EP0643763B1 - Substrats actifs a enrobage permettant leur liberation - Google Patents

Substrats actifs a enrobage permettant leur liberation Download PDF

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Publication number
EP0643763B1
EP0643763B1 EP93910229A EP93910229A EP0643763B1 EP 0643763 B1 EP0643763 B1 EP 0643763B1 EP 93910229 A EP93910229 A EP 93910229A EP 93910229 A EP93910229 A EP 93910229A EP 0643763 B1 EP0643763 B1 EP 0643763B1
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EP
European Patent Office
Prior art keywords
coating
encapsulated
active substrate
final
metal salt
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.)
Expired - Lifetime
Application number
EP93910229A
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German (de)
English (en)
Other versions
EP0643763A1 (fr
Inventor
Barry Neil Love
Colin Young
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.)
Warwick International Group Ltd
Original Assignee
Warwick International Group Ltd
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Filing date
Publication date
Priority claimed from GB929211373A external-priority patent/GB9211373D0/en
Priority claimed from GB929213342A external-priority patent/GB9213342D0/en
Application filed by Warwick International Group Ltd filed Critical Warwick International Group Ltd
Publication of EP0643763A1 publication Critical patent/EP0643763A1/fr
Application granted granted Critical
Publication of EP0643763B1 publication Critical patent/EP0643763B1/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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
    • 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
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the present invention relates to active substrates such as bleach activators releasably encapsulated in a coating thereon and methods of applying the same.
  • bleach activators in detergent formulations.
  • One of the important aspects of such formulations is that they should be capable of being stored over a significantly long period both by the producers of such formulations, the retailers of the product and by the end user, eg the housewife, who usually buys in bulk and likes to use it in small aliquots for washing as and when necessary.
  • the components of such formulations especially the bleaches and bleach activators, may have an unacceptably short storage life due to their tendency to undergo undesirable physical or chemical changes, thereby resulting in deterioration of the formulation which may manifest itself as, eg loss of activity, discolouration, loss of attrition resistance. hygroscopicity and hence caking by absorption of moisture, staining the clothes washed or as malodour. It has been found that bleaches and bleach activators in particular are prone to such undesirable changes.
  • US-A-4105827 describes a process for stabilizing bleaches which are particulate peroxygen compounds by providing a hermetic coating on said compounds with a mixed salt obtained by crystallization of sodium carbonate with another inorganic salt selected from sodium bicarbonate and sodium sulphate. These products are said to be capable of dissolving the peroxygen compounds in a cold wash eg at 20°C but no actual data is given. There is also no evidence in this reference whether such a method of coating minimises dye damage or pinholing caused by the bleach and there is no data on bleach activators.
  • the present invention is an encapsulated active substrate comprising a bleach and/or a bleach activator releasably encapsulated in a coating of at least one metal salt of an inorganic acid, said salt being soluble in an aqueous medium such that upon contacting the encapsulated substrate with the aqueous medium, the active substrate is released into said medium, characterised in that the substrate has a preliminary coating of an alkali metal carbonate or alkali metal bicarbonate and a final encapsulating coating of a metal salt of an inorganic acid.
  • active substrate is meant here and throughout the specification a bleach, a bleach activator, a mixture of the two or either of them as such or admixed with the other when formed into a composite with one or more other components including conventional binders such as eg a bentonite clay; surfactants such as polyoxyalkylene sorbitan oleate esters, eg Tween TM , and an alkali metal salt of a polycarboxylic acid, eg Dispex-G40 TM ; disintegrating aids such as cross-linked carboxymethyl cellulose derivatives, eg Ac-di-sol TM or a polyacrylate; and fillers such as the cellulosic type, eg Avicel TM .
  • conventional binders such as eg a bentonite clay
  • surfactants such as polyoxyalkylene sorbitan oleate esters, eg Tween TM , and an alkali metal salt of a polycarboxylic
