RU2511399C2 - Container - Google Patents

Abstract

FIELD: packing industry.

SUBSTANCE: invention relates to containers. It describes a container including detergent composition, first water-permeable guard wall, and second guard wall containing additional bleaching catalyst and base material containing a polymer material, and the second guard wall is made in the form of a film of 0.10-1.0 mm thickness, where bleaching catalyst comprises 0.001% to 10.00% of the second guard wall, and base material containing a polymer material comprises the rest of composition, and the film is made by extrusion or casting/ solvent casting. Application of container is described as well.

EFFECT: reduced amount of bleaching activation agent without deterioration of bleaching quality, reduced damage to an object.

12 cl, 6 ex

Description

The present invention relates to a container. Inorganic peroxygen compounds, especially hydrogen peroxide and solid peroxygen compounds that dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have been used as oxidizing agents for disinfection and bleaching for a long time. The oxidizing effect of these substances in dilute solutions is highly dependent on temperature; for example, in the case of H ₂ O ₂ or perborate in alkaline bleaching solutions, a sufficiently rapid bleaching of contaminated textiles is achieved only at temperatures above about 80 ° C. At lower temperatures, the oxidative effect of inorganic peroxygen compounds can be enhanced by the addition of components called bleaching activators, for which numerous proposals have been disclosed in the literature, mainly from the classes of N-acyl and O-acyl compounds, examples of which are polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycoluryls, especially tetraacetyl glycoluryl, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, d iketopiperazines, sulfurylamides and cyanurates, as well as carboxylic anhydrides, especially phthalic anhydride, carboxylic esters, especially sodium nonanoyloxybenzenesulfonate, sodium isononoyloxybenzenesulfonate and acylated sugar derivatives such as pentaacetyl glucose. By adding these substances, the whitening effect of aqueous peroxide solutions can be enhanced to such an extent that even at temperatures of about 60 ° C, essentially the same activity takes place as in the case of the peroxide solution at 95 ° C.

Given the interest in energy-saving methods of washing and bleaching, in recent years the use temperature has gained importance significantly below 60 ° C, in particular below 45 ° C, right down to the temperature of cold water 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 bleaching catalysts.

It has now been found that textiles, especially dyed textiles, fade after a series of washes in the presence of a bleaching catalyst. It is believed that some previously used catalysts not only catalyze the activity of the peroxygen compound, but also remain at least partially on the surfaces of the textiles to be bleached, and even after the completion of the cleaning operation. These transition metal salts can subsequently be oxidized and thus cause color damage and, in extreme cases, the risks of oxidative damage to textiles, since they are in direct contact with textiles. For example, the deposition of Mn (II) is easily oxidized to dioxide Mn (IV), which is a very strong oxidizing agent, especially with regard to readily oxidizable substances such as organic coloring compounds.

All of the known whitening catalysts have the disadvantage that they are brought into close contact with the surfaces of the workpieces and for this reason typically a part of the catalyst adheres to said surfaces or even penetrates into said surfaces. This leads to the risk of unwanted color changes and, in rare cases, there may even be holes / tears as a result of fiber damage.

According to a first aspect of the invention, there is provided a container containing a detergent composition comprising a primary (primary) enclosing wall that is water permeable and a secondary (additional) enclosing wall that contains an additive for the bleaching catalyst and a base material.

It has been found that the container of the present invention has a number of advantageous properties. The principal advantageous property is that the bleaching catalyst, especially its transition metal, if present (if used in a washing / bleaching operation), is not present on the item being washed or bleached. Thus, harmful damage to an item is greatly reduced.

Another advantage of the present invention (when used in a washing / bleaching operation) is the catalysis of the oxidizing effect and the bleaching action of an 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 that it allows to reduce the amount of peroxygen compound and / or bleaching activator (e.g., TAED) in the cleaning composition while maintaining the whitening characteristics, which thus makes it possible cost reduction.

