EP1833956B1 - Abgabesystem - Google Patents

Abgabesystem Download PDF

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Publication number
EP1833956B1
EP1833956B1 EP05796209A EP05796209A EP1833956B1 EP 1833956 B1 EP1833956 B1 EP 1833956B1 EP 05796209 A EP05796209 A EP 05796209A EP 05796209 A EP05796209 A EP 05796209A EP 1833956 B1 EP1833956 B1 EP 1833956B1
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EP
European Patent Office
Prior art keywords
dispensing
fluid
capsules
laundry
diameter
Prior art date
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Application number
EP05796209A
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English (en)
French (fr)
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EP1833956A2 (de
Inventor
Andrew Timothy Unilever R & D Port Sunlight HIGHT
Vidyadhar Sudhir Unilever R & D Vlaardingen RANADE
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
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Unilever PLC
Unilever NV
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Publication of EP1833956A2 publication Critical patent/EP1833956A2/de
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Publication of EP1833956B1 publication Critical patent/EP1833956B1/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
    • C11D3/3935—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
    • C11D3/16—Organic compounds
    • C11D3/168—Organometallic compounds or orgometallic complexes
    • 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
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • the present invention relates to a dispensing system comprising a dispensing device and a fluid laundry composition comprising an encapsulated bleach catalyst contained in a dispensing device.
  • Laundry compositions comprising bleaches are known (see GB e.g. 2267911 and US 5747441 ). Bleaches are used to remove stains from fabrics.
  • the invention provides a dispensing system comprising a dispensing device and a laundry fluid comprising capsules containing a bleach catalyst, contained in a dispensing device, the dispensing device comprising:
  • the invention provides a method of dispensing a laundry fluid comprising capsules containing a bleach catalyst, by employing the device of the first aspect of the invention to dispense the fluid and released bleach catalyst e.g. into a washing machine draw, dosing device.
  • the invention provides a method of pretreating a fabric with a laundry bleach catalyst, by employing the device of the first aspect of the invention to dispense the fluid and released bleach catalyst directly on to the fabric.
  • the invention provides a method of directly bleaching a fabric, by employing the device of the first aspect of the invention to dispense the fluid and released bleach catalyst directly on to the fabric.
  • This method may be part of a pre-treating method, that is pre-treating a fabric prior to a subsequent washing operation e.g. a wash cycle carried out in an automatic washing machine.
  • the invention provides a method of washing a fabric or treating a fabric, the method comprising dispensing a laundry fluid comprising capsules containing a bleach catalyst from the device of the first aspect of the invention and applying to the fabric.
  • the bleach catalyst is protected from the naturally occurring process of autoxidation of organic components within the fluid produces alkylhydroperoxides which, over time (e.g. during transport, storage) interact with the bleach catalyst.
  • bleach performance can be maintained until such time as the consumer is ready to use the product.
  • the invention provides a relatively inexpensive dispensing system, in terms of financial and environmental cost in what can be an uncomplicated device which can be used so long as the dispensing outlet is dimensioned relative to the capsule size.
  • capsules can be made very strong to withstand high forces imposed by storage and transport.
  • the extra force to rupture is conveniently provided precisely at the time of dispensing, by means of compression in an outlet conduit so that the active material is released only when required. This allows fine tuning of the capsule properties to enhance strength without risking poor delivery and performance due to lack of capsule rupture.
  • 'fluid' is intended to include a liquid, gel or paste, but excludes dry powder formats.
  • the fluid may be formulated to provide a suspension of the capsules in it, so as to enable uniform dosage, if desired.
  • principal dimensions is intended to include those parameters generally necessary for measurement of a three dimensional space.
  • the principal dimensions are width, depth, height; whereas with standard the case of a spherical reservoir, the diameter will be principal dimension.
  • capsules to be carried by a liquid will be generally spherical.
  • the greater dimension would be the relevant one.
  • the greater diameter would be the relevant one.
  • the dispensing outlet may be a single or multiple nozzle arrangement whereby the diameter/s of the nozzle/s tapers (i.e. gradually) reduces in the direction of the exit, at which point, rupture diameter is reached. This provides the advantage that rupture occurs only at the point of exit.
  • the dispensing outlet may comprise one or more sections of constant diameter upstream (or even downstream) of part having the rupture diameter. This has the advantage that the capsules are ruptured progressively as they move along the section/s of constant diameter.
  • the dispensing outlet may comprise multiple successive, conduits each having one or more sections of rupture diameter for progressive rupture of the capsules e.g. if they are in high concentration. Such sections may each be separated by a section of higher diameter which may be constant or tapered along the length.
  • conduits within the dispensing outlet each having one or more sections with a rupture diameter as described above. Multiple conduits are advantageous for example if a relatively high dosage (which may be 30-100 ml for main wash laundry purposes) is needed to be dispensed for a single use.
  • the largest diameter of the conduit through which the fluid flows may correspond to rupture diameter.
  • the encapsulates are then extended just before the nozzle so that they are ruptured and open to discharge the bleach encapsulate just before they exit from the outlet, along with the liquid/gel/paste into the surroundings.
  • the fluid may be forced out of the reservoir by any suitable means, for example, it may forced out by compressing the reservoir.
  • the reservoir preferably is, in whole or in part, compressible.
  • the reservoir may be in whole or part flexible to allow squeezing.
  • the reservoir may also be, in whole or in part, resilient such that once the compressive force is removed, the reservoir expands again, so as to relieve pressure on its contents thereby enhancing integrity of stored capsules.
  • the material to be encapsulated is present in less than 10% of the total formulation amount. This allows for effective rupture.
  • the bleach catalyst may comprise selected transition metal catalysts in the absence of an added peroxyl source, i.e., where the bleaching composition is substantially devoid of a peroxygen bleach or a peroxy-based or peroxyl-generating bleach system.
  • the term "substantially devoid of a peroxygen bleach or a peroxy-based or peroxyl-generating bleach system” should be construed within spirit of the invention. It is preferred that the composition has as low a content of peroxyl species present as possible. It is preferred that the bleaching formulation contains less that 1 % wt/wt total concentration of peracid or hydrogen peroxide or source thereof, preferably the bleaching formulation contains less that 0.3 % wt/wt total concentration of peracid or hydrogen peroxide or source thereof, most preferably the bleaching composition is devoid of peracid or hydrogen peroxide or source thereof.
