AU2009275368A1 - Container - Google Patents

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AU2009275368A1
AU2009275368A1 AU2009275368A AU2009275368A AU2009275368A1 AU 2009275368 A1 AU2009275368 A1 AU 2009275368A1 AU 2009275368 A AU2009275368 A AU 2009275368A AU 2009275368 A AU2009275368 A AU 2009275368A AU 2009275368 A1 AU2009275368 A1 AU 2009275368A1
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AU
Australia
Prior art keywords
film
container according
bleach
manganese
container
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Granted
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AU2009275368A
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AU2009275368B2 (en
Inventor
Dora Zamuner
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Reckitt Benckiser Vanish BV
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Reckitt Benckiser NV
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Assigned to RECKITT BENCKISER VANISH B.V. reassignment RECKITT BENCKISER VANISH B.V. Request for Assignment Assignors: RECKITT BENCKISER N.V.
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/046Insoluble free body dispenser
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators or bleach catalysts
    • C11D3/3932Inorganic compounds or complexes

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

Description

WO 2010/010334 PCT/GB2009/001793 1 CONTAINER The present invention relates to a container. Inorganic peroxygen compounds, especially hydrogen peroxide and solid peroxygen compounds which dissolve in 5 water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for purposes of disinfection and bleaching. The oxidizing action of these substances in dilute solutions is heavily 10 dependent on the temperature; for instance, with H 2 0 2 or perborate in alkaline bleaching liquors, sufficiently rapid bleaching of soiled textiles is obtained only at temperatures above about 80 0 C. At lower temperatures the oxidizing action of the inorganic peroxygen 15 compounds can be enhanced by adding what are called bleach activators, for which numerous proposals have been disclosed in the literature, principally from the classes of the N-acyl or O-acyl compounds, examples being polyacylated alkylenediamines, especially 20 tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, and also carboxylic anhydrides, especially phthalic 25 anhydride, carboxylic esters, especially sodium nonanoyloxybenzenesulfonate, sodium isononanoyloxybenzenesulfonate and acylated sugar derivatives, such as pentaacetylglucose. By addition of these substances the bleaching action of aqueous 30 peroxide liquors can be increased to such an extent that even at temperatures around 60*C essentially the same WO 2010/010334 PCT/GB2009/001793 2 activities occur as with the peroxide liquor alone at 95 0 C. Given the concern for energy-saving laundering and bleaching methods, in recent years application 5 temperatures well below 60'C have gained in importance, in particular below 45 0 C down to the cold water temperature, below 20'C. Previously the use of transition metal salts and transition metal complexes has been described, for 10 example in European patent applications EP 392 592, EP 443 651, EP 458 397, EP 544 490, EP 549 271 and WO 01/48138, referred to as bleaching catalysts. It has now been observed that textiles, particularly coloured textiles, fade after a number of washes in the 15 presence of a bleach catalyst. It is theorised that some catalysts previously used not only catalyze the activity of the peroxygen compound but also remain at least partly on their surfaces being bleached, and even when the cleaning operation has ended. These transition 20 metal salts can then be oxidized and so cause colour damage, and, in extreme cases, the risks of oxidative damage to the textiles since they directly contact the textile. As an example a deposit of Mn (II), is readily oxidized to Mn (IV) dioxide, which is a very strong 25 oxidizing agent, particularly toward easily oxidizable substances, such as organic dye compounds. All of the bleaching catalysts known have the disadvantage that they are brought into intimate contact with the surfaces of the articles being treated and as 30 such typically a portion of the catalyst adheres to WO 2010/010334 PCT/GB2009/001793 3 those surfaces or even penetrate those surfaces. This gives rise to a risk of unwanted colour changes and in rare cases; there may even be holes / tears, as a result of fibre damage. 5 According to a first aspect of the invention there is provided a container comprising a detergent formulation, the container including a primary enclosing wall which is permeable to water and a secondary enclosing wall which comprises a bleaching catalyst admixture and a 10 support material. It has been found that the container of the present invention has a number of advantageous properties. The principle advantageous property is that the bleach catalyst, particularly the transition metal thereof when 15 present (when used in a washing / bleaching operation) is not substantive upon an item being washed or bleached. Thus detrimental damage to the item is drastically reduced. Another advantage of the present invention (when used in 20 a washing / bleaching operation) is the catalysis of the oxidizing action and bleaching action of inorganic peroxygen compound at low temperatures. Effective catalysis is observed below 80'C and in particular from about 120C to 400C. 25 Another advantage of the present invention (when used in a washing / bleaching operation) is to allow for reduction of peroxygen amount and / or bleach activator (e.g. TAED) in a cleaning formulation while maintaining bleaching performance, thus allowing for cost reduction.