Preferably, the whitening 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 whitening catalyst comprises a manganese-based transition metal compound.

The manganese bleaching catalyst may be selected from a wide range of manganese compounds. Suitable inorganic compounds (often salts) of manganese (e.g., Mn (II)) include hydrated / anhydrous halide (e.g., chloride / bromide), sulfate, sulfide, carbonate, nitrate, oxide. Additional examples of suitable manganese compounds (often salts) (e.g., Mn (II)) include hydrated / anhydrous acetate, lactate, acetylacetonate, cyclohexane butyrate, phthalocyanine, bis (ethylcyclopentadienyl), bis (pentamethylcyclopentadienyl).

Most preferably, the whitening catalyst comprises manganese (II) acetate tetrahydrate and / or manganese (II) sulfate monohydrate.

Alternatively, the whitening catalyst may include

manganese (II) chloride (1,8-diethyl-1,4,8,11-tetraazacyclotetradecane) [Mn-TACTD].

Alternatively, the whitening catalyst may include

Manganese (III) catalyst with an organic tripodal ligand.

Alternatively, the whitening catalyst may include

In general, the whitening catalyst is from 0.001% to 10.00%, preferably from 0.01% to 5.00%, more preferably from 0.15% to 2.5% of the second wall, the remainder of the composition includes a matrix basis.

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

The secondary wall is preferably in the form of a film. The preferred film thickness is in the range 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 manufacture of the secondary wall is preferably from 50 microns to 125 microns.

The matrix base of the secondary wall typically includes polymeric material. Suitable polymeric materials may be selected from the group of polyurethanes; polyolefins / hydrocarbons, for example polypropylene (PP), maleic anhydride-containing polypropylene, polypropylene mixed with polyethylene, polyethylene (PE) mixed with PE ethylene vinyl acetate (PE / VA), polyethylene-ethylene acrylate copolymer (PE / EEA), polystyrene, polybutadiene ; polyamides; polyvinyl chloride; polyesters, for example polymethyl methacrylate, polyvinyl acetate, ethylene vinyl acetate; phenolic resins; copolymers, for example polymethyl methacrylate with n-butyl acrylate and styrene; natural / modified natural polymers, for example cellulose, rubber, latex, styrene-butadiene rubber, butyl rubber, chlorinated / hydrochlorinated rubber, nitrile rubber, vulcanized rubber, silicone rubber; polycarbonates; silicone resins; fluorinated resins, e.g. PTFE.

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

The film may be made by any suitable method. Preferred methods include casting and extrusion. Additional processing may be used, such as hot bending roll processing.

Preferably, casting involves dissolving the base in a suitable solvent, followed by suspending / dispersing the solid catalyst as a fine powder in a mixture of solvent and base. This is preferably followed by deposition of the dispersion on the surface (for example, stainless steel or a semiconducting material) and evaporation of the solvent (at room temperature or at elevated temperature). Suitable solvents include: chlorinated organic solvents (e.g. chloroform), ketones (e.g. acetone or methyl ethyl ketone), dimethyl sulfoxide (DMSO), alcohols, aliphatic or aromatic hydrocarbons, glycol ethers or organic acids (e.g. acetic acid or formic acid), tetrahydrofuran (THF).

Preferably, extrusion and coextrusion involves passing a composition comprising a base and a catalyst through an extrusion machine or a pressing machine. The extrusion is preferably carried out at an elevated temperature, which can be influenced by heat or pressure applied by the extruder.

The extrusion conditions depend in part on the particular nature of the extrudable composition and on the type of machine used. Suitable extrusion operating temperatures are, for example, 90-260 ° C. A suitable screw operating speed during extrusion is, for example, 25-250 rpm (revolutions per minute), preferably 50-125 rpm. Suitable extrusion operating pressures are, for example, 30-250 bar. Suitable torsion forces for the extrusion process are in the range of 10-100 A. The extrudate is preferably in the form of a film, granules or strand or bands.

The primary wall is permeable.