  • alkyl hydroperoxides are kept to a minimum in the bleaching composition.
  • the bleach catalyst per se may be selected from a wide range of transition metal complexes of organic molecules (ligands).
  • the level of the organic substance is such that the in-use level is from 0.05 ⁇ M to 50 mM, with preferred in-use levels for domestic laundry operations falling in the range 1 to 100 ⁇ M. Higher levels may be desired and applied in industrial textile bleaching processes.
  • a mixture of different catalysts may be employed in the bleaching composition.
  • Suitable organic molecules (ligands) for forming complexes and complexes thereof are found, for example in:
  • the ligand forms a complex with one or more transition metals, in the latter case for example as a dinuclear complex.
  • Suitable transition metals include for example: manganese in oxidation states II-V, iron II-V, copper I-III, cobalt I-III, titanium II-IV, tungsten IV-VI, vanadium II-V and molybdenum II-VI.
  • An example of a preferred catalyst is a monomer ligand or transition metal catalyst thereof of a ligand having the formula (I): wherein each R is independently selected from: hydrogen, F, Cl, Br, hydroxyl, C1-C4-alkylO-, -NH-CO-H, -NH-CO-C1-C4-alkyl, -NH2, -NH-C1-C4-alkyl, and C1-C4-alkyl; R1 and R2 are independently selected from: C1-C4-alkyl, C6-C10-aryl, and, a group containing a heteroatom capable of co-ordinating to a transition metal, wherein at least one of R1 and R2 is the group containing the heteroatom; R3 and R4 are independently selected from hydrogen, C1-C8 alkyl, C1-C8-alkyl-O-C1-C8-alkyl, C1-C8-alkyl-O-C6-C10-aryl
  • R1 and R2 may also be independently selected from: C1 to C22-optionally substituted alkyl, and an optionally substituted tertiary amine of the form -C2-C4-alkyl-NR7R8, in which R7 and R8 are independently selected from the group consisting of straight chain, branched or cyclo C1-C12 alkyl, benzyl, the -C2-C4-alkyl- of the -C2-C4-alkyl-NR7R8 may be substituted by 1 to 4 C1-C2-alkyl, or may form part of a C3 to C6 alkyl ring, and in which R7 and R8 may together form a saturated ring containing one or more other heteroatoms.
  • Another preferred class of ligands are macropolycyclic rigid ligands of the formula: wherein m and n are 0 or integers from 1 to 2, p is an integer from 1 to 6, preferably m and n are both 0 or both 1 (preferably both 1), or m is 0 and n is at least 1; and p is 1; and A is a nonhydrogen moiety preferably having no aromatic content; more particularly each A can vary independently and is preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, C5-C20 alkyl, and one, but not both, of the A moieties is benzyl, and combinations thereof.
  • the macropolycyclic ligand is of the formula: wherein "R 1 " is independently selected from H, and linear or branched, substituted or unsubstituted C1-C20 alkyl, alkylaryl, alkenyl or alkynyl; and all nitrogen atoms in the macropolycyclic rings are co-ordinated with the transition metal.
  • the transition metal complex preferably is of the general formula (AI): [M a L k X n ] Y m in which:
  • encapsulates typically ranging from 100 micrometer to 10 mm in size.
  • a system a fluid dispensing system for dispensing a laundry gel comprising capsules containing a bleach catalyst.
  • the dispensing system 1 comprises a container 3 having a reservoir 5 for storing a laundry gel 50, the reservoir 3 having all principal dimensions (height,width,depth)7,9,11 greater than the average diameter of the capsules 13 so as to retain integrity of capsules 13 when stored within the reservoir 5.
  • the system comprises a dispensing outlet referred to generally at 15. This outlet is in fluid communication with the reservoir 5 and comprises a single conduit 17.
  • the conduit has what is diameter 19 which is less than the average diameter of the capsules 13. This diameter is referred to as the rupture diameter.
  • the dispensing outlet 15 is structured so that the largest diameter of the conduit 17 available for gel flow of the nozzle corresponds to rupture diameter 19 i.e. it is smaller than the diameter of the capsules to be ruptured.
  • the rupture diameter (which is an internal diameter) is 1.0 mm and this is smaller than average outer diameter of the capsules.
  • the reservoir 5 is a flexible plastic and to enable the gel 50 to be forced out of the reservoir by compression by the user by hand.
  • the reservoir 5 may also be resilient allowing it to revert to its original, uncompressed state following squeezing so as to relieve pressure on its contents thereby enhancing integrity of stored capsules 13.
  • dispensing is achieved by forcing the gel 50 to exit the reservoir 5 and the dispensing outlet 15, where the rupture diameter 19 of the conduit 17 shears and ruptures the capsules being forced through the conduit 17, thereby releasing the perfume material contained within the capsule, upon gel dispensing. Hence the perfume is protected by the capsule until dispensing when it is released for optimal sensory effect.
  • the laundry gel of this embodiment is used to enable to suspend capsules or 'beads' for uniform dosage.
  • the gel/capsule mix has the following formulation:
  • the bleach catalyst-filled capsules are prepared as follows:
  • a two-polymer material complex is used, namely arabic gum and gelatin.
  • the method involves placing into a two litre beaker, the following:
  • the capsules can be recovered from this vehicle by decantation or filtering, accompanied by drying in an air blast or by sifting with an adsorbent material such as starch or diatomaceous earth, and afterwards cleaned by repeated washings in a highly evaporable liquid medium.
  • 1g of the coacervates mixture, containing the capsules of bleach catalyst (without the capsules having been separated from the vehicle) is then mixed in 80g laundry gel of composition described below.
  • transition metal catalysts or ligands thereof that may be incorporated inside the coacevate.
  • the following are specific preferred but non-limiting transition metal catalysts that may be used. Beside each specific catalyst in parenthesis is a reference to a patent that describes the generic class thereof, in addition to others found therein, that are also applicable for use with the present invention: dimethyl 3,7-dimethyl-9-oxo-2,4-bis(pyridyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate ( WO0248301 ); 5,12-dimethyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane ( WO0029537 ); N,N-bis(pyridin- 2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-aminoethane ( WO0012667 ); and, (dimethyl 2,4-di-(2-pyridyl)-3-methyl
  • peroxyl species Whilst the above will bleach in what is known as an air mode, encapsulation affords the opportunity of incorporating a peroxyl species in liquid medium. Peroxyl species would de-stablise the bleach catalyst however, because the catalyst is segregated from the liquid by encapsulation the catalyst is protected. Examples of peroxyl are sodium percarbonate and peracids, e.g., N,N-phthaloylaminoperoxycaproic acid PAP.
  • the laundry capsules can be made sufficiently strong to withstand forces imposed by storage and transport.
  • the extra force to rupture is conveniently provided precisely at the time of dispensing, by means of compression at (or in) an outlet conduit so that the active material is released only when required. This allows fine tuning of the capsule properties to enhance strength without risking poor delivery of bleach and poor bleach performance due to lack of capsule rupture.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (11)

