WO2022207198A1

WO2022207198A1 - Single-dose detergent unit

Info

Publication number: WO2022207198A1
Application number: PCT/EP2022/054722
Authority: WO
Inventors: Till Überrück; Peter Schmiedel
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2021-04-01
Filing date: 2022-02-24
Publication date: 2022-10-06
Also published as: DE102021203326A1; EP4314230A1

Abstract

The invention relates to a detergent presentation form comprising a) an outer packaging b) detergent shaped bodies having an upper side, a lower side and a cover surface connecting the upper side and the lower side, wherein i) the outer packaging contains at least two detergent shaped bodies which are arranged in a sorted manner in the outer packaging, and ii) the detergent shaped bodies have a rough upper side or a rough lower side, the average roughness of which is from 1 µm to 1000 µm, preferably from 10 µm to 800 µm and in particular from 25 to 500 µm.

Description

, detergent portion unit"

The present invention relates to a detergent portion unit, comprising a gel body and a rigid enveloping substance at least partially covering the gel body. The application also relates to a method for producing this detergent portion unit and a washing method for textiles or crockery using such a detergent portion unit.

Constantly changing requirements are placed on the packaging and supply forms of detergents and cleaning agents. For some time now, the main focus has been on the convenient dosing of detergents and cleaning agents by the consumer and the simplification of the work steps required to carry out a washing or cleaning process. A technical solution is provided by pre-portioned detergents or cleaning agents, for example water-soluble containers with one or more receiving chambers for powdered or liquid detergents or cleaning agents. Another technical solution is provided by detergent tablets, which can be single-phase or multi-phase.

To produce the water-soluble containers, water-soluble polymers are generally formed into receiving chambers, which are then filled with a detergent or cleaning agent and finally sealed. The receiving chambers can be made, for example, from water-soluble polymer films by deep-drawing processes. In an alternative process, a water-soluble polymer is injection molded into a receptacle.

The water-soluble packaging material used to package the filled detergent portion units is generally hygroscopic. During manufacture, packaging, storage and later use by the consumer, the tendency and ability of the packaging to absorb water can result in portion units adhering to the surfaces of machines or packaging materials and being unable to be optimally conveyed, or in adjacent portion units, for example in a common outer packaging, glue together. In order to avoid this tendency for the water-soluble portion units to adhere, it is possible to modify their surface properties by applying a powder agent. The powdering of the water-soluble detergent portion units in turn requires an additional process step.

Due to the portioning in a water-soluble packaging material, the fragrances added to the detergent or cleaning agent only come into their own to a very limited extent or not at all in the case of detergent portion units, in contrast to conventional solid detergent powders. As a reaction to this situation, detergent products are marketed whose outer cardboard packaging is provided, for example, with fragrance-containing adhesives and gives the consumer a scent impression of the detergent or cleaning agent contained. The water-soluble packaging materials used are usually not washing or cleaning active, so they do not contribute to the effect of the product. The reduction in the proportion of packaging in the total weight of the detergent portion units would therefore not result in any loss of performance and would at the same time be welcomed for reasons of sustainability and economy.

Finally, the washing performance provided by the detergent portion unit is directly related to the dissolving properties of the portion unit. Precisely in view of the increasing use of cold washing processes, it is preferable to keep the thickness of the water-soluble film material contained in the detergent portion unit as small as possible in order to accelerate the dissolution process. At the same time, however, the reduction in the thickness of the surrounding film material results in reduced mechanical stability of the portion units. Overcoming this apparent dichotomy of mechanical stability and dissolution rate using water-soluble film-packaged detergent dosage units is still a relevant aspect in the development of water-soluble detergent portion units.

Detergent tablets offer an alternative to the sachets described above, in which however adequate mechanical stability and high dissolution rate are incompatible in a similar way as in the case of sachets.

Against the background of the prior art described above, the application was based on the object of providing detergent portion units that can be produced using simplified processes, have high product and storage stability, can be made up easily using very small amounts of packaging materials and are an appealing olfactory, visual and/or haptic appeal. Finally, the detergent portion units should have a high product performance and be easy and safe to handle for the consumer.

A detergent supply form is suitable for solving these tasks, comprising a) outer packaging b) detergent tablets with an upper side, an underside and a lateral surface connecting the upper side and the lower side, with i) the outer packaging containing at least two detergent tablets which are sorted in the outer packaging and ii) the detergent tablets have a rough upper side or a rough underside, the average roughness of which is from 1 μm to 1000 μm, preferably from 10 μm to 800 μm and in particular from 25 to 500 μm. The outer packaging is preferably designed as a folding box, particularly preferably as a one-piece folding box. Preferred overwraps have a flat bottom surface whose longest diagonal is greater than the height of the overwrap. This configuration of the outer packaging increases its stability and enables it to be opened and removed easily. It is particularly preferred if the outer packaging has a flat bottom surface, the largest diagonal of which is more than twice, preferably more than four times, the height of the outer packaging.

In order to achieve the high degree of filling, it has proven to be advantageous if the outer packaging has a cornered bottom surface, preferably a square bottom surface, very particularly preferably a rectangular bottom surface. For the same reason and to improve the stackability of the outer packaging, it is preferred that the outer packaging has a cover surface that is plane-parallel to the base surface. Outer packaging in the form of a parallelepiped is particularly preferred.

In order to increase the storage stability, in particular the chemical stabilization of the detergent tablets, it has proven to be advantageous if the outer packaging is resealable. For example, adhesive, snap-in, snap-in or plug-in elements are suitable as closure elements, with adhesive and plug-in elements being particularly preferred. Examples of closure elements are plug-in closures or removable adhesive closures.

For reasons of sustainability, recycled and/or recyclable materials are preferred for the production of the outer packaging. The packaging materials are preferably based on renewable raw materials. The use of packaging materials based on cellulose and waste paper is particularly preferred.

