EP1740689B1 - Method for the production of detergent or cleaning agents - Google Patents

Description

The present invention is in the field of detergents or cleaners. In particular, the present invention relates to a process for the preparation of detergents or cleaners, in particular of metering units of detergents or cleaners.

Detergents or cleaners are now available to the consumer in a variety of forms. In addition to washing powders and granules, this offer also includes, for example, detergent concentrates in the form of extruded or tabletted compositions. These fixed, concentrated or compressed forms of supply are characterized by a reduced volume per dosing unit and thus reduce the costs for packaging and transport. In particular, the washing or cleaning agent tablets additionally meet the consumer's desire for simple dosing. The corresponding means are comprehensively described in the prior art. However, in addition to the advantages listed, compacted detergents or cleaners also have a number of disadvantages. Especially tableted supply forms are characterized by their high compression often by a delayed disintegration and thus a delayed release of their ingredients. In order to resolve this "conflict" between sufficient tablet hardness and short disintegration times, numerous technical solutions have been disclosed in the patent literature, reference being made by way of example to the use of so-called tablet disintegrating agents at this point. These disintegrants are added to the tablets in addition to the washing or cleaning-active substances, and as a rule have no washing or cleaning-active properties, and thus increase the complexity and the costs of these agents. A further disadvantage of the tabletting of mixtures of active substances, in particular washing or cleaning substance mixtures, is the inactivation of the active substances contained by the compaction pressure which occurs during tableting. Inactivation of the active substances can also take place due to the increased contact area of the ingredients due to the tableting due to chemical reaction.

As an alternative to the particulate or compacted detergents or cleaners described above, solid or liquid detergents or cleaners which have a water-soluble or water-dispersible packaging are increasingly being described in recent years. These agents are characterized as the tablets by a simplified dosage, since they can be dosed together with the outer packaging in the washing machine or dishwasher, on the other hand, but at the same time they also allow the preparation of liquid or powder detergents or cleaning agents Compared to the compact data by a better resolution and faster effectiveness.

For example, the EP 1 314 654 A2 (Unilever ) a dome-shaped pouch with a receiving chamber containing a liquid.

Subject of the WO 01/83657 A2 (Procter & Gamble), on the other hand, are pouches which contain in a receiving chamber two particulate solids which each exist in fixed regions and do not mix with each other.

In addition to the packages which have only one receiving chamber, the prior art has also disclosed forms of offers which comprise more than one receiving chamber or more than one ready-made form.

Subject of the European application EP 1 256 623 A1 (Procter & Gamble) is a kit of at least two bags of different composition and optics. The bags are separate and not as a compact single product.

A method for producing multi-chamber bags by gluing second single chamber describes the international application WO 02/85736 A1 (Reckitt Benckiser).

In the DE 10062582 A1 Moldings are disclosed in which both temperature and pressure-sensitive and flowable ingredients can be introduced into delimited regions. This is done by using prefabricated moldings for lining a tablet tray.

The object of the present application was to provide a process for the preparation of detergents or cleaners, which enables the joint preparation of solid and liquid or flowable detergent or cleaner compositions in separate areas of a compact dosing unit. The final process product should be characterized by an attractive appearance.

It has now been found that the aforementioned objects can be achieved by a method in which a washing or cleaning-active molded body is provided with a cavity, wherein in this cavity a thermoforming body is formed, which can be filled in connection.

1. a) Bereitstellen eines Formkörpers mit mindestens einer Kavität;
2. b) Auflegen eines ersten Folienmaterials auf die Formkörperoberfläche über die Öffnung der Kavität;
3. c) Tiefziehen des ersten Folienmaterials in die Kavität, indem in der Kavität des Formkörpers ein Unterdruck erzeugt wird;
4. d) Einfüllen einer wasch- oder reinigungsaktiven Substanz auf das Folienmaterial in der Kavität.

The subject matter of the present application is therefore a process for the production of a dosing unit for detergents or cleaners, comprising the steps

1. a) providing a shaped body having at least one cavity;
2. b) placing a first sheet material on the molding surface over the opening of the cavity;
3. c) deep drawing of the first film material into the cavity by creating a negative pressure in the cavity of the shaped body;
4. d) filling a washing or cleaning active substance on the film material in the cavity.

In the first step of the method according to the invention, a shaped body is provided. Such moldings are obtainable, for example, by compaction methods such as tableting, by extrusion, such as extrudate extrusion, by injection molding or by casting. In the context of the present application, moldings which are produced by tabletting or by casting are particularly preferred. The moldings contain or consist of washing or cleaning-active substances or substance mixtures.

The preparation of washing or cleaning agent tablets is carried out in a manner known to those skilled in the art by compressing particulate starting substances. To prepare the tablets, the premix is compressed in a so-called matrix between two punches to form a solid compressed product. This process, hereinafter referred to as tabletting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection. The tabletting is preferably carried out on so-called rotary presses.

• Verwendung von Kunststoffeinlagen mit geringen Dickentoleranzen
• Geringe Umdrehungszahl des Rotors
• Große Füllschuhe
• Abstimmung des Füllschuhflügeldrehzahl auf die Drehzahl des Rotors
• Füllschuh mit konstanter Pulverhöhe
• Entkopplung von Füllschuh und Pulvervorlage

When tableting with rotary presses, it has proven to be advantageous to carry out the tableting with the lowest possible weight fluctuations of the tablet. In this way, the hardness fluctuations of the tablet can be reduced. Small variations in weight can be achieved in the following ways:

• Use of plastic inserts with small thickness tolerances
• Low number of revolutions of the rotor
• Big filling shoes
• Tuning of the filling paddle speed to the speed of the rotor
• Filling shoe with constant powder height
• Decoupling of filling shoe and powder template

To reduce Stempelanbackungen offer all known from the art non-stick coatings. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotary punches have also proved to be advantageous, wherein, if possible, upper and lower punches should be rotatable. With rotating punches can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished.

Preferred processes in the context of the present invention are characterized in that the pressing takes place at pressing pressures of 0.01 to 50 kNcm ^-2 , preferably of 0.1 to 40 kNcm ² and in particular of 1 to 25 kNcm ^-2 .

The production of preferred casting bodies according to the invention is carried out, for example, by casting a washing or cleaning-active preparation into a mold and subsequently demolding the solidified cast body to form a (mold) shaped body. As a "mold" are preferably tools that have cavities that can be filled with pourable substances. Such tools may be formed, for example, in the form of individual cavities but also in the form of plates having a plurality of cavities. The single cavities or cavity plates are preferably mounted on horizontally circulating conveyor belts in industrial processes which allow continuous or discontinuous transport of the cavities, for example along a number of different workstations (e.g., casting, cooling, filling, sealing, demolding, etc.).

The washing or cleaning active preparations are potted in the preferred process and subsequently solidified to a dimensionally stable body. In the context of the present invention, "solidification" characterizes any curing mechanism which delivers a body which is solid at room temperature from a deformable, preferably flowable mixture or such substance or mass, without the need for pressing or compacting forces. "Solidification" in the context of the present invention is therefore, for example, the curing of melts of solid substances at room temperature by cooling. "Solidification processes" in the context of the present application are also the curing of formable materials by time-delayed water binding, by evaporation of solvents, by chemical reaction, crystallization, etc. and the reactive curing of flowable powder mixtures to form stable hollow bodies.

1. i) 10 bis 85 Gew.-% Dispersionsmittel und
2. ii) 15 bis 90 Gew.-% dispergierte Stoffe

enthalten, besonders bevorzugt werden.For processing in the described method are generally all washing or cleaning active preparations that can be processed by casting techniques. With particular preference, however, washing or cleaning active preparations are used in the form of dispersions. In a particularly preferred embodiment of the present application, the washing or cleaning-active preparation poured into the receiving recess of the molding tool is a dispersion of solid particles in a dispersion medium, dispersions based on their total weight

1. i) from 10 to 85% by weight of dispersant and
2. ii) 15 to 90% by weight of dispersed substances

contain, are particularly preferred.

As dispersion in this application a system of several phases is referred to, one of which is dispersed continuously (dispersion medium) and at least one further (dispersed substances).
Suitable dispersants in the context of the present invention are preferably the water-soluble or water-dispersible polymers, in particular the water-soluble or water-dispersible nonionic polymers. The dispersant may be both a single polymer and mixtures of various water-soluble or water-dispersible polymers. In a further preferred embodiment of the present invention, the dispersant or at least 50 wt .-% of the polymer mixture of water-soluble or water-dispersible nonionic polymers from the group of polyvinylpyrrolidone, vinylpyrrolidone / vinyl ester copolymers, cellulose ethers, polyvinyl alcohols, polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol.

Particular preference is given to using dispersions which contain, as dispersants, a nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, the weight fraction of the poly (ethylene) glycol being based on the total weight of all dispersing agents is preferably between 10 and 90% by weight, more preferably between 30 and 80% by weight and in particular between 50 and 70% by weight. Particular preference is given to dispersions in which the dispersant contains more than 92% by weight, preferably more than 94% by weight, more preferably more than 96% by weight, very particularly preferably more than 98% by weight. and in particular to 100 wt .-% of a poly (alkylene) glycol, preferably poly (ethylene) glycol and / or poly (propylene) glycol, but in particular consists poly (ethylene) glycol. Dispersing agents which also contain poly (propylene) glycol in addition to poly (ethylene) glycol preferably have a ratio of the weight proportions of poly (ethylene) glycol to poly (propylene) glycol between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, more preferably between 10: 1 and 1.5: 1 and in particular between 7: 1 and 2: 1 on.

Further preferred dispersants are the nonionic surfactants, which are used alone, but particularly preferably in combination with a nonionic polymer. Detailed information on the usable nonionic surfactants can be found in the description of washing or cleaning-active substances below.

For the purposes of the present application, all materials which are solid at room temperature or are active in washing or cleaning, but in particular washing or cleaning substances from the group of builders (builders and cobuilders), are suitable as dispersed substances washing or cleaning active polymers, bleach, bleach activators, glass corrosion inhibitors, silver protectants and / or enzymes. A more detailed description of these ingredients can be found below in the text.

Dispersions preferably used as detergent tablets according to the invention are characterized in that they are dissolved in water (40 ° C.) in less than 9 minutes, preferably less than 7 minutes, preferably less than 6 minutes, more preferably less than 5 minutes and in particular dissolve in less than 4 minutes. To determine the solubility, 20 g of the dispersion are introduced into the interior of a dishwashing machine (Miele G 646 PLUS). The main rinse of a standard rinse program (45 ° C) is started. The determination of the solubility is carried out by the measurement of the conductivity, which is recorded via a conductivity sensor. The dissolution process is completed when the maximum conductivity is reached. In the conductivity diagram, this maximum corresponds to a plateau. The conductivity measurement starts with the replacement of the circulation pump in the main wash cycle. The amount of water used is 5 liters.

The moldings produced, for example, by tableting or casting may take any geometric form, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal , pentagonal, octagonal and octagonal prismatic as well as rhombohedral forms are preferred. Even completely irregular surfaces such as arrow or animal shapes, trees, clouds, etc. can be realized. If the shaped bodies according to the invention have corners and edges, these are preferably rounded off. As additional optical differentiation, an embodiment with rounded corners and bevelled ("touched") edges is preferred.