WO 2010/010334 PCT/GB2009/001793 4 Preferably the bleach catalyst comprises a transition metal compound based upon one or more of manganese, copper, iron, silver, platinum, cobalt, nickel, titanium, zirconium, tungsten, molybdenum, ruthenium, 5 cerium, lanthanum or vanadium. Most preferably the bleach catalyst comprises a transition metal compound based upon manganese. The manganese bleach catalyst may be selected from wide range of manganese compounds. Suitable inorganic 10 compounds (often salts) of manganese (e.g. Mn (II)) include hydrated / anhydrous halide (e.g. chloride / bromide), sulphate, sulphide, carbonate, nitrate, oxide. Further examples of suitable compounds (often salts) of manganese (e.g. Mn (II)) include hydrated / anhydrous 15 acetate, lactate, acetyl acetonate, cyclohexanebutyrate, phthalocyanine, bis (ethylcyclopentadienyl), bis (pentamethylcyclopentadienyl). Most preferably the bleach catalyst comprises manganese (II) acetate tetrahydrate and/or manganese (II) sulphate 20 monohydrate. Alternatively the bleach catalyst may comprise: (1, 8 - diethyl-1, 4, 8, ll-TetraAzaCycloTetraDecane) manganese (II) chloride [Mn-TACTD].
WO 2010/010334 PCT/GB2009/001793 5 Alternatively the bleach catalyst may comprise: Manganese (Ill) Catalyst with an organic tripodal ligand. .Mn N 5 I Alternatively the bleach catalyst may comprise: 0/ Generally the bleach catalyst comprises from 0.001% to 10 10.00%, preferably from 0.01% to 5.00% more preferably from 0.15% to 2.5% of the second enclosing wall, with the remainder of the composition comprising the support matrix. A mixture of two or more bleach catalysts listed above 15 can be used. The secondary wall is preferably in the form of a film. The preferred film thickness is in the range of from 0.10mm to 1.0mm, more preferably from 0.20 to 0.40mm.
WO 2010/010334 PCT/GB2009/001793 6 The particle size of the catalyst used in the production of the secondary wall is preferably between 50 micron and 125 micron. The support matrix of the secondary wall generally 5 comprises a polymeric material. Suitable polymeric materials may be selected from the group of polyurethanes; polyolefins / hydrocarbons, e.g. polypropylene (PP), poly propylene containing maleic anhydride, poly propylene mixed with poly ethylene, 10 polyethylene (PE), PE mixed with ethylene vinyl acetate (PE/VA), poly ethylene copolymer with ethylene ethyl acrylate, (PE/EEA) polystyrene, polybutadiene; polyamides; polyvinyl chloride; polyesters, e.g. poly methyl methacrylate, poly vinyl acetate, ethylene vinyl 15 acetate; phenolic resins; copolymers, e.g. polymethylmethacrylate with n-butylacrylate and styrene; natural / modified natural polymers, e.g. cellulose, rubber, latex, styrene-butadiene rubber, butyl rubber, chlorinated / hydrochlorinated rubber, nitrile rubber, 20 vulcanized rubber, siliconised rubber; polycarbonates; silicone resins; fluorinated resins, e.g. PTFE. A mixture of two or more plastic materials listed above can also be used for the matrix. The film may be made in any suitable method. Preferred 25 methods include casting and extrusion. Further treatment such as a roller hot press bending machine may be used. Preferably casting involves dissolution of the support in a suitable solvent, followed by suspension / 30 dispersion of the solid catalyst in fine powder into the WO 2010/010334 PCT/GB2009/001793 7 solvent and support mixture. This is preferably followed by deposition of the dispersion onto a surface (e.g. stainless steel or semiconductor material) and evaporation of the solvent (at room temperature or at an 5 elevated temperature). Suitable solvents include: chlorinated organic solvents (e.g. chloroform), ketones (e.g. acetone or methyl ethyl ketone), dimethylsulfoxide (DMSO), alcohols, aliphatic or aromatic hydrocarbons, glycol ethers or organic acids, (e.g. acetic acid or 10 formic acid), tetra hydro furan (THF). Preferably extrusion and co-extrusion involves passing a composition comprising the support and the catalyst through an extrusion machine or a press machine. The extrusion is preferably performed at an elevated 15 temperature which may be affected by heating or by the pressure applied by the extruder. The extrusion conditions depend to a degree upon the exact nature of the composition being extruded and by the type of machine used. A suitable extrusion 20 operating temperature is, for example, 90-260 0 C. A suitable extrusion operating screw velocity is, for example, 25-250 rpm (rotation per minute), preferably 50-125 rpm. A suitable extrusion operating pressure is, for'example, 30-250 bar. A suitable torque force for an 25 extrusion process, is in the range 10-100 Ampere. The extrudate is preferably in the form of film, pellets or strand or noodles. The primary