WO2004054894A1

WO2004054894A1 - Portioned washing or cleaning agent

Info

Publication number: WO2004054894A1
Application number: PCT/EP2003/013283
Authority: WO
Inventors: Sandra Hoffmann
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2002-12-16
Filing date: 2003-11-26
Publication date: 2004-07-01
Also published as: AU2003292122A1; DE10258584A1

Abstract

The invention concerns a container, which is provided for dosing, packaging and storing active substances and which has at least three holding chambers. This container comprises a base body, which is made of a first covering material, and comprises at least one web, which is located inside the base body, and a first sealing area, which is made of a second covering material and which seals the base body. The invention is characterized in that the container also comprises a second sealing area that, together with the web and the base body, delimits at least two holding chambers at least in portions, and the container is characterized by having a high stability in storage and in transport, particularly with regard to the stability of the sealing seams. Containers of this type are particularly suited for the separate dosing, packaging and storage of constituents that are incompatible with one another, preferably of liquid or free-flowing constituents. The use of said webs enable the number of sealing steps required during the production of the container to be minimized.

Description

Portioned detergent or cleaning agent

The present invention is in the field of portion containers for active substances or combinations of active substances. In particular, this invention relates to subdivided or compartmentalized containers, that is to say containers with a plurality of receiving chambers, and means comprising these containers and one or more active substances. These agents are suitable, for example, for dosing active ingredients or combinations of active ingredients which are incompatible with one another. A preferred field of application of the claimed agents is in the field of dosing, packaging, storage of detergent and cleaning substances, such as those used for cleaning textiles, dishes or hard surfaces.

The portioned packaging of active ingredients or combinations of active ingredients plays an important role in many areas of applied chemistry, for example in pharmacy, crop protection, but also in the area of washing or cleaning agents. The portioning avoids a possibly time-consuming and labor-intensive dosage by the user, as well as the direct contact of the user with the corresponding active ingredients.

For example, WO 93/08095 A1 (Rhone-Poulenc) discloses a bag made of water-soluble or water-dispersible material which has two horizontal receiving chambers and is suitable, for example, for packaging toxic substances. The bags can be produced by the thermoforming process.

WO 02/85738 A1 (Reckitt Benckiser) relates to water-soluble containers with at least two receiving troughs arranged one above the other. These containers are manufactured by gradually sealing individual foils or prefabricated, filled individual compartments to the final container.

WO 02/42401 A1 (Procter & Gamble) claims a method for the automatic cleaning of dishes, which is carried out using a container with a plurality of receiving chambers. The corresponding containers have a horizontal arrangement of the individual receiving chambers and are produced by sequential bonding of individual foils to form the receiving chambers, it also being possible to use individual foils which have been shaped by deep drawing.

The multi-chamber containers described in the cited documents are produced by repeatedly filling and sealing preformed receptacles or by gluing several separately prefabricated, filled individual chambers. The process products are in any case necessarily characterized by the arrangement of the receiving chambers with horizontally compartmentalized partition walls. Multi-chamber containers which have been sealed by repeated thermal stress or repeated gluing of the same container regions also have an increased tendency to leakage, in particular along the sealing seams obtained in this way.

The object of the present invention was to avoid the disadvantages described above. In particular, multi-chamber metering units should be provided with at least three receiving chambers, which have a reduced tendency to leak due to an increased stability of the sealing seams. These multi-chamber dosing units should be manufactured without the subsequent gluing of prefabricated, filled individual compartments and should have a minimal number of sealing steps. Furthermore, multi-chamber metering units should be provided which have an increased overall stability. For example, the tilting or twisting of the individual chambers about a web axis, as occurs in the multi-chamber metering units of the prior art, should preferably be reduced or avoided altogether.

It has now surprisingly been found that the number of sealing steps can be minimized in processes for producing multi-chamber containers if the base body of the multi-chamber container has at least one web.

A first subject of the present application is therefore a method for producing a container, comprising the steps: a) shaping processing of a first wrapping material to form a base body of height h which is open at the top, comprising a brim forming the top opening of the base body and at least two receiving chambers separated by at least one web of height h - x; b) sealing the receiving chamber (s) with a second covering material, the sealing seam lying at least partially in a plane of height h-x; c) Filling the remaining container volume.

In the context of the present application, the height h of the base body produced according to the invention is the vertical distance between a first sealing plane formed by the brim and the lowest point of the receiving chambers of the container according to the invention formed in step a). If more than two receiving chambers are formed in step a), the separating webs according to the invention can of course have the same height h - x and / or different heights h - x and h - X | to have. Analogously, in the latter case, step b) is at least partially sealed with a second covering material on the respective different web heights h-Xι.

The containers produced by the method according to the invention have at least one web of height h - x. The value "x" stands for a length that is less than "h". So x <h. The relative difference between the values "h" and "x" in preferred methods is at least 5%, preferably at least 10%, particularly preferably at least 20%, very particularly preferably at least 35% and in particular at least 50%, in each case based on the height h , In other words, the ratio of the height h-x of the web to the height h of the base body in a preferred embodiment is less than 0.95, preferably less than 0.90, particularly preferably less than 0.80, very particularly preferably less than 0, 65 and in particular less than 0.50. Methods according to the invention are very particularly preferred, in which the height h-x of the web is between 10 and 95%, preferably between 15 and 85%, particularly preferably between 25 and 75% and in particular between 35 and 60% of the height h of the base body. In a preferred embodiment of the method according to the invention, the absolute difference between the values "h" and "x" is preferably between 0.1 and 8 cm, particularly preferably between 0.2 and 6 cm, particularly preferably between 0.4 and 5 cm and in particular between 0.5 and 4 cm.

The method according to the invention begins with the shaping processing of a first wrapping material. Suitable shaping processes for processing the wrapping materials, in particular the first wrapping material, are, for example, deep-drawing processes, injection molding processes or casting processes. In the context of the present application, “deep-drawing processes” refer to processes in which a first film-like wrapping material is deformed after being brought into contact with a receiving trough located in a die forming the deep-drawing plane and the shaping of the wrapping material into this receiving trough by the action of pressure and / or vacuum The casing material can be pretreated before or during the molding in by the action of heat and / or solvent and / or conditioning by means of relative atmospheric humidity and / or temperature changes in relation to ambient conditions. The pressure can be applied by two parts of a tool, which can be like Behave positively and negatively to one another and deform a film placed between these tools when compressed, but the pressure forces are also the action of compressed air and / or the weight of the film and / or the weight of one on the top of the film Foil spent active ingredient.

In these deep-drawing processes, it is also possible to distinguish between processes in which the wrapping material is fed horizontally into a molding station and from there in a horizontal manner for filling and / or sealing and / or singling, and processes in which the wrapping material is fed via a continuously rotating die-forming roller (optionally optional with a counter-rotating male mold roll, which guides the shaping upper punches to the cavities of the female mold roll). The first-mentioned process variant of the flatbed process is to be operated both continuously and discontinuously; the process variant using a shaping roller is generally carried out continuously.

In the method according to the invention, a web is formed by shaping a first covering material. This web is preferably designed so that it has no contact point with the side wall of the container. In one According to the preferred method according to the invention, the web formed in step a) has no contact point with the side walls of the container. This means that at least one web located in the base body has no such contact points. Of course, the base body cannot have only one web. Preferred base bodies have two, three, four, five or more separate webs which are not in contact with one another. Methods according to the invention are now characterized in that at least one, but preferably all, of the webs formed in step a) have no contact points with the peripheral brim. The web can run linearly or non-linearly in the top view ("supervision" in the context of this application refers to the observation of the container with a view orthogonal to the deep-drawing plane). It is preferred in the context of the present application that this web is not linear in the top view Such webs can be designed in all technically feasible forms. Preferred embodiments are described in more detail below:

Preferred methods according to the invention are characterized in that the web formed in step a) has no contact point with the side walls of the container. Such a web is necessarily closed to form two separate receiving chambers, has curvatures and / or corners and includes a surface when viewed from above. This surface enclosed by the web in the supervision, that is to say the opening on the top side of a receiving chamber enclosed by such a web, as well as the surface surrounded in the supervision by the self-contained brim, that is to say the opening of the base body on the top side, can be any technically feasible have symmetrical and non-symmetrical shape. If the self-contained web or the self-contained brim has only curvatures and no corners, a circular or oval surface is realized, for example. If the web or brim has opposing curvatures, round or oval surfaces with indentations result (e.g. kidney or peanut shape). If curvatures and corners are combined, surfaces in the form of a drop or an archway can be created, for example. Two, three, four, five, six, seven, eight, or polygonal webs or brims can also be realized and are particularly preferred. In a special embodiment, webs are preferred which have no contact points with the surrounding brim and have no circular shape. In a further preferred embodiment of the method according to the invention, the web has at least one contact point with the side walls of the container. Containers which have two such contact points are particularly preferred. Like the previously described self-contained webs, the webs running from one point of the side wall to another point of the side wall can have curvatures and / or corners. In preferred methods according to the invention, the shaping processing of the first wrapping material takes place in step a) with the formation of a web with at least one, preferably two, three, four, five or more corners. The angle enclosed by the two sections of the web that meet in such a corner is preferably between 1 and 179 °, particularly preferably between 45 and 135 °, very particularly preferably between 70 and 110 ° and in particular between 80 and 100 °.

Methods according to the invention are particularly preferred in which the web formed in step a) by shaping processing of a first covering material has at least one, preferably two, three, four, five or more curvatures. The radii of curvature of these curvatures can vary widely. Based on the maximum diameter d _{max of} the area enclosed by the circumferential brim, preferred radii of curvature have values between 0.1 and 5 d _max , preferably between 0.2 and 3 d _max and in particular between 0.3 and 1.5 dmax.

Of course, a web that is not linear in the view can also be realized by a forked web. In a preferred variant of the method according to the invention, the web formed by the shaping processing in step a) has at least one, preferably two, three, four, five or more forks. Forks are preferred in which three, four or five, but preferably three or four branches of the non-linear web meet. Webs with one fork and three branches and webs with two forks and two branches each are particularly preferred. In a further preferred embodiment, a web, which has a contact point with the peripheral brim, is split into two branches in a first fork, these branches in turn in a second fork are guided to each other and the web then runs out at a second contact point with the surrounding brim. Such a container has three separate receiving chambers.

The width of the webs located between the individual receiving chambers can vary. Preferred methods according to the invention are characterized in that the web formed in step a) has a width between 0.5 and 15 mm, preferably between 0.6 and 12 mm, particularly preferably between 0.7 and 10 mm, very particularly preferably between 0, 8 and 8 mm and in particular between 1.0 and 5.0 mm. Crosspieces which do not have a constant width over their entire length are particularly preferred.

In a preferred embodiment of the method according to the invention, at least one of the receiving chambers is filled after step a). Methods according to the invention are particularly preferred, in which the top opening of the base body is sealed after the remaining container volume has been filled.

A preferred subject of the present application is therefore a method for producing a container, comprising the steps: a) shaping processing of a first wrapping material to form a base body of height h, which comprises an opening opening on the top side, and a brim forming the top opening of the base body, and at least two, receiving chambers separated by at least one web of height h - x; b) filling at least one receiving chamber; c) sealing the filled receiving chamber (s) with a second wrapping material, the sealing seam lying at least partially in a plane of height h - x; d) filling the remaining container volume;

Another preferred subject matter of the present application is further a method for producing a container, comprising the steps: a) shaping processing of a first wrapping material to form a base body of height h which is open at the top and comprising one at the top Brim forming opening of the base body, and at least two receiving chambers separated by at least one web of height h-x; b) sealing the receiving chamber (s) with a second covering material, the sealing seam lying at least partially in a plane of height h-x; c) filling the remaining container volume; d) sealing the top opening of the base body with a third covering material.

Finally, a particularly preferred subject matter of the present application is a method for producing a container, comprising the steps: a) shaping processing of a first wrapping material to form a base body of height h which is open at the top, comprising a brim forming the top opening of the base body, and at least two , receiving chambers separated by at least one web of height h - x; b) filling at least one receiving chamber; c) sealing the filled receiving chamber (s) with a second wrapping material, the sealing seam lying at least partially in a plane of height h - x; d) filling the remaining container volume; e) sealing the top opening of the base body with a third wrapping material.

In steps c) and e) of the method according to the invention, sealing surfaces are applied. The sealing in step c) takes place according to the invention with the formation of a further receiving chamber, which is limited by the sealing surface applied in step c) and parts of the base body. The sealing surface applied in step c) can have one or more sealing seams. Preferably, one of the sealing seams of this sealing surface runs at least partially along the web formed during the shaping processing of the first wrapping material. Methods according to the invention are preferred in which the sealing takes place along the web and along at least one of the side walls forming the base body. In a preferred embodiment, the sealing layer is applied in step e) completely along a circumferential brim surrounding the base body, which preferably forms the opening on the top side of this base body. For the Sealing in steps c) and e), but especially for the sealing in step e) of the method preferred according to the invention, are suitable prefabricated closure parts, in particular closure parts which are produced by injection molding or by compression molding, preferably by compression molding with prior and / or simultaneous heating become. Such prefabricated closure parts can differ significantly in their design from the planar sealing films generally used. Closure parts which have convex and / or concave curvatures, preferably round or rounded curvatures, are particularly preferred here. In a preferred embodiment, these closure parts have wave-like curvatures. In addition to these “organic” shapes, it is of course also possible to produce closure parts which have square bulges projecting outwards or inwards. If an expandable film is used for the sealing in step e), this planar film can be sealed after the sealing by shrinking the sealing film with the sealing film Such shrinkage also occurs to the outside. Such shrinkage occurs particularly in deep-drawn containers. As a result of the shrinkage and the associated reduction in the volume of the receiving chambers, the "level" of the active substances in these containers is well above the brim forming the top opening of the base body , The sealing film is domed outwards.

The brim forming the top opening of the base body is planar in a preferred embodiment of the method according to the invention. The width of this brim results from the chosen manufacturing process. If a deep-drawing process is used for the shaping processing, the width of the brim when separating the base body results from cutting or punching from the distance of the cut lines from the opening of the base body. If an injection molding process is used for the shaping processing, preferably in the formation of a prefabricated base body, this preferably has a circumferential sealing brim; After closing the base body with a last sealing surface, it is possible to punch out on the outside next to this injection-molded brim, but it is preferred to punch through the injection-molded rim sealing surface against the constructional background of a tolerance and fit manufacturing of multi-cavity punching tools. In a preferred variant of the method according to the invention, the sealing seams of the sealing surfaces applied in steps c) and e) have no overlaps or overlaps. For example, it is preferred that the sealing of the first sealing surface takes place exclusively along the web and / or along the inside of the side walls of the base body, while the sealing of the second sealing layer takes place exclusively along a brim with this base body which forms the top opening of the base body.

A further wrapping material is used for sealing, which can be identical to the first and / or second wrapping material mentioned above. The sealing takes place, for example, by means of a film or a preformed closure part. The materials to be sealed can be welded by the action of heat or glued using adhesive. Solvents (e.g. water) are preferred as adhesives, which dissolve the surface of the areas of the wrapping materials to be glued. Solutions of the shell materials are also preferred as adhesives. In addition to (detached) adhesive systems, melt-based adhesives, in particular hotmelts known from packaging technology, can also be preferred. The adhesive can be applied, for example, by spraying and / or by roller application and / or by contacting with capillary wetting systems, for example moistened felt.

In a further preferred variant of the method according to the invention, the seal has a device for pressure equalization between the container interior and the surrounding atmosphere. Such pressure equalization is particularly preferred for those methods according to the invention in which the interior of the container is filled with such liquid or solid active substances which tend to release gas in the course of storage after sealing. Chemical reactions, in particular, are usually the cause of such gas release

Reactions between the agent inside the container and the

Wrapping materials or

- Reactions between the agents in the interior of the container and substances (e.g. water) that have diffused into the interior of the container through the shell material or

- Reactions of the agents in the container interior with one another or - Destruction reactions caused by light or heat in individual

Means inside the container. The active substances which tend to release gas after one of the reactions described include in particular the bleaching agents described below, for example the percarbonates and perborates. Valves, but preferably microholes, preferably microholes with a diameter between 0.1 and 2 mm, particularly preferably between 0.2 and 1.5 mm and in particular between 0.5 and 1 mm, are referred to in the context of the present application as a device for pressure compensation , Microchannels or the use of permeable covering materials are also suitable. In a particularly preferred embodiment, the closure part and / or container have nano holes with a diameter between 0.1 and 100 μm, preferably between 0.2 and 80 μm and in particular between 0.4 and 60 μm.

In a preferred method according to the invention, at least one water-soluble or water-dispersible covering material is used. In a preferred method, the first wrapping material and / or the second wrapping material and / or the third wrapping material is water-soluble or water-dispersible. Preferably at least two of the shell materials, particularly preferably all three of the shell materials used, are water-soluble or water-dispersible. The envelope materials used can be identical or different materials. For example, the shell materials can differ in their thickness and / or their chemical composition. In a particularly preferred embodiment of the method according to the invention, the shell materials used have an identical chemical composition, but differ in their thickness. For example, the side walls of the base body preferably have a greater thickness than the sealing layers obtained in steps c) and e). In a further preferred embodiment, the envelope materials used for sealing differ from the envelope material of the base body both in their chemical composition and in their thickness. In particularly preferred methods according to the invention, different shell materials made of water-soluble or water-dispersible material are used which have different dissolution rates. It is preferred that, in particular, the envelope materials used as the sealing material move faster in an aqueous medium dissolve as the shell materials used to manufacture the base body. The different solubilities can be caused both by a different material thickness and by different chemical compositions.

In general, all envelope materials that can be processed by thermoplastic shaping methods such as injection molding or deep-drawing methods and / or by melt-based casting methods can be used in the method according to the invention, although the use of water-soluble or water-dispersible packaging materials is preferred. Preferred methods according to the invention are accordingly characterized in that at least one of the coating materials used is water-soluble or water-dispersible.

Some particularly preferred water-soluble or water-dispersible coating materials which are suitable both for producing the base body and for sealing it are listed below. The polymers mentioned can be used as the covering material either alone or in combination with one another or in combination with other substances, for example plasticizers or solubilizers.

a) water-soluble nonionic polymers from the group of a1) polyvinylpyrrolidones, a2) vinylpyrrolidone / vinyl ester copolymers, a3) cellulose ethers

b) water-soluble amphoteric polymers from the group of b1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkylacrylic acrylamide / methacrylic amide (meth) acrylic acid copolymers b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b7) alkyl acrylamide / alkyl methacrylate / alkylaminoethyl methacrylate / alkyl methacrylate

Copolymers b8) copolymers of b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids bδiii) optionally further ionic or nonionic monomers

c) water-soluble zwitterionic polymers from the group of d) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts c2) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts c3) methacroylethylbetaine / methacrylate copolymers

d) water-soluble anionic polymers from the group of d 1) vinyl acetate / crotonic acid copolymers d2) vinylpyrrolidoneΛ inylacrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers d4) graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid alone or Mixture copolymerized with crotonic acid, acrylic acid or

Methacrylic acid with polyalkylene oxides and / or polyalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the non-ionic type, d5ii) at least one monomer of the ionic type, dδiii) of polyethylene glycol and d5iv) a crosslinked d6) by copolymerization at least one monomer of each of the following three copolymers: d6i) esters of unsaturated alcohols and short-chain saturated

Carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, d6iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group dθii) with saturated or unsaturated, straight-chain or branched C ₈ .

₁₈ alcohol d7) terpolymers of crotonic acid, vinyl acetate and an allyl or

Methallyl esters d8) tetra- and pentapolymers from d8i) crotonic acid or allyloxyacetic acid dδii) vinyl acetate or vinyl propionate dδiii) branched allyl or methallyl esters dδiv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters copolymers with one or more ethylenic copolymers of throotonic acid with a group of one or more copolymers of ethylene , Vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts d10) terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position

e) water-soluble cationic polymers from the group of e1) quaternized cellulose derivatives e2) polysiloxanes with quaternary groups e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) copolymers with quaternary vinyl derivatives of dialkylaminoacrylate and methacrylate e6) vinylpyrrolidone-methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol eδ) under the INCI names Polyquaternium 2, Polyquatemium 17,

Polyquaternium 1δ and Polyquaternium 27 indicated polymers.