By the term “water permeable”, the authors mean that the material allows water to pass through under the conditions in which the product is used. Preferably, the material has an air permeability of at least 1000 l / m ² / s at 100 Pa according to DIN EN ISO 9237. Furthermore, the network should not be so permeable that it could not be able to hold a granular composition that prevents the transfer of dye (for example, must not have a pore size of more than 150 microns).

Traditional materials used in the manufacture of tea bags or in the production of hygiene or diaper products may be suitable for the primary wall. Preferred materials include polymeric fibers, such as polyolefins (especially polyethylene and polypropylene), poly (haloolefins), poly (vinyl alcohol), polyesters such as ethylene vinyl acetate, polyamides, polyacrylic polymers, protein fibers and cellulose fibers (e.g. cotton, rayon and rayon).

It is convenient when the primary wall includes non-woven material. Methods for the production of nonwovens can be grouped into four main categories, leading to four main types of nonwoven products, namely related to textiles, related to paper, related to extrusion processing of polymers, and hybrid combinations.

Textile. Textile technologies include fiber stripping, carding and aerodynamic spinning into selectively oriented webs. Matter obtained by these systems is called non-woven dry canvas formation materials and they carry terms such as fiberized, combed and pneumo-laid materials. Textile-based nonwovens or fiber-mesh structures are produced using machinery designed to process textile fibers in a dry state. This category also includes structures formed using bundles of fibers or tow tow, and materials formed by staple fibers and stitching threads.

In general, processes based on textile technology provide the maximum variety of products, since most textile fibers and binder systems can be used.

Paper. Paper-based technologies include dry canvas and wet canvas (modified paper production) pulp systems designed to accept short synthetic fibers as well as wood pulp fibers. The materials obtained by these systems are called pulp of dry canvas formation and nonwoven materials of wet canvas formation. Paper-based nonwovens are manufactured using machinery designed to process short fibers suspended in a fluid.

Extrusion. Extrusions include systems for bonding twisted fibers (spunbond), melt blowing (meltblown) and porous films. The materials obtained by these systems are called, separately, non-woven materials from bonded twisted fibers, from meltblown fibers and from textured or hole-woven films, or generally non-woven materials of the canvas forming polymers. Extrusion-based nonwovens are produced using machinery combined with polymer extrusion. In polymer canvas systems, fibrous structures are simultaneously formed and processed.

Hybrids. Hybrids include fiber / sheet combining systems, combining systems, and composite systems. Combination systems utilize layer-by-layer technology or the formation of at least one main non-woven network or densification technology to join two or more substrates of matter. Combination systems utilize at least one core nonwoven network forming element to reinforce at least one substrate of matter. Composite systems integrate two or more core nonwoven fabrication technologies to form network structures. Hybrid processes combine technological advantages for specific applications.

The primary wall of the container may itself act as an additional means of modifying water, for example, having the ability to trap unwanted particles in water and / or release useful particles. Thus, the wall material could be a textile material with ion-collecting and / or ion-releasing properties, for example, the material described above, and such a product can be created following the ideas set forth in WO 02/18533, which describes suitable materials. Alternatively and more preferably, the wall may be modified to provide a dye / dirt collection function. Such a function can be provided by the physical / chemical incorporation of a dye / dirt trapping agent into the wall material / on the surface of the wall material. A preferred example of such a material is a quaternary ammonium compound.

The product may include an indication means which serves to indicate the degree to which the dye transfer preventing function is performed. A preferred example of such an indication means is a color change of the product. This discoloration may occur on the sachet and / or on the body contained within the sachet. A preferred way to achieve a color change is to use a color-capturing compound that is attached to the sachet and / or to the body inside the sachet.

The container can be molded horizontally or vertically from two or more rolls of material that are joined together to form the walls of the sachet.

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

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

Filling an open container can be carried out using various volumetric dispensers, such as a metering auger or measuring cup. The typical dosing accuracy required at a constant density of the product is preferably +/- 1% by weight, minimum +/- 5% by weight.

