(19)
(11) EP 2 609 181 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Mention of the grant of the patent:
19.03.2014 Bulletin 2014/12

(21) Application number: 11748705.8

(22) Date of filing: 12.08.2011
(51) International Patent Classification (IPC): 
C11D 3/12(2006.01)
C11D 7/20(2006.01)
C11D 11/00(2006.01)
C11D 3/22(2006.01)
C11D 7/26(2006.01)
C11D 17/00(2006.01)
(86) International application number:
PCT/GB2011/051524
(87) International publication number:
WO 2012/025736 (01.03.2012 Gazette 2012/09)

(54)

DETERGENT PRODUCT

REINIGUNGSMITTEL

PRODUIT DÉTERGENT


(84) Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30) Priority: 19.05.2011 GB 201108370
27.10.2010 GB 201018095
13.10.2010 GB 201017203
26.08.2010 GB 201014211

(43) Date of publication of application:
03.07.2013 Bulletin 2013/27

(73) Proprietor: Reckitt & Colman (Overseas) Limited
Slough Berkshire SL1 3UH (GB)

(72) Inventors:
  • SMITH, Philip
    Hull Yorkshire HU8 7DS (GB)
  • SCOLAN, Alexandre
    30034 Mira, VE (IT)

(74) Representative: Bowers, Craig Malcolm et al
Reckitt Benckiser Corporate Services Limited Legal Department - Patents Group Dansom Lane
Hull HU8 7DS
Hull HU8 7DS (GB)


(56) References cited: : 
WO-A1-97/15653
US-A1- 2003 045 441
DE-A1-102008 026 932
   
       
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description


    [0001] The present invention relates to a multi-zone detergent unit-dose detergent product.

    [0002] Detergent formats are known in the art. They are typically configured to provide a stable format which is able to release active ingredients to the washing environment. Generally detergents are in the form of powders or liquids.

    [0003] More preferred formats include mono-dose, wherein an amount of detergent is somehow organised for a consumer to use without weighing / measuring and loose materials. For example, detergents may be in the form of a compressed powder body.

    [0004] US2003/045411 describes a water soluble single-use package for detergent or personal care composition.

    [0005] In recent years it has become desirable that detergents contain a number of active ingredients in order to provide numerous detergent benefits brought about by individual active components.

    [0006] Formulating and processing detergents unit dose detergent bodies with multiple active ingredients can lead to problems due to the physical and/or chemical incompatibility of such ingredients.

    [0007] For example, it has become commonplace for detergents to contain a halogen release agent or other bleaching agent. Such materials are powerful chemically reactive species, which are difficult to combine with other oxidation sensitive components (such as enzymes, perfumes). Whilst it is straightforward to come up with a format that can accommodate such antagonistic ingredients in a solid form it has been found to be difficult to devise a stable format for any other physical form.

    [0008] It is an object of the present invention to obviate or mitigate one or more of the problems outlined above.

    [0009] According to a first aspect of the invention there is provided a multi-zone detergent unit-dose detergent product, wherein each zone comprises a gel formulation, wherein the gel comprises a polysaccharide, a polyamide and / or a silica based gelling aid.

    [0010] With products in accordance with the invention it has been found that antagonistic ingredients can be accommodated in a non-solid stable format, which, additionally has especially pleasing aesthetic properties.

    [0011] Ideally the gelling aid is capable of forming a gel which is soluble / dispersible in an aqueous medium. Preferably the gelling aid is capable of forming at gel at a pH which is largely neutral (e.g. between pH 4 - 10). Preferred examples of such gelling aids include gellan gums (polysaccharide), fumed silicas (silica), high molecular weight esters and / or modified vegetable triglycerides.

    [0012] Preferably a single gelling aid is employed for a single zone of the product.

    [0013] Polysaccharide gelling aids have been found to be particularly beneficial in stabilising gels (especially gels with a high water content such as >30wt%) which are then packaged in a water soluble / dispersible material. Where a polysaccharide is used as a gelling it is preferably present in an amount of 0.25-4wt% of that zone. An inorganic salt may be used to enhance the gelling ability of the gelling aid. Preferred examples of such salts include magnesium and calcium salts, e.g. the sulphate and / or chloride thereof.