In a first preferred embodiment, the outer packaging is made of cardboard. In addition to its availability and recyclability, the advantages of cardboard lie in the great variability of the types and grammages available. Preferred cardboards have a grammage of 150 to 400 g/m ² .

Corrugated board, which has proven to be technically superior to cardboard in some respects, is used in a particularly preferred embodiment for manufacturing the outer packaging. Corrugated cardboard is characterized by its low weight and high strength and is a suitable medium for storage and transport, even in large containers.

A feature of preferred outer packaging is the COBB value of the cardboard used to produce it in the range below 25 g/m ² , preferably below 20 g/m ² . The COBB value is a value that describes the resistance of paper and cardboard to moisture being drawn into the material. A high COBB value means water is lighter penetrates. A low COBB value means that it is difficult for water to penetrate the material. The COBB value is determined according to DIN EN ISO 535 under 20 g/m2 at 20 °C and standard pressure. Particularly preferred detergent supply forms are characterized in that the cardboard used to produce the outer packaging has a COBB value below 25 g/m ² , preferably below 20 g/m ² .

Corresponding COBB values can be realized in different ways. In an alternative embodiment, the outer packaging has, for example, a water-insoluble cover film, preferably a polyethylene cover film. Water-insoluble cover films are generally suitable for preventing or at least reducing the entry of water or water vapor through the outer packaging into the interior of the outer packaging.

To avoid superfluous packaging components, water-insoluble cover films are preferably only applied to the outside or inside of the outer packaging. Full-surface coverage is preferred to effectively limit the ingress of moisture.

The term detergent tablet describes a form of presentation in which a measured portion of a detergent or cleaning agent is present. Detergent portion units therefore designate both forms of supply for textile laundry and forms of supply for cleaning hard surfaces such as ceramics, glass, metal or tiles. A detergent tablet preferably weighs from 14 g to 42 g, preferably from 20 g to 38 g, in particular from 24 g to 34 g.

A "molding" is a single body that is self-stabilizing in its imposed shape. This dimensionally stable body is formed from a molding material (e.g. a composition) by bringing this molding material into a predetermined shape in a targeted manner, e.g. by pouring a liquid composition into a mold and then curing the liquid composition or by compressing a particulate premix, for example in as part of a tableting process.

The three-dimensional form of the detergent shaped body can in principle be freely selected; its lateral surface can, for example, be convex, concave or planar. At the same time, however, certain spatial configurations have proven to be particularly advantageous against the background of the producibility, storage and use of the gel bodies.

Correspondingly advantageous detergent tablets have a flat underside, the largest diagonal of which is greater than the height of the detergent tablet. Not only can these bodies be produced in a simple manner, for example by means of a casting process, they can also be packaged in a simple and space-saving manner and are suitable for dosing via the dosing or dispensing compartments of electronic cleaning devices. It is preferred if the gel body is a has a flat underside, the largest diagonal of which is 1.5 times, preferably more than 2 times, the height of the gel body.

For the manufacturability, for example in relation to demolding from a casting or pressing mold, it can prove to be advantageous if the underside of the detergent tablet has no corners. Preferred gel bodies are therefore characterized by oval undersides or alternatively by ellipsoidal or round, preferably round, undersides. Corresponding detergent tablets with a non-angular underside are also preferred by many consumers because of their appearance. Preference is therefore given, for example, to detergent tablets which have an underside and an upper side which are connected to one another by a cylindrical lateral surface.

Advantages in terms of space utilization during production and packaging are realized through angular undersides. If the detergent tablets are cast, for example, in the form of plates which are subsequently cut up, angular undersides are advantageous since such detergent tablets can be cut up without residues and can be packed in a space-saving manner. In an alternative embodiment, preferred detergent tablets therefore have angular undersides, in particular triangular, quadrangular or hexagonal undersides.

With regard to production, packaging and their use, detergent tablets which have an upper side that is plane-parallel to the underside have also proven to be advantageous.

In a first preferred geometric embodiment, the detergent tablet has an underside and an upper side which have the same geometric shape, the underside and the upper side having the same surface area. Corresponding detergent tablets can, as already described above, be produced in a simple manner, for example by casting plates and then cutting the plates into individual detergent tablets. In addition, in any subsequent process steps, during packaging or use by the user, these detergent shaped bodies can be spatially aligned more easily than gel bodies with a lower body symmetry due to the geometric identity of the top and bottom sides. This applies in particular to detergent tablets which at the same time have an upper side that is plane-parallel to the underside. Examples of detergent tablets of this type are circular cylinders, elliptical cylinders, parallelepipeds, rhombohedrons, right or oblique prisms, cuboids or cubes. The group of circular cylinders and elliptical cylinders includes the vertical circular cylinders and elliptical cylinders as well as the oblique circular cylinders and elliptical cylinders. Detergent tablets are preferred due to their simple production by separating them from a sheet in the form of vertical circular cylinders, vertical elliptical cylinders, right prisms, right parallelepipeds or cubes.

In an alternative embodiment, the detergent tablet has an underside and an upper side which have the same geometric shape, the underside and the upper side having different surface areas. Corresponding detergent tablets can be preferred due to their attractive appearance or their optimized fit, while at the same time being comparatively easy to produce. Examples of detergent tablets of this type are circular cylinders or elliptical cylinders with a convex or concave bottom and a flat top. Other examples are truncated cones or truncated pyramids.

It is particularly preferred if the detergent shaped bodies are in the form of tablets or comprise tablets.

Particularly preferred detergent tablets are cuboid. The cuboid shaped detergent bodies comprise an underside, an upper side and a lateral surface connecting the underside and the upper side. It has also proven advantageous for the stability of the tableted detergent tablets if the edges delimiting the underside and the upper side are chamfered. In order to increase the stability of these shaped bodies, it may also be advisable to round off the edges of the lateral surfaces connecting the undersides and the top sides.