  1. Spendersystem, das eine Spendervorrichtung und ein Wäschefluid umfasst, wobei das Wäschefluid Kapseln enthält, die einen Bleichungskatalysator enthalten und in der Spendervorrichtung enthalten sind; wobei die Spendervorrichtung umfasst:
    a. einen Vorratsbehälter, der das Wäschefluid enthält, wobei jede der Hauptabmessungen des Vorratsbehälters größer ist als der durchschnittliche Durchmesser der Kapseln,
    b. einen Spenderauslass, der mit dem Vorratsbehälter in einer Fluidkommunikation steht und wenigstens in einem Teil einen Aufbrechdurchmesser besitzt, der kleiner ist als der durchschnittliche Durchmesser der Kapseln;
    wobei das Wäschefluid von dem Vorratsbehälter dadurch ausgegeben wird, dass das Wäschefluid dazu gezwungen wird, durch den Spenderauslass auszutreten, und der Durchgang von Kapseln durch den Spenderauslass die Kapseln aufbricht, um so den Bleichungskatalysator freizugeben, wenn das Wäschefluid ausgegeben wird.
  2. Spendersystem nach Anspruch 1, wobei das Fluid eine Flüssigkeit, ein Gel oder eine Paste ist.
  3. Spendersystem nach einem vorhergehenden Anspruch, wobei der Spenderauslass eine oder mehrere Leitungen umfasst.
  4. Spendersystem nach einem vorhergehenden Anspruch, wobei sich der Durchmesser des Auslasses in Richtung des Fluidaustritts konisch verjüngt und in dem Aufbrechdurchmesser endet.
  5. Spendersystem nach einem vorhergehenden Anspruch, wobei der Spenderauslass einen oder mehrere Querschnitte mit konstantem Durchmesser aufweist.
  6. Spendersystem nach einem vorhergehenden Anspruch, wobei der Spenderauslass mehrere aufeinander folgende Leitungen mit dem Aufbrechdurchmesser umfasst.
  7. Spendersystem nach einem vorhergehenden Anspruch, wobei die Kapseln vom Typ "Kern in der Schale" sind.
  8. Spendersystem nach einem vorhergehenden Anspruch, wobei die Kapseln einen Durchmesser im Bereich von 100 Mikrometer bis 10 mm haben.
  9. Verfahren zum Spenden eines Wäschefluids, das Kapseln aufweist, die einen Bleichungskatalysator enthalten, indem die Spendervorrichtung nach Anspruch 1 verwendet wird, um das Fluid und den freigesetzten Bleichungskatalysator z. B. in eine Waschmaschinenschubladen-Dosiervorrichtung auszugeben.
  10. Verfahren zum Vorbehandeln eines Stoffs mit einem Wäsche-Bleichungskatalysator durch Verwenden der Spendervorrichtung nach Anspruch 1, um das Fluid und den freigesetzten Bleichungskatalysator direkt auf den Stoff auszugeben.
  11. Verfahren zum direkten Bleichen eines Stoffs durch Verwenden der Spendervorrichtung nach Anspruch 1, um das Fluid und den freigesetzten Bleichungskatalysator direkt auf den Stoff auszugeben.
EP05796209A 2004-11-19 2005-10-12 Abgabesystem Active EP1833956B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0425467A GB0425467D0 (en) 2004-11-19 2004-11-19 Dispensing system
PCT/EP2005/011017 WO2006053614A2 (en) 2004-11-19 2005-10-12 Dispensing system