Of course, the moldings can also be produced in multiple phases. For reasons of process economy, two-layered or three-layered shaped bodies, in particular two-layered or three-layered tablets, have proven particularly useful here.

In a particularly preferred embodiment, tablets and / or compacts, for example roll compacts, and / or extrudates, and / or injection-molded bodies and / or casting bodies and / or molded articles composed of these shaped bodies are used in step a) of the process according to the invention.

To improve its shaped-body optics and / or to influence its dissolution behavior, the shaped body may have a coating. The coating can cover both the entire molded body and individual areas of the molded body.

Particular preference is given to moldings which have a coating on their entire surface. Preference is furthermore given to shaped bodies in which the coating extends only to individual surfaces of the shaped body, for example the shaped body surfaces outside the cavity, or to individual corners or edges of the shaped body.

Suitable coating materials are all materials known to the person skilled in the art. Preferred coating materials in the context of the present application are the water-soluble or water-insoluble natural or synthetic organic polymers, water-soluble or water-dispersible organic polymers being particularly preferred. Also suitable for the coating of the moldings are the salts of organic or inorganic acids. Of the group of organic acids, in particular the salts of mono-, di-, tri, tetra- or polycarboxylic acids are preferred.

Preferred methods according to the invention are accordingly characterized in that the shaped body has a coating.

The term "cavity" in the context of the present invention, both troughs and through the molding through holes or holes, which connect two sides of the molding, preferably opposite sides of the molding, for example, the bottom and roof surface of the molding together.

The shape of the cavity, which is preferably a well, may be chosen freely, with tablets being preferred in which at least one well is a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disk-shaped, tetrahedral, dodecahedral, octahedral , conical, pyramidal, ellipsoidal, pentagonal, pentagonal, octagonal, prismatic and rhombohedral shapes. Completely irregular shapes such as arrow or animal shapes, trees, clouds etc. can also be realized. As with the basic moldings, wells with rounded corners and edges or with rounded corners and chamfered edges are preferred. The bottom surface of the trough can be flat or inclined.

In a particularly preferred embodiment, the cavity is an opening, which connects two opposite sides of the molding together. A corresponding shaped body can be referred to as a ring body. The aperture areas of the aperture in the surface of this annular body may be the same size but may differ in size. If a tablet is used as the shaped body, then the shaped body with such a breakthrough corresponds to a so-called ring tablet. Particularly preferred such shaped bodies are used with breakthrough, in which the opening areas of the opening on the opposite sides of the molding, based on the larger of the two opening surfaces by less than 80%, preferably less than 60%, preferably less than 40%, more preferably less than 20% and in particular differ less than 10%. Particularly preferred ring tablets are used, in which the opening areas of the aperture have the same size. The cross-section of the aperture may be angular or round. Cross sections with one, two, three, four, five, six or more corners can be realized, however, such shaped bodies are particularly preferred in the context of the present application, which have a breakthrough without corners, preferably a breakthrough with a round or oval cross-section. In this case, a "cross section" refers to a surface which is perpendicular to a straight connecting line between the center points of the two opposite opening surfaces of the shaped body.

Of course, the molding may have more than one cavity. Moldings having two, three, four, five, six, seven, eight, nine, ten, eleven, twelve or more cavities are particularly preferred in the present application. If the shaped body has more than one cavity, these cavities can be both the wells described above and the breakthroughs described above. Shaped bodies which have more than one cavity, wherein at least one of the cavities is a trough and at least one further of the cavities is a breakthrough, are particularly preferred in the context of the present application.

The volume of the cavity is preferably between 0.1 and 20 ml, preferably between 0.2 and 15 ml, more preferably between 1 and 10 ml and in particular between 2 and 7 ml.

Before a film material is applied to the cavities of the shaped bodies provided in step a) in step b), in a preferred process variant these cavities can be filled proportionally with a solid or liquid, washing or cleaning-active substance. Such methods, in which the cavity of the shaped body is partially filled with a washing or cleaning substance before applying the first sheet material in step b), are particularly preferred in the context of this application. With preference in the context of the present application between the steps a) and b) flowable washing and cleaning active preparations, preferably liquid (s), in particular melts, and / or gel (s) and / or powder and / or granules (e) and / or extrudate (s) and / or Kompaktat (s) used.

With particular preference, the cavity is filled prior to placing the first film material in step b) partially with a washing or cleaning active powder, granules or extrudate.

The term "liquid" in the present application denotes substances or substance mixtures as well as solutions or suspensions which are in the liquid state of matter.

Powder is a general term for a form of division of solids and / or mixtures obtained by comminution, that is, grinding or crushing in the mortar (pulverization), grinding in mills or as a result of atomization or freeze-drying. A particularly fine division is often called atomization or micronization; the corresponding powders are called micro-powders.

After the grain size is a rough division of the powder in coarse, fine u. Very fine powder usual; A more detailed classification of powdery bulk solids is made by their bulk density and sieve analysis. In the context of the present application, however, preferred powders have lower particle sizes below 5000 .mu.m, preferably less than 3000 .mu.m, preferably less than 1000 .mu.m, very particularly preferably between 50 and 1000 .mu.m and in particular between 100 and 800 .mu.m.

Powders can be compacted and agglomerated by extrusion, pressing, rolling, briquetting, pelleting and related processes. Each of the methods known in the prior art for the agglomeration of particulate mixtures is in principle suitable for producing the solids contained in the agents according to the invention. In the context of the present invention, preferably agglomerates used as solid (s) are, in addition to the granules, the compacts and extrudates.

Granules are aggregates of granules. A granule (granule) is an asymmetric aggregate of powder particles. Granulation methods are widely described in the art. Granules can be prepared by wet granulation, by dry granulation or compaction and by melt solidification granulation.

The most common granulation technique is wet granulation, since this technique is subject to the fewest restrictions and leads most safely to granules with favorable properties. The wet granulation is carried out by moistening the powder mixtures with solvents and / or solvent mixtures and / or solutions of binders and / or solutions of adhesives and is preferably carried out in mixers, fluidized beds or spray towers, said mixer can be equipped, for example, with stirring and kneading tools. However, combinations of fluidized bed (s) and mixer (s) or combinations of different mixers can also be used for the granulation. The granulation takes place Depending on the starting material and the desired product properties under the action of low to high shear forces.

If the granulation in a spray tower so as starting materials, for example, melting (melt solidification) or, preferably aqueous, slurries (spray drying) of solid substances are used, which are sprayed at the top of a tower in a defined droplet size, solidify in free fall or dry and on Floor of the tower incurred as granules. Melt solidification is generally particularly suitable for shaping low-melting substances which are stable in the melting temperature range (eg urea, ammonium nitrate and various formulations such as enzyme concentrates, pharmaceuticals etc.), the corresponding granules are also referred to as prills. Spray drying is used especially for the production of detergents or detergent ingredients.

Further agglomeration techniques described in the prior art are extruder or perforated roll granulations in which powder mixtures optionally mixed with granulating liquid are plastically deformed during perforation by perforated disks (extrusion) or on perforated rolls. The products of extruder granulation are also referred to as extrudates.

Builders, enzymes, bleaches, bleach activators, bleach catalysts, silver protectants or glass corrosion inhibitors are particularly suitable as ingredients of the washing or cleaning-active formulations introduced into the cavities between steps a) and b). Bleaches, in particular peroxygen compounds such as percarbonates or perborates, bleach activators or silver protectants, are particularly preferably introduced. These ingredients are preferably filled into the cavity as part of solid washing or cleaning active preparations between steps a) and b). These ingredients are described in more detail later in the text. To avoid repetition, reference is made at this point to the comments there.

• a) Bereitstellen eines Formkörpers mit mindestens einer Kavität;
• a') Anteilsweises Befüllen der Kavität mit einer wasch- oder reinigungsaktiven Zusammensetzung, vorzugsweise einer festen wasch- oder reinigungsaktiven Zusammensetzung, welche besonders bevorzugt mindestens eine Substanz aus der Gruppe der Gerüststoffe, Enzyme, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, Silberschutzmittel und Glaskorrosionsinhibitoren enthält;
• b) Auflegen eines ersten Folienmaterials auf die Formkörperoberfläche über die Öffnung der Kavität;
• c) Tiefziehen des ersten Folienmaterials in die Kavität; indem in der Kavität des Formkörpers ein Unterdruck erzeugt wird;
• d) Einfüllen einer wasch- oder reinigungsaktiven Substanz auf das Folienmaterial in der Kavität.

A further preferred subject matter of the present application is therefore a process for the preparation of a dosing unit for detergents or cleaners, comprising the steps

• a) providing a shaped body having at least one cavity;
• a ') Partial filling of the cavity with a washing or cleaning active composition, preferably a solid washing or cleaning active composition, which particularly preferably contains at least one substance from the group of builders, enzymes, bleaches, bleach activators, bleach catalysts, silver protectants and glass corrosion inhibitors;
• b) placing a first sheet material on the molding surface over the opening of the cavity;
• c) deep drawing the first sheet material into the cavity; by creating a negative pressure in the cavity of the shaped body;
• d) filling a washing or cleaning active substance on the film material in the cavity.

The volume of the substances introduced between steps a) and b) is preferably between 0.5 and 12 ml, particularly preferably between 0.5 and 8 ml, very particularly preferably between 0.5 and 6 ml and in particular between 0.5 and 4 ml. The cavity of the shaped body is preferably filled between 1 and 80% by volume, preferably between 5 and 60% by volume, very particularly between 10 and 50% by volume and in particular between 20 and 50% by volume.

In step b) of the method according to the invention, a film material is placed on the molding surface over the opening of the cavity. In a preferred embodiment of the process according to the invention, the first film material used in step b) is a water-soluble or water-dispersible film material, preferably a polymeric water-soluble or water-dispersible film material.

In a preferred process variant, the film material in step b) comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and their mixtures.

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten."Polyvinyl alcohols" (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure

in small proportions (about 2%) also structural units of the type

contain.

Commercially available polyvinyl alcohols, which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups. The polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable. The water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax. The coatings of polyvinyl alcohol are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

In the context of the present invention, it is preferred that the film material used in the process according to the invention at least partially comprises a polyvinyl alcohol whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and in particular 82 to 88 mol%. In a preferred embodiment, the first film material used in the process according to the invention comprises at least 20% by weight, more preferably at least 40% by weight, very preferably at least 60% by weight and in particular at least 80% by weight. of a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and more preferably 82 to 88 mol%.

Polyvinyl alcohols having a specific molecular weight range are preferably used as the film material, wherein the film material comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 .

The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88 and Mowiol ^® 8-88.

Further polyvinyl alcohols which are particularly suitable as film material are shown in the following table: description Degree of hydrolysis [%] Molecular weight [kDa] Melting point [° C] Airvol ^® 205 88 15-27 230 Vinex ^® 2019 88 15-27 170 Vinex ^® 2144 88 44-65 205 Vinex ^® 1025 99 15-27 170 Vinex ^® 2025 88 25-45 192 Gohsefimer ^® 5407 30-28 23,600 100 Gohsefimer ^® LL02 41-51 17,700 100

Other suitable polyvinyl alcohols are as the film material ^® ELVANOL 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX 72.5 ^®, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ^® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK).

