ES2424791T3 - Container - Google Patents

Abstract

Container comprising a detergent formulation, the package including a first surrounding wall that is water-impermeable and a second surrounding wall comprising a mixture of bleach catalyst and a support material, in which the second surrounding wall is in the form of a film having a thickness in the range of 0.1 mm to 1 mm, characterized in that the bleaching catalyst comprises from 0.001% to 10% of the second surrounding wall, the rest of the wall composition comprising a support matrix, in which The film is produced in an extrusion or casting technique.

Description

Container

The present invention relates to a container.

Inorganic peroxygen compounds, especially solid hydrogen peroxide and peroxygen compounds that dissolve in water releasing hydrogen peroxide, such as sodium perborate and perhydrated sodium carbonate, have been used as oxidizing agents for disinfection and bleaching purposes. . The oxidizing action of these substances in dilute solutions depends significantly on the temperature; for example, with H2O2 or perborate in alkaline bleaching mother liquors, only sufficiently rapid bleaching of stained textile materials is obtained at temperatures above about 80 ° C. At lower temperatures, the oxidizing action of organic peroxygen compounds can be enhanced by adding what is called bleach activators, for which numerous proposals have been disclosed in the literature,

15 mainly of the classes of the N-acyl or O-acyl compounds, examples being polyacylated alkylenediamines, especially tetraacetylethylenediamine, acetylated glycoluryls, especially tetraacetylglycoluryl, Nacetylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, sulfur diurethmurazines carboxylic anhydrides, especially phthalic anhydride, carboxylic esters, especially sodium nonanoyloxybenzenesulfonate, sodium isononanoyloxybenzenesulfonate and acetylated sugar derivatives, such as pentaacetylglucose. By adding these substances, the bleaching action of aqueous peroxide mother liquors can be increased to such an extent that even at temperatures of approximately 60 ° C essentially the same activities occur as with peroxide mother water alone at 95 ° C.

Given the concern about laundry and bleaching methods that save energy, in recent years the

25 application temperatures well below 60 ° C have gained importance, in particular below 45 ° C with respect to the cold water temperature, below 20 ° C.

The use of transition metal salts and transition metal complexes has previously been described, for example in European patent applications EP 392592, EP 443651, EP 458397, EP 544490, EP 549271 and WO 01/48138, referred to as catalysts of Whitening.

It has now been observed that textile materials, particularly colored textile materials, lose color after several washes in the presence of a bleaching catalyst. It is speculated that some previously used catalysts not only catalyze the activity of the peroxygen compound but also remain at least

35 partially on their surfaces that are bleaching, and even when the cleaning operation is over. Then, these transition metal salts can oxidize and thus cause color damage and, in extreme cases, risks of oxidative damage to textile materials since they are directly in contact with the textile material. As an example, a deposit of Mn (II) is easily oxidized to Mn (IV) dioxide, which is a very strong oxidizing agent, particularly towards easily oxidizable substances, such as organic dye compounds.

All known bleaching catalysts have the disadvantage that they come into intimate contact with the substances of the articles being treated and in themselves normally a part of the catalyst adheres to those surfaces or even penetrates those surfaces. This results in a risk of unwanted color changes and in

45 rare cases; there may even be holes / tears, as a result of damage to the fibers.

According to a first aspect of the invention there is provided a package comprising a detergent formulation, the package including a first surrounding wall that is permeable to water and a second surrounding wall comprising a mixture of bleach catalyst and a support material, in which the second surrounding wall is in the form of a film having a thickness in the range of 0.1 mm to 1 mm, characterized in that the bleaching catalyst comprises from 0.001% to 10% of the second surrounding wall, comprising The rest of the wall composition is a support matrix, in which the film is produced in an extrusion or casting technique.

It has been found that the package of the present invention has several advantageous properties. The main advantageous property is that there is not a substantial amount of bleaching catalyst, particularly the transition metal thereof when present (when used in a wash / bleach operation) on an article to be washed or bleached. Therefore, damaging damage to the article is drastically reduced.

