EP0482807B1 - Wieder freisetzbar eingekapselte, aktive Substrate - Google Patents

Wieder freisetzbar eingekapselte, aktive Substrate Download PDF

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Publication number
EP0482807B1
EP0482807B1 EP91309432A EP91309432A EP0482807B1 EP 0482807 B1 EP0482807 B1 EP 0482807B1 EP 91309432 A EP91309432 A EP 91309432A EP 91309432 A EP91309432 A EP 91309432A EP 0482807 B1 EP0482807 B1 EP 0482807B1
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EP
European Patent Office
Prior art keywords
process according
metal salt
coating
activator
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
EP91309432A
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English (en)
French (fr)
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EP0482807A1 (de
Inventor
Malcolm Gavin John Macduff
Walter Edward Paget
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Warwick International Group Ltd
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Warwick International Group Ltd
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Publication of EP0482807A1 publication Critical patent/EP0482807A1/de
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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
    • C11D3/3907—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
    • 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

Definitions

  • the present invention relates to active substrates such as bleach activators releasably encapsulated in a coating thereon and methods of applying the same.
  • bleaches and 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, e.g. 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 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, e.g.
  • Peroxygen compounds for use in bleaching formulations are protected with barrier coatings comprising metal salts, for example in US-A-4105827 and FR-A-2229768.
  • Bleach activators of various types are encapsulated in metal salt protective coatings in EP-A-174132 and CA-A-0676777.
  • any coating applied should be such that:
  • the present invention relates to a process for encapsulating a bleach activator comprising the steps of:
  • the process is of particular benefit for encapsulating cyclic anhydride activators of the formula I and lactones of the formula II and in the process the activator preferably comprises at least one compound selected from a cyclic anhydride of the structural formula (I) or a lactone of the structural formula (II) below: wherein Q is 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 C2 or higher alkyl, alkaryl, aryl, aralkyl, alkoxyl, haloalkyl, amino, amino alkyl, dialkyl amino, carboxylic or a carbonyl-containing function.
  • Q is 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)
  • active substrate a bleach activator as such or a composite which comprises such bleach activator and one or more other components including conventional binders such as e.g. a bentonite clay; surfactants such as polyoxyalkylene sorbitan oleate esters, e.g. Tween (Registered Trade Mark) an alkali metal salt of a polycarboxylic acid, e.g. Dispex-G40 (Registered Trade Mark, ex Allied Colloids, UK); disintegrating aids such as cross-linked carboxy methyl cellulose derivatives e.g. Ac-di-sol (Registered Trade Mark) or a polyacrylate; and fillers such as the cellulosic type, e.g. Avicel (Registered Trade Mark).
  • conventional binders such as e.g. a bentonite clay
  • surfactants such as polyoxyalkylene sorbitan oleate esters, e.g. Tween (Registered Trade Mark) an alkali
  • Bleach activators of formula (I) are claimed and described in our published EP-A-331300 and those of formula (II) are claimed and described in our published EP-A-332294 and are incorporated herein by reference.
  • such compounds include bleach activators such as 2-hydrocarbyl (4H) 3,1-benzoxazin-4-ones (especially the 2-methyl and 2-aryl 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 N-alkoyl-6-aminoperoxycarboxylic acids and their salts
  • GB-A-2832021 tetraacetyl ethylene diamine
  • 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 metal salts of inorganic acids which can be used to form the encapsulating coating must be soluble in the aqueous medium although it would be advantageous if they are soluble in water.
  • the solubility should preferably be at least 3g/100g of the aqueous medium at ambient temperatures, eg 15°C, although the greater the solubility, the better.
  • examples of such compounds include the water soluble carbonates, sulphates and phosphates of the metals in Groups I-III of the Periodic Table, especially the alkali metals, some alkaline earth metals such as magnesium, zinc and Group III metals such as aluminium. Particularly preferred are the sulphates and phosphates of sodium, potassium, zinc and aluminium. Whichever metal salt is chosen, the salt should be such that it is capable of forming an encapsulating barrier coating on the active substrate.
  • activators of the structure type (II) especially if the compound is a 2-aryl substituted benzoxazin-4-one, such activators cause dye damage.
  • the performance of such activators can be improved by using an encapsulating coating of a zinc salt such as zinc sulphate.
  • activators of the type (I) ie those having an isatoic anhydride type structure, the problems of staining and dye damage can be mitigated by using an encapsulating coating of an aluminium salt such as aluminium sulphate.