wall is water permeable. By water permeable we mean that the material allows 30 water to pass through, under the conditions in which the WO 2010/010334 PCT/GB2009/001793 8 product is used. Suitably the material has an air permeability of at least 1000 l/m 2 /s at 100 Pa according to DIN EN ISO 9237. In addition the web must not be so permeable that it is not able to hold a granular dye 5 transfer inhibition composition (e.g. greater than 150 microns). Conventional materials used in tea bag manufacture or in the manufacture of sanitary or diaper products may be suitable for the primary wall. Preferred materials 10 includes polymeric fibres such as polyolefins (particularly polyethylene and polypropylene), poly(haloolefins), poly(vinylalcohol), polyesters such as ethylene vinyl acetate, polyamides, polyacrylics, protein fibres and cellulosic fibres (for example 15 cotton, viscose and rayon). Conveniently the pr-imary wall comprises a non-woven material. Processes for manufacturing non-woven fabrics can be grouped into four general categories leading to four main types of non-woven products, textile-related, 20 paper-related, extrusion-polymer processing related and hybrid combinations Textiles. Textile technologies include garneting, carding, and aerodynamic forming of fibres into selectively oriented webs. Fabrics produced by these 25 systems are referred to as dry laid nonwovens, and they carry terms such as garneted, carded, and air laid fabrics. Textile-based nonwoven fabrics, or fibre network structures, are manufactured with machinery designed to manipulate textile fibres in the dry state. 30 Also included in this category are structures formed WO 2010/010334 PCT/GB2009/001793 9 with filament bundles or tow, and fabrics composed of staple fibres and stitching threads. In general, textile-technology based processes provide maximum product versatility, since most textile fibres 5 and bonding systems can be utilised. Paper. Paper-based technologies include dry laid pulp and wet laid (modified paper) systems designed to accommodate short synthetic fibres, as well as wood pulp fibres. Fabrics produced by these systems are referred 10 to as dry laid pulp and wet laid nonwovens. Paper-based nonwoven fabrics are manufactured with machinery designed to manipulate short fibres suspended in fluid. Extrusions. Extrusions include spun bond, melt blown, and porous film systems. Fabrics produced by these 15 systems are referred to individually as spun bonded, melt blown, and textured or apertured film nonwovens, or generically as polymer-laid nonwovens. Extrusion-based nonwovens are manufactured with machinery associated with polymer extrusion. In polymer-laid systems, fibre 20 structures simultaneously are formed and manipulated. Hybrids. Hybrids include fabric/sheet combining systems, combination systems, and composite systems. Combining systems employs lamination technology or at least one basic nonwoven web formation or consolidation 25 technology to join two or more fabric substrates. Combination systems utilize at least one basic nonwoven web formation element to enhance at least one fabric substrate. Composite systems integrate two or more basic nonwoven web formation technologies to produce web WO 2010/010334 PCT/GB2009/001793 10 structures. Hybrid processes combine technology advantages for specific applications. The primary wall of the container may itself act as a further means for modifying the water, for example by 5 having the capability of capturing undesired species in the water and/or releasing beneficial species. Thus, the wall material could be of a textile material with ion-capturing and/or ion-releasing properties, for example as described above, such a product may be 10 desired by following the teaching of WO 02/18533 that describes suitable materials. Alternatively and more preferably the wall may be modified to provide a dye / dirt catching function. Such a function may be provided by physically / chemically incorporating a dye / dirt 15 catching agent into / onto the fabric of the wall. A preferred example of such a material is a quaternary ammonium based compound. The product may comprise an indication means which serves to show the extent of performance of the dye 20 transfer inhibition function. A preferred example of such an indication means is a colour change within the product. This colour change may occur on the sachet and / or on the body contained within the sachet. A preferred way of achieving the colour change is to use a 25 colour catching compound which is attached to the sachet and / or to the body within the sachet. Container forming can be done in an horizontal or in a vertical plane from two or more rolls of material that are joined together to form the walls of the sachet.