Another advantage of the present invention (when used in a wash / bleach operation) is the catalysis of the oxidizing action and the bleaching action of the 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 wash / bleach operation) is to allow reduction

65 of the amount of peroxygen and / or bleach activator (for example TAED) in a cleaning formulation while maintaining the bleaching performance, thus allowing cost reduction.

Preferably the bleaching catalyst comprises a transition metal compound based on one or more of manganese, copper, iron, silver, platinum, cobalt, nickel, titanium, zirconium, tungsten, molybdenum, ruthenium, cerium, lanthanum or vanadium. Most preferably the bleaching catalyst comprises a transition metal compound based on manganese.

5 The manganese bleach catalyst can be selected from a wide range of manganese compounds. Suitable inorganic compounds (often salts) of manganese (for example Mn (II)) include halide (for example chloride / bromide), sulfate, sulphide, carbonate, nitrate, hydrated / anhydrous oxide. Additional examples of suitable compounds (often salts) of manganese (for example Mn (II)) include acetate, lactate, acetone

10 acetyl, cyclohexanebutyrate, phthalocyanine, bis (ethylcyclopentadienyl), bis (pentamethylcyclopentadienyl) hydrated / anhydrous.

Most preferably, the bleaching catalyst comprises manganese (II) acetate tetrahydrate and / or manganese (II) sulfate monohydrate. Alternatively, the bleaching catalyst may comprise:

(1,8-diethyl-1,4,8,11-tetraazacyclotetradecane) manganese (II) chloride [Mn-TACTD]. Alternatively, the bleaching catalyst may comprise: manganese (III) catalyst with an organic tripodal ligand

Alternatively, the bleach catalyst may comprise:

The bleaching 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 surrounding wall, the rest of the composition comprising the support matrix.

A mixture of two or more bleach catalysts listed above may be used.

The secondary wall is in the form of a film. The thickness of the film is in the range of from 0.10 mm to 1.0 mm, more preferably from 0.20 to 0.40 mm.

The particle size of the catalyst used in the production of the secondary wall is preferably between 50 micrometers and 125 micrometers.

The supporting matrix of the secondary wall generally comprises a polymeric material. Can be selected

5 suitable polymeric materials of the polyurethane group; polyolefins / hydrocarbons, for example polypropylene (PP), polypropylene containing maleic anhydride, polypropylene mixed with polyethylene, polyethylene (PE), PE mixed with ethylene vinyl acetate (PE / VA), polyethylene copolymer with ethylenenetyl acrylate, (PE / EEA) polystyrene, polybutadiene; polyamides; polyvinylchloride); polyesters, for example poly (methyl methacrylate), poly (vinyl acetate), ethylene vinyl acetate; phenolic resins; copolymers, for example poly (methyl methacrylate)

10 with n-butyl acrylate and styrene; modified natural / natural polymers, for example cellulose, rubber, latex, styrene-butadiene rubber, butyl rubber, chlorinated / hydrochlorinated rubber, nitrile rubber, vulcanized rubber, siliconized rubber; polycarbonates; silicone resins; fluorinated resins, for example PTFE.

A mixture of two or more plastic materials listed above for the matrix can also be used.

15 The film can be made by casting and extrusion. Additional treatment such as a hot roller press bending machine may be used.

Preferably, casting involves dissolving the support in a suitable solvent, followed by

20 suspension / dispersion of the fine powder solid catalyst in the solvent and support mixture. This is preferably followed by deposition of the dispersion on a surface (for example stainless steel or semiconductor material) and evaporation of the solvent (at room temperature or at elevated temperature). Suitable solvents include: chlorinated organic solvents (for example chloroform), ketones (for example acetone or methyl ethyl ketone), dimethyl sulfoxide (DMSO), alcohols, aliphatic or aromatic hydrocarbons, glycol ethers or acids

Organic, (for example acetic acid or formic acid), tetrahydrofuran (THF).