Water-soluble polymers in the sense of the invention are those polymers which are more than 2.5% by weight soluble in water at room temperature. The wrapping material used in the process according to the invention is preferably at least partially a substance from the group (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin.

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

"Polyvinyl alcohols" (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure

which in small proportions (approx. 2%) also structural units of the type

contain.

Commercial polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approximately 100 to 2500 (molar masses from approximately 4000 to 100,000 g / mol), have degrees of hydrolysis of 9δ-99 or δ7-δ9 mol% , therefore still contain a residual content of acetyl groups. The manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically harmless and are biodegradable at least partially. The water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax. The polyvinyl alcohol coatings are largely impervious 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 envelope material used in the process according to the invention at least partially comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably δ0 to 90 mol%, particularly preferably δ1 to δ9 mol% and in particular is δ2 to δδ mol%. In a preferred embodiment, the first shell material used in the process according to the invention consists of at least 20% by weight, particularly preferably at least 40% by weight, very particularly preferably at least 60% by weight and in particular at least δ0% by weight from a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably δO to 90 mol%, particularly preferably δ1 to δ9 mol% and in particular δ2 to 88 mol%.

Polyvinyl alcohols of a specific molecular weight range are preferably used as materials for the containers, it being preferred according to the invention that the shell material comprises a polyvinyl alcohol, the molecular weight of which ranges from 10,000 to 100,000 gmol ^"1 , preferably from 11,000 to 90,000 gmol ^{" 1} , particularly preferably from 12,000 up 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 approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1890, particularly preferably between approximately 240 to approximately 16δ0 and in particular between approximately 260 to approximately 1500.

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (ex Clariant, risen in Kuraray Specialties Europe, KSE). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-δ3, Mowiol ^{® δδ} 4, Mowiol ^® 5-δ8, Mowiol ^® 8-δ8 and L648, L734, Mowiflex LPTC 221 ex KSE and the compounds from Texas Polymers such as Vinex 2034.

Further polyvinyl alcohols that are particularly suitable as wrapping material can be found in the table below:

Other polyvinyl alcohols suitable as wrapping material are 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, Fδδ / 4, Fδδ / 26, Fδδ / 40, Fδδ / 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 changed by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols which have been acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous because of their extremely good solubility in cold water. The reaction products made of PVAL and starch are extremely advantageous to use.

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

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

Polyvinylpyrrolidones, abbreviated as PVP, can be described by the following general formula:

PVPs are made by radical polymerization of 1-vinyl pyrrolidone. Commercial PVPs have molar masses in the range from approx. 2,500 to 750,000 g / mol and are offered 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

which are produced industrially by base-catalyzed polyaddition of ethylene oxide (oxirane) in systems containing mostly small amounts of water with ethylene glycol as the starting molecule. They have molar masses in the range from approx. 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n from approx. 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: approx. 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 acids The composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as a water-soluble coating material is extremely widespread, particularly in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.

Within the scope of the method according to the invention, preference is given to enveloping 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, with the glucose units linked α-glycosidically. Starch is made up of two components of different molecular weights: approx. 20 to 30% straight-chain amylose (MW. Approx. 50,000 to 150,000) and 70 to 60% branched-chain amylopectin (MW. Approx. 300,000 to 2,000,000). It also contains small amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, intertwined chains with about 300 to 1,200 glucose molecules due to the binding in the 1,4 position, the chain in the amylopectin branches after an average of 25 glucose units through 1,6-binding to form a knot-like structure with about 1,500 to 12,000 molecules of glucose. In addition to pure starch, starch derivatives which are obtainable by polymer-analogous reactions from starch are also suitable for producing water-soluble coatings for the detergent, dishwashing detergent and cleaning agent portions. Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 500 to 5,000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

Preferred methods according to the invention are characterized in that one of the envelope materials used is transparent or translucent. The wrapping material used for example for injection molding and / or deep drawing and / or sealing is preferably transparent. For the purposes of this invention, transparency is understood to mean that the transmittance within the visible spectrum of light (410 to δOO nm) is greater than 20%, preferably greater than 30%, most preferably greater than 40% and in particular greater than 50%. As soon as a wavelength of the visible spectrum of light has a transmittance greater than 20%, it is to be regarded as transparent in the sense of the invention.

Other preferred wrapping materials are colored and / or printed. Particularly preferred colored and / or printed envelope materials are transparent or translucent.

Containers produced according to the invention, for the manufacture of which transparent envelope material was used, can contain a stabilizing agent. Stabilizing agents in the sense of the invention are materials which protect the ingredients in the receiving chambers and / or the ingredients located in an intermediate space against decomposition or deactivation by light radiation. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.

Particularly suitable stabilizers in the sense of the invention are the antioxidants. In order to prevent undesired changes to the formulations caused by light radiation and thus radical decomposition, the formulations contain antioxidants. Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants. Further examples are propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long-chain (C6-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, thiodipropionic acid to complex with Cι- ₁₈ -alkanols, in particular Cio-iβ alkanols, metal ion deactivators that are capable of catalyzing the auto-oxidation of metal ions such as copper, - such as ascorbic acid palmitate, organosulfur compounds, such as the esters of 3,3 ^' , such as nitrilotriacetic acid and its derivatives and their mixtures. Antioxidants can 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 stabilizers that can preferably be used are the UV absorbers. UV absorbers can improve the lightfastness of the formulation components. These include organic substances (light protection filters) that are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, eg heat. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles, such as, for example, the water-soluble benzenesulfonic acid 3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Cibafast ^® H), are also substituted in the 3-position phenyl-substituted 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 urocanoic acid. Of particular importance are biphenyl and especially stilbene derivatives, which are commercially available as Tinosorb ^® FD or Tinosorb ^® FR ex Ciba. 3-Benzylidene camphor or 3-benzylidene norcampher and its derivatives, 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 amyl 4- (dimethylamino) benzoate; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene); Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropyl benzyl ester, salicylic acid homomethyl ester; 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, for example, 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'methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, 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-benzylidene camphor, such as 4- (2-oxo-3-bornylidenemethyl) benzene-sulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 4-tert-butyl, are particularly suitable as typical UV-A filters -4'-methoxydibenzoylmethane (Parsol 17δ9), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds. The UV-A and UV-B filters can of course also be used in mixtures. In addition to the soluble substances mentioned, insoluble light-protection pigments, namely finely dispersed, preferably nanoized 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. Silicates (talc), barium sulfate or zinc stearate can be used as salts. 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 exhibit. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs in some other way from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobicized. Typical examples are coated titanium dioxides, such as titanium dioxide T 305 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferably used.

UV absorbers can be used in amounts of up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight, in each case based on the total weight of a contained in a receiving chamber or a space mixture of substances.

Another class of stabilizers to be used with preference are the fluorescent dyes. They include the ^{^{4,4'-diamino-2,2'-stilbenedisulfonic}} acids (flavonic), 4,4'-distyrylbiphenyls, methyl umbelliferone, coumarins,

Dihydroquinolinones, 1, 3-diarylpyrazolines, naphthalic imides, benzoxazole, benzisoxazole and benzimidazole systems as well as the pyrene derivatives substituted by heterocycles. The sulfonic acid salts of the diaminostilbene derivatives and polymeric fluorescent substances are of particular importance.

Fluorescent substances, based on the total weight of a substance mixture located in a receiving chamber or in an intermediate space, in amounts of up to 5% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0.5 and in particular from 0, 03 to 0.1 wt .-% be included.

In a preferred embodiment, the aforementioned stabilizing agents are used in any mixtures. The stabilizing agents are, based on the total weight of a substance mixture located in a receiving chamber or an intermediate space, in amounts of up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20% by weight, in particular from 0.02 to 5 wt .-% used. The shell material (s) used in the process (s) according to the invention is preferably a water-soluble or water-dispersible polymer. If the shaping processing of the water-soluble or water-dispersible polymer is carried out by deep drawing, a film is preferably used for this process. Preferred process variants are characterized in that the film used in step a) of the process according to the invention has a thickness of 5 to 2000 μm, preferably from 10 to 1000 μm, particularly preferably from 15 to 500 μm, very particularly preferably from 20 to 200 μm and in particular from 25 to 100 μm.

The foils used can be single or multi-layer foils (laminate foils). The water content of the films is preferably below 10% by weight, particularly preferably below 7% by weight, very particularly preferably below 5% by weight and in particular below 4% by weight.

Preferred coating materials are water-soluble or water-dispersible. In the context of the present application, therefore, agents are preferably produced which have at least one water-soluble or water-dispersible coating material. The preparation of such agents according to the invention is particularly preferred in which the shell materials used comprise a water-soluble or water-dispersible polymer.

According to the invention, preference is accordingly given to an embodiment in which the container as a whole is water-soluble, that is to say it dissolves completely when used as intended for washing or machine cleaning when the conditions provided for the dissolution have been reached. A major advantage of this embodiment is that the container can be at least partially detached in a practically relevant short time - as a non-limiting example, a few seconds to 5 minutes - under precisely defined conditions in the cleaning liquor and thus the encapsulated content, that is, according to the requirements cleaning-active material or several materials into the fleet. This release can only be controlled or controlled in different ways. In a first embodiment of the invention which is particularly preferred on account of advantageous properties, the water-soluble container comprises areas which are less or not water-soluble at all or areas which are water-soluble only at a higher temperature and areas which are water-soluble or water-soluble at a low temperature. In other words, the container does not consist of a uniform material that has the same water solubility in all areas, but of materials of different water solubility. Areas of good water solubility are to be distinguished on the one hand from areas with less good water solubility, with poor or no water solubility or from areas in which water solubility is only at a higher temperature or at a different pH value or only at a changed electrolyte concentration the desired value achieved, on the other hand. This can lead to certain areas of the container becoming detached when used as intended under adjustable conditions, while other areas remain intact. A container with pores or holes is formed, into which water and / or liquor penetrate, detach active, rinse-active or cleaning-active ingredients and can be discharged from the container. Systems in the form of multi-chamber containers or in the form of containers arranged one inside the other (“onion system”) can also be provided in the same way. In this way, systems with controlled release of the wash-active, rinse-active or cleaning-active ingredients can be manufactured.

The invention is not subject to any restrictions on the formation of such systems. Thus, containers can be made in which a unitary polymer material comprises small areas of incorporated compounds (e.g. salts) which are more water soluble than the polymer material. On the other hand, several polymer materials with different water solubility can also be mixed (polymer blend), so that the more rapidly soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the more slowly soluble.

It corresponds to a particularly preferred embodiment of the invention that the less water-soluble areas or non-water-soluble areas or only at higher temperatures water-soluble areas of the containers are areas made of a material which is chemically essentially that of the readily water-soluble areas Corresponds to areas or areas soluble in water at a lower temperature, but has a higher layer thickness and / or a changed degree of polymerization of the same polymer and / or a higher degree of crosslinking of the same polymer structure and / or a higher degree of acetalization (in the case of PVAL, for example with saccharides, polysaccharides, such as starch ) and / or has a content of water-insoluble salt components and / or has a content of a water-insoluble polymer. Even taking into account the fact that the containers do not completely dissolve, portioned detergent or cleaning agent compositions according to the invention can be provided which have advantageous properties in releasing active substances, in particular active substances from the group of detergents or cleaning agents, into the respective liquor ,

In addition to this controlled release through the targeted choice of the shell materials used, the person skilled in the art has other methods available. An alternative procedure, which is suitable for the controlled release of active substances or active substance mixtures alone or in combination with the above-mentioned control by selecting certain coating materials, is the integration of one or more "switches" in the above-mentioned active substances, active substance mixtures or active substance preparations.

Possible "switches" that influence the dissolution behavior of the active substances enclosed in the containers according to the invention are, in particularly preferred embodiments, physicochemical parameters. Examples include, but should not be construed as a limitation

the mechanical stability of, for example, a capsule, a coating or a compacted shaped body such as a tablet, which - depending on the time, the temperature or other parameters - can be a factor determining the disintegration;

- The solubility of optionally used capsules or coatings or matrices as a function of pH and / or temperature and / or ionic strength; - The dissolution rate of optionally used capsules or coatings or matrices as a function of pH and / or temperature and / or ionic strength;

- The melting behavior (the melting point) of optionally used capsules or coatings or matrices as a function of pH and / or temperature and / or ionic strength;

In a particularly preferred embodiment, the agent produced according to the invention comprises at least one active substance or active substance preparation, the release of which is delayed. The delayed release is preferably delayed by the use of at least one of the agents described above, but in particular by the use of different packaging materials and / or the use of selected coating materials, it being particularly preferred that this delayed release occurs when active substances or mixtures of active substances are used the group of detergents or cleaning agents is carried out at the earliest 5 minutes, preferably at the earliest 7 minutes, particularly preferably at the earliest 10 minutes, very particularly preferably at the earliest 15 minutes and in particular at the earliest 20 minutes after the start of the cleaning or washing process. The use of meltable coating materials from the group of waxes or paraffins is particularly preferred.

A particularly preferred method according to the invention is characterized in that the at least two receiving chambers in step b) are filled with different agents in each case. It is particularly preferred that different agents are used for the filling in steps b) and d), that is to say each of the at least three receiving chambers is filled with agents which differ in their chemical or physical properties. Such agents can have, for example, different chemical compositions or different particle sizes. The agents can differ in their composition, as well as in their composition and state of matter. In the following, a distinction is made between solid and liquid agents with regard to the physical states of the fillable active ingredients or active ingredient combinations, active ingredients and Active ingredient combinations are summarized which have a solid, that is, dimensionally stable, non-flowable consistency. This category includes, for example, substances in the solid state, but also dimensionally stable substances such as dimensionally stable gels and combinations of these substances. Filled bodies with a solid outer shell are also referred to as solids, regardless of the physical state of the fillers contained in these filled bodies. In a particularly preferred embodiment of the method according to the invention, at least one of the receiving chambers is filled with a gas, preferably air. The resulting gas-filled receiving chamber has the function of a buoyancy element or a mechanical buffer, for example, in later use.

In the context of the present application, solids are preferably powders and / or granules and / or extrudates and / or compactates and / or castings, regardless of whether they are pure substances or mixtures of substances. The solids mentioned can be in amorphous and / or crystalline and / or partially crystalline form. In the context of the present invention, preferred solids have a water content (for example determinable as a loss on drying or according to Karl Fischer) below 7% by weight, preferably below 4.5% by weight, and particularly preferably below 2% by weight. The amorphous and / or crystalline and / or partially crystalline solids can be used both as pure substance and as mixtures of substances. The preferred substance mixtures include, in particular, assembled solids in compounded and / or encapsulated and / or coated form.

Powder is a general term for a form of separation of solid substances and / or mixtures of substances which is obtained by comminution, i.e. grinding or crushing in the grinding bowl (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. Preferred powders have a uniform (homogeneous) mixture of the solid, finely divided constituents and, in the case of substance mixtures, in particular do not tend to be separated into individual constituents of these mixtures. Powders which are particularly preferred in the context of the present application therefore have a particle size distribution in which at least 80% by weight, preferably at least 60% by weight, particularly preferably at least 95% by weight and in particular at least 99% by weight of the powder, based in each case on its total weight, to a maximum of 80%, preferably to a maximum of 60% and in particular to a maximum of 40% of the average particle size thereof Powder differ.

According to the grain size, the powders are roughly divided into coarse, fine and. Very fine powder common; A more precise classification of powdered bulk goods is based on their bulk density and by sieve analysis. In principle, powders of any particle size can be used, but preferred powders have average particle sizes of 40 to 500 μm, preferably from 60 to 400 μm and in particular from 100 to 300 μm. Methods for determining the average particle size are usually based on the aforementioned sieve analysis and are described in detail in the prior art.

The unwanted caking of the powders can be countered by using pouring aids or powdering agents. In a preferred embodiment, the powders produced in the process according to the invention therefore contain free-flowing aids or powdering agents, preferably in parts by weight of 0.1 to 4% by weight, particularly preferably of 0.2 to 3% by weight and in particular of 0 , 3 to 2 wt .-%, each based on the total weight of the powder. Preferred pouring aids or powdering agents are, preferably in finely ground form, silicates and / or silicon oxide and / or urea.

As a particulate mixture, powders can be agglomerated using a number of techniques. Any method known in the prior art for agglomeration of particulate mixtures is in principle suitable for converting the solids enclosed in the containers produced according to the invention into larger aggregates. In the context of the present invention, agglomerates which are preferably used as solid (s) are, in addition to the granules, the compactates and extrudates.

Accumulations of granules are referred to as granules. A granulate is an asymmetrical aggregate of powder particles. Granulation processes are widely described in the prior art. Granules can be produced by wet granulation, by dry granulation or compacting and by melt solidification granulation. The most common granulation technique is wet granulation, since this technique is subject to the fewest restrictions and is the safest way to produce granules with favorable properties. Moist 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, it being possible for said mixers to 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 influence of low to high shear forces.

If the granulation takes place in a spray tower, the starting materials used can be, for example, melts (melt solidification) or, preferably aqueous, slurries (spray drying) solid substances which are sprayed at the top of a tower in a defined droplet size, freeze or dry in free fall, and on Bottom of the tower accumulate as granules. Melt solidification is generally particularly suitable for shaping low-melting substances that are stable in the melting temperature range (e.g. 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 particularly for the production of detergents or detergent components.

Further agglomeration techniques described in the prior art are extruder or perforated roll granulation, in which powder mixtures optionally mixed with granulating liquid are plastically deformed when pressed through perforated disks (extrusion) or on perforated rolls. The products of extruder granulation are also called extrudates.

Compactates can be produced, for example, using dry granulation techniques such as tableting or roller compaction. Compacting in tablet presses enables single-phase or multi-phase tablets or briquettes to be produced. The multi-phase tablets include the multi-layer or Sandwich tablets, for example, also the coated tablets and the point tablets (bull-eye tablets). The briquettes, like the slugs produced in compacting rollers, can be comminuted after the compacting by counter-rotating spiked rollers or beaten by sieves.

In the context of the present application, casting bodies are solid substance particles which are produced by solidification and / or crystallization from melts or solutions. The solidification and / or crystallization preferably takes place in prefabricated matrices. Depending on the size of the die and the intended use of the casting body, the casting bodies released from the dies after solidification can subsequently be used in their original size or, if appropriate, after comminution, as solids in the water-soluble containers according to the invention.

Suitable matrix materials for the abovementioned solids, but in particular for castings which are produced by melt solidification, are in particular fusible substances from the group consisting of fats and / or triglycerides and / or fatty acids and / or fatty alcohols and / or waxes and / or parrafins.

Fat (s) or triglyceride (s) is the name for compounds of glycerol in which the three hydroxyl groups of the glycerol are esterified by carboxylic acids. The naturally occurring fats are triglycerides, which usually contain different fatty acids in the same glycerin molecule. By saponification of the fats and subsequent esterification or reaction with acyl chlorides, synthetic triglycerides in which only one fatty acid is bound are also accessible (e.g. tripalmitin, triolein or tristearin). Natural and / or synthetic fats and / or mixtures of the two are preferred as matrix material or matrix component for castings or one of the other solids mentioned in the context of the present invention.

Aliphatic saturated or unsaturated, carboxylic acids with branched or unbranched carbon chain are referred to as fatty acids in the present application. A large number of production methods exist for the production of the fatty acids. While the lower fatty acids mostly based on oxidative processes based on alcohols and / or aldehydes as well as aliphatic or acyclic Hydrocarbons are based, the higher homologues are mostly still most easily accessible today by saponification of natural fats. Advances in the field of transgenic plants mean that there are almost unlimited possibilities for varying the fatty acid spectrum in the storage fats of oil plants. In the context of the present invention, preferred fatty acids have a melting point which allows these fats to be processed as a material or as a component of a casting. Fatty acids which have a melting point above 25 ° C. have proven particularly advantageous. Preferred matrix materials and / or constituents are therefore capric acid and / or undecanoic acid and / or lauric acid and / or tridecanoic acid and / or myristic acid and / or pentadecanoic acid and / or palmitic acid and / or margaric acid and / or stearic acid and / or nonadecanoic acid and / or arachic acid and / or erucic acid and / or elaeosteraric acid. But also fatty acids with a melting point below 25 ° C can be used as a component of the matrix for castings or other solids mentioned above.

