Molded body and method for producing it

Abstract

The present invention relates to a molded body produced in a casting method without the application of pressure, to a detergent or cleaning agent, in particular a dishwasher detergent, especially an automatic dishwasher detergent, comprising the molded body, to methods for producing the molded body and to the detergent or cleaning agent.

Description

[0001] The present invention relates to a molded body produced by a casting process, a washing or cleaning agent comprising the molded body, processes for producing the molded body and the washing or cleaning agent, and their use.

[0002] Pre-packaged detergents and cleaning products have become increasingly common, allowing consumers to easily measure out the dosage. Sachets or compressed tablets have become popular.

[0003] Tablets often have two phases, with one phase being a spatially separated, visually distinguishable area of ​​the tablet. This allows components of a detergent or cleaning agent that may be incompatible to be separated, thus achieving storage stability without compromising the cleaning effect.

[0004] However, the production of compressed forms can be problematic, especially when the formulation contains hygroscopic components. Formulations obtained in this way can no longer be compressed into a stable tablet.

[0005] EP 1 923 456 A1 discloses the production of molded articles by injection molding as an alternative to the production of tablets as compacted molded articles. However, these exhibit a solubility that does not ensure complete dissolution of tableware during machine cleaning.

[0006] The patent applications WO2005019401 A1 and WO2005019402 A1 describe washing or cleaning agents that can be produced by casting processes.

[0007] WO2004085596 A1 discloses washing or cleaning agents which contain a dispersion of solid particles in a dispersing agent.

[0008] It is now the object of the present invention to provide a pre-portioned washing or cleaning agent which at least substantially avoids the disadvantages of forms of provision known in the prior art.

[0009] Surprisingly, it has been found that a shaped body produced by a casting process has particularly good properties and can be used in a washing or cleaning agent. In a first embodiment, the object underlying the present invention is therefore achieved by a shaped body produced by a casting process for a washing or cleaning agent, containing less than 0.1% by weight of phosphate, which is characterized in that it comprises at least one carrier which is meltable at a temperature of 70°C or less and is solid at room temperature (20°C), and at least one powdered or granulated active substance, wherein the active substance is a complexing agent selected from the group of aminocarboxylic acids and their salts, which are methylglycinediacetic acid (MGDA) or its salts, glutamic diacetic acid (GLDA) or its salts, or ethylenediaminediacetic acid or its salts (EDDS).

[0010] Where temperatures are mentioned in this application, they are based on a standard pressure of 1 bar. If states of matter are specified without further information, they are based on room temperature, i.e., a temperature of 20 °C and a standard pressure of 1 bar.

[0011] These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. It is understood that any feature of one aspect of the invention may be employed in any other aspect of the invention. Furthermore, it is understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular, the invention is not limited to these examples. All percentages are by weight unless otherwise indicated. Numerical ranges given in the format "from x to y" include the stated values. Where multiple preferred numerical ranges are given in this format, it is understood that all ranges resulting from the combination of the various endpoints are also encompassed."At least one" or "at least one" as used herein refers to 1 or more, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.

[0012] While the prior art, such as EP 1 923 456 A1, describes molded bodies produced by injection molding, it has surprisingly been found that molded bodies produced by the casting process have significant advantages over those described in the prior art.

[0013] While molded articles produced by injection molding have dissolution times of 22 to 50 minutes at a preheated temperature of 50°C, the molded articles according to the present invention, which are produced by the casting process, are soluble in less than 20 minutes, in particular less than 15 minutes, in conventional washing processes. If a preheated machine is used here too, as in the prior art in the form of EP 1 923 456 A1, the solubility, or the time until solubility is achieved, is less than 15 minutes in total. In a conventional wash cycle, in which rinsing is carried out first with cold water and the temperature is only reached during the rinsing process, the solubility is less than 20 minutes and in particular 18 minutes or less. The solubility or disintegration time indicates the period in which the molded article is essentially completely dissolved in the rinsing water.Shaped bodies according to the invention have a disintegration time of 0 to 30 minutes, in particular of 1 to 20 minutes, preferably of 5 to 15 minutes.

[0014] In injection molding, as described in the prior art, the materials contained in the future molded body are first liquefied and then introduced under pressure into a sealable tool which determines the later shape of the molded body. The pressure required for this is 50 to 200 bar. In addition, any solids contained are restricted in their particle size so that they can be processed in an injection molding device. Possible particle sizes that can still be processed according to the prior art without abrasion on the injection molding device and in particular on the nozzles are in the range of 50 µm to 2000 µm. However, the injection unit / injection nozzle used to generate the necessary pressures wear out due to the solid particles, so that the injection molding process is associated with a high technical complexity and cost.

[0015] In contrast, the present invention offers shaped bodies in which, due to the production process, there are no restrictions with regard to the particle size of the solid active substances contained in the shaped body. Only the visual appearance of the end product and, if applicable, the shape of the shaped body limit the particle size. In the case of shaped bodies according to the invention, a casting composition is produced by heating a meltable carrier material. This carrier material is heated to a temperature at which it is flowable and can be mixed with the active substance. Typically, temperatures of 70°C or less, preferably from 40°C to 70°C, are reached here. The flowable mixture then obtained can be further processed at room temperature by pouring it into a suitable mold without the application of pressure.According to the invention, a shaped body with a high content of active substance can thus be provided without the need to apply pressure during production.

[0016] The molding process according to the invention is also more flexible than injection molding. While injection molding requires a sealable mold that is filled under pressure, the casting process allows for an open mold, resulting in a wider range of possible shapes. Furthermore, the mold in the casting process does not have to withstand any particular pressure, as this only corresponds to the ambient pressure and the pressure resulting from the weight of the casting compound.

[0017] The shaped body according to the invention thus has significantly improved properties compared to the prior art. Furthermore, it can be produced in different dimensions by choosing a suitable mold. For example, according to the invention it is possible for the shaped body to be a three-dimensional structure with any desired shape. However, according to the invention it is preferred that the shaped body has no, 1, 2, 3 or more, in particular 1, 2 or 3, particularly preferably 1 or 2 cavities. Depending on requirements and the desired use, various further formulation ingredients of a washing or cleaning agent can then be introduced into these cavities. Multiple cavities enable the separation of active ingredients which are, for example, incompatible with one another during storage, thus resulting in a product with improved storage stability compared to commercially available tablets.

[0018] If the molded body has one or more cavities, ridges are present at the edge of one cavity, and between the individual cavities in the case of multiple cavities. The ridge width is preferably in the range of 1 mm to 4 mm, especially 1 mm to 2 mm. Smaller ridge widths lead to instability of the cavities. Larger ridge widths result in an unsightly appearance. Furthermore, the cavities themselves are defined by a very small volume, so only small amounts of additional formulation ingredients can be incorporated.

[0019] The total volume of the shaped body is preferably 12 to 25 ml, in particular 15 to 20 ml. This includes the volume of cavities, if present, so that the total volume defines the overall dimension of the shaped body.

[0020] If the shaped body has one cavity, the volume of one cavity is preferably 5 ml to 8 ml, in particular 6 ml to 7 ml. If the shaped body has two cavities, these can be the same or different sizes. They are preferably different sizes. The volume of the first cavity is preferably 1 ml to 3 ml and in particular 1.5 ml to 2.5 ml. The volume of the second cavity is preferably in the range from 3 ml to 6 ml, in particular 4 ml to 5 ml. The ratio of the volumes of the first cavity to the second cavity is preferably in the range from 1:1 to 1:4 and in particular from 1:2 to 1:3. The ratio of the volumes of the cavities (total volume of all cavities) to the total volume of the shaped body is preferably 1:1 to 1:4, in particular 1:2 to 1:3 or 1:2.5.

[0021] The shaped body comprises at least one carrier which is meltable at a temperature of 70°C or less and solid at room temperature. One or more active substances which are in powdered or granulated form can then be incorporated into the molten carrier. The shaped body according to the invention is then obtained from the casting composition thus obtained by a casting process. The proportion of meltable carrier is in particular in the range from 10% by weight to 40% by weight, preferably from 20% by weight to 30% by weight, based on the total weight of the shaped body. The proportion of powdered or granulated active substance is in particular in the range from 50% by weight to 90% by weight, preferably from 60% by weight to 70% by weight, likewise based on the total weight of the shaped body.

