EP2318503B1

EP2318503B1 - Container

Info

Publication number: EP2318503B1
Application number: EP09784746.1A
Authority: EP
Inventors: Dora Zamuner
Original assignee: Reckitt Benckiser NV
Current assignee: Reckitt Benckiser NV
Priority date: 2008-07-23
Filing date: 2009-07-20
Publication date: 2013-06-05
Anticipated expiration: 2029-07-20
Also published as: PL2318503T3; WO2010010334A1; CN102099457B; ES2424791T3; US20110174660A1; CA2730523A1; AU2009275368B2; EP2318503A1; ZA201100284B; RU2011105658A; AU2009275368A1; GB0813460D0; RU2511399C2; BRPI0916454A2; CN102099457A

Description

The present invention relates to a container.
Inorganic peroxygen compounds, especially hydrogen peroxide and solid peroxygen compounds which dissolve in 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 dependent on the temperature; for instance, with H₂O₂ or perborate in alkaline bleaching liquors, sufficiently rapid bleaching of soiled textiles is obtained only at temperatures above about 80°C. At lower temperatures the oxidizing action of the inorganic peroxygen 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 tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, and also carboxylic anhydrides, especially phthalic 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 peroxide liquors can be increased to such an extent that even at temperatures around 60°C essentially the same activities occur as with the peroxide liquor alone at 95°C.
Given the concern for energy-saving laundering and bleaching methods, in recent years application temperatures well below 60°C have gained in importance, in particular below 45°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 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 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 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 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 such typically a portion of the catalyst adheres to 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.
According to a first aspect of the invention there is provided a container comprising a detergent formulation, the container including an first enclosing wall which is permeable to water and a second enclosing wall which comprises a bleaching catalyst admixture and a support material, wherein the second enclosing wall is in the form of a film having a thickness in the range of 0.1mm to 1mm, characterised in that the bleach catalyst comprises from 0.001% to 10% of the second enclosing wall, with the remainder of the wall composition comprising a support matrix, in which the film is produced in a technique of extrusion or casting.
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 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 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 12°C to 40°C.
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.
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, 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 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 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 monohydrate.
Alternatively the bleach catalyst may comprise:-
(1, 8 - diethyl-1, 4, 8, 11-TetraAzaCycloTetraDecane) manganese (II) chloride [Mn-TACTD].
Alternatively the bleach catalyst may comprise:-
Alternatively the bleach catalyst may comprise:-
The bleach catalyst comprises from 0.001% to 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 can be used.
The secondary wall is in the form of a film. The film thickness is in the range of from 0.10mm to 1.0mm, more preferably from 0.20 to 0.40mm.
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 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, 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 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, 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 by 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 / dispersion of the solid catalyst in fine powder into the 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 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 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 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 operating temperature is, for example, 90-260°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 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 water to pass through, under the conditions in which the product is used. Suitably the material has an air permeability of at least 1000 l/m²/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 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 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 cotton, viscose and rayon).
Conveniently the primary 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, 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 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. Also included in this category are structures formed 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 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 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 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 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 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 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 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 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 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 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 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.
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 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.
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.
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 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.
A seal strength of at least 5N / 20mm, preferably at least 10N / 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 and the conditions of the sealing process, for example the following conditions are used to generate good quality seals

heat sealing, preferably using flat sealing bars, 5mm by 100mm, Teflon coated stainless steel, typically 1 sec at 150°C +/-1°C at 20kg/cm² 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;
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 amplitude, actual sealing pressure between 10 and 60 kg/cm², 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.
glue sealing, e.g. applying 10g/m² 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:

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 dimension, the thickness of the container, at least 5 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 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 rectangular) of between 80 to 300 cm², ideally 100 to 200 cm². 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.
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 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 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 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 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 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 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 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, cobuilder, alkalizing agent, 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, phyllosilicate, 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 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.
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 following non-limiting examples.

Example 1: Film Production

Key Equipment Used:

Mono screw extruder Brabender PL 2000 PLE 650 attached to the Brabender Plasti-Corder.
Brabender Bending Machine T 300A Electronic- Roller Hot Press.