The water solubility of PVAL can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols which are acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly advantageous and particularly advantageous on account of their pronounced cold water solubility. To use extremely advantageous are the reaction products of PVAL and starch.

Furthermore, the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values. Films made of PVAL are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

Examples of suitable water PVAL films under the name "SOLUBLON® ^®" from Syntana Handelsgesellschaft E. Harke GmbH & Co. available PVAL films. their Solubility in water can be adjusted to the exact degree and films of this product series are available which are soluble in aqueous phase in all temperature ranges relevant for the application.

Polyvinylpyrrolidones, referred to as PVP for short, can be described by the following general formula:

PVP are prepared by radical polymerization of 1-vinylpyrrolidone. Commercially available PVP have molecular weights in the range of about 2,500 to 750,000 g / mol and are available as white, hygroscopic powders or as aqueous solutions.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula

H- [O-CH ₂ -CH ₂ ] _n -OH

the technically by alkaline-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems are prepared with ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.

Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance.

In the context of the process according to the invention, preference is given to film materials which comprise a polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose, and mixtures thereof.

Starch is a homoglycan, wherein the glucose units are linked α-glycosidically. Starch is composed of two components of different molecular weight: from about 20 to 30% straight chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched chain amylopectin (MW about 300,000 to 2,000,000). In addition, small amounts of lipids, phosphoric acid and cations are still included. While the amylose forms long, helical, entangled chains with about 300 to 1,200 glucose molecules as a result of the binding in the 1,4-position, the chain branched in amylopectin after an average of 25 glucose building blocks by 1,6-bonding to a branch-like structure with about 1,500 to 12,000 molecules of glucose. In addition to pure starch, starch-derivatives which are obtainable from starch by polymer-analogous reactions are also suitable for the preparation of water-soluble coatings of the detergent, detergent and cleaner portions in the context of the present invention. Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5,000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.

Other preferred film materials are characterized by comprising hydroxypropyl methylcellulose (HPMC) which has a degree of substitution (average number of methoxy groups per anhydroglucose unit of cellulose) of from 1.0 to 2.0, preferably from 1.4 to 1.9, and a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of cellulose) of from 0.1 to 0.3, preferably from 0.15 to 0.25.

Preferred methods according to the invention are characterized in that at least one of the film materials used is transparent or translucent.

The film material used, for example, for deep-drawing and / or sealing is preferably transparent. For the purposes of this invention, transparency means that the transmittance within the visible spectrum of the light (410 to 800 nm) is greater than 20%, preferably greater than 30%, more preferably greater than 40% and in particular greater than 50%. Thus, once a wavelength of the visible spectrum of the light has a transmittance greater than 20%, it is to be regarded as transparent within the meaning of the invention.

Preparations made according to the invention, for the production of which transparent film material has been used, may contain a stabilizing agent. Stabilizing agents in the context of the invention are materials which protect the ingredients at least partially enclosed by the film material from decomposition or deactivation by light irradiation. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.

Particularly suitable stabilizing agents in the context of the invention are the antioxidants. In order to prevent undesirable changes in the formulations caused by light irradiation and thus radical decomposition, the formulations may contain antioxidants. Examples of antioxidants which may be used here are sterically hindered groups, substituted phenols, bisphenols and thiobisphenols. Further examples are propyl gallate, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long chain (C8-C22) esters of gallic acid, such as dodecyl gallate. Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives such as isopropyl citrate, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic palmitate, organosulfur compounds such as the esters of 3,3'-thiodipropionic acid with C _1-18 alkanols, especially C _10-18 alkanols, metal ion deactivators capable of auto-oxidation catalyzing metal ions such as copper, to complex such as nitrilotriacetic acid and its derivatives and their mixtures. Antioxidants may be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.

Another class of preferably usable stabilizers are the UV absorbers. UV absorbers can improve the light stability of the formulation ingredients. Below are Organic substances (sunscreen) to understand that are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, eg heat to give back. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. In addition, substituted benzotriazoles, such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) 4-hydroxy-5- (methylpro-pyl) monosodium salt (Ciba Fast ^® H), phenyl-substituted in the 3-position acrylates (cinnamic acid derivatives ), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid. The biphenyl and especially stilbene derivatives which are available commercially as Tinosorb ^® FD or Tinosorb ^® FR available ex Ciba. 3-benzylidene camphor or 3-benzylidene norcamphor and derivatives thereof, for example 3- (4-methylbenzylidene) camphor, may be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives such as 2,4,6-trianilino (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyl triazone or dioctyl butamido triazone (Uvasorb® HEB); Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'-methoxy-phenyl) -propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-Benzylidencamphers, such as 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.

As a typical UV-A filter in particular derivatives of benzoylmethane are suitable, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione and enamine compounds. Of course, the UV-A and UV-B filters can also be used in mixtures. In addition to the soluble substances mentioned, insoluble photoprotective pigments, namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide and in addition oxides of iron, zirconium, silicon, manganese, aluminum and cerium, and mixtures thereof. As salts silicates (talc), barium sulfate or zinc stearate can be used. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape. The pigments may also be surface-treated, ie hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. Preferably, micronized zinc oxide is used.

Another preferred class of stabilizers to be used are the fluorescent dyes. These include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and Benzimidazole systems and substituted by heterocycles pyrene derivatives. Of particular importance are the sulfonic acid salts of diaminostilbene derivatives and polymeric fluorescent substances.

Preferred process variants are characterized in that the film materials used in step b) of the process according to the invention have a thickness between 5 and 2000 .mu.m, preferably between 10 and 1000 .mu.m, more preferably between 15 and 500 .mu.m, very particularly preferably between 20 and 200 .mu.m and in particular between 25 and 100 microns have.

The films used may be single-layer or multi-layer films (laminate films). Regardless of their chemical or physical structure, the water content of the film materials is preferably below 10 wt .-%, more preferably below 7 wt .-%, most preferably below 5 wt .-% and in particular below 4 wt .-%.

In step c) of the method according to the invention, the first film material is deep-drawn into the cavity; by creating a negative pressure in the cavity of the molded body.

In a preferred process variant, the packaging film used is conditioned before molding. Such methods according to the invention are particularly preferred, in which the packaging film is pretreated before thermoforming in step c) by heating and / or solvent application. If the film material is pretreated by the action of heat before or during the deep drawing into the cavity of the shaped body, this is preferably for this purpose for up to 5 seconds, preferably for 0.1 to 4 seconds, particularly preferably for 0.2 to 3 seconds and in particular for 0 , 4 to 2 seconds to temperatures above 60 ° C, preferably above 80 ° C, more preferably between 100 and 120 ° C and in particular heated to temperatures between 105 and 115 ° C. Such pretreated film materials, in preferred process variants in step c), already form into the cavity of the molded article due to their own weight.

To generate the negative pressure, all known to those skilled in the art for these purposes, pumps are particularly preferably used for a rough vacuum water jet, Flüssigkeitsdampfstrahl-, Wasserring- u. Piston pumps. However, it is also possible to use, for example, rotary slide valves, slide gate valves, trochoidal and sorption pumps as well as so-called Roots blowers and cryopumps. To set a fine vacuum, rotary vane pumps, diffusion pumps, Roots blowers, positive displacement, turbomolecular, sorption, ion getter pumps (getters) are preferred.

In a preferred embodiment of the method according to the invention, the negative pressure generated is between -100 and -1013 mbar, preferably between -200 and -1013 mbar, particularly preferably between -400 and -1013 mbar and in particular between -800 and -1013 mbar.

The negative pressure can be generated in the cavity by different procedures. In the simplest case, the cavity is one of the breakthroughs described at the outset. By applying a negative pressure to one of the openings of the opening, which was not covered by a first film material in step b), the film material can be deep-drawn into the cavity.

1. a) Bereitstellen eines Formkörpers mit mindestens einer Kavität in Form eines Durchbruchs;
2. b) Auflegen eines ersten Folienmaterials auf die Formkörperoberfläche über eine Öffnung des Durchbruchs;
3. c) Tiefziehen des ersten Folienmaterials in den Durchbruch durch Anlegen eines Unterdrucks an eine Öffnung des Durchbruchs, welcher nicht von dem ersten Folienmaterial bedeckt ist;
4. d) Einfüllen einer wasch- oder reinigungsaktiven Substanz auf das Folienmaterial in der Kavität.

Accordingly, within the scope of the present application, a process for the production of a dosing unit for detergents or cleaners, comprising the steps, is preferred

1. a) providing a shaped body having at least one cavity in the form of an opening;
2. b) placing a first sheet material on the shaped body surface via an opening of the opening;
3. c) deep drawing the first sheet material into the aperture by applying a negative pressure to an aperture of the aperture which is not covered by the first sheet material;
4. d) filling a washing or cleaning active substance on the film material in the cavity.

1. a) Bereitstellen einer Ringtablette;
2. b) Auflegen eines ersten Folienmaterials auf die Formkörperoberfläche über eine Öffnung der Ringtablette;
3. c) Tiefziehen des ersten Folienmaterials in die Kavität der Ringtablette durch Anlegen eines Unterdrucks an die weitere Öffnung;
4. d) Einfüllen einer wasch- oder reinigungsaktiven Substanz auf das Folienmaterial in der Kavität.

As explained above, the shaped body with the opening is preferably a ring tablet. In a particularly preferred embodiment, the application therefore particularly comprises a process for the production of a dosing unit for detergents or cleaners, comprising the steps

1. a) providing a ring tablet;
2. b) placing a first sheet material on the shaped body surface via an opening of the ring tablet;
3. c) deep drawing the first film material into the cavity of the ring tablet by applying a negative pressure to the further opening;
4. d) filling a washing or cleaning active substance on the film material in the cavity.

Ring shaped bodies or ring tablets are those shaped bodies which have two interconnected openings in their surface. These interconnected openings form a passage penetrating the body or tablet, which preferably connects two mutually opposite sides.

If ring tablets are used in the process according to the invention for producing the washing or cleaning agent dosing units, deep drawing of the film material takes place in the opening of these ring tablets in a particularly preferred embodiment after a molding tool has been introduced into the opening of the ring tablet. This mold may be inserted into the aperture before or after the first film material is placed on the mold surface over the aperture of the ring tablet. Of course, the introduction of the mold can also be done simultaneously with the laying of the film material. The mold is used in this process variant as a "placeholder" and reduces the void volume of the opening, in which the film material can be thermoformed. Consequently, the receiving chamber formed by the deep drawing of the foil material does not become the entire breakthrough but only the void volume remaining in the breakthrough after the insertion of the forming tool fill out. The receiving chamber formed from the film material consequently fills the breakthrough only in part.

