary die process. In this known process two continuous ribbons of gelatin are formed and subsequently pressed together between two rotating drums having dies on their surfaces, whereby the liquid is added between the ribbons. Round capsules were produced containing approximately 7.5g liquid detergent. The properties of these capsules were evaluated with regard to release, storage stability and performance.
    • A. Release
  • The release rates and total delivery of the capsules were measured in a modified AEG drum-type washing machine, of which the front walls of both inner and outer drum were replaced by transparent plastic plates. The release of the capsule contents was registered by means of on-line conductivity in a 40°C heat-up cycle with a water intake of 15 l of tap water and a wash load of 1 kg of mixed cotton. In all experiments, a number of capsules was dosed corresponding to approximately 30 g of NAL. The possible occurrence of mechanical loss was checked by recirculating the suds via the machine drain at the end of each experiment.
  • For all capsules, the time required to reach equilibrium concentration in the washing machine ranged between 8 and 9 minutes. The average temperature at which the initial release of NAL was observed, was equal to 26°C, while the average temperature at the time of complete release was 33°C. These results were obtained at a water-intake temperature of 19°C and a heating rate of 1.4-1.5°C/min.
  • In the experimental AEG machine, the percentage of mechanical loss was less than 10 % in the majority of all measurements.
    • B. Storage stability
  • Spherical capsules containing non-aqueous liquid including l % savinase were stored under various conditions. The samples which were stored in closed cups at 37°C showed a remaining activity after four weeks of 75 %, which figure is comparable with normal proteolytic enzyme stability in current non-aqueous liquids. No degradation of the polypeptide gelatine capsule wall was observed under these conditions.
    • C. Performance
  • In an appraisal test, the performance of the encapsulated NAL was compared with the performance of standard NAL on various test cloths. The test was carried out in a top loading drum-­type washing machine, main wash only (40°C, 30 min), a water hardness of 15° FH and 3 kg of standard soiled load. The performance of six spherical capsules (correponding to 45 g of NAL), with and without Savinase, was compared to the performance of 45 g non-encapsulated NAL, without savinase, as a control. The products were dosed in the drum between the load. The results of the test are shown in Table 1 Table 1
    Single wash performance on testcloths (ΔR⁴⁶⁰)
    Example 1 2 Control
    Testcloths:
    AS09 24.4 23.9 19.9
    PC09 17.4 17.0 15.2
    WFK10c 10.3 10.6 8.5
    EMPA101 15.9 14.2 11.7
    BC-1 -1.1 -1.9 -2.0
    AS10 28.3 6.0 5.7
    PC10 22.3 5.8 5.5
    EMPA116 21.1 4.7 4.4
    Terry Towel -2.0 -3.2 -3.2
  • The experiments show that the encapsulated NAL'S, with and without the proteolytic enzyme, have very satisfying wash performance as measured by the delta-R values. Surprisingly, it was found that the performance of the NAL actually has been improved by the encapsulation in gelatine. These findings suggest the occurrence of mechanical loss for the non-encapsulated liquids, resulting in a performance decrease.

Claims (6)

1. Encapsulated, essentially non-aqueous liquid detergent composition, wherein the liquid detergent component comprises a non-aqueous organic solvent and particles of a solid material dispersed therein, encapsulated in a water-dispersible substance.
2. Encapsulated detergent composition according to claim 1, wherein the dispersed solid material comprises a builder.
3. Encapsulated detergent composition according to claim 2, wherein the builder is sodium tripolyphosphate.
4. Encapsulated detergent composition according to any of claims 1-3, wherein the liquid detergent composition contains one or more enzymes.
5. Encapsulated detergent composition according to any of claims 1-4, wherein the water-dispersible substance comprises a water-soluble substance.
6. Encapsulated detergent composition according to any of claims 1-5, wherein the capsule is a gelatin capsule.
EP19890200931 1988-04-29 1989-04-13 Encapsulated liquid detergent composition Expired - Lifetime EP0339707B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8810197 1988-04-29
GB888810197A GB8810197D0 (en) 1988-04-29 1988-04-29 Encapsulated liquid detergent composition

Publications (4)

Publication Number Publication Date
EP0339707A2 true EP0339707A2 (en) 1989-11-02
EP0339707A3 EP0339707A3 (en) 1990-10-17
EP0339707B1 EP0339707B1 (en) 1994-11-30
EP0339707B2 EP0339707B2 (en) 1998-04-08

Family

ID=10636112

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19890200931 Expired - Lifetime EP0339707B2 (en) 1988-04-29 1989-04-13 Encapsulated liquid detergent composition

Country Status (5)