  • the encapsulating coating should suitably form 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 of the encapsulated product and most preferably from 65-80% w/w.
  • the thickness of the coating encapsulating the active substrate is suitably such that it does not peel off or is not readily removed by attrition and is preferably at least 0.03 micrometers.
  • the encapsulation should however be such that it completely covers the active substrate coated.
  • the active substrate is suitably in the form of a powder or granules prior to encapsulation.
  • the initial particle size of the substrate should be preferably from 50-200 micrometers for the powder and from 200-2000 micrometers for the granules.
  • Substrates having particle sizes within this range can be produced from commercially available material by milling and/or grinding, granulation or preferably by the technique of extrusion and spheronisation.
  • the powder or granules of the active substrate they may be in the form of a composite comprising the bleach activator, binders, dispersing aids, surfactants and fillers as described above.
  • the encapsulating coating can be applied on the substrate by conventional means. It is preferable to create a fluidised bed of the substrate particles and to spray them with a solution of the metal salt. In using this technique the conditions should be controlled carefully in order to achieve satisfactory encapsulation. For instance, the fluidisation of the substrate particles should be such that they float in the fluidising medium as separate and distinct particles for a sufficiently long time in the coating environment so as to enable the spray of the metal salt to substantially completely encapsulate and hermetically seal substantially all of the particles individually. At the same time the residence time within the coating environment and the temperature within the coating environment should be 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.
  • An example of a suitable fluidising medium is air.
  • the above components were formed into a dough in water and subjected to extrusion followed by spheronisation to obtain granules having a particle size of 500-1000 micrometers.
  • the granules were then fluidised in a Strea-1 fluidiser at a spray rate of about 6g/min through two-fluid nozzle with atomising air pressure of about 0.8 bar.
  • Air was used as the fluidising medium at an air volume of 10 units on Strea 1.
  • the inlet air temperature was 48°C and the outlet air temperature was 36°C.
  • a solution of 150g of anhydrous sodium sulphate in 700g of water was used as the encapsulating solution.
  • This sodium sulphate solution was sprayed in a direction cocurrent with the fluidising air using a Wurster column. The spraying of the solution took about 1.5 hours to encapsulate the granules. The encapsulated granules were then dried for a further 20 minutes during which time the temperature was increased to 52°C at the inlet and 46°C at the outlet to bake the encapsulating coating into a solid, dry barrier.
  • the encapsulated granules so produced were mixed at a concentration of 5% w/w with a detergent powder containing 80% w/w ECE Base (ex Westlairds Limited, North Green, Datchet, Slough SL3 9JH, Berkshire, UK) and 15% w/w of a perborate bleach and stored in open packs at 37°C and 70% relative humidity.
  • the resultant detergent formulation did not suffer any discolouration or substantial loss of activity after storage for 2 months.
  • solubility of the coating in the aqueous medium is unaffected is illustrated by a comparison of coated and uncoated spheres made with the above formulation where it can be seen that there is no significant difference between whole and crushed spheres:
  • Granules containing 80% isatoic anhydride bleach activator were encapsulated with the inorganic salts detailed below. These coated granules (20 parts) were mixed with a phosphate-free detergent base which contained 25% sodium perborate monohydrate (80 parts). Samples from the detergent formulations thus prepared were then spread in narrow strips of ca. 2cm width onto a test cloth of white cotton (EMPA 221). This cloth had previously been placed in a tray and dampened with sufficient water to absorb into and dampen the strips of detergent formulation. After 30 minutes the cotton test cloth was thoroughly rinsed in running tap water and air dried.
  • EMPA 221 white cotton
  • Granules containing 82% 2-phenyl benzoxazine-4-one (2PB4) bleach activator were encapsulated with the inorganic salts detailed below. These coated granules (20 parts) were mixed with a phosphate-free detergent base which contained 25% sodium perborate monohydrate (80 parts). Samples from the detergent formulations thus prepared were then spread in narrow strips of ca. 2cm width onto a test cloth of cotton dyed with immedial black (EMPA 115). This cloth had previously been placed in a tray and dampened with sufficient water to absorb into and dampen the strips of detergent formulation. After 30 minutes the cotton test cloth was thoroughly rinsed in running tap water and air dried. The above test was repeated.
  • 2PB4 2-phenyl benzoxazine-4-one

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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)
  • Formation Of Insulating Films (AREA)
  • Cosmetics (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Laminated Bodies (AREA)

Claims (11)