Fatty alcohol is a collective name for the linear, saturated or unsaturated primary alcohols with 6 to 22 carbon atoms that can be obtained by reducing the triglycerides, fatty acids or fatty acid esters. The fatty alcohols can be saturated or unsaturated depending on the manufacturing process. Myristyl alcohol and / or 1-pentadecanol and / or cetyl alcohol and / or 1-heptadecanl and / or stearyl alcohol and / or erucyl alcohol and / or 1-nonadecanol and / or arachidyl alcohol and / or 1-heneicosanol and / or behenyl alcohol and / or erucyl alcohol and / or brassidyl alcohol are preferred components of the matrix of castings or other solids enclosed by the containers produced according to the invention.

It has also proven to be advantageous if the solids enclosed in the containers produced according to the invention, in particular the preferably enclosed casting bodies, contain waxes as matrix material. Preferred waxes have a melting range that is between approximately 45 ° C. and approximately 75 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range. Waxes with such a melting range are dimensionally stable at room temperature however, melt at typical temperatures for machine dishwashing from 30 ° C to 90 ° C and are therefore more easily water-dispersible at these temperatures.

"Waxing" is understood to mean a number of natural or artificially obtained substances which, as a rule, melt above 40 ° C. without decomposition and are relatively low-viscosity and not stringy just above the melting point. They have a strongly temperature-dependent consistency and solubility.

The waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes.

Natural waxes include, for example, vegetable waxes such as candelilla wax, camauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walrus, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

The chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material which meet the stated softening point requirements can also be used as meltable or softenable substances for the masses hardening by cooling. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ^® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ^® ETLP (Condea). Conversely, synthetic or semi-synthetic esters from lower alcohols with fatty acids from native sources can also be used. Tegin ^® 90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances. Also shellac, for example shellac KPS three ring SP (Kalkhoff GmbH) can be used according to the invention as a matrix material in solids, preferably in castings.

The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating of the present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to be triterpenoid and Steroidaikohole, for example, lanolin understood, which is obtainable for example under the trade name Argowax ^® (Pamentier & Co).

In a further preferred embodiment, one or more of the solids enclosed in the containers produced according to the invention, but preferably a casting made by solidification, predominantly contains paraffin wax (parrafins) as the matrix material. This means that at least 50% by weight of the total meltable or softenable substances contained, preferably more, consist of paraffin wax. Paraffin wax contents (based on the total weight of the matrix materials) of approximately 60% by weight, approximately 70% by weight or approximately δ0% by weight are particularly suitable, with even higher proportions of, for example, more than 90% by weight being particularly preferred , In a particular embodiment of the invention, the entire material of one or more of the solids filled into the containers produced according to the invention consists of paraffin wax.

Paraffin waxes have the advantage over the other natural waxes mentioned in the context of the present invention that when the containers produced according to the invention are used as dosing units for detergents and cleaning agents in an alkaline cleaning agent environment, there is no hydrolysis of the waxes (as is the case, for example, with the wax esters is to be expected) since paraffin wax contains no hydrolyzable groups. Paraffin waxes consist mainly of alkanes and low levels of iso- and cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C.

Preferred solids, in particular castings, contain at least one paraffin wax with a melting range of 40 ° C. to 60 ° C. as matrix material and / or matrix constituent.

Preferably, the paraffin wax content of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature (generally about 10 to about 30 ° C.) is as high as possible. The more solid wax components present in a wax at room temperature, the more useful it is within the scope of the present invention.

Further advantageous constituents of the matrix of solids, in particular castings, are wax alcohols, i.e. fatty alcohols with approx. 24-36 carbon atoms, which are the main constituent of many natural waxes in the form of wax esters of higher molecular weight fatty acids (wax acids). Examples of preferred wax alcohols are lignoceryl alcohol, cetyl alcohol, myricyl alcohol or melissyl alcohol.

Dispersions are particularly suitable for processing as castings, dispersions with washing or cleaning-active substances or mixtures of active substances being used with particular preference. In a particularly preferred embodiment of the present application, the washing- or cleaning-active preparation used to produce the casting is a dispersion of solid particles in a dispersing agent, dispersions which, based on their total weight i), comprise 10 to 35% by weight of dispersing agent and ü) contain 15 to 90% by weight of dispersed substances, are particularly preferred. In this application, dispersion is a system consisting of several phases, one of which is continuous (dispersant) and at least one other is finely divided (dispersed substances).

Particularly preferred dispersions are characterized in that they contain the dispersant in amounts above 11% by weight, preferably above 13% by weight, particularly preferably above 15% by weight, very particularly preferably above 17% by weight and in particular above 19 % By weight, based in each case on the total weight of the dispersion. Dispersions which have a dispersion with a proportion by weight of dispersant above 20% by weight, preferably above 21% by weight and in particular above 22% by weight, in each case based on the total weight of the dispersion, can furthermore preferably be used. The maximum dispersant content of preferred dispersions, based on the total weight of the dispersion, is preferably less than 63% by weight, preferably less than 57% by weight, particularly preferably less than 52% by weight, very particularly preferably less than 47% by weight .-% and in particular less than 37 wt .-%. In the context of the present invention, in particular those active washing or cleaning preparations which, based on their total weight, contain dispersing agents in amounts of 12 to 62% by weight, preferably 14 to 49% by weight and in particular 16 to 36% by weight. % contain. Dispersions with a dispersant content of between 16 and 30% by weight, preferably between 16 and 26% by weight and in particular between 16 and 22% by weight, in each case based on the total weight of the dispersion, are particularly preferred.

The dispersants used are preferably water-soluble or water-dispersible. The solubility of these dispersants at 25 ° C. is preferably more than 200 g / l, preferably more than 300 g / l, particularly preferably more than 400 g / l, very particularly preferably between 430 and 620 g / l and in particular between 470 and 530 g / l.

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 can be either a single polymer or a mixture of different water-soluble or water-dispersible polymers. In a further preferred embodiment of the present invention, the dispersant or at least 50% by weight of the polymer mixture consists of water-soluble or water-dispersible nonionic polymers from the group of polyvinylpyrrolidones, vinylpyrrolidone / vinyl ester copolymers, cellulose ethers, polyvinyl alcohols, polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol.

Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol which have the general formula III

H- (O-CH ₂ -CH ₂ ) _n -OH (III)

are sufficient, where n can take values between 1 (ethylene glycol) and several thousand. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the formula VII mentioned above. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), for example, PEG-4, PEG-6, PEG-δ, PEG-9 , PEG-10, PEG-12, PEG-14 and PEG-16 can be used. Commercially available polyethylene glycols are, for example, under the trade name Carbowax ^® PEG 200 (Union Carbide), Emkapol ^® 200 (ICI Americas), Lipoxol ^® 200 MED (Huls America), polyglycol ^® E-200 (Dow Chemical), Alkapol ^® PEG 300 (Rhone -Poulenc), Lutrol ^® E300 (BASF) and the corresponding trade names with higher numbers. The average relative molecular weight of at least one of the dispersants used in the washing or cleaning agents according to the invention, in particular at least one of the poly (alkylene) glycols used, is preferably between 200 and 36,000, preferably between 200 and 6000 and particularly preferably between 300 and 5000. Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula IV

H- (O-CH-CH ₂ ) _π -OH (IV)

I CH ₃

are sufficient, where n can take values between 1 (propylene glycol) and several thousand. Technically important here are in particular di-, tri- and tetrapropylene glycol, i.e. the representatives with n = 2, 3 and 4 in formula IV.

Dispersions are particularly preferably used which contain a nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, the proportion by weight of the poly (ethylene) glycol in the total weight of all dispersants is preferably between 10 and 90% by weight, particularly preferably between 30 and 30% by weight and in particular between 50 and 70% by weight. Dispersions in which the dispersant is more than 92% by weight, preferably more than 94% by weight, particularly preferably more than 96% by weight, very particularly preferably more than 9δ% by weight are particularly preferred. and in particular 100% by weight of a poly (alkylene) glycol, preferably poly (ethylene) glycol and / or poly (propylene) glycol, but in particular poly (ethylene) glycol. Dispersing agents which, in addition to poly (ethylene) glycol, also contain poly (propylene) glycol, preferably have a ratio by weight of poly (ethylene) glycol to poly (propylene) glycol of between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, particularly preferably between 10: 1 and 1, 5: 1 and in particular between 7: 1 and 2: 1.

Other preferred dispersants are the nonionic surfactants, which are used both alone, but particularly preferably in combination with a nonionic polymer. Detailed information on the nonionic surfactants that can be used can be found below in the description of detergent or cleaning substances. Dispersions which are preferably used are characterized in that at least one dispersant has a melting point above 25 ° C., preferably above 35 ° C. and in particular above 40 ° C. The use of dispersants with a melting point or melting range between 30 and 80 ° C., preferably between 35 and 75 ° C., particularly preferably between 40 and 70 ° C. and in particular between 45 and 65 ° C. is particularly preferred, these dispersants based on the total weight of the dispersants used, a weight fraction above 10% by weight, preferably above 40% by weight, particularly preferably above 70% by weight and in particular between 60 and 100% by weight.

Suitable dispersed substances in the context of the present application are all substances which are active in washing or cleaning at room temperature, but in particular substances which are active in washing or cleaning from the group of builders (builders and cobuilders), active polymers for washing or cleaning, bleaching agents and bleach activators , the glass corrosion protection agent, the silver protection agent and / or the enzymes. A more detailed description of these ingredients can be found below in the text.

The water content of the dispersions preferably used in the process according to the invention is, based on their total weight, preferably less than 30% by weight, preferably less than 23% by weight, preferably less than 19% by weight, particularly preferably less than 15% by weight .-% and in particular less than 12 wt .-%. Dispersions preferably used according to the invention are low in water or anhydrous. Dispersions used with particular preference are characterized in that, based on their total weight, their free water content is below 10% by weight, preferably below 7% by weight, particularly preferably below 3% by weight and in particular below 1% by weight. -% exhibit.

The dispersions, which are preferably used as washing or cleaning active preparations, are distinguished by a high density. Dispersions with a density above 1.040 g / cm ³ are particularly preferably used. Preferred methods according to the invention are characterized in that the washing and cleaning active preparation has a density above 1.040 g / cm ³ , preferably above 1.15 g / cm ³ , particularly preferably above 1.30 g / cm ³ and in particular above 1.40 g / cm ³ having. This high density not only reduces the total volume of a dosing unit cast body but also improves its mechanical stability. Particularly preferred methods according to the invention are therefore characterized in that the dispersion has a density between 1,050 and 1,670 g / cm ³ , preferably between 1,120 and 1,610 g / cm ³ , particularly preferably between 1,210 and 1,570 g / cm ³ , very particularly preferably between 1.290 and 1.510 g / cm ³ , and in particular between 1.340 and 1.480 g / cm ^3. The information on the density relates in each case to the densities of the compositions at 20 ° C. In order to avoid segregation processes during the processing of these dispersions, in particular in the course of the vibration of the molds, dispersing agents and dispersed substances preferably have densities which are less than 0.6 g / cm ³ , preferably less than 0.4 g / cm ³ and differ in particular by less than 0.3 g / cm ³ .

Dispersions preferably used according to the invention as a detergent or cleaning preparation are distinguished in that they disperse in water (40 ° C.) in less than 9 minutes, preferably less than 7 minutes, preferably in less than 6 minutes, particularly preferably in less than 5 Minutes, especially in less than 4 minutes. To determine the solubility, 20 g of the dispersion are introduced into the interior of a dishwasher (Miele G 646 PLUS). The main wash cycle of a standard wash program (45 ° C) is started. The solubility is determined by measuring the conductivity, which is recorded by a conductivity sensor. The dissolving process ends when the maximum conductivity is reached. In the conductivity diagram, this maximum corresponds to a plateau. The conductivity measurement begins with the insertion of the circulation pump in the main wash cycle. The amount of water used is 5 liters.

Dimensionally stable gels are another solid which is particularly preferred in the context of the present invention. The term “dimensionally stable” here means gels which have an inherent dimensional stability which enables them to assume a non-disintegrating spatial form which is stable against breakage under the usual conditions of manufacture, storage, transport and handling by the consumer, whereby these form Spatial shape under the conditions mentioned, also over a longer period of time, preferably 4 weeks, particularly preferably 8 weeks and in particular 32 weeks, did not change, that is to say under the usual conditions of manufacture, storage, Transport and handling by the consumer persists in the spatial-geometric shape caused by the production, that is, for example does not melt, or when exposed to an external force customary in the conditions of production, storage, transport and handling spatial geometric shape returns.

In order to achieve the desired dimensional stability, the gels with good product properties (solubility, washing and cleaning performance, stability of the gel), it is preferred in the context of the present invention to use one or more substances from the group agar-agar, carrageenan, Tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose, corn flour ether, polyacrylic and. Polymethacrylic verb., Vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonites, zeolites and silicas contain, where it has proven to be particularly advantageous if the gels these or one of the following thickeners in amounts between 0.2 and 10 % By weight, preferably between 0.3 and 7% by weight and particularly preferably between 0.4 and 4% by weight, based on the total weight of the shaped body.

Polymers derived from nature, which are used as thickeners in the context of the present invention, are, for example, agar agar, carrageenan, tragacanth, acacia, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, as described above and casein. Modified natural products come primarily from the group of modified starches and celluloses, examples include carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and corn flour ether.

A large group of thickeners that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes. Thickening agents from these classes of compounds are widely available commercially and are, for example, under the trade names Acusol ^® -820

(Methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ^® -GT-2δ2-S (alkyl polyglycol ether, Akzo), Deuterol ^® polymer 11 (dicarboxylic acid copolymer, Schönes GmbH), Deuteron ^® -XG (anionic heteropolysaccharide based on ß-D-glucose, D-Manose, D-Glucuronic Acid, Schönes GmbH), Deuteron ^® -XN (non-ionogenic polysaccharide, Schönes GmbH), Dicrylan ^® -Dickener-0 (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA ^® - δ1 and EMA ^® -91 (ethylene-maleic anhydride copolymer, Monsanto), thickener-QR-1001 (polyurethane emulsion, 19-21% in water / diglycol ether, Rohm & Haas), Mirox ^® -AM (anionic acrylic acid-acrylic acid ester- Copolymer dispersion, 25% in water, Stockhausen), SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo ^® -S (high molecular polysaccharide, stabilized with formaldehyde, Shell) and Shellflo ^® -XA (xanthan Biopolymer, stabilized with formaldehyde, Shell).

Due to their manufacturing process and to optimize their dissolving behavior, preferred gels contain various solvents, gels having proven particularly advantageous in terms of their product properties, the water and / or one or more water-miscible solvents in amounts of 5 to 70% by weight, preferably of Contain 10 to 65 wt .-% and particularly preferably from 15 to 60 wt .-%.

It has also proven to be particularly advantageous if the water-miscible solvents contain one or more substances from the group consisting of ethanol, n- or i-propanol, n- or sec- or tert-butanol, glycol, propane or butanediol, glycerol, Diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, di-propylene or glycol-methyl-monomethyl-ether, , or -ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether contain.

The capsules are further preferred solids enclosed in containers produced according to the invention. "Capsule" is a name for a frequently used form of packaging, which is available in different sized, possibly colored, layers of gelatin, Wax or wafer material contains solid, semi-solid or liquid substances. The most common are the gelatin capsules (made of hard or soft gelatin).

In a special embodiment of the present invention, one or more or all of the solids filled into the containers produced according to the invention, ie for example one, several or all of the powders and / or granules and / or extrudate (s) filled into these containers. and / or compact (s) and / or cast body and / or dimensionally stable gel (s) and / or capsule (s), a coating (coating). Such a coating can serve different purposes. On the one hand, coating can, for example, prevent undesired contact of active substances which are sensitive to hydrolysis or oxidation in the solids, with the outside air or other solids enclosed in the water-soluble container according to the invention. On the other hand, an advantageous visual effect can also be achieved by a coating.

According to the above, liquids and solids are suitable as ingredients for the receiving chambers. In the case of solids, a distinction is made between powders, granules, extrudates, compactates, castings and dimensionally stable gels. In the context of this application, liquids are not only low-viscosity, flowable liquids or flowable gels, but also flowable dispersions, for example emulsions or suspensions. Active substances or combinations of active substances are considered to be flowable if they have no inherent dimensional stability which enables them to assume a non-disintegrating spatial form under the usual conditions of manufacture, storage, transport and handling by the consumer, this spatial form under the conditions mentioned also not changed over a longer period of time, preferably 4 weeks, particularly preferably δ weeks and in particular 32 weeks, that is to say under the usual conditions of manufacture, storage, transport and handling by the consumer in the spatially geometric shape persists, that is, does not melt away. The determination of the flowability relates in particular to the conditions customary for storage and transport, that is to say in particular to temperatures below 50 ° C., preferably below 40 ° C. Active substances or combinations of active substances are therefore particularly considered to be liquids a melting point below 25 ° C, preferably below 20 ° C, particularly preferably below 15 ° C.

The table below describes preferred process variations for carrying out the process according to the invention while filling two receiving chambers in step b) (receiving chambers 1 and 2) and a further receiving chamber in step d) (receiving chamber 3). The filling of the receiving chambers 1 and 2 in step b) of the method according to the invention can take place simultaneously or at different times.

4δ

Processes according to the invention which are particularly preferred in the context of the present application are characterized in that at least one receiving chamber is filled with a liquid, at least one further receiving chamber is filled with a solid. Methods according to the invention are particularly preferred in which a receiving chamber is filled with a liquid, a further receiving chamber with a solid and a third receiving chamber with a melt.

The deep-drawn containers can be made before, at the same time as or after they have been removed from the receiving troughs of the die, for example by cutting or punching be isolated. The cutting or punching takes place in the area of the wrapping material film, which after deep-drawing is not located inside the receiving trough, but rather next to the receiving trough on the flat (flat) upper side of the die. The container isolated in this way consequently has a brim which protrudes outward at an angle from the receiving chambers formed by the covering material and at least partially encloses the openings of these receiving chambers. The surface surrounded by the closed brim in the view, that is to say the entire upper sealing surface of the containers produced by the method according to the invention, can have any technically feasible symmetrical or non-symmetrical shape. The total length of the brim, that is to say the top circumference of the containers produced according to the invention, is preferably between 1 and 75 cm, particularly preferably between 2 and 60 cm, very particularly preferably between 4 and 40 cm and in particular between 5 and 20 cm.

Another object of this application is therefore a container of height h made of a first wrapping material, comprising at least three receiving chambers and a brim forming a first sealing plane and rotating at height h, characterized in that the container has at least one seal made of a second wrapping material along one Sealing seam which does not run in the sealing plane formed by the peripheral brim.

Particularly preferred containers according to the invention are characterized in that the sealing seam, which does not run in the sealing plane formed by the circumferential brim, runs at least partially along a web of height h-x located in the container.

In the context of the present application, the height h of the containers according to the invention is the vertical distance between the first sealing plane formed by the brim and the lowest point of the container according to the invention.

The containers according to the invention have at least one web of height h - x. The value "x" stands for a length that is less than "h". So x <h. The relative difference between the values "h" and "x" is in preferred containers at least 5%, preferably at least 10%, particularly preferably at least 20%, very particularly preferably at least 35% and in particular at least 50%, in each case based on the height h. In other words, the ratio of the height h - x of the web to the height h of the base body in a preferred embodiment is less than 0.95, preferably less than 0.90, particularly preferably less than 0.30, very particularly preferably less than 0, 65 and in particular less than 0.50. Containers according to the invention are particularly preferred in which the height h-x of the web is between 10 and 95%, preferably between 15 and 65%, particularly preferably between 25 and 75% and in particular between 35 and 60% of the height h of the base body. The absolute difference between the containers is preferably between 0.1 and 8 cm, particularly preferably between 0.2 and 6 cm, particularly preferably between 0.4 and 5 cm and in particular between 0.5 and 4 cm.

