(19)
(11) EP 0 339 707 B2

(12) NEW EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mentionof the opposition decision:
08.04.1998 Bulletin 1998/15

(45) Mention of the grant of the patent:
30.11.1994 Bulletin 1994/48

(21) Application number: 89200931.7

(22) Date of filing: 13.04.1989
(51) International Patent Classification (IPC)6C11D 17/00, C11D 3/43, C11D 3/386

(54)

Encapsulated liquid detergent composition

Eingekapselte, flüssige Detergenszusammensetzung

Composition détergente liquide encapsulée


(84) Designated Contracting States:
CH DE ES FR GB IT LI NL SE

(30) Priority: 29.04.1988 GB 8810197

(43) Date of publication of application:
02.11.1989 Bulletin 1989/44

(73) Proprietors:
  • UNILEVER N.V.
    3013 AL Rotterdam (NL)
    Designated Contracting States:
    CH DE ES FR IT LI NL SE 
  • UNILEVER PLC
    London EC4P 4BQ (GB)
    Designated Contracting States:
    GB 

(72) Inventors:
  • Appel, Peter Willem
    NL-3062 DG Rotterdam (NL)
  • Van den Brekel, Lucas Dominicus Maria
    NL-2624 KV Delft (NL)

(74) Representative: Waldren, Robin Michael et al
MARKS & CLERK, 57-60 Lincoln's Inn Fields
London WC2A 3LS
London WC2A 3LS (GB)


(56) References cited: : 
EP-A- 0 233 231
EP-A- 0 316 054
FR-A- 2 143 832
GB-A- 1 207 777
GB-A- 2 158 838
US-A- 2 870 062
US-A- 3 528 925
EP-A- 0 266 199
DE-A- 2 166 054
FR-A- 2 169 720
GB-A- 1 600 981
GB-A- 2 195 649
US-A- 3 520 971
US-A- 3 779 942
   
  • PATENT ABSTRACTS OF JAPAN, vol. 12, no. 84 (C-482)(2931), 17 March 1988; & JP-A-62223111 (Tsumura Juntendo Inc.) 01.10.1987
  • Gardner's Chemical Synonyms and Trade Names, 9th ed. pp. 485-486
  • Drug Development and Industrial Pharmacy, 14 (2 & 3), 391-412 (1988), J. Rakucewicz
   


Description


[0001] The present invention relates to an encapsulated, essentially non-aqueous liquid detergent composition.

[0002] 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 µm (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.

[0003] 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.

[0004] 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.

[0005] GB-A-2,192,404 (Scherer) relates to a foam bath product comprising 40-60% of amino 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.

[0006] 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.

[0007] DE-A-2 166 054 (Lion Fat & Oil Co., Ltd) discloses a general purpose detergent composition especially suitable for removing fatty materials which contains a water-insoluble (or low-soluble), but fat-soluble solvent which lowers the melting point of the fatty materials so that this is more easily removed. The low (or non-) water-soluble solvent is encapsulated by a water-soluble film. The disclosed detergent composition comprises a fixture of surfactants and builders (granules or powder) and an encapsulated organic solvent. According to the examples builders may also be present.
The low (or non-) water-soluble solvents used are solvents for oils and fats and comprise low-boiling hydrocarbons, halogenated hydrocarbons, ethers, esters etc (p. 5, lines 10-6 from the bottom). The encapsulated solvent amounts to 3 to 23% by weight of the total composition.

[0008] 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.

[0009] FR-A-2 143 832 (The Procter & Gamble Co) discloses a bathing composition having both satisfactory foaming properties and emollient properties for the skin in the form of a free flowing granular composition (page 2, lines 9 and 28/29). The bathing composition comprises detergent granules and microcapsules of an emollient composition. Numerous types of surfactants and optionally builders can be present. The water-insoluble emollient for the skin is encapsulated and comprises known oils such as mineral and hydrocarbon oils (light, heavy or medium), vegetable oils, synthetic esters, lanoline, cholesterol derivatives, and silicon oil. The encapsulating material can be gelatin, gum arabic etc.

[0010] 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.

[0011] 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.

[0012] In accordance with the present invention there is provided a capsule according to claim 1. As liquid detergent compositions, preferably the liquid cleaning products are used which are described in the co-pending European patent application 87.309568.1 (EP-A-0266199).

[0013] 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.

[0014] 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).

[0015] 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.

[0016] 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.

[0017] The invention will now be further illustrated by the following examples.

Examples 1 - 2



[0018] 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 --


[0019] 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



[0020] 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.

[0021] 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.

[0022] In the experimental AEG machine, the percentage of mechanical loss was less than 10 % in the majority of all measurements.

B. Storage stability



[0023] Spherical capsules containing non-aqueous liquid including 1 % 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



[0024] In an appraisal test, the performance of the encapsulated NAL was compared with the performance of standard NAL on varicus test cloths. The test was carried out in a top coating drum-type washing machine, main wash only (40°C, 30 min), a water hardness of 150 mg CaO per 1000 ml water (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


[0025] The experiments show that the encapsulated NAL'S, with and without the proteolytic enzyme, have very satisfying was 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

1. A capsule containing a non-aqueous liquid detergent composition, wherein the liquid detergent component comprises a non-aqueous organic solvent and particles of a solid material dispersed therein, wherein the capsule comprises a water-dispersible substance, wherein the liquid detergent composition contains a proteolytic enzyme and the capsule is a gelatin capsule.
 
2. A capsule according to claim 1, wherein the dispersed solid material comprises a builder.
 
3. A capsule according to claim 2, wherein the builder is sodium tripolyphosphate.
 


Ansprüche

1. Kapsel, enthaltend eine nicht-wäßrige, flüssige Detergenszusammensetzung, worin der flüssige Detergensbestandteil ein nicht-wäßriges organisches Lösungsmittel und darin dispergierte Feststoffteilchen umfaßt, worin die Kapsel eine wasserdispergierbare Substanz umfaßt, worin die flüssige Detergenszusammensetzung ein proteolytisches Enzym enthält und die Kapsel eine Gelatinekapsel ist.
 
2. Kapsel nach Anspruch 1, worin der dispergierte Feststoff einen Builder umfaßt.
 
3. Kapsel nach Anspruch 2, worin der Builder Natriumtripolyphosphat ist.
 


Revendications

1. Capsule contenant une composition détergente liquide non aqueuse, dans laquelle le composant détergent liquide comprend un solvant organique non aqueux et des particules d'une matière solide dispersée, la capsule comprenant une substance dispersable dans l'eau, la composition détergente liquide contenant une enzyme protéolytique et la capsule étant une capsule de gélatine.
 
2. Capsule selon la revendication 1, dans laquelle la matière solide dispersée comprend un adjuvant.
 
3. Capsule selon la revendication 2, dans laquelle l'adjuvant est le tripolyphosphate de sodium.