Preferably, extrusion and coextrusion involve passing a composition comprising the support and the catalyst through an extrusion machine or a pressing machine. The extrusion is preferably carried out at an elevated temperature which can be carried out by heating or by pressure

30 applied by the extruder press.

Extrusion conditions depend to some extent on the exact nature of the composition to be extruded and the type of machine used. A suitable extrusion operating temperature is, for example, 90260 ° C. A suitable extrusion operation spindle speed is, for example, 25-250 rpm (rotation by

35 minutes), preferably 50-125 rpm. A suitable extrusion operating pressure is, for example, 30250 bar. A suitable torque force for an extrusion process is in the range of 10-100 amps. The extrudate is preferably in the form of a film, granules or strands or noodles.

The primary wall is permeable to water.

40 By water permeable it is meant that the material allows water to pass through it, 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 veil should not be so permeable that it cannot contain a dye transfer inhibition composition. granular (for example greater than 150 micrometers).

45 Conventional materials used in the manufacture of tea bags or in the manufacture of sanitary products or diapers may be suitable for the primary wall. Preferred materials include polymeric fibers such as polyolefins (particularly polyethylene and polypropylene), poly (haloolefins), polyvinyl alcohol, polyesters such as ethylene vinyl acetate, polyamides, polyacrylics, protein fibers and cellulose fibers (for example

50 cotton, viscose and rayon).

Conveniently, the primary wall comprises a nonwoven material. The procedures for manufacturing nonwoven fabrics can be grouped into four general categories that lead to four main types of nonwoven products, related to textile, paper related, related to polymer processing by

55 extrusion and hybrid combinations

Textile materials. Textile materials technologies include abrasion, carding and aerodynamic fiber formation in selectively oriented veils. The fabrics produced by these systems are called non-woven materials deposited by air and carry terms such as scorched, carded and air-deposited fabrics. The

60 nonwoven fabrics based on textile materials, or fiber network structures, are manufactured with machinery designed to handle textile fibers in the dry state. Also included in this category are structures formed with filament bundles or continuous filament tape and fabrics composed of cut fibers and sewing threads.

In general, procedures based on textile materials technology provide a maximum product versatility, since most textile bonding and fiber systems can be used.

Paper. Paper-based technologies include dry deposition and wet deposition systems of pulp (modified paper) designed to accommodate short synthetic fibers, as well as wood pulp fibers. The fabrics produced by these systems are called non-woven materials of dry deposition and wet deposition of pulp. Paper-based nonwovens are manufactured with machinery designed to

5 manipulate short fibers suspended in liquid.

Extrusions Extrusions include spunbonded, blown softened and porous film systems. The fabrics produced by these systems are individually called spunbonded, blown softened and textured or open film or generically nonwoven polymer deposition materials. Nonwoven fabrics based on extrusion are manufactured with machinery associated with polymer extrusion. In polymer deposition systems, fiber structures are formed and manipulated simultaneously.

Hybrids Hybrids include tissue / sheet combination systems, combinatorial systems and composite systems. Combination systems employ lamination technology or at least one technology of

15 basic non-woven veil formation or consolidation to join two or more tissue substrates. Combinatorial systems use at least one basic nonwoven web forming element to enhance at least one tissue substrate. Composite systems integrate two or more basic nonwoven veil formation technologies to produce veil structures. Hybrid procedures combine the advantages of technology for specific applications.

The primary wall of the container can act by itself as an additional means to modify the water, for example having the ability to capture unwanted species in the water and / or release beneficial species. Therefore, the wall material could be of a textile material with ion capture and / or ion release properties, for example as described above, such a product may be desired by following the teachings of the

WO 02/18533 describing suitable materials. Alternatively and more preferably, the wall can be modified to provide a dye / dirt capture function. Such a function can be provided by physically / chemically incorporating a dye / dirt capture agent into / on the wall tissue. A preferred example of such a material is a quaternary ammonium based compound.

The product may comprise an indication medium that serves to show the degree of performance of the dye transfer inhibition function. A preferred example of such an indication medium is a color change within the product. This color change can happen in the sachet and / or in the body contained within the sachet. A preferred way to achieve color change is to use a color capture compound that is attached to the bag and / or the body inside the bag.