In an embodiment that is particularly attractive from the consumer's point of view, the detergent shaped body comprises b1) a dimensionally stable gel body and b2) an encapsulating substance in the form of a tablet, which partially covers the surface of the dimensionally stable gel body.

Gel bodies are bodies that exhibit elastic deformation behavior under the action of force. Objects are considered dimensionally stable if they have an inherent dimensional stability that enables them to assume a non-disintegrating three-dimensional shape under the usual conditions of manufacture, storage, transport and handling by the consumer, with this three-dimensional shape also changing over longer periods under the conditions mentioned Time, preferably 4 weeks, particularly preferably 8 weeks and in particular 32 weeks, not changed, i.e. under the usual conditions of production, storage, transport and handling by the consumer in the spatial-geometric shape caused by the production , that is, does not flow. The gel body and the enveloping substance are preferably adhesively bonded to one another. The gel body preferably occupies at least 50% by volume, preferably at least 60% by volume, of the detergent supply form.

For reasons of simplified production, reduced packaging and improved aesthetics, detergent tablets are preferred in which the gel component forms at least 16%, preferably at least 25% and in particular at least 30% of the total surface area of the detergent tablet. For the same reasons, it is preferred if the coating substance covers 10 to 70%, preferably 30 to 65% and in particular 40 to 60% of the surface of the gel body.

It is also preferred if the water-soluble coating substance covers the surface of the gel body on two opposite sides of the gel body, since this makes it easier for the consumer to handle the detergent portion unit. In addition, this type of surface covering has advantages with regard to the packaging of the detergent portion units, in particular when packaging several detergent portion units together, for example when the detergent portion units are stacked in an outer packaging.

For the aforementioned reasons, particular preference is given to detergent portion units in which the gel body has an underside and an upper side and the water-soluble coating substance at least partially covers both the underside and the upper side of the gel body. Both the underside and the upper side of the gel body are preferably covered to an extent of at least 40%, preferably at least 60% and in particular at least 80%.

In a special embodiment, the gel body has an underside and an upper side, and the water-soluble coating substance covers both the underside and the upper side of the gel body over the entire surface.

The detergent portion units according to the invention are particularly suitable for the formulation of surfactant-containing compositions, since these compositions tend to adhere and stick to a particular extent, for example, when exposed to moisture. In preferred embodiments, the gel body therefore contains 30 to 70% by weight, preferably 40 to 60% by weight and in particular 45 to 55% by weight of surfactant.

For the manufacturability and the subsequent dissolving power of the gel bodies, it has proven to be advantageous if they contain 15 to 35% by weight, preferably 20 to 30% by weight, of an aqueous-organic solvent. Preferred gel bodies also contain dye. Preferred detergent dosage units comprise a transparent gel body. Those gel bodies are referred to as “transparent” which have a transmission in the wavelength range from 410 to 800 nm at at least one wavelength, preferably at 600 nm, above 20%, preferably above 30% and in particular above 35%. The transmission is determined by means of VIS spectrometry at a sample temperature of 20° C. and a cuvette length of 10 mm.

For the production and subsequent storage and transport properties of the gel body, it has proven advantageous to use low-molecular gel formers with a molar mass of up to 2000 g/mol in the gel body, with their proportion by weight of the total weight of the gel body preferably being less than 5% by weight 0.1 to 5% by weight and particularly preferably 0.1 to 2.5% by weight.

In a preferred embodiment, the low molecular weight gelling agent has a solubility in water of less than 0.1 g/L (20° C.). The solubility of the organic gelator compound is determined at 20°C in double-distilled, demineralized water.

Furthermore, gel formers are preferably suitable which have a structure containing at least one hydrocarbon structural unit with 6 to 20 carbon atoms (preferably at least one carbocyclic, aromatic structural unit) and additionally an organic structural unit covalently bonded to the aforementioned hydrocarbon unit, the at least two groups selected from -OH, -NH-, or mixtures thereof.

Particularly preferred gel bodies are characterized in that said gel bodies contain at least one benzylidene alditol compound of the formula (GB-I) as gel former

*- stands for a single covalent bond between an oxygen atom of the alditol backbone and the intended residue, n is 0 or 1, preferably 1, m is 0 or 1, preferably 1,

R ¹ , R ² and R ³ independently represent a hydrogen atom, a halogen atom, a Ci-C ₄ alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxy group, a group -C(=0)- NH-NH ₂ , a group -NH-C(=0)-(C ₂ -C ₄ -alkyl), a Ci-C ₄ -alkoxy group, a Ci-C ₄ -alkoxy-C ₂ -C ₄ -alkyl group, two of the radicals together with the rest of the molecule form a 5- or 6-membered ring,

R ⁴ , R ⁵ and R ⁶ independently represent a hydrogen atom, a halogen atom, a Ci-C ₄ -alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxy group, a group -C(=0)- NH-NH ₂ , a group -NH-C(=0)-(C ₂ -C ₄ -alkyl), a Ci-C ₄ -alkoxy group, a Ci-C ₄ -alkoxy-C ₂ -C ₄ -alkyl group, two of the residues together with the remainder molecule form a 5- or 6-membered ring.

Due to the stereochemistry of the alditols, it should be mentioned that both said benzylidene alditols in the L configuration or in the D configuration or a mixture of both are suitable according to the invention. Because of their natural availability, the benzylidene alditol compounds in the D configuration are preferably used according to the invention. It has been found to be preferable if the alditol skeleton of the benzylidene alditol compound according to formula (GB-I) contained in the shaped body is composed of D-glucitol, D-mannitol, D-arabinitol, D-ribitol, D-xylitol, L -glucitol, L-mannitol, L-arabinitol, L-ribitol or L-xylitol.

Those gel bodies which are characterized in that R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ according to the benzylidene alditol compound of the formula (GB-I) independently of one another are a hydrogen atom, methyl, ethyl, chlorine are particularly preferred , fluorine or methoxy, preferably a hydrogen atom. n according to the benzylidene alditol compound of the formula (GB-I) is preferably 1. m according to the benzylidene alditol compound of formula (GB-I) preferably represents 1.