1. a) Bereitstellen eines Ringformkörpers, vorzugsweise einer Ringtablette;
2. b) Einbringen eines Formwerkzeugs durch eine erste Öffnung des Durchbruchs der Ringtablette in diesen Durchbruch;
3. c) Auflegen eines ersten, vorzugsweise wasserlöslichen Folienmaterials auf die Formkörperoberfläche über die zweite Öffnung des Durchbruchs;
4. d) Tiefziehen des ersten Folienmaterials in den Durchbruch der Ringtablette unter Ausbildung einer Aufnahmekammer, die den Durchbruch nur anteilsweise ausfüllt;
5. e) Einfüllen einer wasch- oder reinigungsaktiven Substanz in die in Schritt d) gebildete Aufnahmekammer.

A preferred subject matter of the present application is therefore a process for the preparation of a dosing unit for detergents or cleaners, comprising the steps

1. a) providing a ring shaped body, preferably a ring tablet;
2. b) introducing a molding tool through a first opening of the annular tablet breakthrough in this opening;
3. c) placing a first, preferably water-soluble film material on the molding surface via the second opening of the opening;
4. d) deep drawing of the first sheet material in the breakthrough of the ring tablet to form a receiving chamber which fills the breakthrough only partially;
5. e) filling a washing or cleaning-active substance in the receiving chamber formed in step d).

As already stated, the method steps b) and c) in this preferred variant of the method can be carried out in the reverse order or at the same time.

By introducing the mold into the breakthrough of the ring tablet this breakthrough partially but not completely filled. Particularly preferred are those processes in which the mold between 5 and 95 vol .-%, preferably between 10 and 90 vol .-%, preferably between 15 and 85 vol .-% and in particular between 20 and 80 vol .-% of the opening the ring tablet fills out.

Suitable materials for the production of molds are in particular metals or metal alloys and, preferably, polymers. Alternatively, of course, metallic molds with, preferably polymeric, coatings can be used. Such coatings are suitable, for example, for increasing the chemical or physical stability of the molds, for example against corrosion or mechanical stress. Furthermore, polymeric coatings are suitable for preventing adhesion to the surface of the mold.

In preferred methods, the mold introduced into the aperture of the ring tablet is adapted, in terms of its spatial shape, to the spatial shape of the aperture of the ring tablet. Thus, the mold is preferably close to the inner wall of the ring tablet, that is, on the wall of the opening to. Particularly preferred are those methods in which the distance between the introduced in the breakthrough mold and the inner wall of the Ring tablet is less than 10 mm, preferably less than 5 mm, preferably less than 3 mm and in particular between 0.1 and 2 mm.

The molding tool preferably has a rotationally symmetrical horizontal cross section. Particularly preferred molds are characterized by a triangular or quadrangular, preferably square, horizontal cross-section. The corners of these molds are preferably rounded. In an alternative, likewise preferred embodiment, the horizontal cross section of the mold introduced into the annular shaped body is oval or circular.

The upper side of the molding tool, that is to say the side of the molding tool facing the first film material placed on the opening of the ring tablet, can be designed in different ways. Since the in step c) applied to the opening of the Ringtablette sheet material in step d) of this preferred embodiment is deep drawn in the at least partially filled with the molding breakthrough, preferably deep-drawn so that this film material fits tightly against the top of the mold, can by the spatial configuration of the upper side of the molded body is also directly influenced by the spatial configuration of the bottom surface of the receiving chamber produced by the deep-drawing process. So results from the use of a mold with a flat top one. taking into account the shrinkage of the deep-drawn sheet material that naturally occurs during thermoforming processes, essentially flat bottom surface of the receiving chamber.

With particular preference in this process variant molds with a flat, concave or convex top, but in particular molds are used with a concave top. In a particularly preferred variant, the upper side of the molding tool has both planar and curved sections, as concave and / or convex sections. Very particular preference is given to molds having a peripheral, planar edge region and a concave inner part enclosed by this planar edge region, that is to say a depression surrounded by this planar edge region.

With particular preference, the introduced in the breakthrough of the ring tablet mold is designed such that by applying a negative pressure to the mold, the gas space between the mold and the applied to the opening of the ring tablet film material can be evacuated. Therefore, preferred molding tools have notches, grooves or holes, by means of which by applying a negative pressure, the gas space between the mold and the first placed on the opening of the ring tablets first Foil material at least partially evacuated and in this way the film material can be deep-drawn into the opening.

If after the introduction of the mold into the opening of the ring tablet in step d) of this preferred process variant, the sheet material deep-drawn into the opening of the ring tablet, the receiving chamber formed by the deep drawing of the sheet material can naturally fill the space in the breakthrough, which does not by the Mold is taken. By filling a washing or cleaning-active substance in this receiving chamber in the subsequent step e), the breakthrough of the ring tablets is therefore also only partially filled. The deep drawing is preferably carried out by applying a negative pressure, but can for example also be effected by the action of a punch.

The receiving chamber formed by the deep drawing of the first film material is preferably filled with a flowable substance. The flowable substances may be solids or liquids, with particular preference liquid (s) and / or gel (s) and / or powder and / or granules (e) and / or extrudate (s) and / or Kompaktat (e) are used. A more detailed description of these flowable substances is given below in the text.

After filling the receiving chamber with the washing or cleaning active substance, this receiving chamber is preferably sealed. Suitable sealing materials are, for example, solidifying melts or liquids or, preferably, precisely fitting shaped bodies. With particular preference, however, water-soluble film materials are used as sealing materials.

1. a) Bereitstellen eines Ringformkörpers, vorzugsweise einer Ringtablette;
2. b) Einbringen eines Formwerkzeugs durch eine erste Öffnung des Durchbruchs der Ringtablette in diesen Durchbruch;
3. c) Auflegen eines ersten, vorzugsweise wasserlöslichen Folienmaterials auf die Formkörperoberfläche über die zweite Öffnung des Durchbruchs;
4. d) Tiefziehen des ersten Folienmaterials in den Durchbruch der Ringtablette unter Ausbildung einer Aufnahmekammer, die den Durchbruch nur anteilsweise ausfüllt;
5. e) Einfüllen einer wasch- oder reinigungsaktiven Substanz in die in Schritt d) gebildete Aufnahmekammer;
6. f) Versiegeln der befüllten Aufnahmekammer.

A further preferred subject of the present application is thus a process for the preparation of a dosing unit for detergents or cleaners, comprising the steps

1. a) providing a ring shaped body, preferably a ring tablet;
2. b) introducing a molding tool through a first opening of the annular tablet breakthrough in this opening;
3. c) placing a first, preferably water-soluble film material on the molding surface via the second opening of the opening;
4. d) deep drawing of the first sheet material in the breakthrough of the ring tablet to form a receiving chamber which fills the breakthrough only partially;
5. e) filling a washing or cleaning-active substance in the receiving chamber formed in step d);
6. f) sealing the filled receiving chamber.

For sealing and adhesive bonding of the first film material with the further water-soluble film material, for example, solvents and / or adhesives can be used. With particular preference, however, the sealing takes place by means of heat, preferably by laser welding or heat sealing.

The sealing can be carried out in principle in the region of the shaped body of the ring tablet itself and / or in the region of the opening. In the first case, the metering units have a, preferably circumferential, sealing seam, which is in direct contact with the shaped body; in the second case, the, preferably circumferential, sealing seam lies in the region of the opening and does not touch the shaped body.

As already stated above, in this preferred variant of the method molds are used with particular advantage, the upper side of which has a peripheral, planar edge region and a concave inner part, that is to say a hollow enclosed by this flat edge region. With particular preference, the sealing of the thermoformed first sheet material with the used for sealing further water-soluble sheet material by means of heat sealing, wherein the receiving chamber occluding, preferably circumferential sealing seam, with particular preference, the shaped body is not affected, that is generated for example in the region of the opening.

1. a) Bereitstellen eines Ringformkörpers, vorzugsweise einer Ringtablette;
2. b) Einbringen eines Formwerkzeugs, dessen Oberseite einen umlaufenden planen Randbereich aufweist, durch eine erste Öffnung des Durchbruchs der Ringtablette in diesen Durchbruch;
3. c) Auflegen eines ersten, vorzugsweise wasserlöslichen Folienmaterials auf die Formkörperoberfläche über die zweite Öffnung des Durchbruchs;
4. d) Tiefziehen des ersten Folienmaterials in den Durchbruch der Ringtablette unter Ausbildung einer Aufnahmekammer, die den Durchbruch nur anteilsweise ausfüllt;
5. e) Einfüllen einer wasch- oder reinigungsaktiven Substanz in die in d) gebildete Aufnahmekammer;
6. f) Versiegeln der befüllten Aufnahmekammer durch Aufbringen eines wasserlöslichen Folienmaterials auf die befüllte Aufnahmekammer und Heißsiegelung des ersten Folienmaterials mit dem wasserlöslichen Folienmaterials im planen Randbereichs des Formwerkzeugs.

A further preferred subject of the present application is thus a process for the preparation of a dosing unit for detergents or cleaners, comprising the steps

1. a) providing a ring shaped body, preferably a ring tablet;
2. b) introducing a molding tool, the upper side of which has a peripheral, planar edge region, through a first opening of the annular tablet breakthrough into this opening;
3. c) placing a first, preferably water-soluble film material on the molding surface via the second opening of the opening;
4. d) deep drawing of the first sheet material in the breakthrough of the ring tablet to form a receiving chamber which fills the breakthrough only partially;
5. e) filling a washing or cleaning-active substance in the receiving chamber formed in d);
6. f) sealing the filled receiving chamber by applying a water-soluble film material to the filled receiving chamber and Heat-sealing the first film material with the water-soluble film material in the planar edge region of the molding tool.

By sealing the two film materials forming the receiving chamber in the region of the planar edge region of the molding tool, the tightness of the sealed receiving chambers can be significantly increased in comparison to conventional methods. With particular preference in this process variant metallic molds are used. With particular preference, the molds used are heated.

After completion of the seal resulting detergent or Reinigungsmitteldosiereinheiten comprising a ring tablet and the breakthrough of the ring tablet partially fills, filled, preferably water-soluble receiving chamber. Ring tablet and filled receiving chamber are preferably adhesively bonded together. This adhesive connection can be made, for example, by gluing the ring tablet to the first film material placed over the opening of the ring tablet in step c) or by heat-sealing the first film material to the surface of the ring tablet. The breakthrough of the ring tablet is not filled below the water-soluble receiving chamber.

In a preferred embodiment of the method variant described above, the mold is removed after completion of the seal from the opening and the cavity located in the opening below the filled receiving chamber filled with another, preferably flowable, washing or cleaning-active substance. For this purpose, the partially filled ring tablet is preferably first turned over. After filling, the second opening of the opening is preferably also sealed, with the sealing materials mentioned above, in particular water-soluble film materials, being used with particular preference.