35 The formation of the container can be carried out in a horizontal plane or in a vertical plane from two or more rolls of material that join together to form the walls of the sachet.

Machine assemblies for forming, filling and sealing the sachet can be obtained from VAI, IMA, Fuso for vertical machines; Volpack, Iman Pack for horizontal bag machines; Rossi, Optima, Cloud for horizontal capsule machines.

The open container is preferably configured as a pocket or bag, preferably sealed or otherwise closed at three edges, and which can be filled through an edge, for example the fourth open side.

The filling of the open container can be performed with a variety of volumetric devices, such as a dosing screw or as a measuring cuvette. The typical dosage accuracy required at constant product density is preferably +/- 1% by weight, +/- 5% by weight at least.

The filling devices are supplied by the companies mentioned above as part of the machine package.

Feedback control mechanisms that act on the speed of the dosing screw or on the volume of the measuring cuvette can be installed to maintain high dosing accuracy when

55 changes the product density.

The strength of the seal is important, since the container must not be opened during the wash cycle or other type of water cleaning or softening operation, otherwise any water insoluble component could stain the washed items.

A seal strength of at least 5 N / 20 mm, preferably at least 10 N / 20 mm and most preferably at least 15 N / 20 mm according to the ISO R-527 test method measured before the sealed pouch Wash undergo a wash. The strength of any seal depends a lot on the materials used and the conditions of the sealing procedure, for example the following conditions are used to generate good quality seals

• heat sealing, preferably using flat sealing bars, 5 mm by 100 mm, Teflon coated stainless steel, usually 1 s at 150 ° C +/- 1 ° C at actual sealing pressure of 20 kg / cm2, as achieved in a heat sealer Desktop Kopp and heat sealing devices of most of the machine suppliers mentioned above;

5 • ultrasonic sealing, preferably using notched sealing bars, 5 mm by 150 mm, pattern with diagonal notches at 45 degrees with respect to the seal side, 15 mm inclination and 5 mm bar width with coverage of nominal seal area of 33%, from 0.1 to 0.3 s at 20 kHz and vibration amplitude of 70 micrometers, actual sealing pressure between 10 and 60 kg / cm2, typical absorbed power of 300 to 1200 W, Typical absorbed energy from 30 to 180 W, using ultrasonic sealing equipment produced by companies such as Mecasonic or Branson or Herrmann or Sonic or Dukane or Sonobond.

• sealed with adhesive, for example by applying 10 g / m2 of hot melt adhesive such as Prodas 1400, PP, from Beardow Adams. Polyethylene (PE) or polyamides or polyurethanes or UV-curable acrylic adhesives or epoxy resins can also be used.

15 Therefore, the procedure as a whole may include:

a) form an open container from two or more veils;

b) filling the open container with a dye transfer inhibition composition; Y

c) seal the container.

The package is preferably flat, that is, with one dimension, the thickness of the package, at least 5 times more

25 small, preferably at least 10 times smaller, ideally at least 30 times smaller than the other two, the width and length of the sachet (which are equal to each other, corresponding to the diameter of the sachet, if it were circular in the flat). Preferred thicknesses are in the range of 10-20 mm, for example 10 mm, 15 mm

or 20 mm

Preferably, the package covers a surface (i.e., the product of width and length (when the bag is rectangular) of between 80 and 300 cm2, ideally from 100 to 200 cm2. Preferred lengths / widths are in the range of 5-30 cm, for example 6 cm, 10 cm, 12 cm, 15 cm, 20 cm, 25 cm or 30 cm.

The package may comprise a flexible body of at least 10 mm in one dimension and 10 mm in another direction.

Preferably, the body is such that no dimension is greater than 20 mm. Ideally, each dimension is between 10-20 mm, for example 12 mm, 15 mm or 18 mm.