Filling devices are supplied by the companies mentioned above as part of the machine kit.

Feedback control mechanisms can be installed that affect the speed of the metering screw or the volume of the measuring cup to maintain high metering accuracy when the density of the product changes.

The strength of the sealing compound is important because the container must not open during a washing cycle or other type of cleaning or water softening operation, otherwise any water-insoluble ingredients could contaminate the washed item.

The strength of the sealing compound is at least 5 N / 20 mm, preferably at least 10 N / 20 mm and most preferably at least 15 N / 20 mm when measured according to the test method of ISO R-527 before the sealed bag is washed. The strength of any sealing compound is highly dependent on the materials used and the conditions of the sealing method, for example, to create good quality sealing compounds, the following conditions apply:

- thermal sealing, preferably using flat sealing strips, 5 mm per 100 mm, made of Teflon-coated stainless steel, typically 1 s at 150 ° C +/- 1 ° C with a true sealing pressure of 20 kg / cm ² , which is achieved on a bench apparatus thermal sealing Corr and on thermal sealing devices of most of the previously mentioned machine suppliers;

- ultrasonic sealing, preferably using grooved sealing strips, 5 mm by 150 mm, a pattern with diagonal grooves at an angle of 45 degrees to the side of the sealing joint, a pitch of 15 mm and a width of 5 mm, with a nominal coverage area of 33%, from 0, 1 to 0.3 s at 20 kHz and an oscillation amplitude of 70 microns, a true sealing pressure of 10 to 60 kg / cm ² , a typical absorbed power of 300 to 1200 W, a typical absorbed energy of 30 to 180 W, using ultrasonic sealing equipment, produced th companies like Mecasonic or Branson or Hermann or Sonic or Dukane or Sonobond;

- adhesive sealing, for example by applying 10 g / m ^{2 of} hot molten glue, such as Prodas 1400, PP, from Beardow Adams. Polyethylene (PE) or polyamides or polyurethanes or UV curable acrylic adhesives or epoxies can also be used.

Thus, in general, the method may include:

a) forming an open container of two or more networks;

b) filling the open container with a composition that prevents the transfer of dye; and

c) sealing the container.

The container is preferably flat, that is, with one dimension, the thickness of the container is at least 5 times smaller, preferably at least 10 times smaller, ideally at least 30 times smaller than the other two dimensions, width and length of the bag (which are the same, corresponding to the diameter of the bag if it is round in shape). Preferred thicknesses are in the range of 10-20 mm, for example 10 mm, 15 mm or 20 mm.

Preferably, the container covers the surface (i.e. the product of width and length (when the bag is rectangular)) from 80 to 300 cm ² , ideally from 100 to 200 cm ² . 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 container may include a flexible body of at least 10 mm in one dimension and 10 mm in the other direction.

Preferably, the body is such that there is no measurement of more than 20 mm. Ideally, this measurement is 10-20 mm, for example 12 mm, 15 mm or 18 mm.

The body can be given a configuration that provides a function of increasing the volume, for example, due to its elasticity, so that it expands with the removal of compressive forces. It was shown that the inclusion of such a volume-increasing element (when used in an automatic washing operation) reduces the frequency of cases when the device is stuck in the seal of the loading hole, the device sticks to the sealing of the loading hole, facilitates the detection of the device after the washing operation and can facilitate the flow of water through the device.

This in turn has a positive effect from an environmental point of view by reducing the amount of packaging material required for each package. When a large number of packages are produced and sold, this also has a positive effect on transportation costs.

In a preferred embodiment, the body includes foam, which may include any suitable material, such as polypropylene, polyester and / or PE / EVA. The body may include a number of separate elements, each formed from a different material from the others.

Preferably, the detergent composition is a composition for washing dishes, for washing, cleaning hard surfaces and / or for disinfection. In general, the composition is intended for use in a suitable washing operation in a washing machine or in another washing vessel, such as a sink, bucket, and so on. Alternatively, the composition may be used in an additive (for example, in additives that complement the detergent product used in the washing operation) or in addition to a product that contains bleach.