WO 2010/010334 PCT/GB2009/001793 11 Machine assemblies for sachet forming, filling and sealing can be sourced from, VAI, IMA, Fuso for vertical machines; Volpack, Iman Pack for horizontal sachet machines; Rossi, Optima, Cloud for horizontal pod 5 machines. The open container is preferably configured as a pocket or pouch, preferably sealed or otherwise closed on three edges, and which can be filled through an edge, for example the fourth, open, side. 10 Filling of the open container can be done with a variety of volumetric devices, such as a dosing screw or as a measuring cup. Typical dosing accuracy required at constant product density is +/-1% wt preferably, +/-5% wt minimum. 15 Filling devices are supplied by the companies mentioned above as part of the machine package. Feedback control mechanisms acting on the speed of the dosing screw or on the volume of the measuring cup can be installed to maintain high dosing accuracy when the 20 product density changes. Seal strength is important, as the container must not open during the wash cycle or other type of cleaning or water-softening operation, otherwise any water insoluble ingredients might soil the items washed. 25 A seal strength of at least 5N / 20mm, preferably at least 1ON / 20mm and most preferably at least 15N / 20mm according to -test method ISO R-527 measured before the wash sealed sachet is subjected to a wash. The strength of any seal is very much dependent on the materials used WO 2010/010334 PCT/GB2009/001793 12 and the conditions of the sealing process, for example the following conditions are used to generate good quality seals e heat sealing, preferably using flat sealing bars, 5mm 5 by 100mm, Teflon coated stainless steel, typically 1 sec at 150 0 C +/-1 0 C at 20kg/cm 2 actual sealing pressure, as achieved on a bench scale Kopp heat sealer and on the heat sealing devices of most of the machine suppliers mentioned before; 10 * ultrasound sealing, preferably using grooved sealing bars, 5mm by 150mm, pattern with diagonal grooves at 45 degrees to the side of the seal, pitch of 15mm and bar width of 5mm with a nominal seal area coverage of 33%, 0.1 to 0.3 s at 20kHz and 70 microns vibration 15 amplitude, actual sealing pressure between 10 and 60 kg/cm 2 , typical absorbed power 300 to 1200W, typical absorbed energy 30 to 180W, using ultrasound sealing equipment produced by companies like Mecasonic or Branson or Herrmann .or Sonic or Dukane or Sonobond. 20 e glue sealing, e.g. applying lOg/m 2 of hot melt glue like Prodas 1400, PP, from Beardow Adams. Polyethylene (PE) or polyamides or polyurethanes or UV curable acrylics glues or epoxy resins can be used as well. Thus overall the process may comprise: 25 a) forming an open container from two or more webs; b) filling the open container with a dye transfer inhibition composition; and c) sealing the container. The container is preferably flat, i.e. with one 30 dimension, the thickness of the container, at least 5 WO 2010/010334 PCT/GB2009/001793 13 times smaller preferably at least 10 times smaller, ideally at least 30 times smaller than the other two, the width and the length of the sachet (which are the same as each other, corresponding to the diameter of the 5 sachet, should it be circular in plan). Preferred thicknesses are in the range of 10 - 20mm, e.g. 10mm, 15mm or 20mm. Preferably the- container covers a surface (i.e. the product of width and length (when the sachet is 10 rectangular) of between 80 to 300 cm 2 , ideally 100 to 200 cm 2. Preferred lengths/widths are in the range of 5 30cm, e.g. 6cm, 10cm, 12cm, 15cm, 20cm, 25cm or 30cm. The container may comprise a flexible body of at least 10mm in one dimension and 10mm in another direction. 15 Preferably the body is such that no dimension is greater than 20mm. Ideally each dimension is between 10 - 20mm, e.g. 12mm, 15mm or 18mm. The body may be configured to provide a volume adding function e.g. by being resilient so it expands on 20 removal of compression forces. The inclusion of such a volume adding member has been shown [when used in an automatic washing operation] to decrease the incidence of lodging of the device within the door seal, posting of the device in the door seal, facilitate the finding 25 of the device after a washing operation, and can favour water flow through the device. This in turn has a positive environmental impact by reducing the amount of packaging material required for each pack. When great numbers of packs are produced and WO 2010/010334 PCT/GB2009/001793 14 sold, this has also positive influence on transport costs. In a preferred embodiment the body