The containers according to the invention are obtained from a first covering material by shaping processing. Suitable molding processes are, for example, deep-drawing processes, injection molding processes or casting processes. The containers according to the invention are therefore preferably deep-drawn containers, injection-molded containers or molded containers. In the context of the present application, “deep-drawn containers” are containers that are made from a first film-like wrapping material after this material has been brought about, via a receiving trough located in a die forming the deep-drawing plane and molding the wrapping material into this receiving trough by the action of pressure and / or The wrapping material can be pretreated before or during molding by the action of heat and / or solvent, the pressure can be applied by two parts of a tool which behave like positive and negative to one another and a film placed between these tools However, the action of compressed air and / or the weight of the film and / or the weight of an active substance placed on the top of the film are also suitable as compressive forces material can be conditioned by the action of selected relative air humidity and / or temperature. In these deep-drawing processes, it is also possible to distinguish between processes in which the wrapping material is fed horizontally into a molding station and from there in a horizontal manner for filling and / or sealing and / or singling, and processes in which the wrapping material is fed via a continuously rotating die-forming roller (optionally optional with a counter-rotating male mold roll, which guides the shaping upper punches to the cavities of the female mold roll). The first-mentioned process variant of the flatbed process is to be operated both continuously and discontinuously; the process variant using a shaping roller is generally carried out continuously.

The deep-drawn containers can be separated, for example by cutting or punching, before, at the same time as or after they have been removed from the receiving troughs of the die. The cutting or punching takes place in the area of the wrapping material film, which after deep-drawing is not located inside the receiving trough, but rather next to the receiving trough on the flat (flat) upper side of the die. The container isolated in this way consequently has a brim which protrudes outward at an angle from the receiving chambers formed by the covering material and at least partially encloses the openings of these receiving chambers. The surface surrounded by the closed brim in the view, that is to say the entire upper sealing surface of containers according to the invention, can have any technically feasible symmetrical or non-symmetrical shape. The total length of the brim, that is to say the top circumference of the container according to the invention, is preferably between 1 and 75 cm, particularly preferably between 2 and 60 cm, very particularly preferably between 4 and 40 cm and in particular between 5 and 20 cm.

In a preferred embodiment of the containers according to the invention, the sealing seam, which does not run along the circumferential brim, runs at least partially along a web of height h-x located in the container. This web can run linearly or non-linearly in the top view ("supervision" in the context of this application refers to the observation of the container with a direction orthogonal to the deep-drawing plane). It is preferred in the context of the present application that this web is not linear in the top view Such webs can be used in all technically feasible forms. Preferred embodiments are described in more detail below:

Preferred containers according to the invention are characterized in that the web has no contact point with the side walls of the container. Such a web is necessarily closed to form two separate receiving chambers, has curvatures and / or corners and includes a surface when viewed from above. This surface enclosed by the web when viewed from above, that is to say the opening on the top side of one of the receiving chambers, can have any technically feasible symmetrical or non-symmetrical shape, just like the previously described area surrounded by the closed brim when viewed from above. If the self-contained web or the self-contained brim has only curvatures and no corners, a circular or oval surface is realized, for example. If the web or brim has opposing curvatures, round or oval surfaces with indentations result (e.g. kidney or peanut shape). If curvatures and corners are combined, surfaces in the form of a drop or an archway can be created, for example. Two, three, four, five, six, seven, eight, or polygonal webs or brims can also be realized and are particularly preferred. In a special embodiment, webs are preferred which have no contact points with the surrounding brim and have no circular shape.

In a further preferred embodiment of the container according to the invention, the web has at least one contact point with the side walls of the container. Containers which have two such contact points are particularly preferred. Furthermore, such containers are particularly preferred, the side walls of which have protuberances in the contact area with the web (s), the surface of these protuberances located on the inside of the container preferably forming a smooth, preferably planar surface with the top of the web (s). The transition of the web (s) to the side wall accordingly has no corner in these preferred embodiments and is particularly suitable for applying a sealing seam. Like the previously described self-contained webs, the webs running from one point of the side wall to another point of the side wall can have curvatures and / or corners. preferred Containers are characterized in that the web has at least one, preferably two, three, four, five or more corners. The angle enclosed by the two sections of the web that meet in such a corner is preferably between 1 and 179 °, particularly preferably between 45 and 135 °, very particularly preferably between 70 and 110 ° and in particular between 60 and 100 °.

In another embodiment, preferred containers according to the invention are characterized in that the web has at least one, preferably two, three, four, five or more curvatures. The radii of curvature of these curvatures can vary widely. Relative to the maximum diameter d _max of the area enclosed by the circumferential rim opening, preferred radii of curvature values between 0.1 and 5 d _max, preferably between 0.2 and 3 d χ _ma, and in particular between 0.3 and 1, 5 to dmax ,

Of course, a bridge can also be realized by a forked bridge. A preferred container according to the invention is accordingly characterized in that the web has at least one, preferably two, three, four, five or more forkings. Forks are preferred in which three, four or five, but preferably three or four branches of the non-linear web meet. Webs with one fork and three branches and webs with two forks and two branches each are particularly preferred. In a further preferred embodiment, a web, which has a contact point with the peripheral brim, is split into two branches in a first fork, these branches in turn being guided to one another in a second fork and the web then at a second contact point with the peripheral brim expires. Such a container has three separate receiving chambers.

The width of the webs located between the individual receiving chambers can vary. Preferred containers according to the invention are characterized in that the web has a width between 0.5 and 15 mm, preferably between 0.6 and 12 mm, particularly preferably between 0.7 and 10 mm, very particularly preferably between 0. δ and δ mm and in particular between 1.0 and 5.0 mm. Crosspieces which do not have a constant width over their entire length are particularly preferred.

The receiving chambers can have any technically feasible shape. Spherical, dome-shaped, cylindrical or cubic chambers are particularly preferred. Preferred receiving chambers have at least one edge and one corner, receiving chambers with two, three, four, five, six, seven, eight nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty or more edges or two, three, four, five, six, seven, eight nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty or more corners are also realizable and preferred according to the invention. Further realizable and preferred in alternative embodiments of the means according to the invention receiving chambers have a dome-shaped structure. The side walls of the receiving chambers are preferably planar. Spatially opposite side walls can be arranged both parallel and not parallel to one another. The base area of the receiving chambers can be convex, concave or planar, planar base areas being preferred with regard to the subsequent filling of the intermediate space (s) located between the receiving chambers. The base area itself can be designed as a circle, but can also have corners. Base areas with a corner (teardrop shape), two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty or more corners are in Preferred within the scope of the present application. In preferred embodiments of this application, the transition from the base area to the side wall (s) or the transition of the side walls into one another is designed in a rounded form. The receiving chambers therefore have no pointed or sharp, but rather rounded edges.

A preferred container according to the invention is characterized in that the base areas of the receiving chambers are planar.

The dimensions and the volume of preferred containers will primarily be based on the later application of the resulting containers. Containers preferred according to the invention have a total volume of Receiving chambers between 0.1 and 1000 ml, preferably between 1 and 100 ml, particularly preferably between 2 and 50 ml, very particularly preferably between 4 and 30 ml and in particular between 5 and 25 ml. Agents preferred according to the invention have at least two receiving chambers with the same spatial shape and an identical volume. In another preferred embodiment, the at least two receiving chambers present in the container have different volumes, the ratio of these volumes preferably being between 25: 1 and 1.05: 1, preferably between 20: 1 and 2: 1 and in particular between 15: 1 and 4: 1. In preferred means, the container has two receiving chambers of different volumes, the volume of the smaller receiving chamber being at least 2%, preferably at least 5%, particularly preferably at least 10% and in particular at least 20%, 30%, 40%, 50%, 60%, 65%, 70%, 75% or 30% of the volume of the larger receiving chamber is. The volume of the individual chambers is preferably between 0.05 and 900 ml, particularly preferably between 0.1 and 90 ml, very particularly preferably between 0.5 and 40 ml and in particular between 1.0 and 25 ml.

In a preferred embodiment, the containers according to the invention have receiving chambers with different depths. There is not necessarily a direct connection with the chamber depth and the chamber volume. For example, in a container with two receiving chambers, the receiving chamber with the smaller chamber depth can certainly have the larger chamber volume, while the receiving chamber with the greater chamber depth has a smaller volume. The two or more chambers can also have the same volume despite different chamber depths. However, in the context of the present application, a container is preferred in which the receiving chamber with the smaller chamber depth also has a smaller volume in comparison with the further receiving chamber (s), with reference to the above in terms of the absolute volumes and the volume ratios Information is referenced.

Containers preferred according to the invention comprise receiving chambers with, apart from those required in terms of process engineering, usually slightly and preferably between Deformation angles of 0.5 ° and 5 °, essentially vertically sloping side walls and / or web walls. However, containers in which at least one receiving chamber has at least one inclined side wall and / or web wall are particularly preferred. In such receiving chambers, the angle which lies between the side wall and / or the web wall and an imaginary seal which closes the receiving chamber is accordingly less than 90 °. Of course, this angle can vary for the different side walls and / or web walls of an individual receiving chamber. If the receiving chamber has only a single side wall (cylinder-like receiving chambers), even a single side wall can have different angles with the corresponding shaping of the deep-drawing troughs used in deep-drawing. Preference is given to receiving chambers in which the said angle is between 30 and 90 °, preferably between 35 and 89 °, particularly preferably between 40 and 88 ° and in particular between 45 and 87 °.

The receiving chambers can also have gradations. The corresponding, preferred containers have receiving chambers without flat side walls and / or web walls, but rather have side walls, which are characterized by steps or curvatures. The number of curvatures can vary, containers according to the invention are preferred in which the number of steps and / or curvatures in one or more receiving chamber (s) per chamber is a maximum of 10, preferably between 1 and 9, particularly preferably between 1 and 8, is very particularly preferably between 2 and 7 and in particular between 2 and 6. The steps or curvatures can be circumferential in the respective receiving troughs or only on individual side walls and / or web walls. The course of the steps or curvatures is preferably horizontal. Steps and / or curvatures with an upward or downward course similar to a screw thread can, however, also be realized and are preferred for certain fields of application.

In the context of this application, the “volume” of the receiving chambers refers to the filling volume that can be achieved when the chambers or intermediate spaces are filled with a liquid without this liquid overflowing onto the preferably planar sealing edges. As a seal, preferred containers according to the invention have prefabricated closure parts, in particular closure parts which are produced by injection molding or by compression molding, preferably by compression molding with prior and / or simultaneous heating. Such prefabricated closure parts can differ significantly in their design from the planar sealing films generally used. Closure parts which have convex and / or concave curvatures, preferably round or rounded curvatures, are particularly preferred here. In a preferred embodiment, these closure parts have wave-like curvatures. In addition to these “organic” shapes, it is of course also possible to implement closure parts which have square bulges projecting outwards or inwards. If a stretchable film is used as the sealing unit, this planar film can also be re-sealed after the sealing by shrinking the container provided with the sealing film Such shrinkage occurs particularly in deep-drawn containers. As a result of the shrinkage and the associated reduction in the volume of the receiving chambers, the “level” of the active substances in these containers is clearly above the brim forming the top opening of the base body. The sealing film is domed outwards. Such containers are particularly preferred in the context of the present application.

Particularly preferred containers according to the invention have a device in the seal for pressure compensation between the container interior and the surrounding atmosphere. Such pressure equalization is particularly preferred for those containers according to the invention in which the container interior is filled with such liquid or solid active substances which tend to release gas in the course of storage after sealing. Chemical reactions, in particular, are usually the cause of such gas release

- Reactions between the active substances in the interior of the container and the casing materials or

- Reactions between the active substances in the interior of the container and substances (e.g. water) or diffused from outside through the shell material into the interior of the container

- Reactions of the active substances in the container interior with one another or - Destruction reactions caused by light or heat in individual

Active substances inside the container. The active substances which tend to release gas after one of the reactions described include in particular the bleaching agents described below, for example the percarbonates and perborates. Valves, but preferably micro-holes, preferably micro-holes with a diameter between 0.1 and 2 mm, particularly preferably between 0.2 and 1.5 mm and in particular between 0.5 and 1 mm are used as devices for pressure compensation in the context of the present application designated. Microchannels or the use of permeable covering materials are also suitable. In a particularly preferred embodiment, the closure part and / or container have nano holes with a diameter between 0.1 and 100 μm, preferably between 0.2 and 80 μm and in particular between 0.4 and 60 μm.

Containers preferred according to the invention comprise at least one water-soluble or water-dispersible polymer. Some particularly preferred water-soluble or water-dispersible coating materials, which are suitable both as coating material, are listed below:

b) water-soluble amphoteric polymers from the group of b1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkylacrylic acrylamide / methacrylic amide (meth) acrylic acid copolymers b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid

Copolymers b7) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate

copolymers bδ) copolymers of bδi) unsaturated carboxylic acids bδii) cationically derivatized unsaturated carboxylic acids bδiii) optionally further ionic or nonionic monomers

d) water-soluble anionic polymers from the group of d1) vinyl acetate / crotonic acid copolymers d2) vinyl pyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers d4) graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid alone Mixture copolymerized with crotonic acid, acrylic acid or

Carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, d6iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d6ii) saturated or unsaturated, straight-chain or branched C ₈ -C ₈ alcohol d7) terpolymers of crotonic acid, vinyl acetate and an allyl or

Methallylester dδ) tetra- and pentapolymers from dδi) crotonic acid or allyloxyacetic acid dδii) vinyl acetate or vinyl propionate dδiii) branched allyl or methallyl esters dδiv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters copolymers with one or more monomers from crotonic acid

Group ethylene, vinylbenzene, vinylmethylether, acrylamide and their water-soluble salts d10) Terpolymers from vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position

e) water-soluble cationic polymers from the group of e1) quaternized cellulose derivatives e2) polysiloxanes with quaternary groups e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) copolymers of vinylpyrrolidone derivatives with quaternary acid of the dialkylaminoacrylate and methacrylate e6) vinylpyrrolidone-methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol eδ) under the INCI names Polyquaternium 2, Polyquaternium 17,

Polyquaternium 1δ and Polyquaternium 27 indicated polymers.

Water-soluble polymers in the sense of the invention are those polymers which are more than 2.5% by weight soluble in water at room temperature. Preferred coating materials preferably comprise at least partially a substance from the group (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin.

which in small proportions (approx. 2%) also structural units of the type

contain.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly 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 at least partially biodegradable. The water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax. The coatings made of polyvinyl alcohol are largely impenetrable for gases such as Oxygen, nitrogen, helium, hydrogen, carbon dioxide, however, allow water vapor to pass through.

In the context of the present invention, it is preferred that a container according to the invention has at least one shell material which at least partially comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and is in particular 82 to 8δ mol%. In a preferred embodiment, the at least one wrapping material consists of at least 20% by weight, particularly preferably at least 40% by weight, very particularly 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 δO to 90 mol%, particularly preferably δ1 to δ9 mol% and in particular 82 to 68 mol%. This can be both the first wrapping material, which forms the side walls of the receiving chambers and the intermediate spaces, and the second wrapping material, which is used as the sealing material. The entire envelope material used preferably consists of at least 20% by weight, particularly preferably at least 40% by weight, very particularly preferably at least 60% by weight and in particular at least δO% by weight, of a polyvinyl alcohol whose degree of hydrolysis is 70 is up to 100 mol%, preferably δO to 90 mol%, particularly preferably δ1 to δ9 mol% and in particular δ2 to δ8 mol%.

Polyvinyl alcohols of a certain molecular weight range are preferably used as the coating materials, it being preferred according to the invention that the coating 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 approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1690, particularly preferably between approximately 240 to approximately 16δ0 and in particular between approximately 260 to approximately 1500. The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (ex Clariant, risen in Kuraray Specialties Europe, KSE). Particularly suitable in the context of the present invention, polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^{® 4-8δ,} Mowiol ^® 5-88, Mowiol ^® 8-δ8 and L648, L734, Mowiflex LPTC 221 ex KSE as well as the compounds of Texas polymer such as Vinex 2034.

Other polyvinyl alcohols suitable as wrapping material are ELVANOL ^® 51-05, 52-22, 50- 42, 35-δ2, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX ^® 72.5, 78, B72, F80 / 40, Fδδ / 4, Fδδ / 26, Fδδ / 40, Fδδ / 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 changed by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols which have been acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous because of their extremely good solubility in cold water. The reaction products made of PVAL and starch are extremely advantageous to use. Furthermore, the solubility in water can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus specifically adjusted to the desired values. Films made of PVAL are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

H- [0-CH ₂ -CH ₂ ] _n -OH

which are produced industrially by base-catalyzed polyaddition of ethylene oxide (oxirane) in systems containing mostly small amounts of water with ethylene glycol as the starting molecule. They have molar masses in the range from approx. 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n from approx. 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: approx. 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 the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as a water-soluble coating material is extremely widespread, particularly in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.

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

Starch is a homoglycan, with the glucose units linked α-glycosidically. Starch is made up of two components of different molecular weights: approx. 20 to 30% straight-chain amylose (MW. Approx. 50,000 to 150,000) and 70 to 60% branched-chain amylopectin (MW. Approx. 300,000 to 2,000,000). It also contains small amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, intertwined chains with about 300 to 1,200 glucose molecules as a result of the binding in the 1,4-position, the chain in the amylopectin branches to an knot-like structure after an average of 25 glucose units through 1,6-binding with about 1,500 to 12,000 molecules of glucose. In addition to pure starch, starch derivatives which are obtainable by polymer-analogous reactions from starch are also suitable for producing water-soluble coatings for the detergent, dishwashing detergent and cleaning agent portions. Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches. Pure cellulose has the formal gross composition (C ₆ Hι ₀ O ₅ ) _n and, formally speaking, is a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 500 to 5,000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

In preferred containers according to the invention, at least one of the envelope materials is transparent or translucent. The envelope material used is preferably transparent. For the purposes of this invention, transparency is understood to mean that the transmittance within the visible spectrum of light (410 to 600 nm) is greater than 20%, preferably greater than 30%, most preferably greater than 40% and in particular greater than 50%. As soon as a wavelength of the visible spectrum of light has a transmittance greater than 20%, it is to be regarded as transparent in the sense of the invention.

Preferred containers have colored and / or printed envelope materials. Particularly preferred containers are characterized by colored and / or printed transparent or translucent covering materials.

Containers according to the invention can consist of a single or several different wrapping materials. In a preferred embodiment, a container according to the invention comprises at least two different shell materials, preferably two different water-soluble or water-dispersible polymers, which have different dissolution rates. Containers according to the invention are particularly suitable for portioning, packaging and metering and for the safe transport of active substances or active substance mixtures. The present application therefore also relates to an agent comprising a container according to the invention and at least one active substance.

Preferred agents comprise active substance or active substance mixtures from the fields of pharmaceuticals, cosmetics, feed, crop protection or fertilizers, adhesives, foods and / or personal care products, but preferably washing and cleaning-active substances. A particularly preferred agent according to the invention is accordingly characterized in that it comprises an active substance from the group of agricultural chemicals, cosmetics or detergents and cleaning agents.

Preferred active substances or active substance mixtures from the field of cosmetics are, in particular, hair setting agents, hair shaping agents and hair coloring agents. In addition to hair washing and hair care products, the preferred personal care products also include pre-treatment agents, hairdressing aids and course rinses. Active substances from the area of bath additives, such as bath salts or bath tablets, but also shower, foam or cream baths, are also preferred.

A particularly preferred agent according to the invention is characterized in that two different active substances are present separately from one another in different receiving chambers, that is to say that at least two receiving chambers contain different active substances.

The active substances can differ in their composition as well as in their composition and state of matter. In the following, a distinction is made with respect to the physical states of the fillable active substances or combinations of active substances between solid and liquid agents, whereby as solid substances within the scope of the present application active substances and active substance combinations are summarized which have a solid, that is to say dimensionally stable, non-flowable consistency. This category includes, for example, substances in the solid state, but also dimensionally stable substances such as dimensionally stable gels and combinations of these Substances. Filled bodies with a solid outer shell are also referred to as solids, regardless of the physical state of the fillers contained in these filled bodies. In a particularly preferred embodiment of the method according to the invention, at least one of the receiving chambers is filled with a gas, preferably air. The resulting gas-filled receiving chamber has the function, for example, of a buoyancy element or a mechanical buffer.