The detergent composition may include a homogeneous product, for example a uniform powder / liquid, or, alternatively, the detergent composition may have many individual phases, for example, such as a multiphase tablet.

The detergent composition typically includes at least one of the components: a surfactant (anionic, nonionic, cationic or amphoteric), detergent component, bleach, bleach activator, bleach stabilizer, bleach catalyst, enzyme, polymer, auxiliary detergent component, alkalizing agent, acidifying agent, anti-precipitation agent, silver protection agent, dye, optical brightener, UV stabilizer, fabric softener, flavoring, dirt repellent, pro anti-skimmer, antibacterial agent, coloring agent, stain inhibitor, vitamin, phyllosilicate, odor complexing agent, rinse aid, foaming inhibitor, foaming agent, preservative or adjuvant.

According to a second aspect of the invention, there is provided the use of a container according to a first aspect of the invention in a dishwashing operation, washing and / or cleaning hard surfaces and / or a sanitization / disinfection operation.

The container may be placed with the item to be washed in an automatic washer.

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

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

Example 1: Obtaining a film

Main equipment used:

- Single screw extruder Brabender PL 2000 PLE 650, attached to the Brabender Plasti-Corder.

- Bending machine Brabender T 300A Electronic-Roller Hot

Press

Used raw materials

Ingredient Commercial name Provider Appearance Catalyst (CH ₃ COO) ₂ Mn 4H ₂ O Manganese Acetate Tetrahydrate Kemira Pink fine powder 50-125 microns Catalyst (CH ₃ COO) ₂ Mn Anhydrous Manganese Acetate Alldrich Pink very fine powder Catalyst MnSO ₄ · 1H ₂ O Manganese Sulphate Monohydrate, 99% Fluka Pink very fine powder 50-125 microns Polymethyl Methacry Base
Lats PMMA PMMA VM 100ALTUGLAS Arkema Granules 3 × 3 × 2.5 mm, shiny, transparent The basis
Polypropylene Copolymer Copolymer PP401-CA20 BP Granules 3 × 3 × 2.5 mm, white / opaque Base Polypropylene + Maleic Anhydride Fusabond PP MD-511D Du pont Granules 3 × 3 × 2.5 mm, white Lubricant Paraffin oil Petroleum jelly A. sella Viscous oil, clear

Phase 1: Raw Material Preparation

Kemira manganese acetate tetrahydrate was pulverized using a laboratory grinder. After sieving, a product with a particle size distribution of 50-125 μm was selected to obtain a film.

Fluka manganese sulfate monohydrate was also sieved, a product with a particle size distribution of 50-125 μm was selected to obtain a film.

The PMMA VM 100 was heated in an oven for 2 hours at 80 ° C to remove traces of water.

PP polypropylene was used as received from the supplier, without drying.

Phase 2: Getting Premixes

Several premixes weighing 500 g were prepared. The ratio / amount of raw materials was chosen to have the same molar concentration of manganese in the final film prototypes (calculated manganese concentration = 4800 ppm Mn).

Ingredient (g) Premix 3 Premix 4 Premix 5 Premix 6 Premix 7 Premix 8 (CH ₃ COO) ₂ Mn - - 7.6 7.6 - - MnSO ₄ .1 H ₂ O 7.3 7.6 - - - - (CH ₃ COO) ₂ Mn. 4H ₂ O - - - - 11.0 11.0 PMMA VM 100 492.4 dried 492.4 Dried 492.4 dried 492.4 dried 492.4 dried 492.4 dried Paraffin oil 0.3 0.3 0.3 0.3 0.3 0.3