comprises a foam material which may comprise any suitable material such 5 as polypropylene, polyester and / or PE/EVA. The body may comprise a number of separate elements each being formed of a different material. Preferably the detergent composition is a dishwashing, laundry, hard surface cleaning and / or disinfecting 10 composition. Generally the composition is for use in the appropriate washing operation in a washing machine or other washing vessel such as a sink, bucket, etc. Alternatively the composition may be used in an additive (e.g. additives which are complementary to a detergent 15 product used in a washing operation) or in addition to a product which contains a bleach. The detergent composition may comprise a homogenous product, e.g. a uniform powder / liquid or alternatively the detergent composition may have a plurality of 20 individual phases, e.g. such as a multi-phase tablet. The detergent composition typically comprises at least one of surfactant (anionic, non-ionic, cationic or amphoteric), builder, bleach, bleach activator, bleach stabilizer, bleaching catalyst, enzyme, polymer, co 25 builder, alkalizing agent, acidifying agent, anti redeposition agent, silver protectant, colourant, optical brightener, UV stabilizer, fabric softener, fragrance, soil repellent, anticrease substance, antibacterial substance, colour protectant, 30 discolouration inhibitor, vitamin, phyllosilicate, WO 2010/010334 PCT/GB2009/001793 15 odour-complexing substance, rinse aid, foam inhibitor, foaming agent, preservative, or auxiliary. According to a second aspect of the invention there is provided the use of a container according to the first 5 aspect of the invention in a dishwashing, laundry and / or hard surface cleaning operation and/ or a sanitizer/disinfectant operation. The container may be placed with the items to be washed in an automatic washing machine. 10 Alternatively the container may pack into the flow pathway for the rinse or wash water of a ware washing machine such that the water is compelled to flow through it. The invention is now illustrated by reference to the 15 following non-limiting examples. Example 1: Film Production Key Equipment Used: e Mono screw extruder Brabender PL 2000 PLE 650 attached to the Brabender Plasti-Corder. 20 e Brabender Bending Machine T' 300A Electronic- Roller Hot Press. Raw Materials Used Ingredient Commercial Name Supplier Physical Aspect Catalyst Manganese Acetate Kenira Pink fine powder 50
(CH
3
COO)
2 Mn.4 H 2 0 Tetra Hydrate 125 pm Catalyst Manganese Acetate Aldrich Pink.very fine powder
(CH
3
COO)
2 Mn Anhydrous Catalyst Manganese Sulfate Keluka Pink very fine powder MnSO 4 .1 H 2 0 Mono Hydrate, 99% 50-125 pm Support PMMA VM 100ALTUGLAS Arkema Pellet 3x3x2.5mm, WO 2010/010334 PCT/GB2009/001793 16 Poly Methyl brilliant transparent Methacrylate PMMA Support PP401-CA20 BP Pellet 3x3x2.5mm, Poly Propylene copolymer white/ opaque copolymer Support Fusabond PP MD-511D Du Pont Pellet 3x3x2.5mm, Poly Propylene + white maleic anhydride Lubricant Vaseline A. Sella Viscous oil Paraffin Oil transparent Phase 1: Raw Material Preparation Manganese acetate tetra hydrate from Kemira was milled into a fine powder using the laboratory grinder. After sieving, a granulometry of 50-125 pm was selected for 5 film production. Manganese sulphate monohydrate from Fluka was also sieved, a granulometry of 50-125 pm was selected for film production. PMMA VM 100 was heated in an over for 2 hours at 80'C to 10 remove traces of water. PP poly propylene was used as supplied, without being dried. Phase 2: Pre-Mix preparation 15 Several pre-mixes of 500g were prepared. The ratio / amount of raw materials was selected in order to have parity molar concentration of manganese in final film prototypes (calculated Manganese concentration = 4800 ppm Mn). Ingredient Pre Mix Pre Mix Pre Mix Pre Mix Pre Mix Pre Mix (g) 3 4 5 6 7 8
(CH
3
COO)
2 Mn -- -- 7.6 7.6 -- - MnSO 4 .1 H20 7.3 7.6 -- -- -- -
(CH
3
COO)
2 Mn.4 -- -- -- -- 11.0 11.0
H
2 0 PMMA VM 100 492.4 492.4 492.2 492.2 489.0 489.0 dried dried dried dried dried dried Paraffin Oil 0.3 0.3 0.3 0.3 0.3 0.3 WO 2010/010334 PCT/GB2009/001793 17 Ingredient (g) Pre Mix 9 Pre Mix Pre Mix Pre Mix Pre Mix 10 11 12 13 MnSO 4 .1 H 2 0 7.7 -- 7.7 -- -
(CH
3
COO)
2 Mn.4 -- 11.0 -- 11.1 -
H
2 0
(CH
3
COO)