1. a) Bereitstellen eines Ringformkörpers, vorzugsweise einer Ringtablette;
2. b) Einbringen eines Formwerkzeugs, dessen Oberseite vorzugsweise einen umlaufenden planen Randbereich aufweist, durch eine erste Öffnung des Durchbruchs der Ringtablette in diesen Durchbruch;
3. c) Auflegen eines ersten, vorzugsweise wasserlöslichen Folienmaterials auf die Formkörperoberfläche über die zweite Öffnung des Durchbruchs;
4. d) Tiefziehen des ersten Folienmaterials in den Durchbruch der Ringtablette bis auf die Oberseite des Formwerkzeugs unter Ausbildung einer Aufnahmekammer, die den Durchbruch nur anteilsweise ausfüllt;
5. e) Einfüllen einer wasch- oder reinigungsaktiven Substanz in die in d) gebildete Aufnahmekammer;
6. f) Versiegeln der befüllten Aufnahmekammer durch Aufbringen eines wasserlöslichen Folienmaterials auf die befüllte Aufnahmekammer und Heißsiegelung des ersten, vorzugsweise wasserlöslichen Folienmaterials mit diesem wasserlöslichen Folienmaterials, wobei die Versiegelung vorzugsweise im planen Randbereichs des Formwerkzeug erfolgt;
7. g) Entfernen des Formwerkzeugs durch die erste Öffnung aus dem Durchbruch der Ringtablette und Einfüllen einer weiteren wasch- oder reinigungsaktiven Substanz in den zuvor von dem Formwerkzeug eingenommen Bereich des Durchbruchs;
8. h) Versiegeln der ersten Öffnung des befüllten Durchbruchs mit einem, vorzugsweise wasserlöslichen, Foliematerial.

A further preferred subject of the present application is thus a process for the preparation of a dosing unit for detergents or cleaners, comprising the steps

1. a) providing a ring shaped body, preferably a ring tablet;
2. b) introducing a mold, the top of which preferably has a circumferential planar edge region, through a first opening of the opening of the annular tablet in this opening;
3. c) placing a first, preferably water-soluble film material on the molding surface via the second opening of the opening;
4. d) deep drawing of the first sheet material in the breakthrough of the ring tablet to the top of the mold to form a receiving chamber which fills the breakthrough only partially;
5. e) filling a washing or cleaning-active substance in the receiving chamber formed in d);
6. f) sealing the filled receiving chamber by applying a water-soluble film material to the filled receiving chamber and heat-sealing the first, preferably water-soluble film material with this water-soluble film material, wherein the sealing preferably takes place in the planar edge region of the mold;
7. g) removing the molding tool through the first opening from the opening of the annular tablet and filling another washing or cleaning substance in the previously occupied by the mold portion of the opening;
8. h) sealing the first opening of the filled opening with a, preferably water-soluble, film material.

Process variants are particularly preferred in which a washing or cleaning-active liquid or a washing or cleaning-active gel is introduced into at least one of the process steps e) or h). Very particular preference is given to processes in which a washing or cleaning-active liquid or a washing or cleaning-active gel is introduced in step e), while in step h) a flowable, washing or cleaning-active solid, preferably a powder or granules or a Extrudate, is filled.

Regardless of the nature of the process variant, the first film material in step c) or in step d) of the process according to the invention is preferably deep-drawn by applying a negative pressure. In a further preferred variant of the method, the negative pressure in the cavity is produced by applying a negative pressure to a hole or notch which connects the cavity to the part of the surface of the shaped body (outside the cavity) which does not extend through the first foil material Step b) is covered. Such a hole may, for example, be a bore which connects the cavity to a side surface or the lower side of the molded body. Such a bore preferably has a diameter below 5 mm, preferably below 3 mm and in particular below 2 mm. Of course, the cavity can also be connected by more than one hole with one or more outsides. the molded body also have more than one bore. Alternatively or additionally, the shaped body can furthermore have notches. These notches or grooves open into the opening of the cavity opening and lead from there preferably to a side surface of the molding. The width of these notches is preferably less than 10 mm, preferably less than 7 mm, more preferably less than 4 mm and in particular less than 2 mm. The depth of the notches is preferably in the range between 1 and 15 mm, preferably between 1 and 10 mm and in particular between 1 and 5 mm.

In a further variant of the method according to the invention, the first film material is applied by applying a negative pressure to a hole or indentation which connects the cavity to the part of the surface of the molded article (outside the cavity), not through the first film material from step b) is covered, deep drawn into the cavity.

• a) Bereitstellen eines Formkörpers mit mindestens einer Kavität in Form einer Mulde;
• a') Optional anteilsweises Befüllen der Mulde mit einer wasch- oder reinigungsaktiven Zusammensetzung, vorzugsweise einer festen wasch- oder reinigungsaktiven Zusammensetzung, welche besonders bevorzugt mindestens eine Substanz aus der Gruppe der Gerüststoffe, Enzyme, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, Silberschutzmittel und Glaskorrosionsinhibitoren enthält;
• b) Auflegen eines ersten Folienmaterials auf die Formkörperoberfläche über die Öffnung der Mulde;
• c) Tiefziehen des ersten Folienmaterials in die Mulde durch Anlegen eines Unterdrucks an ein Loch oder eine Einkerbung erzeugt, welche(s) die Mulde mit dem Teil der Oberfläche des Formkörpers (außerhalb der Mulde) verbindet, der nicht durch das erste Folienmaterial aus Schritt b) bedeckt ist;
• d) Einfüllen einer wasch- oder reinigungsaktiven Substanz auf das Folienmaterial in der Mulde.

A further preferred subject of this application is therefore a process for the preparation of a dosing unit for detergents or cleaners, thus comprising the steps

• a) providing a shaped body having at least one cavity in the form of a trough;
• a ') Optional partial filling of the well with a washing or cleaning active composition, preferably a solid washing or cleaning active composition, particularly preferably at least one substance from the group of builders, enzymes, bleach, bleach activators, bleach catalysts, silver protectants and glass corrosion inhibitors;
• b) placing a first sheet material on the molding surface over the opening of the well;
• c) deep drawing the first sheet material into the trough by applying a negative pressure to a hole or indentation which connects the trough to that part of the surface of the shaped body (outside the trough) that is not penetrated by the first sheet material from step b ) is covered;
• d) filling a washing or cleaning-active substance on the film material in the trough.

If the shaped body has a corrosive porosity, the negative pressure in the cavity can be generated by applying a negative pressure to the shaped body surface (outside the cavity). Surprisingly, it has been found that the abovementioned washing or cleaning agent tablets are suitable for such a process. By compaction, preferably tabletting, particulate starting mixtures can thus produce moldings which have sufficient porosity to generate by applying a negative pressure on the surface of the shaped body, which is not covered by the film material within the cavity sufficient negative pressure to the Deep-draw opening of the cavity covering foil material in this cavity.

A further preferred variant of the method according to the invention, the first sheet material is produced by applying a negative pressure to the part of the surface of the shaped body (outside the cavity), which is not covered by the sheet material from step b) deep drawn into the cavity.

• a) Bereitstellen eines Formkörpers mit mindestens einer Kavität in Form einer Mulde;
• a') Optional anteilsweises Befüllen der Kavität mit einer wasch- oder reinigungsaktiven Zusammensetzung, vorzugsweise einer festen wasch- oder reinigungsaktiven Zusammensetzung, welche besonders bevorzugt mindestens eine Substanz aus der Gruppe der Gerüststoffe, Enzyme, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, Silberschutzmittel und Glaskorrosionsinhibitoren enthält;
• b) Auflegen eines ersten Folienmaterials auf die Formkörperoberfläche über eine Öffnung der Kavität;
• c) Tiefziehen des ersten Folienmaterials in die Kavität durch Anlegen eines Unterdrucks an den Teil der Oberfläche des Formkörpers (außerhalb der Kavität) erzeugt wird, der nicht durch das Folienmaterial aus Schritt b) bedeckt ist;
• d) Einfüllen einer wasch- oder reinigungsaktiven Substanz auf das Folienmaterial in der Kavität.

A further subject of this application is therefore a process for the preparation of a dosing unit for detergents or cleaners, thus comprising the steps

• a) providing a shaped body having at least one cavity in the form of a trough;
• a ') Optional partial filling of the cavity with a washing or cleaning active composition, preferably a solid washing or cleaning active composition, particularly preferably at least one substance from the group of builders, enzymes, bleach, bleach activators, bleach catalysts, silver protectants and glass corrosion inhibitors;
• b) placing a first film material on the shaped body surface via an opening of the cavity;
• c) drawing the first sheet material into the cavity by applying a negative pressure to the part of the surface of the shaped body (outside the cavity) which is not covered by the sheet material from step b);
• d) filling a washing or cleaning active substance on the film material in the cavity.

In the preferred method variants described hitherto, the negative pressure in the cavity is produced by the air in the cavity below the film material applied in step b) "passing through the tablet", that is to say by applying a negative pressure to holes specially provided for this purpose, Notches or holes, or by taking advantage of tablet porosity was removed from this cavity. In a further particularly preferred variant of the method, the negative pressure in the cavity is produced by removing the air in the cavity below the film placed in step b) through holes in this film material from the cavity.

• a) Bereitstellen eines Formkörpers mit mindestens einer Kavität;
• a') Optional anteilsweises Befüllen der Kavität mit einer wasch- oder reinigungsaktiven Zusammensetzung, vorzugsweise einer festen wasch- oder reinigungsaktiven Zusammensetzung, welche besonders bevorzugt mindestens eine Substanz aus der Gruppe der Gerüststoffe, Enzyme, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, Silberschutzmittel und Glaskorrosionsinhibitoren enthält;
• b) Auflegen eines ersten Folienmaterials auf die Formkörperoberfläche über die Öffnung der Kavität;
• c) Tiefziehen des ersten Folienmaterials in die Kavität, indem in der Kavität dadurch ein Unterdruck erzeugt wird, dass die in der Kavität unterhalb der Folie befindliche Luft wenigstens anteilsweise durch Öffnungen in dem in Schritt b) aufgelegten Folienmaterial entweicht;
• d) Einfüllen einer wasch- oder reinigungsaktiven Substanz auf das Folienmaterial in der Kavität;

werden im Rahmen dieser Anmeldung besonders bevorzugt.Process for the preparation of a dosing unit for detergents or cleaners, comprising the steps

• a) providing a shaped body having at least one cavity;
• a ') Optional partial filling of the cavity with a washing or cleaning active composition, preferably a solid wash or cleaning-active composition, which particularly preferably contains at least one substance from the group of builders, enzymes, bleaching agents, bleach activators, bleach catalysts, silver protectants and glass corrosion inhibitors;
• b) placing a first sheet material on the molding surface over the opening of the cavity;
• c) deep-drawing the first film material into the cavity by creating a negative pressure in the cavity in that the air in the cavity below the film escapes at least partially through openings in the film material applied in step b);
• d) filling a washing or cleaning substance on the film material in the cavity;

are particularly preferred in the context of this application.

Processes according to the invention in which the negative pressure is generated both in the cavity, ie below the film material applied in step b) and also outside the cavity, above the film material applied in step b), are particularly preferred. Such a particularly advantageous process procedure can be realized, for example, by the fact that the molded body covered with the film material is brought into a vacuum chamber. Due to the openings in the film material, when a vacuum is applied to the vacuum chamber both in the cavity of the molded body, ie below the film material applied in step b), and outside the molded body, above the film material applied in step b) is produced the air located below the film material applied in step b) passes through these openings into the space above the film material applied in step b) and is removed therefrom by the applied vacuum from the vacuum chamber. In a subsequent process step, the film web applied in step b) is sealed with the filled container in such a way that the container is closed on all sides and in particular no air can pass through the openings of the film web applied in step c) into the container. If the sealed container is then removed from the vacuum chamber, the atmospheric pressure acting on the container from outside causes the outer walls of the container, in particular the film web applied in step b), to fit tightly against the molded body into the cavity.