[0022] A corresponding suspension of carrier and active ingredient can be cast into virtually any desired shape, both to meet the consumer's aesthetic requirements and to exclude temperature-sensitive formulation ingredients such as enzymes, bleach activators, bleaching agents, or builders such as percarbonates. These can then be introduced into one or more cavities, if available.

[0023] Certain requirements must be met by the casting compound in the form of a suspension (melt compound) or the casting obtained as a molded article. The flowability of the melt compound, i.e. the casting compound, must be such that it can be poured into a suitable mold. The quantities of meltable carrier and active substance must be selected to ensure that precisely this requirement is met. If the proportion of solid active substance is too high, this can influence the flowability and possible web widths in the casting mold. Shrinkage effects in volume can also occur with different sizes. The solid or granulated active substance should also have a particle size that minimizes the influence on the surface appearance and solubility. The meltable carrier substance, in turn, influences the hardness, stability, and strength of the molded article.It influences the solubility of the shaped body and the active substance content.

[0024] The curing time of the melt is not relevant for its subsequent use as a molded body. However, the curing should be such that economical production in large quantities is possible. The curing time of the melt, i.e., the casting compound in the corresponding mold, is preferably in the range of 1 to 20 minutes, in particular 1 to 15 minutes, and particularly preferably 1 to 10 minutes. Longer curing times may occur if the molded body has no cavity. With one or more cavities, the curing time should preferably be in the range of 1 to 15 minutes, and in particular 5 to 10 minutes.

[0025] Surprisingly, it has been shown that the casting process can achieve a solubility of the molded body in water that cannot be achieved with other molded body manufacturing processes. This enables rapid availability of all formulation ingredients, which in turn is necessary for a high cleaning performance spectrum.

[0026] The stability of the molded bodies produced by the casting process also does not represent a disadvantage compared to the prior art. Depending on the exact composition, the molded body according to the invention preferably has a strength of 80 to 200 N, in particular of 100 to 180 N. The strength is the fracture hardness of the molded body in N, regardless of the number of cavities.

[0027] The fracture hardness of the molded bodies can be determined using standard force measuring devices, such as a Chatillon TCM 201-M (Wagner Instruments, Greenwich, USA), and suitable load cells, such as the PCE FG 200 (PCE Deutschland GmbH, Meschede, Germany). The molded body to be tested is placed on a support (usually a round mandrel with a diameter of approximately 8 mm) and sheared from above with a wedge (usually with a width of approximately 30 mm) until the molded body fractures. The feed rate is typically 25 mm / min.

[0028] Furthermore, it has surprisingly been found that the resulting molded articles do not form a close bond with water-soluble packaging. In a preferred embodiment, the molded article further comprises a water-soluble covering, in particular in the form of a water-soluble film. This can be applied around the molded article as a whole. If the molded article has cavities, the water-soluble film can also simply cover the cavities, so that they serve as a type of closure. It has been found that the molded article according to the invention exhibits non-stick properties compared to corresponding water-soluble films, and in particular those containing polyvinyl alcohols (PVA), thereby enabling improved producibility.

[0029] According to the invention, the molded body can comprise one or more meltable carriers. The meltable carrier is selected in particular from polymers, xylitol, 2-ethyl-2-hydroxymethyl-1,3-propanediol (EHPD), nonionic surfactants, and mixtures thereof. Suitable polymers are, in particular, polyalkylene glycols, polyvinylpyrrolidones, vinylpyrrolidone vinyl ester copolymers, and / or cellulose ethers, with polyalkylene glycols being particularly preferred polymers. In a preferred embodiment, the meltable carrier is therefore selected from polyalkylene glycols, xylitol, 2-ethyl-2-hydroxymethyl-1,3-propanediol (EHPD), nonionic surfactants, and mixtures thereof; particularly preferably, the meltable carrier is selected from polyalkylene glycols, 2-ethyl-2-hydroxymethyl-1,3-propanediol (EHPD), nonionic surfactants, and mixtures thereof.Particularly preferred molded bodies according to the invention contain at least one nonionic polymer and / or preferably a poly(alkylene) glycol, preferably a poly(ethylene) glycol and / or a poly(propylene) glycol, as a meltable carrier. The nonionic surfactants preferred as meltable carriers, as well as preferred polymers and polyalkylene glycols preferred here, are described in more detail below.

[0030] Conventional nonionic surfactants known to those skilled in the art can be used as nonionic surfactants. However, in preferred embodiments, nonionic surfactants from the group of alkoxylated alcohols are used. One class of preferred nonionic surfactants, which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants as a meltable carrier, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters.

[0031] In this context, preference is given in particular to those nonionic surfactants which are end-capped, poly(oxyalkylated) nonionic surfactants according to the formula R 1< O[CH 2 CH 2 O] x R 2<, where R 1< stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms and R 2< stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, and where x stands for values ​​between 1 and 80, preferably for values ​​between 15 and 50 and in particular for values ​​between 20 and 25.Very particular preference is given to end-capped fatty alcohol ethoxylates in which R 1< represents a linear or branched C 12-20 alkyl radical, in particular a linear or branched C 16-18 alkyl radical, and / or R 2< represents a linear or branched C 4-22 alkyl radical, preferably a C 4-14 alkyl radical, even more preferably a C 6-12 alkyl radical, in particular a linear or branched C 8-10 alkyl radical.

[0032] In a further embodiment, the end-capped, poly(oxyalkylated) nonionic surfactants described above as a meltable carrier are combined with a further surfactant from the group of non-end-capped, poly(oxyalkylated) nonionic surfactants according to the formula R 1< O[CH 2 CR 3< HO x H], where R 1< represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, each R 3< independently represents H, CH 3 or CH 2 -CH 3 , preferably H or CH 3, and x represents values ​​between 1 and 80, preferably values ​​between 15 and 50 and in particular values ​​between 20 and 25. Very particular preference is given to fatty alcohol ethoxylates or fatty alcohol ethoxypropoxylates in which R 1< represents a linear or branched C 12-20 alkyl radical, in particular a linear or branched C 16-18 alkyl radical.

[0033] Generally, the nonionic surfactants used as meltable carriers have a melting point above room temperature. Nonionic surfactants with a melting point above 25°C, preferably between 40°C and 70°C, are particularly preferred.

[0034] Suitable polymers include, for example, those polymers mentioned as dispersants in WO 2004 / 085592 A1 on pages 3 to 7, which are hereby expressly incorporated by reference. The polyalkylene glycols described on pages 6 and 7 are particularly preferred. Suitable polyalkylene glycols include, in particular, polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol that satisfy the general formula I: H-(O-CH 2 -CH 2 )-OH (I), where n can assume values ​​between 1 (ethylene glycol) and several thousand. Various nomenclatures exist for polyethylene glycols, which can lead to confusion. It is customary in industry to state the average relative molecular weight following the term "PEG," 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 preceded by a hyphen, and the hyphen is immediately followed by a number corresponding to the number n in the above-mentioned formula (I). According to this nomenclature (so-called INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), PEG-4, PEG-6, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, and PEG-16 can be used, for example. Polyethylene glycols are commercially available, for example, under the trade names Carbowax ®< PEG 200 (Union Carbide), Emkapol ®< 200 (ICI Americas), Lipoxol ®< 200 MED (HÜLS 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 the preferably used poly(alkylene) glycols is preferably between 200 and 36,000, preferably between 200 and 6,000 and particularly preferably between 300 and 5,000. PEG with an average relative molecular weight of 1,500 to 6,000, in particular of 3,000 to 5,000, is particularly preferred.

[0035] Polypropylene glycols (abbreviation PPG) are polymers of propylene glycol, which have the general formula II: where n can assume values ​​between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri-, and tetrapropylene glycol, i.e., the representatives with n=2, 3, and 4 in formula II.

[0036] Particularly preferred shaped bodies according to the invention contain at least one non-ionic polymer, preferably a poly(alkylene) glycol, more preferably a poly(ethylene) glycol and / or a poly(propylene) glycol, as the meltable carrier, wherein the weight fraction of the poly(ethylene) glycol in the total weight of the meltable carriers is particularly preferably between 10 and 90 wt. %, more preferably between 30 and 80 wt. % and in particular between 50 and 70 wt. %. Particularly preferred are shaped bodies according to the invention in which the meltable carrier consists of more than 92 wt. %, preferably more than 94 wt. %, more preferably more than 96 wt. %, very particularly preferably more than 98 wt. % and in particular 100 wt. % of a poly(alkylene) glycol, preferably poly(ethylene) glycol and / or poly(propylene) glycol, but in particular poly(ethylene) glycol.Meltable carriers which contain poly(ethylene) glycol as well as poly(propylene) glycol preferably have a ratio of the weight fractions of poly(ethylene) glycol to poly(propylene) glycol 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.