    [0014] Silica gelling aids have been found to be particularly beneficial in stabilising gels containing bleaching agents (i.e. the bleaching agents such as per-salts have been found to be stable in gels gelled by silica gelling aids). Additionally / alternatively silica gelling aids have been found to be advantageous since the formation of gels with suitable aesthesis properties such as transparent / translucent gels.

    [0015] Where a silica is used as a gelling it is preferably present in an amount of 2-15wt% of that zone, more preferably 4-10wt% of that zone.

    [0016] The silica is preferably used as a gelling aid for a zone wherein an aggressive agent (e.g. such as a bleaching agent is present) which could detrimentally interact with a polysaccharide.

    [0017] Where a polyamide is used as a gelling it is preferably present in an amount of 2-12wt% of that zone.

    [0018] A zone may be water free. Alternatively a zone may contain water. Where water is present preferably the water content of a zone is from 0.1 to 90wt%, more preferably from 10wt% to 80wt%, more preferably from 20wt% to 70wt%, more preferably from 25 to 50wt%, and most preferably from 30 to 40wt%.

    [0019] Preferably the product comprises two or more, such as three or four separate zones. It will be appreciated the two zones may be spatially arranged in any suitable fashion. Preferably the zones are arranged in a concentric fashion, e.g. wherein a first zone is enveloped by a second zone. Generally both zones are based on a spheroid shape. Preferably the outmost zone is translucent so that the inner zone may be seen. The inner zone may have a different colouring from the / an outer zone. Where there are two zones, preferably the inner zone is smaller in size than the outer zone.

    [0020] Where two (or more) zones are present the separate zones may be used to house antagonistic components (e.g. bleach in a first zone and enzyme in a second zone). Additionally and / or alternatively the zone may be used (since in a preferred arrangement the zones are arranged concentrically) so that the timing of the release of actives from zones may be delayed relative to a second zone.

    [0021] A border may be provided between two zones or on the outermost surface of the product adjacent. The border is preferably free of active detersive components. The border preferably has a low water content (e.g. <50wt% water). The border is preferably structurally compatible with the neighbouring zone or zones. The border preferably comprises one or more of PVOH, silica or Crothix (a high molecular weight ester and modified vegetable triglyceride).

    [0022] Examples of bleaches that may be used are oxygen / peroxygen bleaches.

    [0023] Peroxygen bleaching actives are: perborates, peroxides, peroxyhydrates, persulfates. A preferred compound is sodium percarbonate and especially the coated grades that have better stability. The percarbonate can be coated with silicates, borates, waxes, sodium sulfate, sodium carbonate and surfactants solid at room temperature. Hydrogen peroxide may be used.

    [0024] Optionally, the product may comprise a bleach precursor. Suitable bleach precursors are peracid precursors, i.e. compounds that upon reaction with hydrogen peroxide product peroxyacids. Examples of peracid precursors suitable for use can be found among the classes of anhydrides, amides, imides and esters such as acetyl triethyl citrate (ATC), tetra acetyl ethylene diamine (TAED), succinic or maleic anhydrides.

    [0025] Suitable surfactants that may be employed include anionic or nonionic surfactants or mixture thereof. The nonionic surfactant is preferably a surfactant having a formula RO(CH2CH2O)nH wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C12H25 to C16H33 and n represents the number of repeating units and is a number of from about 1 to about 12. Examples of other non-ionic surfactants include higher aliphatic primary alcohol containing about twelve to about 16 carbon atoms which are condensed with about three to thirteen moles of ethylene oxide per mole of alcohol (i.e. equivalents).

    [0026] Other examples of nonionic surfactants include primary alcohol ethoxylates (available under the Neodol tradename from Shell Co.), such as C11 alkanol condensed with 9 equivalents of ethylene oxide (Neodol 1-9), C12-13 alkanol condensed with 6.5 equivalents ethylene oxide (Neodol 23-6.5), C12-13 alkanol with 9 equivalents of ethylene oxide (Neodol 23-9), C12-15 alkanol condensed with 7 or 3 equivalents ethylene oxide (Neodol 25-7 or Neodol 25-3), C14-15 alkanol condensed with 13 equivalents ethylene oxide (Neodol 45-13), C9-11 linear ethoxylated alcohol, averaging 2.5 moles of ethylene oxide per mole of alcohol (Neodol 91-2.5), and the like.