The gel body very particularly preferably contains at least one compound of the formula (GB-11) as the benzylidene alditol compound of the formula (GB-I)

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are as defined in formula (I). Most preferably, according to formula (GB-11), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently represent a hydrogen atom, methyl, ethyl, chlorine, fluorine or methoxy, preferably a hydrogen atom.

Most preferably the benzylidene alditol compound of formula (GB-I) is selected from 1,3:2,4-di-0-benzylidene-D-sorbitol; 1,3:2,4-di-0-(p-methylbenzylidene)-D-sorbitol; 1,3:2,4-di-O-(p-chlorobenzylidene)-D-sorbitol; 1,3:2,4-di-0-(2,4-dimethylbenzylidene)-D-sorbitol; 1,3:2,4-di-0-(p-ethylbenzylidene)-D-sorbitol; 1,3:2,4-di-0-(3,4-dimethylbenzylidene)-D-sorbitol or mixtures thereof.

Preferred gel bodies contain at least one 2,5-diketopiperazine compound of the formula (GB-II) as gel former

wherein

R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a

Hydroxy group, a (Ci-C6) alkyl group, a (C2-C6) alkenyl group, a (C2-C6) acyl group, a (C2-C6) acyloxy group, a (Ci-C6) alkoxy group, an amino group, a (C2-C6) - acylamino group, a (Ci-C6) -alkylaminocarbonyl group, an aryl group, an aroyl group, an aroyloxy group, an aryloxy group, an aryl (Ci-C ₄ ) -alkyloxy group, an aryl (Ci-C3) - alkyl group, a heteroaryl group, a hetroaryl (Ci-C3) alkyl group, a (C1-C4) - hydroxyalkyl group, a (Ci-C ₄ ) -aminoalkyl group, a carboxy (Ci-C3) alkyl group, wherein at least two the radicals R ¹ to R ⁴ together with the rest of the molecule can form a 5 or 6-membered ring,

R ⁵ represents a hydrogen atom, a linear (Ci to C6) alkyl group, a branched (C3 to Cio) alkyl group, a (C3 to C6) cycloalkyl group, a (C2-C6) alkenyl group, a (C2-C6 )- alkynyl group, a (Ci-C ₄ )-hydroxyalkyl group, a (Ci-C ₄ )-alkoxy-(Ci-C ₄ )-alkyl group, a (C1-C ₄ )-acyloxy-(Ci-C ₄ )- alkyl group, an aryloxy-(Ci-C ₄ )-alkyl group, a 0-(aryl-(Ci-C ₄ )-alkyl)oxy-(Ci-C ₄ )-alkyl group, a (Ci-C ₄ )-alkylsulfanyl- (Ci-C ₄ ) alkyl group, an aryl group, an aryl (Ci-C3) alkyl group, a heteroaryl group, a hetroaryl (Ci-C3) alkyl group, a (C1-C4) - hydroxyalkyl group, a (Ci- C4)-aminoalkyl group, an N-(Ci-C4)-alkylamino-(Ci-C4)-alkyl group, an N,N-(Ci-C4)-dialkylamino-(Ci-C4)-alkyl group, an N-(C2 -C8)-acylamino-(Ci-C4)- alkyl group, a N-(C ₂ -C8)-acyl-N-(Ci-C ₄ )-alkylamino-(Ci-C ₄ )-alkyl group, a N-( C2-Cs)-aroyl-N-(Ci-C ₄ )-alkylamino-(Ci-C ₄ )-alkyl group, a N,N-(C ₂ -C8)-diacylamino-(Ci-C ₄ )-alkyl group, an N- (ary l-(Ci-C4)-alkyl)amino-(Ci-C4)-alkyl group, a N,N-di(aryl-(Ci-C4)-alkyl)amino-(Ci-C4)- alkyl group, a (Ci-C ₄ )-carboxyalkyl group, a (Ci-C ₄ )-alkoxycarbonyl-(Ci-C3)-alkyl group, a (Ci-C ₄ )-acyloxy-(Ci-C3)-alkyl group, a guanidino -(Ci-C3)-alkyl group, an aminocarbonyl-(Ci-C ₄ )-alkyl group, an N-(Ci-C ₄ )-alkylaminocarbonyl-(Ci-C ₄ )-alkyl group, an N,N-di(( Ci-C ₄ )-alkyl)aminocarbonyl-(Ci-C ₄ )-alkyl group, an N-(C2-C8)-acylaminocarbonyl-(Ci-C ₄ )-alkyl group, an N,N-(C ₂ -C8) -diacylaminocarbonyl-(Ci-C ₄ )-alkyl group, an N-(C2-Cs)-acyl-N-(Ci-C4)-alkylaminocarbonyl-(Ci-C4)-alkyl group, an N-(aryl-(Ci- C4)-alkyl)aminocarbonyl-(Ci-C4)-alkyl group, an N-(aryl-(Ci-C4) _-alkyl )-N-(Ci-C6)-alkylaminocarbonyl-(Ci-C4) _-alkyl group or an N,N-di(aryl(Ci-C ₄ )alkyl)aminocarbonyl(Ci-C ₄ )alkyl group.

It is preferred according to the invention if R ³ and R ⁴ according to formula (GB-II) stand for a hydrogen atom. According to the invention, it is particularly preferred if R ² , R ³ and R ⁴ according to formula (GB-II) stand for a hydrogen atom. Very particularly preferred shaped bodies according to the invention therefore contain at least one 2,5-diketopiperazine compound of the formula (GB-IIa)

wherein R ¹ and R ⁵ are as defined under formula (GB-II) (vide supra).