[0037] Likewise, in addition to the active substance according to the invention, one or more different active substances can additionally be contained in the shaped body. These can be components commonly found in washing or cleaning agents, which can be processed stably and without loss of effectiveness at temperatures of up to 70°C. The additional powdered or granulated active substance is selected in particular from surfactants, in particular non-ionic surfactants, stabilizers, builders, buffers, corrosion inhibitors, alkali carriers, and mixtures thereof. These active substances can also be introduced into any cavities present as a formulation component of a washing or cleaning agent according to the invention and are then also explained in this context. The compounds particularly preferred as active substances for the shaped body are described below.

[0038] The total surfactant content of molded articles according to the invention is in the range from 2 to 25 wt.%, in particular from 5 to 20 wt.%, preferably from 10 to 15 wt.%, based on the total weight of the molded article. This includes surfactants contained as active substances, meltable carriers, and liquid carriers.

[0039] The active substance required according to the invention is a complexing agent selected from the group of aminocarboxylic acids and their salts, which are methylglycinediacetic acid (MGDA) or its salts, glutamic acid (GLDA) or its salts, or ethylenediaminediacetic acid or its salts (EDDS). According to a preferred embodiment, the complexing agent is methylglycinediacetic acid.

[0040] Suitable builders are silicates, disilicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids, and mixtures of these substances. Builders include, in particular, carbonates, citrates, phosphonates, organic builders, and silicates and disilicates. Organic builders suitable according to the invention are, for example, polycarboxylic acids (polycarboxylates) usable in the form of their sodium salts. Polycarboxylic acids are understood to mean carboxylic acids that carry more than one, in particular two to eight acid functions, preferably two to six, in particular two, three, four, or five acid functions in the entire molecule. The polycarboxylic acids can also carry further functional groups, such as hydroxyl or amino groups. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA, and mixtures thereof.Also suitable as organic builders are polymeric polycarboxylates (organic polymers with a large number of (especially more than ten) carboxylate functions in the macromolecule), polyaspartates, polyacetals and dextrins.

[0041] In addition to their builder effect, free acids typically also have the property of an acidifying component and can therefore, if desired, also be used to adjust a lower pH value. Examples include citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixtures thereof.

[0042] Particularly preferred is the use of carbonate(s) and / or hydrogencarbonate(s), preferably alkali carbonate(s), particularly preferably sodium carbonate (soda), as well as citrates (as dihydrate or anhydrate).

[0043] Suitable preferred alkali carriers are alkali metal carbonates, especially sodium carbonate. Zinc salts, especially zinc acetate, are particularly preferred as corrosion inhibitors.

[0044] Suitable surfactants are, in particular, nonionic surfactants, which are described below. Suitable nonionic surfactants as active substances include, for example, alkyl glycosides of the general formula RO(G) x , in which R corresponds to a primary straight-chain or methyl-branched, in particular 2-methyl-branched, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G is the symbol representing a glycose unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably, x is between 1.2 and 1.4.

[0045] Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably no more than that of the ethoxylated fatty alcohols, in particular no more than half that amount.

[0046] Other suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.

[0047] However, low-foaming non-ionic surfactants are preferred as the active ingredient, especially alkoxylated, especially ethoxylated, low-foaming non-ionic surfactants. The molded articles particularly preferably contain non-ionic surfactants from the group of alkoxylated alcohols as the active ingredient.

[0048] A class of usable non-ionic surfactants, which can be used either as the sole non-ionic surfactant or in combination with other non-ionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

[0049] Surfactants preferred for use as active ingredients come from the group of ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are characterized by good foam control.

[0050] Suitable nonionic surfactants are those that have alternating ethylene oxide and alkylene oxide units. Among these, surfactants with EO-AO-EO-AO blocks are preferred, where one to ten EO or AO groups are bonded to one another before a block of the other groups follows. These are nonionic surfactants of the general formula preferred in which R 1< represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 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. Of these, particular preference is given to non-ionic surfactants which have a C 9-5 alkyl radical with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units. Preferred nonionic surfactants are those of the general formula R 1< -CH(OH)CH 2 O-(AO) w -(A'O) x -(A"O) y -(A‴O) z -R 2< , in which R 1< represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; R 2< represents H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A, A', A" and A‴ independently of one another represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH(CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH(CH 3 )-CH 2 -, - CH 2 -CH(CH 2 -CH 3 ), w, x, y and z represent values ​​between 0.5 and 120, where x, y and / or z can also be 0.

[0051] Particularly preferred are those end-capped, poly(oxyalkylated) nonionic surfactants which, according to the formula R 1< O[CH 2 CH 2 O] x CH 2 CH(OH)R 2< , in addition to a radical R 1< which stands for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore have a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2< having 1 to 30 carbon atoms, where x stands for values ​​between 1 and 90, preferably for values ​​between 10 and 80 and in particular for values ​​between 20 and 60. Particularly preferred surfactants are those of the above formula in which R 1< is C 7 to C 13 , x is an integer from 16 to 28 and R 2< is C 8 to C 12.

[0052] Also preferred are surfactants of the formula R 1< O[CH 2 CH(CH 3 )O] x [CH 2 CH 2 O] y CH 2 CH(OH)R 2< , in which R 1< is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2< is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 1.5 and y is at least 15.

[0053] The group of these non-ionic surfactants includes, for example, the C 2-26 fatty alcohol (PO) 1 -(EO) 15-40 -2-hydroxyalkyl ethers, in particular the C 8-10 fatty alcohol (PO) 1 -(EO) 22 -2-hydroxydecyl ethers. Particularly preferred are also those end-capped poly(oxyalkylated) nonionic surfactants of the formula R 1< O[CH 2 CH 2 O] x [CH 2 CH(R 3< )O] y CH 2 CH(OH)R 2< , in which R 1< and R 2< independently of one another represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R 3< independently of one another is selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH(CH 3 ) 2 , but preferably represents -CH 3 , and x and y independently of one another represent values ​​between 1 and 32, with nonionic surfactants with R 3< = -CH 3 and values ​​for x from 15 to 32 and y from 0.5 to 1.5 being very particularly preferred.

[0054] Further nonionic surfactants which can preferably be used are the end-group-capped poly(oxyalkylated) nonionic surfactants of the formula R 1< O[CH 2 CH(R 3< )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2< , in which R 1< and R 2< are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3< is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is between 1 and 30, k and j are between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R 3< in the above formula R 1< O[CH 2 CH(R 3< )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2< 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, with radicals having 8 to 18 carbon atoms being particularly preferred.For the radical R 3<, H, -CH 3 or -CH 2 CH 3 are particularly preferred. Particularly preferred values ​​for x are in the range from 1 to 20, in particular from 6 to 15.

[0055] 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 value 3 for x has been chosen here as an example and can certainly be larger, whereby the range of variation increases with increasing values ​​of x and includes, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa.

[0056] Particularly preferred end-capped poly(oxyalkylated) alcohols of the above formula have values ​​of k = 1 and j = 1, so that the above formula is simplified to R 1< O[CH 2 CH(R 3< )O] x CH 2 CH(OH)CH 2 OR 2<. In the latter 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. Particular preference is given to surfactants in which the radicals R 1< and R 2< have 9 to 14 C atoms, R 3< stands for H and x assumes values ​​from 6 to 15.

[0057] Finally, the non-ionic surfactants of the general formula R 1< -CH(OH)CH 2 O-(AO) w -R 2< have proven to be particularly effective, in which R 1< represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; R 2< represents a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; A represents a radical from the group CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH(CH 3 ), preferably CH 2 CH 2 , and w represents values ​​between 1 and 120, preferably 10 to 80, in particular 15 to 50.

[0058] The group of these non-ionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ethers and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.

[0059] In various embodiments of the invention, the corresponding non-end-capped hydroxy mixed ethers can also be used instead of the above-defined end-capped hydroxy mixed ethers. These can satisfy the above formulas, but where R 2< is hydrogen and R 1< , R 3< , A, A', A", A‴, w, x, y, and z are as defined above.