    [0027] Other examples of nonionic surfactants suitable for use include ethylene oxide condensate products of secondary aliphatic alcohols containing 11 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 equivalents of ethylene oxide. Examples of commercially available non-ionic detergents of the foregoing type are C11-15 secondary alkanol condensed with either 9 equivalents of ethylene oxide (Tergitol 15-S-9) or 12 equivalents of ethylene oxide (Tergitol 15-S-12) marketed by Union Carbide, a subsidiary of Dow Chemical.

    [0028] Octylphenoxy polyethoxyethanol type nonionic surfactants, for example, Triton X-100, as well as amine oxides can also be used as a nonionic surfactant.

    [0029] Other examples of linear primary alcohol ethoxylates are available under the Tomadol tradename such as, for example, Tomadol 1-7, a C11 linear primary alcohol ethoxylate with 7 equivalents EO; Tomadol 25-7, a C12-15 linear primary alcohol ethoxylate with 7 equivalents EO; Tomadol 45-7, a C14-15 linear primary alcohol ethoxylate with 7 equivalents EO; and Tomadol 91-6, a C9-11 linear alcohol ethoxylate with 6 equivalents EO.

    [0030] Other nonionic surfactants are amine oxides, alkyl amide oxide surfactants.

    [0031] Preferred anionic surfactants are frequently provided as alkali metal salts, ammonium salts, amine salts, aminoalcohol salts or magnesium salts. Contemplated as useful are one or more sulfate or sulfonate compounds including: alkyl benzene sulfates, alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamide sulfonates, alkylarylsulfonates, olefinsulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfosuccinamate, alkyl sulfoacetates, alkyl phosphates, alkyl ether phosphates, acyl sarconsinates, acyl isethionates, and N-acyl taurates. Generally, the alkyl or acyl radical in these various compounds comprise a carbon chain containing 12 to 20 carbon atoms.

    [0032] Other surfactants which may be used are alkyl naphthalene sulfonates and oleoyl sarcosinates and mixtures thereof.

    [0033] Any suitable soil catcher may be employed. Unlike detergents or surfactants, which simply aid in the removal of soils from surfaces, the soil catcher actively binds to the soil allowing it to be removed from the surface of the laundry. Once bound, the soil is less likely to be able to redeposit onto the surface of the laundry. Preferred soil catchers have a high affinity to both oily and water-soluble soil. Preferably, the soil catcher is a mixture of two or more soil catchers, each soil catcher may have a different affinity for different soils. Preferred soil catchers for oily soils have a non polar structure with high absorption capability. Preferred water based soil catchers are generally charged and have a high surface area in order to attract the soil by electrostatic charge and collect it. Suitable soil catchers include polymers, such as acrylic polymers, polyesters and polyvinylpyrrolidone (PVP). The polymers may be crosslinked, examples of which include crosslinked acrylic polymers and crosslinked PVP. Super absorbing polymers are mainly acrylic polymers and they are useful for the scope of this patent.

    [0034] Other important polymers are ethylidene norbene polymers, ethylidene norbene/ethylene copolymers, ethylidene norbene/propylene/ethylidene ter-polymers. Inorganic materials may also be employed. Examples include zeolites, talc, bentonites and active carbon. The latter may be used to absorb and/or degrade coloured parts of stain and/or absorb odours. Alginates, carrageneans and chitosan may also be used. Preferred water insoluble agents are selected from at least one of acrylic polymer, polyester, polyvinylpyrrolidone (PVP), silica, silicate, zeolite, talc, bentonites, active carbon, alginates, carrageneans, ethylidene mor-bene/propylene/ethylidene ter-polymers and chitosanl.

    [0035] Preferred examples of water-insoluble soil catcher compounds comprise a solid cross-linked polyvinyl N-oxide, or chitosan product or ethylidene norbene/propylene/ethylidene ter-polymers or blend of the same, as discussed more fully hereafter.