Powder is a general term for a form of separation of solid substances and / or mixtures of substances which is obtained by comminution, i.e. grinding or crushing in the grinding bowl (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. Preferred powders have a uniform (homogeneous) mixture of the solid, finely divided constituents and, in the case of substance mixtures, in particular do not tend to be separated into individual constituents of these mixtures. Powders which are particularly preferred in the context of the present application therefore have a particle size distribution in which at least 80% by weight, preferably at least 60% by weight, particularly preferably at least 95% by weight and in particular at least 99% by weight of the powder, each based on its total weight, up to a maximum of δO%, preferably a maximum of 60% and in particular a maximum of 40% of the average particle size of this powder.

The unwanted caking of the powders can be countered by using pouring aids or powdering agents. In a preferred embodiment, the powders therefore contain pouring aids or powdering agents, preferably in proportions by weight of 0.1 to 4% by weight, particularly preferably 0.2 to 3% by weight and in particular 0.3 to 2% by weight. %, each based on the total weight of the powder. Preferred pouring aids or powdering agents are, preferably in finely ground form, silicates and / or silicon oxide and / or urea.

Accumulations of granules are referred to as granules. A granulate is an asymmetrical aggregate of powder particles. Granulation processes are widely described in the prior art. Granules can be produced by wet granulation, by dry granulation or compacting and by melt solidification granulation.

The most common granulation technique is wet granulation, since this technique is subject to the fewest restrictions and the safest way to use granules 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, it being possible for said mixers to 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 influence of low to high shear forces.

Compactates can be produced, for example, using dry granulation techniques such as tableting or roller compaction. Compacting in tablet presses enables single-phase or multi-phase tablets or briquettes to be produced. In addition to the multi-layer or sandwich tablets, the multi-phase tablets also include, for example, the coated tablets and the point tablets (bull-eye tablets). The briquettes, like those produced in compacting rollers, can Schülpen are crushed after the compaction by opposing spiked rollers or beaten by sieves.

Aliphatic saturated or unsaturated, carboxylic acids with branched or unbranched carbon chain are referred to as fatty acids in the present application. A large number of production methods exist for the production of the fatty acids. While the lower fatty acids are mostly based on oxidative processes based on alcohols and / or aldehydes as well as aliphatic or acyclic hydrocarbons, the higher homologues are mostly still most easily accessible today by saponification of natural fats. Through the Advances in the field of transgenic plants have meanwhile given almost unlimited possibilities for varying the fatty acid spectrum in the storage fats of oil plants. In the context of the present invention, preferred fatty acids have a melting point which allows these fats to be processed as a material or as part of a casting. Fatty acids which have a melting point above 25 ° C. have proven particularly advantageous. Preferred matrix materials and / or constituents are therefore capric acid and / or undecanoic acid and / or lauric acid and / or tridecanoic acid and / or myristic acid and / or pentadecanoic acid and / or palmitic acid and / or margaric acid and / or stearic acid and / or nonadecanoic acid and / or arachic acid and / or erucic acid and / or elaeosteraric acid. But also fatty acids with a melting point below 25 ° C can be used as a component of the matrix for castings or other solids mentioned above.

It has also proven to be advantageous if the solids included in the agents according to the invention, in particular the casting bodies preferably included, contain waxes as matrix material. Preferred waxes have a melting range that is between approximately 45 ° C. and approximately 75 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range. Waxes with such a melting range are on the one hand dimensionally stable at room temperature, but melt at temperatures of 30 ° C. to 90 ° C. which are typical for machine dishwashing and are therefore more readily water-dispersible at these temperatures. "Waxing" is understood to mean a number of natural or artificially obtained substances which, as a rule, melt above 40 ° C. without decomposition and are relatively low-viscosity and not stringy just above the melting point. They have a strongly temperature-dependent consistency and solubility.

The natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material which meet the stated softening point requirements can also be used as meltable or softenable substances for the masses hardening by cooling. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ^® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ^® ETLP (Condea). Conversely, synthetic or semi-synthetic esters from lower alcohols with fatty acids from native sources can also be used. Tegin ^® 90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances. Shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used according to the invention as a matrix material in solids, preferably in castings. The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating of the present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ^® (Pamentier & Co).

In a further preferred embodiment, one or more of the solids comprised in the agents according to the invention, but preferably a casting produced by melt solidification, contain paraffin wax (parrafins) as the matrix material in the majority. This means that at least 50% by weight of the total meltable or softenable substances contained, preferably more, consist of paraffin wax. Paraffin wax contents (based on the total weight of the matrix materials) of approximately 60% by weight, approximately 70% by weight or approximately 80% by weight are particularly suitable, with even higher proportions of, for example, more than 90% by weight being particularly preferred , In a particular embodiment of the invention, the entire material of one or more of the solids included in the agents according to the invention consists of paraffin wax.

Paraffin waxes have the advantage over the other natural waxes mentioned in the context of the present invention that when the containers produced according to the invention are used as dosing units for detergents and cleaning agents in an alkaline cleaning agent environment, there is no hydrolysis of the waxes (as is the case, for example, with the wax esters is to be expected) since paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C. Preferred solids, in particular castings, contain at least one paraffin wax with a melting range of 40 ° C. to 60 ° C. as matrix material and / or matrix constituent.

Further advantageous constituents of the matrix of solids, in particular castings, are wax alcohols, i.e. fatty alcohols with approx. 24-36 carbon atoms, which are the main constituent of many natural waxes in the form of wax esters of higher molecular weight fatty acids (wax acids). Examples of preferred wax alcohols are lignoceryl alcohol, ceryl alcohol, myricyl alcohol or melissyl alcohol.

Dispersions are particularly suitable for processing as castings, dispersions with washing or cleaning-active substances or mixtures of active substances being used with particular preference. In a particularly preferred embodiment of the present application, the washing- or cleaning-active preparation used to produce the casting is a dispersion of solid particles in a dispersing agent, dispersions which, based on their total weight iii), comprise 10 to 85% by weight of dispersing agent and iv) contain 15 to 90% by weight of dispersed substances, are particularly preferred.

In this application, dispersion is a system consisting of several phases, one of which is continuous (dispersant) and at least one other is finely divided (dispersed substances).

Particularly preferred dispersions are characterized in that they contain the dispersant in amounts above 11% by weight, preferably above 13% by weight, particularly preferably above 15% by weight, very particularly preferably above 17 % By weight and in particular above 19% by weight, in each case based on the total weight of the dispersion. Dispersions which have a dispersion with a proportion by weight of dispersant above 20% by weight, preferably above 21% by weight and in particular above 22% by weight, in each case based on the total weight of the dispersion, can furthermore preferably be used. The maximum dispersant content of preferred dispersions, based on the total weight of the dispersion, is preferably less than 63% by weight, preferably less than 57% by weight, particularly preferably less than 52% by weight, very particularly preferably less than 47% by weight .-% and in particular less than 37 wt .-%. In the context of the present invention, in particular those washing or cleaning-active preparations which, based on their total weight, contain dispersing agents in amounts of 12 to 62% by weight, preferably 14 to 49% by weight and in particular 16 to 38% by weight. % contain. Dispersions with a dispersant content of between 16 and 30% by weight, preferably between 16 and 26% by weight and in particular between 16 and 22% by weight, in each case based on the total weight of the dispersion, are particularly preferred.

The dispersants used are preferably water-soluble or water-dispersible. The solubility of these dispersants at 25 ° C. is preferably more than 200 g / l, preferably more than 300 g / l, particularly preferably more than 400 g / l, very particularly preferably between 430 and 620 g / l and in particular between 470 and 580 g / l.

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 can be either a single polymer or a mixture of different water-soluble or water-dispersible polymers. In a further preferred embodiment of the present invention, the dispersant or at least 50% by weight of the polymer mixture consists of water-soluble or water-dispersible nonionic polymers from the group of polyvinylpyrrolidones, vinylpyrrolidone / vinyl ester copolymers, cellulose ethers, polyvinyl alcohols, polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol. Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol which have the general formula III

H- (0-CH ₂ -CH ₂ ) _n -OH (III)

are sufficient, where n can take values between 1 (ethylene glycol) and several thousand. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the formula VII mentioned above. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), for example, PEG-4, PEG-6, PEG-8, PEG-9 , PEG-10, PEG-12, PEG-14 and PEG-16 can be used. Commercially available polyethylene glycols are, for example, under the trade name Carbowax ^® PEG 200 (Union Carbide), Emkapol ^® 200 (ICI Americas), Lipoxol ^® 200 MED (Huls America), polyglycol ^® E-200 (Dow Chemical), Alkapol ^® PEG 300 (Rhone -Poulenc), Lutrol ^® E300 (BASF) and the corresponding trade names with higher numbers. The average relative molecular weight of at least one of the dispersants used in the washing or cleaning agents according to the invention, in particular at least one of the poly (alkylene) glycols used, is preferably between 200 and 36,000, preferably between 200 and 6000 and particularly preferably between 300 and 5000.

Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula IV

H- (O-CH-CH ₂ ) _n -OH (IV)

I

CH ₃ are sufficient, where n can take values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetrapropylene glycol, ie the representatives with n = 2, 3 and 4 in formula IV.

Other preferred dispersants are the nonionic surfactants, which are used both alone, but particularly preferably in combination with a nonionic polymer. Detailed information on the nonionic surfactants that can be used can be found below in the description of detergent or cleaning substances.

Dispersions which are preferably used are characterized in that at least one dispersant has a melting point above 25 ° C., preferably above 35 ° C. and in particular above 40 ° C. Particularly preferred is the use of dispersants with a melting point or melting range between 30 and δ0 ° C, preferably between 35 and 75 ° C, particularly preferably between 40 and 70 ° C and in particular between 45 and 65 ° C, these dispersants, based on the total weight of the dispersants used, a weight fraction above 10% by weight, preferably above 40% by weight, particularly preferably above 70% by weight and in particular between 80 and 100% by weight.

The dispersions, which are preferably used as washing or cleaning active preparations, are distinguished by a high density. Dispersions with a density above 1.040 g / cm ³ are particularly preferably used. Processes preferred according to the invention are characterized in that the washing and cleaning-active preparation has a density above 1.040 g / cm ³ , preferably above 1.15 g / cm ³ , particularly preferably above 1.30 g / cm ³ and in particular above 1.40 g / cm ³ . This high density not only reduces the total volume of a dosing unit cast body but also improves its mechanical stability. Particularly preferred methods according to the invention are therefore characterized in that the dispersion has a density between 1,050 and 1,670 g / cm ³ , preferably between 1, 120 and 1,610 g / cm ³ , particularly preferably between 1,210 and 1,570 g / cm ³ , very particularly preferably between 1.290 and 1.510 g / cm ³ , and have in particular between 1.340 and 1.480 g / cm ^3. The information on the density relates in each case to the densities of the compositions at 20 ° C. In order to avoid segregation processes during the processing of these dispersions, in particular in the course of the vibration of the molds, dispersing agents and dispersed substances preferably have densities which are less than 0.6 g / cm ³ , preferably less than 0.4 g / cm ³ and differ in particular by less than 0.3 g / cm ³ .

Dimensionally stable gels are another solid which is particularly preferred in the context of the present invention. The term “dimensionally stable” here means gels which have an inherent dimensional stability which enables them to assume a non-disintegrating spatial form which is stable against breakage under the usual conditions of manufacture, storage, transport and handling by the consumer, whereby these form Spatial shape under the conditions mentioned, even over a longer period of time, preferably 4 weeks, particularly preferably 8 weeks and in particular 32 weeks, has not changed, that is to say under the usual conditions of manufacture, storage, transport and handling by the consumer in the course of the production-related spatial-geometric form persists, that is, does not flow, for example, or returns to this spatial-geometric form under the influence of an external force which is customary under the conditions of production, storage, transport and handling. In order to achieve the desired dimensional stability, the gels with good product properties (solubility, washing and cleaning performance, stability of the gel), it is preferred within the scope of the present invention to use one or more substances from the group agar-agar, carrageenan, Tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose, corn flour ether, polyacrylic and. Polymethacrylic compound, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonites, zeolites and silicas contain, it having proven to be particularly advantageous if the gels contain these or one of the following thickeners in amounts between 0.2 and 10 % By weight, preferably between 0.3 and 7% by weight and particularly preferably between 0.4 and 4% by weight, based on the total weight of the shaped body.

(Methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ^® -GT-232-S (alkyl polyglycol ether, Akzo), Deuterol ^® polymer 11 (dicarboxylic acid copolymer , Schönes GmbH), Deuteron ^® -XG (anionic heteropolysaccharide based on ß-D-glucose, D-manose, D-glucuronic acid, Schönes GmbH), Deuteron ^® -XN (non-ionic polysaccharide, Schönes GmbH), Dicrylan ^® -Verdicker- 0 (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA ^® -81 and EMA ^® -91 (ethylene-maleic anhydride copolymer, Monsanto), Thickener-QR-1001 (polyurethane emulsion, 19-21% in water / diglycol ether, Rohm & Haas), Mirox ^® -AM (anionic acrylic acid-acrylic acid ester copolymer dispersion, 25% in water, Stockhausen), SER-AD -FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo ^® -S (high molecular polysaccharide, stabilized with formaldehyde, Shell) and Shellflo ^® -XA (xanthan biopolymer, stabilized with formaldehyde, Shell).

Due to their manufacturing process and to optimize their dissolving behavior, preferred gels contain various solvents, gels having proven particularly advantageous in terms of their product properties, the water and / or one or more water-miscible solvents in amounts of 5 to 70% by weight, preferably Contain from 10 to 65 wt .-% and particularly preferably from 15 to 60 wt .-%.

The capsules are further preferred solids used in agents according to the invention. "Capsule" is a term for a frequently used form of packaging that contains solid, semi-solid or liquid substances in differently sized, possibly colored, layers of gelatin, wax or wafer material. The most common are the gelatin capsules (made of hard or Soft gelatin) is used.

In a particular embodiment of the present invention, one, more or all of the solids used in the agents according to the invention, that is to say for example one, more or all of the powders and / or granules (e) and / or extrudate (s) and / or compact (s) and / or cast body and / or dimensionally stable gel (s) and / or capsule (s), a coating (coating). Such a coating can serve different purposes. On the one hand, coating can, for example, prevent undesired contact of active substances which are sensitive to hydrolysis or oxidation in the solids, with the outside air or other solids enclosed in the water-soluble container according to the invention. On the other hand, an advantageous visual effect can also be achieved by a coating.

According to the above, liquids and solids are suitable as ingredients for the receiving chambers. In the case of solids, a distinction is made between powders, granules, extrudates, compactates, castings and dimensionally stable gels. In the context of this application, liquids are not only low-viscosity, flowable liquids or flowable gels, but also flowable dispersions, for example emulsions or suspensions. Active substances or combinations of active substances are considered to be flowable if they have no inherent dimensional stability which enables them to assume a non-disintegrating spatial form under the usual conditions of manufacture, storage, transport and handling by the consumer, this spatial form under the conditions mentioned also not changed over a longer period of time, preferably 4 weeks, particularly preferably 8 weeks and in particular 32 weeks, that is under the usual conditions of manufacture, storage, transport and handling by the consumer in the spatial conditions caused by the manufacture. geometric shape persists, that is, does not melt away. The determination of the flowability relates in particular to the conditions customary for storage and transport, that is to say in particular to temperatures below 50 ° C., preferably below 40 ° C. Liquids are therefore in particular active substances or combinations of active substances with a melting point below 25 ° C., preferably below 20 ° C., particularly preferably below 15 ° C.

The table below shows the preferred agents according to the invention with three filled receiving chambers. The receiving chambers filled with liquid, powder or granules preferably have a seal. In the case of the receiving chambers filled with compactates, extrudates, casting bodies or dimensionally stable gels, the sealing is optional, but is preferred.

Agents which are particularly preferred in the context of the present application are characterized in that at least one receiving chamber contains a liquid active substance. Other particularly preferred agents are characterized in that at least one receiving chamber contains a solid active substance. However, it is particularly preferred in the context of the present invention that at least one receiving chamber of the agents according to the invention is filled with a liquid, at least one further receiving chamber with a solid, preferably a powder. A further preferred embodiment has three receiving chambers, one of which is filled with a liquid, a second receiving chamber with a powder and a third receiving chamber with a solidified melt.

As disclosed above, the containers of the invention may include transparent or translucent wrapping materials. Agents preferred according to the invention, which at least partially have a transparent covering material, can therefore contain stabilizing agents. Stabilizing agents in the sense of the invention are materials which are in the receiving chambers and / or in an intermediate space Protect existing ingredients from decomposition or deactivation by exposure to light. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.

Particularly suitable stabilizers in the sense of the invention are the antioxidants. In order to prevent undesired changes to the formulations caused by light radiation and thus radical decomposition, the formulations can contain antioxidants. Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants. Further examples are propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (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 acid palmitate, organosulfur compounds, such as the esters of 3,3 ^'- thiodipropionic acid with C s alkanols, in particular C ₁₀ -ι ₈ alkanols, metal ion deactivators that are capable of catalyzing the auto-oxidation of metal ions such as copper, to complex, such as nitrilotriacetic acid and its derivatives and their mixtures. Antioxidants can 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 stabilizers that can preferably be used are the UV absorbers. UV absorbers can improve the lightfastness of the formulation components. These include organic substances (light protection filters) that are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, eg heat. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles, such as, for example, water-soluble benzenesulfonic acid 3- (2H-benzotriazol-2-yl) -4- Hydroxy-5- (methylpropyl) monosodium salt (Cibafast ^® H), in the 3-position phenyl-substituted 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 urocanoic acid , Of particular importance are biphenyl and especially stilbene derivatives, which are commercially available as Tinosorb ^® FD or Tinosorb ^® FR ex Ciba. 3-Benzylidene camphor or 3-benzylidene norcampher and its derivatives, 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 amyl 4- (dimethylamino) benzoate; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene); Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropyl benzyl ester, salicylic acid homomethyl ester; 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, for example, 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'methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, 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-benzylidene camphor, such as 4- (2-oxo-3-bornylidene methyl) benzene sulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl-, are particularly suitable as typical UV-A filters. 4'-methoxydibenzoylmethane (Parsol 1739), 1-phenyl-3- (4'-isopropylphenyl) propane-1, 3-dione and enamine compounds. The UV-A and UV-B filters can of course also be used in mixtures. In addition to the soluble substances mentioned, insoluble light-protection pigments, namely finely dispersed, preferably nanoized 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. Silicates (talc), barium sulfate or zinc stearate can be used as salts. 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 can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs in some other way from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobicized. Typical examples are coated titanium dioxides, such as titanium dioxide T 305 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferably used.

Dihydroquinolinones, 1, 3-diarylpyrazolines, naphthalic imides, benzoxazole, benzisoxazole and benzimidazole systems as well as the pyrene derivatives substituted by heterocycles. Of particular importance are the sulfonic acid salts of the diaminostilbene derivatives and polymeric fluorescent substances.

Fluorescent substances, based on the total weight of a substance mixture located in a receiving chamber or in an intermediate space, in amounts of up to 5% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0.5 and in particular from 0, 03 to 0.1 wt .-% be included. In a preferred embodiment, the aforementioned stabilizing agents are used in any mixtures. The stabilizing agents are, based on the total weight of a substance mixture located in a receiving chamber, in amounts of up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20% by weight, in particular from 0.02 up to 5 wt .-% used.

At least two of the receiving chambers of containers according to the invention are sealed. All of the receiving chambers of a container according to the invention are preferably sealed. The first and second enveloping materials mentioned above can be the same but also different materials. However, it is particularly preferred if the first and second shell material differ, for example, in their chemical composition or in their thickness and have different dissolution rates.