• a) Bereitstellen eines Formkörpers mit mindestens einer Kavität;
• a') Optional anteilsweises Befüllen der Kavität mit einer wasch- oder reinigungsaktiven Zusammensetzung, vorzugsweise einer festen wasch- oder reinigungsaktiven Zusammensetzung, welche besonders bevorzugt mindestens eine Substanz aus der Gruppe der Gerüststoffe, Enzyme, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, Silberschutzmittel und Glaskorrosionsinhibitoren enthält;
• b) Auflegen eines ersten Folienmaterials auf die Formkörperoberfläche über die Öffnung der Kavität;
• c) Tiefziehen des ersten Folienmaterials in die Kavität, indem der mit der Folienbahn bedeckte Formkörper in eine Unterdruckkammer verbracht wird und in dieser Kammer ein Unterdruck erzeugt wird, wodurch in der Kavität dadurch ein Unterdruck erzeugt wird, dass die in der Kavität unterhalb der Folie befindliche Luft wenigstens anteilsweise durch Öffnungen in dem in Schritt b) aufgelegten Folienmaterial entweicht;
• d) Einfüllen einer wasch- oder reinigungsaktiven Substanz auf das Folienmaterial in der Kavität.

werden im Rahmen dieser Anmeldung ebenfalls besonders bevorzugt.Process for the preparation of a dosing unit for detergents or cleaners, comprising the steps

• a) providing a shaped body having at least one cavity;
• a ') Optional partial filling of the cavity with a washing or cleaning active composition, preferably a solid washing or cleaning active composition, particularly preferably at least one substance from the group of builders, enzymes, bleach, bleach activators, bleach catalysts, silver protectants and glass corrosion inhibitors;
• b) placing a first sheet material on the molding surface over the opening of the cavity;
• c) deep drawing of the first film material in the cavity by the covered with the film web moldings is placed in a vacuum chamber and in this chamber, a negative pressure is generated, whereby a negative pressure is generated in the cavity, that in the cavity located below the film Air escapes at least partially through openings in the film material applied in step b);
• d) filling a washing or cleaning active substance on the film material in the cavity.

are also particularly preferred in the context of this application.

By deep-drawing the film material into the cavity in step c) of the method according to the invention, the film material is molded into the cavity to form a receiving trough. This receiving trough is then filled in the subsequent step d) with a detergent or cleaning substance. The shape and the volume of the receiving trough will of course depend on the shape and the volume of the cavity of the molded article on which the process is based. Preference is given in particular to those processes in which the volume of the receiving trough formed by the film material is at least 40% by volume, preferably at least 60% by volume, very particularly preferably at least 80% by volume, in particular at least 90% by volume and particularly preferably at least 95 vol .-% of the volume of the cavity of the molding in step a) or in step a ').

For the spatial fixation of shaped bodies and foil material before the subsequent filling in step d), the shaped body and the foil material are adhesively bonded together in a preferred embodiment of the method according to the invention. The adhesive bond preferably takes place in spatial proximity to the opening of the cavity into which the film material was deep-drawn in step c). Particularly preferred is the adhesive compounds along a circumferential sealed seam. This sealed seam can be realized by a number of different procedures. However, preference is given to those processes in which the adhesive compound is formed by the action of adhesives and / or solvents and / or compressive or squeezing forces. However, particularly preferred are those inventive Method in which the molded body before, simultaneously with or after the deep drawing of the first film material in step c) is adhesively bonded to this first film material by a bond and / or a heat seal. Also in the case of heat sealing, a circumferential sealing seam, that is, a self-contained sealing seam is particularly preferred. For heat sealing of molded articles and film material, a number of different tools and processes are available to the person skilled in the art.

In a first preferred embodiment, the heat seal is effected by the action of heated sealing tools.

In a second preferred embodiment, the heat seal is effected by the action of a laser beam.

In a third preferred embodiment, the heat seal is effected by the action of hot air.

In step d) of the process according to the invention, a washing or cleaning-active substance is filled onto the film material in the cavity. As washing or cleaning substances are suitable solids as well as liquids. The washing or cleaning-active substance can be filled onto the film material in the cavity by means of all dosing methods known to those skilled in the art.

In a first preferred embodiment, in step d) prefabricated molded bodies, for example cast bodies, tablets or extrudates are placed on the film material in the cavity. If a tablet or a ring tablet is used as the shaped body in step a), the end product of this preferred variant of the method corresponds to a core tablet or a bullet-shaped tablet in which the cavity of the tablet obtained in step a ) is filled with a casting, another tablet or an extrudate, wherein the tablet and the inserted core are separated from each other by the in step c) deep-drawn in the cavity sheet material.

The washing or cleaning-active substance filled in step d) preferably has a density above 1.0 g / cm 3, preferably above 1.1 g / cm 3, particularly preferably above 1.2 g / cm 3, very particularly preferably above 1.3 g / cm3 and in particular above 1.4 g / cm 3. The volume ratio of the shaped body provided in step a) to the volume of substance introduced into the cavity in step d) is preferably between 1: 1 and 20: 1 and in particular between 3: 1 and 15: 1.

In the context of the present application, particular preference is given in particular to those processes in which a flowable detergent or cleaning substance is introduced in step d). These solid or liquid flowable substances or substance mixtures are preferably poured onto the film material in the cavity. Liquid (s) and / or gel (s) and / or powder and / or granules (e) and / or extrudate (s) and / or compact (e) are preferably used as flowable substances.

If particulate substances, for example powders, granules or extrudates, are used as solid flowable substances or substance mixtures, these particulate substances or substance mixtures have an average particle size below 5000 μm, preferably less than 3000 μm, preferably less than 1000 μm, very particularly preferably between 50 and 1000 μm and in particular between 100 and 800 μm.

In a further preferred embodiment, the flowable washing or cleaning substance is a liquid. In this context, substances or mixtures of substances in their liquid state of aggregation are referred to as liquid. The term "liquid" therefore also comprises, in addition to liquid pure substances, also solutions, suspensions, emulsions or melts. Preference is given to using substances or mixtures of substances which are in the liquid state at 20 ° C. As a preferred constituent, the liquids contain at least one substance from the group of nonionic surfactants and / or polymers and / or organic solvents. The liquid may in turn have several phases.

As flowable washing or cleaning-active substances, it is also possible to use molten substances or substance mixtures.

• a) Bereitstellen eines Formkörpers mit mindestens einer Kavität;
• a') Optional anteilsweises Befüllen der Kavität mit einer wasch- oder reinigungsaktiven Zusammensetzung, vorzugsweise einer festen wasch- oder reinigungsaktiven Zusammensetzung;
• b) Auflegen eines ersten Folienmaterials auf die Formkörperoberfläche über die Öffnung der Kavität;
• c) Tiefziehen des ersten Folienmaterials in die Kavität, indem in der Kavität des Formkörpers ein Unterdruck erzeugt wird;
• d) Einfüllen einer zweiten wasch- oder reinigungsaktiven Substanz, vorzugsweise einer flüssigen wasch- oder reinigungsaktiven Substanz, auf das Folienmaterial in der Kavität.

Preference is therefore given in particular to those processes according to the invention for producing a metering unit for detergents or cleaners, comprising the steps

• a) providing a shaped body having at least one cavity;
• a ') Optional partial filling of the cavity with a washing or cleaning active composition, preferably a solid washing or cleaning active composition;
• b) placing a first sheet material on the molding surface over the opening of the cavity;
• c) deep drawing of the first film material into the cavity by creating a negative pressure in the cavity of the shaped body;
• d) filling a second washing or cleaning active substance, preferably a liquid washing or cleaning substance, on the film material in the cavity.

In step d), the cavity is preferably filled with a liquid. This liquid-filled cavity is then preferably sealed. In a particularly preferred embodiment, in addition to the liquid, a gas or gas mixture is additionally enclosed during the sealing in the cavity. For example, this gas or gas mixture may be an inert gas (e.g., argon or nitrogen), a reactive gas such as carbon dioxide, but also, for example, natural ambient air. Processes according to the invention in which the cavity is filled with a liquid in step d) and subsequently sealed with the inclusion of a gas bubble are particularly preferred. The volume of the gas bubble is preferably between 1 and 25% by volume, preferably between 2 and 20% by volume and in particular between 4 and 10% by volume of the volume of the sealed cavity.

In a further preferred embodiment, the shaped bodies provided in step a) have a coating of a water-soluble or water-dispersible material, preferably an envelope of a water-soluble or water-dispersible film material, more preferably of a water-soluble or water-dispersible polymer-based film material. Particularly preferred film materials are the materials described above from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof. This enclosure may include the shaped body completely or only partially. Particularly preferred are processes in which the shaped body in step a) is partially surrounded by a water-soluble or water-dispersible film material. Such a partial coating can be realized, for example, by deforming a first water-soluble or water-dispersible film material, for example by deep drawing to form a receiving chamber and the shaped body is moved in step a) in this resulting receiving chamber. Alternatively, the water-soluble or water-dispersible receiving chamber may also be made by injection molding a water-soluble or water-dispersible material. After the shaped body has been moved into this receiving chamber in step a), the remaining steps of the method according to the invention are carried out as described above, with the difference that in this variant of the method, the shell material of the shaped body from step a) in the course of the process with the first or second preferably water-soluble film material from steps b) or e) to connect adhesively and in this way to achieve a complete enclosure of the provided in step a), a ') and d) washing or cleaning-active substances. The resulting final process product is not only distinguished by the separation of the active substances introduced in steps a) and a ') or d), but also makes possible the Preparation of readily soluble and thus highly active active substances in powder form or in the form of liquid compositions in a prefabricated dosing unit.

• a) Bereitstellen eines Formkörpers in einer wasserlöslichen oder wasserdispergierbaren Aufnahmekammer, wobei der Formkörper mindestens eine Kavität aufweist;
• a') Optional anteilsweises Befüllen der Kavität mit einer wasch- oder reinigungsaktiven Zusammensetzung, vorzugsweise einer festen wasch- oder reinigungsaktiven Zusammensetzung;
• b) Auflegen eines ersten Folienmaterials auf die Formkörperoberfläche über die Öffnung der Kavität;
• c) Tiefziehen des ersten Folienmaterials in die Kavität, indem in der Kavität des Formkörpers ein Unterdruck erzeugt wird;
• d) Einfüllen einer zweiten wasch- oder reinigungsaktiven Substanz, vorzugsweise einer flüssigen wasch- oder reinigungsaktiven Substanz, auf das Folienmaterial in der Kavität.

Preference is thus further given to a process for the preparation of a dosing unit for detergents or cleaners, comprising the steps

• a) providing a shaped body in a water-soluble or water-dispersible receiving chamber, wherein the shaped body has at least one cavity;
• a ') Optional partial filling of the cavity with a washing or cleaning active composition, preferably a solid washing or cleaning active composition;
• b) placing a first sheet material on the molding surface over the opening of the cavity;
• c) deep drawing of the first film material into the cavity by creating a negative pressure in the cavity of the shaped body;
• d) filling a second washing or cleaning active substance, preferably a liquid washing or cleaning substance, on the film material in the cavity.