2 Mn -- -- 7.8 Anhydrous PP Poly PP401 PP401 Fusabond Fusabond Fusabond Propylene CA20 CA20 492.5 489.0 492.2 492.4 489.0 Paraffin Oil 0.3 0.3 0.3 0.3 0.3 Phase 3: Extrusion The three heating zones of the extruder were set up as 5 follows: Heating Zone Heating Zone Heating Zone Head T4 T1 T2 T3 Temperature 170 175 180 184-185 C Average screw velocity was 30 rpm. The head opening was set up at 0.3mm. The bending machine was set up at 60 0 C with a velocity of 2.2 metres per minute. 10 These process parameters were set up at the beginning of the trial and maintained constant throughout production using PMMA. Summary of trials and film produced in the table below: Trial - CATALYST SUPPORT Torque Observation Ampere Opaque-white smooth film FILM 3 MnSO 4 .1 H 2 0 PMMA 60 Good salt distribution. Average thickness 0.18-0.22mm Opaque-white smooth film FILM 4 MnSO 4 .1 H 2 0 PMMA 60 Good salt dispersion. Average thickness 0.18-0.22mm (CH3COO)2Mn 60 Translucent-pink rough film FILM 5 PMMA Good salt distribution. Average thickness 0.25mm WO 2010/010334 PCT/GB2009/001793 18 (CH3COO)2Mn 60 Translucent-pink rough film FILM 6 PMMA Good salt distribution. Average thickness 0.25mm (CH3COO)2Mn. 55 Translucent beige film FILM 7 4 H20 PMMA Rough surface. Average thickness 0.35mm (CH3COO)2Mn. 55 Translucent beige film FILM 8 4 H20 PMMA Rough surface. Average thickness 0.35mm Average production capacity was 2 kg / hour. Example 2: Chemical characterization of film produced Chemical analyses were conducted on film 4, film 6 and 5 film 8 to assess the level of manganese present in the solid film. Analytical results confirmed the theoretical/calculated amount of manganese added by weight in the premix is found in the final solid prototype: Film ppm Mn (metal) FILM 4 4545 FILM 6 4721 FILM 8 4838 PMMA alone (no catalyst added) <0.005 (beneath detection limit) 10 Example 3: Oxidation Catalysis Study The following reagents and solution were prepared, in deionised water. Solution Reagent g/L A PCB Sodium Percarbonate (2Na 2
CO
3 .3H 2 0 2 )+ 1.38 TAED Tetra Acetyl Ethylene Diamine 0.30 +Saffron 0.035 B PCB + TAED + (CH 3
COO)
2 Mn x4 H20 0.005 +Saffron C PCB + TAED + MnSO 4 . 1 H 2 0+ 0.0034 +Saffron D PCB + TAED + Film 4 (from example 1) 0.25 +Saffron E PCB + TAED + Film 6 (from example 1) 0.25 +Saffron F PCB + TAED + Film 8 (from example 1) 0.25 +Saffron WO 2010/010334 PCT/GB2009/001793 19 A solution containing sodium percarbonate and TAED was compared with a solution containing PCB, TAED and a catalyst in homogeneous phase (manganese acetate OR manganese sulphate) and with a solution containing PCB + 5 TAED + the corresponding catalysts in solid film format (film 4, or film 6 or film 8). Protocol Used: Saffron Beaker Test Saffron solution (fresh, protected from light) Deionised water 10 Temperature: 20'C Reaction studied over 30 minutes. UV/VIS Abs at 430 nm to monitor the oxidation rate on substrate, via measurement of de-colouration of saffron solution. 15 Results from laboratory experimental measurement of absorbance residue after 30 minutes are summarized in the following table A B C D E F Absorbance 70 58 62 66 65 62 Residue (%) 20 Data reported are the average of two measurement/experimental run. The results show that film 4, film 6 and film 8 are effective as oxidation catalysts (vs. no catalyst), with 25 film 8 delivering the highest catalyses efficiency on the bleaching of saffron. Example 4: Analysis of Washing Liquors The saffron solution from the above oxidative study (example 3) were filtered to remove the solid catalyst, WO 2010/010334 PCT/GB2009/001793 20 acidified and analysed via atomic absorption for manganese presence to assess if any metal (Mn) was released from the solid film to the water solution. Results summarised as follows: 5 A B C D EF ppm Mn 0.042 0.775 0.573 0.057 0.050 0.074 Analytical data for Mn presence shows there is no significant release of Mn from the solid film: the level found is in line with the Mn found in the solution A 10 containing the traditional bleach system PCB/TAED and the substrate saffron (saffron used as oxidative substrate). Example 5: Performance under Washing Conditions. Film 8 was used in a washing machine test to assess the 15 catalytic activity on the bleaching of standard soils. A test under consumer relevant washing condition was conducted comparing the cleaning performance delivered by a compact laundry detergent alone (Tandil Ultra Plus dose at 68 g/wash, containing a traditional bleach 20 system based on percarbonate and TAED) with the performance delivered by the same detergent plus the addition in wash of the solid catalyst in film format (film 8, dosed at 5 g/wash). The following test protocol was used. 25 Water Hardness: 25OF Temperature: 30 0 C Program: Cotton cycle (heavy soil) Load: 3.5kg new cotton Washing machine: EU front load; 14.5 litre wash WO 2010/010334 PCT/GB2009/001793 21 Replications: 