Manufacturing process for detergent or cleaning agent portion units

Abstract

A method for producing a washing or cleaning agent portion unit, comprising the steps: a) providing a mould with at least one mould cavity; b) feeding a first water-soluble film to the mold cavity; c) molding the first water-soluble film into the mold cavity to form a receiving chamber; d) at least partially filling the receiving chamber by d1) introducing at least one first gelling agent-containing, liquid washing or cleaning-active composition to form a first washing or cleaning-active phase; d2) introducing at least one second liquid washing or cleaning-active composition, different from the first composition, onto the upper side of the first washing or cleaning-active phase in the receiving chamber to form a second washing or cleaning-active phase completely covering the upper side of the first washing or cleaning-active phase; d3) introducing at least one third solid washing or cleaning-active composition, different from the first and second compositions, onto the upper side of the second washing or cleaning-active phase in the receiving chamber to form a third washing or cleaning-active phase completely covering the upper side of the second washing or cleaning-active phase; e) feeding a second water-soluble film; f) Sealing the at least partially filled receiving chamber with the second water-soluble film to form a washing or cleaning agent portion unit comprising a water-soluble wrapping.

Description

The present invention relates to a process for the production of detergent or cleaning agent portion units which are coated with water-soluble film. In particular, the application relates to a multistage production process for producing multiphase washing or cleaning agent portion units.The confection and supply forms of washing or cleaning agents are subject to continuously changing requirements. A focus has been on the convenient metering of washing or cleaning agents by the consumer for some time and the simplification of the working steps required for carrying out a washing or cleaning process. A solution offers pre-sized washing or cleaning agents, for example foil bags with one or more receiving chambers for solid or liquid compositions.In order to be commercially successful, a detergent or cleaning agent portioning unit must meet the consumer interests in the best possible manner. An essential means for communicating product quality and product promising is the optic and haptics of the portion unit. This applies in particular to water-soluble film bags, the soluble films of which are generally transparent and expose the view to the solid or liquid washing or cleaning agents present. In particular in the case of multi-phase detergents or cleaners, the communication of product quality and product compatibility is supported by clear phase boundaries within a portion unit and a structural design and visual impression of the same portion units which are substantially identical. The film bags preferably also have a firm grip and a low mechanical deformability, i.e. are not slack.The production of detergent or cleaning agent portion units with water-soluble film packaging is generally carried out by means of a sequential process, during which the water-soluble film and the constituents of the detergent are combined with one another to form a portion unit.International patent application WO 2002 / 16205 A1 describes methods for producing detergents and cleaning agents in the form of water-soluble film bags filled with impact.The granted European patent EP 2 944 578 B1 describes a method for wrapping laundry or cleaning agent tablets by means of a shrunk-on water-soluble film.The object of the present application was to provide an efficient method for producing multi-phase detergent or cleaning agent portion units, the process products of which are distinguished by appealing visual appearance and haptics.To achieve this object, a method for producing a detergent or cleaning agent portion unit is provided, comprising the steps: a) providing a mold having at least one mold cavity; b) supplying a first water-soluble film to the mold cavity; c) forming the first water-soluble film into the mold cavity to form a receiving chamber; d) at least partially filling the receiving chamberd1) introducing at least one first gelling agent-containing, liquid washing- or cleaning-active composition, with formation of a first washing- or cleaning-active phase;d2) introducing at least one second liquid washing- or cleaning-active composition different from the first composition onto the top side of the first washing- or cleaning-active phase in the receiving chamber, forming a second washing- or cleaning-active phase completely covering the top side of the first washing- or cleaning-active phase;d3) introducing at least one third solid detergent-active composition different from the first and the second composition onto the top side of the second detergent-active phase in the receiving chamber, forming a third detergent-active phase completely covering the top side of the second detergent-active phase;e) feeding a second water-soluble film; f) sealing the at least partially filled receiving chamber with the second water-soluble film to form a washing or cleaning agent portion unit comprising a water-soluble casing.The method described in its details below serves for the production of washing or cleaning agent portion units. Portioned detergents or cleaning agents are referred to as detergent or cleaning agent portioning units. These portions are generally sufficient for carrying out a manual or mechanical, preferably mechanical, washing or cleaning process. Preferred washing or cleaning agent portion units have a weight of 10 to 35 g, preferably 12 to 28 g and in particular 14 to 22 g.In a first step of the method, a mold having at least one mold cavity is provided. In a preferred method variant, a deep-drawing die with a cavity as a mold cavity is provided as the mold.The deep-drawing die itself can be designed in the form of a horizontally revolving belt or in the form of a rotating drum. The use of a deep-drawing die with at least one cavity based on a horizontally revolving conveyor belt is preferred.In step b) of the method, a first water-soluble film is supplied to the mold cavity. In a preferred embodiment, a thermoplastic water-soluble