The water-soluble or water-dispersible receiving chamber is preferably adhesively bonded in a further process step with the first film material from step b). The adhesive connection is preferably carried out subsequent to the deep-drawing of the first film material in step c), but can also take place with preference in the Anschlu8 to the steps b) or d).

As mentioned above, the cavity can be a depression or a breakthrough. With particular preference, the latter method variant is carried out with a shaped body which has a breakthrough as a cavity. The process product of this process variant is then a ring-core tablet ("bull-eye tablet"), the breakthrough is closed on both sides by means of a water-soluble or water-dispersible material, the breakthrough itself by another water-soluble or water-dispersible Material, which may be identical to the aforementioned water-soluble or water-dispersible material, but may also differ from this material, is divided into two separate chambers, which preferably have a different filling.

• a) Bereitstellen eines Formkörpers in einer wasserlöslichen oder wasserdispergierbaren Aufnahmekammer, wobei der Formkörper mindestens einen Durchbruch aufweist;
• a') Anteilsweises Befüllen des Durchbruchs mit einer ersten wasch- oder reinigungsaktiven Zusammensetzung, vorzugsweise einer festen wasch- oder reinigungsaktiven Zusammensetzung;
• b) Auflegen eines ersten Folienmaterials auf die Formkörperoberfläche, über die Öffnung des Durchbruchs;
• c) Tiefziehen des ersten Folienmaterials in den Durchbruch, indem in der Kavität des Formkörpers ein Unterdruck erzeugt wird;
• d) Einfüllen einer zweiten wasch- oder reinigungsaktiven Substanz, vorzugsweise einer flüssigen wasch- oder reinigungsaktiven Substanz, auf das Folienmaterial in der Kavität.

A further subject of the present application is therefore a process for the preparation of a dosing unit for detergents or cleaners, comprising the steps

• a) providing a shaped body in a water-soluble or water-dispersible receiving chamber, wherein the shaped body has at least one breakthrough;
• a ') Partial filling of the opening with a first washing or cleaning active composition, preferably a solid washing or cleaning active composition;
• b) placing a first sheet material on the shaped body surface, over the opening of the opening;
• c) deep-drawing of the first sheet material into the opening by creating a negative pressure in the cavity of the shaped body;
• d) filling a second washing or cleaning active substance, preferably a liquid washing or cleaning substance, on the film material in the cavity.

In the methods described above, it is preferred to seal the cavity opening following step d) in a further step e). In a preferred variant of the method, this sealing takes place by applying a second film material to the cavity opening and subsequent heat sealing and / or ultrasonic sealing and / or high-frequency sealing. This second film material may be the same or a different film material from the first film material used in step b). The second film material may differ from the first film material, for example, by its thickness and / or its composition. Of course, the sealing of the second film material via the cavity opening can also take place by gluing the second film material to the first film material or to the shaped article. In addition to adhesives known to the person skilled in the art, in particular solvents, particularly preferably water or aqueous solutions, are suitable for sealing the cavity opening of the bonding.

The sealed cavity preferably has an overpressure. Such a crowning can be achieved, for example, by adding gas-releasing components to the washing or cleaning-active substances filled in step d). As a result of the release of gas after the cavity has been sealed in step e), the film material used for the sealing bulges and forms a visually appealing, convex curvature.

It is preferred that the molded article is adhesively bonded to the first film material and / or to the second film material by the heat-sealing and / or ultrasonic sealing and / or high-frequency sealing and / or gluing.

• a) Bereitstellen eines Formkörpers mit mindestens einer Kavität;
• a') Optional anteilsweises Befüllen der Kavität mit einer wasch- oder reinigungsaktiven Zusammensetzung, vorzugsweise einer festen wasch- oder reinigungsaktiven Zusammensetzung;
• b) Auflegen eines ersten Folienmaterials auf die Formkörperoberfläche über die Öffnung der Kavität;
• c) Tiefziehen des ersten Folienmaterials in die Kavität, indem in der Kavität des Formkörpers ein Unterdruck erzeugt wird;
• d) Einfüllen einer zweiten wasch- oder reinigungsaktiven Substanz, vorzugsweise einer flüssigen wasch- oder reinigungsaktiven Substanz, auf das Folienmaterial in der Kavität;
• e) Versiegelung der in Schritt d) befüllten Kavität, vorzugsweise durch Auflegen eines zweiten Folienmaterials und haftende Verbindung des zweiten Folienmaterials mit dem Formkörper aus Schritt a) und/oder dem ersten Folienmaterial aus Schritt b).

According to the invention, preference is furthermore given to a process for the production of a dosing unit for detergents or cleaners, comprising the steps

• a) providing a shaped body having at least one cavity;
• a ') Optional partial filling of the cavity with a washing or cleaning active composition, preferably a solid washing or cleaning active composition;
• b) placing a first sheet material on the molding surface over the opening of the cavity;
• c) deep drawing of the first film material into the cavity by creating a negative pressure in the cavity of the shaped body;
• d) filling a second washing or cleaning active substance, preferably a liquid washing or cleaning substance, on the film material in the cavity;
• e) sealing the cavity filled in step d), preferably by applying a second film material and adhesive bonding of the second film material to the shaped article from step a) and / or the first film material from step b).

• a) Bereitstellen eines Formkörpers in einer wasserlöslichen oder wasserdispergierbaren Aufnahmekammer, wobei der Formkörper mindestens eine Kavität aufweist;
• a') Optional anteilsweises Befüllen der Kavität mit einer wasch- oder reinigungsaktiven Zusammensetzung, vorzugsweise einer festen wasch- oder reinigungsaktiven Zusammensetzung;
• b) Auflegen eines ersten Folienmaterials auf die Formkörperoberfläche über die Öffnung der Kavität;
• c) Tiefziehen des ersten Folienmaterials in die Kavität, indem in der Kavität des Formkörpers ein Unterdruck erzeugt wird;
• d) Einfüllen einer zweiten wasch- oder reinigungsaktiven Substanz, vorzugsweise einer flüssigen wasch- oder reinigungsaktiven Substanz, auf das Folienmaterial in der Kavität;
• e) Versiegelung der in Schritt d) befüllten Kavität, vorzugsweise durch Auflegen eines zweiten Folienmaterials und haftende Verbindung des zweiten Folienmaterials mit dem Formkörper aus Schritt a) und/oder dem ersten Folienmaterial aus Schritt b);

wobei die wasserlösliche oder wasserdispergierbare Aufnahmekammer in einem weiteren Verfahrensschritt mit dem ersten Folienmaterial aus Schritt b) und/oder dem zweiten Folienmaterial aus Schritt e) haftend verbunden wird. Die haftende Verbindung erfolgt dabei vorzugsweise zusammen mit der Versiegelung der in Schritt d) befüllten Kavität in Schritt e).Preference is thus furthermore given to a method according to the invention for producing a dosing unit for detergents or cleaners, comprising the steps

• a) providing a shaped body in a water-soluble or water-dispersible receiving chamber, wherein the shaped body has at least one cavity;
• a ') Optional partial filling of the cavity with a washing or cleaning active composition, preferably a solid washing or cleaning active composition;
• b) placing a first sheet material on the molding surface over the opening of the cavity;
• c) deep drawing of the first film material into the cavity by creating a negative pressure in the cavity of the shaped body;
• d) filling a second washing or cleaning active substance, preferably a liquid washing or cleaning substance, on the film material in the cavity;
• e) sealing the cavity filled in step d), preferably by applying a second film material and adhesive bonding of the second film material to the shaped article from step a) and / or the first film material from step b);

wherein the water-soluble or water-dispersible receiving chamber is adhesively bonded in a further process step with the first film material from step b) and / or the second film material from step e). The adhesive connection preferably takes place together with the sealing of the cavity filled in step d) in step e).

Process product is thus in particular a molded article with a breakthrough (ring-core tablet or "bull-eye tablet"), the breakthrough is closed on both sides by means of a water-soluble or water-dispersible material, the breakthrough itself by another water-soluble or water-dispersible Material is divided into two separate chambers, which preferably have a different filling. Particular preference is given to those shaped bodies which contain one of the chambers a solid washing or cleaning substance, more preferably a solid washing or cleaning substance in the form of a powder, granules or extrudate, while the second chamber contains a liquid detergent or cleaning substance. The water-soluble or water-dispersible materials, which close the breakthrough on both sides or subdivide the breakthrough into two separate chambers, may be identical, but may also differ from one another.

The volume of the chambers located in the breakthrough is preferably between 0.5 and 15 ml, preferably between 0.5 and 12 ml, more preferably between 0.5 and 8 ml and in particular between 0.5 and 6 ml Chambers to each other is preferably between 10: 1 and 1:10, preferably between 8: 1 and 1: 8, more preferably between 6: 1 and 1: 6 and in particular between 4: 1 and 1: 4.

The shaped bodies with filled breakthrough described above enable the combined formulation of solid and liquid washing and cleaning substances using minimal amounts of packaging materials. By using water-soluble or water-dispersible packaging materials, these means are also suitable for direct metering into the metering chamber or the interior of a dishwasher or washing machine. The shaped bodies of this particular embodiment according to the invention are distinguished by at least three phases (shaped body, first washing or cleaning substance in chamber 1, second detergent or cleaning substance in chamber 2) and thus allows the visualization complex drug combinations (eg "2in1" - or "3in1" automatic dishwashing or combination products of a laundry detergent and conditioner such as a softener, a dye transfer inhibitor or a crease inhibitor.

Following the process according to the invention, the process end products are preferably separated and compounded. If, for example, a film web is used as first or second film material, which film is processed to more than one of the metering units according to the invention, then this film material is cut into shape during or after completion of the process. Inventive method, characterized in that the first or second sheet material in the course of the process, preferably after a Sealing step is severed by a mechanical and / or thermal process to form a cutting line, wherein the cutting line preferably extends circumferentially on the surface of the molding, are particularly preferred.

The process according to the invention may also be followed by packaging of the process end products in "flow packs", stand-up pouches or cardboard packaging.

In the method according to the invention, a film material, preferably a water-soluble or water-dispersible film material, is thermoformed to form a receiving chamber in the cavities of detergent tablets or detergent tablets. Process products are therefore furthermore metering units for detergents or cleaners, comprising a molding having at least one cavity, a film material deep-drawn into the cavity to form a receiving chamber, and a washing or cleaning substance located on the film material in the cavity. By the deep-drawing process, the film material is applied tightly against the inner walls of the cavity. This method is thus distinguished from alternative approaches, such as the pressing or inserting of a film material through an optimized use of space.

As described above, the shaped body is preferably a tablet, a compact, an extrudate, an injection molding or a casting. With regard to the preferred manufacturing method of these moldings and their preferred spatial forms, reference is made at this point to avoid repetition of the statements above in the description.

According to the invention, preference is given to those metering units which have a cavity or an opening as a cavity. The volume of the cavity is preferably between 0.1 and 20 ml, preferably between 0.2 and 15 ml, more preferably between 1 and 10 ml and in particular between 2 and 7 ml.