Ingredient (g) Premix 9 Premix 10 Premix 11 Premix 12 Premix 13 MnSO ₄ .1 H ₂ O 7.7 - 7.7 - - (CH ₃ COO) ₂ Mn. 4H ₂ O - 11.0 - 11.1 - (CH ₃ COO) ₂ Mn Anhydrous - - - - 7.8 PP Polypropylene PP401CA20492.4 PP401CA20489.0 Fusabond492.5 Fusabond489.0 Fusabond492.2 Paraffin oil 0.3 0.3 0.3 0.3 0.3

Phase 3: Extrusion

The temperatures of the three heating zones of the extruder were set as follows:

Heating zone T1 Heating zone T2 Heating zone T3 T4 head Temperature ° C 170 175 180 184-185

The average screw speed was 30 rpm. The hole in the head was set equal to 0.3 mm.

For a bending machine, a temperature of 60 ° C. was set at a speed of 2.2 meters per minute.

These process parameters were set at the beginning of the test and maintained constant during production using PMMA. The table below summarizes the data for the tests and the resulting films:

Test Catalyst The basis Torque Amps Observational data Film 3 MnSO ₄ · 1H ₂ O PMMA 60 Opaque white smooth film Good salt distribution. Average thickness 0.18-0.22 mm Film 4 MnSO ₄ · 1H ₂ O PMMA 60 Opaque white smooth film. Good dispersion of salt. Average thickness 0.18-0.22 mm Film 5 (CH ₃ COO) ₂ Mn PMMA 60 Translucent pink coarse film. Good salt distribution. Average thickness 0.25 mm Film 6 (CH ₃ COO) ₂ Mn PMMA 60 Translucent pink coarse film. Good salt distribution. Average thickness 0.25 mm Film 7 (CH ₃ COO) ₂ Mn 4H ₂ O PMMA 55 Translucent beige film. Rough surface. Average thickness 0.35 mm Film 8 (CH ₃ COO) ₂ Mn 4H ₂ O PMMA 55 Translucent beige film. Rough surface. Average thickness 0.35 mm

The average production capacity was 2 kg / h.

Example 2: Chemical characterization of the obtained film

Chemical analyzes were performed for film 4, film 6 and film 8 to evaluate the content of manganese present in the solid film. Analytical results found for the final - solid - prototype - confirmed the theoretical / calculated amount of added manganese by weight in the premix:

Film Mn (metal), parts per million Film 4 4545 Film 6 4721 Film 8 4838 PMMA alone (no catalyst added) <0.005 (below detection limit)

Example 3: Study of the oxidation catalyst

The following reagents and solutions were prepared in deionized water.

Solution Reagent g / l A PCB Sodium Percarbonate (2Na ₂ CO ₃ · 3H ₂ O ₂ ) + TAED Tetraacetylethylenediamine + Saffron 1,380,300,035 B PCB + TAED + (CH ₃ COO) ₂ Mn × 4H ₂ O + saffron 0.005 C PCB + TAED + MnSO ₄ · 1H ₂ O + 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 a homogeneous phase (manganese acetate or manganese sulfate), and with a solution containing PCB + TAED + corresponding catalysts in the format of a solid film (film 4, film 6 or film 8).

Protocol used: Test using saffron in a glass

Saffron solution (fresh, protected from light)

Deionized water

Temperature: 20 ° C

The reaction was investigated for 30 minutes.

In the UV / visible region at 430 nm, absorbance was measured to track the oxidation rate of the substrate by measuring the bleaching of the saffron solution.

The results of laboratory experimental measurements of residual absorption after 30 minutes are summarized in the following table

A B C D E F Residual Absorption (%) 70 58 62 66 65 62

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

The results show that film 4, film 6 and film 8 are effective as oxidation catalysts (relative to the absence of catalyst), and film 8 gives the highest catalytic efficiency of saffron bleaching.