    [0036] Water soluble polymeric soil catcher agents that are suitable to be bound to insoluble carriers, or to be made insoluble via cross-linking are those polymers known in the art to inhibit the transfer of dyes from coloured fabrics onto fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to become attached to other articles in the wash. Especially suitable polymeric soil catcher agents are polyamine N-oxide polymers, polymers and copolymers of N-vinylpyrrolidone and N-vinylimidazole, vinyloxazolidones, vinylpyridine, vinylpyridine N-oxide, other vinylpyridine derivatives or mixtures thereof.

    [0037] The product advantageously additionally comprises cleaning agents selected from the group consisting of, fillers, builders, chelating agents, activators, fragrances, enzymes or a mixture thereof. These active agents are generally water soluble, so dissolve during the wash. Thus the additional active agents are released over a period of time when exposed to water in the laundry washing machine.

    [0038] Suitable fillers include bicarbonates and carbonates of metals, such as alkali metals and alkaline earth metals. Examples include sodium carbonate, sodium bicarbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate, magnesium bicarbonate and sesqui-carbonates of sodium, calcium and/or magnesium. Other examples include metal carboxy glycine and metal glycine carbonate. Chlorides, such as sodium chloride; citrates; and sulfates, such as sodium sulfate, calcium sulfate and magnesium sulfate, may also be employed.

    [0039] The product may comprise at least one builder or a combination of them. Builders may be used as chelating agents for metals, as anti-redeposition agents and/or as alkalis.

    [0040] Examples of builders are described below:
    • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
    • borate builders, as well as builders containing borate-forming materials than can produce borate under detergent storage or wash conditions can also be used.
    • iminosuccinic acid metal salts.
    • polyaspartic acid metal salts.
    • ethylene diamino tetra acetic acid and salt forms.
    • water-soluble phosphonate and phosphate builders are useful. Examples of phosphate builders are the alkali metal tripolyphosphates, sodium potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate sodium polymeta/phosphate in which the degree of polymerisation ranges from 6 to 21, and salts of phytic acid. Specific examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from 6 to 21, and salts of phytic acid. Such polymers include polycarboxylates containing two carboxy groups, water-soluble salts of succinic acid, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.


    [0041] Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivates such as the carboxymethloxysuccinates described in GB-A-1,379,241, lactoxysuccinates described in GB-A-1,389,732, and aminosuccinates described in NL-A-7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in GB-A-1,387,447.

    [0042] Polycarboxylate containing four carboxy groups include oxydisuccinates disclosed in GB-A-1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarobyxlates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in GB-A-1,398,421, GB-A-1,398,422 and US-A-3,936448, and the sulfonated pyrolysed citrates described in GB-A-1,439,000.

    [0043] Alicylic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5,6-hexane - hexacarboxylates and carboxymethyl derivates of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in GB-A-1,425,343.

    [0044] Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

    [0045] Suitable polymer water-soluble compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two carbon atoms, carbonates, bicarbonates, borates, phosphates, and mixtures of any of the foregoing.

    [0046] The carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.

    [0047] Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivates such as the carboxymethloxysuccinates described in GB-A-1,379,241, lactoxysuccinates described in GB-A-1,389,732, and aminosuccinates described in NL-A-7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in GB-A-1,387,447.

    [0048] Polycarboxylate containing four carboxy groups include oxydisuccinates disclosed in GB-A-1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarobyxlates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in GB-A-1,398,421, GB-A-1,398,422 and US-A-3,936448, and the sulfonated pyrolysed citrates described in GB-A-1,439,000.

    [0049] Alicylic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5,6-hexane - hexacarboxylates and carboxymethyl derivates of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in GB-A-1,425,343.

    [0050] Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

    [0051] More preferred polymers are homopolymers, copolymers and multiple polymers of acrylic, fluorinated acrylic, sulfonated styrene, maleic anhydride, methacrylic, isobutylene, styrene and ester monomers.

    [0052] Examples of these polymers are Acusol supplied from Rohm & Haas, Syntran supplied from Interpolymer and the Versa and Alcosperse series supplied from Alco Chemical, a National Starch & Chemical Company.

    [0053] The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.

    [0054] Examples of bicarbonate and carbonate builders are the alkaline earth and the alkali metal carbonates, including sodium and calcium carbonate and sesqui-carbonate and mixtures thereof. Other examples of carbonate type builders are the metal carboxy glycine and metal glycine carbonates.