[0060] The stated carbon chain lengths and degrees of ethoxylation or alkoxylation of the nonionic surfactants represent statistical averages, which can be whole or fractional numbers for a specific product. Due to the manufacturing processes, commercial products of the formulas mentioned usually do not consist of a single representative, but of mixtures, which can result in averages and, consequently, fractional numbers for both the carbon chain lengths and the degrees of ethoxylation or alkoxylation.

[0061] Of course, the aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures consisting of two, three, four, or more surfactants. Surfactant mixtures do not refer to mixtures of nonionic surfactants that, as a whole, fall under one of the general formulas mentioned above, but rather to mixtures containing two, three, four, or more nonionic surfactants that can be described by different ones of the general formulas mentioned above.

[0062] In addition to the meltable carrier and the powdered or granulated active substance, the shaped body may further comprise one or more liquid carriers according to the invention. These are present in a proportion of 0 wt.% to 15 wt.%, in particular 2 wt.% to 10 wt.%, based on the total weight of the shaped body. These are in particular liquid surfactants and particularly preferably nonionic surfactants, fragrances, or perfume oils that are liquid at room temperature (20°C).

[0063] The presence of liquid carriers or even hygroscopic components as active substances is not problematic according to the invention. During the production of compacted tablets, an excessively high proportion of liquid or hygroscopic components can lead to the tablets not being able to be stably compressed. This disadvantage is avoided by the process and the moldings according to the invention.

[0064] In a further embodiment, the object underlying the present invention is achieved by a washing or cleaning agent which comprises a shaped body according to the invention. The shaped body can in this case already represent a washing or cleaning agent as such. However, it can also have 0 to 6, in particular 1 to 3, cavities. The at least one cavity can then contain one or more powdered or granulated formulation ingredients. This not only enables the separation of temperature-sensitive ingredients that are not currently contained in the shaped body from temperature-insensitive ingredients of the shaped body. If the shaped body has more than one cavity, ingredients that may interact with one another during storage can also be separated from one another.According to the invention, the formulation ingredient(s) is / are preferably selected from enzymes, bleach activators, bleaching agents, pH adjusters, builders, dyes, fragrances, surfactants (anionic, cationic, amphoteric, non-ionic), polymers, bleach catalysts, thickeners, sequestering agents, electrolytes, corrosion inhibitors, glass corrosion inhibitors, foam inhibitors, dyes, additives to improve drainage and drying behavior, disintegration aids, preservatives and perfume carriers as well as mixtures thereof.

[0065] The formulation ingredients and preferred embodiments thereof are explained below, with preferred embodiments also applying to the powdered or granulated active substances of the shaped body, insofar as they are contained therein. Amounts given are, unless otherwise stated, in wt. % and refer to the washing or cleaning agent as a whole.

[0066] The washing or cleaning agent is preferably one for hard surfaces, especially for dishes. It is particularly preferably a dishwashing detergent for machine cleaning of dishes. The formulation ingredients can be adapted as required depending on the specific application.

[0067] Suitable anionic surfactants in the washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, are all anionic surface-active substances. These are characterized by a water-solubilizing anionic group, such as a carboxylate, sulfate, sulfonate, or phosphate group, and a lipophilic alkyl group having approximately 8 to 30 carbon atoms. The molecule may also contain glycol or polyglycol ether groups, ester, ether, and amide groups, as well as hydroxyl groups. Suitable anionic surfactants are preferably in the form of sodium, potassium, and ammonium salts, as well as mono-, di-, and trialkanolammonium salts containing 2 to 4 carbon atoms in the alkanol group. Zinc, manganese(II), magnesium, calcium, or mixtures thereof can also serve as counterions.

[0068] Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

[0069] Instead of the aforementioned surfactants or in combination with them, cationic and / or amphoteric surfactants, such as betaines or quaternary ammonium compounds, can also be used. However, it is preferable that cationic and / or amphoteric surfactants are not used.

[0070] Suitable builders are silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids, and mixtures of these substances. The use of appropriate builders, especially water-soluble builders, can be advantageous. Builders include, in particular, carbonates, citrates, phosphonates, organic builders, and silicates. The weight proportion of the total builders in the total weight of the compositions according to the invention is preferably 15 to 80 wt.% and in particular 20 to 70 wt.%.

[0071] Organic builders suitable for the invention include, for example, polycarboxylic acids (polycarboxylates) usable in the form of their sodium salts. Polycarboxylic acids are understood to be carboxylic acids that carry more than one, in particular two to eight, acid functions, preferably two to six, in particular two, three, four, or five acid functions in the entire molecule. Preferred polycarboxylic acids are therefore dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, and pentacarboxylic acids, in particular di-, tri-, and tetracarboxylic acids. The polycarboxylic acids may also carry additional functional groups, such as hydroxyl or amino groups.Examples include citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and glucaric acid), aminocarboxylic acids, especially aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids such as nitrilotriacetic acid (NTA), glutamic-N,N-diacetic acid (also known as N,N-bis(carboxymethyl)-L-glutamic acid or GLDA), methylglycinediacetic acid (MGDA)), and their derivatives, as well as mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA, and mixtures thereof.

[0072] Also suitable as organic builders are polymeric polycarboxylates (organic polymers with a large number of (especially more than ten) carboxylate functions in the macromolecule), polyaspartates, polyacetals and dextrins.

[0073] In addition to their builder effect, free acids typically also have the property of an acidifying component and can therefore, if desired, also be used to adjust a lower pH value. Examples include citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixtures thereof.

[0074] Particularly preferred washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, contain one or more salts of citric acid, i.e., citrates, as one of their essential builders. These are preferably present in a proportion of 2 to 40 wt.%, in particular 5 to 30 wt.%, especially 7 to 28 wt.%, particularly preferably 10 to 25 wt.%, and very particularly preferably 15 to 20 wt.%, in each case based on the total weight of the agent.

[0075] Particularly preferred is also the use of carbonate(s) and / or bicarbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate (soda), in amounts of 2 to 50% by weight, preferably 4 to 40% by weight and in particular 10 to 30% by weight, very particularly preferably 10 to 24% by weight, in each case based on the weight of the agent.

[0076] Particularly preferred washing or cleaning agents according to the invention, in particular dishwashing agents, preferably automatic dishwashing agents, are characterized in that they contain at least two builders from the group of silicates, phosphonates, carbonates, aminocarboxylic acids and citrates, wherein the weight fraction of these builders, based on the total weight of the cleaning agent according to the invention, is preferably 5 to 70 wt. %, more preferably 15 to 60 wt. % and in particular 20 to 50 wt. %. The combination of two or more builders from the above-mentioned group has proven advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing agents, preferably automatic dishwashing agents. In addition to the builders mentioned here, one or more other builders may additionally be present.

[0077] Preferred washing or cleaning agents, in particular dishwashing detergents, preferably automatic dishwashing detergents, are characterized by a builder combination of citrate and carbonate and / or bicarbonate.

[0078] In a particularly preferred embodiment according to the invention, a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40 wt.%, in particular 10 to 35 wt.%, very particularly preferably 15 to 30 wt.% and the amount of citrate preferably being from 5 to 35 wt.%, in particular 10 to 25 wt.%, very particularly preferably 15 to 20 wt.%, in each case based on the total amount of the cleaning agent, the total amount of these two builders preferably being 20 to 65 wt.%, in particular 25 to 60 wt.%, preferably 30 to 50 wt.%. In addition, one or more further builders may also be included.

[0079] The washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, can contain, in particular, phosphonates as a further builder. A hydroxyalkane and / or aminoalkanephosphonate is preferably used as the phosphonate compound. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Suitable aminoalkanephosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and their higher homologues. Phosphonates are preferably present in agents according to the invention in amounts of 0.1 to 10 wt. %, in particular in amounts of 0.5 to 8 wt. %, very particularly preferably 2.5 to 7.5 wt. %, based in each case on the total weight of the agent.

[0080] The combined use of citrate, (hydrogen)carbonate, and phosphonate is particularly preferred. These can be used in the amounts stated above. In particular, amounts of 10 to 25 wt.% citrate, 10 to 30 wt.% carbonate (or hydrogen carbonate), and 2.5 to 7.5 wt.% phosphonate are used in this combination, based on the total weight of the agent.