It has turned out to be preferred if the radical R ¹ according to formula (GB-II) and according to formula (GB-IIa) binds in the para-position of the phenyl ring. For the purposes of the present invention, therefore, preference is given to moldings according to the invention which contain at least one 2,5-diketopiperazine compound of the formula (GB-IIb),

wherein R ¹ and R ⁵ are as previously defined under formula (GB-II) (vide supra). For illustrative purposes, the numbers 3 and 6 positioned on the ring atoms in formula (GB-IIb) mark only the positions 3 and 6 of the diketopiperazine ring, as are generally used within the scope of the invention for naming all 2,5-diketopiperazines according to the invention.

The 2,5-diketopiperazine compounds of formula (GB-II) have centers of chirality at least at the carbon atoms in positions 3 and 6 of the 2,5-diketopiperazine ring. the Numbering of the ring positions 3 and 6 was illustrated as an example in formula (GB-IIb). The 2,5-diketopiperazine compound of the formula (GB-II) of the compositions according to the invention is preferably the configuration isomer 3S,6S, 3R,6S, 3S based on the stereochemistry of the carbon atoms in the 3- and 6-positions of the 2,5-diketopiperazine ring ,6R, 3R,6R or mixtures thereof, particularly preferably 3S,6S.

Preferred gel bodies contain at least one 2,5-diketopiperazine compound of the formula (GB-II) as gelling agent, selected from 3-benzyl-6-carboxyethyl-2,5-diketopiperazine, 3-benzyl-6-carboxymethyl-2,5- diketopiperazine, 3-Benzyl-6-(p-hydroxybenzyl)-2,5-diketopiperazine, 3-Benzyl-6-iso-propyl-2,5-diketopiperazine, 3-Benzyl-6-(4-aminobutyl)-2, 5-diketopiperazine, 3,6-di(benzyl)-2,5-diketopiperazine, 3,6-di(p-hydroxybenzyl)-2,5-diketopiperazine, 3,6-di(p-(benzyloxy)benzyl)- 2,5-diketopiperazine, 3-benzyl-6-(4-imidazolyl)methyl-2,5-diketopiperazine, 3-benzyl-6-methyl-2,5-diketopiperazine, 3-benzyl-6-(2-(benzyloxycarbonyl). )ethyl)-2,5-diketopiperazine or mixtures thereof. Here again, compounds with the aforementioned configurational isomers are preferably suitable for selection.

It is also possible for the gel bodies according to the invention to contain at least one diarylamidocystine compound of the formula (GB-III) as gel former a).

wherein

X ⁺ independently represents a hydrogen atom or an equivalent of a cation,

R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a halogen atom, a C1-C4 alkyl group, a Ci-C ₄ alkoxy group, a C ₂ -C ₄ hydroxyalkyl group, a hydroxyl group, an amino group, an N-(Ci-C ₄ -alkyl)amino group, an N,N-di(Ci-C ₄ -alkyl)amino group, an N-(C2-C ₄ -hydroxyalkyl)amino group, an N,N-di(C ₂ -C ₄ -hydroxyalkyl)amino group or R ¹ with R ² or R ³ with R ⁴ forms a 5- or 6-membered fused ring, which in turn each has at least one group from Ci-C ₄ -alkyl group, Ci-C ₄ -Alkoxy group, C ₂ -C ₄ -hydroxyalkyl group, hydroxyl group, amino group, N-(Ci-C ₄ -alkyl)amino group, N,N-di(Ci-C ₄ -alkyl)amino group, N-(C ₂ -C ₄ -hydroxyalkyl)amino group, N,N-di(C ₂ -C ₄ -hydroxyalkyl)amino group may be substituted. Each of the stereocenters contained in the compound of formula (GB-III) can independently represent the L or D stereoisomer. It is preferred according to the invention if said cystine compound of the formula (GB-III) is derived from the L-stereoisomer of cysteine.

Said gel bodies can contain at least one compound of the formula (GB-III) in which R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a halogen atom, a C1-C4 alkyl group, a Ci-C ₄ - Alkoxy group, a C ₂ -C ₄ hydroxyalkyl group, a hydroxyl group, or R ¹ with R ² or R ³ with R ⁴ forms a 5- or 6-membered fused ring, which in turn each has at least one group from Ci-C ₄ - Alkyl group, Ci-C ₄ alkoxy group, C2-C4 hydroxyalkyl group, hydroxyl group may be substituted. In particular, those moldings are particularly suitable which, as a diarylamidocystine compound of the formula (GB-III) N,N'-dibenzoylcystine (R ¹ = R ² = R ³ = R ⁴ = hydrogen atom; X ⁺ = independently for a hydrogen atom or a equivalent of a cation), in particular N,N'-dibenzoyl-L-cystine.

The N-(C8-C24) _{-hydrocarbylglyconamide} compounds suitable as gel formers a) preferably have the formula (GB-IV).

where n is 2 to 4, preferably 3 or 4, especially 4;

R ¹ is selected from hydrogen, C1-C16 alkyl, C1-C3 hydroxy or

methoxyalkyl radicals, preferably C1-C3 alkyl, hydroxyalkyl or methoxyalkyl radicals, particularly preferably methyl;

R ² is selected from Cs-C ₂₄ alkyl, Cs-C ₂₄ monoalkenyl, C8-C24

dialkenyl radicals, C8-C ₂₄ trialkenyl radicals, Cs-C ₂₄ hydroxyalkyl radicals, Cs-C ₂₄ hydroxyalkenyl radicals, C1-C3 hydroxyalkyl radicals or methoxy-Ci-C3 alkyl radicals, preferably Cs-Cis alkyl radicals and mixtures thereof, more preferably Cs, C10 , C12, C14, C16 and cis-alkyl radicals and mixtures thereof, most preferably C12 and C14 alkyl radicals or a mixture thereof. In particularly preferred embodiments, the group HO-CH2-(CHOH) _n -C- is one of one

II or

Glycuronic acid, in particular the glycuronic acid of a hexose (n=4), derived residue. Here, glucuronic acid is to be mentioned in particular as a preferred residue. R ¹ is preferably H or a short-chain alkyl radical, especially methyl. R ² is preferably a long-chain alkyl group, for example a Cs-Cis-alkyl group.