4 Drying: RT, linen Ironing: Domestic Iron Evaluation: Datacolour 650 spectrophotometer 5 The following results were achieved: Ultra Plus Detergent 68 g Y-values-Instrumental Evaluation Ultra Plus Detergent + solid bleach catalyst (5 g) Stains 68 g/wash FILM in PMMA + Mn Acetate Tea on cotton empa 167 63,8 67,7 Tea PES/Cotton empa 168 64,9 67,3 Red wine cotton WFK 1OLI 76,6 78,3 Coffee on cotton WFK 10K 80,7 81,1 Ribes on cotton CFT CS-12 63,1 65,2 Blueberry Juice on cotton CFT CS-15 72,4 73,4 Peach Juice on cotton CFT CS-19 81,2 82,2 Tea on cotton BC-01 62,2 63,0 Tea on PES/cotton BC-03 58,4 59,0 Spinach on cotton CFT CS-25 83,9 84,3 These performance test results clearly shows that the addition of solid catalyst in film format increase and improves significantly the performance results/cleaning 10 action. Example 6: Film Production Key Equipment Used: e Mono screw extruder Brabender PL 2000 PLE 650 attached to the Brabender Plasti-Corder. 15 e Brabender Bending Machine T 300A Electronic- Roller Hot Press. Raw Materials Used Ingredient Commercial Name Supplier Physical Aspect Catalyst Manganese Aldrich Pink very fine
(CH
3
COO)
2 Mn Acetate powder, below 50 Anhydrous micron Catalyst Cyclam type, Mn Clariant Very fine beige CAT 3657 powder Support LOTRIL Arkema Pellet 3x3x2.5mm, WO 2010/010334 PCT/GB2009/001793 22 EEA Ethylene white Ethyl Acrylate (PE/EEA) Support OREVAC, ESCORENE Arkema, Exo Pellet 3x3x2.5mm, EVA (PE/EVA) Mobil white Lubricant Vaseline A. Sella Viscous oil Paraffin Oil transparent Phase 1: Raw Material Preparation EEA was pre-dried in oven at 90'C for 2-4 hours. PE / EVA was not pre-dried. Phase 2: Pre-Mix 5 Several pre-mixes of 500g were prepared. The ratio / amount of raw materials was selected in order to have parity molar concentration of manganese in final film prototypes (calculated Manganese concentration = 4800 ppm Mn). 10 Ingredient Pre Mix Pre Mix Pre Mix Pre Mix Pre Mix (g) 20 21* 22 23 23 bis
(CH
3
COO)
2 Mn 7.6 -- -- 7.6 7.6 Anhydrous CAT 3657 -- 7.0 -- -- - EEA 492.1 184.0 -- -- - EVA -- -- 100 492.1 491.7 Paraffin 0.3 0.3 0.3 0.3 0.4 Oil The pre-measured plastic pellets were inserted into a plastic PE bag. The Vaseline oil was added via pipette. The admixture was agitated manually until the oil was homogeneously distributed onto the pellets. The 15 manganese catalyst was added into the bag and mixing was resumed.
WO 2010/010334 PCT/GB2009/001793 23 Phase 3: Extrusion: The three heating zone of the extruder were set up as follows: Head T4 Heating Zone Heating Zone Heating Zone T3 T2 TI Temperature 180 175 173 170 0C Average screw velocity was 30 rpm. The head opening was 5 set up at 0.3mm. The bending machine was set up at 600C with a velocity of 3.0 metres per minute. Trial CATALYST SUPPORT Torque Observation Ampere
(CH
3
COO)
2 Mn Smooth and soft film, FILM 20 EEA 14 homogeneous catalyst dispersion. Good catalyst dispersion FILM 21 CAT 3657 EEA 14 Good catalyst dispersion FILM 22 (CH 3
COO)
2 Mn EVA 16 Elastic transparent film Good catalyst dispersion FILM 23 (CH 3
COO)
2 Mn EVA 13 Average production capacity was 2 kg / hour. The 10 cleaning procedure was applied after each trial/each film production.

Claims (15)

1. A container comprising a detergent formulation, the container including an first enclosing wall which is permeable to water and a second enclosing wall which 5 comprises a bleaching catalyst admixture and a support material.
2. A container according to claim 1, wherein the second enclosing wall is in the form of a film.
3. A container according to claim 2, wherein the bleach 10 catalyst comprises a transition metal compound based upon one or more of manganese, copper, iron, silver, platinum, cobalt, nickel, titanium, vanadium, cerium, lanthanum, zirconium, tungsten, molybdenum, ruthenium.
4. A container according to claim 3, wherein the bleach 15 catalyst comprises a transition metal compound based upon manganese.
5. A container according to claim 4, wherein the bleach catalyst comprises a hydrated / anhydrous compound of manganese selected from the group comprising the halide 20 (chloride/bromide), sulphate, sulphide, carbonate, nitrate, oxide, acetate, lactate, acetyl acetonate, cyclohexanebutyrate, phthalocyanine, gluconate, bis (ethylcyclopentadienyl), bis (pentamethylcyclopentadienyl), polyol, sorbitol, iditol, 25 mannitol, xylithol, arabintol, lactose, dulsitol, adonitol, erythritol, inositol, cathecol. WO 2010/010334 PCT/GB2009/001793 25
6. A container according to claim 4, wherein the bleach catalyst comprises: (1, 8 - diethyl-1 , 4, 8, 11 - TetraAzaCycloTetraDecane) 5 Manganese (II) chloride.