The dissolving behavior of the container and the closure part can, in addition to the chemical composition of the shell materials used, also be influenced, for example, by the thickness of the container walls or the closure parts. In the context of the present application, preferred containers are characterized in that the side walls of the receiving chambers, which are made of the first covering material, have a thickness of 5 to 2000 μm, preferably 10 to 1000 μm, particularly preferably 15 to 500 μm, very particularly preferably 20 to 200 μm and in particular from 25 to 100 μm. The second covering material used for sealing preferably has a thickness of 5 to 100 μm, particularly preferably 6 to δOμm and in particular 7 to 50 μm. It is particularly preferred that the container and the sealing material have different thicknesses, whereby those containers whose sealing material have a smaller wall thickness than the associated containers are advantageous.

Preferred coating materials are water-soluble or water-dispersible. Agents within the scope of the present application are therefore preferred which have at least one water-soluble or water-dispersible coating material. Agents according to the invention are particularly preferred in which the coating materials used comprise a water-soluble or water-dispersible polymer. As can be seen from the above information, the agents according to the invention are particularly suitable for the controlled release of the active substances contained, in particular the active substances from the group of washing or cleaning agents.

According to the invention, preference is accordingly given to an embodiment in which the container as a whole is water-soluble, ie. H. dissolves completely when used as intended for washing or machine cleaning, if the conditions for loosening have been reached. A major advantage of this embodiment is that the container can be at least partially detached in the cleaning liquor within a practically relevant short time - as a non-limiting example, a few seconds to 5 minutes - under precisely defined conditions, and thus, according to the requirements, the encapsulated content, ie. H. the active cleaning material or several materials into the fleet. This release can only be controlled or controlled in different ways.

In a first embodiment of the invention, which is particularly preferred on account of advantageous properties, the water-soluble container comprises areas which are less or not water-soluble at all or areas which are water-soluble only at higher temperatures and areas which are water-soluble or water-soluble at low temperatures. In other words, the container does not consist of a uniform material that has the same water solubility in all areas, but of materials of different water solubility. Areas of good water solubility are to be distinguished on the one hand from areas with less good water solubility, with poor or no water solubility or from areas in which water solubility is only at a higher temperature or at a different pH value or only at a changed electrolyte concentration the desired value achieved, on the other hand. This can lead to certain areas of the container becoming detached when used as intended under adjustable conditions, while other areas remain intact. A container with pores or holes is formed, into which water and / or liquor penetrate, detach active, rinse-active or cleaning-active ingredients and can be discharged from the container. Systems in the form of multi-chamber containers or in the form of one another can also be used in the same way arranged containers ("onion system") are provided. In this way, systems with controlled release of the wash-active, rinse-active or cleaning-active ingredients can be manufactured.

The invention is not subject to any restrictions on the formation of such systems. Thus, containers can be provided in which a uniform polymer material comprises small areas of incorporated compounds (for example salts) which are more water-soluble than the polymer material. On the other hand, several polymer materials with different water solubility can also be mixed (polymer blend), so that the more rapidly soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the more slowly soluble.

It corresponds to a particularly preferred embodiment of the invention that the less readily water-soluble areas or not at all water-soluble areas or only at higher temperatures water-soluble areas of the containers are areas made of a material which chemically essentially corresponds to that of the readily water-soluble areas or at lower temperatures water-soluble areas corresponds, but has a higher layer thickness and / or has a changed degree of polymerization of the same polymer and / or has a higher degree of crosslinking of the same polymer structure and / or has a higher degree of acetalization (in the case of PVAL, for example with saccharides, polysaccharides, such as starch) and / or a content has water-insoluble salt components and / or has a content of a water-insoluble polymer. Even taking into account the fact that the containers do not completely dissolve, portioned detergent or cleaning agent compositions according to the invention can be provided which have advantageous properties in releasing active substances, in particular active substances from the group of detergents or cleaning agents, into the respective liquor ,

In addition to this controlled release through the targeted choice of the shell materials used, the person skilled in the art has other methods available. An alternative procedure, which alone or in combination with the above-mentioned control by selecting certain envelope materials for controlled Release of active substances or active substance mixtures is suitable, the integration of one or more "switches" in the aforementioned active substances, active substance mixtures or active substance preparations.

- The solubility of optionally used capsules or coatings or matrices as a function of pH and / or temperature and / or ionic strength;

- The dissolution rate of optionally used capsules or coatings or matrices as a function of pH and / or temperature and / or ionic strength;

In a particularly preferred embodiment, the agent according to the invention comprises at least one active substance or active substance preparation, the release of which is delayed. The delayed release is preferably delayed by the use of at least one of the agents described above, but in particular by the use of different packaging materials and / or the use of selected coating materials, it being particularly preferred that this delayed release occurs when active substances or mixtures of active substances are used the group of detergents or cleaning agents is carried out at the earliest 5 minutes, preferably at the earliest 7 minutes, particularly preferably at the earliest 10 minutes, very particularly preferably at the earliest 15 minutes and in particular at the earliest 20 minutes after the start of the cleaning or washing process. Especially the use of meltable coating materials from the group of waxes or paraffins is preferred.

In a preferred embodiment, the agents according to the invention comprise active substances or active substance mixtures from the fields of pharmaceuticals, cosmetics, feed, crop protection or fertilizers, adhesives, food and / or personal care products, but preferably from the field of detergent and cleaning substances.

Particularly preferred agents according to the invention are characterized in that at least one receiving chamber and / or at least one intermediate space is filled with a washing or cleaning agent. All of the receiving chambers are preferably filled with substances that are active in washing or cleaning. Washing and cleaning-active substances from the group of bleaching agents, bleach activators, polymers, builders, surfactants, enzymes, disintegration aids, electrolytes, pH regulators, fragrances, perfume carriers, dyes, hydrotropes, foam inhibitors, anti-redeposition agents, optical brighteners, graying inhibitors, are particularly preferred. Anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, phobing and impregnating agents, swelling and anti-slip agents, non-aqueous solvents, fabric softeners, protein hydrolyzate and UV absorbers.

Bleaching agents and bleach activators can be included in the agents according to the invention as important components of detergents and cleaning agents. Among the compounds which serve as bleaching agents and supply H ₂ 0 ₂ in water are sodium percarbonate, sodium perborate tetrahydrate and the sodium perborate monohydrate are of particular importance. Further useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ 0 ₂ -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.

Detergent tablets for automatic dishwashing can also contain bleaches from the group of organic bleaches. Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoxythoxy acid peroxoxy acid, (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperocysebacassoxy acid, diperocysebacassoxy acid, Decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

If the agents according to the invention are used as automatic dishwashing agents, they can contain bleach activators in order to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C. and below. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

Further bleach activators which are preferably used in the context of the present application are compounds from the group of the cationic nitriles, in particular cationic nitrile of the formula

R ¹

R ² -N ⁽⁺⁾ - (CH ₂ ) -CN X «

I

R ³

in R ¹ for -H, -CH ₃ , a C ₂ . ₂ alkyl or alkenyl radical, a substituted C ₂ . ₂₄ - alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a Cι- ₂ alkyl group, or for a substituted alkyl or Alkenylarylrest with a C-ι- ₂₄ alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ - CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ - CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -0) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion.

A particularly preferred agent according to the invention is a cationic nitrile of the formula

R, 4th

R ⁵ -N ⁽⁺⁾ - (CH ₂ ) -CN X ^H ,

R ⁶ contain, in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , - CH ₂ -CH3, -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , where R ⁴ can also be -H and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH (CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , or (HO-CH ₂ - CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^"are particularly preferred, with the cationic nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , in which X ^" for a Anion, which is selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate, is particularly preferred.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the agents. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

The surfactants include in particular the anionic surfactants in acid form, aqueous solutions or pastes of the neutralized anionic surfactant acids, nonionic surfactants and / or cationic surfactants or amphoteric surfactants. Depending on the choice of the surfactant (s) used, surfactant-containing agents according to the invention can be used, for example, in the removal of grease or oil soiling, their field of use extending from textile cleaning to the removal of oil soiling in nature. In the context of the present application, granules are preferred which have a surfactant content of 1 to 70% by weight, particularly preferably 2 to 60% by weight, particularly preferably 4 to 50% by weight, in each case based on the total weight of the compositions , exhibit.

In addition to the bleach and bleach activator ingredients mentioned, builders are other important ingredients of detergents. Preferred agents according to the invention can contain all builders commonly used in cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates. The builders mentioned can of course also be used in surfactant-free compressed products. Suitable crystalline, layered sodium silicates have the general formula NaMSi _x 0 _{2x +} ι Η ₂ 0, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ 0 ₅ ^• yH ₂ 0 are preferred.

Amorphous sodium silicates with a module Na ₂ 0: Si0 ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite that can be used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which was developed by CONDEA Augusta SpA is sold under the brand name VEGOBOND AX ^® and through the formula

nNa ₂ 0 ^• (1-n) K ₂ 0 ^• AI ₂ O ₃ ^■ (2 - 2.5) Si0 ₂ ^■ (3.5 - 5.5) H ₂ 0

can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

Alkali metal phosphates is the summary name for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric acid H ₃ P0 _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ P0 ₄ , disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HP0 ₄ , trisodium phosphate, tertiary sodium phosphate, Na ₃ P0 ₄ , tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ 0 ₇ and by condensation of NaH ₂ P0 ₄ or NaH ₂ P0 ₄ or KH ₂ P0 ₄ arise higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates, as well as the pentasodium triphosphate, Na ₅ P ₃ Oι ₀ (sodium tripolyphosphate) are further within the scope of the present Registration with advantage used builders.

Usable organic builders are, for example, the polycarboxylic acids, such as citric acid, which can be used in the form of their alkali metal salts and in particular sodium salts. Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Alkali carriers can be present as further constituents. Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates,

Alkali metal sesquicarbonates, alkali silicates, alkali metasilicates, and mixtures of the abovementioned substances, the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, preferably being used for the purposes of this invention.

If the agents according to the invention are used in automatic dishwashing, water-soluble builders are preferred, since they generally have less tendency to form insoluble residues on dishes and hard surfaces. Common builders are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and silicates. Trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicate and / or metasilicate are preferably used for the production of tablets for machine dishwashing. A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred. A builder system which contains a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.

Organic cobuilders which can be used in the cleaning agents in the context of the present invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, polycarboxylic acids being those Carboxylic acids are understood that carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic acid, sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Polymeric polycarboxylates are also suitable as builders; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, the molecular weights from 1000 to 1000, can in turn be selected from this group 10000 g / mol, and particularly preferably from 1200 to 4000 g / mol, may be preferred.

Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention. The copolymers containing sulfonic acid groups are described in detail below.

However, it is also possible to provide agents according to the invention which, as so-called “3in1” products, combine the conventional cleaners, rinse aids and a salt replacement function. For this purpose, automatic dishwashing agents according to the invention are preferred which additionally contain 0.1 to 70% by weight of copolymers out

i) unsaturated carboxylic acids ii) monomers containing sulfonic acid groups iii) optionally further ionic or nonionic monomers

contain.

These copolymers have the effect that the items of tableware treated with such agents become significantly cleaner in subsequent cleaning operations than items of tableware that have been washed with conventional agents.

As an additional positive effect, there is a shortening of the drying time of the dishes treated with the cleaning agent, ie the consumer can take the dishes out of the machine and reuse them earlier after the cleaning program has ended. In the context of the teaching according to the invention, drying time is generally understood to mean the meaning in words, i.e. the time which elapses until a dish surface treated in a dishwasher is dried, but in particular the time which elapses, up to 90% of one with a cleaning or Rinse aid is dried in a concentrated or diluted form treated surface. In the context of the present invention, unsaturated carboxylic acids of the formula I are preferred as the monomer,

R ¹ (R ² ) C = C (R ³ ) COOH (I),

in which R ¹ to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂₎ -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by formula I are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H; R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) preferred.

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula II

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (II),

in which R ⁵ to R ⁷ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group , which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH- C (CH ₃ ) ₂ - and -C (0) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas Ha, IIb and / or IIc,

H ₂ C = CH-X-S0 ₃ H (Ha), H ₂ C = C (CH ₃ ) -X-S0 ₃ H (llb),

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H

(IIc)

in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH- C (CH ₃ ) ₂ - and - C (0) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (0) NH-CH (CH ₂ CH) in formula IIa), 2-acrylamido-2-propanesulfonic acid (X = -C (0 ) NH-C (CH ₃ ) ₂ in formula Ila), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (0) NH-C (CH ₃ ) ₂ CH ₂ - in formula Ila), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (0) NH-C (CH ₃ ) ₂ CH ₂ - in formula IIb), 3-methacrylamido-2-hydroxy-propanesulfonic acid (X = -C (0 ) NH-CH ₂ CH (OH) CH ₂ - in formula IIb) allyl sulfonic acid (X = CH ₂ in formula IIa), methallyl sulfonic acid (X = CH ₂ in formula IIb), allyloxybenzenesulfonic acid (X = -CH ₂ -0-C ₆ H ₄ - in formula Ila), methallyloxybenzenesulfonic acid (X = -CH ₂ -0-C ₆ H ₄ - in formula Xlb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1- sulfonic acid (X = CH ₂ in formula IIb), styrene sulfonic acid (X = C ₆ H ₄ in formula IIa), vinyl sulfonic acid (X not present in formula IIa), 3-acrylamido-propanesulfonic acid (X = -C (0) NH-CH ₂ CH ₂ CH ₂ - in formula IIa), 3-methacrylamido-propanesulfonic acid (X = -C (0) NH-CH ₂ CH ₂ CH ₂ - in formula IIb), sulfomethacrylamide (X = -C (0) NH- in formula IIb), sulfomethyl methacrylamide ( X = - C (0) NH-CH ₂ - in formula IIb) and water-soluble salts of the acids mentioned.

Other suitable ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds. The content of monomers of group iii) in the polymers used according to the invention is preferably less than 20% by weight, based on the polymer. Polymers to be used with particular preference consist only of monomers of groups i) and ii).

In summary, copolymers are made of

i) unsaturated carboxylic acids of formula I. R ¹ (R ² ) C = C (R ³ ) COOH (I),

in which R ¹ to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,

ii) Monomers of the formula II containing sulfonic acid groups

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (II),

in which R ⁵ to R ⁷ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group , which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (0) -NH-C (CH ₃ ) ₂ - and -C (0) -NH-CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers

particularly preferred.

Particularly preferred copolymers consist of

i) one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and / or maleic acid ii) one or more monomers of the formulas IIa, IIb and / or IIc containing sulfonic acid groups:

H ₂ C = CH-X-S0 ₃ H (Ila),

H ₂ C = C (CH ₃ ) -X-S0 ₃ H (llb),

H0 ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-S0 ₃ H (llc),

in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) - NH-C (CH ₃ ) ₂ - and - C (0) -NH-CH (CH ₂ CH ₃ ) -

iii) optionally further ionic or nonionic monomers.

The copolymers contained in the compositions can contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) with all representatives from group ii) and all representatives from group iii) can be combined. Particularly preferred polymers have certain structural units, which are described below.

For example, agents according to the invention are preferred which are characterized in that they contain one or more copolymers, the structural units of the formula

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (III),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic

Hydrocarbon radicals with 1 to 24 carbon atoms, with spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH- CH (CH ₂ CH ₃ ) -, are preferred. These polymers are produced by copolymerization of acrylic acid with a sulfonic acid group-containing acrylic acid derivative. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have structural units of the formula IV

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] p- (IV),

Hydrocarbon radicals with 1 to 24 carbon atoms, with spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH- CH (CH ₂ CH ₃ ) -, are preferred.

Completely analogously, acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Agents according to the invention which contain one or more copolymers which have structural units of the formula V

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (V),

Hydrocarbon radicals with 1 to 24 carbon atoms, with spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH- CH (CH ₂ CH ₃ ) - are preferred, are also a preferred embodiment of the present invention, just as agents are preferred which are characterized in that they contain one or more copolymers which contain structural units of formula VI

- [CH ₂ -C (CH ₃ ) COOH] m- [CH C (CH ₃ ) C (0) -Y-S0 ₃ H] p- (VI), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic

Instead of or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly preferred monomer from group i). In this way, preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers, the structural units of the formula VII

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VII),

Hydrocarbon radicals with 1 to 24 carbon atoms, with spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH- CH (CH ₂ CH ₃ ) - are preferred and to agents which are characterized in that they contain one or more copolymers, the structural units of the formula VIII

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p - (VIII),

Hydrocarbon radicals with 1 to 24 carbon atoms, with spacer groups in which Y for -0- (CH ₂ ) _n - with n = 0 to 4, for -0- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH- CH (CH ₂ CH ₃ ) -, are preferred. In summary, automatic dishwashing agents according to the invention are preferred which contain, as ingredient b), one or more copolymers which have structural units of the formulas III and / or IV and / or V and / or VI and / or VII and / or VIII

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (III),

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] p- (IV),

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (V),

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (0) -Y-S0 ₃ H] _p - (VI),

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (0) -Y-S0 ₃ H] _p - (VII),

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (0) 0-Y-S0 ₃ H] _p - (VIII),

All or part of the sulfonic acid groups in the polymers can be in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions. Corresponding agents which are characterized in that the sulfonic acid groups in the copolymer are partially or fully neutralized are preferred according to the invention.

The monomer distribution of the copolymers used in the agents according to the invention is preferably 5 to 95% by weight i) or ii), particularly preferably 50 to 90% by weight, in the case of copolymers which contain only monomers from groups i) and ii). % Of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer. In the case of terpolymers, those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred ,

The molar mass of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the intended use. Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol ^"1 , preferably from 4000 to 25,000 gmol ^{" 1} and in particular from 5000 to 15,000 gmol ^"1 .

The content of one or more copolymers in the agents according to the invention can vary depending on the intended use and the desired product performance, preferred dishwasher detergents according to the invention being characterized in that they contain the copolymer (s) in amounts of 0.25 to 50% by weight. %, preferably from 0.5 to 35% by weight, particularly preferably from 0.75 to 20% by weight and in particular from 1 to 15% by weight.

As already mentioned further above, it is particularly preferred to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers in the agents according to the invention. The polyacrylates were described in detail above. Combinations of the above-described copolymers containing sulfonic acid groups with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons, are particularly preferred. Such polyacrylates are commercially available under the trade names Sokalan ^® PA15 or Sokalan ^® PA25 (BASF).

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is in general 2000 to 100000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,

Anionic surfactants in acid form are preferably one or more substances from the group of carboxylic acids, sulfuric acid half-esters and sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and alkylarylsulfonic acids. In order to have sufficient surface-active properties, the compounds mentioned should have longer-chain hydrocarbon radicals, that is to say they should have at least 6 carbon atoms in the alkyl or alkenyl radical. The C chain distributions of the anionic surfactants are usually in the range from 6 to 40, preferably 8 to 30 and in particular 12 to 22 carbon atoms.

Carboxylic acids, which are used as soaps in detergents and cleaning agents in the form of their alkali metal salts, are technically largely obtained from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps), today only water is used on an industrial scale that splits the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage. Carboxylic acids which can be used as anionic surfactants in the context of the present invention are for example hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid etc. The use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid) is preferred in the context of the present compound ), Hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotinic acid), triacotanoic acid (melissic acid) as well as the unsaturated octadic acid 9c- hexadecenoic acid 9c- paladic acid (Petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c Octadecatreic acid (linolenic acid) For reasons of cost, it is preferred not to use the pure species, but rather Technical mixtures of the individual acids, as are accessible from fat cleavage. Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6% by weight C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% _C14, 10 wt .-% C _16, 2 wt .-% _C18, 8 wt .-% C ₁₈ - 1 wt .-% C ₁₈ -), Palmkemölfettsäure (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt .-% C _i2 , 15% by weight C ₁₄ , 7% by weight C ₁₆ , 2% by weight C ₁₈ , 15% by weight C ₁₈ -, 1% by weight C ₁₈ -), tallow fatty acid (approx. 3% by weight C ₁₄ , 26% by weight C ₁₆ , 2% by weight d ₆ -, 2% by weight C ₁₇ , 17% by weight C ₁₈ , 44% by weight Cι ₈ -, 3 wt% C ₁₈ -, 1 wt% C ₁₈ -), hardened tallow fatty acid (approx. 2 wt% C ₁₄ , 28 wt% Ciβ, 2 wt% C ₁₇ , 63 wt. -% C ₁₈ , 1% by weight C ₁₈ -), technical oleic acid (approx. 1% by weight C ₁₂ , 3% by weight C ₁₄ , 5% by weight C ₁₆ , 6% by weight Cι ₆ -, 1 wt .-% C ₁₇ , 2 wt .-% C ₁₈ , 70 wt .-% C ₁₈ -, 10 wt .-% Cι ₈ -, 0.5 wt .-% C ₁₈ -), technical palmitic / stearic acid (about 1 wt .-% C _12, 2 wt .-% C ₁₄ 45 wt .-% C _16, 2 wt .-% C ₁₇ 47 wt .-% Cι _8, 1 wt % C- | ₈ ) and soybean oil fatty acid (approx. 2% by weight C ₁₄ , 15 Ge w .-% C ₁₆ , 5 wt .-% C «, 25 wt .-% C ₁₈ -, 45 wt .-% Ciβ", 7 wt .-% Cι ₈ -).