[0081] Further particularly preferred washing or cleaning agents, in particular dishwashing detergents, preferably automatic dishwashing detergents, are characterized in that, in addition to citrate and (hydrogen) carbonate and optionally phosphonate, they contain at least one further phosphorus-free builder. This is particularly selected from the aminocarboxylic acids, with the further phosphorus-free builder preferably being selected from methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS), and ethylenediamine disuccinate (EDDS), particularly preferably from MGDA or GLDA. A particularly preferred combination is, for example, citrate, (hydrogen) carbonate, and MGDA, and optionally phosphonate.

[0082] The wt. % proportion of the further phosphorus-free builder, in particular of MGDA and / or GLDA, is preferably 0 to 40 wt. %, in particular 5 to 30 wt. %, above all 7 to 25 wt. Particular preference is given to using MGDA or GLDA, in particular MGDA, in the form of granules. MGDA granules which contain as little water as possible and / or have lower hygroscopicity (water absorption at 25°C, atmospheric pressure) compared to the non-granulated powder are advantageous. The combination of at least three, in particular at least four builders from the above-mentioned group has proven advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents. In addition, further builders may also be present.

[0083] Polymeric polycarboxylates are also suitable as organic builders. These include, 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. Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Due to their superior solubility, the short-chain polyacrylates, which have molecular weights of 2,000 to 10,000 g / mol, and particularly preferably of 3,000 to 5,000 g / mol, may be preferred from this group.

[0084] The content of (homo)polymeric polycarboxylates in the washing or cleaning agent according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, is preferably 0.5 to 20 wt.%, preferably 2 to 15 wt.% and in particular 4 to 10 wt.%.

[0085] Detergents or cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, can further contain crystalline layered silicates of the general formula NaMSi x O 2x+1 y H 2 O as builder, in which M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values ​​for x being 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. Amorphous sodium silicates with a modulus Na 2 O : SiO 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, which are preferably delayed in dissolution and have secondary washing properties, can also be used.

[0086] In certain washing or cleaning agents according to the invention, in particular dishwashing agents, preferably automatic dishwashing agents, the content of silicates, based on the total weight of the washing or cleaning agent, is limited to amounts below 10 wt.%, preferably below 5 wt.% and in particular below 2 wt.%.

[0087] In addition to the aforementioned builders, the detergents or cleaning agents according to the invention may further contain alkali metal hydroxides or alkali metal carbonates. These alkali carriers are used in the detergents or cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably between 0.1 and 5% by weight, and in particular between 0.5 and 5% by weight, in each case based on the total weight of the detergent or cleaning agent. Alternative detergents according to the invention are free from alkali carriers and in particular from alkali metal hydroxides.

[0088] The washing or cleaning agent according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, may further contain various polymers. According to the invention, for example, homopolymers of α,β-ethylenically unsaturated carboxylic acids can be used in various embodiments. As unsaturated carboxylic acid(s) it is / are particularly preferred to use unsaturated carboxylic acids of the formula R 1< (R 2< )C=C(R 3< )COOH, in which R 1< to R 3< independently of one another represent -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, alkyl or alkenyl radicals substituted by -NH 2 , -OH or -COOH as defined above or represent -COOH or -COOR 4<, where R 4< is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

[0089] Particularly preferred unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid (methylmaleic acid), methylenemalonic acid, sorbic acid, cinnamic acid, or mixtures thereof. Acrylic acid is very particularly preferred. In various embodiments of the invention, the homopolymer is therefore a polyacrylic acid.

[0090] In the polymers, the carboxylic acid groups may be present entirely or partially in neutralized form, i.e., the acidic hydrogen atom of the carboxylic acid group in some or all of the carboxylic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions. The use of partially or fully neutralized polymers is preferred according to the invention.

[0091] The molar mass of the homopolymers used can be varied to adapt the properties of the polymers to the desired application. Preferred detergents or cleaning agents, in particular dishwashing detergents, preferably automatic dishwashing detergents, are characterized in that the homopolymers, in particular the polyacrylic acids, have molar masses M n of 1000 to 20,000 g / mol. Due to their superior solubility, the short-chain polyacrylates, which have molar masses of 1000 to 10,000 g / mol, and particularly preferably of 1500 to 5000 g / mol, may be preferred from this group.

[0092] In various preferred embodiments of the invention, the washing or cleaning agents, in particular dishwashing detergents, preferably automatic dishwashing detergents, further contain at least one sulfopolymer as a formulation ingredient. The polymers usable in this context are, in particular, copolymers that may have two, three, four, or more different monomer units, with at least one monomer unit carrying a sulfonic acid group. Preferred copolymers contain, in addition to monomer(s) containing sulfonic acid groups, at least one monomer from the group of unsaturated carboxylic acids.

[0093] The unsaturated carboxylic acids described above are particularly preferred as unsaturated carboxylic acids. Acrylic acid is especially preferred.

[0094] Among the sulfonic acid group-containing monomers, those of the formula R 5< (R 6< )C=C(R 7< )-X-SO 3 H are preferred, in which R 5< to R 7< independently of one another represent -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, alkyl or alkenyl radicals substituted by -NH 2 , -OH or -COOH or -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 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 -, -C(O)-NH-C(CH 3 ) 2 -CH 2 - and -C(O)-NH-CH(CH 3 )-CH 2 -,

[0095] Preferred among these monomers are those of the formulas H 2 C=CH-X-SO 3 H H 2 C=C(CH 3 )-X-SO 3 H HO 3 SX-(R 6< )C=C(R 7< )-X-SO 3 H, in which R 6< and R 7< are independently selected from -H, -CH 3 , -CH 2 CH 3 , - CH 2 CH 2 CH 3 and -CH(CH 3 ) 2 and X represents an optionally present spacer group 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 -, -C(O)-NH-C(CH 3 ) 2 -CH 2 - and -C(O)-NH-CH(CH 3 )-CH 2 -.

[0096] Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water-soluble salts.

[0097] The acid groups in the copolymers can also be completely or partially neutralized, meaning that the acidic hydrogen atom of the sulfonic and / or carboxylic acid group in some or all of the acid groups can be exchanged for metal ions, preferably alkali metal ions and especially sodium ions. The use of partially or fully neutralized copolymers is preferred according to the invention.

[0098] The monomer distribution of the preferably used copolymers is preferably 5 to 95 wt.% in each case for copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90 wt.% and the proportion of the monomer containing carboxylic acid groups is 10 to 50 wt.%, the monomers are preferably selected from those mentioned above.

[0099] In various embodiments, the copolymers may contain, in addition to the carboxylic acid group-containing monomers and sulfonic acid group-containing monomers described above, further monomers, in particular unsaturated carboxylic acid ester group-containing monomers. In such terpolymers, the carboxylic acid ester group-containing monomers are, for example, those of the formula R 1< (R 2< )C=C(R 3< )COOR 4< , in which R 1< to R 3< are as defined above and R 4< is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

[0100] Particularly preferred unsaturated carboxylic acid esters are alkyl esters of monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenylacrylic acid, sorbic acid, cinnamic acid, or mixtures thereof. Very particular preference is given to C 1-8 alkyl esters of acrylic acid, such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. Ethyl acrylate is especially preferred.

[0101] The molecular weight of the copolymers used can be varied to adapt the properties of the polymers to the desired application. Preferred dishwashing detergents are characterized by copolymers having molecular weights M n of 2000 to 200,000 g / mol, preferably of 4000 to 25,000 g / mol, and in particular of 5000 to 15,000 g / mol.

[0102] The homopolymers and copolymers described above can each be used in amounts of 0.5 to 10 wt.%, preferably 1 to 5 wt.%, based on the total weight of the composition. Absolute amounts are typically in the range of 0.1 to 2 g / job, preferably in the range of 0.2 to 1.0 g / job. The mass ratio of the polymers to one another, i.e., homopolymer to copolymer, is in various embodiments 5:1 to 1:5, preferably 2:1 to 1:2.

[0103] The detergents or cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, may alternatively or additionally contain further polymers. Suitable polymers include, in particular, cleaning-active amphoteric, zwitterionic, or cationic polymers, for example, rinse aid polymers and / or polymers effective as water softeners.

[0104] Preferred amphoteric polymers that can be used come from the group of alkylacrylamide / acrylic acid copolymers, alkylacrylamide / methacrylic acid copolymers, alkylacrylamide / methylmethacrylic acid copolymers, alkylacrylamide / acrylic acid / alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide / methacrylic acid / alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide / alkylmethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

[0105] Other usable zwitterionic polymers come from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts, acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts and methacroylethylbetaine / methacrylate copolymers.