  • bleaches which may be encapsulated in this manner include the peroxygenated compounds such as the percarbonates, the perpyrophosphates. the pertripolyphosphates, the perborates, the percarboxylates such as peracetates, peroxymonosulphates and peroxyphthalates.
  • bleach activators which can be encapsulated in this manner include cyclic anhydrides of the structural formula (I) or a lactone of the structural formula (II) shown below: where Q is at least a divalent organic grouping such that Q and N together with the carbonyl and oxygen functions form one or more cyclic structures and in (I) R is H, an alkyl, aryl, halogen, a carboxylic- or a carbonyl-containing function, and in (II) R is a C 2 or higher alkyl, alkaryl, aryl, aralkyl, alkoxy, haloalkyl, amino, alkylamino, dialkylamino, carboxylic- or a carbonyl-containing function.
  • Q is at least a divalent organic grouping such that Q and N together with the carbonyl and oxygen functions form one or more cyclic structures and in (I) R is H, an alkyl, aryl, halogen, a carboxylic- or a carbony
  • such compounds include bleach activators such as 2-hydrocarbyl-(4H)-3,1-benzoxazin-4-ones (especially the 2-methyl and the 2-phenyl derivatives), the 2-N,N-dialkylamino-(4H)-3,1-benzoxazin-4-ones (especially the 2-N,N-dimethyl derivative), and isatoic anhydride and its homologues and derivatives.
  • bleach activators described in published EP-A-170386 eg N-alkoyl-6-aminoperoxycarboxylic acids and their salts
  • GB-A-2832021 eg tetra-acetyl ethylenediamine
  • aqueous medium as used herein and throughout the specification is meant to include the aqueous alkaline medium encountered in a wash cycle or during a washing procedure.
  • the active substrate is suitably in the form of a powder or granules prior to the preliminary coating with an alkali metal carbonate or bicarbonate.
  • the initial particle size of the substrate should be preferably from 0.1-200 ⁇ m for powder and from 200-2000 ⁇ m for the granules.
  • the choice of particle size of the powder to be granulated will depend upon the nature of the bleach or the bleach activator used. For instance, in the case of 2-phenyl-(4H)-3,1-benzoxazin-4-one (hereafter referred to as "2PB4"), it may be necessary to grind this bleach activator a very fine particle size, eg below 10 ⁇ m before being granulated.
  • substrates having the desired particle size within this range can be produced from commercially available material by milling and/or grinding followed by granulation, preferably by the technique of extrusion and spheronisation. Methods of extrusion and spheronisation are described extensively in our published EP-A-0482806.
  • the powder or granules of the active substrate they may be in the form of a composite comprising the bleach and/or bleach activator, binders, dispersing aids, surfactants and fillers as described above.
  • the initial coating of the carbonate or bicarbonate can be applied on the substrate by conventional means. It is preferable to create a fluidised bed of the active substrate particles and to spray the particles with a solution of the alkali metal carbonate or bicarbonate.
  • the active substrate particles In this initial step it is not necessary for the active substrate particles to be completely encapsulated by the alkali metal carbonate or bicarbonate coating. This is due to the fact that the function of the alkali metal carbonate or bicarbonate coating is to facilitate the final encapsulating coating of the inorganic acid metal salt to be broken up upon contact with water thereby releasing the active substrate into the wash system..
  • the preliminary coating is suitably of sodium carbonate or sodium bicarbonate, but is preferably that of sodium carbonate.
  • the thickness of the preliminary coating is such that it suitably forms less than 5%w/w of the final coated product, preferably less than 2%w/w, eg 1%w/w of the final coated product.
  • the final encapsulating coating with the metal salt of an inorganic acid can be applied in a manner similar to that described for the preliminary coating of an alkali metal carbonate or bicarbonate.
  • the conditions used for coating should be controlled to ensure that the active substrate already having a preliminary coating of an alkali metal carbonate or bicarbonate thereon is substantially completely encapsulated by the final coating.
  • the fluidisation of the particles in this case should be such that they float in the fluidising medium as separate distinct particles for a sufficiently long time in the coating environment so as to enable the spray of the metal salt solution to completely encapsulate and hermetically seal all of the particles individually.