The body can be configured to provide a volume addition function, for example, being elastic so that it expands by removing compression forces. The inclusion of such a volume addition element has shown [when used in an automatic washing operation] that the incidence of housing of the device within the door closure decreases, that the device is directed to the door closure , which makes it easier to find the device after a washing operation and can favor water flowing through the device.

45 This, in turn, has a positive environmental impact by reducing the amount of packaging material required for each package. When large quantities of packages are produced and sold, this also has a positive influence on transportation costs.

In a preferred embodiment the body comprises a foam material that can comprise any suitable material such as polypropylene, polyester and / or PE / EVA. The body can comprise several separate elements each being formed of a different material.

Preferably, the detergent composition is a dishwashing, laundry, cleaning

55 hard surfaces and / or disinfection. Generally, the composition is for use in the proper washing operation in a washing machine or other washing container such as a sink, bucket, etc. Alternatively, the composition can be used in an additive (for example additives that are complementary to a detergent product used in a washing operation) or in addition to a product containing a bleaching agent.

The detergent composition may comprise a homogeneous product, for example a uniform powder / liquid or alternatively the detergent composition may have a plurality of individual phases, for example such as a multi-phase tablet.

The detergent composition typically comprises at least one of surfactant (anionic, nonionic, cationic or

65 amphoteric), adjuvant, bleaching agent, bleaching activator, bleaching stabilizer, bleaching catalyst, enzyme, polymer, adjuvant, alkalizing agent, acidifying agent, anti-redeposition agent, silver protector, dye, optical brightener, UV stabilizer, fabric softener, fragrance, stain repellent, wrinkle substance, antibacterial substance, color protector, color alteration inhibitor, vitamin, phyllosilicate, odor complexing substance, rinse aid, foam inhibitor, foaming agent, preservative or auxiliary component.

According to a second aspect of the invention, the use of a container according to the first aspect of the invention is provided in a dishwashing, laundry and / or hard surface cleaning operation and / or a sterilization / disinfection operation .

10 The container can be placed with items to be washed in an automatic washing machine.

Alternatively, the container can be placed in the flow path of the rinsing or washing water of a scrubbing machine so that water is forced to flow through it.

The invention is now illustrated by reference to the following non-limiting examples.

Example 1: Film production

Key equipment used: 20

• Single-screw extruder press PL 2000 PLE 650 from Brabender coupled to Plasti-Corder from Brabender.

• T 300A Electronic bending machine - Brabender hot roller press. 25 Used starting materials

Component

Tradename Provider Physical appearance

Catalyst (CH3COO) 2Mn. 4 H2O

Tetrahydrate Manganese Acetate Kemira 50-125 μm fine pink powder

Catalyst (CH3COO) 2Mn

Anhydrous Manganese Acetate Aldrich very fine pink powder

MnsO4.1 H2O Catalyst

99% Manganese Sulfate Monohydrate Fluka very fine pink powder of 50-125 μm

Poly (methyl methacrylate) PMMA support

PMMA VM 100ALTUGLAS Arkema 3x3x2.5 mm granules, bright transparent

Polypropylene Copolymer Support

PP401-CA20 copolymer BP 3x3x2.5 mm granules, white / opaque color

Polypropylene + maleic anhydride support

Fusabond PP MD-511D Du pont 3x3x2.5 mm granules, white

Paraffin oil lubricant

Vaseline A. Sella Clear viscous oil

Phase 1: Preparation of starting material

30 Kemira tetrahydrate manganese acetate was ground to give a fine powder using the laboratory crusher. After screening, a granulometry of 50-125 μm was selected for film production.

Fluka monohydrate manganese sulfate was also screened, a granulometry of 50-125 μm was selected for film production. 35 PMMA VM 100 was heated in an oven for 2 hours at 80 ° C to remove traces of water.

PP polypropylene was used as supplied, without drying it.

40 Phase 2: Preparing the premix

Several 500 g premixes were prepared. The ratio / amount of starting materials was selected in order to have parity of manganese molar concentration in the final film prototypes (calculated manganese concentration = 4800 ppm of Mn).