Very particular preference is therefore given to compounds of the formula (GB-IV1) HO-CH2-(CHOH) ₄ -CN(CH ₃ )-R ² (GB-IV1) II o where R ² has the meanings given for formula (GB-IV).

In a particularly preferred embodiment, the at least one low molecular weight gel former is selected from the group consisting of the cyclic dipeptides, the cyclic dipeptide derivatives and dibenzylidene sorbitol. Due to its technical effect, the at least one gelling agent is particularly preferred, dibenzylidene sorbitol (DBS).

In a preferred embodiment, the enveloping substance is opaque. Those enveloping substances are referred to as “non-transparent” which have a transmission below 10%, preferably below 5% and in particular below 1% in the wavelength range from 410 to 800 nm at at least one wavelength, preferably at 600 nm. The transmission is determined by means of VIS spectrometry at a sample temperature of 20° C. and a cuvette length of 10 mm.

The use of non-transparent enveloping substances creates a product appearance, especially when used in combination with transparent gel bodies, which enables the consumer to distinguish between the surfaces covered by the enveloping substance and those not covered by the enveloping substance and the detergent portion unit, for example when removing it from a container , which comprises several detergent portion units, to specifically grip the surfaces covered by the enveloping substance and in this way to avoid direct contact with the gel body.

For the above reasons, the gel body and the enveloping substance preferably have a color difference DE of more than 20, preferably more than 40.

Because of their optical properties and their simpler production, preferred coating substances are white, ie not colored. The white color of the enveloping substance is particularly suitable for printing.

As an alternative to a preferably non-transparent white configuration of the enveloping substance, it can also be colored. The colored design of the enveloping substance enables, for example, the optical communication of specific product properties, for example with regard to its effect or smell. In order to ensure that the gel body and the enveloping substance can be distinguished visually, the colored enveloping substance preferably does not have the same color as the gel body. Colored enveloping substances can of course also be printed. To improve the integrity of the detergent tablets, they can have a film packaging, it being particularly preferred if each of the detergent tablets has a separate film packaging.

If film packaging is used, film packaging made from a water-soluble film material is preferred. The water-soluble film material may comprise one or more structurally distinct water-soluble polymer(s). Particularly suitable as water-soluble polymer(s) are polymers from the group of (possibly acetalized) polyvinyl alcohols (PVAL) and their copolymers.

Water-soluble film materials are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 gmof ¹ , preferably from 20,000 to 500,000 gmof ¹ , particularly preferably from 30,000 to 100,000 gmof ¹ and in particular from 40,000 to 80,000 gmof ¹ .

The preparation of the polyvinyl alcohol and polyvinyl alcohol copolymers typically involves the hydrolysis of intermediate polyvinyl acetate. Preferred polyvinyl alcohols and polyvinyl alcohol copolymers have a degree of hydrolysis of 70 to 100 mol %, preferably 80 to 90 mol %, particularly preferably 81 to 89 mol % and in particular 82 to 88 mol %.

In addition to vinyl alcohol, preferred polyvinyl alcohol copolymers include an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, sulfonic acids such as 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), acrylic acid, methacrylic acid, acrylic esters, methacrylic esters or mixtures thereof; among the esters, Ci- ₄ -alkyl esters or - hydroxyalkyl esters are preferred. Other suitable monomers are ethylenically unsaturated dicarboxylic acids, for example itaconic acid, maleic acid, fumaric acid and mixtures thereof.

Because of their availability, ease of processing and biodegradability, preference is given to film packaging which consists of at least 40% by weight, preferably at least 60% by weight and in particular at least 80% by weight of polyvinyl alcohol.

In order to increase the stability of the detergent tablets and to ensure a sufficient degree of filling in the outer packaging, it is preferable to shrink the film packaging onto the detergent tablets.

For reasons of sustainable design of the detergent portion units, it may be advisable to dispense with film packaging. Particularly preferred detergent tablets therefore do not have an outer packaging made of a water-soluble or water-insoluble film material.

If a larger number of detergent tablets are integrated into the detergent supply form, their stability can be further improved by a targeted arrangement of the tablets. Detergent supply forms which comprise at least ten, preferably at least twenty, particularly preferably at least thirty detergent tablets have proven to be advantageous.

The detergent tablets are preferably arranged sorted in the outer packaging in such a way that each of the detergent tablets is in direct contact with at least one other detergent tablet.

In a particularly preferred embodiment, the detergent tablets are sorted in the outer packaging so that each of the detergent tablets has at least one rough top or bottom in direct contact with at least one rough top or bottom of another detergent tablet. Such a form of supply is distinguished by high storage and transport stability of the detergent tablets. Particularly in the case of detergent tablets without individual film packaging, low adhesion of detergent tablets to one another and to the outer packaging is observed on the one hand, and a low tendency to abrasion of the tablets on the other. The particularly preferred sortings described below are also particularly advantageous for detergent supply forms in which the outer packaging has no water-insoluble cover film on its inside.

Preference is therefore given to detergent supply forms comprising a) outer packaging b) detergent tablets with an upper side that is plane-parallel to the underside and a lateral surface connecting the upper side and the lower side, the detergent tablets having a rectangular lower side whose largest diagonal is more than double, preferably more than four times is the height of the detergent tablet, wherein i) the outer packaging contains at least ten, preferably at least twenty, particularly preferably at least thirty detergent tablets, which are sorted in the outer packaging, and ii) the detergent tablets have an upper side or an underside, the average roughness of which is between 10pm and 500pm, where iii) the detergent tablets are sorted in the outer packaging so that - at least 25% of the detergent tablets have their underside in direct contact with the bottom surface of the outer packaging,

- at least 25% of the detergent tablets are in direct contact with the top surface of the outer packaging,

- All detergent tablets with at least one rough top or bottom are in direct contact with at least one rough top or bottom of another detergent tablet.