Example 4: Wash Fluid Analysis

Saffron solutions from the above oxidation study (Example 3) were filtered to remove the solid catalyst, acidified and analyzed by atomic absorption to evaluate the presence of manganese in the event that any metal (Mn) was released from the solid film into the aqueous solution. The results are summarized as follows:

A B C D E F Mn ppm 0,042 0.775 0.573 0,057 0,050 0,074

Analytical data on the presence of Mn show that there is no significant release of Mn from the solid film:

the content found corresponds to Mn found in solution A containing the traditional PCB / TAED bleaching system and saffron substrate (saffron was used as an oxidation substrate).

Example 5: Washing Performance

Film 8 was used for a washer test to evaluate the catalytic activity of whitening standard contaminants. The test under the washing conditions appropriate to the consumer used was carried out by comparing the washing performance shown by the compact detergent for washing alone (Tandil Ultra Plus, dosage 68 g / sink containing a traditional percarbonate bleach system and TAED) with the performance shown the same detergent when adding a solid catalyst in a film format when washing (film 8, dosage 5 g / wash).

The following test protocol was used.

Water hardness: 25 ° F

Temperature: 30 ° C

Program: Cycle - Cotton (Heavy Pollution)

Loading: 3.5 kg of new cotton

Washer: EU production, front loading; 14.5 liter sink

Repeats: 4

Drying: room temperature, linen

Ironing: household iron

Rating: Datacolour 650 Spectrophotometer

The following results were obtained:

Detergent Ultra Plus 68 g Detergent Ultra Plus + solid whitening catalyst (5g) Stains 68 g / sink PMMA film + Mn acetate Tea on cotton Empa 167 63.8 67.7 PES Tea / Cotton Empa 168 64.9 67.3 Red wine on cotton WFK 10LI 76.6 78.3 Coffee on cotton WFK 10K 80.7 81.1 Currants 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 PES Tea / Cotton BC-03 58.4 59.0 Spinach on cotton CFT CS-25 83.9 84.3

The results of this performance test clearly show that the addition of a solid catalyst in film format significantly increases and improves work results / cleaning effect.

Example 6: Film Production

Main equipment used:

Single screw extruder Brabender PL 2000 PLE 650 attached to a Brabender Plasri-Corder.

- Bending machine Brabender T 300A Electronic-Roller Hot Press.

Used raw materials

Ingredient Commercial name Provider Appearance Catalyst (CH ₃ COO) ₂ Mn Anhydrous Manganese Acetate Alldrich Pink very fine powder, less than 50 microns Catalyst CAT 3657 Cyclam type, Mn Clariant Extremely fine beige powder Base EEA Ethylene Ethyl Acrylate (PE / EEA) Lotril Arkema Granules 3 × 3 × 2.5 mm, white Foundation EVA (PE / EVA) OREVAC, ESCORENE Arkema, Exo Mobil Granules 3 × 3 × 2.5 mm, white Lubricant Paraffin oil Petroleum jelly A.Sella Viscous oil, clear

Phase 1: Raw Material Preparation

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

PE / EVA was not pre-dried.

Phase 2: Premixes

Several premixes weighing 500 g were prepared. The ratio / amount of raw materials was chosen to have the same molar concentration of manganese in the final film prototypes (calculated manganese concentration = 4800 ppm Mn).

Ingredient (g) Premix 20 Premix 21 * Premix 22 Premix 23 Premix 23bis (CH ₃ COO) ₂ Mn Anhydrous 7.6 - - 7.6 7.6 CAT 3657 - 7.0 - - - EEA 492.1 184.0 - - - EVA - - one hundred 492.1 491.7 Paraffin oil 0.3 0.3 0.3 0.3 0.4

Pre-measured plastic granules were placed in a plastic PE bag. Petroleum jelly was added using a pipette. The mixture was stirred manually until a homogeneous distribution of the oil on the granules. The manganese catalyst was added to the bag and mixing was resumed.

Phase 3: Extrusion

The temperatures of the three heating zones of the extruder were set as follows:

T4 head Heating zone T3 Heating zone T2 Heating zone T1 Temperature ° C 180 175 173 170

The average screw speed was 30 rpm. The hole in the head was set equal to 0.3 mm.