[0106] Usable cationic polymers come from the groups of quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and methacrylic acid and their esters and amides, copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, vinylpyrrolidone-methoimidazolinium chloride copolymers, quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

[0107] In a particularly preferred embodiment of the present invention, the aforementioned amphoteric, zwitterionic, or cationic polymers are present in prefabricated form. Suitable for the preparation of the polymers are, among other things, the encapsulation of the polymers by means of water-soluble or water-dispersible coating agents, preferably by means of water-soluble or water-dispersible natural or synthetic polymers; the encapsulation of the polymers by means of water-insoluble, meltable coating agents, preferably by means of water-insoluble coating agents from the group of waxes or paraffins with a melting point above 30°C; the cogranulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing or cleaning-active substances, particularly preferably from the group of builders or cobuilders.

[0108] As a further formulation ingredient, washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, preferably contain one or more enzymes. These include, in particular, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases, or oxidoreductases, and preferably mixtures thereof. These enzymes are essentially of natural origin; based on the natural molecules, improved variants are available for use in cleaning agents and are therefore preferably used. Washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, preferably contain enzymes in total amounts of 1 × 10 -6 wt.% to 5 wt.%, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

[0109] Among the proteases, those of the subtilisin type are preferred. Examples include subtilisins BPN' and Carlsberg, as well as their more advanced forms, protease PB92, subtilisins 147 and 309, alkaline protease from Bacillus lentus, subtilisin DY, and the enzymes thermitase, proteinase K, and proteases TW3 and TW7, which are classified as subtilases but no longer as subtilisins in the narrower sense.

[0110] Examples of amylases that can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger, and A. oryzae, as well as the improved versions of the aforementioned amylases for use in cleaning agents. Also suitable for this purpose are the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

[0111] Lipases or cutinases can also be used according to the invention, particularly for their triglyceride-cleaving activities, but also for generating peracids in situ from suitable precursors. These include, for example, the lipases originally obtained from Humicola lanuginosa (Thermomyces lanuginosus) or further developed lipases, in particular those with the amino acid substitution at positions D96L, T213R, and / or N233R, particularly preferably all of the substitutions D96L, T213R, and N233R.

[0112] Enzymes collectively referred to as hemicellulases can also be used. These include, for example, mannanases, xanthan lyases, pectin lyases (=pectinases), pectinesterases, pectate lyases, xyloglucanases (=xylanases), pullulanases, and β-glucanases.

[0113] To increase the bleaching effect, oxidoreductases, for example, oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin-, glucose-, or manganese-peroxidases, dioxygenases, or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention. Advantageously, organic compounds, particularly aromatic ones, that interact with the enzymes are also added to enhance the activity of the oxidoreductases in question (enhancers) or to ensure electron flow in the event of significantly different redox potentials between the oxidizing enzymes and the soils (mediators). A protein and / or enzyme can be protected, particularly during storage, against damage such as inactivation, denaturation, or degradation, for example, due to physical influences, oxidation, or proteolytic cleavage.When the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Detergents or cleaning agents according to the invention, in particular dishwashing agents, preferably automatic dishwashing agents, may contain stabilizers for this purpose; the provision of such agents represents a preferred embodiment of the present invention.

[0114] Cleaning-active proteases and amylases are generally not supplied in the form of pure proteins, but rather in the form of stabilized, storable, and transportable preparations. These prefabricated preparations include, for example, solid preparations obtained by granulation, extrusion, or lyophilization or, particularly in the case of liquid or gel-like products, solutions of the enzymes, preferably as concentrated as possible, with little water content, and / or containing stabilizers or other additives.

[0115] Alternatively, the enzymes can be encapsulated, 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 enzymes are enclosed as if in a solidified gel, or in core-shell capsules in which an enzyme-containing core is coated with a water-, air-, and / or chemical-impermeable protective layer. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers. Such capsules are applied using methods known per se, for example by shake or roll granulation or in fluid-bed processes. Such granules, for example by applying polymeric film formers, are advantageously low in dust and, due to the coating, are storage-stable.

[0116] Furthermore, it is possible to package two or more enzymes together so that a single granulate has multiple enzyme activities.

[0117] As can be seen from the above, the enzyme protein constitutes only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40 wt.%, preferably between 0.2 and 30 wt.%, particularly preferably between 0.4 and 20 wt.%, and in particular between 0.8 and 10 wt.% of the enzyme protein. Particularly preferred are cleaning agents which, based on their total weight, contain 0.1 to 12 wt.%, preferably 0.2 to 10 wt.%, and in particular 0.5 to 8 wt.% of the respective enzyme preparations.

[0118] The washing or cleaning agent, in particular dishwashing detergent, preferably automatic dishwashing detergent, may further contain one or more enzyme stabilizers. Examples of suitable enzyme stabilizers include boron-containing compounds such as boric acid or boronic acids, as well as their salts and esters, polyols such as glycerin or 1,2-ethylene glycol, sugars, sugar alcohols, lactic acid, or antioxidants.

[0119] In a preferred embodiment, washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, contain as a further component at least one zinc salt as a glass corrosion inhibitor. The zinc salt can be an inorganic or organic zinc salt. The zinc salt to be used according to the invention preferably has a solubility in water of above 100 mg / l, preferably above 500 mg / l, particularly preferably above 1 g / l, and in particular above 5 g / l (all solubilities at a water temperature of 20°C). The inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate, and zinc sulfate.The organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group consisting of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, and zinc p-toluenesulfonate. In a particularly preferred embodiment of the invention, zinc acetate is used as the zinc salt.

[0120] The zinc salt is preferably present in the cleaning agent according to the invention in an amount of 0.01 wt.% to 5 wt.%, particularly preferably in an amount of 0.05 wt.% to 3 wt.%, in particular in an amount of 0.1 wt.% to 2 wt.%, based on the total weight of the cleaning agent.

[0121] In addition or alternatively to the above-mentioned zinc salts, polyethyleneimines, such as those available under the name Lupasol ® (BASF), can be used as glass corrosion inhibitors, preferably in an amount of 0 to 5 wt.%, in particular 0.01 to 2 wt.%.

[0122] The washing or cleaning agent, in particular dishwashing detergent, preferably automatic dishwashing detergent, may further contain a bleaching agent as a formulation ingredient, in particular an oxygen bleaching agent and optionally a bleach activator and / or bleach catalyst.

[0123] As a preferred bleaching agent, washing or cleaning agents according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, contain an oxygen bleaching agent from the group consisting of sodium percarbonate, sodium perborate tetrahydrate, and sodium perborate monohydrate. Other useful bleaching agents include, for example, peroxypyrophosphates, citrate perhydrates, and H2O2-yielding peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid, or diperdodecanedioic acid. Furthermore, bleaching agents from the group consisting of organic bleaching agents can also be used. Typical organic bleaching agents are diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxyacids, with particular examples being alkyl peroxyacids and aryl peroxyacids. Sodium percarbonate is particularly preferred due to its good bleaching performance.A particularly preferred oxygen bleaching agent is sodium percarbonate.

[0124] Bleach activators that can be used are compounds that, under perhydrolysis conditions, yield aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, especially 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those containing O- and / or N-acyl groups with the stated number of carbon atoms and / or optionally substituted benzoyl groups. Polyacylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) having proven particularly suitable.

[0125] The bleach catalysts are bleach-enhancing transition metal salts or transition metal complexes, such as Mn, Fe, Co, Ru, or Mo salen 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 ammine complexes, can also be used as bleach catalysts. Particular preference is given to using manganese complexes in oxidation state II, III, IV, or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O, and / or S. Ligands with nitrogen donor functions are preferred.It is particularly preferred to use bleach catalyst(s) in the agents according to the invention which contain 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN) as macromolecular ligands. Suitable manganese complexes are, for example, [Mn III< 2 (µ-O) 1 (µ-OAc) 2 (TACN) 2 ](ClO 4 ) 2 , [Mn III< Mn IV< (µ-O) 2 (µ-OAc) 1 (TACN) 2 ](BPh 4 ) 2 , [Mn IV< 4 (µ-O) 6 (TACN) 4 ](ClO 4 ) 4 , [Mn III< 2 (µ-O) 1 (µ-OAc) 2 (Me-TACN) 2 ](ClO 4 ) 2 , [Mn III< Mn IV< (µ-O) 1 (µ-OAc) 2 (Me-TACN) 2 ](ClO 4 ) 3 , [Mn IV< 2 (µ-O) 3 (Me-TACN) 2 ](PF 6 ) 2 and [Mn IV< 2 (µ-O) 3 (Me / Me-TACN) 2] (PF 6 ) 2 (with OAc = OC(O)CH 3 ).