film is supplied in step b).The water-soluble film can be supplied continuously or discontinuously. To increase process efficiency, a continuous procedure is preferred. In a particularly preferred embodiment of the process, the transport of the first water-soluble film in step b) is continuous. From the standpoints of process economy and process safety, it is preferred to feed the first water-soluble film in step b) at a rate of 0.04 m / s, preferably above 0.08 m / s.The water-soluble film may comprise one or more structurally different water-soluble polymer(s). Suitable water-soluble polymer(s) for the first water-soluble film are, in particular, polymers from the group of (optionally acetalized) polyvinyl alcohols (PVAL) and copolymers thereof.Water-soluble films for producing the portion unit are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which is preferably in the range from 10,000 to 1,000,000 gmol-1, preferably from 20,000 to 500,000 gmol-1, particularly preferably from 30,000 to 100,000 gmol-1 and in particular from 40,000 to 80,000 gmol-1. Preferred water-soluble films comprise at least 30 wt %, preferably at least 50 wt % and in particular at least 70 wt % polyvinyl alcohol or polyvinyl alcohol copolymers.The preparation of the polyvinyl alcohol and polyvinyl alcohol copolymers typically involves the hydrolysis of intermediate polyvinyl acetate. Preferred polyvinyl alcohols and polyvinyl alcohol copolymers have a degree of hydrolysis of 70 to 100 mol %, preferably 80 to 90 mol %, particularly preferably 81 to 89 mol % and in particular 82 to 88 mol %.Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Particularly preferably, such polyvinyl alcohol copolymers contain, in addition to vinyl alcohol, sulfonic acids such as 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), acrylic acid, methacrylic acid, acrylic esters, methacrylic esters or mixtures thereof; among the esters, C 1-4- alkyl esters or hydroxyalkyl esters are preferred. Other suitable monomers are ethylenically unsaturated dicarboxylic acids, for example itaconic acid, maleic acid, fumaric acid and mixtures thereof.Suitable water-soluble films for use in the portion units according to the invention are films which are sold by the company MonoSol LLC, for example under the name M8630, M8720, M8310, C8400 or M8900. Other suitable films include Solublon® PT, Solublon® GA, Solublon® KC, or Solublon® KL films from Aicello Chemical Europe GmbH, or Kuraray's VF-HP films, as well as the Hi-Selon Series from Mitsubishi Chemical Corporation.The first water-soluble film supplied in step b) preferably has a thickness of from 60 to 2000 μm, preferably from 60 to 800 μm and in particular from 60 to 200 μm.The water-soluble film can be shaped into the mold cavity in step c) in a manner known to the skilled person. Both cold and thermoforming processes can be used. The film can furthermore be formed into the mould cavity under the action of a force, for example its weight force, the force of a punch or a vacuum. On the basis of the advantageous process results achieved, it is preferred if the first water-soluble film is formed in in step c) under the action of heat. Reproducibly good results could be achieved in particular by heating the first film and then vacuum forming it.The molding is preferably preceded by an optional pretreatment of the film by heat and / or solvent. The water-soluble film can subsequently be shaped into the cavity, as described, by means of a tool, by the action of a vacuum, by the action of compressed air and / or by the action of its own weight.From the series of deep-drawing processes, preference is given to processes in which the water-soluble film is transported above the cavities of a deep-drawing die and is formed there into the depressions of the die by the action of compressed air on the upper side of the film or by the action of a vacuum on the lower side of the film, particularly preferably with simultaneous action of compressed air and vacuum. Particularly advantageous methods are distinguished in that the film is pretreated by exposure to heat and / or solvents before molding.The action of heat and / or solvents on the water-soluble film serves to facilitate plastic deformation thereof. The heating of the film can be effected, for example, by heat radiation, hot air or, particularly preferably, by direct contact with a heating plate. The duration of the heat treatment and the temperature of the heat radiation, hot air or heating plate surface used are naturally dependent on the type of enveloping material used. For water-soluble or water-dispersible materials such as PVA-containing polymers or copolymers, a temperature of between 90 and 130° C., in particular between 105 and 115° C., is preferred. The duration of the heat treatment, in particular the contact time when using a heating plate, is preferably between 0.1 and 7 seconds, particularly preferably between 0.2 and 6 seconds and in particular between 0.3 and 4 seconds. Contact times below one second, in particular in the range from 400 to 900 milliseconds, preferably between 500 and 800 milliseconds, have proven to be particularly advantageous for polyvinyl alcohol materials.For reasons of process efficiency, the method according to the invention is designed in such a way that not only a single detergent portion unit but also a plurality of detergent portion units are produced in parallel in one process pass. In step c), the first water-soluble film is preferably used to form a sheet material having at least 14, preferably at least 20, receptacles.In this sheet material, the receiving chambers formed are preferably arranged in rows. With regard to the subsequent filling, the accommodation chambers formed in step c) are arranged in rows which are arranged orthogonally to the transport direction of the water-soluble film.In an alternative embodiment, in step c) a sheet material is formed in which the receiving chambers are arranged in rows which run orthogonally to the transport direction of the water-soluble film and are offset from one another in each case by one third of the width of a receiving container, preferably by half of the width of a receiving container.The receiving chambers are preferably arranged in the sheet material in such a way that each receiving container is adjacent to at least one intermediate region which is in turn