For a bending machine, a temperature of 60 ° C. was set at a speed of 3.0 meters per minute.

Test Catalyst The basis Torque A Observational data Film 20 (CH ₃ COO) ₂ Mn EEA fourteen Smooth and soft film, homogeneous dispersion of the catalyst. Film 21 CAT 3657 EEA fourteen Good catalyst dispersion Film 22 (CH ₃ COO) ₂ Mn EVA 16 Good Catalyst Dispersion / Elastic Transparent Film Film 23 (CH ₃ COO) ₂ Mn EVA 13 Good catalyst dispersion

The average production capacity was 2 kg / h. The purification procedure was applied after each test / each film preparation.

Claims (12)

1. A container containing a detergent composition comprising a first enclosing wall that is water permeable and a second enclosing wall that contains an addition of a bleaching catalyst and a base material comprising a polymeric material, the second enclosing wall being made in the form of a film having a thickness in the range of 0.10 mm to 1.0 mm, the whitening catalyst being 0.001% to 10.00% of the second enclosing wall, the remainder of the composition comprising a base material comprising a polymer terial, the film being made by extrusion or casting / casting using a solvent. 2. The container according to claim 1, in which the second enclosing wall has the form of a film. 3. The container of claim 2, wherein the whitening catalyst comprises a manganese-based transition metal compound. 4. The container according to claim 3, in which the whitening catalyst includes a hydrated / anhydrous manganese compound selected from the group consisting of halide (chloride / bromide), sulfate, sulfide, carbonate, nitrate, oxide, acetate, lactate, acetylacetonate, cyclohexane butyrate, phthalocyanine , gluconate, bis (ethylcyclopentadienyl), bis (pentamethylcyclopentadienyl), polyol, sorbitol, idit, mannitol, xylitol, arabitol, lactose, dulcite, adonite, erythritol, inositol, catechol. 5. The container according to claim 3, in which the whitening catalyst includes

manganese (II) chloride (1,8-diethyl-1,4,8,11-tetraazacyclotetradecane) 6. The container according to claim 3, in which the whitening catalyst includes

manganese (III) catalyst. 7. The container according to claim 3, in which the whitening catalyst includes manganese (II) acetate tetrahydrate and / or manganese (II) sulfate monohydrate. 8. The container according to claim 2, in which the film has porosity. 9. The container according to claim 2, in which the film includes a polymeric material selected from the group of polymethyl methacrylate, polyurethanes; polyolefins / hydrocarbons, for example polypropylene, polyethylene, polystyrene, polybutadiene; polyamides; polyvinyl chloride; polyesters, polyvinyl acetate; phenolic resins; copolymers, for example polymethyl methacrylate with n-butyl acrylate and styrene; natural / modified natural polymers, for example cellulose, rubber, latex, styrene-butadiene rubber, butyl rubber, chlorinated / hydrochlorinated rubber, nitrile rubber, vulcanized rubber, silicone rubber; polycarbonates; silicone resins; fluorinated resins, e.g. PTFE. 10. The container according to claim 2, in which the film is obtained by a technology that uses casting / casting using a solvent. 11. The container according to claim 2, in which the detergent composition contains at least one of the components: a surfactant (nonionic, anionic, cationic or amphoteric), a washing component, a bleach, a bleach activator, a bleach stabilizer, a bleaching catalyst, an enzyme, polymer, auxiliary detergent component, alkalizing agent, acidifying agent, anti-redeposition agent, silver protection agent, dye, optical brightener, UV stabilizer, fabric softener, flavor, grease eottalkivatel, protivosminatel, antibacterial substance, color protection agent, an inhibitor of discoloration, vitamin, phyllosilicate substance complexes odor, rinse aid, foam inhibitor, foaming agent, a conservative or adjuvant. 12. The use of the container according to claim 11 for washing dishes, washing and / or cleaning hard surfaces and / or sanitizing / disinfection.