  • the residence time within the coating environment and the temperature within the coating environment are preferably such that before the encapsulated particles emerge from the environment, they are substantially dry and resistant to (a) loss of coating by attrition and (b) agglomeration.
  • a fluidising medium is also important in that it should be substantially inert to the encapsulating process and should not adversely affect the nature of the substrate being encapsulated or the encapsulating coating. Examples of suitable fluidising media include air and nitrogen.
  • the metal salt of the inorganic acid used to form the final encapsulating coating must be soluble in the aqueous medium although it would be advantageous if they are soluble in water.
  • the solubility should be preferably at least 3g/100g of the aqueous medium at ambient temperatures, eg 15°C, although the greater the solubility the better.
  • metal salts suitably include the water-soluble sulphates, phosphates and carbonates of the metals in Groups II and III of the Periodic Table, preferably the salts of magnesium, zinc and aluminium.
  • the final encapsulating coating is most preferably that of aluminium sulphate or zinc sulphate.
  • the thickness of the final encapsulating coating should be such that it does not peel off or is not readily removed or dislodged from the active substrate surface by eg attrition and preferably has a thickness of at least 0.03 ⁇ m.
  • the final encapsulating coating only forms a minor proportion of the encapsulated product. That is, the active substrate should be at least 50% w/w of the encapsulated product, preferably greater than 65% w/w and most preferably from 65-85Zw/w of the encapsulated product. This means that the encapsulating coating itself suitably forms only 15-35%w/w, eg 18% of the final product, It has been found that ideally, the mole ratio of the preliminary coating material to the final encapsulating coating material is no greater than 1:1.
  • the function of the preliminary coating of an alkali metal carbonate or bicarbonate is to facilitate the release of the active substrate from its encapsulating final coating into the wash system.
  • the final encapsulating coating step eg with the aluminium or zinc salt, will in itself result in a premature reaction between the encapsulating metal salt and the preliminary coating of carbonate and bicarbonate, thereby damaging the encapsulating coating and hence detracting from the desired storage stability or release rate of the final product.
  • This intermediate coating should be of a compound readily soluble in water or at least in the aqueous medium used for the wash and is suitably, though not necessarily, an alkali metal salt of the same inorganic acid as that used for producing the aluminium or zinc salt of the final coating.
  • the intermediate coating is preferably that of sodium sulphate.
  • the intermediate coating can be applied using the same technique as described above and should cover all the carbonate/bicarbonate sites on the active substrate surface formed in the preliminary coating step in order to prevent premature reaction thereof with the final encapsulating coating.
  • the thickness of the intermediate coating should be such that it suitably forms less than 10%w/w, preferably from 2-5%w/w of the final encapsulated product.
  • 2PB4 was sieved to ⁇ 1mm prior to fine grinding in a Hosokawa Micron Ltd AF G100 fluid air jet mill and classifier.
  • the resulting product had a particle size of ⁇ 10 ⁇ m as determined by a Sympatec laser diffraction spectrometer.
  • Granules were then prepared from the components tabulated below by mixing with water to form a dough, followed by extrusion, spheronisation and drying to obtain granules having a particle size of up to 2 mm.
  • Granules A and B were produced on a Caleva Ltd model 10 extruder and model 120 spheroniser.
  • Granules C, D and E were produced on a NICA System AB model E140 extruder and model S320 spheroniser. Drying was carried out in an Aeromatic Strea-l fluid bed drier. The dry granules were sieved and the fraction between 600 and 1180 ⁇ m retained. Granule Ref.
  • Granules A, B and C are comparative granules and granules D and E illustrate the invention.
  • the granules produced as above were mixed with the following materials to give a detergent formulation containing 4% 2PB4 (expressed as 100% active bleach activator).
  • Samples of the detergent powders containing the granules D, E and C were spread in narrow strips of ca. 1 cm width onto a test cloth of cotton dyed with immedial black (EMPA 115). This cloth had been placed in a tray and dampened with sufficient water to absorb into and dampen the strips of detergent formulation. After 30 minutes the test cloth was thoroughly rinsed in running tap water and air dried.
  • EMPA 115 immedial black