surrounded by three receiving chambers.The production of the washing or cleaning agent portion units by filling a shaped water-soluble film enables the production of a wide variety of three-dimensional shapes and geometries. The production of the washing or cleaning agent portion units by filling a shaped water-soluble film also makes it possible to produce portion units having two or more phases, i.e. two or more regions whose filling differs from one another. The phases are preferably optically distinguishable from each other.In a preferred alternative method, the receiving chamber formed in step c) has at least one, preferably two, three or four depressions in its base region. The formation of these depressions makes it possible to provide washing or cleaning agent portion units with differentiable optics. If the depressions are filled with compositions different from the remaining volume of the receiving chamber, the formation of the depressions additionally allows the production of multi-phase detergent or cleaning agent portion units.In a preferred process variant, the first composition introduced in step d1) is introduced into the depression(s) located in the base region of the receiving chamber. It is preferred in particular if the receiving chamber formed in step c) has two, preferably three or four, depressions in its base region and the first composition is introduced into these depressions in step d1).Particularly preferred are methods in which the receiving chamber formed in step c) has two, preferably three or four, depressions in its base region and the first composition is introduced into these depressions in step d 1), wherein the first composition in one of the depressions differs from at least one first composition in a further depression.Because of their optics and the manifold possibilities for separating mutually incompatible ingredients, process variants are very particularly preferred in which the receiving chamber formed in step c) has three or four depressions in its base region and the first composition is introduced into these depressions in step d 1), wherein the first composition in each of the depressions differs from the first composition in each further depression.The first composition introduced in step d1) preferably has a liquefaction point at temperatures above 80° C. (1013 mbar), particularly preferably above 100° C. (1013 mbar) and in particular above 115° C. (1013 mbar). This high liquefaction point makes it possible, under the ambient temperatures customary in the industrial production of detergent or cleaning agent portion units, to meter the first composition in liquid with simultaneous rapid solidification of the first composition in the receiving chamber.The first composition introduced in step d1) preferably comprises, based on its total weight, a) 4 to 40% by weight of gelling agent; b) 0.1 to 40% by weight of active substance which is active on washing or cleaning; c) 30 to 90% by weight of organic solvent.The rheological properties of this preferred first composition are influenced, among other constituents, in particular by the gel former present. In preferred first compositions, the proportion by weight of the gel former in the total weight is 6 to 30% by weight, preferably 7 to 24% by weight and in particular 8 to 22% by weight.Preferred gelling agents are selected from the group of polymeric gelling agents, preferably from the group of optionally acetalized polyvinyl alcohol, gelatin and xanthan or mixtures thereof. Very particular preference is given to the use of optionally acetalized polyvinyl alcohol.Preferred gelling agents are based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which is in the range from 10,000 to 1,000,000 gmol -1, preferably from 20,000 to 500,000 gmol -1, particularly preferably from 30,000 to 100,000 gmol -1 and in particular from 40,000 to 80,000 gmol -1.The preparation of the polyvinyl alcohol and polyvinyl alcohol copolymers typically involves the hydrolysis of intermediate polyvinyl acetate. Preferred polyvinyl alcohols and polyvinyl alcohol copolymers have a degree of hydrolysis of 70 to 100 mol %, preferably 80 to 90 mol %, particularly preferably 81 to 89 mol % and in particular 82 to 88 mol %.Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Particularly preferably, such polyvinyl alcohol copolymers contain, in addition to vinyl alcohol, sulfonic acids such as 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), acrylic acid, methacrylic acid, acrylic esters, methacrylic esters or mixtures thereof; among the esters, C 1-4- alkyl esters or hydroxyalkyl esters are preferred. Other suitable monomers are ethylenically unsaturated dicarboxylic acids, for example itaconic acid, maleic acid, fumaric acid and mixtures thereof.The gelling agent is preferably selected from the group of hydrolyzed polyvinyl alcohol homopolymers and polyvinyl alcohol copolymers having a molar mass of 30,000 to 60,000 g / mol.As a second component, the preparation preferably used as the first composition contains active washing- or cleaning-active ingredient. The proportion by weight of the active washing- or cleaning-active ingredient relative to the total weight of the first composition is preferably 1 to 35% by weight, preferably 5 to 30% by weight and in particular 10 to 25% by weight.Although the selection of the active washing- or cleaning-active ingredient is not subject to any substantial restriction, active washing- or cleaning-active ingredients are selected from the group of the active washing- or cleaning-active polymers, the surfactants, the corrosion inhibitors and mixtures thereof are preferred because of their simple processing in the washing or cleaning agent.The group of the wash- or cleaning-active polymers includes in particular the polycarboxylates. The active substance with washing or cleaning activity is preferably selected from the group of polycarboxylates, in particular the copolymeric polyacrylates, particularly preferably the copolymeric polyacrylates containing sulphonic acid groups.The copolymers may have two, three, four or more different monomer units. Preferred copolymeric polysulfonates contain, in addition to monomer(s) containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids.Particularly preferably, the first composition comprises an anionic copolymer as active washing or cleaning agent, wherein