[0126] In general, the pH of the washing or cleaning agent, in particular dishwashing detergent, preferably automatic dishwashing detergent, can be adjusted using conventional pH regulators, whereby the pH is selected depending on the desired application. In various embodiments, the pH is in a range from 5.5 to 11, preferably 6 to 10.5, more preferably 7 to 10.5, in particular greater than 7, especially in the range 8.5 to 10.5. Acids and / or alkalis, preferably alkalis, serve as pH adjusters. Suitable acids are, in particular, organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or also amidosulfonic acid. In addition, the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used.Suitable bases come from the group of alkali and alkaline earth metal hydroxides and carbonates, especially alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide are preferred. However, volatile alkali is particularly preferred, for example in the form of ammonia and / or alkanolamines, which can contain up to 9 carbon atoms per molecule. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanolamine, and propanolamine, and mixtures thereof.

[0127] To adjust and / or stabilize the pH, the washing or cleaning agent according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, may also contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5 wt.%. Buffer substances that are also complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or citrates, in particular sodium and

[0128] Potassium citrates, for example trisodium citrate 2H 2 O and tripotassium citrate H 2 O.

[0129] Individual fragrance compounds, e.g., synthetic products of the ester, ether, aldehyde, ketone, alcohol, and hydrocarbon type, can be used as perfume oils or fragrances within the scope of the present invention. However, mixtures of different fragrances are preferably used, which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures, such as those obtainable from plant sources, e.g., pine, citrus, jasmine, patchouli, rose, or ylang-ylang oil. Furthermore, preservatives can be present in the washing or cleaning agent according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents.Suitable preservatives include, for example, alcohols, aldehydes, antimicrobial acids and / or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl butyl carbamate, iodine, iodophores and peroxides.Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerin, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2-benzyl-4-chlorophenol, 2,2'-methylene-bis-(6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N-(4-chlorophenyl)-N-(3,4-dichlorophenyl)urea, N,N'-(1,10-decanediyldi-1-pyridinyl-4-ylidene)-bis-(1-octanamine) dihydrochloride, N,N'-bis-(4-chlorophenyl)-3,12-diimino-2,4,11,13-tetraazatetradecanediimidamide, antimicrobial quaternary surfactants, guanidines. However, particularly preferred preservatives are selected from the group comprising salicylic acid, quaternary surfactants, especially benzalkonium chloride, and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.

[0130] According to the invention, both the shaped body according to the invention and the washing or cleaning agent according to the invention, in particular dishwashing agents, preferably automatic dishwashing agents, are phosphate-free, ie the agents contain less than 0.1% by weight of phosphate(s).

[0131] In a further embodiment, the object on which the present invention is based is achieved by a process for producing a shaped body, which is characterized in that the at least one meltable carrier substance is melted, the at least one solid active substance is homogeneously distributed therein, so that a dispersion is obtained. The casting compound thus obtained is then poured into a suitable mold without the formation of bubbles and without the application of pressure. After curing, the mold can be removed. The process according to the invention thus describes a simple pouring of a casting compound into any desired mold. No special conditions are required during the actual casting process.This can be done at room temperature. Curing also preferably takes place at room temperature.

[0132] If the molded body has a cavity, the method includes the step of filling at least one cavity with at least one formulation ingredient. If two, three, or more cavities are present, they can be filled with the same formulation ingredient(s). However, the formulation ingredients in one cavity are preferably different from the formulation ingredients in the other cavity. This enables, for example, the separation of bleaching agents and enzymes or other incompatible formulation ingredients.

[0133] After the cavity(ies) have been filled, the resulting washing or cleaning agent, in particular dishwashing detergent, preferably automatic dishwashing detergent, is partially or fully coated with a water-soluble film. This film is then shrink-wrapped to conform to the shape of the molded body, sealing the cavities on the one hand and creating a stable coating on the other. During use by the end consumer, there is therefore no direct contact between the skin and the molded body or washing or cleaning agent; only the water-soluble coating needs to be touched. However, this dissolves during the washing process, so the cleaning performance is not adversely affected.

[0134] The term "water-soluble," as used herein, means "water-soluble" in the true sense, but also "water-disintegratable." The term "water-soluble" in the true sense refers to the property of a substance or object that it has a solubility in distilled water, measured at 25°C, of ​​at least 0.1 g / L. In some embodiments, the substance and object have a solubility of at least 0.1 to 500 g / L, measured at 25°C. The term "water-disintegratable" means that the substance or object disintegrates into small pieces within 15, preferably within 10, minutes upon contact with water at temperatures between 15 and 60°C, and especially between 20 and 45°C.

[0135] The water-soluble film preferably comprises a water-soluble polymer. Some preferred water-soluble polymers that are preferably used as water-soluble packaging are polyvinyl alcohols, acetalized polyvinyl alcohols, polyvinylpyrrolidones, polyethylene oxides, celluloses, and gelatin, with polyvinyl alcohols and acetalized polyvinyl alcohols being particularly preferred.

[0136] "Polyvinyl alcohols" (abbreviation PVA, occasionally also PVOH) is the name for polymers with the general structure which in small proportions (approx. 2%) also contain structural units of the type contain.

[0137] Commercially available polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range of approximately 100 to 2500 (molar masses of approximately 4000 to 100,000 g / mol), have degrees of hydrolysis of 87-99 mol%, thus still containing a residual amount of acetyl groups.

[0138] Within the scope of the present invention, it is preferred that the water-soluble packaging at least partially comprises a polyvinyl alcohol whose degree of hydrolysis is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 mol% and especially 82 to 88 mol%. In a preferred embodiment, the water-soluble packaging consists of at least 20 wt.%, particularly preferably at least 40 wt.%, very particularly preferably at least 60 wt.% and in particular at least 80 wt.% of a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

[0139] Preferably, polyvinyl alcohols of a specific molecular weight range are used as materials for the packaging, wherein it is preferred according to the invention that the packaging material comprises a polyvinyl alcohol whose molecular weight is in the range from 5,000 g mol -1< to 100,000 g mol -1<, preferably from 10,000 g mol -1< to 90,000 g mol -1<, particularly preferably from 12,000 g mol -1< to 80,000 g mol -1< and in particular from 15,000 g mol -1< to 70,000 g mol -1<.

[0140] The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.

[0141] The water solubility of polyvinyl alcohol can be modified by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols that are acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides, or mixtures thereof, have proven particularly preferred and particularly advantageous due to their exceptionally good cold-water solubility. The reaction products of polyvinyl alcohol and starch are particularly advantageous. Furthermore, the water solubility can be modified by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, or borax, thus allowing the desired values ​​to be precisely adjusted.

[0142] The water-soluble film ((tight) wrapping) particularly preferably comprises polyvinyl alcohol, as described above, wherein the starting thickness used is preferably a thickness of 10 µm to 100 µm, in particular of 12 µm to 60 µm, particularly preferably of 15 µm to 50 µm, especially of 20 µm to 40 µm, in particular of 22 µm to 35 µm.

[0143] In the case of a tight coating, each single-dose portion of the washing or cleaning agent is encased. For the coated single-dose washing or cleaning agent according to the invention, it is important that the coating fits tightly against the surface of the tablets at every point. Ideally, the coating is even under tension, although this is not absolutely necessary. This tight fit of the coating promotes disintegration: upon first contact with water, the coating will allow a small amount of water to pass through at some point, although it does not necessarily have to dissolve at all initially. At this point, the disintegrant contained in the tablet begins to swell. This causes the coating to suddenly tear open due to the increase in volume of the tablet, releasing the tablet.If the coating is not tightly fitting, the mechanism described here does not work, as the tablet can swell without bursting the coating. In this case, the use of a swellable disintegrant is superior to a gas-evolving system, as its explosive effect always leads to the rupture of the coating. With a gas-evolving system, the explosive effect can fizzle out if the gas escapes from a leak in the coating.

[0144] Preferred washing or cleaning agent single portions according to the invention are characterized in that the distance between the single portion and the water-soluble coating over the entire surface is 0.1 to 1000 µm, preferably 0.5 to 500 µm, particularly preferably 1 to 250 µm and in particular 2.5 to 100 µm.