Component (g)

Premix 3 Premix 4 Premix 5 Premix 6 Premix 7 Premix 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 drying 492.4 drying 492.2 drying 492.2 drying 489.0 drying 489.0 drying

Paraffin oil

0.3 0.3 0.3 0.3 0.3 0.3

Component (g)

Premix 9 Premix 10 Premix 11 Premix 12 Premix 13

MnSO4.1 H2O

7.7 - 7.7  - -

(CH3COO) 2Mn. 4 H2O

- 11.0  - 11.1 -

(CH3COO) 2Mn anhydrous

- - - - 7.8

PP polypropylene

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 configured as follows:

T1 heating zone

T2 heating zone T3 heating zone T4 head

Temperature ºC

170 175 180 184-185

The average spindle speed was 30 rpm. The head opening was set to 0.3 mm. The bending machine was set at 60 ° C with a speed of 2.2 meters per minute. These procedure parameters were configured at the beginning of the test and were kept constant throughout

of all production using PMMA. Summary of the essays and the film produced in the table below:

Test

 CATALYST SUPPORT Torque Amps Observation

Smooth white-opaque film

MOVIE 3

MnSO4.1 H2O PMMA 60 Good salt distribution. Average thickness of 0.18-0.22 mm

MOVIE 4

MnSO4.1 H2O PMMA 60 Smooth white-opaque film. Good salt dispersion. Average thickness of 0.188.22 mm

FILM 5

(CH3COO) 2Mn  PMMA 60 Rough pink-translucent film. Good salt distribution. 0.25mm average thickness

FILM 6

(CH3COO) 2Mn  PMMA 60 Rough pink-translucent film. Good salt distribution. 0.25mm average thickness

FILM 7

(CH3COO) 2Mn. 4 H2O PMMA 55 Rough surface of beistranslucent film. Average thickness of 0.35 mm

FILM 8

(CH3COO) 2Mn. 4 H2O PMMA 55 Rough surface of beistranslucent film. Average thickness of 0.35 mm

The average production capacity was 2 kg / hour

fifteen

8

Example 2: Chemical characterization of the film produced

Chemical analyzes were carried out on film 4, film 6 and film 8 to assess the level of manganese present in the solid film. The analytical results confirmed that the theoretical / calculated amount of manganese added by weight in the premix is in the final solid prototype:

Movie

ppm of Mn (metal)

MOVIE 4

4545

FILM 6

4721

FILM 8

4838

PMMA alone (no catalyst added)

<0.005 (below detection limit)

Example 3: Oxidation Catalysis Study

10 The following reagents and solutions were prepared in deionized water.

Dissolution

 Reagent g / l

TO

PCB sodium percarbonate (2Na2CO3.3H2O2) + TAED tetracetylethylenediamine + 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

AND

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 homogeneous phase catalyst (manganese acetate or manganese sulfate) and with a solution containing PCB + TAED + corresponding format catalysts solid film (movie 4 or movie 6

or movie 8).

Protocol used: Saffron beaker test

20 Saffron dissolution (fresh, protected from light)

Deionized water

Temperature: 20ºC 25 Reaction studied over 30 minutes

Abs. UV / VIS at 430 nm to monitor the rate of oxidation in the substrate, by measuring the discoloration of saffron solution.

30 The results of experimental laboratory measurements of the absorbance residue after 30 minutes are summarized in the following table

TO

B C D AND F

Absorbance residue (%)

70 58 62 66 65 62

35 The reported data is the average of two experimental measurements / runs.

The results show that film 4, film 6 and film 8 are effective as oxidation catalysts (as opposed to without a catalyst), with film 8 providing the highest catalysis efficiency in saffron bleaching.

Example 4: Washing mother liquor analysis

The saffron solution from the previous oxidative study (example 3) was filtered to remove the solid catalyst, acidified and analyzed by means of atomic absorption to determine the presence of manganese to assess whether any metal (Mn) had been released from the film. solid to the aqueous solution. The results are summarized as follows:

TO

B C D AND F

ppm of Mn

0.042  0.775 0.573 0.057  0.050  0.074

Analytical data for the presence of Mn show that there is no significant release of Mn from the film

10 solid: the level found conforms to the Mn found in solution A which contained the traditional PCB / TAED bleaching system and the saffron substrate (saffron used as an oxidative substrate).