Raw Materials Used

Ingredient	Commercial Name	Supplier	Physical Aspect
Catalyst	Manganese Acetate Tetra Hydrate	Kemira	Pink fine powder 50-125 µm
(CH₃COO)₂Mn.4 H₂O	Manganese Acetate Tetra Hydrate		Pink fine powder 50-125 µm
Catalyst	Manganese Acetate Anhydrous	Aldrich	Pink very fine powder
(CH₃COO)₂Mn	Manganese Acetate Anhydrous
Catalyst	Manganese Sulfate Mono Hydrate, 99%	Fluka	Pink very fine powder 50-125 µm
MnsO₄.1 H₂O	Manganese Sulfate Mono Hydrate, 99%		Pink very fine powder 50-125 µm
Support	PMMA VM 100ALTUGLAS	Arkema	Pellet 3x3x2.5mm, brilliant transparent
Poly Methyl Methacrylate PMMA			Pellet 3x3x2.5mm, brilliant transparent
Support	PP401-CA20	BP	Pellet 3x3x2.5mm, white/ opaque
Poly Propylene copolymer	copolymer		Pellet 3x3x2.5mm, white/ opaque
Support	Fusabond PP MD-511D	Du Pont	Pellet 3x3x2.5mm, white
Poly Propylene + maleic anhydride			Pellet 3x3x2.5mm, white
Lubricant	Vaseline	A. Sella	Viscous oil transparent
Paraffin Oil			Viscous 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 µm was selected for film production.
Manganese sulphate monohydrate from Fluka was also sieved, a granulometry of 50-125 µm was selected for film production.
PMMA VM 100 was heated in an over for 2 hours at 80°C to remove traces of water.
PP poly propylene was used as supplied, without being dried.

Phase 2: Pre-Mix preparation

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 (g)	Pre Mix 3	Pre Mix 4	Pre Mix 5	Pre Mix 6	Pre Mix 7	Pre Mix 8
(CH₃COO)₂Mn	--	--	7.6	7.6	--	--
MnSO₄.1 H₂O	7.3	7.6	--	--	--	--
(CH₃COO)₂Mn.4 H₂O	--	--	--	--	11.0	11.0
PMMA VM 100	492.4 dried	492.4 dried	492.2 dried	492.2 dried	489.0 dried	489.0 dried
Paraffin Oil	0.3	0.3	0.3	0.3	0.3	0.3

Ingredient (g)	Pre Mix 9	Pre Mix 10	Pre Mix 11	Pre Mix 12	Pre Mix 13
MnSO₄.1 H₂O	7.7	--	7.7	--	--
(CH₃COO)₂Mn.4 H₂O	--	11.0	--	11.1	--
(CH₃COO)₂Mn Anhydrous	--	--	--	--	7.8
PP Poly Propylene	PP401 CA20 492.4	PP401 CA20 489.0	Fusabond 492.5	Fusabond 489.0	Fusabond 492.2
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 follows:

Heating Zone T1 Heating Zone T2 Heating Zone T3 Head T4

Temperature °C 170 175 180 184-185
Average screw velocity was 30 rpm. The head opening was set up at 0.3mm.
The bending machine was set up at 60°C with a velocity of 2.2 metres per minute.

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 Ampere	Observation
				Opaque-white smooth film
FILM 3	MnSO₄.1 H₂O	PMMA	60	Good salt distribution. Average thickness 0.18-0.22mm
FILM 4	MnSO₄.1 H₂O	PMMA	60	Opaque-white smooth film Good salt dispersion. Average thickness 0.18-0.22mm
FILM 5	(CH₃COO)₂Mn	PMMA	60	Translucent-pink rough film Good salt distribution. Average thickness 0.25mm
FILM 6	(CH₃COO)₂Mn	PMMA	60	Translucent-pink rough film Good salt distribution. Average thickness 0.25mm
FILM 7	(CH₃COO)₂Mn. 4 H₂O	PMMA	55	Translucent beige film Rough surface, Average thickness 0.35mm
FILM 8	(CH₃COO)₂Mn. 4 H₂O	PMMA	55	Translucent beige film 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 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)

Example 3: oxidation Catalysis Study

The following reagents and solution were prepared, in deionised water.

Solution	Reagent	g/L
A	PCB Sodium Percarbonate (2Na₂CO₃.3H₂O₂)+ TAED Tetra Acetyl Ethylene Diamine +Saffron	1.38
		0.30
		0.035
B	PCB + TAED + (CH₃COO)₂Mn x4 H₂O +Saffron	0.005
C	PCB + TAED + MnSO₄. 1 H₂O+ +Saffron	0.0034
D	PCB + TAED + Film 4 (from example 1) +Saffron	0.25
E	PCB + TAED + Film 6 (from example 1) +Saffron	0.25
F	PCB + TAED + Film 8 (from example 1) +Saffron	0.25

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 + 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
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.

Results from laboratory experimental measurement of absorbance residue after 30 minutes are summarized in the following table

A B C D E F

Absorbance Residue (%) 70 58 62 66 65 62
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 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, 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:

A B C D E F

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 containing the traditional bleach system PCB/TAED and the substrate saffron (saffron used as oxidative substrate).

Example 5: Performance under Wasting Conditions.

Film 8 was used in a washing machine test to assess the 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 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.

Water Hardness:	25°F
Temperature:	30°C
Program:	Cotton cycle (heavy soil)
Load:	3.5kg new cotton
Washing machine:	EU front load; 14.5 litre wash
Replications:	4
Drying:	RT, linen
Ironing:	Domestic Iron
Evaluation:	Datacolour 650 spectrophotometer

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 10LI	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 cotto.	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 action.