a copolymer comprising as anionic copolymeri) Monomers containing carboxylic acid groupsii) Monomers containing sulphonic acid groupsiii) non-ionic monomers, in particular hydrophobic monomerscontains.A further group of preferred active washing or cleaning agents comprised by the first composition are the nonionic surfactants, preferably the nonionic surfactants having a melting point above 30° C., particularly preferably in the range from 40 to 60° C. The melting point of the surfactant (in ° C.) is determined by means of differential calorimetry (DSC) according to ISO standard 11357. In this context, the melting point in the context of the invention is considered to be the peak temperature determinable by means of DSC in the second heating run. This is the temperature at which the peak / maximum deflection (on the y-axis) is present in the DSC diagram. If a plurality of peaks-within the scope of 5% of the maximum deflection observed in the second heating run-are present in a surfactant (commercial product), the temperature of the first peak is regarded as the melting point according to the invention.Suitable surfactants are, in particular, linear, saturated fatty acid alcohol ethoxylates having 14 to 18 carbon atoms in the alkyl chain and 10 to 100 ethylene oxide units, which are preferably not end group-capped.As a further preferred active substance with washing or cleaning activity, preferred first compositions contain glass corrosion inhibitors, preferably from the group of water-soluble zinc salts, particularly preferably zinc sulfate and zinc acetate, in particular zinc acetate.The first compositions introduced in step d1) preferably also comprise a consistency promoter from the group of polyethylene glycols, preferably from the group of polyethylene glycols having an average molar mass of 200 to 600 g / mol, preferably from the group of polyethylene glycols having an average molar mass of 300 to 500 g / mol. When, in the context of this application, "average molecular weight of polyalkylene glycols" is referred to, these data relate in each case to the number-average molecular weights (Mn) which result from the OH number measured according to DIN 53240-1:2012-07 by calculation.The proportion by weight of the consistency agent relative to the total weight of the first composition is preferably 5 to 30 wt %, more preferably 8 to 26 wt % and in particular 10 to 22 wt %.As a third essential constituent, the first compositions preferably introduced in step d1) comprise organic solvent. The proportion by weight of the organic solvent relative to the total weight of the first composition is preferably 35 to 80% by weight and in particular 40 to 70% by weight.The use of organic solvent from the group of polyhydric alcohols has proven to be particularly advantageous for the processability and the solidification behavior. Polyhydric alcohols for the purposes of the present invention are hydrocarbons in which two, three or more hydrogen atoms are replaced by OH groups. The OH groups are bonded to different carbon atoms. One carbon atom does not have two OH groups.The first composition particularly preferably comprises at least one alkanetriol and / or at least one alkanediol, in particular at least one C 3- to C 10- alkanetriol and / or at least one C 3- to C 10- alkanediol, preferably at least one C 3- to C 8- alkanetriol and / or at least one C 3- to C 8- alkanediol, in particular at least one C 3- to C 6- alkanetriol and / or at least one C_NER17to C_NER18alkanediol as polyhydric alcohol. The combination of a C 3- to C 10- alkanediol with a C 3- to C 10- alkanetriol is particularly preferred. Very particular preference is given to the use of organic solvent selected from the group consisting of 1,3-propanediol and glycerol.The amount by weight of the first composition introduced in step d1) is preferably 0.1 g to 4 g, particularly preferably 0.4 to 3 g and particularly preferably 0.7 to 2.5 g.The first composition solidifies at least partially, preferably completely, after step d 1) and before step d 2).The second composition introduced in step d2) preferably has a liquefaction point at temperatures in the range from 40 to 80° C. (1013 mbar), more preferably in the range from 45 to 75° C. (1013 mbar) and in particular in the range from 50 to 70° C. ° C. (1013 mbar). For the process control, the curing of the first and second compositions and the optics of the detergent or cleaning agent portion unit, it has proven advantageous if the liquefaction point of the first composition and of the second composition differ by at least 10° C. (1013 mbar), preferably by at least 20° C. (1013 mbar) and in particular by at least 30° C. (1013 mbar).The rheological properties of the second composition can be influenced, for example, by the selection of a corresponding carrier. In preferred process variants, the second composition comprises, in addition to active washing or cleaning ingredient, also fusible carriers having a melting point in the range from 40 to 80° C. (1013 mbar), more preferably in the range from 45 to 75° C. (1013 mbar) and in particular in the range from 50 to 70° C. ° C. (1013 mbar).Preferred processes are characterized in that the second composition comprises, based on its total weight a), 40 to 95% by weight of fusible carrier; b) 0.1 to 40% by weight of active substance which is active on washing or cleaning.The second composition preferably comprises fusible carriers from the group of polyethylene glycols, more preferably from the group of polyethylene glycols having an average molecular weight (Mn) of >1500 g / mol, preferably an average molecular weight between 3,000 and 15,000, even more preferably having an average molecular weight between 4,000 and 13,000, further preferably having an average molecular weight between 4000 and 6000, 6000 and 8000 or 9,000 and 12,000, and in particular preferably having an average molecular weight of 4000 to 6000 g / mol.The proportion by weight of the active washing- or cleaning-active ingredient relative to the total weight of the second composition is 1 to 40% by weight, preferably 5 to 35% by weight and in particular 10 to 30% by weight.The amount by weight of the second composition introduced in step d2) is preferably 0.5 g and 12 g, preferably from 1 to 9 g and particularly preferably 2 to 7 g.For better perception, the first composition and the second