Example 5: Performance under consumption conditions.

15 Film 8 was used in a washing machine test to evaluate the catalytic activity in bleaching conventional stains. A test was performed under washing conditions relevant to the consumer comparing the cleaning performance provided by a laundry detergent of compact clothing only (Tandil Ultra Plus, dose at 68 g / wash, which contained a traditional bleaching system based on percarbonate and TAED) with the yield supplied by the same detergent plus the addition of the solid catalyst in the film format

20 (film 8, dosed at 5 g / wash).

The following test protocol was used.

Water hardness: 25ºF Temperature: 30ºC Program: Cotton cycle (difficult stains) Load: 3.5 kg of new cotton Washing machine: EU front load; 14.5 liters of washing Repeats: 4

Drying: TA, linen Ironing: Household iron Evaluation: Datacolour 650 spectrophotometer

25 The following results were achieved: These performance test results clearly show that the addition of solid catalyst in film format significantly increases and improves the performance / cleaning action results.

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

Cotton tea PES / cotton tea Red wine in cotton Coffee in cotton Currants in cotton Cranberry juice in cotton Peach juice in cotton Tea in cotton Tea in PES / cotton Spinach in cotton

Empa 167 Empa 168 WFK 10LI WFK 10K CFT CS-12 CFT CS-15 CFT CS-19 BC-01 BC-03 CFT CS-25 63.8 64.9 76.6 80.7 63.1 72.4 81.2 62.2 58.4 83.9 67.7 67.3 78.3 81.1 65.2 73.4 82.2 63.0 59.0 84.3

Example 6: Film production

5 Key equipment used:

• single-screw extruder press PL 2000 PLE 650 from Brabender coupled to Plasti-Corder from Brabender.

10 • T 300A Electronic bending machine - Brabender hot roller press. Used starting materials

Component

Tradename Provider Physical appearance

Catalyst (CH3COO) 2 Mn

Anhydrous Manganese Acetate Aldrich very fine pink powder, less than 50 micrometers

CAT 3657 Catalyst

Type Cyclam, Mn Clariant Very fine beige powder

EEA support ethylene ether acrylate (PE / EEA)

LOTRIL Arkema 3x3x2.5 mm granules, white

EVA support (PE / EVA)

OREVAC, ESCORENE Arkema, Exo Mobil 3x3x2.5 mm granules, white

Paraffin oil lubricant

Vaseline A. Sella Clear viscous oil

15 Phase 1: Preparation of starting materials

EEA was previously dried in an oven at 90 ° C for 2-4 hours.

PE / EVA was not previously dried. twenty

Phase 2: Premix

Several 500 g premixes were prepared. The ratio / quantity of raw materials was selected in order to have

Molar concentration parity of manganese in the final film prototypes (calculated manganese concentration 25 = 4800 ppm of Mn).

Component (g)

premix 20 premix 21 * premix 22 premix 23 premix 23 bis

(CH3COO) 2Mn anhydrous

7.6 - - 7.6 7.6

CAT 3657

- 7.0 - - -

EEA

492.1 184.0 - - -

EVE

- - 100 492.1 491.7

Paraffin oil

0.3 0.3 0.3 0.3 0.4

The previously measured plastic granules were inserted into a plastic PE bag. Paraffin oil was added by means of a pipette. The mixture was stirred manually until the oil was distributed homogeneously over the granules. The manganese catalyst was added to the bag and mixing resumed.

Phase 3: Extrusion

The three heating zones of the extruder were configured as follows:

T4 head

T3 heating zone T2 heating zone T1 heating zone

Temperature ºC

180 175 173 170

The average spindle speed was 30 rpm. The head opening was set to 0.3 mm. The bending machine was set at 60 ° C with a speed of 3.0 meters per minute.