Country Link
EP (1) EP0339707B2 (en)
JP (1) JPH0216198A (en)
CA (1) CA1336485C (en)
DE (1) DE68919518D1 (en)
GB (1) GB8810197D0 (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999000471A1 (en) * 1997-06-27 1999-01-07 The Procter & Gamble Company Non-aqueous liquid detergent compositions containing enzyme particles having reduced density
DE19918265A1 (en) * 1999-04-22 2000-10-26 Henkel Kgaa Abrasive-containing aqueous liquid cleaning or scouring agent for hard surfaces contains microcapsules containing an ingredient to be protected e.g. a perfume
WO2001085895A1 (en) * 2000-05-12 2001-11-15 Unilever N.V. Unit dose cleaning product
DE10040724A1 (en) * 2000-08-17 2002-03-07 Henkel Kgaa Mechanically stable, liquid formulated detergent, detergent or cleaning agent portions
WO2002057402A1 (en) * 2001-01-19 2002-07-25 The Procter & Gamble Company Liquid composition in a pouch
WO2002068577A1 (en) * 2001-02-28 2002-09-06 Unilever Plc Unit dose cleaning product
WO2002102956A1 (en) * 2001-06-18 2002-12-27 Unilever Plc Water soluble package and liquid contents thereof
WO2003048293A1 (en) * 2001-12-05 2003-06-12 Henkel Kommanditgesellschaft Auf Aktien Dosed washing and cleaning agent composition
WO2006024415A1 (en) * 2004-09-02 2006-03-09 Henkel Kommanditgesellschaft Auf Aktien Liquids manufactured in solid form for use in particle-shaped detergents and cleansers
US7074748B2 (en) 2001-01-19 2006-07-11 The Procter & Gamble Company Liquid composition
EP0907711B2 (en) † 1996-06-28 2007-01-10 The Procter & Gamble Company Nonaqueous detergent compositions containing specific alkyl benzene sulfonate surfactant
EP1431384B2 (en) † 2002-12-19 2009-02-11 The Procter & Gamble Company Single compartment unit dose fabric treatment product comprising pouched compositions with non-cationic fabric softener actives

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1207777A (en) * 1968-03-29 1970-10-07 Unilever Ltd Detergents
DE2166054A1 (en) * 1970-03-03 1972-12-21 Lion Fat & Oil Co , Ltd , Tokio Detergent and cleaning agent excretion from 2109892
FR2143832A1 (en) * 1971-06-29 1973-02-09 Procter & Gamble
FR2169720A1 (en) * 1972-01-05 1973-09-14 Majorica Heusch Sa Sol bath capsule - of pearl-like lustre replaces bath curbes and salts
JPS62223111A (en) * 1986-03-26 1987-10-01 Tsumura Juntendo Inc Bathing agent composition

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8308508D0 (en) * 1983-03-28 1983-05-05 Ici Plc Detergent compositions
IN166360B (en) * 1985-08-05 1990-04-14 Colgate Palmolive Co

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1207777A (en) * 1968-03-29 1970-10-07 Unilever Ltd Detergents
DE2166054A1 (en) * 1970-03-03 1972-12-21 Lion Fat & Oil Co , Ltd , Tokio Detergent and cleaning agent excretion from 2109892
FR2143832A1 (en) * 1971-06-29 1973-02-09 Procter & Gamble
FR2169720A1 (en) * 1972-01-05 1973-09-14 Majorica Heusch Sa Sol bath capsule - of pearl-like lustre replaces bath curbes and salts
JPS62223111A (en) * 1986-03-26 1987-10-01 Tsumura Juntendo Inc Bathing agent composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, vol. 12, no. 84 (C-482)(2931) 17-03-1988 & JP-A-62223111 (TSUMURA JUNTENDO INC.) 01-10-1987 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0907711B2 (en) † 1996-06-28 2007-01-10 The Procter & Gamble Company Nonaqueous detergent compositions containing specific alkyl benzene sulfonate surfactant
WO1999000471A1 (en) * 1997-06-27 1999-01-07 The Procter & Gamble Company Non-aqueous liquid detergent compositions containing enzyme particles having reduced density
DE19918265A1 (en) * 1999-04-22 2000-10-26 Henkel Kgaa Abrasive-containing aqueous liquid cleaning or scouring agent for hard surfaces contains microcapsules containing an ingredient to be protected e.g. a perfume
WO2001085895A1 (en) * 2000-05-12 2001-11-15 Unilever N.V. Unit dose cleaning product
DE10040724A1 (en) * 2000-08-17 2002-03-07 Henkel Kgaa Mechanically stable, liquid formulated detergent, detergent or cleaning agent portions
WO2002057402A1 (en) * 2001-01-19 2002-07-25 The Procter & Gamble Company Liquid composition in a pouch
US7074748B2 (en) 2001-01-19 2006-07-11 The Procter & Gamble Company Liquid composition
WO2002068577A1 (en) * 2001-02-28 2002-09-06 Unilever Plc Unit dose cleaning product
WO2002102956A1 (en) * 2001-06-18 2002-12-27 Unilever Plc Water soluble package and liquid contents thereof
WO2003048293A1 (en) * 2001-12-05 2003-06-12 Henkel Kommanditgesellschaft Auf Aktien Dosed washing and cleaning agent composition
EP1431384B2 (en) † 2002-12-19 2009-02-11 The Procter & Gamble Company Single compartment unit dose fabric treatment product comprising pouched compositions with non-cationic fabric softener actives
WO2006024415A1 (en) * 2004-09-02 2006-03-09 Henkel Kommanditgesellschaft Auf Aktien Liquids manufactured in solid form for use in particle-shaped detergents and cleansers

Also Published As

Publication number Publication date
EP0339707B1 (en) 1994-11-30
EP0339707B2 (en) 1998-04-08
EP0339707A3 (en) 1990-10-17
GB8810197D0 (en) 1988-06-02
DE68919518D1 (en) 1995-01-12
CA1336485C (en) 1995-08-01
JPH0216198A (en) 1990-01-19

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