composition preferably contain dye, wherein it is particularly preferred if the dyes of the first and the second composition differ.The second composition solidifies at least partially, preferably completely, after step d 2) and before step d 3). The cured second composition stabilizes the receiving chamber, but in particular stabilizes the final process product.In step d3), a third composition in powder form is preferably introduced. By dispensing with a further melt, the cooling time of the intermediate product is reduced and the process efficiency is increased.For the efficient filling of the receiving chamber with the powder, it has proven advantageous if the powder has a flowability of greater than 40%, preferably of greater than 50%, in particular of greater than 60%, based on the standard.The flowability of the powder relates to its ability to free flow under its own weight. The flowability is determined by measuring the outflow time of 1000 ml of detergent powder from a standardized trickle test funnel which is initially closed at its outflow direction and has an outflow of 16.5 mm diameter by measuring the time for complete outflow of the granular mixture, in particular of the pulverulent phase, preferably of the powder and / or granulate, for example of the powder after opening of the outflow, and comparing it with the outflow speed (in seconds) of a standard test sand whose outflow speed is defined as 100%. The defined sand mixture for calibrating the shower apparatus is dry sea sand. Sea sand with a particle diameter of 0.4 to 0.8 mm is used, available for example from Carl Roth, Germany CAS-No. [14808-60-7]. For drying, the sea sand is dried for 24 h at 60° C. in a drying cabinet on a plate at a maximum layer height of 2 cm, before the measurement.The filling degree of the receiving chamber is preferably from 60 to 120 vol. %, particularly from 80 to 110 vol. % and in particular from 90 to 100 vol. %, after step d3).Surprisingly, the second composition is distinguished by a higher adhesion to the inner wall of the receiving chamber than the first composition, for which reason the third composition introduced in step d 3) does not undertravel the two previously introduced compositions, i.e. does not enter the interspace between the inner wall of the receiving chamber and the composition. The first composition is not subtransbed by the third composition because this first composition is completely covered by the second composition. The second composition is not undertraveled because of its high adhesion to the inner wall.In summary, a particularly preferred variant of the method comprises the steps: a) providing a mold having at least one mold cavity; b) supplying a first water-soluble film to the mold cavity; c) forming the first water-soluble film into the mold cavity to form a receiving chamber; d) at least partially filling the receiving chamber byd1) introducing at least one first gelling agent-containing, liquid washing- or cleaning-active composition to form a first washing- or cleaning-active phase, wherein the first composition comprises, based on its total weight a), 4 to 40 wt % of gelling agent; b) 0.1 to 40 wt % of washing- or cleaning-active active ingredient; c) 30 to 90 wt % of organic solvent;d2) introducing at least one second, liquid, wash- or cleaning-active composition different from the first composition onto the top side of the first wash- or cleaning-active phase in the receiving chamber, forming a second, wash- or cleaning-active phase which completely covers the top side of the first wash- or cleaning-active phase, wherein the second composition comprises, based on its total weight a), 40 to 95% by weight of fusible carrier; b) 0.1 to 40% by weight of wash- or cleaning-active active ingredient;d3) introducing at least one third solid detergent-active composition different from the first and the second composition onto the top side of the second detergent-active phase in the receiving chamber, forming a third detergent-active phase completely covering the top side of the second detergent-active phase, wherein the third composition is present in the form of a powder;e) feeding a second water-soluble film; f) sealing the at least partially filled receiving chamber with the second water-soluble film to form a washing or cleaning agent portion unit comprising a water-soluble casing.In step e) of the process, a second water-soluble film is supplied. As already in step b), the supplied film in step e) is likewise a thermoplastic water-soluble film in a preferred embodiment.The water-soluble film can be supplied continuously or discontinuously. To increase process efficiency, a continuous procedure is preferred. In a particularly preferred embodiment of the process, the transport of the second water-soluble film in step e) is continuous. From the standpoints of process economy and process safety, it is preferred to feed the second water-soluble film in step e) at a rate of 0.04 m / s, preferably above 0.08 m / s.The water-soluble film supplied in step e) may comprise one or more structurally different water-soluble polymer(s). Suitable water-soluble polymer(s) for the second water-soluble film are, in particular, polymers from the group of (optionally acetalized) polyvinyl alcohols (PVAL) and copolymers thereof.The second water-soluble film supplied in step e) preferably has a thickness of 80 μm or less, in particular of 65 μm or less, very particularly preferably of 55 μm or less.With regard to the mechanical stability of the cleaning agent portion unit with at the same time little use of packaging agents, it is preferred if the ratio of the thickness of the first water-soluble film to the thickness of the second water-soluble film is from 3:1 to 1:1, preferably from 2.5:1 to 1.1:1, in particular from 2:1 to 1.2:1. Preferably, the second water-soluble film supplied in step e) is thinner than the first water-soluble film supplied in step a).The at least partially filled receiving chamber is sealed in step f) of the method. The sealing is preferably effected under the influence of solvent or under the influence of heat.Following the sealing, the water-soluble film of the washing or cleaning agent portion unit is shrunk in a preferred variant of the method. The shrinkage of the water-soluble film takes place in a device which is set up for this purpose and is referred to as a