7. A container according to claim 4, wherein the bleach catalyst comprises: Manganese (1II) Catalyst with an organic tripodal ligand. .Mn -- N 10 0-- N N
8. A container according to claim 3, wherein the bleach catalyst comprises: manganese (II) acetate tetrahydrate and/or manganese (II) sulphate monohydrate. 15
9. A container according to any one of the preceding claims, wherein the bleach catalyst comprises from 0.0001% to 20%, preferably from 0.001% to 10.00%, preferably from 0.01% to 5.00% more preferably from 0.15% to 2.5% of the composition. 20
10. A container according to any one of the preceding claims where the film exhibits porosity. WO 2010/010334 PCT/GB2009/001793 26
11. A container according to claim 10, wherein the film has a thickness in the range of from 0.1 to 1.0mm.
12. A container in accordance with any one of preceding claims in which the film comprises a polymeric material 5 selected from the group of poly methyl methacrylate, polyurethanes; polyolefins / hydrocarbons, e.g. polypropylene, polyethylene, polystyrene, polybutadiene; polyamides; polyvinyl chloride; polyesters, poly vinyl acetate; phenolic resins; copolymers, e.g. 10 polymethylmethacrylate with n-butylacrylate and styrene; natural / modified natural polymers, e.g. cellulose, rubber, latex, styrene-butadiene rubber, butyl rubber, chlorinated / hydrochlorinated rubber, nitrile rubber, vulcanized rubber, siliconised rubber; polycarbonates; 15 silicone resins; fluorinated resins, e.g. PTFE.
13. A container according to any one of the proceeding claims in which the film is produced in a technique of, in which the technique of casting / solvent casting is used. 20
14. A container detergent comprising the composition any one of claims 1 to 13 and at least one of surfactant (non-ionic, anionic, cationic or amphoteric), builder, bleach, bleach activator, bleach stabilizer, bleaching catalyst, enzyme, polymer, cobuilder, alkalizing agent, 25 acidifying agent, antiredeposition agent, silver protectant, colourant, optical brightener, UV stabilizer, fabric softener, fragrance, soil repellent, anticrease substance, antibacterial substance, colour protectant, discolouration inhibitor, vitamin, 30 phyllosilicate, odor-complexing substance, rinse aid, WO 2010/010334 PCT/GB2009/001793 27 foam inhibitor, foaming agent, preservative, or auxiliary.
15. Use of a container according to claim 14 in a dishwashing, laundry and / or hard surface cleaning 5 operation and/ or a sanitizer/disinfectant operation.
AU2009275368A 2008-07-23 2009-07-20 Container Ceased AU2009275368B2 (en)

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GB0908642D0 (en) * 2009-05-20 2009-06-24 Reckitt Benckiser Nv Composition
GB0909362D0 (en) * 2009-06-01 2009-07-15 Reckitt Benckiser Nv Composition
DE102010003022A1 (en) * 2010-03-18 2011-09-22 Henkel Ag & Co. Kgaa Kit with performance enhancing effect
EP3444328A1 (en) * 2017-08-18 2019-02-20 The Procter & Gamble Company Cleaning agent
US11441105B2 (en) * 2017-12-15 2022-09-13 Rhodia Operations Composition containing lanthanide metal complex

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GB8908416D0 (en) 1989-04-13 1989-06-01 Unilever Plc Bleach activation
GB9003741D0 (en) 1990-02-19 1990-04-18 Unilever Plc Bleach activation
ES2100925T3 (en) 1990-05-21 1997-07-01 Unilever Nv WHITENING ACTIVATION.
CA2083661A1 (en) 1991-11-26 1993-05-27 Rudolf J. Martens Detergent bleach compositions
CA2085642A1 (en) 1991-12-20 1993-06-21 Ronald Hage Bleach activation
DK0979864T3 (en) * 1998-07-17 2002-04-22 Procter & Gamble Process for the preparation of detergent tablets
MXPA02006273A (en) 1999-12-23 2002-12-05 Unilever Nv Bleaching composition.
CA2420927A1 (en) 2000-09-01 2002-03-07 Reckitt Benckiser (Uk) Limited Cleaning method
DE10163331A1 (en) * 2001-12-21 2003-07-10 Henkel Kgaa Support-fixed bleach catalyst complex compounds are suitable as catalysts for peroxygen compounds
GB2416539A (en) * 2004-07-24 2006-02-01 Reckitt Benckiser Liquid cleaning composition, catalyst therefor and methods of cleaning
ITMI20061598A1 (en) * 2006-08-08 2008-02-09 Bolton Manitoba S P A ARTICLE PEER CLEANSING
US20100298195A1 (en) * 2007-04-25 2010-11-25 Reckitt Benckiser N.V. Composition
EP2133410B1 (en) * 2008-06-13 2011-12-28 The Procter & Gamble Company Multi-compartment pouch

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EP2318503A1 (en) 2011-05-11
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CA2730523A1 (en) 2010-01-28
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RU2011105658A (en) 2012-08-27
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GB0813460D0 (en) 2008-08-27
ES2424791T3 (en) 2013-10-08

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