  1. Verfahren zur Verkapselung eines Bleichaktivators, umfassend die folgenden Schritte:
    i) Bilden eines teilchenförmigen Kompositsubstrats mit einer Teilchengröße im Bereich von 200-2000 »m, das aus dem Bleichaktivator und einem Bindemittel besteht und gegebenenfalls ein Zerfallshilfsmittel, ein Tensid und/oder einen Füllstoff enthält,
    ii) Beschichten des teilchenförmigen Kompositsubstrats mit einer Lösung eines Metallsalzes einer anorganischen Säure, die in Wasser bis zu einem Grad von mindestens 3 g pro 100 g bei 15°C löslich ist, und
    iii) Trocknen der beschichteten Teilchen.
  2. Verfahren nach Anspruch 1, bei welchem das teilchenförmige Kompositsubstrat während des Beschichtungsschrittes in einem Fließbett in Luft suspendiert ist.
  3. Verfahren nach irgendeinem vorhergehenden Anspruch, bei welchem das Metallsalz in einer eine Schädigung der Farbe und/oder eine Verschmutzung des Gewebes hemmenden Menge verwendet wird.
  4. Verfahren nach Anspruch 3, bei welchem die Dicke der Salzschicht des Produkts mindestens 0,03 »m beträgt.
  5. Verfahren nach irgendeinem vorhergehenden Anspruch, bei welchem das Metall des Metallsalzes aus Alkalimetallen, Erdalkalimetallen, Zink und Metallen der Gruppe III ausgewählt ist.
  6. Verfahren nach Anspruch 5, bei welchem das Metallsalz ein Zink- oder Aluminiumsalz ist.
  7. Verfahren nach Anspruch 6, bei welchem das Metallsalz aus Zinksulfat und Aluminiumsulfat ausgewählt ist.
  8. Verfahren nach irgendeinem vorhergehenden Anspruch, bei welchem der verkapselte Aktivator in ein Waschpulver eingebracht wird, das eine Peroxid-Bleichquelle enthält.
  9. Verfahren nach irgendeinem vorhergehenden Anspruch, bei welchem der Aktivator mindestens eine aus einem cyclischen Anhydrid der Strukturformel I oder einem Lacton der Strukturformel II unten ausgewählte Verbindung ist
    Figure imgb0005
     worin Q eine zweiwertige organische Gruppe ist, so daß Q und N zusammen mit den Carbonyl- und Sauerstoff-Funktionen eine oder mehrere cyclische Strukturen bilden, und R in (I) H, eine Alkyl-, Aryl-, Halogen-, eine Carboxyl- oder eine Carbonyl-haltige Funktion ist und R in (II) eine C₂- oder eine höhere Alkyl-, Alkaryl-, Aryl-, Aralkyl-, Alkoxyl-, Halogenalkyl-, Amino-, Aminoalkyl-, Dialkylamino-, Carboxyl- oder eine Carbonyl-haltige Funktion ist.
  10. Verfahren nach Anspruch 9, bei welchem der Bleichaktivator aus einem 2-Hydrocarbyl-(4H)-3,1-benzoxazin-4-on, 2-Aryl-(4H)-3,1-benzoxazin-4-on, 2-N,N-Dialkylamino-(4H)-3,1-benzoxazin-4-on und Isatosäureanhydrid ausgewählt ist.
  11. Verfahren nach irgendeinem vorhergehenden Anspruch, bei welchem das Bindemittel eine Bentonit-Tonerde, das Tensid ein Polyoxyalkylensorbitanoleat-Ester oder ein Alkalimetallsalz einer Polycarbonsäure, das Zerfallshilfsmittel ein vernetztes Hydroxymethyl-cellulose-Derivat und der Füllstoff ein Füllstoff vom Cellulose-Typ ist.
EP91309432A 1990-10-23 1991-10-14 Wieder freisetzbar eingekapselte, aktive Substrate Expired - Lifetime EP0482807B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB909023000A GB9023000D0 (en) 1990-10-23 1990-10-23 Barrier coatings
GB9023000 1990-10-23

Publications (2)

Publication Number Publication Date
EP0482807A1 EP0482807A1 (de) 1992-04-29
EP0482807B1 true EP0482807B1 (de) 1995-12-20

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EP (1) EP0482807B1 (de)
JP (1) JPH04314799A (de)
AT (1) ATE131864T1 (de)
CA (1) CA2054003A1 (de)
DE (1) DE69115637T2 (de)
ES (1) ES2081441T3 (de)
GB (1) GB9023000D0 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6878680B2 (en) 2002-05-02 2005-04-12 Procter & Gamble Detergent compositions and components thereof
US7790664B2 (en) 2008-10-27 2010-09-07 The Procter & Gamble Company Methods for making a nil-phosphate liquid automatic dishwashing composition
US8026203B2 (en) 2008-06-02 2011-09-27 The Procter & Gamble Company Surfactant concentrate