Sulfuric acid semiesters of longer-chain alcohols are also anionic surfactants in their acid form and can be used in the context of the present invention. Their alkali metal, in particular sodium salts, the fatty alcohol sulfates, are commercially available from fatty alcohols which are reacted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to give the alkyl sulfuric acids concerned and are subsequently neutralized. The fatty alcohols are obtained from the fatty acids or fatty acid mixtures concerned by high-pressure hydrogenation of the fatty acid methyl esters. The most significant industrial process for the production of Fatty alkyl sulfuric acids is the sulfonation of the alcohols with S0 ₃ / air mixtures in special cascade, falling film or tube bundle reactors.

Another class of anionic surfactant acids that can be used according to the invention are the alkyl ether sulfuric acids, the salts of which, the alkyl ether sulfates, are distinguished by a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts) compared to the alkyl sulfates. Like the alkyl sulfuric acids, alkyl ether sulfuric acids are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 93% of the alkyl ether sulfuric acids concerned.

Alkanesulfonic acids and olefin sulfonic acids can also be used as anionic surfactants in acid form in the context of the present invention. Alkanesulfonic acids can contain the sulfonic acid group in a terminal bond (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), only the secondary alkanesulfonic acids being of commercial importance. These are made by sulfochlorination or sulfoxidation of linear hydrocarbons. In Reed sulfochlorination, n-paraffins are reacted with sulfur dioxide and chlorine under irradiation with UV light to give the corresponding sulfochlorides, which, when hydrolysed with alkalis, provide the alkanesulfonates directly, and when reacted with water, the alkanesulfonic acids. Since di- and polysulfochlorides and chlorinated hydrocarbons can occur as by-products of the radical reaction in the sulfochlorination, the reaction is usually carried out only up to degrees of conversion of 30% and then terminated.

Another process for the production of alkanesulfonic acids is sulfoxidation, in which n-paraffins are reacted with sulfur dioxide and oxygen under irradiation with UV light. This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylpersulfonyl radicals. The reaction with unreacted paraffin provides an alkyl radical and the alkyl persulfonic acid, which breaks down into an alkyl peroxysulfonyl radical and a hydroxyl radical. The reaction of the two Radicals with unreacted paraffin provide the alkyl sulfonic acids or water, which reacts with alkyl persulfonic acid and sulfur dioxide to form sulfuric acid. In order to keep the yield of the two end products alkylsulfonic acid and sulfuric acid as high as possible and to suppress side reactions, this reaction is usually carried out only up to degrees of conversion of 1% and then stopped.

Olefin sulfonates are produced industrially by the reaction of α-olefins with sulfur trioxide. Intermediate hermaphrodites form here, which cyclize to form so-called sultons. Under suitable conditions (alkaline or acidic hydrolysis), these sultones react to give hydroxylalkanesulfonic acids or alkenesulfonic acids, both of which can also be used as anionic surfactant acids.

Alkylbenzenesulfonates as powerful anionic surfactants have been known since the 1930s. At that time, alkylbenzenes were produced by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution. In the early 1950s, to produce alkylbenzenesulfonates, propylene was tetramerized to give branched α-dodecylene and the product was converted to tetrapropylenebenzene via a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride, which was subsequently sulfonated and neutralized. This economical possibility of producing tetrapropylene benzene sulfonates (TPS) led to the breakthrough of this class of surfactants, which subsequently displaced the soaps as the main surfactant in washing and cleaning agents.

Due to the lack of biodegradability of TPS, there was a need to prepare new alkylbenzenesulfonates that are characterized by improved ecological behavior. These requirements are met by linear alkyl benzene sulfonates, which today are almost exclusively alkyl benzene sulfonates and are given the abbreviation ABS or LAS.

Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which in turn are accessible from linear olefins. For this purpose, petroleum fractions are separated on an industrial scale with molecular sieves into the n-paraffins of the desired purity and dehydrated to the n-olefins, both α- and i-olefins result. The resulting olefins are then reacted with benzene in the presence of acidic catalysts to give the alkylbenzenes, the choice of Friedel-Crafts catalyst having an influence on the isomer distribution of the linear alkylbenzenes formed: when using aluminum trichloride, the content of the 2-phenyl isomers is in the mixture with the 3, 4, 5 and other isomers at approx. 30% by weight, on the other hand, if hydrogen fluoride is used as a catalyst, the 2-phenyl isomer content can be reduced to approx. 20% by weight , Finally, the sulfonation of linear alkylbenzenes is now possible on a large industrial scale with oleum, sulfuric acid or gaseous sulfur trioxide, the latter being by far the most important. For the sulfonation, special film or tube bundle reactors are used which deliver a 97% by weight alkylbenzenesulfonic acid (ABSS) as product, which can be used as anionic surfactant acid in the context of the present invention.

By choosing the neutralizing agent, a wide variety of salts, i.e. Alkylbenzenesulfonates. For reasons of economy, it is preferred to prepare and use the alkali metal salts and, among them, the sodium salts of the ABSS. These can be described by the general formula IX:

in which the sum of x and y is usually between 5 and 13. C ₈ are preferred according to the invention as anionic surfactants in acid form. ₁₆ -, preferably C ₉ - ₁₃ - alkylbenzenesulfonic acids. In the context of the present invention, it is further preferred C ₈ . Use ₁₆ -, preferably C ₉ - ₁₃ alkylbenzenesulfonic acids which are derived from alkylbenzenes and which have a tetralin content below 5% by weight, based on the alkylbenzene. It is further preferred to use alkylbenzenesulfonic acids whose alkylbenzenes have been prepared by the HF process, so that the C ₈ .ι ₆ employed -, C ₉ -ι ₃ -alkylbenzenesulfonic acids preferably have a content of 2-phenyl isomer below 22 wt .-%, based on the alkylbenzenesulfonic acid.

The above-mentioned anionic surfactants in their acid form can be used alone or in a mixture with one another. However, it is also possible and preferred that the anionic surfactant in acid form, before addition to the carrier material (s), contains further, preferably acidic, ingredients of detergents and cleaning agents in amounts of 0.1 to 40% by weight, preferably of 1 to 15 wt .-% and in particular from 2 to 10 wt .-%, each based on the weight of the mixture to be reacted.

Suitable acidic reactants in the context of the present invention are, in addition to the “surfactant acids”, also the fatty acids, phosphonic acids, polymer acids or partially neutralized polymer acids as well as “builder acids” and “complex builder acids” (details later in the text) alone and in any mixtures. As ingredients of washing Acid detergents and cleaning agents are particularly suitable, for example phosphonic acids, which in neutralized form (phosphonates) are components of many detergents and cleaning agents as incrustation inhibitors. The use of (partially neutralized) polymer acids such as polyacrylic acids is also an option According to the invention, it is also possible to mix acid-stable ingredients with the anionic surfactant acid, for example so-called small components, which would otherwise have to be added in complex further steps, for example se optical brighteners, dyes etc., whereby the acid stability must be checked in individual cases.

Of course, it is also possible to use the anionic surfactants partially or fully neutralized. These salts can then be present as a solution, suspension or emulsion in the granulating liquid, but can also be part of the solid bed as a solid. In addition to the alkali metals (in particular here according to claim and K salts), ammonium and mono-, di- or triethanolalkonium ions are suitable as cations for such anionic surfactants. Instead of mono-, di- or triethanolamine, the analog representatives of mono-, di- or trimethanolamine or those of the alkanolamines of higher alcohols can also be quaternized and present as a cation. Cationic surfactants can also be used with advantage as active substances. The delivery form of the cationic surfactant can be added directly to the mixer, or it can be sprayed onto the solid carrier in the form of a liquid to pasty form of cationic surfactant. Such cationic surfactant preparation forms can be prepared, for example, by mixing commercially available cationic surfactants with auxiliaries such as nonionic surfactants, polyethylene glycols or polyols. Lower alcohols such as ethanol and isopropanol can also be used, the amount of such lower alcohols in the liquid cationic surfactant preparation form being below 10% by weight for the reasons mentioned above.

All customary substances are suitable as cationic surfactants for the agents according to the invention, cationic surfactants having a fabric softening effect being clearly preferred.

The agents according to the invention can contain one or more cationic, fabric softening agents of the formulas X, XI or XII as cationic active substances with fabric softening effect:

R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (XI)

(CH ₂ ) _n -TR ²

R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -CH-CH ₂ (XII)

I I I

R ¹ TT

R ² R ² R ¹

R ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (XIII)

R ⁴

wherein each R ^{1 group is} independently selected from Ci-e alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C ₈ . ₂₈ alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n - TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

In preferred embodiments of the present invention, the solid (s) additionally contain nonionic surfactant (s) as active substance.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₄ alcohols with 3 EO or 4 EO, Cg.n-Alkor.ol with 7 EO, C ₁₃ - ₁₅ alcohols with 3 EO, 5 EO, 7 EO or δ EO , C ₁₂ . ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ . ₁₄ -alcohol with 3 EO and Cι ₂ -ι ₈ -alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. In the context of the present invention, weakly foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants. Among these, surfactants with EO-AO-EO-AO blocks are preferred, with one to ten EO or AO groups being bonded to one another before a block follows from the other groups. Agents according to the invention which contain nonionic surfactant (s) of the general formula XIV are preferred here

R ¹ -0- (CH ₂ -CH ₂ -0) _w - (CH ₂ -CH-0) _x - (CH ₂ -CH ₂ -0) _y - (CH ₂ -CH-0) _z -H (XIV )

R ² R ³

in R ¹ for a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂ alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently represent integers from 1 to 6.

The preferred nonionic surfactants of the formula XIV can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethyl or alkylene oxide. The radical R ¹ in the above formula XIV can vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is generally not shown, the linear radicals being from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol are preferred. Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or in the mixture methyl-branched or linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, compositions according to the invention are preferred in which R ¹ in formula XIV for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms. In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit. However, other alkylene oxides in which R ² or R ³ are selected independently of one another from -CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are also suitable. Preferred agents are characterized in that R ² or R ³ for a radical -CH ₃ , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.

In summary, for use in the inventive compositions, in particular non-ionic surfactants are preferred which have a C ₉ of L .ι ₅ alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed of L to 4 ethylene oxide followed to 4 propylene oxide units.

The specified C chain lengths and degrees of ethoxylation or degrees of alkoxylation represent statistical mean values which can be an integer or a fraction for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned usually do not consist of an individual representative, but of mixtures, which can result in mean values and fractional numbers for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation.

In addition, aikylglycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula XV,

l

R-CO-N- [Z] (XV)

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula XVI,

R ¹ -0-R ²

I

R-CO-N- [Z] (XVI)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical with 1 to 8 Carbon atoms, C 1-4 alkyl or phenyl radicals are preferred and [Z] stands for a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

It is particularly preferred for many applications if the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2 is. Containers according to the invention which contain surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), are preferred in amounts of 5 to 80% by weight, preferably 7.5 to 70% by weight. %, particularly preferably from 10 to 60% by weight and in particular from 12.5 to 50% by weight, in each case based on the weight of the enclosed solids.

As already mentioned, the use of surfactants in cleaning agents for automatic dishwashing is preferably limited to the use of nonionic surfactants in small amounts. If the containers according to the invention are intended to enclose such agents, these agents preferably contain only certain nonionic surfactants, which are described below. Usually only weakly foaming nonionic surfactants are used as surfactants in automatic dishwashing detergents. By contrast, representatives from the groups of anionic, cationic or amphoteric surfactants are of lesser importance. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably δ to 1δ C atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linearly branched or preferably in the 2-position methyl or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO preferred per mole of alcohol. The preferred ethoxylated alcohols include, for example, C ₁₂ . ₁ -alcohols with 3 EO or 4 EO, C ₉ .n-alcohol with 7 EO, C ₁₃ . ₁₅ - alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ . ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ . ₁ alcohol with 3 EO and Cι ₂ --ι ₈ alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In particular in the case of water-soluble containers according to the invention for the portioning, packaging and metering of detergents for machine dishwashing, it is preferred that they contain a nonionic surfactant which has a melting point above room temperature, preferably a nonionic surfactant with a melting point above 20 ° C. Nonionic surfactants to be used preferably have melting points above 25 ° C, particularly preferred nonionic surfactants have melting points between 25 and 60 ° C, in particular between 26.6 and 43.3 ° C.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants which are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature originate from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control. In a preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16th ₂₀ alcohol), preferably a C ₁₈ alcohol and at least 12 mole, preferably at least 15 mol and recovered in particular at least 20 moles of ethylene oxide , Among these, the so-called "narrow ranks ethoxylates" (see above) are particularly preferred.

The nonionic surfactant, which is solid at room temperature, preferably has additional propylene oxide units in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants.

Other nonionic surfactants to be used with particular preference and having melting points above room temperature contain 40 to 70% of one

Polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blends containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-13 from Olin Chemicals. Another preferred surfactant can be represented by the formula

R ¹ 0 [CH ₂ CH (CH ₃ ) 0] _x [CH ₂ CH ₂ 0] _y [CH ₂ CH (OH) R ² ]

describe in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having 4 to 13 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1, 5 and y represents a value of at least 15.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] iOR ²

in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula can be different if x ≥ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which can be joined together in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The The value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa.

Particularly preferred end-capped poly (oxyalkyüerte) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 represents} H and x assumes values from 6 to 15.

Preferred agents according to the invention, which are used as automatic dishwashing detergents, also contain amphoteric or cationic polymers in addition to the surfactants mentioned to improve the rinse aid result.

Agents according to the invention can contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all the enzymes established in the prior art for these purposes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are accordingly preferred. Agents according to the invention preferably contain enzymes in total amounts of 1 × 10 ^"6 to 5 percent by weight based on active protein. The protein concentration can be determined using known methods, for example the BCA process (bicinchoninic acid; 2,2'-bichinolyl-4,4 '-dicarboxylic acid) or the biuret method can be determined. Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtiüsin DY and the enzymes thermitase, proteinase K and the enzyme which can no longer be assigned to the subtilisins in the narrower sense Proteases TW3 and TW7. Subtiüsin Carlsberg is available in a further developed form under the trade name Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. The variants listed under the name BLAP ^{® are} derived from the protease from Bacillus lentus DSM 5483.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, which is sold under the trade name Protosol ^® by Advanced Biochemicals Ltd., Thane, India, which is sold under the trade name Wuxi ^® by Wuxi Snyder Bioproducts Ltd., China, and in the trade name Proleather ^® and Protease P ^® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from β. amyloliquefaciens or from ß. stearothermophiius and their further developments for use in detergents and cleaning agents. The enzyme from ß. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar ^® ST. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase from ß. Amyloliquefaciens is sold by Novozymes under the name BAN ^® , and derived variants from the α-amylase from β. stearothermophiius under the names BSG ^® and Novamyl ^® , also from Novozymes. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from ß. highlight agaradherens (DSM 994δ); fusion products of the molecules mentioned can also be used.

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae. Another commercial product is the Amylase-LT ^® .

Agents according to the invention can contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^® , Lipolase ^® Ultra, LipoPrime ^® , Lipozyme ^® and Lipex ^® . Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. Lipase ^® , Lipase AP ^® , Lipase M-AP ^® and Lipase AML ^® available. For example, the Genencor company can use the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products, the preparations originally sold by Gist-Brocades M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention, also the product Lumafast ^® from Genencor.

Agents according to the invention, especially if they are intended for the treatment of textiles, can contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement one another with regard to their various performance aspects. These performance aspects include contributions to Primary washing performance, for secondary washing performance of the agent (anti-redeposition or graying inhibition) and finishing (tissue effect), up to the exertion of a "stone washed" effect.

A useful fungal, endoglucanase (EG) -rich cellulase preparation or its further developments are offered by the Novozymes company under the trade name Celluzyme ^® . The products Endolase ^® and Carezyme ^{®, which} are also available from Novozymes, are based on the 50 kD-EG and the 43 kD-EG from H. insolens DSM 1300. Other possible commercial products from this company are Cellusoft ^® and Renozyme ^® . The 20 kD EG cellulase from Melanocarpus, which is available from AB Enzymes, Finland, under the trade names Ecostone ^® and Biotouch ^® , can also be used. Other commercial products from AB Enzymes are Econase ^® and Ecopulp ^® . Another suitable cellulase from Bacillus sp. CBS 670.93 is available from Genencor under the trade name Puradax ^® . Other commercial products from Genencor are "Genencor detergent cellulase L" and IndiAge ^® Neutra.

Agents according to the invention can contain further enzymes, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and ß-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, United States. The from ß. subtilis .beta.-glucanase obtained is available under the name Cereflo ^® from Novozymes.

To increase the bleaching effect, washing or cleaning agents according to the invention can use oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain. Suitable commercial products are Denilite ^® 1 and 2 from Novozymes. Advantageously, organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally preferably added to the To increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons in the case of very different redox potentials between the oxidizing enzymes and the soiling (mediators).

The enzymes used in agents according to the invention either originate from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological processes known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.

The enzymes in question are advantageously purified by methods which are in themselves established, for example by means of precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.

Agents according to the invention can be added to the enzymes in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the enzyme is enclosed in a solidified gel are or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers. Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageous, for example due to the application of polymeric film formers, low dust and storage stable due to the coating.

Furthermore, it is possible to assemble two or more enzymes together, so that a single granulate has several enzyme activities.

A protein and / or enzyme contained in an agent according to the invention can be protected, particularly during storage, against damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage. When the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Agents according to the invention can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.

A group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used, including above all derivatives with aromatic groups, for example ortho, meta- or para-substituted phenylboronic acids, or their salts or esters. Pepfidaldehydes, ie ougopepfids with a reduced C-terminus, are also suitable. Ovomucoid and leupeptin may be mentioned as peptide protease inhibitors; an additional option is the formation of fusion proteins from proteases and peptide inhibitors.

Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and - propanolamine and their mixtures, aliphatic carboxylic acids up to C, ₂ , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End group-capped fatty acid amide alkoxylates can also be used as stabilizers.

Lower aliphatic alcohols, but above all polyols, such as glycerol, ethylene glycol, propylene glycol or sorbitol are further frequently used enzyme stabilizers. Di-glycerol phosphate also protects against denaturation by physical influences. Calcium salts are also used, such as calcium acetate or calcium formate, and magnesium salts. Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or, such as cellulose ethers, acrylic polymers and / or polyamides, stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polymers containing polyamine-N-oxide act simultaneously as enzyme stabilizers and as color transfer inhibitors. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkyl polyglycosides can also stabilize the enzymatic components of the agent according to the invention and even increase their performance. Crosslinked N-containing compounds fulfill a double function as soil release agents and as enzyme stabilizers.

Reducing agents and antioxidants such as sodium sulfite or reducing sugars increase the stability of the enzymes against oxidative breakdown.

Combinations of stabilizers are preferably used, for example made of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The action of peptide-aldehyde stabilizers can be increased by the combination with boric acid and / or boric acid derivatives and polyols and can be further enhanced by the additional use of divalent cations, such as calcium ions.