    [0055] In the context of the present application it will be appreciated that builders are compounds that sequester metal ions associated with the hardness of water, e.g. calcium and magnesium, whereas chelating agents are compounds that sequester transition metal ions capable of catalysing the degradation of oxygen bleach systems. However, certain compounds may have the ability to do perform both functions.

    [0056] Suitable chelating agents to be used herein include chelating agents selected from the group of phosphonate chelating agents, amino carboxylate chelating agents, polyfunctionally-substituted aromatic chelating agents, and further chelating agents like glycine, salicylic acid, aspartic acid, glutamic acid, malonic acid, or mixtures thereof.

    [0057] Suitable phosphonate chelating agents to be used herein may include ethydronic acid as well as amino phosphonate compounds, including amino alkylene poly (alkylene phosphonate), alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates. The phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities. Preferred phosphonate chelating agents to be used herein are diethylene triamine penta methylene phosphonates. Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST TM.

    [0058] Polyfunctionally-substituted aromatic chelating agents may also be useful. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-disulfobenzene.

    [0059] A preferred biodegradable chelating agent for use herein is ethylene diamine N,N'-disuccinic acid, or alkali metal, or alkaline earth, ammonium or substituted ammonium salts thereof or mixtures thereof. Ethylenediamine N,N'-disuccinic acids, especially the (S,S) isomer have been extensively described in US patent 4, 704, 233, November 3, 1987, to Hartman and Perkins. Ethylenediamine N,N'-disuccinic acid is, for instance, commercially available under the tradename ssEDDS TM from Palmer Research Laboratories.

    [0060] Suitable amino carboxylates to be used herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA),N- hydroxyethylethylenediamine triacetates, nitrilotri-acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates, ethanol-diglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine diacetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms. Particularly suitable amino carboxylates to be used herein are diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASF under the trade name Trilon FS TM and methyl glycine di-acetic acid (MGDA).

    [0061] The product may comprise a solvent. The solvent constituent may include one or more alcohol, glycol, acetate, ether acetate, glycerol, polyethylene glycol with molecular weights ranging from 200 to 1000, silicones or glycol ethers. Exemplary useful alcohols include C2-8 primary and secondary alcohols which may be straight chained or branched, preferably pentanol and hexanol.

    [0062] Preferred solvents are glycol ethers. Examples include those glycol ethers having the general structure Ra-O-[CH2-CH(R)-(CH2)-0]n-H, wherein Ra is C1-20 alkyl or alkenyl, or a cyclic alkane group of at least 6 carbon atoms, which may be fully or partially unsaturated or aromatic; n is an integer from 1 to 10, preferably from 1 to 5; and each R is selected from H or CH3. Specific and preferred solvents are selected from propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol n-butyl ether, diethylene glycol methyl ether, propylene glycol, ethylene glycol, isopropanol, ethanol, methanol, diethylene glycol monoethyl ether acetate, and, especially, propylene glycol phenyl ether, ethylene glycol hexyl ether and diethylene glycol hexyl ether.

    [0063] The product may, for example, comprise one enzyme or a combination of them. Enzymes in granular form are preferred. Examples of suitable enzymes are proteases, modified proteases stable in oxidisable conditions, amylases, lipases and cellulases.

    [0064] According to a second aspect of the invention there is provided a method of producing the product of the first aspect of the invention.

    [0065] One preferred method of production is that of extrusion / co-extrusion. In the co-extrusion method the materials for making up the zone are fed into and then simultaneously extruded through a concentric arrangement of tubes. At the exit point of the tubes an amount of co extruded material is collected (an amount of co extruded material may be separated from the extrudate, e.g. by cutting). Surprisingly it has been found that when co-extrusion is used as a production technique the outer zone(s) of the product coalesce over the inner zone(s) of the product forming a product having a concentric arrangement.

    [0066] Generally the extrusion process is carried out with a temperature gradient such that the temperature of the extrudate reduces with its passage through the extruder. Preferably the extruder is operated with an input temperature of about 80°C and an exit temperature of about 60°C.