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  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Paper (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)
  • Medicinal Preparation (AREA)
  • Lubricants (AREA)
  • Materials For Medical Uses (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Claims (10)

  1. Substrat actif encapsulé comprenant un agent de blanchiment, un activateur de blanchiment ou leurs mélanges encapsulés de façon à pouvoir être émis, dans un revêtement d'au moins un sel de métal d'un acide minéral, ledit sel étant soluble dans un milieu aqueux tel que par mise en contact du substrat d'encapsulation avec le milieu aqueux, le substrat actif est émis dans ledit milieu, caractérisé en ce que le substrat a un revêtement préliminaire de carbonate de métal alcalin ou de bicarbonate de métal alcalin et un revêtement d'encapsulation finale d'un sel de métal d'un acide minéral.
  2. Substrat actif encapsulé selon la revendication 1, où l'agent de blanchiment ainsi encapsulé est un composé peroxygéné choisi dans le groupe constitué des percarbonates, perpyrophosphates, pertripolyphosphates, perborates, percarboxylates, permonosulfates et peroxyphtalates.
  3. Substrat actif encapsulé selon la revendication 1, où l'activateur de blanchiment ainsi encapsulés sont soit un anhydride cyclique de formule (I) soit une lactone de formule (II) :
    Figure imgb0005
     où Q est au moins un groupe organique divalent tel que Q et N forment avec les fonctions carbonyles et oxygène une ou plusieurs structures cycliques et dans (I) R est H, un alkyle, aryle, halogène, une fonction carboxylique ou une fonction contenant un carbonyle, et dans (II) R est un alkyle, alcaryle, aryle, aralkyle, alcoxy, haloalkyle, amino, alkylamino, dialkylamino, une fonction carboxylique ou une fonction contenant un carbonyle en C2 ou plus.
  4. Substrat actif encapsulé selon l'une quelconque des revendications précédentes, où le revêtement d'encapsulation finale est celui d'un sel de métal d'acide minéral, choisi dans le groupe constitué d'un sulfate, un phosphate ou un carbonate d'un métal des groupes II et III du tableau périodique.
  5. Substrat actif encapsulé selon l'une quelconque des revendications précédentes, où le revêtement d'encapsulation finale est celui d'un sel de métal d'un acide minéral qui est un sel de magnésium, de zinc ou d'aluminium.
  6. Substrat actif encapsulé selon l'une quelconque des revendications précédentes, où le revêtement d'encapsulation finale a une épaisseur d'au moins 0,03 µm.
  7. Substrat actif encapsulé selon l'une quelconque des revendications précédentes, où le rapport molaire du revêtement préliminaire de carbonate ou de bicarbonate de métal alcalin au revêtement d'encapsulation finale du sel de métal d'un acide minéral n'est pas supérieur à 1:1.
  8. Substrat actif encapsulé selon l'une quelconque des revendications précédentes, où un revêtement intermédiaire d'un composé minéral soluble dans l'eau ou dans le milieu aqueux est appliqué sur le substrat qui a un revêtement préliminaire d'un carbonate ou bicarbonate de métal alcalin sur lui avant l'application du revêtement d'encapsulation finale.
  9. Procédé d'encapsulation d'un substrat actif comprenant un agent de blanchiment et/ou un activateur de blanchiment dans le revêtement, ledit procédé comprenant de :
    a. fluidiser un lit de particules de substrat actif en poudre ou en forme granulaire et pulvériser sur lesdites particules une pulvérisation de solution d'un carbonate de métal alcalin ou d'un bicarbonate de métal alcalin de façon à former un revêtement préliminaire sur lui,
    b. fluidiser encore les particules ayant le revêtement préliminaire d'un carbonate de métal alcalin ou de bicarbonate de métal alcalin sur lui dans un milieu de fluidisation tel que les particules avec le revêtement préliminaire sur lui flottent séparées dans le milieu de fluidisation pendant un temps suffisamment long pour permettre l'application d'un revêtement d'encapsulation d'un sel de métal minéral sur elles,
    c. appliquer sur les particules qui ont le revêtement préliminaire ainsi mises en suspension une pulvérisation d'une solution d'un sel de métal minéral jusqu'à ce que chaque particule portant le revêtement préliminaire soit complètement encapsulée et hermétiquement scellée par le revêtement final du sel de métal minéral.
  10. Procédé selon la revendication 9, où la fluidisation des particules portant le revêtement préliminaire sur elles et la durée dudit revêtement final avec le sel de métal minéral sont maîtrisées de façon que les particules encapsulées sortant de l'étape finale de revêtement soient sensiblement sèches et résistantes à la perte de revêtement par attrition et agglomération.
EP93910229A 1992-05-29 1993-05-19 Substrats actifs a enrobage permettant leur liberation Expired - Lifetime EP0643763B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB9211373 1992-05-29
GB929211373A GB9211373D0 (en) 1992-05-29 1992-05-29 Releasably encapsulated active substrates
GB929213342A GB9213342D0 (en) 1992-06-24 1992-06-24 Releasably encapsulated active substrates
GB9213342 1992-06-24
PCT/GB1993/001022 WO1993024604A1 (fr) 1992-05-29 1993-05-19 Substrats actifs a enrobage permettant leur liberation