Test

CATALYST SUPPORT Motor torque amps Observation

MOVIE 20

(CH3COO) 2Mn  EEA 14 Soft and smooth film, homogeneous catalyst dispersion.

MOVIE 21

CAT 3657 EEA 14 Good catalyst dispersion

FILM 22

(CH3COO) 2Mn  EVE 16 Good catalyst dispersion. Elastic transparent film

MOVIE 23

(CH3COO) 2Mn EVE 13 Good catalyst dispersion

The average production capacity was 2 kg / hour. The cleaning procedure was applied after each test / each film production.

Claims (8)

1. Container comprising a detergent formulation, the package including a first surrounding wall that is permeable to water and a second surrounding wall comprising a mixture of bleaching catalyst and a 5 support material, in which the second surrounding wall is in the form of a film having a thickness in the range of 0.1 mm to 1 mm, characterized in that the bleaching catalyst comprises from 0.001% to 10% of the second surrounding wall, the rest of the wall composition comprising a support matrix, in which the film is produced in an extrusion or casting technique. A container according to claim 1, wherein the bleaching catalyst comprises a transition metal compound based on one or more of manganese, copper, iron, silver, platinum, cobalt, nickel, titanium, vanadium, cerium, lanthanum. , zirconium, tungsten, molybdenum, ruthenium. 3. A container according to claim 2, wherein the bleaching catalyst comprises a transition metal compound based on manganese. 4. Container according to claim 3, wherein the bleaching catalyst comprises a hydrated / anhydrous manganese compound selected from the group comprising halide (chloride / bromide), sulfate, sulphide, carbonate, nitrate, oxide, acetate, lactate, acetyl acetone, cyclohexanebutyrate, phthalocyanine, gluconate, 20 bis (ethylcyclopentadienyl), bis (pentamethylcyclopentadienyl), polyol, sorbitol, iditol, mannitol, xylitol, arabintol, lactose, dulsitol, adonitol, erythritol, inositol, catechol. 5. Container according to claim 3, wherein the bleaching catalyst comprises: (1,8-diethyl-1,4,8,11-tetraazacyclotetradecane) manganese (II) chloride. 6. Container according to claim 3, wherein the bleaching catalyst comprises: manganese catalyst (III) with an organic tripodal ligand

A container according to claim 2, wherein the bleaching catalyst comprises: manganese (II) tetrahydrate acetate and / or manganese (II) monohydrate sulfate.

8. Packaging according to any one of the preceding claims, wherein the film has porosity.

A package according to any one of the preceding claims, wherein the film comprises a polymeric material selected from the group of poly (methyl methacrylate), polyurethanes; polyolefins / hydrocarbons, for example polypropylene, polyethylene, polystyrene, polybutadiene; polyamides; polyvinylchloride); polyesters, polyvinyl acetate; phenolic resins; copolymers, for example poly (methyl methacrylate) with n-butyl acrylate and styrene; modified natural / natural polymers, for example cellulose, rubber, latex, styrene rubber

Butadiene, butyl rubber, chlorinated / hydrochlorinated rubber, nitrile rubber, vulcanized rubber, siliconized rubber; polycarbonates; silicone resins; fluorinated resins, for example PTFE.

10.

 Container according to any one of claims 1 to 9, wherein the detergent formulation comprises at least one of surfactant (nonionic, anionic, cationic or amphoteric), adjuvant, bleaching agent, activator of the

bleaching, bleaching stabilizer, bleaching catalyst, enzyme, polymer, adjuvant, alkalizing agent, acidifying agent, anti-redeposition agent, silver protector, colorant, optical brightener, UV stabilizer, fabric softener, fragrance, stain repellent, wrinkle substance , antibacterial substance, color protector, color alteration inhibitor, vitamin, phyllosilicate, odor complexing substance, rinsing adjuvant, foam inhibitor, foaming agent, preservative or auxiliary component.

eleven.

 Use of a container according to claim 10 in an operation of dishwashing, washing of clothes and / or cleaning of hard surfaces and / or a sterilization / disinfection operation.