shrink tunnel. A shrink tunnel enables the targeted heating of the water-soluble film enclosing the washing or cleaning agent portion unit.The shrink tunnel has a conveying system with the aid of which the washing or cleaning agent portion unit is transported through the shrink tunnel. This conveying system can be, for example, a revolving conveyor belt.The heat transfer in the shrink tunnel can be effected, for example, by heat radiation or hot air. In processes according to the invention, the water-soluble film is shrunk, following step f), preferably by exposure to hot air. The hot air preferably has a temperature of 120 to 290° C., preferably of 140 to 260° C., and in particular of 175 to 230° C.For the purpose of transport, storage and marketing, the sealed detergent or cleaning agent portion units are packaged in a secondary packaging in bulk form following step f) and following any shrinkage of the water-soluble film. It has been found that the portion units produced according to the invention have a high mechanical stability, for which reason no sorted packaging is required. Furthermore, the portion units do not necessarily require a mechanically strong secondary packaging because of their stability. To reduce the packaging outlay with simultaneously ensured mechanical stability, preference is therefore given to production methods in which the washing or cleaning agent portion unit is packaged in a stand-up bag in bulk form following step f) and following any shrinkage of the water-soluble film which may take place.In summary, a very particularly preferred variant of the method comprises the steps: a) providing a mold having at least one mold cavity; b) supplying a first water-soluble film to the mold cavity; c) forming the first water-soluble film into the mold cavity to form a receiving chamber; d) at least partially filling the receiving chamber byd1) introducing at least one first gelling agent-containing, liquid washing- or cleaning-active composition to form a first washing- or cleaning-active phase, wherein the first composition comprises, based on its total weight a), 4 to 40 wt % of gelling agent; b) 0.1 to 40 wt % of washing- or cleaning-active active ingredient; c) 30 to 90 wt % of organic solvent;d2) introducing at least one second, liquid, wash- or cleaning-active composition different from the first composition onto the top side of the first wash- or cleaning-active phase in the receiving chamber, forming a second, wash- or cleaning-active phase which completely covers the top side of the first wash- or cleaning-active phase, wherein the second composition comprises, based on its total weight a), 40 to 95% by weight of fusible carrier; b) 0.1 to 40% by weight of wash- or cleaning-active active ingredient;d3) introducing at least one third solid detergent-active composition different from the first and the second composition onto the top side of the second detergent-active phase in the receiving chamber, forming a third detergent-active phase completely covering the top side of the second detergent-active phase, wherein the third composition is present in the form of a powder;e) feeding a second water-soluble film; f) sealing the at least partially filled receiving chamber with the second water-soluble film to form a washing or cleaning agent portion unit comprising a water-soluble casing. g) shrinking the water-soluble film h) packaging the washing or cleaning agent portion unit in loose fill in a standing bag.This application provides, inter alia, the following subject matters:1. A method for producing a detergent or cleaning agent portion unit, comprising the steps of: a) providing a mould having at least one mould cavity; b) supplying a first water-soluble film to the mould cavity; c) forming the first water-soluble film into the mould cavity to form a receiving chamber; d) at least partially filling the receiving chamber byd1) introducing at least one first gelling agent-containing, liquid washing- or cleaning-active composition, with formation of a first washing- or cleaning-active phase;d2) introducing at least one second, liquid, wash- or cleaning-active composition different from the first composition onto the top side of the first wash- or cleaning-active phase in the receiving chamber, forming a second, wash- or cleaning-active phase completely covering the top side of the first wash- or cleaning-active phase;d3) introducing at least one third solid detergent-active composition different from the first and the second composition onto the top side of the second detergent-active phase in the receiving chamber, forming a third detergent-active phase completely covering the top side of the second detergent-active phase;e) feeding a second water-soluble film; f) sealing the at least partially filled receiving chamber with the second water-soluble film to form a washing or cleaning agent portion unit comprising a water-soluble casing.2. Method according to Item 1, wherein the washing or cleaning agent portion unit has a weight of 10 to 35 g, preferably of 12 to 28 g and in particular of 14 to 22 g.3 Method according to one of the preceding points, wherein in step a) a deep-drawing die with at least one cavity is provided.4. Method according to Item 3, wherein the deep-drawing die has a horizontally revolving conveyor belt with at least one cavity.5. The process according to any of the preceding items, wherein in step b) a thermoplastic water-soluble film is supplied.6. The process according to any of the preceding points, wherein the water-soluble film in step b) is selected from the group of films of optionally acetalized polyvinyl alcohols or copolymers thereof.7. The method according to any one of the preceding items, wherein the first water-soluble film supplied in step b) has a thickness of 60 to 2000 μm, preferably of 60 to 800 μm and in particular of 60 to 200 μm.8. The method of any preceding claim, wherein the first water soluble film is thermally molded in step c).9. Method according to one of the preceding points, wherein the receiving chamber formed in step c) has at least one, preferably two, three or four depressions in its base region.10. The method according to item 9, wherein the first composition introduced in step d1) is introduced into the depression(s) located in the base region of the receiving chamber.11. Method according to one of Items 9 or 10, wherein