Publications (2)

Publication Number Publication Date
EP1833956A2 EP1833956A2 (de) 2007-09-19
EP1833956B1 true EP1833956B1 (de) 2012-07-11

Family

ID=33548523

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05796209A Active EP1833956B1 (de) 2004-11-19 2005-10-12 Abgabesystem

Country Status (4)

Country Link
EP (1) EP1833956B1 (de)
ES (1) ES2391279T3 (de)
GB (1) GB0425467D0 (de)
WO (1) WO2006053614A2 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2576987T3 (es) 2010-04-06 2016-07-12 The Procter & Gamble Company Encapsulados

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0490436A1 (de) * 1990-12-10 1992-06-17 Unilever N.V. Verwendung nicht wässriger Waschmittelzusammensetzungen
GB2267911A (en) * 1992-04-30 1993-12-22 Unilever Plc Solid granulate detergent additives
US5460743A (en) * 1994-05-09 1995-10-24 Lever Brothers Company, Division Of Conopco, Inc. Liquid cleaning composition containing polyvinyl ether encapsulated particles
US5480577A (en) * 1994-06-07 1996-01-02 Lever Brothers Company, Division Of Conopco, Inc. Encapsulates containing surfactant for improved release and dissolution rates
AU703533B2 (en) * 1995-10-16 1999-03-25 Unilever Plc Encapsulated bleach particles

Also Published As

Publication number Publication date
WO2006053614A2 (en) 2006-05-26
WO2006053614A3 (en) 2007-07-12
ES2391279T3 (es) 2012-11-23
GB0425467D0 (en) 2004-12-22
EP1833956A2 (de) 2007-09-19

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