The use of liquid enzyme formulations is particularly preferred in the context of the present invention. Agents according to the invention are preferred here, which additionally contain enzymes and / or enzyme preparations, preferably solid and / or liquid protease preparations and / or amylase preparations, in amounts of 1 to 5% by weight, preferably of 1.5 to 4.5 and in particular from 2 to 4% by weight, based in each case on the total composition.

In order to facilitate the disintegration of the solids, such as tablets or granules, optionally included in the agents according to the invention, these compresses can contain disintegration aids, so-called tablet disintegrants. According to Rompp (9th edition, Vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1937, p. 162-164) understood auxiliary substances which are necessary for the rapid disintegration of tablets in water or gastric juice and for the release of the pharmaceuticals in provide resorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives. All of the disintegration aids mentioned can be used according to the invention.

In the context of the present invention, preferred disintegration aids are Ceululose-based disintegration aids, preferably in granular, cogranulated or compacted form.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ θ5) _n and, viewed formally, is a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions can also be used as disintegrants based on cellulose. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrants based on cellulose, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the disintegrant based on cellulose. Pure cellulose, which is free of cellulose derivatives, is particularly preferably used as the disintegrant based on cellulose. Microcrystalline cellulose can be used as a further disintegrant based on cellulose or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. Subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm.

In addition to or instead of the disintegration auxiliaries based on cellulose, the agents according to the invention can contain a gas-releasing system of organic acids and carbonates / bicarbonates.

The solid mono-, oligo- and polycarboxylic acids, for example, can be used as organic acids which release carbon dioxide from the carbonates / bicarbonates in aqueous solution. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).

The acids mentioned do not have to be used stoichiometrically to the carbonates or hydrogen carbonates contained in the compressed products. A detergent and cleaning agent compact preferred in the context of the present invention additionally contains a shower system.

In the agents according to the invention, the gas-developing shower system consists of carbonates and / or bicarbonates in addition to the organic acids mentioned. For reasons of cost, the alkali metal salts are clearly preferred among representatives of this class of substances. In the case of the alkali metal carbonates or bicarbonates, in turn, the sodium and potassium salts are clearly preferred over the other salts for reasons of cost. Of course, the pure alkali metal carbonates or bicarbonates in question do not have to be used; rather, mixtures of different carbonates and hydrogen carbonates may be preferred.

A wide number of different salts can be used as electrolytes from the group of inorganic salts. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl ₂ in the granules according to the invention is preferred.

In order to bring the pH of solutions of the water-soluble containers according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or bases can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 1% by weight of the total formulation.

In the context of the present invention, individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, ethyl cyclohexyl benzylatepyl propionate, ethyl cyclohexyl propylate. The ethers include, for example, benzyl ethyl ether, the aldehydes include the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones eg the Jonone, ∞-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The general description of the perfumes that can be used (see above) generally represents the different substance classes of fragrance substances. In order to be perceptible, a fragrance substance must be volatile, whereby in addition to the nature of the functional groups and the structure of the chemical compound, the molar mass also plays an important role plays. Most odoriferous substances have molecular weights of up to about 200 daltons, while molecular weights of 300 daltons and more are an exception. Due to the different volatility of odoriferous substances, the smell of a perfume or fragrance composed of several odoriferous substances changes during evaporation, the odor impressions being described as "top note", "heart or middle note" (middle note or body ) and "base note" (end note or dry out). Since the smell is largely based on the intensity of the smell, the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note largely consists of less volatile, i.e. non-stick fragrances. When composing perfumes, more volatile fragrances can be bound to certain fixatives, for example, which prevents them from evaporating too quickly. In the subsequent classification of the fragrances into "more volatile" or "adherent" fragrances, nothing is said about the odor impression and whether the corresponding fragrance is perceived as a top or heart note.

The smell of the water-soluble containers according to the invention, or that contained therein, can be selected by a suitable selection of the fragrances or perfume oils mentioned enclosed solids (product fragrance), and, after the cleaning and care process has ended, the laundry fragrance, for example, can also be influenced. Due to their design, in particular due to the openings in the outer wall, water-soluble containers according to the invention are particularly suitable in comparison to completely closed containers to ensure an unmistakable product fragrance even when using smaller amounts of fragrance, whereby in particular also more volatile fragrances can be used, while To achieve a sufficient scent of laundry, the use of stronger odoriferous substances is advantageous. Adhesive odoriferous substances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, bergamot oil, champagne flower oil, noble fir oil, noble pine cone oil, elemi oil, eucalyptus oil, fennel oil, geranium oil, spruce oil, spruce oil, spruce oil, spruce oil, oil spruce oil, spruce oil, spruce oil, spruce oil, spruce oil Guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil, iris oil, kajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, copaϊvabalsam oil, coriander oil,

Spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, mandarin oil, lemon balm oil, musk seed oil, myrrh oil, clove oil, neroü oil, niaouu oil, oübanum oil, orange oil, origanum oil, palmarosa oil, pepper oil, pet oil, peritamin oil, peritamin oil, peritamin oil Rose oil, rosemary oil, sandalwood oil, celery oil, spik oil, stemanis oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, lemon oil and lemon oil. However, the higher-boiling or solid odorants of natural or synthetic origin can also be used in the context of the present invention as adherent odorants or odorant mixtures, that is to say fragrances. These compounds include the compounds mentioned below and mixtures of these: ambrettolide, α-amyl cinnamaldehyde, anethole, anisaldehyde, anise alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzyl benzate, boryl formate benzyl benzyl benzate, benzyl formate benzyl benzyl benzate, benzyl formate benzyl benzyl benzate, benzyl benzate benzyl benzyl benzate benzyl benzyl benzate benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzoate , Bomylacetate, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, famesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin,

Heptincarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether,

Hydroxycinnamaldehyde, Hydroxyzimtalkohol, Indol, Iran, Isoeugenol,

Isoeugenol methyl ether, isosafrol, jasmon, camphor, karvakrol, karvon, p- Cresol methyl ether, coumarin, p-methoxyacetophenone, methyl-n-amyl ketone, methyl anthranilic acid methyl ester, p-methylacetophenone, methyl chavicol, p-methyl quinoline, methyl-ß-naphthyl ketone, methyl-n-nonylacetaldehyde, methyl-n-nonol ketone, musyl ß-naphthol methyl ether, nerol, nitrobenzene, n-nonyl aldehyde, nony alcohol, n-octyl aldehyde, p-oxy-acetophenone, pentadecanolide, ß-phenylethyl alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegon, safrol, salicyl ethyl acid ethyl ester, salicyl ethyl acid ethyl ester, Skatol, Terpineol, Thymen, Thymol, γ-undelactone, Vanilin, Veratrumaldehyde, Cinnamaldehyde, Zimatalkohol, Cinnamic acid, Cinnamic acid ethyl ester, Cinnamic acid benzyl ester. The more volatile fragrances include, in particular, the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more volatile fragrances are alkyisothiocyanates (alkyl mustards), butanedione, limonene, linalool, linaylacetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinylacetate, citral, citronellal.

In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a long shelf life and are insensitive to the other ingredients of the compositions and to light. If the containers according to the invention contain detergents and cleaning agents for textile cleaning, the dyes used should furthermore have no pronounced substantivity towards textile fibers in order not to stain them.

Hydrotropes or solubilizers are substances that, through their presence, make other compounds that are practically insoluble in a certain solvent soluble or emulsifiable in this solvent (solubilization). There are solubilizers that form a molecular compound with the poorly soluble substance and those that work through Miceü-Büdung. It can also be said that solubilizers only give a so-called latent solvent its solvency. When water is used as a (latent) solvent, one speaks mostly of hydrotropes instead of solubilizers, in some cases better of emulsifiers. Foam inhibitors which can be used in the agents according to the invention include soaps, oils, fats, paraffins or silicone oils, which can optionally be applied to carrier materials. Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the aforementioned materials. Agents preferred in the context of the present application contain paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are structured according to the scheme (R ₂ SiO) x and are also referred to as silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids with a molecular weight between 1000-150,000, and viscosities between 10 u. 1,000,000 mPa ^■ s.

Suitable anti-redeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether and the polymers of phthalic acid and / or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of the phthalic acid and terephthalic acid polymers are particularly preferred.

Optical brighteners (so-called "whiteners") can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances attach to the fibers and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and results in pure white with the yellow tone of the grayed or yellowed laundry. Suitable compounds come, for example, from the substance classes of 4,4'-diamino-2,2'-stübensisulfonic acids ( Flavonic acids), 4,4'-distyryl-biphenyls, methylumbelüferones, coumarins, dihydrochinoünones, 1, 3-diarylpyrazoones, naphthalic imides, benzoxazole, Benzisoxazole and benzimidazole systems and the pyrene derivatives substituted by heterocycles.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. Also usable as graying inhibitors are cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.

Since textile fabrics, in particular made from rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers prevent bending and kinking. If pressing and squeezing across the grain are sensitive, the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters. A substance that is particularly suitable for textile finishing and care is cottonseed oil, which can be produced, for example, by pressing out the brown, cleaned cottonseed and refining it with about 10% sodium hydroxide or by extraction with hexane at 60-70 ° C. Such cotton oils contain 40 to 55% by weight of linoleic acid, 16 to 26% by weight of oleic acid and 20 to 26% by weight of palmitic acid. Further agents which are particularly preferred for fiber smoothing and fiber care are the glycerides, in particular the monoglycerides of fatty acids such as, for example, glycerol monooleate or glycerol monostearate. To combat microorganisms, the agents according to the invention can contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halogenophenols and phenol mercuric acetate, although these compounds can also be dispensed with entirely in the agents according to the invention.

In order to prevent undesirable changes in the washing and cleaning agents and / or the treated textiles caused by the action of oxygen and other oxidative processes, the agents according to the invention can contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

Increased wearing comfort can result from the additional use of antistatic agents, which are additionally added to the agents according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to detergents, with an additional finishing effect.

Phobing and impregnation processes are used to finish textiles with substances that prevent dirt from accumulating or make it easier to wash out. Preferred waterproofing and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum and. Zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or polymerizable compounds coupled with perfluorinated acyl or sulfonyl radical. Antistatic agents can also be included. The dirt-repellent finish with phobing and impregnating agents is often classified as an easy-care kit. The penetration of the impregnating agent in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension. Another area of application of waterproofing and impregnating agents is the water-repellent finishing of textile goods, tents, tarpaulins, leather etc., which, in contrast to waterproofing, does not close the fabric pores, which means that the fabric remains breathable (hydrophobic). The hydrophobizing agents used for hydrophobizing coat textiles, leather, paper, wood etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups. Suitable water repellents are e.g. B. paraffins, waxes, metal soaps, etc. with additives to aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, silicones, organic tin compounds and Glutardialdehyde and perfluorinated compounds. The hydrophobized materials do not feel greasy; nevertheless - similar to greased substances - water drops roll off them without wetting them. So z. B. silicone-impregnated textiles a soft handle u. are water u. stain-resistant; Stains from ink, wine, fruit juices and the like are easier to remove.

The non-aqueous solvents which can be used in the agents according to the invention include, in particular, the organic solvents, of which only the most important can be listed here: alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, diethylene glycol) ), Ether and the like Glycol ether (diethyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ether), ketones (acetone, butanone, cyclohexanone), esters (acetic acid esters, glycol esters), amides and the like. a. Nitrogen compounds (dimethylformamide, pyridine, N-methylpyrrolidone, acetonitrile), sulfur compounds (carbon disulfide, dimethyl sulfoxide, sulfolane), nitro compounds (nitrobenzene),

Halogenated hydrocarbons (dichloromethane, chloroform, tetrachloromethane, tri-, tetrachlorethylene, 1,2-dichloroethane, chlorofluorocarbons), hydrocarbons (petrol, petroleum ether, cyclohexane, methylcyclohexane, decalin, terpene solvent, benzene, toluene, xylenes). Alternatively, instead of the pure solvents, their mixtures, which for example advantageously combine the solution properties of different solvents, can also be used. Such and within the scope of the present A particularly preferred solvent mixture is, for example, benzine, a mixture of various hydrocarbons suitable for chemical cleaning, preferably with a content of C12 to C14 hydrocarbons above 60% by weight, particularly preferably above 80% by weight and in particular above 90% by weight, each based on the total weight of the mixture, preferably with a boiling range of 81 to 110 ° C.

To care for the textiles and to improve the textile properties such as a softer "handle" (finish) and reduced electrostatic charging (increased wearing comfort), the agents according to the invention can contain fabric softeners. The active ingredients in fabric softener formulations are "esterquats", quaternary ammonium compounds with two hydrophobic residues, such as, for example, disteraryldimethylammonium chloride, which, however, due to its insufficient biodegradability, is increasingly being replaced by quaternary ammonium compounds which contain ester groups in their hydrophobic residues as predetermined breaking points for biodegradation. Such "esterquats" with improved biodegradability can be obtained, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products with alkylating agents in a manner known per se. Dimethylolethylene urea is also suitable as a finish.

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, for example silicone derivatives can be used in the agents according to the invention. These additionally improve the rinsing behavior of the agents according to the invention due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are wholly or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which have, for example, polyethylene glycols, and the polyalkylene oxide-modified dimethyl polysiloxanes. Because of their fiber-caring effect, protein hydrolyzates are further active substances preferred in the field of detergents and cleaning agents in the context of the present invention. Protein hydrolyzates are product mixtures that are obtained by acidic, basic or enzymatically catalyzed breakdown of proteins (proteins). According to the invention, protein hydrolyzates of both vegetable and animal origin can be used. Animal protein hydrolyzates are, for example, elastin, collagen, keratin, silk and liquid protein protein hydrolyzates, which can also be in the form of salts. According to the invention, the use of protein hydrolysates of plant origin, e.g. B. soy, almond, rice, pea, potato and wheat protein hydrolyzates. Although the use of the protein hydrolyzates as such is preferred, amino acid mixtures or individual amino acids, such as arginine, lysine, histidine or pyrroglutamic acid, which have otherwise been obtained, can optionally be used in their place. It is also possible to use derivatives of the protein hydrolyzates, for example in the form of their fatty acid condensation products.

Finally, the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in 2- and / or 4-control. Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in 2-position, salicylates, organic Ni complexes and natural substances such as umbelüferone and the body's own urocanoic acid are also suitable.

Detergents for automatic dishwashing can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents and glass corrosion inhibitors in particular being particularly important in the field of automatic dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and / or are particularly preferably to be used Alkylaminotriazole. In addition, detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate, as well as the manganese complexes

[Me-TACN) Mn ^lv (m-0) ₃ Mn ^lv (Me-TACN)] ²⁺ (PF ₆ -) ₂ , [Me-MeTACN) Mn ^lv (m-0) ₃ Mn ^lv (Me-MeTACN) ] ²⁺ (PF ₆ ^" ) ₂ , [Me-TACN) Mn ^III (m-0) (m-0Ac) ₂ Mn ^III (Me-TACN)] ²⁺ (PF ₆ -) ₂ and

[Me-MeTACN) Mn ^III (m-0) (m-0Ac) ₂ Mn ^III (Me-MeTACN)] ²⁺ (PF ₆ -) ₂ , where Me-TACN is for

1, 4,7-trimethyl-1, 4,7-triazacyclononan and Me-MeTACN stands for 1,2,4,7-tetramethyl-1,4,7-triazacyclononane. Zinc compounds can also be used to prevent corrosion on the wash ware.

In the context of the present invention, it is preferred to additionally select at least one silver protective agent from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.001 to 1% by weight, preferably from 0.01 to 0.5% by weight and in particular from 0.05 to 0.25% by weight, in each case based on the total weight of the solids enclosed in the water-soluble containers according to the invention.

In addition to the aforementioned silver protection agents, agents according to the invention can also contain one or more substances for reducing glass corrosion. In the context of the present application, in particular additives of zinc and / or inorganic and / or organic zinc salts and / or silicates, for example the layered crystalline sodium disilicate SKS 6 from Clariant GmbH, and / or water-soluble glasses, for example glasses which have a loss in mass of at least 0.5 mg under the conditions specified in DIN ISO 719, are preferred for reducing glass corrosion. Particularly preferred agents contain at least one zinc salt of an organic acid, preferably selected from the group zinc oleate, zinc stearate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate.

Claims

claims

1. A method for producing a container, comprising the steps of: a) shaping processing of a first wrapping material to form a base body of height h which is open at the top, comprising a brim forming the top opening of the base body, and at least two by at least one web of height h - x separate compartments; b) sealing the receiving chamber (s) with a second covering material, the sealing seam lying at least partially in a plane of height h-x; c) Filling the remaining container volume.

2. The method according to claim 1, characterized in that the shaping processing of the first shell material is carried out by injection molding or by deep drawing.

3. The method according to any one of claims 1 or 2, characterized in that the web has no contact point with the side walls of the container.

4. The method according to any one of claims 1 to 3, characterized in that the web has at least one contact point with the side walls of the container.

5. The method according to any one of claims 1 to 4, characterized in that the web has at least one, preferably two, three, four, five or more corners.

6. The method according to any one of claims 1 to 5, characterized in that the web has at least one, preferably two, three, four, five or more forks.

7. The method according to any one of claims 1 to 6, characterized in that the web has at least one, preferably two, three, four, five or more curvature (s).

8. The method according to any one of claims 1 to 7, characterized in that the web has a width between 0.5 and 15 mm, preferably between 0.6 and 12 mm, particularly preferably between 0.7 and 10 mm, very particularly preferably between 0.8 and δ mm and in particular between 1.0 and 5.0 mm.

9. The method according to any one of claims 1 to δ, characterized in that at least one of the shell materials used is water-soluble or water-dispersible.

10. The method according to any one of claims 1 to 11, characterized in that one of the envelope materials used is transparent or translucent.

11. The method according to any one of claims 1 to 12, characterized in that one of the shell materials used consists of a water-soluble or water-dispersible polymer.

12. Container of height h made of a first wrapping material, comprising at least three receiving chambers and a brim forming a first sealing plane and encircling at height h, characterized in that the container has at least one seal made of a second wrapping material along a sealing seam, which is not in the sealing plane formed by the peripheral brim.

13. A container according to claim 13, characterized in that the sealing seam, which does not run in the sealing plane formed by the circumferential brim, runs at least partially along a web of height h - x located in the container.

14. Container according to one of claims 12 or 13, characterized in that the web has no contact point with the side walls of the container.

15. Container according to one of claims 12 to 14, characterized in that the web has at least one contact point with the side walls of the container.

16. Container according to one of claims 12 to 15, characterized in that the web has at least one, preferably two, three, four, five or more corners.

17. Container according to one of claims 12 to 16, characterized in that the web has at least one, preferably two, three, four, five or more crotches.

18. Container according to one of claims 12 to 17, characterized in that the web has at least one, preferably two, three, four, five or more curvatures.

19. Container according to one of claims 12 to 18, characterized in that the web has a width between 0.5 and 15 mm, preferably between 0.6 and 12 mm, particularly preferably between 0.7 and 10 mm, very particularly preferably between 0.8 and 8 mm and in particular between 1.0 and 5.0 mm.

20. Container according to one of claims 12 to 19, characterized in that at least one of the envelope materials is water-soluble or water-dispersible.

21. Container according to one of claims 12 to 20, characterized in that at least one of the envelope materials is transparent or translucent.

22. Container according to one of claims 12 to 21, characterized in that at least one of the shell materials comprises a water-soluble or water-dispersible polymer.

23. Container according to one of claims 12 to 22, characterized in that the envelope materials consist of water-soluble or water-dispersible material and have different dissolution rates.

24. Means comprising a container according to one of claims 12 to 23 and at least one active substance.

25. Composition according to claim 24, characterized in that it comprises an active substance from the group of agricultural chemicals, cosmetics or detergents and cleaning agents.

26. Agent according to one of claims 24 or 25, characterized in that at least two receiving chambers contain different active substances.

27. Composition according to one of claims 24 to 26, characterized in that at least one receiving chamber contains a liquid active substance.

2δ. Agent according to one of claims 24 to 27, characterized in that it comprises at least one active substance or active substance preparation, the release of which is delayed.