the receiving chamber formed in step c) has two, preferably three or four, depressions in its base region, and the first composition is introduced into these depressions in step d1).12. Method according to either of Items 9 and 10, wherein the receiving chamber formed in step c) has two, preferably three or four, depressions in its base region, and the first composition is introduced into these depressions in step d1), wherein the first composition in one of the depressions differs from at least one first composition in a further depression.13. The method according to item 12, wherein the accommodation chamber formed in step c) has three or four recesses in its bottom region, and the first composition is introduced into these recesses in step d 1), wherein the first composition in each of the recesses differs from the first composition in each further recess.14. The method according to any of the preceding points, wherein the first composition has a liquefaction point at temperatures above 80°C (1013 mbar), particularly preferably above 100°C (1013 mbar) and in particular above 115°C (1013 mbar).15. The method according to any of the preceding points, wherein the first composition contains, based on its total weight a), 4 to 40 wt.% gelling agent; b) 0.1 to 40 wt.% active washing or cleaning agent; c) 30 to 90 wt.% organic solvent.16. The method according to any of the preceding items, wherein the first composition contains, based on its total weight, 6 to 30 wt.%, preferably 7 to 24 wt.% and in particular 8 to 22 wt.% gelling agent.17. Method according to one of the preceding points, wherein the first composition contains gelling agents from the group of polymeric gelling agents, preferably from the group of polyvinyl alcohol, gelatin and xanthan or mixtures thereof.18. The method according to any of the preceding points, wherein the first composition contains gelling agents from the group of hydrolyzed polyvinyl alcohol homopolymers and polyvinyl alcohol copolymers having a molar mass of 30,000 to 60,000 g / mol.19. Method according to one of the preceding points, wherein the first composition contains, based on its total weight, 1 to 35% by weight, preferably 5 to 30% by weight and in particular 10 to 25% by weight, of active substance with washing or cleaning activity.20. The method according to any of the preceding items, wherein the first composition contains, based on its total weight, 35 to 80 wt.%, preferably 40 to 70 wt.% of organic solvent.21. The method according to any one of the preceding points, wherein the first composition contains organic solvent from the group of polyhydric alcohols, preferably from the group of C 3- to C 10- alkanediols and C 3- to C 10- alkanetriols.22. The method of any preceding claim, wherein the first composition comprises organic solvent selected from the group consisting of 1,3-propanediol and glycerol.23. The method according to any one of the preceding items, wherein the first composition contains water in a weight amount, based on its total weight, below 5 wt.%, preferably below 2 wt.% and in particular below 0.5 wt.%.24. The method according to any one of the preceding points, wherein the first composition contains, based on its total weight, 5 to 30 wt.%, preferably 8 to 26 wt.% and in particular 10 to 22 wt.% consistency promoter.25. Method according to one of the preceding points, wherein the first composition contains consistency regulators from the group of polyethylene glycols, preferably from the group of polyethylene glycols having an average molecular weight (Mn) of 200 to 600 g / mol, preferably from the group of polyethylene glycols having an average molecular weight (Mn) of 300 to 500 g / mol.26. Method according to one of the preceding points, wherein the amounts by weight of 0.1 g and 4 g, preferably of 0.4 to 3 g, particularly preferably 0.7 to 2.5 g of the first composition is introduced in step d1).27. Method according to one of the preceding points, wherein the first composition at least partially, preferably completely solidifies after step d1) and before step d2).28. The method according to any one of the preceding points, wherein the second composition has a liquefaction point at temperatures in the range of 40 to 80°C (1013 mbar), particularly preferably in the range of 45 to 75°C (1013 mbar) and in particular in the range of 50 to 70°C °C (1013 mbar).29. The method according to any one of the preceding points, wherein the liquefaction point of the first composition and the second composition differ by at least 10°C (1013 mbar), preferably by at least 20°C (1013 mbar) and in particular by at least 30°C (1013 mbar).30. The method according to any of the preceding points, wherein the second composition comprises fusible carrier having a melting point in the range from 40 to 80°C (1013 mbar), particularly preferably in the range from 45 to 75°C (1013 mbar) and in particular in the range from 50 to 70°C °C (1013 mbar) and comprises active substance with washing or cleaning activity.31. The method according to any of the preceding points, wherein the second composition contains, based on its total weight a), 40 to 95% by weight of meltable carrier; b) 0.1 to 40% by weight of active substance with washing or cleaning activity.32. The method according to any one of the preceding points, wherein the second composition contains fusible carriers from the group of polyethylene glycols, preferably from the group of polyethylene glycols having an average molecular weight (Mn) of >1500 g / mol, preferably an average molecular weight between 3,000 and 15,000, more preferably having an average molecular weight between 4,000 and 13,000, further preferably having an average molecular weight between 4000 and 6000, 6000 and 8000 or 9,000 and 12,000, and in particular preferably having an average molecular weight of 4000 to 6000 g / mol.33. Method according to one of the preceding points, wherein the second composition contains, based on its total weight, 1 to 40 wt.%, preferably 5 to 35 wt.% and in particular 10 to 30 wt.