Example 6: Film Production

Key Equipment Used:

Raw Materials Used

Ingredient	Commercial Name	Supplier	Physical Aspect
Catalyst	Manganese Acetate Anhydrous	Aldrich	Pink very fine powder, below 50 micron
(CH₃COO)₂ Mn	Manganese Acetate Anhydrous		Pink very fine powder, below 50 micron
Catalyst	Cyclam type, Mn	Clariant	Very fine beige powder
CAT 3657			Very fine beige powder
Support	LOTRIL	Arkema	Pellet 3x3x2.5mm, white
EEA Ethylene Ethyl Acrylate (PE/EEA)			Pellet 3x3x2.5mm, white
Support	OREVAC, ESCORENE	Arkema, Exo Mobil	Pellet 3x3x2.5mm, white
EVA (PE/EVA)		Arkema, Exo Mobil	Pellet 3x3x2.5mm, white
Lubricant	Vaseline	A. Sella	Viscous oil transparent
Paraffin Oil			Viscous 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

Ingredient (g)	Pre Mix 20	Pre Mix 21*	Pre Mix 22	Pre Mix 23	Pre Mix 23 bis
(CH₃COO)₂Mn Anhydrous	7.6	--	--	7.6	7.6
CAT 3657	--	7.0	--	--	--
EEA	492.1	184.0	--	--	--
EVA	--	--	100	492.1	491.7
Paraffin Oil	0.3	0.3	0.3	0.3	0.4

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 manganese catalyst was added into the bag and mixing was resumed.

Phase 3: Extrusion:

The three heating zone of the extruder were set up as follows:

Head T4 Heating Zone T3 Heating Zone T2 Heating Zone T1

Temperature °C 180 175 173 170
Average screw velocity was 30 rpm. The head opening was set up at 0.3mm.

The bending machine was set up at 60°C with a velocity of 3.0 metres per minute.

Trial	CATALYST	SUPPORT	Torque Ampere	Observation
FILM 20	(CH₃COO)₂Mn	EEA	14	Smooth and soft film, homogeneous catalyst dispersion.
FILM 21	CAT 3657	EEA	14	Good catalyst dispersion
FILM 22	(CH₃COO)₂Mn	EVA	16	Good catalyst dispersion Elastic transparent film
FILM 23	(CH₃COO)₂Mn	EVA	13	Good catalyst dispersion

Average production capacity was 2 kg / hour. The cleaning procedure was applied after each trial/each film production.

Claims

A container comprising a detergent formulation, the container including an first enclosing wall which is permeable to water and a second enclosing wall which comprises a bleaching catalyst admixture and a support material, wherein the second enclosing wall is in the form of a film having a thickness in the range of 0.1mm to 1mm, characterised in that the bleach catalyst comprises from 0.001% to 10% of the second enclosing wall, with the remainder of the wall composition comprising a support matrix, in which the film is produced in a technique of extrusion or casting.
A container according to claim 1, wherein the bleach 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.
A container according to claim 2, wherein the bleach catalyst comprises a transition metal compound based upon manganese.
A container according to claim 3, wherein the bleach catalyst comprises a hydrated / anhydrous compound of manganese selected from the group comprising the halide (chloride/bromide), sulphate, sulphide, carbonate, nitrate, oxide, acetate, lactate, acetyl acetonate, cyclohexanebutyrate, phthalocyanine, gluconate, bis (ethylcyclopentadienyl), bis (pentamethylcyclopentadienyl), polyol, sorbitol, iditol, mannitol, xylithol, arabintol, lactose, dulsitol, adonitol, erythritol, inositol, cathecol.
A container according to claim 3, wherein the bleach catalyst comprises:-
(1, 8 - diethyl-1 , 4, 8, 11 - TetraAzaCycloTetraDecane) Manganese (II) chloride.
A container according to claim 3, wherein the bleach catalyst comprises:-
A container according to claim 2, wherein the bleach catalyst comprises: manganese (II) acetate tetrahydrate and/or manganese (II) sulphate monohydrate.
A container according to any one of the preceding claims where the film exhibits porosity.
A container in accordance with any one of preceding claims in which the film comprises a polymeric material 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. 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; silicone resins; fluorinated resins, e.g. PTFE.
A container according to any one of claims 1 to 9 wherein the detergent formulation comprises at least one of surfactant (non-ionic, anionic, cationic or amphoteric), builder, bleach, bleach activator, bleach stabilizer, bleaching catalyst, enzyme, polymer, cobuilder, alkalizing agent, 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, phyllosilicate, odor-complexing substance, rinse aid, foam inhibitor, foaming agent, preservative, or auxiliary.
Use of a container according to claim 10 in a dishwashing, laundry and / or hard surface cleaning operation and/ or a sanitizer/disinfectant operation.