    [0067] Another preferred method of production is that of sequential moulding. In this method preferably the following process steps are involved:-
    1. a) A first zone is formed in a first mould,
    2. b) The first zone is allowed / encouraged to at least partially solid,
    3. c) The first zone is removed from the first mould,
    4. d) The first zone s disposed into a second mould,
    5. e) The formulation of a second zone is added to the second mould,
    6. f) The formulation of the second zone is allowed / encouraged to at least partially solid, and
    7. g) The finished product is removed form the second mould.


    [0068] Clearly more than two zones may be moulded in this process if more moulding steps are used. Intermediate / final non-moulding steps, such as spraying and / or dipping are not precluded.

    [0069] Preferably the first zone is suspended in the second mould so that it does not contact a surface of the second mould. Generally the meads used for this suspension comprise a pin / rod. The pin / rod may be inserted into the first zone at or after the removal of the first zone from the first mould. The pin / rod may remain inserted in the first zone throughout any subject moulding steps. The pin / rod may be used as an aid to finished product is removed form the final mould.

    [0070] Each of these processes is preferably automated.

    [0071] Following production the product may be wrapped in a packaging material. The packaging material may be in the form of a film. The film may comprise a water soluble component, e.g. be based on polyvinyl alcohol. In this way the product may be used without the need for unwrapping.

    [0072] In one embodiment each zone of the product has a film (e.g. an outer film) of a packaging material.

    [0073] The finalized product is intended for used in a washing operation, e.g. machine dishwash, automatic laundry. Ideally the product dissolves within 10 minutes when used in an automatic washing process.

    Example 1 (Not in accordance with the invention)



    [0074] A multi-zone fabric detergent product having the following formulation was prepared in a sequential moulding process.
    Zone Volume of Zone (cm3) Raw Material Wt% of zone Wt% of product
    1 7 H2O2 86.9 17.3
    Phosphonate 3.0 0.6
    Silica 8.0 1.6
    Red Dye 0.1 0.02
    2 1 Triglyceride 8.0 0.2
    Non-ionic surfactant 92.0 2.6
    3 27 Water 87.0 67.1
    Non-ionic surfactant 11.3 8.8
    salt 0.1 0.08
    Enzyme 1.05 0.8
    Polysaccharide 1.5 1.2


    [0075] The material of the first zone was added together and mixed slowly before being allowed to gel in a spherical mould. The moulded form was then frozen.

    [0076] The non-ionic surfactant of the second zone was heated to 50-100°C. The triglyceride was added and the mixture was cooled to 50-60°C.

    [0077] The frozen first zone was dipped into the material of the second zone to be coated. (A pin was inserted into the first zone to retain it during dipping).

    [0078] The material of the third zone (with the exception of the enzyme) was added together and mixed slowly at 90°C. The mixture was cooled to 50-60°C and added to a mould in which the enzyme was present and in which the coated first zone was suspended by its pin. The material of the third zone was allowed to gel.

    Example 2 (Not in accordance with the invention)



    [0079] A multi-zone automatic dishwashing detergent product having the following formulation was prepared in a sequential moulding process.
    Zone Volume of Zone (cm3) Raw Material Wt% of zone
    1 5.5 PAP 22.3
    Silica 5.8
    Water 72.0
    2 1 Triglyceride 8.0
    Mineral Oil 92.0
    3 18.5 Acticide 0.4
    Non-ionic surfactant 90.8
    Calcium salt 0.1
    Enzyme 3.3
    Sulphonated polymer 1.5
    Zinc salt 3.6
    Triglyceride 0.5


    [0080] Alternative formulations for Zone 1 are as follows:-
    Zone Volume of Zone (cm3) Raw Material Wt% of zone
    1 5.5 Sodium Percarbonate 60.00
    Fumed Silica 4.00
    Nonionic surfactant 36.00

    Example 3 (Not in accordance with the invention)



    [0081] A multi-zone automatic dishwashing detergent product having the following formulation was prepared in a sequential moulding process.
      Silica Bleach Zone Silica Zone Polyamide Zone
      8.30 5.70g 5.5g
    Sodium Citrate   2.51  
    Sodium Percarbonate 60.00    
    TAED   35.10  
    Fumed Silica 1.80 5.97  
    Rokanol L7A (nonionic) 37.70 38.87 95.00
    Sanolin Red Dye 0.001 0.001  
    Protease   10.36  
    Amylase   3.68  
    Pectate Lyase   3.51  
    Sylvaclear WF 1500     5.00
    HEDP 4Na 0.50    