The dosing units according to the invention comprise, in addition to a shaped body, a receiving trough filled with washing or cleaning-active ingredients and preferably made of a water-soluble or water-dispersible foil material. In the case of a simple, single-phase molded body, the dosing unit thus has two phases separated from one another. These separate phases allow, for example, the separation of incompatible ingredients or the joint dosage of detergents or cleaning agents with different states of aggregation or Konfektionsformen.

In a particularly preferred embodiment of the compositions according to the invention, the dosing unit is characterized in that the receiving chamber formed from the thermoformed sheet material with a flowable, preferably a liquid washing or cleaning substance, more preferably with one or more active substance (s) from the group of Group of nonionic surfactants and / or polymers and / or organic solvents, is filled.

The flowable washing or cleaning substances may be solid or liquid. Liquid (s) and / or gel (s) and / or powder and / or granules (e) and / or extrudate (s) and / or compact (e) are preferably used as flowable substances.

In a further preferred embodiment, the flowable washing or cleaning substance is a liquid. In this context, substances or mixtures of substances in their liquid state of aggregation are referred to as liquid. The term "liquid" therefore also comprises, in addition to liquid pure substances, also solutions, suspensions, emulsions or melts. Preference is given to using substances or mixtures of substances which are in the liquid state at 20 ° C. As a preferred constituent, the liquids contain at least one substance from the group of nonionic surfactants and / or polymers and / or organic solvents.

The number of these phases of metering units according to the invention can be increased by increasing the number of phases of the shaped body and / or the number of phases filled into the cavity.

In a preferred embodiment, therefore, the shaped body has two, three, four or more phases. In a further preferred embodiment, the washing or cleaning active material filled in the cavity has two, three, four or more phases. For example, a plurality of different washing or cleaning-active substances or substance mixtures can be filled into the one receiving chamber formed from the thermoformed sheet material. An example of such a preferred embodiment is a dosing unit according to the invention, in which the receiving chamber formed from the thermoformed sheet material is filled with a two- or multi-phase liquid phase. Alternatively, a multi-phase filling of this receiving chamber, for example, be realized by two or more or above flowable, solid washing or cleaning-active substances are layered in the receiving chamber filled.

A dosing unit, characterized in that the cavity additionally in part with a washing or cleaning active substance, preferably a substance from the group Builders, enzymes, bleach, bleach activators, bleach catalysts, silver protectants or glass corrosion inhibitors is filled, which is not in the formed from the thermoformed sheet material receiving chamber is particularly preferred.

Particularly preferred is an embodiment of the dosing unit according to the invention, in which
the cavity underneath the deep-drawn sheet material is partially filled with a washing or cleaning-active substance, preferably a solid washing or cleaning-active substance. The resulting dosing unit then comprises a mono- or multiphase shaped body with a cavity, a washing or cleaning substance filled into the cavity, which only partially fills the cavity, and a receiving chamber made of film material filled with a further detergent or cleaning substance Partially filled cavity was deep-drawn. If the cavity is a well, the washing or cleaning active substance filled in the cavity is enclosed between the bottom of the well and the receiving chamber formed from the thermoformed sheet material, and, if the filled receiving chamber is not at least partially transparent, in usually not visible from the outside. On the other hand, if the cavity is an opening with two openings facing one another, then the washing or cleaning-active substance filled in the cavity is through one of the openings filled with the washing or cleaning-active substance filled in the receiving chamber of deep-drawn sheet material visible, noticeable.

It is preferred that the washing- or cleaning-active substances which are filled into the cavity of the shaped body outside the receiving chamber on deep-drawn sheet material are selected from the group of builders, enzymes, bleaches, bleach activators, bleach catalysts, silver protectants or glass corrosion inhibitors. Bleaches, in particular peroxygen compounds such as percarbonates or perborates, bleach activators or silver protectants, are particularly preferably introduced. These ingredients are preferably filled into the cavity as part of solid washing or cleaning active preparations between steps a) and b). These ingredients are described in more detail later in the text. To avoid repetition, reference is made at this point to the comments there.

In order to prevent that the washing or cleaning-active substances filled in the receiving chamber formed from the deep-drawn sheet material, in particular the pourable washing or cleaning-active substances do not fall out of this receiving chamber, these substances are preferably fixed in the receiving chamber. This fixation can be done for example by adhesion promoters. However, a preferred Dosing unit according to the invention, in which the receiving chamber filled with the washing or cleaning active substance and formed from the thermoformed sheet material is sealed. Suitable sealing materials are, for example, melts of organic polymers or sugar melts. Preferably, however, the receiving chamber formed by the deep-drawn sheet material and filled with the washing or cleaning substance is sealed with another sheet material. As before, this sheet material is preferably a water-soluble or water-dispersible sheet material. In the case of shaped bodies which have a breakthrough as a cavity, preferably both opening surfaces of the opening are sealed. The sealing material may partially cover the shaped body surface, for example, in the targeted sealing of individual cavity openings with a water-soluble or water-dispersible sheet material. However, the sealing material can also be used to completely encase the molded body.

Dosing units according to the invention are therefore particularly preferred, comprising a molding having at least one cavity, a film material deep-drawn into the cavity to form a receiving chamber, and a washing or cleaning substance present on the film material in the cavity, the molding additionally comprising a coating of a water-soluble or water-soluble material having water-dispersible material. Such a water-soluble or water-dispersible coating may comprise, for example, a deep-drawn or injection-molded packaging.

In a further preferred embodiment, the shaped body is adhesively bonded to the film material deep-drawn in the cavity and / or to the further film material used for sealing the thermoformed sheet material by means of heat sealing and / or ultrasonic sealing and / or high-frequency sealing.

Unlike conventional multiphase detergents or cleaning agents, for example the marketed mortar tablets with molding or casting core, the ingredients of the detergent or cleaning product according to the invention are spatially separated from the ingredients contained in the receiving chamber formed from the sheet material. The resulting dosing unit is thus distinguished, in addition to the advantageous multiphase product appearance, by increased product and storage stability.

The detergents or cleaners according to the invention can be used for textile cleaning as well as for cleaning hard surfaces or dishes.

In addition to the abovementioned substances which are active in washing or cleaning, the detergents or cleaners prepared according to the invention preferably contain further washing and cleaning agents cleaning-active substances, in particular washing and cleaning-active substances from the group of bleaches, bleach activators, builders, surfactants, enzymes, polymers, disintegration aids, electrolytes, pH adjusters, fragrances, perfume carriers, dyes, hydrotropes, foam inhibitors, corrosion inhibitors and glass corrosion inhibitors.

In addition, detergents and cleaners according to the invention may contain further ingredients which further improve the performance and / or aesthetic properties of these compositions. In the context of the present invention, preferred agents comprise one or more substances from the group of electrolytes, pH regulators, fluorescers, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides. Antioxidants, antistatic agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents and UV absorbers.

Claims (21)

1. A method for producing a dosage unit for washing or cleaning agents, comprising the steps

   a) providing a molded article that has at least one cavity,

   b) applying a first film material onto the surface of the molded article over the opening of the cavity;

   c) deep drawing the first film material into the cavity by generating a reduced pressure in the cavity of the molded article;

   d) introducing a washing or cleaning active substance onto the film material in the cavity.
2. The method according to claim 1, characterized in that the molded article concerns a tablet, a compactate, an extrudate, an injection molded article, a cast article or a molded article made up of these molded articles.
3. The method according to one of claims 1 or 2, characterized in that the molded article possesses a coating.
4. The method according to one of claims 1 to 3, characterized in that the ratio of the volume of the molded article to the volume of the substance added into the cavity in step d) is between 1:1 and 20:1, preferably between 3:1 and 15:1.
5. The method according to one of claims 1 to 4, characterized in that the cavity of the molded article is partially filled with a washing or cleaning active substance before the first film material is applied in step b).
6. The method according to claim 5, characterized in that the washing or cleaning active substance concerns a washing or cleaning active powder, granule or extrudate, which preferably includes one or more active substances from the group of builders, enzymes, bleaching agents, bleach activators, bleach catalysts, silver protection agents or glass corrosion inhibitors.
7. The method according to one of claims 1 to 6, characterized in that a water-soluble or water-dispersible film material, preferably a polymeric water-soluble or water-dispersible film material, is employed as the first film material in step b).
8. The method according to claim 1, characterized in that the low pressure is generated in the cavity of the molded article by applying a reduced pressure on the part of the surface of the molded article (outside the cavity), which is not covered by the film material from step b).
9. The method according to one of claims 1 or 8, characterized in that the reduced pressure in the cavity of the molded article is generated by applying a reduced pressure to a hole or a notch, which connects the cavity with a part of the surface of the molded article (outside the cavity), which is not covered by the first film material of step b).
10. The method according to one of claims 1 to 9, characterized in that the molded article, before, at the same time or after the first film material was deep drawn in step c), is adhesively bonded with this first film material by adhesive bonding and/or heat sealing.
11. The method according to one of claims 1 to 10, characterized in that in step d) a free-flowing washing or cleaning active substance is poured in.
12. The method according to claim 11, characterized in that in step d) a liquid is poured in, which preferably comprises one or more active substances from the group of the non-ionic surfactants and/or the polymers and/or the organic solvents.
13. The method according to one of claims 1 to 12, characterized in that the cavity opening in connection with step d) is sealed in a further step e).
14. The method according to claim 13, characterized in that the cavity opening is sealed by applying a second film material onto the cavity opening and subsequently heat sealed and/or ultra-sound sealed and/or high frequency sealed.
15. The method according to claim 14, characterized in that the molded article is adhesively bonded with the first film material and/or the second film material by heat sealing and/or ultra-sound sealing and/or high frequency sealing.
16. The method according to one of claims 1 to 15, characterized in that the first or second film material in the course of the method, preferably after a sealing step, is cut through by a mechanical and/or a thermal method to form a cut line, wherein the cut line preferably runs circumferentially on the surface of the molded article.
17. A method for producing a dosage unit for washing or cleaning agents, comprising the steps

    i. providing a ring tablet;

    ii. introducing a mold through a first orifice of the aperture of the ring tablet into this aperture;

    iii. applying a first, preferably water-soluble film material onto the molded article surface over the second orifice of the aperture;

    iv. deep drawing the first film material into the aperture of the ring tablet to form a receiving chamber that only partly fills the aperture;

    v. introducing a washing or cleaning active substance into the receiving chamber formed in d).
18. The method according to claim 17, characterized in that the mold has a circumferential planar edge region on its upper side.
19. The method according to one of claims 17 or 18, characterized in that the filled receiving chamber is sealed in an additional step f), wherein the sealing is preferably effected by heat sealing the first film material to the water-soluble film material in the planar edge region of the mold.
20. The method according to one of claims 17 to 19, characterized in that the mold after sealing in step f) is removed in another step g) from the first orifice out of the aperture and another washing or cleaning active substance is introduced into the region of the aperture of the ring tablet that had been occupied by the mold beforehand.
21. The method according to one of claims 17 to 20, characterized in that the first orifice of the aperture is sealed in a further step g).