An alternative arrangement of the detergent tablets in the outer packaging, in which the detergent tablets are sorted in the outer packaging so that at least one cylindrical lateral surface of each of the detergent tablets is in direct contact with at least one cylindrical lateral surface of another detergent tablet, has proven to be technically advantageous . Once again, the adhesion of the detergent tablets to one another and to the outer packaging is prevented and the abrasion of the tablets is reduced. At the same time, the removal of the detergent tablets from the outer packaging can be facilitated in this way. This applies in particular to a detergent presentation form, comprising a) outer packaging with a base surface, a top surface opposite the base surface and side surfaces connecting the base surface and the top surface, b) detergent tablets with an upper side that is plane-parallel to the underside and a lateral surface connecting the upper side and the underside, wherein the detergent tablets have a rectangular underside, the largest diagonal of which is more than twice, preferably more than four times, the height of the detergent tablet, wherein i) the outer packaging contains at least two, preferably at least four, particularly preferably at least eight detergent tablets, which are sorted in the outer packaging are arranged, and ii) the detergent tablets have an upper side or an underside with an average roughness of between 10 μm and 500 μm, iii) the detergent tablets being sorted in the outer packaging are arranged in such a way that that

- all detergent tablets are in direct contact with the bottom surface of the outer packaging with one end of their lateral surface and

- preferably all detergent shaped bodies are in direct contact with the side surface of the outer packaging with their upper side and lower side.

Surprisingly, it has been found that in outer packaging with a high degree of filling, the storage and transport stability of the detergent tablets is improved. preferred Detergent supply forms are therefore characterized in that the outer packaging in the closed state has a filling level above 85% by volume, preferably between 90% by volume and

99% by volume.

In summary, items provided by this application include:

1 . Detergent supply form, comprising a) outer packaging b) detergent tablets with an upper side, an underside and a lateral surface connecting the upper side and the lower side, wherein i) the outer packaging contains at least two detergent tablets, which are sorted in the outer packaging, and ii) the detergent tablets one have a rough upper side or a rough underside, the mean roughness of which is from 1 μm to 1000 μm, preferably from 10 μm to 800 μm and in particular from 25 to 500 μm.

2. Detergent dosage form according to point 1, wherein the outer packaging has a flat bottom surface, the largest diagonal of which is greater than the height of the outer packaging.

3. Detergent supply form according to one of the previous points, with the outer packaging being in the form of a folding box.

4. Detergent supply form according to one of the previous points, with the outer packaging being resealable.

5. Detergent supply form according to one of the previous points, with the outer packaging being made of cardboard.

6. Detergent dosage form according to one of the previous points, wherein the outer packaging has no water-insoluble cover film, preferably no polyethylene cover film, on its inside.

7. Detergent supply form according to one of the preceding points, the detergent tablets having a weight of 14 g to 42 g, preferably 20 g to 38 g, in particular 24 g to 34 g.

8. Detergent dosage form according to one of the previous points, wherein the detergent shaped bodies are in the form of tablets or comprise tablets. Detergent offer form according to one of the previous points, wherein the

Detergent supply form comprises at least ten, preferably at least twenty, particularly preferably at least thirty detergent tablets. Detergent offer form according to one of the previous points, wherein the

Detergent shaped body has a flat underside, the largest diagonal of which is greater than the height of the detergent shaped body. Detergent offer form according to one of the previous points, wherein the

Detergent tablets have a flat underside, the largest diagonal of which is 1.5 times, preferably more than 2 times, the height of the gel body. Detergent offer form according to one of the previous points, wherein the

Detergent molding has an oval underside. Detergent offer form according to one of the previous points, wherein the

Detergent molding has an ellipsoidal or round, preferably a round underside. Detergent offer form according to one of the previous points, wherein the

Detergent tablet has a square bottom. Detergent offer form according to one of the previous points, wherein the

Detergent tablet has a triangular, square or hexagonal underside. Detergent offer form according to one of the previous points, wherein the

Detergent tablet has a top side that is plane-parallel to the underside. Detergent offer form according to one of the previous points, wherein the

Detergent tablet has a bottom and a top, which have the same geometric shape and the bottom and the top have the same surface area. Detergent offer form according to one of the previous points, wherein the

Detergent tablet has a bottom and a top, which have the same geometric shape and the bottom and the top have different surface areas. Detergent offer form according to one of the previous points, wherein the

Detergent molding is cuboid. Detergent offer form according to one of the previous points, wherein the

Detergent tablets b1) a dimensionally stable gel body and b2) an encapsulating substance in the form of a tablet which partially covers the surface of the dimensionally stable gel body. Detergent dosage form according to point 20, wherein the gel body and the enveloping substance are adhesively connected to one another. Detergent supply form according to one of points 20 or 21, wherein the gel body forms at least 16%, preferably at least 25% and in particular at least 30% of the total surface area of the detergent tablet. Detergent dosage form according to one of points 20 to 22, wherein the enveloping substance covers 10% to 70%, preferably 30% to 65% and in particular 40% to 60% of the surface of the gel body. Detergent dosage form according to any one of points 20 to 23, wherein the gel body contains a dye. Detergent dosage form according to any one of items 20 to 24, wherein the gel body is transparent. Detergent dosage form according to one of points 20 to 25, wherein the enveloping substance is opaque. Detergent dosage form according to any one of points 20 to 26, wherein the coating substance is white. Detergent dosage form according to one of points 20 to 27, wherein the coating substance is colored. Detergent dosage form according to one of points 20 to 28, wherein the gel body and the enveloping substance have a color difference DE above 20, preferably above 40. Detergent dosage form according to one of points 20 to 29, wherein the enveloping substance is printed. Detergent dosage form according to one of points 20 to 30, wherein the water-soluble coating substance covers the surface of the gel body on two opposite sides of the gel body. Detergent dosage form according to one of points 20 to 31, wherein the gel body has an underside and an upper side and the water-soluble encapsulating substance at least partially covers both the underside and the upper side of the gel body. Detergent dosage form according to one of points 20 to 32, wherein the gel body has an underside and an upper side and the water-soluble enveloping substance covers both the underside and the upper side of the gel body by at least 40%, preferably at least 60% and in particular at least 80%. Detergent dosage form according to one of points 20 to 33, wherein the gel body has an underside and an upper side and the water-soluble enveloping substance covers both the underside and the upper side of the gel body over the entire surface. Detergent dosage form according to any one of points 20 to 34, wherein the gel body makes up at least 50% by volume, preferably at least 60% by volume, of the detergent dosage form. Detergent offer form according to one of the previous points, wherein the