Publications (2)

Publication Number Publication Date
EP0643763A1 EP0643763A1 (fr) 1995-03-22
EP0643763B1 true EP0643763B1 (fr) 1996-07-31

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP93910229A Expired - Lifetime EP0643763B1 (fr) 1992-05-29 1993-05-19 Substrats actifs a enrobage permettant leur liberation

Country Status (8)

Country Link
EP (1) EP0643763B1 (fr)
JP (1) JPH10500433A (fr)
AT (1) ATE140955T1 (fr)
AU (1) AU4081693A (fr)
CA (1) CA2136833A1 (fr)
DE (1) DE69303900T2 (fr)
ES (1) ES2090997T3 (fr)
WO (1) WO1993024604A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10136211B4 (de) * 2001-07-25 2007-05-24 Henkel Kgaa Verfahren zur Herstellung teilchenförmiger Wasch-oder Reinigungsmittel
WO2004050810A2 (fr) * 2002-12-02 2004-06-17 Diamond Chemical Company, Inc. Nouvelle classe de compositions de lessive
EP2292725B2 (fr) 2009-08-13 2022-08-24 The Procter & Gamble Company Procédé de nettoyage de tissus à basse température
GB0918914D0 (en) 2009-10-28 2009-12-16 Revolymer Ltd Composite
GB201106408D0 (en) 2011-04-15 2011-06-01 Revolymer Ltd Novel composite
GB201106391D0 (en) 2011-04-15 2011-06-01 Reckitt & Colman Overseas Novel composite
GB201106409D0 (en) 2011-04-15 2011-06-01 Revolymer Ltd Novel composite
GB201106377D0 (en) 2011-04-15 2011-06-01 Reckitt & Colman Overseas Novel composite
EP3661989B1 (fr) * 2017-07-31 2022-09-07 Dow Global Technologies LLC Composition additive et procédé

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3494787A (en) * 1966-12-19 1970-02-10 Ppg Industries Inc Encapsulated perphthalic acid compositions and method of making same
US4105827A (en) * 1973-04-20 1978-08-08 Interox Particulate peroxygen compounds coated with sodium sesquicarbonate or Na2 SO4 mNa2 CO3
DE3504628A1 (de) * 1985-02-11 1986-08-14 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung eines rieselfaehigen granulats
US4657784A (en) * 1986-03-10 1987-04-14 Ecolab Inc. Process for encapsulating particles with at least two coating layers having different melting points
GB9023000D0 (en) * 1990-10-23 1990-12-05 Bp Chem Int Ltd Barrier coatings

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Publication number Publication date
AU4081693A (en) 1993-12-30
DE69303900D1 (de) 1996-09-05
ES2090997T3 (es) 1996-10-16
CA2136833A1 (fr) 1993-12-09
EP0643763A1 (fr) 1995-03-22
WO1993024604A1 (fr) 1993-12-09
JPH10500433A (ja) 1998-01-13
ATE140955T1 (de) 1996-08-15
DE69303900T2 (de) 1996-11-28

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