[0145] In a preferred embodiment, the film wrapping is first loosely placed around a single-dose detergent or cleaning agent, sealed, and then shrunk onto it, ensuring close contact between the film packaging and the cleaning agent concentrate. Accordingly, single-dose detergent or cleaning agent packages according to the invention are characterized in that the wrapping is a film package shrunk onto the package.

[0146] For example, this wrapping can be done by placing a water-soluble bottom film on a conveyor chain or a forming tool, then placing one or more detergent or cleaning agent portions on the bottom film; then placing a water-soluble top film on the detergent or cleaning agent portion(s) on the bottom film and then fixing this to the bottom film, enclosing the detergent or cleaning agent portion(s). Alternatively, this step can also be done using a single-strand film, which is then wrapped around the single-use portions as a tube. The films are then sealed and optionally cut. The film can then be shrink-fitted using hot air or infrared radiation, optionally with pressure.

[0147] Such water-soluble coatings have also been described in patent applications WO 2004 / 031338 A and WO 2003 / 099985 A, the disclosures of which are hereby incorporated by reference in their entirety.

[0148] The washing or cleaning agents described herein, in particular dishwashing detergents, preferably automatic dishwashing detergents, are preferably pre-packaged into dosing units. These dosing units preferably comprise the amount of washing or cleaning-active substances required for one cleaning cycle. Preferred dosing units have a weight between 12 and 30 g, preferably between 14 and 26 g, and in particular between 15 and 22 g. The volume of the aforementioned dosing units and their spatial shape are particularly preferably selected to ensure that the pre-packaged units can be dosed via the dosing chamber of a dishwasher. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.

[0149] The washing or cleaning agent according to the invention is particularly preferably one for cleaning hard surfaces, and in particular for the automatic, mechanical cleaning of hard surfaces. The washing or cleaning agent is particularly preferably an agent for the mechanical cleaning of dishes, so that the use of the shaped body or the washing or cleaning agent according to the present invention is particularly preferred for the mechanical cleaning of hard surfaces, in particular dishes.

[0150] The embodiments described in the context of the washing or cleaning agents according to the invention, in particular dishwashing agents, preferably automatic dishwashing agents, are readily transferable to the methods and uses according to the invention, and vice versa. The present invention is further explained in a non-limiting manner in the following exemplary embodiments. Examples of implementation: Example 1:

[0151] Molded bodies with the following composition were produced: Carrier (T) / Active substance (A) raw material Amount [wt%] T (fusible) PEG 4000 30-40 T (liquid) Alcohol polyglycol ether 10-15 A Complexing agent (MGDA) 15-25 A Sulfonic acid group-containing acrylate copolymer 8-12 A Phosphonate 6-10 A sodium citrate 3-8 A soda 12-16 A dye 0-0,5

[0152] The molded bodies had two cavities. The first cavity was filled with a composition containing enzymes, surfactant, and bleaching agent. The second cavity was filled with a composition containing a bleach activator.

[0153] The automatic dishwashing detergents produced according to the invention were tested against commercially available phosphate-free dishwashing detergents (Somat®< 12) for filming and spotting properties on glass and stainless steel. The tests were conducted in both a Miele (GSL) and a Bosch (SMS68M62) dishwasher.

[0154] The dishwashing detergents according to the invention showed the same performance as the commercially available dishwashing detergent. Example 2:

[0155] Different molded bodies with a size of 28 mm × 50 mm × 12 mm were produced with the following recipes (data for the raw materials in wt.%): raw material EM1 EM2 EM3 EM4 EM5 PEG4000 30 25 35 30 30 Alcohol polyglycol ether (liquid) 12 12 12 12 12 MGDA 20 20 20 20 15 Sulfonic acid group-containing acrylate copolymer 10 10 10 10 10 Phosphonate 8 8 8 8 8 sodium citrate 5 5 5 5 5 soda 14,8 14,8 14,8 14,8 14,8 dye 0,2 0,2 0,2 0,2 0,2 Fracture hardness [N] 136,4 125,0 136,4 139,9 115,8

[0156] The fracture hardness of the specimens was determined using a Chatillon TCM 201-M force gauge (Wagner Instruments, Greenwich, USA) and a PCE FG 200 load cell (PCE Deutschland GmbH, Meschede, Germany). The specimen to be tested was placed on a support (a round mandrel with a diameter of 8 mm) and sheared from above with a wedge (width: 30 mm) until the specimen fractured. The feed rate was 25 mm / min.

[0157] The fracture hardness of all molded bodies was in the range of 100 to 140 N.

Claims

1. Shaped article produced by casting for a detergent or cleaning agent, characterized in that it comprises at least one carrier which is meltable at a temperature of 70°C or less and which is solid at room temperature (20°C), and at least one powdery or granulated active substance, the active substance being a complexing agent selected from the group consisting of aminocarboxylic acids and their salts.

2. Shaped article according to claim 1, characterized in that it has no, one, two, three or more cavities, in particular one, two or three cavities, particularly preferably one or two cavities.

3. Shaped article according to claim 1 or 2, characterized in that it comprises the at least one carrier material in a proportion of 10 wt.% to 40 wt.%, preferably from 20 wt.% to 30 wt.%, based on the total weight of the shaped article.

4. Shaped article according to claim 3, characterized in that the carrier is selected from xylitol, 2-ethyl-2-hydroxymethyl-1,3-propanediol (EHPD), nonionic surfactants, polymers, in particular polyalkylene glycol, and mixtures thereof, preferably from xylitol, 2-ethyl-2-hydroxymethyl-1,3-propanediol (EHPD), nonionic surfactants, polyalkylene glycol, in particular polyethylene glycol, and mixtures thereof.

5. Shaped article according to any one of claims 1 to 4, characterized in that it comprises the at least one active substance in a proportion of from 50% by weight to 90% by weight, preferably from 60% by weight to 70% by weight, based on the total weight of the shaped article.

6. Shaped article according to claim 5, characterized in that the active substance is selected from complexing agents, surfactants, in particular non-ionic surfactants, stabilizers, buffers, builders, corrosion inhibitors, alkali carriers and mixtures thereof.

7. Shaped article according to any one of claims 1 to 6, further comprising liquid carriers, selected from liquid nonionic surfactants, fragrances or perfume oils, which are liquid at room temperature (20 °C) in a proportion of from 2% by weight to 15% by weight, in particular from 2% by weight to 10% by weight, based on the total weight of the molded article.

8. Washing or cleaning composition comprising a shaped article according to any one of claims 1 to 7.

9. Washing or cleaning composition comprising a shaped article according to any one of claims 2 to 7 with at least one cavity, wherein the at least one cavity has one or more powdery or granulated formulation components.

10. Washing or cleaning composition according to claim 9, characterized in that the formulation ingredient(s) is / are selected from enzymes, bleach activators, bleaching agents, pH adjusters, builders, dyes, fragrances, surfactants (anionic, cationic, amphoteric, nonionic), polymers, bleaching catalysts, thickeners, sequestering agents, electrolytes, corrosion inhibitors, glass corrosion inhibitors, foam inhibitors, dyes, additives to improve drainage and drying behavior, disintegration aids, preservatives and perfume carriers as well as mixtures of these.

11. Washing or cleaning composition according to any one of claims 8 to 10, characterized in that it further comprises a water-soluble coating, in particular comprising polyvinyl alcohol.

12. Process for producing a shaped article according to one of claims 1 to 7, characterized in that the at least one fusible carrier material is heated to a temperature at which it melts, the at least one active substance is then homogeneously distributed therein and the casting mass thus obtained is then poured into a suitable mould at room temperature without the application of pressure, the casting mass is cured at room temperature and, after curing, the shaped article now obtained is removed from the mould.

13. Process for the production of a washing or cleaning agent according to one of claims 8 to 11, characterized in that a shaped article is first produced according to the process according to claim 12, and the at least one cavity, if present, is filled with at least one formulation component.

14. Process according to claim 13, characterized in that the shaped article is coated with a water-soluble film.

15. Process according to claim 14, characterized in that the water-soluble film comprises polyvinyl alcohol .

16. Use of a shaped article according to any one of claims 1 to 7 or of a washing or cleaning agent according to any one of claims 8 to 11 for cleaning hard surfaces, in particular tableware, in particular for machine cleaning of hard surfaces and preferably for machine cleaning of tableware.

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