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4134770A1 (de) * 1991-10-22 1993-04-29 Basf Ag Koernige bleichaktivatorzusammensetzung
DE4203169A1 (de) * 1992-02-05 1993-08-12 Basf Ag Koernige bleichaktivatorzusammensetzung aus heterogen aufgebauten koernern
JPH10500433A (ja) * 1992-05-29 1998-01-13 ワーウィック・インターナショナル・グループ・リミテッド 放出可能にカプセル化した活性基体およびその製造方法
JPH11514027A (ja) * 1996-06-28 1999-11-30 ザ、プロクター、エンド、ギャンブル、カンパニー コートされた粒子を含有している非水性液体クリーニング組成物
GB2320254A (en) 1996-12-12 1998-06-17 Procter & Gamble Process for making tabletted detergent compositions
US5905067A (en) * 1997-02-10 1999-05-18 Procter & Gamble Company System for delivering hydrophobic liquid bleach activators
US20070015674A1 (en) 2005-06-30 2007-01-18 Xinbei Song Low phosphate automatic dishwashing detergent composition
CA2671810A1 (en) 2006-12-11 2008-06-19 The Procter & Gamble Company Improved visual perceptibility of images on printed film
ES2385748T3 (es) 2007-08-16 2012-07-31 The Procter & Gamble Company Procedimiento para producir una composición detergente
EP2484747A1 (de) 2007-08-16 2012-08-08 The Procter & Gamble Company Verfahren zur Hertellung einer Waschmittelzusammensetzung
ES2379951T3 (es) 2008-06-13 2012-05-07 The Procter & Gamble Company Bolsa multicompartimental
ES2774183T3 (es) 2009-06-02 2020-07-17 Procter & Gamble Bolsa hidrosoluble
PL2295530T3 (pl) 2009-09-14 2012-04-30 Procter & Gamble Kompozycja detergentu
JP5133460B2 (ja) 2009-09-15 2013-01-30 ザ プロクター アンド ギャンブル カンパニー キレート剤の混合物を含む洗剤組成物
EP2302026A1 (de) 2009-09-15 2011-03-30 The Procter & Gamble Company Waschmittelzusammensetzung mit Tensidladungspolymeren
WO2011118340A1 (ja) * 2010-03-26 2011-09-29 ライオン株式会社 漂白活性化剤造粒物及びその製造方法
US8629093B2 (en) 2010-09-01 2014-01-14 The Procter & Gamble Company Detergent composition comprising mixture of chelants
EP2821474A1 (de) 2011-01-12 2015-01-07 The Procter and Gamble Company Verfahren zur Steuerung der Plastifizierung eines wasserlöslichen Films
US8853142B2 (en) 2012-02-27 2014-10-07 The Procter & Gamble Company Methods for producing liquid detergent products
BR112015012915A2 (pt) 2012-12-06 2017-07-11 Procter & Gamble saco de contenção solúvel compreendendo corante tonalizante
EP2740785A1 (de) 2012-12-06 2014-06-11 The Procter and Gamble Company Verwendung einer Zusammensetzung zur Reduzierung des Nässens und Übergehens durch einen wasserlöslichen Film
US20140249067A1 (en) 2013-03-04 2014-09-04 The Procter & Gamble Company Premix containing optical brightener
JP6466468B2 (ja) 2014-03-27 2019-02-06 ザ プロクター アンド ギャンブル カンパニー 印刷された水溶性パウチ
EP2955219B1 (de) 2014-06-12 2020-03-25 The Procter and Gamble Company Wasserlöslicher Beutel mit geprägtem Bereich

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US4105827A (en) * 1973-04-20 1978-08-08 Interox Particulate peroxygen compounds coated with sodium sesquicarbonate or Na2 SO4 mNa2 CO3
CA1001361A (en) * 1973-05-16 1976-12-14 Ppg Industries, Inc. Bleaching formulation
GB8422158D0 (en) * 1984-09-01 1984-10-03 Procter & Gamble Ltd Bleach compositions
GB8618106D0 (en) * 1986-07-24 1986-09-03 British Petroleum Co Plc Bleach activators
DE3807921A1 (de) * 1988-03-10 1989-09-21 Henkel Kgaa Aktivator fuer anorganische perverbindungen

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6878680B2 (en) 2002-05-02 2005-04-12 Procter & Gamble Detergent compositions and components thereof
US8026203B2 (en) 2008-06-02 2011-09-27 The Procter & Gamble Company Surfactant concentrate
US7790664B2 (en) 2008-10-27 2010-09-07 The Procter & Gamble Company Methods for making a nil-phosphate liquid automatic dishwashing composition

Also Published As

Publication number Publication date
GB9023000D0 (en) 1990-12-05
ATE131864T1 (de) 1996-01-15
CA2054003A1 (en) 1992-04-24
ES2081441T3 (es) 1996-03-16
JPH04314799A (ja) 1992-11-05
DE69115637D1 (de) 1996-02-01
EP0482807A1 (de) 1992-04-29
DE69115637T2 (de) 1996-05-30

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