    [0082] Alternative formulations for the "Silica Zone" are as follows:-
    2 27 Water 29.03
    Sorbitol 57.61
    Liquid Maltitol 80/55 3.81
    Low Acyl Gellan Gum 0.70
    Magnesium Sulphate 0.05
    Sodium Citrate 6.42
    Enzyme 2.38
    Zone Volume of Zone (cm3) Raw Material Wt% of zone
    2 5.5 Nonionic Surfactant 90.0
    Sylvaclear WF 1500 10.0
    2 5.5 Nonionic Surfactant 90.0
    Fumed Silica 10.0



    Claims

    1. A multi-zone detergent unit-dose detergent product, wherein each zone comprises a gel formulation, wherein the gel comprises a polysaccharide and / or silica based gelling aid.
     
    2. A product according to claim 1, wherein the product comprises two zones.
     
    3. A product according to claim 2, wherein the zones are arranged in a concentric fashion.
     
    4. A product according to any preceding claim, wherein a border layer may be disposed between two zones of the product.
     
    5. A production method for the product of any preceding claim wherein the gel formulations are extruded / coextruded.
     
    6. A production method for the product of claims 1 to 4 wherein the gel formulations are sequentially moulded.
     
    7. A production method according to claim 5, wherein the finished product is wrapped in a film, e.g. a water soluble film.
     
    8. Use of the product according to any one of claims 1 to 4 in a washing operation.
     


    Ansprüche

    1. Einzeldosis-Reinigungsmittelprodukt mit Mehrzonen-Reinigungsmittel, wobei jede Zone eine Gelformulierung umfasst, wobei das Gel ein auf Polysaccharid und/oder Siliciumdioxid basierendes Gelierungshilfsmittel umfasst.
     
    2. Produkt nach Anspruch 1, wobei das Produkt zwei Zonen umfasst.
     
    3. Produkt nach Anspruch 2, wobei die Zonen konzentrisch angeordnet sind.
     
    4. Produkt nach einem der vorhergehenden Ansprüche, wobei zwischen zwei Zonen des Produkts eine Grenzschicht angeordnet sein kann.
     
    5. Herstellungsverfahren für das Produkt nach einem der vorhergehenden Ansprüche, bei dem man die Gelformulierungen extrudiert/coextrudiert.
     
    6. Herstellungsverfahren für das Produkt nach den Ansprüchen 1 bis 4, bei dem man die Gelformulierungen nacheinander abformt.
     
    7. Herstellungsverfahren nach Anspruch 5, bei dem man das fertige Produkt in einer Folie, z.B. einer wasserlöslichen Folie, verpackt.
     
    8. Verwendung des Produkts nach einem der Ansprüche 1 bis 4 bei einem Waschvorgang.
     


    Revendications

    1. Produit détergent à dose unitaire de détergent multi-zone, dans lequel chaque zone comprend une formulation de gel, dans lequel le gel comprend un polysaccharide et/ou un promoteur de gélification à base de silice.
     
    2. Produit selon la revendication 1, dans lequel le produit comprend deux zones.
     
    3. Produit selon la revendication 2, dans lequel les zones sont agencées de façon concentrique.
     
    4. Produit selon l'une quelconque des revendications précédentes, dans lequel une couche de séparation peut être disposée entre deux zones du produit.
     
    5. Procédé de production du produit selon l'une quelconque des revendications précédentes, dans lequel les formulations de gel sont extrudées / co-extrudées.
     
    6. Procédé de production du produit selon l'une quelconque des revendications 1 à 4, dans lequel les formulations de gel sont moulées de façon séquentielle.
     
    7. Procédé de production selon la revendication 5, dans lequel le produit fini est enroulé dans un film, par exemple un film soluble dans l'eau.
     
    8. Utilisation du produit selon l'une quelconque des revendications 1 à 4 lors d'une opération de lavage.
     






    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description