Detergent molding has no film packaging made of a water-soluble film material. Detergent offer form according to one of the previous points, wherein the

Detergent molding has no film packaging made of a water-insoluble film material. Detergent offer form according to one of the previous points, wherein the

Detergent tablets are sorted in the outer packaging so that each of the detergent tablets is in direct contact with at least one other detergent tablet. Detergent offer form according to one of the previous points, wherein the

Detergent shaped body is arranged sorted in the outer packaging that each of the detergent shaped body is in direct contact with at least one rough upper or lower side to at least one rough upper or lower side of another detergent shaped body. Detergent supply form according to one of the above points, comprising a) outer packaging b) detergent tablets with an upper side that is plane-parallel to the underside and a lateral surface connecting the upper side and the lower side, the detergent tablets having a rectangular lower side whose largest diagonal is more than double, preferably more than that Is four times the height of the detergent tablet, where i) the outer packaging includes at least ten, preferably at least twenty, particularly preferably at least thirty detergent tablets, which are sorted in the outer packaging, and ii) the detergent tablets have an upper side or an underside with an average roughness of between 10 μm and 500 μm, iii ) the detergent tablets are sorted in the outer packaging in such a way that

- at least 25% of the detergent tablets have their underside in direct contact with the bottom surface of the outer packaging,

- All detergent tablets with at least one rough top or bottom are in direct contact with at least one rough top or bottom of another detergent tablet. . Detergent supply form according to one of the preceding points, wherein the detergent tablets are sorted in the outer packaging so that each of the detergent tablets has at least one cylindrical lateral surface in direct contact with at least one cylindrical lateral surface of another detergent tablet. Ashtray dispenser form according to one of the above points, comprising a) an outer packaging with a base surface, a lid surface opposite the base surface and side surfaces connecting the base surface and the lid surface, b) detergent tablets with an upper side plane-parallel to the underside and a lateral surface connecting the upper side and the underside, wherein the detergent tablets have a rectangular underside, the largest diagonal of which is more than twice, preferably more than four times, the height of the detergent tablet, wherein i) the outer packaging contains at least two, preferably at least four, particularly preferably at least eight detergent tablets, which are sorted in the outer packaging are arranged, and ii) the detergent tablets have an upper side or an underside with an average roughness of between 10 μm and 500 μm, iii) the detergent tablets being sorted in the outer packaging are arranged in such a way that that

- all detergent tablets are in direct contact with the bottom surface of the outer packaging with one end of their lateral surface and - preferably all detergent shaped bodies are in direct contact with the side surface of the outer packaging with their upper side and lower side. Detergent supply form according to one of the preceding points, wherein the outer packaging in the closed state has a filling level of more than 85% by volume, preferably between 90% by volume and 99% by volume.

Claims

patent claims

2. Detergent dosage form according to claim 1, wherein the detergent tablet comprises b1) a dimensionally stable gel body and b2) an encapsulating substance in the form of a tablet which partially covers the surface of the dimensionally stable gel body.

3. detergent dosage form according to any one of the preceding claims, wherein the enveloping substance is printed.

4. Detergent supply form according to one of the preceding claims, wherein the gel body has a bottom and a top and the water-soluble coating substance covers both the bottom and the top of the gel body to at least 40%, preferably at least 60% and in particular at least 80%.

5. Detergent dosage form according to one of the preceding claims, wherein the gel body occupies at least 50% by volume, preferably at least 60% by volume, of the detergent dosage form.

6. detergent dosage form according to any one of the preceding claims, wherein the

Detergent molding has no film packaging made of a water-soluble film material.

7. detergent dosage form according to any one of the preceding claims, wherein the

Detergent molding has no film packaging made of a water-insoluble film material.

8. Detergent supply form according to one of the preceding claims, comprising a) an outer packaging b) detergent tablets with an upper side plane-parallel to the underside and a die

Top and bottom connecting lateral surface, wherein the Detergent tablets have a rectangular underside, the largest diagonal of which is more than twice, preferably more than four times, the height of the detergent tablet, wherein i) the outer packaging includes at least ten, preferably at least twenty, particularly preferably at least thirty detergent tablets, which are sorted in the outer packaging are arranged, and ii) the detergent tablets have an upper side or an underside, the mean roughness of which is between 10 pm and 500 pm, wherein iii) the detergent tablets are sorted in the outer packaging so that

9. Detergent dosage form according to one of Claims 1 to 7, comprising a) outer packaging with a base surface, a cover surface opposite the base surface and side surfaces connecting the base surface and the cover surface, b) detergent tablets with an upper side plane-parallel to the underside and a top and underside connecting Lateral surface, wherein the detergent tablets have a rectangular underside, the largest diagonal of which is more than twice, preferably more than four times, the height of the detergent tablet, wherein i) the outer packaging contains at least two, preferably at least four, particularly preferably at least eight detergent tablets, which in are sorted in the outer packaging, and ii) the detergent tablets have an upper side or an underside with an average roughness of between 10 μm and 500 μm, iii) the detergent tablets are arranged in the external packaging in a sorted manner, that

10. Detergent dispensing form according to one of the preceding claims, wherein the outer packaging in the closed state has a filling level above 85% by volume, preferably between 90% by volume and 99% by volume.