% active washing- or cleaning-active ingredient.34. Method according to one of the preceding points, wherein the amounts by weight of 0.5 g and 12 g, preferably of 1 to 9 g, in particular preferably 2 to 7 g, of the second composition is introduced in step d2).35. The method of any preceding item, wherein the first composition and the second composition contain dye, preferably different dye.36. Method according to one of the preceding points, wherein the second composition at least partially, preferably completely solidifies after step d2) and before step d3).37. The method of any preceding claim, wherein the third composition is in the form of a powder.38. The method according to item 37, wherein the powder has a flowability of greater than 40%, preferably of greater than 50%, in particular of greater than 60%, based on the standard.39. Method according to one of the preceding points, wherein the receiving chamber following step d3) has a filling degree of 60 to 120 vol.-%, preferably of 80 to 110 vol.-% and in particular of 90 to 100 vol.-%.40. The process according to any of the preceding points, wherein in step e) a thermoplastic water-soluble film is supplied.41. The process according to any of the preceding points, wherein the second water-soluble film supplied in step e) is selected from the group of films of optionally acetalized polyvinyl alcohols or copolymers thereof.42. The method according to any one of the preceding items, wherein the second water-soluble film supplied in step e) has a thickness of 80 μm or less, in particular of 65 μm or less, very particularly preferably of 55 μm or less.43. The process according to any of the preceding points, wherein the ratio of the thickness of the first water-soluble film fed in step a) to the thickness of the second water-soluble film fed in step e) is 3:1 to 1:1, preferably 2.5:1 to 1.1:1 and in particular 2:1 to 1.2:1.44. The method according to any one of the preceding items, wherein the second water-soluble film supplied in step e) is thinner than the first water-soluble film supplied in step a).45. Method according to one of the preceding points, wherein the sealing in step f) is effected under the influence of solvent.46. Method according to one of the preceding points, wherein the sealing in step f) takes place under the influence of heat.47. Method according to one of the preceding points, wherein the water-soluble film is shrunk by exposure to hot air following step f).48. The process according to item 47, wherein the hot air has a temperature of 120 to 290°C, preferably of 140 to 260°C and in particular of 175 to 230°C.49. Method according to one of the preceding points, wherein the washing or cleaning agent portion unit is packed in a loose fill in a secondary packaging following step f).50. Method according to one of the preceding points, wherein washing or cleaning agent portion unit is packed in loose fill in a standing bag following step f).References included in the specificationThis list of documents cited by the applicant has been produced in an automated manner and is only included for the better information of the reader. The list is not part of the German patent application or utility model application. The DPMA does not take any adhesion for any faults or omissions.Patent Literature citedWO 2002 / 16205 A1

[0005] EP 2 944 578 B1

[0006]

Claims

A method for producing a detergent or cleaning agent portion unit, comprising the steps of: a) providing a mold having at least one mold cavity; b) supplying a first water-soluble film to the mold cavity; c) forming the first water-soluble film into the mold cavity to form a receiving chamber; d) at least partially filling the receiving chamber by d1) introducing at least one first gel-former-containing, liquid detergent or cleaning-active composition to form a first detergent or cleaning-active phase; d2) introducing at least one second liquid detergent or cleaning-active composition different from the first composition onto the upper side of the first detergent or cleaning-active phase in the receiving chamber to form a second detergent or cleaning-active phase completely covering the upper side of the first detergent or cleaning-active phase; d3) introducing at least one third solid washing- or cleaning-active composition different from the first and the second composition onto the upper side of the second washing- or cleaning-active phase in the receiving chamber, forming a third washing- or cleaning-active phase completely covering the upper side of the second washing- or cleaning-active phase; e) feeding a second water-soluble film; f) sealing the at least partially filled receiving chamber with the second water-soluble film, forming a washing- or cleaning-agent portion unit comprising a water-soluble casing.Method according to claim 1, wherein the receiving chamber formed in step c) has at least one, preferably two, three or four depressions in its base region.Method according to one of the preceding claims, wherein the receiving chamber formed in step c) has two, preferably three or four, depressions in its base region and the first composition is introduced into these depressions in step d1), wherein the first composition in one of the depressions differs from at least one first composition in a further depression.The method according to any one of the preceding claims, wherein the first composition has a liquefaction point at temperatures above 80°C (1013 mbar), particularly preferably above 100°C (1013 mbar) and in particular above 115°C (1013 mbar).The method according to any one of the preceding claims, wherein the first composition contains, based on its total weight a), 4 to 40 wt.% gelling agent; b) 0.1 to 40 wt.% active washing or cleaning agent; c) 30 to 90 wt.% organic solvent.The method according to any one of the preceding claims, wherein the second composition has a liquefaction point at temperatures in the range of 40 to 80°C (1013 mbar), particularly preferably in the range of 45 to 75°C (1013 mbar) and in particular in the range of 50 to 70°C °C (1013 mbar).The method according to any one of the preceding claims, wherein the second composition contains, based on its total weight a), 40 to 95% by weight of meltable carrier; b) 0.1 to 40% by weight of active substance with washing or cleaning activity.Method according to one of the preceding claims, wherein the second composition solidifies at least partially, preferably completely, after step d2) and before step d3).The method of any preceding claim, wherein the third composition is in the form of a powder.The method according to any one of the preceding claims, wherein the water-soluble film is shrunk by exposure to hot air at the end of step f).